j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 3 ; 2 4 : 5 2 3 5 e5 2 4 9

Available online at www.sciencedirect.com

journal homepage: www.elsevier.com/locate/jmrt

Original Article

Evaluation of cracking damage in electrode

materials of a LMO/Al-Lix lithium-ion battery
through analysis of acoustic emission signals

Seung-Mi Lee a,1, Jae-Yeon Kim b,1, Jaeheon Lee b,**, Jai-Won Byeon a,*
a
Department of Materials Science and Engineering, Seoul National University of Science and Technology, Seoul,
01811, Republic of Korea
b
Mining Engineering Department, Colorado School of Mines, Golden, CO, 80401, USA

article info abstract

Article history: Damage due to the internal degradation of electrode materials in lithium-ion batteries
Received 17 December 2022 (LIBs) during charge-discharge cycles can cause capacity fading and safety issues. There-
Accepted 14 April 2023 fore, it is essential to assess damage to LIBs using nondestructive methods. In this study,
Available online 21 April 2023 the relationship between the damage mechanism and acoustic emission (AE) activity of a
commercial lithium manganese oxide (LMO)/Al-Lix alloy battery is systematically investi-
Keywords: gated. Microstructural observations of the electrodes revealed that the damage mecha-
Acoustic emission nisms of the LMO cathode and Al-Lix anode during accelerated charge-discharge were
Lithium-ion battery identical to those of microcracking. Energy, amplitude, duration, rise time, and peak fre-
Lithium manganese oxide quency were considered as possible AE parameters for real-time damage detection. The
Al-Lix alloy anode generation of AE hits was prominent during the later stages of the charging and dis-
Damage evaluation charging processes. The AE signals produced by damage to the Al-Lix alloy anode during
Cracking charging had a lower amplitude (0e60 dB) and energy (0e10 aJ). In comparison, those
produced by damage to the LMO cathode during charging had a relatively high amplitude
(100 dB) and energy (120 aJ). Additionally, the energy levels and amplitudes of the AE sig-
nals obtained during discharging decreased with an increasing number of cycles, indi-
cating that they can be used as indicators for evaluating the damage progression of the
primary, secondary, and tertiary cracks in LMOs. The AE technique offers the possibility of
monitoring and evaluating the damage to the anode and cathode of a commercial full cell
separately, as well as predicting the remaining capacity of the battery by monitoring the AE
hits.
© 2023 The Authors. Published by Elsevier B.V. This is an open access article under the CC
BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

* Corresponding author.
** Corresponding author.
E-mail addresses: smlee@seoultech.ac.kr (S.-M. Lee), jaeyeonkim@mines.edu (J.-Y. Kim), jaeheonlee@mines.edu (J. Lee), byeonjw@
seoultech.ac.kr (J.-W. Byeon).
1
Seung-Mi Lee and Jae-Yeon Kim contributed equally for this paper.
https://doi.org/10.1016/j.jmrt.2023.04.121
2238-7854/© 2023 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://
creativecommons.org/licenses/by-nc-nd/4.0/).
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1. Introduction

Rechargeable lithium-ion batteries (LIBs) are widely used as

energy sources in portable electronic devices and vehicles.
The recent increase in the use of rechargeable LIBs in electric
vehicles has rendered it essential to ensure that they are safe
for use and have high capacities [1,2]. A lithium secondary
battery comprises four components: a positive electrode
(cathode), negative electrode (anode), liquid electrolyte, and
polymer separator. Positive electrode materials are preferen-
tially made from lithium transition metal oxides, such as
lithium cobalt oxide (LCO), lithium manganese oxide (LMO),
lithium nickel oxide (LNO), and lithium iron phosphate,
whereas graphite or metal alloys, such as Mg, Al, Zn, Ag, Si,
and Sn, have been used as negative electrode materials [3e7].
As electrolytes, LiPF6, LiClO4, organics (e.g., acetonitrile and
polypropylene carbonate), and ionic liquids (e.g., [Emmim]
[BF4], EMImTFSI etc.) have been utilized [4,8]. Recently, for the
sake of high capacity, rapid charging, better cycle stability,
and environmental effectiveness, various nanostructured
organic and inorganic electrode materials modified via doping
and coating processes have been investigated, such as Si/C,
Sn/C, Sb2O3, TiO2/MoS2, Al/C, and Cu/Al as anodic materials
[4,5,9e11], and FeS2/C, V2O5, and triplite LiFeSO4F as cathodic
materials [4,5].
Charge-discharge damage, such as fracturing of the
electrode material, dissolution of metal ions, and/or forma-
tion of a solid electrolyte interface (SEI) layer, may occur in
the above-mentioned electrode materials [12e15]. It has been
reported that damage to the electrodes (i.e., cathode and
anode) can cause capacity fading and safety issues such as Fig. 1 e Typical waveform of an AE signal and AE
external short circuits [16]. Therefore, it is crucial to assess parameters.
the degradation of rechargeable LIBs. To evaluate the inter-
nal damages of batteries through non-destructive means,
neutron radiography [17], X-ray diffraction [18], ultrasonic
sensor [19], electrochemical impedance spectroscopy [20], Particularly, the characteristics of AE signals (i.e., duration,
and acoustic emission (AE) techniques [21e35] have been amplitude, energy, and peak frequency) depend on damage
attempted. mechanisms and electrode materials [21e28]. To date, AE
The AE technique records spontaneous transient elastic studies on LIBs have mostly been conducted using either
waves using a piezoelectric sensor. Fracturing in quasi- anode (e.g., Si [21] and graphite [22]) or cathode (e.g., man-
brittle materials releases transient elastic waves known as ganese oxide (MO) [23], LCO [24], sulfur powder [25], LNO [26],
AE [36e38]. These waves propagate through the medium Co0$2Cu0$2Mg0$2Ni0$2Zn0$2O [27], and NiSb2 [28]) half-cell
from the fracturing points to the material surface. The AE electrodes. Kircheva et al. attributed the AE signals ob-
signals can be detected in real time using the piezoelectric tained from a carbon anode half-cell to the formation of a SEI
sensor in contact with the sample. As shown in Fig. 1, AE layer on the anode surface, which generally accompanies the
signals have specific waveforms that can be characterized by formation of gas bubbles as chemical reaction products [22].
counts, energy, amplitude, duration, and frequency. The AE Gas bubbling by the formation of a SEI layer or electrolyte
technique has traditionally been applied to evaluate real- decomposition emitted continuous-type AE signals with
time macro and microdamage, such as cracking in rocks, longer rise times, longer durations, and relatively low peak
fatigue cracking in heavy industrial components, and frequencies [22]. The AE signals detected from cathode half-
delamination/fractures in composites [36e38]. Several cells of lithium transition metal oxides [23,24,26,27] and
studies have investigated the feasibility of using the AE anode half-cells of Si particles [21] were attributed to the
technique to evaluate in situ damage to the electrode mate- formation and propagation of cracks in the oxide or Si par-
rials of rechargeable LIBs during charge-discharge cycles. ticles. The cracking of the electrode materials emitted burst-
Cumulative AE hits [21e27], cumulative absolute energy [28], type AE signals with short rise times, short durations, and
duration and amplitude in the time-domain AE waveforms, relatively high peak frequencies. Villevieille et al. reported
and peak frequency in the fast Fourier-transformed fre- that the AE signals collected during the charge-discharge
quency spectrum [21,22,25e27] can be used as possible in- cyclic test of NiSb2 cathode half-cells were attributed to
dicators to evaluate damage to electrode materials. structural (i.e., crystallite / amorphous) and morphological
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Table 1 e Summarization of previous studies on AE technique for battery monitoring.

Ref, year Type Anode Cathode AE parameter Main topics AE source
[21] Half cell Si e  Cumulative AE hits  Damage monitoring of  Anode: Si particle
2010  Amplitude the Si anode cracking
 Duration
 Energy
 Rise time
[22] Half cell Carbon e  Cumulative AE hits  Study of SEI formation on  Anode: Gas generation
2011  Absolute energy anode due to SEI formation and
the cracking of the SEI
layer
[23] Half cell Li metal MO1)  Cumulative AE hits  Damage monitoring of  MO: Particle fracture
1997  Rate of AE hits cathode
[24] Half cell Li metal LCO2)  Cumulative AE hits  Feasibility of AE  Not discussed
2010 monitoring
[25] Half cell Li metal Sulfur powder  Cumulative AE hits  Damage monitoring of  Cathode: Collapse of
2019  Amplitude sulfur cathode electrode due to the
 Frequency (FFT) dissolution of sulfur
 Mechanical stress by Li2S
formation
[26] Half cell Li metal LNO3)  Cumulative AE hits  Damage monitoring of  LNO: Particle fracture
2020  Rate of AE hits cathode  SEI layer formation
 Frequency (FFT)
[27] Half cell Li metal (Co0$2Cu0$2Mg0$2Ni0$2Zn0.2)O  Cumulative AE hits  Damage monitoring of  Cathode: Crack formation
2021  Rate of AE hits the conversion-type and propagation, bulk/
 Frequency (FFT) cathode surface restructuring
 SEI layer formation
[28] Half cell Li metal NiSb2  Cumulative AE energy  Evolution of morpholog-  NiSb2: Structural (crystal-
2010 ical change in the con- lite / amorphous) and
version cathode morphological (micro/
nano) modification
[29] Full cell LiAl LMO4)  Cumulative AE hits  SoH6) evolution  LiAl: Crystalline change
2013  Amplitude due to phase transition
 LMO: Cracks,
fragmentation
[30] Full cell Carbon LCO  Cumulative AE hits  SoH evolution  Anode: Gas generation
2015  Amplitude  Damage monitoring of due to SEI formation
 Duration both electrodes  LCO: Cracks
 Frequency (FFT)
[31] Full cell e NCM5)  Frequency (FFT)  Monitoring of external  Not discussed
2022 short circuit
[32] Full cell Commercial 18,650 type  Cumulative AE hits  Evolution of bending  Not discussed
2019  Energy damage
 Frequency (FFT)
[33] Full cell Not mentioned  Energy  Development of the  Not discussed
2019 remaining useful life
estimation model
[34] Full cell Panasonic ICR 18650-22P LIB7)  Amplitude  SoH evolution  Not discussed
2021  Frequency (FFT)
[35] Full cell Graphite Mixture of LCO and NCM  Cumulative AE hits  Thermal abuse of battery  LCO & NMC: Microcracks
2019  Frequency (FFT)

Abbreviation: 1) MO: Manganese oxide, 2) LCO: Lithium cobalt oxide, 3) LNO: Lithium nickel oxide, 4) LMO: Lithium manganese oxide, 5) NCM:
Lithium nickel cobalt manganese oxide, 6) SoH: State of Health, 7) LIB: Lithium-ion battery.

(i.e., micro size / nano size) modifications of NiSb2 [28]. In
the field of batteries, the AE technique has also been inves-
tigated for other applications such as external short-circuit
monitoring [31], thermal abuse monitoring [35], and me-
chanical bending damage evaluation of flexible batteries [32].
The aforementioned studies on AE techniques are summa-
rized in Table 1.
To date, there have been many preliminary studies on half-
cell batteries to evaluate the damage to the electrode material
using the AE technique. In future research, the AE technique
should be applied to various commercial full-cell batteries to
improve its applicability. In the case of full-cell batteries,
during the charge-discharge cycles, the anode and cathode
electrodes experience degradation damage at the same time.
To evaluate the internal damage to each electrode using the
AE technique, the AE signals collected from the full cell must
be classified as those of the anode or cathode. Furthermore,
the relationship between the damage mechanisms of each
electrode and the classified AE signals must be studied in
detail.
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Previously, our group evaluated the damage in LCO/

graphite full-cell LIBs by means of the AE technique [30]. The
major degradation mechanisms of the LCO and graphite
electrodes were the cracking of LCO particles and the for-
mation of a SEI layer on the surface of the graphite electrode,
respectively. Normally, the cracking and formation of the
SEI layer release burst- and continuous-type AE signals,
respectively. Therefore, in the case of the LCO/graphite full
cell, the damage to each electrode could be individually
evaluated based on the waveform type (i.e., burst or
continuous) and the cumulative AE hits of each waveform.
However, the aforementioned evaluation criterion based on
the waveform type might not be applicable to other full-cell
batteries because damage mechanisms differ depending on
the electrode material. For instance, in LIBs using Li or Si
alloys as anode materials, the main degradation damage
mechanism is cracking. This damage mechanism is iden-
tical to that of commercial oxide cathode materials such as
LCO, LMO, and others [39e44]. Further case studies are
necessary to identify AE parameters other than the wave-
form type to evaluate the damage to various types of
rechargeable LIBs.
To date, few researchers have applied the AE technique to
the damage evaluation of commercial rechargeable lithium
metal batteries [19]. And, there have been no in-depth
studies on the relationship between the damage mecha-
nism and the acoustic activity of lithium metal anode ma-
terials. In this study, the relationship between the damage
mechanism and acoustic activity of a LMO/Al-Lix battery was
systemically investigated. The damage mechanisms of the
LMO and Al-Lix electrodes during the charge-discharge cy-
cles were found to be identical to cracking of the electrode
material. The charge-discharge voltage curves were divided
into four stages based on the specific cycle voltage at which
damage occurred. The characteristics of the AE signal
generated at each stage were analyzed in terms of energy,
amplitude, duration, and rise time in the time domain, and
peak frequency range in the frequency domain. The evolu-
tion of the AE parameters at each stage was correlated with
the damage mechanism in the electrode materials. Conse-
quently, specific AE parameters were proposed as possible
indicators to evaluate the damage to the anode and cathode
materials separately.

2. Materials and methods Fig. 2 e (a) Schematic of a 2032 coin cell LMO/AleLi battery
and (b) its internal structure.
2.1. Charge-discharge test of battery

A coin-cell-type battery with a nominal voltage of 3.3 V and a

capacity of 65 mAh was used. The internal structure of the
battery cell is shown in Fig. 2. This battery consisted of a LMO
cathode, an Al-Lix alloy anode, a separator, and a liquid elec-
trolyte in a coin-type stainless-steel case. The thicknesses of
the LMO cathode and Al-Lix alloy anode were approximately
1.6 and 0.7 mm, respectively. A polyethylene (PE) film with a
thickness of approximately 1 mm was used as a separator. The
liquid electrolyte comprised 1 M LiClO4 polycarbonate, 1,3-
dioxolane, and 1,2-dimethoxyethane in a 1:1:1 vol ratio. The
cell was cycled using a charge-discharge cycler (WBCS 1000,
Won-A Tech, Korea). Charging and discharging were
performed at a C-rate of 0.15 with a 5 min resting period
before the subsequent charging and discharging steps.
The highly accelerated charge-discharge cycles were
performed at a constant current of 9.5 mA with charging
and discharge voltage limits of 3.5 and 2.0 V at room tem-
perature (25  C).
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Fig. 3 e Actual image and schematic of the experimental setup to detect AE signals during the charge-discharge test of the
coin-type lithium-ion battery.

2.2. Acoustic emission analysis mechanism owing to microdamage in the two electrode ma-
terials was analyzed using scanning electron microscopy
The experimental setup shown in Fig. 3 was used to detect the (SEM) and X-ray diffraction (XRD).
AE signals from the cell during the cycling test. The AE signals
were detected using a resonant-type sensor (R15, Physical
Acoustic Corp., USA) with a nominal resonant frequency of 3. Results and discussion
150 kHz and frequency range of 50e200 kHz. The AE trans-
ducer was attached to the cell using high-viscosity silicone 3.1. Damage mechanism of the LMO/Al-Lix alloy
grease. To measure only the damage signal from the battery, a electrode
threshold value of 27 dB was set to exclude signals from
background noise. This implies that the AE activity was Fig. 4 shows the variation in the discharge capacity and cu-
recorded as a hit by the system when the signal exceeded a mulative AE hits with the number of charge-discharge cycles.
threshold of 27 dB.
The preamplifier value was set to 40 dB to amplify the small
signals collected from the AE transducer. AE signals were
collected using an acquisition device (PCI-2 with AEwin soft-
ware, Physical Acoustic Corp., USA). The AE waveform pa-
rameters of the recorded signals (the number of hits,
amplitude, energy, and peak frequency) were analyzed. A fast
Fourier transformation (FFT) was performed on the AE signals
to determine their frequency components.

2.3. Microstructural analysis

The batteries were disassembled in a glove box in a nitrogen

gas atmosphere to prevent further damage from the reactions
of the electrolyte with the atmosphere. The electrodes were
then washed in dimethyl carbonate to remove any remaining Fig. 4 e Variation of discharge capacity and cumulative AE
Li salts from the electrode surface. The degradation hits during the charge-discharge cyclic test.
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Fig. 5 e SEM images of the LMO cathode electrode: (a) as-received and after (b) 1 cycle (only charge), (c) 1 cycle (discharge),
(d) 2 cycles, (e) 5 cycles, and (f) 10 cycles. The allows in each images indicate the cracks of LMO power.

Capacity fading occurred at a rapid rate in the initial cycle but
slowed down thereafter. Capacity fading with an increasing
number of charge-discharge cycles is attributed to microscale
degradation damage to both electrodes.
Fig. 5 shows the SEM images of the microstructure of the
disassembled LMO cathode after a specific number of cycles.
Many cracks appeared in individual particles during the
discharge process of the first cycle (Fig. 5 (b, c)). Subsequent
short secondary or tertiary branching cracks occurred in the
LMO particles with cycling over repeated charge-discharge
cycles, following the initial primary crack generation (Fig. 5
(d-f)).
Fig. 6 (a) and (b) show the XRD patterns of the cathode
material when the state of charges (SoC) were 100 and 0%,
respectively. For the 100% SoC (Fig. 6 (a)), a-MnO2, Mn3O4 and
graphite were observed. Conversely, for the 0% SoC (Fig. 6 (b)),
Li0$88Mn2O4 and graphite were mainly observed. During the
discharging process, the a-MnO2 and Mn3O4 in the fully
charged state were transformed into the LMO phase (i.e.,
Li0$88Mn2O4) by lithiation. Graphite is usually used as a
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Fig. 6 e XRD patterns of the cathode material: (a) 100% state of charge and (b) 0% state of charge.

conductive mixing material to improve the conductivity of
cathode electrodes.
The cracking damage of the cathode materials observed
during the discharge process (Fig. 5) is attributed to the phase
transition (i.e., change in the crystal structure during the
cycle) of the LMO particles (Fig. 6). The tetragonal crystal
structure of a-MnO2 and Mn3O4 in the charged state begins to
transform into the cubic crystal structure of Li0$88Mn2O4 dur-
ing the discharging process, as shown in Fig. 6. The phase
transformation of the LMO electrode can occur at approxi-
mately 3.0 V owing to the intercalation of lithium ions during
the discharge process [39e42]. Theoretically, the structural
changes either from a-MnO2 to Li0$88Mn2O4 or from Mn3O4 to
Li0$88Mn2O4 can accompany a unit cell volume expansion of 78
or 104%. This volume expansion of the unit cell is known to
cause microcracks in the particles [39e42]. Based on the JCPDS
information, the lattice parameters of the unit cell for each
phase were as follows: (1) a-MnO2:9.7847  9.7847  2.863
A, a
unit volume of 313.8
A3, (2) Mn3O4: 5.765  5.765  9.442

A, a
unit volume of 274.1
A3, and (3) Li0$88Mn2O4:
8.2468  8.2468  8.2468 A, a unit volume of 560.9


A3.
Fig. 7 shows SEM images of the microstructures of the
disassembled Al-Lix alloy anode after a specific number of
cycles. After one cycle, relatively large cracks were observed
on the surface of the Al-Lix alloy electrode. As the number of
charge-discharge cycles increased, small separated particles
were observed.
Fig. 8 (a) and (b) show the XRD patterns of the anode elec-
trode materials when the charging state (SoC) was 100 and 0%,
respectively. In the 100 and 0% SoC, both AlLi and Al phases
were observed. Meanwhile, the relative amount of the AlLi
phase was higher for the 100% SoC than for 0% SoC, which

Fig. 7 e SEM images of the Al-Lix alloy anode electrode (a) as-received and after (b) 1 cycle, (c) 5 cycles, and (d) 10 cycles.
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Fig. 8 e XRD patterns of the anode material: (a) 100% state of charge and (b) 0% state of charge.

means the Al phase was transformed into the AlLi phase of approximately 290%. This elastic lattice expansion caused
during the charging process (i.e., from 0% SoC to 100% SoC) cracking in the Al-Lix alloy anode. It has been reported that an
owing to the lithiation. The phase transformation from Al to increase in the number of cracks over repeated cycles results
AlLi could also theoretically cause a lattice volume expansion in the pulverization of the alloy electrode [44]. Based on the

Fig. 9 e Illustration of the cracking and pulverization behavior of the Al-Lix anode electrode over repeated cycles.
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Fig. 10 e Charging-discharging voltage profile and
occurrence of AE hits at specific cycles: (a) the first cycle,
(b) the second cycle, (c) the fifth cycle, and (d) the 10th cycle.
5243
JCPDS information, the lattice parameters of the unit cell for
each phase were as follows: (1) LiAl: 6.370  6.370  6.370
A, a
unit volume of 258.47
A3, and (2) Al: 4.049  4.049  4.049

A, a
unit volume of 66.38
A3. The damage mechanism of the Al-Lix
alloy anode in this study is consistent with that in a previous
report [44]. The cracking and pulverization behavior of the Al-
Lix alloy anode over repeated cycles is schematically illus-
trated in Fig. 9.
In summary, the main microscale damage mechanism in
both electrodes was the same: cracking of the electrode ma-
terials. The cracking of the LMO and Al-Lix alloy electrode
materials mainly occurred during the discharge and charge
processes, respectively. Microscale damage in the two elec-
trode materials (Figs. 5 and 7) can block the passage of current
through the electrodes, leading to capacity fading of the bat-
tery, as shown in Fig. 4. In particular, the rapid capacity fading
during the initial cycle seems to be the result of a large
number of cracks in the LMO electrode at the initial cycle.
3.2. Relationship between AE signals and damage
The cracking of metallic (Al), intermetallic (AlLi), and ceramic
(LMO) materials emits acoustic signals of elastic waves from
the cracking sites [20e31]. AE signals have specific waveforms
that can be characterized by their counts, amplitudes, dura-
tions, and frequencies (Fig. 1). These AE parameters were
found to be sensitive to the shear stiffness of the materials,
the stress imposed on cracking, and the cracking magnitude
[37]. In Sections 3.2, and 3.3, the AE signals are systemically
characterized to separately evaluate the damage of each
electrode.
During the degradation of the LMO/Al-Lix battery, the cu-
mulative number of AE hits (i.e., the number of AE signals)
gradually increased after a large number of AE hits were
initially generated (Fig. 4). The increase in the accumulated AE
hits was attributed to an increase in the number of microscale
cracks in the electrode materials. Fig. 10 shows the occurrence
of AE hits and changes in the charge-discharge voltage after
various numbers of cycles. AE signals were detected during
both the charge and discharge processes. Considering the SEM
observations and the corresponding discussion in Section 3.1,
the AE signals in the charge and discharge processes were
associated with cracking in the Al-Lix alloy and LMO electrode
materials, respectively.
Meanwhile, the generation of AE hits was noticeably
prominent during the later stages of both the charge and
discharge processes, as shown in Fig. 10. In contrast, few AE
signals were observed during the early stages of the charge-
discharge cycles. This can be explained by the accumulation
of sufficient internal stress that causes cracking during the
late charging and discharging stages [45e47]. The internal
stress varied with the Li concentration in the active material.
During lithium-ion intercalation, the Li concentration on the
surface of the electrode material was higher than that in its
interior. Therefore, the phase transition to a Li-rich phase and
the corresponding volume expansion occurred preferentially
on the surface of the electrode material. The resulting grada-
tion in the phase and volume causes a lattice mismatch be-
tween the surface and interior of the material, thereby
inducing internal stress. The internal stress induced during
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Fig. 11 e (a) Division of charge-discharge curve into four specific stages and (b) damage progression mechanism in the two
electrodes at each stage.

Fig. 12 e Evolution of cumulative AE hits at each stage over repeated charge-discharge cycles.
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Fig. 13 e (a) Typical AE waveform obtained during the
charge-discharge cycle test and (b) its FFT spectrum.
the early stages of charging and discharging may not have
exceeded the critical stress required to cause cracking. How-
ever, the continued volume expansion of the constrained
electrode material caused the internal stress to increase to the
critical value for fractures and cracking to occur, thereby
generating AE hits at the late stages of charge and discharge.
Based on the above discussion on the microstructure and
AE signals, the full charge-discharge curve (i.e., the AE gen-
eration stages) can be divided into four stages, as shown
schematically in Fig. 11 (a). As mentioned in Section 3.1, 3 V is
the critical voltage at which the original cubic crystal structure
of LMO begins to transform into a tetragonal structure (i.e., the
elongated cube-like structure), and structural damage can
occur in the electrode materials [39]. Therefore, the stages are
defined as follows: stage A: 2.0e3.0 V (charge), stage B:
3.0e3.5 V (charge), stage C: 3.5 to 3.0 V (discharge), and stage D:
3.0 to 2.0 V (discharge). The simultaneous microstructural
changes and damage progression in both electrodes at each
stage are shown in Fig. 11 (b).
Fig. 12 shows the evolution of the cumulative AE hits in
each damage stage as the number of cycles increased. The
accumulated AE hits in the later stages of the charging (stage
B) and discharging (stage D) processes are higher than those in
the early stages (stages A and C). This confirms that electrode
5245
damage was mostly produced in the late stages of the charge
and discharge processes, as discussed above. Moreover,
except for the first few cycles, the number of cumulative AE
hits in stages B and D increased linearly with the number of
cycles in the investigated range. The increase in the cumula-
tive AE hits in stages B and D indicates that cracking damage
to the Al-Lix alloy anode during the charging process (Fig. 7)
and to the LMO cathode during the discharging process (Fig. 5)
accumulated over the cycles. Therefore, the AE curves at the B
and D stages quantitatively reflect the degree of microdamage
to each electrode material after a specific time of use. The
degree of cyclic degradation in the LMO/Al-Lix battery can be
inferred from the observed inverse relationship between the
capacity and AE hits, as shown in Fig. 4. Using the above
classification of the damage stages, the progressive damage to
each electrode in the battery can be tracked and predicted
separately by analyzing the AE signals generated at each
stage.
3.3. Evolution of AE parameters and correlation with
damage progress
Various waveform parameters of the AE signals obtained at
each stage were analyzed to compare the characteristics of
the AE signals obtained from the two electrodes. Fig. 13 shows
a typical AE signal waveform and its frequency spectrum.
Regardless of the number of cycles or AE stages within a cycle,
only burst-type waveforms with short rise times and short
durations were observed, and the frequency ranges of all the
analyzed signals were in the range 100e250 kHz. Because of
these non-distinct features of the signals, the damage to the
Al-Lix alloy anode and LMO cathode could not be separately
evaluated from the frequency values of the spectrum.
Another AE characteristic parameter is the cross plot of the
amplitude and energy of the AE signals collected at each stage
(Fig. 10), as shown in Fig. 14. Based on the amplitude and en-
ergy of the AE signals, the AE hits in the cross-plot (Fig. 14 (d))
can be grouped into the following three categories:
Group I (low-energy signal): amplitude: 0e60 dB; energy:
0e10 aJ.
Group II (medium-energy signal): amplitude: 60e80 dB;
energy: 10e25 aJ.
Group III (high-energy signal): amplitude: 80e100 dB; en-
ergy: 25e120 aJ.
The AE hits in stages A and C exhibited only low-energy
signals (Group I). Those in stage B displayed low-energy
(Group I) and medium-energy signals (Group II). Those in
stage D exhibited medium- and high-energy signals (Groups II
and III, respectively). As shown in Fig. 11, the signals at stages
B (Fig. 14 (b)) and D (Fig. 14 (d)) were attributed to cracking in
the Al-Lix anode during the charging process and cracking in
the LMO cathode during the discharging process, respectively.
Comparing the AE signals between stages B and D, the
cracking of LMO emitted higher-energy acoustic signals rela-
tive to the cracking of the Al-Lix alloy anode. These results
show that the amplitudes and energy levels depend on the
type of damaged material. The different characteristics of the
AE signals are believed to be associated with the higher frac-
ture toughness of the LMO ceramic (Young's modulus:
194 GPa) [47] compared with those of Al (Young's modulus:
5246 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 3 ; 2 4 : 5 2 3 5 e5 2 4 9

Fig. 14 e Amplitude-energy cross plots of AE hits at Fig. 15 e Amplitude-energy cross plots of AE signals at
different charge-discharge stages of the second cycle: stage D of various cycles: (a) first cycle, (b) second cycle,
(a) stage A, (b) stage B, (c) stage C, and (d) stage D. (c) fifth cycle, and (d) 10th cycle.
 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 3 ; 2 4 : 5 2 3 5 e5 2 4 9
Fig. 16 e (aed) Schematic of the cracking behavior of the LMO cathode material and resulting energy levels of the AE signal.
70 GPa) and AlLi intermetallic compound (Young's modulus:
105 GPa) [48].
To monitor the discharge cracking procedure of the LMO
cathode material in detail, the energy levels of the AE signals
in stage D at various numbers of cycles are compared in the
energy-amplitude cross plots in Fig. 15. As the number of
charge-discharge cycles increased, the number of medium-
energy (Group II) and high-energy (Group III) signals
decreased. Generally, higher-energy pulses are emitted from
the larger cracks in a given material [23]. The decrease in AE
energy over repeated charge-discharge cycles implies that
subsequent short secondary or tertiary branching cracks
occurred in the LMO particles with cycling over repeated
charge-discharge cycles following the initial primary crack
generation. This explanation is supported by the micro-
structural features shown in Fig. 5. The detailed LMO
cracking progression and resulting AE features are presented
in Fig. 16.
In conclusion, this study shows that it is possible to sepa-
rately evaluate the degree of degradation damage of both
electrodes exhibiting the same damage mechanism (i.e.,
cracking) by monitoring the cumulative AE hits of each
charge-discharge stage. Furthermore, the amplitude and en-
ergy level of the AE signals can be proposed as possible in-
dicators for evaluating the damage levels (i.e., cracking size)
and damage progress. The overall performance of the battery
can be estimated using the empirical correlation between the
cumulative AE hits and the overall capacity fading. Although
the feasibility of the AE technique for nondestructive evalua-
tion of the degradation damage in the LMO/Al-Lix alloy LIB
5247
was studied, further study of LIBs consisting of other types of
electrode materials are required in the future.
4. Conclusions
In this study, progressive cyclic charge-discharge damage to a
LMO/Al-Lix rechargeable battery was evaluated using AE
signal analysis during an accelerated cycling test. The
following conclusions were drawn.
As the number of charge-discharge cycles increased, the
cumulative number of AE hits increased at a specific rate after
an initial abrupt increase. AE hits were mostly detected during
the late stages of the charge and discharge cycles. Micro-
structural observations revealed that the capacity fading and
occurrence of AE hits were due to cracking of the LMO cathode
material during the discharge process and cracking and pul-
verization of the Al-Lix alloy anode during the charging
process.
Based on the cross-plots of the amplitude and energy at
each specific cycle, the AE hits produced from LMO cracking
were found to possess relatively higher energy, whereas those
from the cracking of the Al-Lix alloy had lower or medium
energy. In the LMO cathode, damage progression with an
increasing number of cycles (i.e., generation of short second-
ary and tertiary cracks) can be evaluated by tracking the
transition of the amplitude and energy level from high to low
values.
The degree of damage in each electrode (i.e., the micro-
cracking of the LMO cathode and Al-Lix alloy anode) could also
5248 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 3 ; 2 4 : 5 2 3 5 e5 2 4 9
be predicted separately from the increase in AE hits and cross-
plots of amplitude and energy. The empirical inverse corre-
lation between the cumulative AE hits and the overall capacity
is a feasible method for AE monitoring of the predicted
remaining life of a battery.
Data availability statement
The complete data supporting the findings of this study are
available from the corresponding author upon reasonable
request.
Funding statement
This study was supported by a Research Program funded by
SeoulTech (Seoul National University of Science and
Technology).
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
references
[1] Vetter J, Nova k P, Wagner MR, Veit C, Mo€ ller KC,
Besenhard JO, et al. Ageing mechanisms in lithium-ion
batteries. J Power Sources 2005;147(1e2):269e81.
[2] Broussely M, Biensan P, Bonhomme F, Blanchard P,
Herreyre S, Nechev K, et al. Main aging mechanisms in Li ion
batteries. J Power Sources 2005;146(1e2):90e6.
[3] Obrovac MN, Chevrier VL. Alloy negative electrodes for Li-ion
batteries. Chem Rev 2014;114(23):11444e502.
[4] Mishra A, Mehta A, Basu S, Malode SJ, Shetti NP, Shukla SS,
et al. Electrode materials for lithium-ion batteries. Mater Sci
Energy Technol 2018;1(2):182e7.
[5] Shetti NP, Dias S, Reddy KR. Nanostructured organic and
inorganic materials for Li-ion batteries: a review. Mater Sci
Semicond Process 2019;104:104684.
[6] Ji B, Zhang F, Sheng M, Tong X, Tang Y. A novel and
generalized lithium-ion-battery configuration utilizing Al foil
as both anode and current collector for enhanced energy
density. Adv Mater 2017;29(7):1604219.
[7] Jiang C, Zheng Y, Wang D, Zheng Y, Xie C, Shi L, et al.
Unusual size effect in ion and charge transport in micron-
sized particulate aluminum anodes of lithium-ion batteries.
Angew Chem Int Ed 2022;61(38):e202208370.
[8] Mishra A, Shetti NP, Basu S, Reddy KR, Aminabhavi TM.
Recent developments in ionic liquid-based electrolytes for
energy storage supercapacitors and rechargeable
batteries. In: Inamuddin, Asiri Abdullah M, Kanchi S,
editors. Green Sustainable Process for Chemical and
Environmental Engineering and Science. Elsevier; 2020.
p. 199e221.
[9] Tong X, Zhang F, Chen G, Liu X, Gu L, Tang Y. Coreeshell
aluminum@carbon nanospheres for dual-ion batteries with
excellent cycling performance under high rates. Adv Energy
Mater 2018;8(6):1701967.
[10] Qin P, Wang M, Li N, Zhu H, Ding X, Tang Y. Bubble-sheet-
like interface design with an ultrastable solid electrolyte
layer for high-performance dual-ion batteries. Adv Mater
2017;29(17):1606805.
[11] Zhang M, Xiang L, Galluzzi M, Jiang C, Zhang S, Li J, et al.
Uniform distribution of alloying/dealloying stress for high
structural stability of an Al anode in high-areal-density
lithium-ion batteries. Adv Mater 2019;31(18):1900826.
[12] Fergus JW. Recent developments in cathode materials for
lithium ion batteries. J Power Sources 2010;195(4):939e54.
[13] Zhao K, Pharr M, Vlassak JJ, Suo Z. Inelastic hosts as
electrodes for high-capacity lithium-ion batteries. J Appl
Phys 2011;109:016110.
[14] Agubra V, Fergus J. Lithium ion battery anode aging
mechanisms. Materials 2013;6(4):1310e25.
[15] Benedek R, Thackeray MM. Lithium reactions with
intermetallic-compound electrodes. J Power Sources
2002;110(2):406e11.
[16] Tran MK, Mevawalla A, Aziz A, Panchal S, Xie Y, Fowler M. A
review of lithium-ion battery thermal runaway modeling
and diagnosis approaches. Processes 2022;10(6):1192.
[17] Goers D, Holzapfel M, Scheifele W, Lehmann E, Vontobel P,
Nova  k P. In situ neutron radiography of lithium-ion
batteries: the gas evolution on graphite electrodes during the
charging. J Power Sources 2004;130(1e2):221e6.
[18] Morcrette M, Chabre Y, Vaughan G, Amatucci G, Leriche JB,
Patoux S, et al. In situ X-ray diffraction techniques as a
powerful tool to study battery electrode materials.
Electrochim Acta 2002;47(19):3137e49.
[19] Kim JY, Jo JH, Byeon JW. Ultrasonic monitoring performance
degradation of lithium ion battery. Microelectron Reliab
2020;114:113859.
[20] Messing M, Shoa T, Habibi S. Estimating battery state of
health using electrochemical impedance spectroscopy and
the relaxation effect. J Energy Storage 2021;43:103210.
[21] Rhodes K, Dudney N, Lara-Curzio E, Daniel C. Understanding
the degradation of silicon electrodes for lithium-ion batteries
using acoustic emission. J Electrochem Soc
2010;157(12):A1354.
[22] Kircheva N, Genies S, Brun-Buisson D, Thivel PX. Study of
solid electrolyte interface formation and lithium
intercalation in Li-ion batteries by acoustic emission. J
Electrochem Soc 2011;159(1):A18.
[23] Ohzuku T, Tomura H, Sawai K. Monitoring of particle
fracture by acoustic emission during charge and discharge of
Li/MnO2 cells. J Electrochem Soc 1997;144(10):3496.
[24] Komagata S, Kuwata N, Baskaran R, Kawamura J, Sato K,
Mizusaki J. Detection of degradation of lithium-ion batteries
with acoustic emission technique. ECS Trans 2010;25(33):163.
[25] Lemarie Q, Alloin F, Thivel PX, Idrissi H, Roue L. Study of
sulfur-based electrodes by operando acoustic emission.
Electrochim Acta 2019;299:415e22.
[26] Schweidler S, Bianchini M, Hartmann P, Brezesinski T,
Janek J. The sound of batteries: an operando acoustic
emission study of the LiNiO2 cathode in Lieion cells. Batter
Supercaps 2020;3(10):1021e7.
[27] Schweidler S, Dreyer SL, Breitung B, Brezesinski T. Operando
acoustic emission monitoring of degradation processes in
lithium-ion batteries with a high-entropy oxide anode. Sci
Rep 2021;11(1):1e8.
[28] Villevieille C, Boinet M, Monconduit L. Direct evidence of
morphological changes in conversion type electrodes in Li-
ion battery by acoustic emission. Electrochem Commun
2010;12(10):1336e9.
[29] Kircheva N, Genies S, Chabrol C, Thivel PX. Evaluation of
acoustic emission as a suitable tool for aging
characterization of LiAl/LiMnO2 cell. Electrochim Acta
2013;88:488e94.
 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 3 ; 2 4 : 5 2 3 5 e5 2 4 9
[30] Choe CY, Jung WS, Byeon JW. Damage evaluation in lithium
cobalt oxide/carbon electrodes of secondary battery by
acoustic emission monitoring. Mater Trans
2015;56(2):269e73.
[31] Zhou N, Cui X, Han C, Yang Z. Analysis of acoustic
characteristics under battery external short circuit based on
acoustic emission. Energies 2022;15(5):1775.
[32] Hao W, Yuan Z, Xu Y, Zhu S, Chen H, Fang D. Damage
analysis of cylindrical lithium-ion cells under three-points
bending using acoustic emission. J Power Sources
2019;444:227323.
[33] Beganovic N, So € ffker D. Estimation of remaining useful
lifetime of lithium-ion battery based on acoustic emission
measurements. J Energy Resour Technol 2019;141(4).
[34] Zhang K, Yin J, He Y. Acoustic emission detection and
analysis method for health status of lithium ion batteries.
Sensors 2021;21(3):712.
[35] Kim JY, Wang ZL, Lee SM, Byeon JW. Failure analysis of
thermally abused lithium-ion battery cell by microscopy,
electrochemical impedance spectroscopy, and acoustic
emission. Microelectron Reliab 2019;100:113363.
[36] Kao C-S, Carvalho FCS, Labuz JF. Micromechanisms of
fracture from acoustic emission. Int J Rock Mech Min Sci
2011;48(4):666e73.
[37] Gu B, Nihei KT, Myer LR, Pyrak-Nolte LJ. Fracture
interface waves. J Geophys Res Solid Earth
1996;101(B1):827e35.
[38] Karimian SF, Modarres M, Bruck HA. A new method for
detecting fatigue crack initiation in aluminum alloy using
acoustic emission waveform information entropy. Eng Fract
Mech 2020;223:106771.
5249
[39] Li X, Xu Y, Wang C. Suppression of JahneTeller distortion of
spinel LiMn2O4 cathode. J Alloys Compd 2009;479(1e2):310e3.
[40] Ohzuku T, Kitagawa M, Hirai T. Electrochemistry of
manganese dioxide in lithium nonaqueous cell: III. X-ray
diffractional study on the reduction of spinel-related
manganese dioxide. J Electrochem Soc 1990;137(3):769.
[41] Vitins G, West K. Lithium intercalation into layered LiMnO2. J
Electrochem Soc 1997;144(8):2587.
[42] Christensen J, Newman J. A mathematical model of stress
generation and fracture in lithium manganese oxide. J
Electrochem Soc 2006;153(6):A1019.
[43] Winter M, Besenhard JO. Electrochemical lithiation of tin and
tin-based intermetallics and composites. Electrochim Acta
1999;45(1e2):31e50.
[44] Li H, Yamaguchi T, Matsumoto S, Hoshikawa H, Kumagai T,
Okamoto NL, et al. Circumventing huge volume strain in alloy
anodes of lithium batteries. Nat Commun 2020;11(1):1e8.
[45] Cheng YT, Verbrugge MW. Application of Hasselman's crack
propagation model to insertion electrodes. Electrochem Solid
State Lett 2010;13(9):A128.
[46] Woodford WH, Chiang YM, Carter WC. Electrochemical
shock” of intercalation electrodes: a fracture mechanics
analysis. J Electrochem Soc 2010;157(10):A1052.
[47] Qi Y, Hector LG, James C, Kim KJ. Lithium concentration
dependent elastic properties of battery electrode materials
from first principles calculations. J Electrochem Soc
2014;161(11):F3010.
[48] Noble B, Harris SJ, Dinsdale K. The elastic modulus of
aluminium-lithium alloys. J Mater Sci 1982;17(2):461e8.