Journal of Power Sources 542 (2022) 231775

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Journal of Power Sources

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

Correlative electrochemical acoustic time-of-flight spectroscopy and X-ray

imaging to monitor the performance of single-crystal and polycrystalline
NMC811/Gr lithium-ion batteries
H. Michael a, b, R.E. Owen a, b, J.B. Robinson a, b, T.M.M. Heenan a, b, C. Tan a, b, A.J. Wade a, b,
R. Jervis a, b, D.J.L. Brett a, b, P.R. Shearing a, b, *
a
The Electrochemical Innovation Lab, Department of Chemical Engineering, University College London, WC1E 7JE, United Kingdom
b
The Faraday Institution, Quad One, Harwell Science and Innovation Campus, Didcot, OX11 0RA, UK

H I G H L I G H T S

• Acoustic testing can detect lithium-ion cell degradation during cycling.

• Acoustic behaviour of lithium-ion cells is influenced by electrode morphology.
• Battery performance is affected by electrode morphology.
• X-ray imaging can inform acoustic interpretation of lithium-ion cells.

A R T I C L E I N F O A B S T R A C T

Keywords: LiNixMnyCozO2 (NMC) electrodes typically consist of anisotropic single-crystal primary particles aggregated to
NMC form polycrystalline secondary particles. Electrodes composed of polycrystalline NMC particles have a
Single crystal comparatively high gravimetric capacity and good rate capabilities but do not perform as well as single crystal
Polycrystalline
equivalents in terms of volumetric energy density and cycling stability. This has prompted research into well-
Time-of-Flight
X-ray computed tomography
dispersed single-crystalline NMC products as an alternative solution for high-energy-density batteries. Here,
for the first time known to the authors, electrochemical acoustic time-of-flight (EA-ToF) spectroscopy has been
shown to be effective in distinguishing between Li-ion batteries composed of either single-crystal NMC811 (SC-
NMC811) or polycrystalline NMC811 (PC-NMC811) electrodes. Cells composed of PC-NMC811 electrodes had a
higher degree of gas evolution compared to cells containing SC-NMC811 electrodes. Cells composed of PC-
NMC811 electrodes also underwent larger changes in the acoustic signal’s time-of-flight (ToF) during constant
current cycling at a range of C-rates indicating expansion, fracture or dislocation of the reflective interfaces
inside the cell. In addition, X-ray computed tomography (X-ray CT) has been used to confirm significant
morphological differences between SC-NMC811 electrodes and PC-NMC811 electrodes including the electrode’s
particle size distribution (PSD) that is suggested to have an effect on acoustic signal interaction with these
electrode interfaces.

1. Introduction can withstand fast-charging and can maintain high capacities for
long-distance use. The range of an EV is determined by the energy of the
Li-ion batteries (LiBs) have become ubiquitous in modern life due to Li-ion cell (and subsequently the battery pack), which is highly depen­
their use in an array of applications ranging from consumer electronics, dent on the electrode chemistry and operating conditions. In commercial
to domestic appliances and electric vehicles (EVs) [1]. While the applications, the cathode is most critical to cell capacity and therefore
ever-increasing market share of EVs will inevitably aid the transition to a battery electric vehicle (BEV) range [2].
low carbon future, it is imperative that the batteries used are affordable, Many layered transition metal cathodes have been developed and a

* Corresponding author. The Electrochemical Innovation Lab, Department of Chemical Engineering, University College London, WC1E 7JE, United Kingdom.
E-mail address: [email protected] (P.R. Shearing).

https://doi.org/10.1016/j.jpowsour.2022.231775
Received 7 February 2022; Received in revised form 27 May 2022; Accepted 18 June 2022
Available online 8 July 2022
0378-7753/© 2022 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
H. Michael et al. Journal of Power Sources 542 (2022) 231775

wide range of LiNixMnyCozO2 (NMC) chemistries are currently used in with minimal cost and high time-resolution results, making it an
LiBs. They have been deployed in electric and hybrid-electric vehicles attractive proposition for detailed on-board diagnostics of operating
and are amongst the most promising LiB cathodes because their layered batteries [10,14]. Whilst X-ray CT is a valuable diagnostic tool for
structures provide higher reversible capacities (>200 mAh g− 1) and capturing images of LiBs before and after cycling, it is impractical and
favourable rate capabilities (electronic conductivity ≈ 2.8 × 10− 5 S expensive to carry out large scale cycling of cells inside an X-ray CT
cm− 1 and Li+ diffusivity of 10− 8 to 10− 9 cm2 s− 1) than previously instrument for a long period of time; however, many significant findings
commercialised LiCoO2 (LCO) cathodes to enable longer-range opera­ from lab-based X-ray CT experiments have emerged in recent years
tion and faster-charging [2]. The NMC particles’ crystallinity and related to the link between microstructure and performance, cracking
morphology has a large influence on the energy density, cycling stabil­ and cell-level failure, amongst others [15–18].
ity, and rate capability of the electrode in practical applications. For During prolonged cycling, EA-ToF spectroscopy measurements of
instance, the evolution of micro-cracks in NMC811 (where x ≈ 0.8) is far whole cell assemblies can be complicated by various phenomena
more prevalent in polycrystalline NMC811 (PC-NMC811) particles including gas formation, material stress changes and thermal expansion.
compared to single crystal NMC811 (SC-NMC811) particles, due to an In addition, intrinsic physical properties such as particle size, electrode
unconstrained expansion in SC-NMC811 particles which lowers the risk density, local electrode composition and tortuosity provide significant
of intergranular microcrack formation [2,3]. Though both materials are challenges to directly measuring thicknesses in LiBs, as these factors can
composed of crystallites of the same material (NMC811 with R3m vary considerably between different cells and influence their acoustic
symmetry), the morphology of these crystallites, and the particles they behaviour. Therefore, some familiarity with the acoustic signature of
form, are significantly different. The PC-NMC811 electrode is made up different full cells is beneficial for discerning changes in acoustic sig­
of large (~10 μm), spherical agglomerates of multiple small crystallites natures due to intrinsic physical properties and structural changes dur­
of around ~300–500 nm, each of which tends to have an oblong or ing cycling.
anisotropic morphology. In contrast, the SC-NMC811 electrode is made In this study, correlative X-ray CT was used alongside EA-ToF spec­
up of individual particles of ostensibly single crystallites that are larger troscopy to provide new insights into how varying the crystallinity of the
than the primary particles, but smaller than their agglomerates in the cathode effects the acoustic behaviour of LiBs. To the authors’ knowl­
PC-NMC811 electrode. These particles are of the order of 1–5 μm in size, edge, this is the first time EA-ToF spectroscopy has been carried out on
less oblong in shape and are composed of one, or only a few, crystal LiBs composed of SC-NMC811 cathodes, to explore whether EA-ToF
grains [4]. spectroscopy can provide a sensitivity capable of detecting the
In recent years, there has been a move towards the application of intrinsic difference in bulk electrode properties caused by the different
new characterisation techniques on batteries to better understand the particle morphology of the tested NMC811 electrodes. EA-ToF spec­
degradation processes and extend their lifetimes. Of these, acoustic troscopy was also used to evaluate changes in the acoustic signal’s ToF
techniques have increased in popularity extremely rapidly [5], with between LiBs composed of either SC-NMC811 electrodes or PC-NMC811
electrochemical acoustic time-of-flight (EA-ToF) spectroscopy being electrodes during cycling and whether these ToF changes correlated
used to study various degradation phenomena in LiBs such as gas for­ with changes in exterior cell temperature. X-ray CT was used to ascertain
mation [6], cell stiffness [7], and cathode dissolution [8]. Electro­ the cell assembly parameters and arrangement, to inform the acoustic
chemical acoustic time-of-flight (EA-ToF) spectroscopy involves passing interpretation. In addition, X-ray nano computed tomography (nano-CT)
an ultrasonic pulse (acoustic signal) through a sample and recording the was used to further understand differences in morphology between SC-
reflected signal that passes though the sample’s respective layers. NMC811 and PC-NMC811 electrodes that can cause differing acoustic
EA-ToF spectroscopy was first carried out on a battery system by Hsieh signal interactions and thus influence the acoustic signature of SC-
et al. to examine the state of health (SoH) of LiCoO2/graphite pouch cells NMC811/Gr and PC-NMC811/Gr cells.
[9]. The key parameter obtained from this type of acoustic experiment is
the acoustic time-of-flight (ToF). ToF can be calculated using Eq. (1): 2. Experimental methodology
L L
ToF = = √̅̅ (1) LiBs comprising NMC811 and graphite electrodes were supplied by
Cs E
ρ LiFUN Technology Ltd (Zhuzhou City, China) in a 5-layer wounded
pouch cell configuration with dimensions of 30 mm × 20 mm. The
where L is the path length travelled, E is the elastic modulus, and ρ is the NMC811 and graphite electrodes were fabricated at LiFUN Technology
density of the material. The square root of E/ρ is the speed of sound, Cs, Ltd, and the cells were obtained dry and sealed. The cells were trans­
through a given medium [10]. The operating principles of electro­ ferred to a vacuum oven and dried under vacuum at 100 ◦ C overnight
chemical acoustic time-of-flight spectroscopy have recently been (approx. 12 h) to remove any air and moisture from the cell before
described elsewhere [5,6,8]. transferring to an argon filled glovebox. Pouch cells were filled with 0.8
Studies have also commonly coupled EA-ToF spectroscopy with mL of 1.0 M LiPF6 dissolved in a mixture of ethylene carbonate (EC):
complementary characterisation tools including X-ray diffraction (XRD) ethyl methyl carbonate (EMC) in the ratio 3:7 by volume with 2% (by
[11] and X-ray computed tomography (X-ray CT) [6,8] to further weight) vinylene carbonate (VC) additive (Soulbrain MI) and then
enhance the understanding of structural changes taking place in these sealed at − 70 kPa gauge pressure using a vacuum chamber (Audionvac
materials and architectural changes at the device level [6]. It is widely VMS 53, Audion Elektro). A small vacuum is needed to account for
acknowledged that there are multiple degradation mechanisms at play vapour pressure of the EMC electrolyte additive. Within 30 min of
in the ageing of a LiB and enabling the prediction of which mechanism - sealing, cells were held at 1.5 V overnight using a multi-channel battery
or combination of mechanisms - is most critical in particular conditions cycler (BCS-805, Biologic). This avoids dissolution of the copper current
is vital to understanding and mitigating degradation, particularly for collector and gives sufficient time for wetting of the electrodes and
ostensibly similar cells [12,13]. In particular, progress in EA-ToF in­ separator.
vestigations of LiB material property changes can improve the mecha­ EA-ToF measurements were carried out using an Olympus Epoch 650
nistic understanding of structural changes during charge/discharge and ultrasonic flaw detector (Olympus Corp, Japan) with a pulse-echo con­
provide a greater understanding of these LiB dynamics, something tact transducer (M110-RM, Olympus Corp, Japan). A frequency of 2.25
which will help to overcome limitations in current density, battery MHz was chosen for all EA-ToF measurements using a piezoelectric
lifetime and capacity fade and ultimately minimise the total cost of transducer element (6 mm diameter), capable of frequencies of up to 5
battery systems. In addition, EA-ToF spectroscopy is a non-invasive, MHz. Ultrasonic couplant (H-2, Olympus Corp, Japan) was applied to
non-destructive operando technique that can be applied to batteries maintain interfacial contact between the cell and transducer to facilitate

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H. Michael et al. Journal of Power Sources 542 (2022) 231775

propagation of the ultrasonic pulse into the pouch cell. Constant pres­ (PicoTech, U.K.).
sure was applied behind the transducer with a 200 g weight placed on A Nikon XTH 225 ST laboratory X-ray microscope was used to probe
top of the sensor (Fig. 1). A uniform weight is placed on the transducer to the internal cell structure of each SC-NMC811/Gr and PC-NMC811/Gr
ensure a consistent signal is obtained throughout the measurements. The pouch cell before electrochemical cycling. These scans were obtained
magnitude of this weight was determined based on the experimental at an accelerating voltage of 180 kV and an incident beam power of 18.5
setup to optimise the signal amplitude through the LiB. However, a W, using a W target and a 0.5 mm Cu filter. 3176 projections were ob­
lower value may be used with a higher initial gain in the acoustic signal tained for each scan with the geometric magnification of the system
to achieve the same results (and vice versa) throughout the measure­ resulting in a pixel size of approximately 24.5 μm “Nikon CT Agent”
ments, by ensuring consistent contact between the transducer and the software was used to reconstruct all radiographic images using a cone
cell. beam filtered back projection algorithm. Visualisation of all recon­
The magnitude of the measured acoustic response by the transducer structed X-ray imaging scans was performed using Avizo software (FEI,
is in part determined by the gain, which was set at 58 dB to optimise the France). The software allows for visualisation of all the electrode layers
magnitude of the received signal over the time range of interest. The and current collection tabs inside the cell.
voltage applied to the piezoelectric transducer was 200 V. The resolu­ To provide electrode morphology information, nano-CT was per­
tion of each waveform data sample, with 8000 discrete mapping points formed on pristine (uncycled) samples of SC-NMC811 and PC-NMC811
equally spaced across the range of 20 μs, provides a ToF resolution of electrodes. An A Series/Compact Laser Micromachining System (Oxford
20.2 ns for each data point. The ultrasound waveform data was trans­ Lasers, Oxford, UK) with a 532 nm wavelength laser was used to prepare
ferred from the Epoch 650 through an RS232 connection and output files samples for nano-CT [19]. Tomographic scans were performed using an
acquired by a custom python code. All acoustic data collected was Ultra 810 X-ray instrument (Zeiss Xradia 810 Ultra, Carl Zeiss., CA, USA)
analysed using Python 3.7. equipped with a rotating Cr anode source producing a
Electrochemical testing was carried out using an SP-200 potentiostat quasi-monochromatic beam with a characteristic emission peak at 5.4
(BioLogic, France). Pouch cells were initially put through a formation KeV (Cr–Kα). X-ray CT scans were carried out with an X-ray source tube voltage of 30
cycle using a constant current protocol with an applied rate of C/20 and kVp with exposure time of 60 s per projection image, and a total of 1001
a potential window of 2.5 V–4.3 V for one cycle. The applied current was projection images were collected. All radiographic data reported have
based on the nominal capacity of the cells (210 mAh). After initial isotropic voxel lengths of 126 nm. All reconstructions were achieved
cycling, pouch cells were disconnected and returned to the glovebox, using commercial software employing parallel-beam filter­
degassed and resealed for C-rate dependency testing, and acoustic data ed-back-projection (FBP) algorithms (“Reconstructor Scout-and-Scan”,
was collected during cell cycling. Carl Zeiss., CA, USA). 3D visualizations of reconstructed tomograms
Cells were cycled at room temperature. The cell’s external temper­ were processed using Avizo software (FEI, France) which allows parti­
ature was recorded by attaching two K-Type thermocouples to the bot­ cles to be separated and identified. A thresholding algorithm derived
tom surface of the cell (Fig. 1) and temperature was logged using a TC- from Otsu’s method [20] was adopted for segmentation of the NMC
08 thermocouple interface (PicoTech, U.K.) and PicoLog software particles using the Auto-Threshold module in Avizo [21]. Neighbouring
particles that were in contact with one another were separated using the
Separate Objects Avizo module which identifies boundaries (lines) be­
tween objects and separates them along these boundaries using a 3D
watershed algorithm on the segmented binarized image stack [21]. This
module also assigns a unique label to each separated object. The Label
Analysis Avizo module, was then used to extract volumetric PSD, par­
ticle sphericity and surface area. Histograms were plotted for each data
range using 24 bins and fitted with Gaussian curves to determine cu­
mulative frequency. The standard deviation and mean values were
tabulated for each plotted histogram and correspond to the peak of the
Gaussian curves. Border particles were effectively removed from the 3D
volume rendering of electrodes using “border kill” function for volu­
metric PSD analysis, ensuring any subsequent analysis was conducted
only on particles that were wholly within the field of view of the im­
aging. The Volume Fraction module was used to determine the volume
fraction of active material, carbon-binder domain (CBD) and pores of
each NMC811 electrode.

3. Results and discussion

3.1. EA-ToF spectroscopy measurements of a SC-NMC811/Gr and a PC-

NMC811/Gr cell

Naturally, the acoustic signal response received by the ultrasonic

flaw detector can vary considerably depending on the sample under
investigation. This is to be expected due to the variation in material
interfaces across different tested samples. In this work, all EA-ToF ex­
periments were conducted on the same pouch cell geometry to minimise
variations between the tested pouch cells. Fig. 2 explains the acoustic
response received by the ultrasonic flaw detector-receiver from a SC-
NMC811/Gr pouch cell.
The acoustic amplitude of the reflected peaks in an EA-ToF response
Fig. 1. A photograph of an EA-ToF spectroscopy test set up with a pouch cell are in part determined by the reflection coefficient (R). This coefficient
top-view (a) and side-view with an ultrasound transducer and weight (b). describes the amount of reflection of an incident acoustic wave and is

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H. Michael et al. Journal of Power Sources 542 (2022) 231775

peak (labelled as 8 in Fig. 2) occurs at ~18.0 μs. By the time the sound
pulse has passed through the active layers and towards the back wall of
the pouch cell the signal has dissipated significantly.
The acoustic response of PC-NMC811/Gr and SC-NMC811 cells was
monitored for gas formation during their formation cycle because sig­
nificant gas accumulation is expected as an SEI layer forms on the anode
surface [7,25]. EA-ToF measurements were carried out to determine
whether the accumulated gas affects the acoustic signal propagating
through the cell and in turn effect the EA-ToF response. The cells were
then degassed and resealed before continuing acoustic measurements
with cell cycling.
The EA-ToF spectrograms plotted with respect to time for the SC-
NMC811/Gr and PC-NMC811/Gr cells during formation cycles are
shown in Fig. 3 with the red regions representing high amplitude peaks
and the blue regions representing low amplitude troughs. White regions
correspond to regions where no change in amplitude of the initial
generated acoustic pulse is recorded. The first horizonal line at
approximately 0.6 μs corresponds to the initial saturation of the trans­
ducer and is present in all EA-ToF spectrograms evaluated in this work.
The subsequent lines in the EA-ToF spectrograms represent each active
Fig. 2. The initial acoustic waveform generated by pulsing through the layers layer interface.
of a SC-NMC811/Gr pouch cell. Eight ‘echo’ peaks are identified and annotated Significant acoustic signal attenuation was observed during the first
as well as the active layers and initial saturation peak due the transducer-pouch 6 h of cycling of the SC-NMC811/Gr cell and PC-NMC811/Gr cell (see
cell interface. Fig. 3). The gas that forms during SEI formation significantly attenuates
the acoustic signal because the impedance mismatch between trans­
highly influenced by the relative acoustic impedance (Z) of the two ducer/gas is higher than for transducer/liquid. A loss of acoustic signal
materials at a given interface [8]. Signal attenuation from the cell will was evident throughout the entire formation cycle; however, most sig­
also play a role in the amplitude of the peaks; the deeper the acoustic nificant signal attenuation occurs during charging, as most electrolyte
signal propagates into a cell, the more material the signal has to pass decomposition occurs at these potentials [26]. The gas that forms on the
through, so the more attenuated it is and the lower the amplitude of the electrode during SEI formation then diffuses out into other regions of the
peak caused at each material interface [22]. The acoustic impedance and pouch cell which causes the reappearance of the acoustic signal. The
reflection coefficient can be calculated as shown in Eqs. (3) and (4). [8]: EA-ToF spectrograms collected for the PC-NMC811/Gr cells would
suggest that more gas forms during SEI formation in these cells
Z = ρc (3)
compared to the SC-NMC811/Gr cells (Fig. 3). Signal attenuation due to
Z2 − Z1 2 gas formation perseveres throughout the entire duration of the first
R=( ) (4) charge/discharge cycle to a greater extent than was observed for
Z1 − Z2
SC-NMC811/Gr cells.
Typically, numerous material flaws such as inter- and intra-particle Once a stable SEI layer has formed, it is expected that cell degrada­
cracking are expected to alter the ensemble electrode morphology and tion will occur due to gradual anode passivation, as opposed to the
thus appear on the EA-ToF spectrogram within the peaks associated with significant gassing that is recorded during the first cycle at C/20 and that
the active layers (where an active layer consists of the combination of LiBs with different anode compositions will exhibit different levels of
cathode-separator-anode-separator), for example dampening in acoustic first cycle signal attenuation [7]. Bommier et al. [7] found that signifi­
amplitude or intermittent loss of acoustic signal. Gas/SEI formation can cant gas formation occurs during the first 20 h of a C/20 formation cycle
cause non discriminative signal attenuation for numerous active layers for cells containing silicon-graphite anodes. Therefore, gaseous
in the cell simultaneously. The initial acoustic ToF response (Fig. 2) by-products that arise during SEI formation in silicon anodes are likely
contains several key features that are present throughout all acoustic to cause acoustic signals to be attenuated differently to silicon-graphite
experiments presented in this work. Firstly, a sharp peak is present at anodes and graphite anodes, respectively. However, these cells have the
approximately 0.63 μs. This peak is associated with the generation of an same anode composition but differing cathode compositions, which
ultrasonic pulse. This peak was in the same location for all SC-NMC811/ implies that differences in first cycle gas evolution caused by different
Gr and PC-NMC811/Gr pouch cells measured and was thus treated as an cathode compositions can also be detected with EA-ToF measurements.
artefact of the signal response [6,10,22]. The following peaks are Whilst the SEI formation principally occurs at the anode, it is established
indicative of the internal structure of the cell. Each peak indicates an in the literature that there are synergistic effects from anode, cathode
interface in the sample, in this case an active layer in the pouch cell [22]. and electrolyte that determine the nature of the SEI which are also likely
As the ultrasonic sound waveform penetrates deeper through the pouch to influence the resultant gassing behaviour [27–29]. As was previously
cell, the amplitude of the signal decreases. This decay in acoustic signal mentioned, SC-NMC811 particles are less likely to have intra-particle
is expected as a result of numerous physical phenomena acting on the cracks compared to PC-NMC811 particles [2]. As in the case of
sound waveform including wave spreading, signal attenuation and inter-particle cracks, intra-particle cracks are associated with additional
acoustic waves interfering with each other as they pass through the electrolyte decomposition, new cathodic SEI layer formation, gas evo­
battery medium [10,22]. A portion of the ultrasound propagates lution and aggravated electrochemical resistance [30]. There are
through the entire length of the pouch cell and reaches the back wall various reports that suggest more gas evolution occurs in cells that
[23]. This signal is mostly reflected, as opposed to transmitted. This is contain PC-NMC811 electrodes compared to SC-NMC811 electrodes
due to the large difference in acoustic impedance of the air and the [31,32]. Li et al. [32] carried out a detailed in-situ gas evolution com­
pouch cell packaging which results in equally spaced ‘echo’ peaks that parison between SC-NMC811 and Al-coated PC-NMC811 electrodes. The
generally have higher acoustic amplitude than other peaks with similar results revealed that PC-NMC811 electrodes release more gas than
ToF [10,24]. Eight ‘echo’ peaks can be identified in Fig. 2. The first SC-NMC811 electrodes. In fact, SC-NMC811 electrodes were also found
‘echo’ peak (labelled as 1 in Fig. 2) occurs at ~1.5 μs and the final ‘echo’ to release negligible gas at 4.6 V. In addition, whilst O2 release from

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H. Michael et al. Journal of Power Sources 542 (2022) 231775

Fig. 3. (a) EA-ToF spectrogram plotted with respect to time with the region where most signal attenuation occurs in white (top); potential profile of the first cycle at
a current rate of 0.0105 A (C/20) (middle); and potential profile versus capacity (bottom) of SC NMC811/Gr cell (a, left column) and PC-NMC811/Gr cell (b,
right column).

NMC was expected to be higher with increasing voltage, SC-NMC811 √̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅

electrodes showed lower oxygen intensity indicating that less oxygen K + 43 G
c= (5)
release occurs in SC-NMC811 compared with Al-coated PC-NMC811 and ρ
uncoated PC-NMC811 electrodes at each voltage.
A C-rate dependency test was carried out on both of the NMC811/Gr E
K= (6)
cells to determine how EA-ToF measurements are affected by changing 3(1 − 2v)
the current rate and for determining ToF shift patterns during different
C-rates. After the SC-NMC811/Gr cells and PC-NMC811/Gr cells had G=
E
(7)
been formed at C/20, they were tested at constant current rates of C/10, 2(1 + v)
C/5, C/2.5 and 1C. The C-rate was brought back to the initial C-rate (C/ Acoustic signals change in their maximum amplitude with respect to
10) at the end of the experiment. time, indicating physical change in the corresponding electrode layers.
EA-ToF signals are highly affected by the state of charge (SoC) of the For example, a highly lithiated anode will have a lower material density
LiB as lithiation can affect the density and Young’s modulus of elec­ and be less dense than the same anode with less lithiation [35]. Graphite
trodes [9,33]. The effect of SoC on electrode properties such as the (C6) has a density of 2.26 g cm− 3, whereas lithiated graphite (LiC6) has a
Young’s modulus (E), density (ρ) and Poisson ratio (υ) which directly density of 2.20 g cm− 3. Materials with a higher density are expected to
affect the speed of sound (c) are shown in Eq. (5) K and G are the bulk be associated with lower acoustic signal amplitudes than materials with
and shear moduli respectively (Eqs. (6) and (7)) [34].

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H. Michael et al. Journal of Power Sources 542 (2022) 231775

lower density. However, graphite’s (C6) Young’s modulus (E) increases The nickel current collector tab is clearly visible in Fig. 5; possible
from 32 GPa to 109 GPa when it is fully lithiated (LiC6) [33,34]. A higher complications can be caused in the acoustic response of pouch cells by
Young’s modulus causes a higher acoustic signal amplitude. Therefore, the current collector tabs running through the length of the cell for
properties can have complicated and opposite effects on the acoustic approximately 15 mm as the transducer is placed at the centre of the cell,
signal, and therefore the implications of the EA-ToF measurements and thus the acoustic signal would have to propagate through the
require care in interpretation. The EA-ToF spectrograms obtained for the respective tabs (Fig. 5(a) and (b)) [10]. It was ensured that the trans­
SC-NMC811/Gr and PC-NMC811/Gr cells during the C-rate dependency ducer was placed directly in the centre of each cell during EA-ToF
test are shown in Fig. 4. spectroscopy to avoid differences in acoustic response between cells
Lower signal attenuation is present in the EA-ToF spectrogram of the caused by the transducer’s location along the length of the current
SC-NMC811/Gr cell during the C-rate dependency test than during collector inside the cell.
formation (Fig. 4). EA-ToF signals are more distinct for each active layer Nano-CT imaging was carried out to visualise differences in
in the SC-NMC811/Gr cells. This suggests that most gas formation morphology between pristine SC-NMC811 and PC-NMC811 electrodes
occurred during the initial SEI formation cycle and that a stable SEI layer and quantitatively analyse whether these differences could influence the
had been formed before these experiments. It also confirms that gases acoustic response of the SC-NMC811/Gr and PC-NMC811/Gr cells. As
formed during the formation cycle were effectively evacuated by the expected, the polycrystalline particles of the PC-NMC811 electrode are
cells’ degassing after formation, and before conducting the C-rate de­ far larger than the single crystal particles of the SC-NMC811 electrode
pendency test. Nonetheless, there are stark differences between the EA- (shown in Fig. 5(g) and (h)). As single crystal particles are smaller than
ToF spectrograms of the SC-NMC811/Gr cell and the PC-NMC811/Gr the agglomerated PC-NMC811 particles, optimising the size is critical for
cell. The acoustic amplitude of the active layers reduces significantly the single-crystalline particles to maintain rate capabilities similar to
after cycling at 1C in the EA-ToF spectrogram of the PC-NMC811/Gr those of polycrystalline particles. Research has suggested a median size
cell, indicating the formation of gas during the C-rate dependency test of 1–4 μm is sufficient to ensure rate capabilities are maintained in SC
in the PC-NMC811/Gr, even after the initial formation cycle was systems [36]. The equivalent diameter of particles and pores was
completed. A significant difference is shown in acoustic amplitude in the extracted from the volume rendering of the SC-NMC811 and
peaks between the first and final waveform for the PC-NMC811/Gr cell. PC-NMC811 electrodes to better understand the transmitted acoustic
There are large differences in amplitude of acoustic signals for each signal propagation through the cell during cycling. Particles in the
active layer between the SC-NMC811/Gr and PC-NMC811/Gr cell. This SC-NMC811 electrode range between 0.1 and 3.0 μm in diameter and
can occur due to the difference in morphology of the electrode compo­ particles in the PC-NMC811 electrode range between 1 and 13 μm in
sitions, in particular due to electrode density and Young’s modulus. diameter (Fig. 6(a) and Fig. 6(b)). Furthermore, larger pore diameters
Differences in acoustic intensity measured at active layer interfaces arise are recorded between active material particles in the PC-NMC811
from differences in the physical properties of the materials at those in­ electrode (1.0–7.5 μm) compared to the SC-NMC811 electrode
terfaces [9]. Although the bulk moduli of the anode and cathode change (around 0.1–1.2 μm) (Fig. 6(c) and (d)). This may be because single
during cycling, the anode composition is the same in both cells and crystal particles can be more tightly packed into the electrode than the
therefore differences in amplitude are considered to be primarily polycrystalline particles due to their smaller size. As a result, a higher
attributed to differences in the cathode layer. Higher amplitude EA-ToF solid phase volume fraction and a lower porosity is recorded for the
signals are present in the EA-ToF spectrogram for the SC-NMC811/Gr SC-NMC811 electrode (see Table 1).
cell compared to the PC-NMC811/Gr cell. This demonstrates the capa­ Consequently, different acoustic amplitudes are recorded for the
bility of using EA-ToF spectroscopy to identify differences in cells that active layers between these cells. The PC-NMC811/Gr cell showed more
vary only in the morphology of the cathode. The difference in attenuation than the SC-NMC811/Gr during cycling and displayed lower
morphology between SC-NMC811 electrodes and PC-NMC811 elec­ acoustic amplitude peaks corresponding to the active layers that are also
trodes can have direct consequences on the EA-ToF measurements of the present in the SC-NMC811/Gr cell. It is expected that the SC-NMC811
NMC811/Gr cells. electrodes will have a higher Young’s modulus than PC-NMC811 elec­
trodes owing to the higher solid phase volume fraction and smaller
3.2. Morphological characterisation interstitial distances between particle grains in the SC-NMC811 elec­
trode, which should result in an overall stiffer electrode with higher
The internal architecture of each SC-NMC811/Gr and PC-NMC811/ signal reflectance and therefore higher acoustic amplitude recordings
Gr pouch cell was examined before electrochemical cycling to identify (see Table 1). It is also possible that PC-NMC811 particles themselves
whether differences in acoustic response between these cells could be have a lower Young’s modulus than SC-NMC811 particles due to SC-
attributed to differences in cell build rather than the microstructure of NMC811 particles having larger grains compared to smaller, more
the NMC811 electrode. loosely bound agglomerated grains in the PC-NMC811 particle.
The X-ray CT datasets shown in Fig. 5 demonstrate the similarity in The volumetric particle size distributions (PSDs) (Fig. 6(e) and (f))
internal architecture between the SC and PC cells examined in this work. extracted from the volume renderings of the SC-NMC811 and PC-
The SC-NMC811/Gr and PC-NMC811/Gr cells each have the same NMC811 electrodes are very different, correlating with the particle
number of wound active layers [cathode-separator-anode-separator] sizes in the horizontal cross sections through the X-ray tomography
which result in an equal number of internal interfaces at which acous­ scans shown in Fig. 5(e) and (f). The single crystal particles range in
tic reflections can occur in both cell types (Fig. 5(c) and (d)) [22]. There volume between 0.5 and 600 μm3 and the polycrystalline (secondary)
are also no detectable differences in the internal architecture or defects particles range in volume between 10 and 1000 μm3. In addition, a
present in either of the SC-NMC811/Gr cell and PC-NMC811/Gr cells, higher number of particles is recorded in the SC-NMC811 electrode re­
suggesting that differences in acoustic response between the gion of interest (ROI) compared to the number of particles in the PC-
SC-NMC811/Gr cell and PC-NMC811/Gr cell principally arise as a result NMC811 electrode ROI. Based on these findings, it is expected that
of differences in the transmission characteristics of the SC-NMC811 and acoustic signals will propagate through the SC-NMC811 electrode in a
PC-NMC811 cathodes (as the anodes in both instances are the same), more facile manner than the PC-NMC811 electrode as acoustic signals
caused by the material properties of the NMC811 electrodes. The propagate through solid media with less attenuation than liquid media
graphite anode in the SC-NMC811/Gr and PC-NMC811/Gr cells have (electrolyte), which will fill the interstitial sites in a working cell [37].
the same active mass loading (94.8%) and tap density (1.5 g cm− 3). Solid media that is higher in density will reduce ToF and increase signal
Therefore, acoustic signals are not expected to vary between the cells attenuation – in this case, the changes caused by different elastic moduli
due to differences in these electrodes. are far more significant than those caused by the material density as

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H. Michael et al. Journal of Power Sources 542 (2022) 231775

Fig. 4. EA-ToF spectrograms plotted with respect to time for the SC-NMC811/Gr cell (a) and the PC-NMC811/Gr cell (b) during the C-rate dependency test. The
potential profile (c) and current profile (d) plotted with respect to time for the SC-NMC811/Gr cell and the PC-NMC811/Gr cell during the C-rate dependency test
along with their respective first and final acoustic waveforms received by the ultrasonic flaw detector (e).

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H. Michael et al. Journal of Power Sources 542 (2022) 231775

Fig. 5. X-ray CT images of the SC-NMC811/Gr pouch cell showing (a) the volume rendering of the entire cell in the XY plane with the anode current collecting tab,
(b) X-ray CT orthogonal slices taken in the XZ plane with the anode current collecting tab present and after the anode current collector tab. X-ray CT renderings of a
pristine SC-NMC811/Gr cell (c) and a pristine PC-NMC811/Gr cell (d). Horizontal cross sections through a nano-CT scan of an SC-NMC811 electrode (e) and PC-
NMC811 electrode (f). 3D volume rendering of the active material particle network of the SC-NMC811 electrode (g) and PC-NMC811 electrode (h) after recon­
struction and segmentation and with a border kill operation applied. Particles are randomly coloured to assist in visualisation.

more signal attenuation is recorded for the PC-NMC811/Gr cell. Particle size and shape affect material properties of the electrode layer
The shape factor (or sphericity) characterises how closely a particle such as electrode density, which alters the signal’s wavelength, affect
resembles a sphere. A particle that has a shape factor of 1 is perfectly ToF and signal attenuation [40]. Theoretically speaking, it is possible to
spherical with smaller values indicating less sphericity [38]. The shape detect morphological changes such as particle cracking by increasing the
factor, S, of a particle with a volume of V and surface area of A can be frequency of the acoustic signal and thereby shortening its wavelength.
calculated from Eq. (2): However, there is a trade-off as lower ultrasonic frequencies provide
√̅̅̅ V better wave penetration through an entire LiB cell, whereas higher fre­
S = 6 π √̅̅̅̅̅ (2) quency provides higher resolution and focal sharpness [5].
A3
The particle surface area and particle volume specific surface area
The polycrystalline particles of the PC-NMC811 electrode consist of (VSSA) were obtained from the reconstructed microstructure of each
numerous SC-NMC811 particles agglomerated into larger spherical NMC811 electrode (Fig. 6(i–l)). VSSA can provide both structural and
secondary particles (see Fig. S1) [39]. The SC-NMC811 electrode fea­ cycling performance-related information for LiB electrodes, as the
tures a more diverse array of particle shapes and sizes than the particle-pore interface is where charge transfer reactions occur during
PC-NMC811 electrode (Fig. 6(g) and (h)). Nonetheless, the differences in battery cycling between the active material and the electrolyte. There
particle shapes between the SC-NMC811 electrodes and PC-NMC811 are large differences in VSSA between particles in the SC-NMC811
electrodes are not expected to influence the degree of reflection of the electrode and PC-NMC811 electrode. The SC NMC particles have a
incident acoustic signal because the particles are smaller than the inci­ larger VSSA despite particles in the PC-NMC811 electrode having sur­
dent acoustic signal wavelength [34]. For instance, when passing face areas ~7 times larger than the largest surface areas in the SC-
through air λ = 70 μm, aluminium λ = 1200 μm and copper λ = 452 μm. NMC811 electrode. However, the majority of SC and PC NMC parti­
The acoustic signal wavelength changes according to the material cles have surface areas below 100 μm2. On average, the SC NMC parti­
interface it passes through due to differences in material density and cles have a smaller surface area than the PC NMC particles. However,
Young’s modulus. Therefore, differences in density/morphology be­ polycrystalline particles have been found to crack extensively during
tween the PC-NMC811 and SC-NMC811 electrodes will cause a differ­ cycling, which increases the surface area of the ensemble electrode and
ence in acoustic signal wavelength as it passes through these electrodes. provides more sites for Li intercalation/deintercalation [2]. In contrast,

8
H. Michael et al. Journal of Power Sources 542 (2022) 231775

Fig. 6. Equivalent particle diameter and pore diameter for the SC-NMC811
electrode (a) and (c) and PC-NMC811 electrode (b) and (d). Volumetric parti­
cle size distribution (PSD) of electrode particles in the SC-NMC811 electrode (e)
and PC-NMC811 electrode (f). Shape factor (or sphericity) of particles in the SC-
NMC811 electrode (g) and PC-NMC811 electrode (h). The surface area of
particles in the SC-NMC811 electrode (i) and PC-NMC811 electrode (j). The
volume specific surface area of particles in the SC-NMC811 electrode (k) and
the PC-NMC811 electrode (l).

single crystal particles do not undergo cracking during cycling [3,41,

42]. Therefore, more gas formation and capacity fading occurs in the
PC-NMC811/Gr cell during repeated cycling [32,43–46].
Heenan et al. [2] report that various polycrystalline NMC811 parti­
cles undergo cracking prior to cycling owing to calendering of the
electrode during electrode processing stages. This gives rise to various
individual smaller secondary particles that originate from larger parti­
cles. These findings suggest that the wider variety of particle surface
areas that exist in the PC-NMC811 electrode may be caused by particle
cracking which occurred during calendering (see Fig. 6(j)). Both
SC-NMC811 and PC-NMC811 electrodes were calendered, which would
further suggest that calendering is more detrimental for polycrystalline
electrodes. Particle cracking is not expected to occur in the SC-NMC811
electrode to the same degree as the PC-NMC811 electrode owing to their
initial size and lack of internal grains (Fig. 6(e)). Larger particles are also
more prone to cracking during expansion/contraction of the electrode
after repeated charge/discharge cycling leading to various degradation
mechanisms such as phase transformation [47], cathode-electrolyte
parasitic reactions [48–50] and transition metal dissolution [51,52].
Manganese dissolution from NMC electrodes has been reported to
induce elevated rates of electrolyte reduction at the graphite electrode,
causing further SEI formation reactions [53]. The gas evolution caused
by these reactions would exacerbate signal attenuation.

3.3. Electrochemical characterisation

Fig. 7 indicates that the SC-NMC811/Gr cell underwent minimal

capacity loss during the C-rate dependency test. The SC-NMC811/Gr cell
has better rate capability as more capacity fading occurs in PC-NMC811/
Gr cells compared to SC-NMC811/Gr cells as C-rate is increased (Fig. 7
(c) and (d)). Nonetheless, as expected, neither cells experience signifi­
cant capacity fading after 20 cycles, suggesting that no deleterious
degradation processes are incurred due to higher C-rate cycling for the
relatively low number of cycles conducted in this experiment. This
observation is reinforced by the absence of changes in the acoustic
amplitude of the active layers when the cells are cycled at different C-
rates. In fact, the acoustic amplitude measured for each respective
electrode layer remains fairly consistent throughout cycling in the
NMC811/Gr cells. Measured amplitude is governed by physical changes
in the electrode interfaces and intrinsic physical properties. Therefore, it
is likely that the different microstructural properties of the SC-NMC811
and PC-NMC811 cathodes cause different degrees of cell polarisation
and therefore ionic resistance in the tested cells. The PC-NMC811/Gr
cells appear to have higher polarisation than the SC-NMC811/Gr cell
as lower capacities are measured at higher C-rates for the PC-NMC811/
Gr cell.
According to Fig. 7(e), the highest dQ/dV peak occurs for the slowest
charge/discharge cycle (C/10). The height of this peak is similar for all
subsequent C-rates including for the cycle that returns to C/10. The dQ/
dV curve at 1C is significantly more shifted to higher voltages than the
dQ/dV curves for the other C-rates. Charging at increasing C-rates
produces the same information, as evidenced by the same shape of the
dQ/dV curve; however, the IR-drop is higher at faster C-rates and thus
the peak positions appear more shifted [54]. Shifting of dQ/dV curves is
(caption on next column) also evidence of capacity fade, which agrees with the fall in capacity
shown in Fig. 7(b). However, the cell voltage is largely determined by
the cathode potential, as opposed to the anode potential. This presents a

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H. Michael et al. Journal of Power Sources 542 (2022) 231775

Table 1 signal travels faster through the cell i.e., a shorter duration of time
Active material and pore and CBD volume fraction recorded for each electrode elapses before the acoustic signal encounters the material interface in
determined using the Volume Fraction module in Avizo. question. A positive ToF shift means the acoustic signal takes longer to
Electrode Active material (vol. %) Pore and CBD (vol. %) travel through the cell. This method can be used to track changes in
SC-NMC811 73.2 26.8
density and Young’s modulus during cycling [5]. When the material
PC-NMC811 68.8 31.2 properties remain constant, a positive ToF shift can correspond to cell
expansion, as a thicker cell would ultimately lead to a greater distance
through which the ultrasonic wave has to travel. Conversely, a negative
drawback in using a dQ/dV plot for full cell systems because peaks are ToF shift can be attributed to cell contraction [5,7,34]. Fig. 8 shows the
caused by changes in the overall cell voltage, which is the difference ToF shift recorded for the third echo peak of the SC-NMC811/Gr cell and
between the anode and cathode potentials. Therefore, processes that PC-NMC811/Gr cell during the C-rate dependency test and the associ­
occur at the anode are more difficult to discern [55,56]. ated exterior cell temperature profiles. ToF shift is normalised to zero at
the start of charge/discharge cycling. The third echo peak was chosen
3.4. ToF shift measurements of a SC-NMC811/Gr cell and a PC- because it is easily identifiable in the acoustic waveform for both
NMC811/Gr cell SC-NMC811/Gr and PC-NMC811/Gr cells and has a high acoustic
amplitude throughout cycling. The first and second echo peaks also have
The 1D displacement of a material interface causes the acoustic a high acoustic amplitude but have ToF values that are similar to the
signal to pass through the material at a different time during its flight, active layers in the cell, making it more difficult to isolate during data
causing an apparent ToF shift. A negative ToF shift means the acoustic processing. Nonetheless, all echo peaks represent the signal that has

Fig. 7. Electrochemical characterisation for each cell during the C-rate dependency testing: Potential vs capacity plot at each C-rate for the SC-NMC811/Gr cell (a)
and PC-NMC811/Gr cell (b), Charge, and discharge capacity and coulombic efficiency vs cycle number for all C-rates for the SC-NMC811/Gr cell (c) and the PC-
NMC811/Gr cell (d) and differential capacity vs cell potential curves for the first cycle at each C-rate for the SC-NMC811/Gr cell (e) and PC-NMC811/Gr cell (f).

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H. Michael et al. Journal of Power Sources 542 (2022) 231775

Fig. 8. ToF shift obtained at current rates of C/10, C/

5, C/2.5 and 1C for the SC-NMC811/Gr (black) and
PC-NMC811/Gr cell (red) (a). (b) The exterior cell
temperature during C-rate dependency testing for the
SC-NMC811/Gr cell (black) and PC-NMC811/Gr cell
(red). Shaded areas in each graph indicate each C-
rate: C/10 (blue), C/5 (green), C/2.5 (yellow), 1C
(red) and the second C/10 cycling stage (grey). (For
interpretation of the references to colour in this figure
legend, the reader is referred to the Web version of
this article.)

travelled through the entire cell and is reflected back. Therefore, these electrode are larger than changes in the NMC811 electrode.
echo peaks give the same information as each other about the cumula­ The PC-NMC811/Gr cell undergoes a positive ToF shift during C/10
tive properties of all the layers within the cell. Other peaks are related to cycling, as ToF shift increases above 0 μs and reaches nearly 0.08 μs after
reflections from active layers within the cell and thus will only show the first charge/discharge during C/5 cycling (see Fig. 8(a)). Both cell
changes occurring in those respective layers before the reflection occurs capacity and ToF shift then decline with increasing C-rate over time [7].
from the back wall of the cell. These changes in ToF shift can arise from cumulative changes in stress
ToF shift and acoustic amplitude of peaks are highly influenced by and strain of the active layers of the cell during repeated cycling. The
thickness changes of the cell, as well as the interaction between material largest negative ToF shift occurs during the second C/10 cycling stage,
properties such as electrode density, Young’s modulus and electrolyte as the cell cools despite PC-NMC811/Gr cell capacity returning to 210
viscosity, which can also impact ToF shift and acoustic amplitude, mAh which suggests cell cooling plays a confounding role in ToF shift
resulting in a complex decoupling process of the acoustic signal inter­ patterns (see Fig. 8(b)). As mentioned in Section 3.2, the PC-NMC811
action with the cell [57,58]. For instance, in Fig. 8, during charging a electrodes has larger interstitial voids than the SC-NMC811 electrode.
negative ToF shift is observed; if ToF shift was solely attributed to These interstitial voids can aid in rapid cooling of the PC-NMC811
thickness changes, a positive ToF shift would be expected during the first electrode despite the higher overpotential and ohmic heating, which
charge at C/10, as lithiation of the graphite anode would cause these would explain why cell cooling is more evident in the PC-NMC811/Gr at
electrodes to get thicker. This trend in ToF shift during first charging is faster C-rates and the second C/10 cycling stage than the
due to other material properties playing a confounding role on the ToF SC-NMC811/Gr cell. It should be noted that although changes in ToF
shift. Stage 1 corresponds to fully lithiated graphite (LiC6 stoichiometry) shift occur between cycles, the magnitude of these ToF shifts are very
which results in an increase in the Young’s modulus of graphite which in small which suggest that no severe cell degradation or damage have
turn causes a negative ToF shift according to Eq. (1) [7,34]. In this case, occurred throughout cycling.
graphite expands ~8% when charging, but the modulus changes by ca. The SC-NMC811/Gr cell is largely characterised by a negative ToF
~300%, as such material property changes are dominant [59,60]. shift pattern throughout the entire C-rate dependency test with a
NMC811 electrodes only undergo ~2% volume expansion [59,61,62]. maximum ToF shift of 0 μs at 1C. This is most apparent when a C/2.5 C-
This increase in Young’s modulus of the graphite electrode increases rate is applied with ToF shift reaching nearly − 0.10 μs. The SC-
wave propagation speed and ultimately causes a negative ToF shift. NMC811/Gr cell stays relatively stable around a centre line (~− 0.04
Similar results were reported in acoustic studies conducted by Bommier μs ToF shift) whereas the PC-NMC811/Gr cell moves away from a stable
et al. [7], Ladpli et al. [63] and Knehr et al. [64]. Rong Xu et al. [65] ToF, potentially indicating expansion, fracture or dislocation of the
reported that NMC electrodes undergo a decrease in Young’s modulus reflective interfaces inside the PC-NMC/Gr cell [6]. As both NMC/Gr
and stiffness during Li extraction from the layered crystalline particles cells contain the same anode composition, the significantly positive ToF
due to Jahn-Teller distortion, depletion of electrostatic interactions of shift recorded for the PC-NMC811/Gr cell throughout cycling can be
Li–O, and charge localization cumulatively weakening ionic TMs-O attributed to the PC-NMC811 electrodes. The ToF shift patterns for the
bonding. To our knowledge, quantitative information on the Young’s SC-NMC811/Gr cell suggests that it undergoes less changes in stress and
modulus of PC-NMC811 and SC-NMC811 electrodes has not yet been strain of the active layers between cycles compared to the
reported. During charging, Li extraction and the accompanying decrease PC-NMC811/Gr cell. The ToF shift pattern of the SC-NMC811/Gr cell
in Young’s modulus of the NMC811 electrode occur during Li interca­ then increases during 1C cycling towards 0 μs ToF shift. It is the general
lation of graphite and the associated increase in Young’s modulus of the consensus that higher C-rate operation can lead to thermal expansion in
graphite electrode. Given that a negative ToF shift is recorded during LiBs [66,67]. However, as this increase in ToF shift is not also recorded
charging, it is evident that changes in Young’s modulus of the graphite for the PC-NMC811/Gr cell during 1C operation, it is likely that this

11
H. Michael et al. Journal of Power Sources 542 (2022) 231775

trend is attributed to other physical changes in the NMC811 electrodes. SC-NMC811 or PC-NMC811 electrodes. It has been demonstrated that
The most negative ToF shift value recorded (− 0.10 μs) for the the acoustic behaviour of LiBs is influenced by the morphology of the
SC-NMC811/Gr cell is not correlated with the lowest cell temperature, NMC811 electrodes, with the different particle sizes influencing density
implying that other physical properties influence the ToF shift pattern and Young’s modulus of the cathode. Consequently, acoustic signals
recorded for the SC-NMC811/Gr cell. It has been reported that particles propagate through these respective materials with varying reflectance
in a SC-NMC electrode undergo less cracking and reduced lattice strains and transmission. Furthermore, differences in acoustic signal attenua­
compared to particles in a PC-NMC electrode during repeated cycling, tion were recorded during formation cycling of the SC-NMC811/Gr and
resulting in a more ordered, higher density electrode [68,69]. Increased PC-NMC811/Gr cells which was attributed to gas evolution and SEI
electrode density, higher electrolyte viscosity, and reduced cell thick­ layer formation. EA-ToF spectrograms indicated that more gas formed
ness would exacerbate a negative ToF shift as the cell is cooled [58,70, throughout the formation cycle in the PC-NMC811/Gr than the SC-
71]. NMC811/Gr cell, despite the SC-NMC811/Gr cell having more gas for­
ToF shift maxima do not correlate entirely with exterior cell tem­ mation at the beginning of first charging and both cells containing the
perature maxima at slower C-rates. This is expected given the ohmic same anode composition. This was likely attributed to additional elec­
heating of Li-ion cells during slower CC cycling (slower heating of the trolyte decomposition, new cathodic SEI layers formation, gas evolution
cell at slower C-rates), except for at 1C when the ohmic heating is high and aggravated electrochemical resistance in the PC-NMC811 elec­
enough to heat up the cell. This means that the fluctuations/peaks and trodes. Furthermore, differences in acoustic amplitude of the active
troughs of the ToF measurements at slower C-rates are more attributable layers were recorded for the PC-NMC811/Gr cell and SC-NMC811/Gr
to the ambient room temperature than the electrochemistry of the cell during the C-rate dependency test with gas formation present in the
and subsequent changes in material properties. PC-NMC811/Gr cell during later cycles. Generally, a lower acoustic
After the C-rate dependency test, both cells return to their original amplitude was detected for the majority of active layers in the PC-
ToF (i.e., 0 μs) suggesting there is no change in cell thickness after NMC811/Gr cell compared to the SC-NMC811/Gr cell which was
cycling and that the thickness changes that occur during cycling are attributed to differences in particle morphology of the NMC811
reversible. The trend in ToF shift during each cycle is consistent electrodes.
throughout charge/discharge cycling with a negative ToF shift during Use of X-ray CT revealed some interesting aspects of the interior cell
graphite lithiation and positive ToF shift with graphite delithiation. architecture of the tested LiBs. For instance, the elongated tabs that run
There is no evidence of any further degradation mechanisms occurring through around half the length of the cell may affect acoustic signal
during cycling that contribute to the ToF shift measurements of the cell propagation through the cell. Numerous geometrical parameters such as
at this length-scale. As expected, the intracycle trends in magnitude of particle sphericity, equivalent particle/pore diameter and volumetric
ToF shift are similar for both NMC811/Gr cells given that intracycle ToF PSD were assessed for each NMC811 electrode. The PC-NMC811 elec­
shift patterns are dominated by the graphite electrodes, present in both trode was largely characterised as having much larger particles with
cells. Throughout charge/discharge cycling, the cell periodically ex­ larger interstitial distances between active particles. The SC-NMC811
pands and contracts as the graphite electrode undergoes Li intercala­ electrode had far smaller particles, with smaller interstitial distances
tion/deintercalation [62]. The cell could be said to periodically breathe between them. These differences were hypothesised to influence elec­
with charge/discharge cycling. During these reversible processes, trode density and Young’s modulus, both critical physical properties
simultaneous changes in electrode stress and strain occur at the active that can alter EA-ToF recordings for either material.
layers and effect the speed at which the signal passes through the active Finally, ToF shift patterns revealed differences between cells that
layers [72]. This demonstrates the usefulness of ToF shift measurements vary in particle morphology of the NMC811 cathode. For instance, the
for gathering information on numerous physical changes that occur PC-NMC811/Gr cell largely underwent positive ToF shifts during C-rate
during cycling LiBs compared to devices such as push-piston di­ testing whilst the SC-NMC811/Gr cell predominately underwent nega­
latometers, thickness gauges and micrometers that are solely designed to tive ToF shift during cycling. Nonetheless, an interchanging positive/
measure cell thickness changes [73,74]. However, the use of these de­ negative ToF shift was recorded between charge/discharge for the SC-
vices in tandem with EA-ToF spectroscopy could be useful to discern NMC811/Gr cell and PC-NMC811/Gr cells before both returned to
which ToF measurements can be attributed to thickness changes of the their original ToF. Whilst there are numerous physical processes that can
cell, rather than other functional parameters such as Young’s modulus affect EA-ToF spectroscopy measurements, it is a powerful technique for
and electrode density. measuring physical changes in ostensibly similar cells and using other
These two cell chemistries are composed of the same graphite elec­ techniques such as X-ray CT alongside EA-ToF spectroscopy can improve
trode, but different NMC811 electrodes. The difference in ToF shift our understanding of cell architecture, and electrode morphology by
patterns between the SC-NMC811/Gr and PC-NMC811/Gr cells is revealing intrinsic physical attributes that can directly impact EA-ToF
therefore most likely to be due to the different physical properties of the measurements.
NMC811 electrodes which directly cause a variation in the Young’s
modulus of these respective electrodes. However, there are numerous CRediT authorship contribution statement
physical processes that can alter the cell’s ToF shift, such as external
temperature, cell gassing and material properties. The SC-NMC811 and H. Michael: Conceptualization, Methodology, Investigation, Formal
PC-NMC811 electrodes also have different C-rate dependencies, so at a analysis. R.E. Owen: Investigation, Software, Visualization, Formal
given C-rate the state of lithiation will be different in the two materials – analysis. J.B. Robinson: Methodology, Formal analysis. T.M.M.
this may also cause some differences in the ToF as the assumed SoC is Heenan: Investigation, Formal analysis. C. Tan: Sample procurement
different for a given point in the cycle. As the SC-NMC811 and PC- and preparation. A.J. Wade: Investigation. R. Jervis: Methodology,
NMC811 electrodes have different Young’s modulus and density, the Formal analysis, Supervision, Funding acquisition. D.J.L. Brett:
acoustic signal will inevitably vary in its interaction with them (refer to Conceptualization, Supervision, Funding acquisition. P.R. Shearing:
Eqs. (5)–(7)). Difference in density and Young’s modulus of these elec­ Conceptualization, Methodology, Supervision, Funding acquisition.
trodes has a direct influence on the ToF shift.
Declaration of competing interest
4. Conclusion
The authors declare the following financial interests/personal re­
For the first time known to the authors, EA-ToF spectroscopy has lationships which may be considered as potential competing interests:
successfully been used to distinguish between LiBs composed of either Paul. R Shearing reports financial support was provided by The Faraday

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H. Michael et al. Journal of Power Sources 542 (2022) 231775

Institution. Paul R. Shearing reports financial support was provided by [28] B.L.D. Rinkel, D.S. Hall, I. Temprano, C.P. Grey, J. Am. Chem. Soc. 142 (2020)
15058–15074.
Royal Academy of Engineering. Paul. R Shearing reports financial sup­
[29] S. Solchenbach, G. Hong, A.T.S. Freiberg, R. Jung, H.A. Gasteiger, J. Electrochem.
port was provided by Engineering and Physical Sciences Research Soc. 165 (2018) A3304–A3312.
Council. [30] B. You, Z. Wang, F. Shen, Y. Chang, W. Peng, X. Li, H. Guo, Q. Hu, C. Deng, S. Yang,
G. Yan, J. Wang, Small Methods 5 (2021) 1–28.
[31] Y. Kim, ACS Appl. Mater. Interfaces 4 (2012) 2329–2333.
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A. Botton, J.R. Dahn, J. Electrochem. Soc. 164 (2017) A1534–A1544.
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EP/S003053/1), grant number FIRG001, FIRG014, FIRG024; and The [34] G. Davies, K.W. Knehr, B. Van Tassell, T. Hodson, S. Biswas, A.G. Hsieh, D.
Royal Academy for Engineering CiET1718\59. Access to the lab-based A. Steingart, J. Electrochem. Soc. 164 (2017) A2746–A2755.
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