An in-situ SEM study of failure modes in sulphide-based

all-solid-state batteries throughout cycling has been As featured in:

performed by a group of researchers from the Laboratory
of Reactivity and Chemistry of Solids, Université de
Picardie Jules Verne in France (LRCS, CNRS UMR 7314).

Study of failure modes in two sulphide-based solid

electrolyte all-solid-state batteries via in situ SEM

The failure modes of two sulphide based all-solid-state

batteries have been investigated in real time throughout
cycling by in-situ SEM. We were able to follow and classify
the observed degradation processes (e.g., dendrite)
into three interconnected failure modes: i) electrical, ii)
electrochemical, and iii) mechanical failures.
See Mathieu Morcrette,
Carine Davoisne et al.,
J. Mater. Chem. A, 2022, 10, 17142.

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Study of failure modes in two sulphide-based solid

electrolyte all-solid-state batteries via in situ SEM†
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Cite this: J. Mater. Chem. A, 2022, 10,

17142
Neelam Ghanshyam Yadav,ab Nicolas Folastre,ab Mickael Bolmont,ab Arash Jamali,c
Mathieu Morcrette *ab and Carine Davoisne *ab

Received 9th March 2022
Accepted 18th July 2022
DOI: 10.1039/d2ta01889f
rsc.li/materials-a
Lithium metal was left unused for a long time in conventional liquid-based batteries, with a fear of catching
fire for safety reasons. However, with advancements in solid electrolytes, these were considered the holy
grail in the development of Li metal-based all-solid-state batteries (ASSBs) alongside NMC which is
considered the next-generation cathode material. Unfortunately, Li metal faces tremendous challenges
when brought into contact with many currently considered promising solid electrolytes (SEs). The
associated challenges are electrical, electro-(chemical) and mechanical instabilities. Surprisingly, if one
studies the literature thoroughly, it seems that batteries based on SEs show much faster dendrite
formation than liquid electrolytes. For this particular study, thanks to in situ and operando SEM, we
studied these sulfide-based SEs, viz. b-Li3PS4 (LPS) and Li6PS5Cl (LPSCl). We highlight the key differences
in failure modes of two sulfide-based SEs, by keeping the anode (Li metal) and cathode (NMC111)
constant. For both the SEs, initially, electro-chemo-mechanical stress is induced, due to volume
expansion of active materials and plating during cycling. However, in the case of LPS, this leads to
electrical failure causing a short circuit, whereas in the case of LPSCl it leads to further mechanical
damage-causing delamination of the cathode. Thus, the porous structure of SEs heavily determines the
mechanical behaviour of the ASSB, the distribution of the induced electro-chemo-mechanical stress and
in turn, the mechanism of ASSB failure. The other striking observations are: (1) cracks travel ahead of the
dendrites (2) cracks grow and propagate at a much faster rate in the case of b-LPS than in LPSCl (3)
higher surface roughness of LPSCl gives rise to many different morphologies of Li deposition/dendrites
(4) the cathode electrolyte interface (CEI) forms and grows at a much faster rate in the case of LPS than
in LPSCl. We demonstrate that differences in cycling performance and mode of failure are due to the
differences in SEs. We also highlight that the key limitation in implementing Li metal as an anode in
ASSBs is the dendrite formation and mechanical instability. These findings again emphasize the
importance of coating active materials, the introduction of a buffer layer between the SE/Li metal
interface, coating of SE, or the need for using composite/hybrid or bilayer solid electrolytes at least.

density, thanks to its huge theoretical capacity. However, it

Introduction
Currently commercial liquid electrolyte-based Li-ion batteries
show excellent performance, thanks to their stable or less
degrading liquid electrolytes with an anode/cathode interface.
However, with increasing global CO2 emissions, it is imperative
today to switch from fossil fuels to electric vehicles. This
requires batteries with high energy and power densities. Usage
of Li metal as an anode can solve the issues of high energy
a
Laboratoire de Réactivité et Chimie des Solides (LRCS), CNRS UMR 7314, Université
de Picardie Jules Verne, 33 Rue Saint Leu, 80039 Amiens Cedex, France. E-mail:
mathieu.morcrette@u-picardie.fr; carine.davoisne@u-picardie.fr
b
Réseau sur le Stockage Electrochimique de l'Energie (RS2E), FR CNRS 3459, France
c
Plateforme de microscopie électronique, Université de Picardie Jules Verne, 33 Rue
Saint Leu, 80039 Amiens Cedex, France
† Electronic supplementary information (ESI) available. See
https://doi.org/10.1039/d2ta01889f
could not be employed with liquid-based electrolytes, due to
safety reasons. Replacing liquid electrolytes with solid electro-
lytes could allow the employment of the Li metal anode. Thus,
all-solid-state batteries (ASSBs) are considered to be next-
generation batteries or the future alternative to the current
battery technology. They can offer both safety and high energy
density. They hold the power to revolutionize the electric
transportation market. To reach such an achievement, the key
component is the solid electrolyte (SE) and different classes can
be found such as polymers, oxides, sulphides, uorides, phos-
phides, etc. Sulphide solid electrolytes (see ESI-1† for an over-
view of properties) such as b-Li3PS4 (LPS) and Li6PS5Cl (LPSCl)
are among the few promising SEs heavily explored in the liter-
ature. They can be easily processed simply by cold pressing,
thanks to their ductile nature (young modulus
20 GPa).1 Also,
they offer high ionic conductivity at room temperature (103 to

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102 S cm1)2,3, remarkably close to the values of liquid elec-
trolytes etc. The electrochemical stability window for most of the
known sulphides lies in the range of 1.7–2.3 V.4–6 Although
sulphides offer high ionic conductivity values, a lower operating
potential window is still among its big limitations. These are
important prerequisites for the development of ASSBs. The
solid electrolyte plays a twofold role in ASSBs, by acting both as
a solid electrolyte and a solid separator. Despite such promising
values that are even higher than those for liquid electrolytes
(LP30
10 mS cm1), ASSBs have not been able to achieve
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reliable electrochemical performance when compared to
commercial batteries. This is due to ASSBs challenges which
mainly lie in the interfaces.7 Different research groups around
the world have investigated the interfacial challenges8 and they
can be categorized into different types such as chemical or
electrochemical instability,9 and physical or mechanical insta-
bility. All these types of instabilities/challenges impact the key
parameter, which is the ion transport at the interfaces.
The chemical or electrochemical instability arises from solid
ionic conductors and especially in the case of sulphide-based
SEs their instability against Li metal10 or with transition metal
oxides. Such SEs oen degrade at higher voltages, forming
decomposed products known as “interphases” at the anode/
cathode interface. LPS and LPSCl when in contact with Li metal
are known to form Li3P, Li2S and LiX.11 Similarly, transition
metal oxides, such as LCO or NMC etc. when in contact with
thiophosphate-based SE, oen degrade the SE.12,13 Chemical
characterisation performed on the cathode composite aer
cycling showed the formation of S and Li2P2S6 (ref. 14 and 15)
from LGPS/LCO and S, Li2Sn, P2Sx, phosphate-based
compounds, and LiCl at the interface of Li6PS5Cl and LCO and
NMC111 and LNMO.16
Such chemical or electrochemical instability leads to huge
interfacial resistance as highlighted by electrochemical
impedance spectroscopy (EIS)17–19 and X-ray photoelectron
spectroscopy (XPS).11,18,20 These formed decomposed products/
interphases can either allow or block the ion transfer across this
interface depending on the nature of this formed interphase.
The interfaces can thus be broadly categorized into 3 types: (i)
ion transfer interphase considered as non-reactive and ther-
modynamically stable, (ii) electronically conductive interphase
which is thermodynamically unstable and results in constant
electrolyte decomposition and (iii) insulating interphase also
considered as unstable and whose growth depends on its ionic
conduction properties.21
Sulphide-based SEs such as LPS and LPSCl fall into the 3rd
category of the interface type described above. Li2S specically
is low in ionic and electronic conductivities and hence forms
a highly resistive SEI at the anode interface that could lead to
the formation of decomposed products that might be insulating
in nature resulting in poor kinetics.22 Suyama et al.23 showed
that the ionic conductivity of the formed interphase is one of
the leading factors in determining the fate of failure. They
studied two sulde based SEs, namely Li2S–P2S5 and Li4P2S6.
Though similar compounds, Li2S and Li3P were formed at both
the SE interfaces in contact with the Li metal anode, the latter
SE had higher ionic conductivity. The higher ionic conductivity
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Journal of Materials Chemistry A
at the interphase of Li4P2S6 allowed the battery to cycle stably
even at higher current densities without a short circuit. This
study highlights that interfacial behaviour can be very much
different even if the two SEs belong to the same category of
electrolytes. This is because, even if the nature of the formed
interphases is similar, the amount and the rate of such degra-
dation might be different affecting the total ionic conductivity
at the interphase.
The physical/mechanical instability arises rst due to poor
solid–solid contact. Even if one establishes a good contact
during cell fabrication with the application of stack pressure,
due to volume expansion in the active materials upon cycling,24
this physical contact is subjected to change. Also, the Li elec-
trochemical deposition is known to generate stresses as high as
135 MPa,25 and this further adds to the huge loss of contact,
especially at the anode interface. The phenomena such as Li
deposition/plating26,27 and Li dissolution/stripping28,29 are
studied by in situ Auger electron microscopy and spectroscopy
techniques,30 in situ transmission electron microscopy (TEM),27
and operando X-ray tomography.31 Plating during the charging
process is responsible for dendrite30 formation whereas the
stripping process is known to form voids.32 Dendrites are
formed due to non-uniform plating. Nagao et al.33 showed via in
situ SEM of the bulk type solid state battery with Li2S–P2S5, that
uniform lithium deposition (plating) and dissolution (strip-
ping) are the key to suppression of dendrites and occurrence of
unfavourable cracks. In situ Auger electron spectroscopy/
microscopy (in situ AES/AEM) showed that Li deposition on the
Li metal anode was strongly dependent upon the applied force
to the sample.30 Several factors are known to affect this inho-
mogeneity of plating, such as the local surface topography, non-
uniform contact between SE/Li,34 applied stack pressure,28
operating current density,35 etc. to name a few. Voids are formed
when the Li ions are removed/stripped at a much faster rate
than the rate of Li self-diffusion that can replenish back the Li-
ions at this interface. Operando X-ray tomography-based studies
on solid state batteries have conrmed the formation of voids at
the anode interface.31 Such voids reduce the contact area31
creating local current densities that drive dendrite formation
during the next plating cycle,28 dendrite penetration and nally
cell death via a short circuit. Also, less studied Li surface
impurities27 and other surface aws are some of the intrinsic
issues associated with the usage of Li metal anodes. A study by
X-ray tomography of Li–LPSCl–Li showed that cracks are formed
in the SE, during the process of Li plating and when the Li
plated structures relieve their stress around the edge.36 This
study also pointed out the fact that the absence of short circuits
when even huge cracks are formed, shows that cracks are
formed rst and only later does lithium ll up the crack.
The volume expansion in active materials is another leading
reason for physical/mechanical instability. Such volume
expansion is known to develop stress/strain. This strain leads to
the cracking of active materials, causing loss of contact at the
AM/SE interface. Such damage is known to be the leading
reason for capacity fade.19
In summary, interfaces with solid electrolytes are at the core
of the limitations of ASSBs and the understanding of the
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Journal of Materials Chemistry A
mechanisms involved there is the key to the success of all solid
state batteries. Chemical, morphological and microstructural
investigations of solid–solid interfaces without causing any
damage are challenging. Though many characterization tech-
niques exist and are used (EIS, XPS, X-ray tomography, TEM,
AFM, neutrons, and X-ray diffraction), some of them are
versatile enough to allow chemical and morphological analyses
at the same time on “bulk” batteries without very specic
preparation such as SEM coupled with EDX. For example, TEM
based in situ/operando requires the preparation of lamellar
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based37 or nanobatteries which can show completely different
behaviour than bulk-type batteries. Also, beam energy has been
known to induce damage in structures such as dendrites which
gave birth to the idea of using cryo-TEM for observing such
structures. XPS will mainly provide chemical insight with few
imaging possibilities. In situ SEM has been used to investigate
Li metal-based polymer solid state batteries.38 Thus in this
work, in situ SEM in combination with EDX was used to study
sulde-based ASSBs. We studied the failure modes of two
sulphide-based solid electrolytes, namely b-Li3PS4 (LPS) and
Li6PS5Cl (LPSCl) via live morphological and chemical investi-
gation. The electrochemical, chemical and morphological
evolution will be discussed and the categorisation of the failure
modes is proposed.
Experimental section
Battery assembly/fabrication
Materials. Two commercially available sulphide-based solid
electrolytes (SEs), viz. b-Li3PS4 and Li6PS5Cl were used for this
study. LPS with SE particles in the range of 0.01–7 mm was
purchased from NEI. Corp, while LPSCl with SE particle size
ranging from 50 to 150 mm was purchased from Ampcera. Both
SEs, b-Li3PS4 and Li6PS5Cl were studied separately. NMC111
from Targray was used as an active material (AM). Two different
kinds of electronic carbon additives, viz., C45 from Timcal and
VGCF from Showa-Denko respectively were used. Li (0.75 mm
thick) was purchased from Alfa Aesar.
Cathode composites. The cathode composites were prepared
by hand milling in a mortar and pestle. NMC111 along with
carbon additives was rst mechanically milled and later either
LPS or LPSCl was added. The following weight fractions of active
materials, solid electrolytes, and carbon additives were used:
AM (66.5%) + SE (28.5%) + C45 (2.5%) + VGCF (2.5%). Their
respective volume fractions are as follows: AM (30.74%) + SE
(32.59%) + C45 (33.94%) + VGCF (2.71%).
Li surface cleaning process. The as obtained Li surface was
cleaned using a razor blade. Later this foil was pressed in
between two polypropylene sheets, to obtain a rather uniform Li
surface.
Battery assembly. A 10 mm diameter die pelletizer with three
pieces as shown in Fig. 1(b) was used to fabricate an ASSB. For
the battery assembly, rst, SE powder (
80 mg) is added to the
10 mm pelletizer and densied by the cold press for approxi-
mately 1 min at 1 ton. Next, the cathode composite powder (
10
mg) is added and the two layers are pressed together at 3 tons
for approx. 3 minutes. A self-standing pellet with SE and the
17144 | J. Mater. Chem. A, 2022, 10, 17142–17155
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Fig. 1 Battery assembly steps (a) self-standing pellet with SE and
a cathode composite. (b) Mechanical breaking of the pellet inside a die
pelletizer to obtain three pieces of battery. (c) The mounted battery in
a homemade in situ cell (IS_cell).
cathode composite is obtained as shown in Fig. 1(a). A thin
cathode layer with an approximate thickness of 64 mm was used
purposely, to study battery failure based on morphological
changes and eliminate many possible transport issues related
to the thick cathode. Since we needed a at section of the
battery for better imaging and visualization during in situ SEM
experiments, we broke this pellet inside the die pelletizer to
obtain three small pieces of battery as shown in Fig. 1(b). The
AM loading is evaluated from the surface area of the pellet and
the weight fraction of the pellet with respect to the entire pellet.
Finally, 0.75 mm thick Li is punched into 1/3rd of 8 mm in
diameter and is hand-pressed on the other side of the SE/
cathode composite. The prepared battery is then mounted on
a homemade in situ cell (IS cell), which is placed between two
stainless steel current collectors as shown in Fig. 1(c). The
initial mechanical integrity and the contact between different
layers in the battery are maintained via the screw on the top of
the cell.
The process of battery assembly and cell mounting was kept
constant for the study of both the solid electrolytes. The entire
cell assembly was carried out in a glove box (Jacomex) under an
argon atmosphere with H2O and O2 at 1 and 0.6 ppm
respectively.
Electrochemical measurements
Ionic conductivity (EIS) and electronic conductivity (DC
polarization). EIS and DC polarization measurements were
carried out for the two solid electrolytes to verify their ionic and
electronic conductivity values, respectively shown in Fig. ESI-2.†
For EIS and DC measurements, pellets with a diameter of 10
mm with
80 mg of SE, fabricated at 3 tons of pressure were
used. The EIS measurements were carried out with an MTZ
impedance analyser provided by Biologic, with a frequency in
This journal is © The Royal Society of Chemistry 2022
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Paper Journal of Materials Chemistry A

the range of 30 MHz to 1 Hz and a classical ion blocking setup
with a 10 mV potential perturbation. The SE pellet was placed
between gold-coated Cu plates during the measurements. The
pressure during EIS measurements is controlled by a spring in
an MTZ impedance cell provided by Biologic. A circular ring
controls the compression in the spring. The spring is
compressed until the last circular motion is possible in the cell
and thus the force per unit area (pressure) in each case remains
constant. The pressure is enough to keep the electrodes in
contact with the pellet during the measurement. For DC
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battery, post-mortem SEM analyses were further performed
aer the in situ analysis.
Results and discussion
In situ electrochemical analysis
To verify the electrochemistry before carrying out experiments
with the homemade IS-cell inside the SEM, electrochemical
testing outside the SEM was carried out as shown in Fig. ESI-3.†

measurements, a Bio-logic SP-200 battery cycler potentiostat The electrochemistry obtained with a classical ASSB cell with
with a sensitivity of current up to nano-amps (nA) was used. The uni-axial pressure like in a pmma (polymethyl methacrylate)
DC measurement set-up allowed a constant stack to be applied, matrix with two pistons/plungers on each side is provided in
and thus 9 Nm of torque was applied (similar setup as shown in Fig. ESI-3(a)† and was used as a reference to verify the obtained
ESI-3(a)†). The 9 Nm is the reference torque that is used during electrochemistry with the in situ cell shown in Fig. ESI-3(c).† For
battery cycling with the Li metal anode and hence the same both the cells, LPSCl–SE, with NMC111 as the cathode and Li
condition for electronic conductivity measurement was fol- metal as the anode was used. The cells were 1st cycled at C/50,
lowed. DC polarization experiments were also carried out under corresponding to a current density of 59 mA cm2. The electro-
ion blocking conditions with SE placed between two stainless chemistry with the homemade in situ cell (ESI-3(c-1)†) looked
steel pistons in the potential range from 0.1 V to 1 V with 0.1 V promising and was comparable to that of the pmma cell, con-
steps each. At each potential step, 3 hours of rest were allocated rming the reliability of the electrochemistry with the newly
to allow the stabilization of the current. developed cell.
Fig. 2(a) depicts the electrochemistry obtained during the in
situ SEM experiments for LPS at a current density of 36 mA cm2
Galvanostatic cycling with potential limitation (GCPL)
(
C/25). There's a sudden potential drop during the 1st charge
The battery cycling was carried out in constant current mode at
3.75 V, indicating the possibility of a short circuit. We also
(GCPL) between 2.3 V and 4.3 V, the potential range used for the prepared batteries based on LPS–SE and LPSCl–SE with our
study of both the SEs. A high accuracy Biologic potentiostat reference ASSB cells as shown in Fig. ESI-3(a-1) and (a-2)†
SP200 was used for cycling. respectively. Though the cell does not fail at 1st charge, high
polarization and low capacity values are evident, depicting poor
In situ/operando scanning electron microscopy setup (in situ electrochemistry compared to LPSCl (Fig. ESI-3(a-2)†). Better
SEM) and uniform control of pressure by the two pistons could
A scanning electron microscope (SEM) FEI quanta-200 F was
used for all the in situ experiments. The prepared IS-cell is
positioned in a homemade airtight box that allows battery
transfer without air exposure to and from an argon glove box
and the SEM chamber and also allows its cycling inside the
SEM. The SEM chamber has been modied for the cable inlet
and outlet and to allow the opening and closing of the transfer
box. All the cycling and analysis processes were performed in
high vacuum mode. Morphological analysis was carried out by
secondary electron imaging (SE). The backscattered electron
(BSE) imaging providing images linked to the atomic number of
the elements was carried out to gain a visual understanding of
the differences in the chemical composition especially at buried
interfaces where EDX isn't accessible. The chemical composi-
tion and distribution were obtained using an X-ray energy
dispersive spectroscope INCA OXFORD (Bruker).
The following steps were performed to monitor the specic
area throughout the cycling: at 0 min the positions of different
areas of interest (electrodes, electrode–electrolyte interfaces,
etc.) were marked in the battery. These positions were followed
throughout the cycling and tracked for morphological and
chemical changes.
To carry out automatic imaging at a specied time interval
and especially during night cycling, we used a small “routine” Fig. 2 Electrochemistry inside the in situ cell with (a) Li3PS4 (LPS) and
code. To investigate further, and carry out analysis inside the (b) Li6PS5Cl (LPSCl).

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Journal of Materials Chemistry A
explain the improved electrochemistry obtained inside the
reference cell when compared to our IS-cell. Pressure plays a key
role in lithium plating and dendrite formation and hence a lack
of good pressure control inside the SEM chamber could be
a possible reason for faster dendrite formation. This problem
aids our experiment and helps to visualize battery degradations
in the allotted SEM time. To investigate the potential drop and
the possibility of a short circuit, in situ SEM imaging was per-
formed before any electrochemical analysis, i.e. at 0 min,
intermediate imaging and one aer the short circuit during the
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1st charge. As for the solid-state system, there's no complete
short circuit, so we let the system evolve aer the short circuit to
increase the probability of observing dendrites, if any during
the in situ experiments.
Fig. 2(b) depicts the electrochemistry obtained during the in
situ SEM experiments for LPSCl. We began our experiment at
a C rate of
C/15, corresponding to a current density of
130 mA
cm2. The choice of the C rate was made for practical reasons
(SEM availability). However, cycling at
C/15 showed some
noise in the cycling data as evident from the 1st two cycles of the
cycling curve. We thought that such noises were due to a high
rate/growth of dendrites at higher C rates so we lowered the C
rate to
C/49 corresponding to a current density value of
40
mA cm2. From the 5th discharge onwards cycling was carried
out, outside the SEM chamber (SEM unavailability) under an
airtight atmosphere. The electrochemical curve from the 5th
cycle until the 15th charge is provided in Fig. ESI-4.† One
observes a constant capacity fade with increasing polarization.
A similar imaging strategy was followed for LPSCl, i.e. imaging
at 0 min and end of charge (4.3 V) & discharge (2.3 V) steps and
nal imaging was carried out at the end of the 15th charge. No
imaging at intermediate potential was carried out unless stated.
In the case of LPS, the battery (possibly) short circuits even at
a lower C rate such as C/25, while for LPSCl though cycling at C/
15 results in increased cell polarization and lower capacity
values, no such potential drop or short circuit is visible. These
observations from an electrochemical point of view show that
LPSCl performs better compared to LPS.
From our theoretical understanding, the possible reasons for
differences in electrochemistry could be:
(a) Ionic conductivity of LPS (105 S cm1) is two orders of
magnitude less than that of LPSCl (103 S cm1) as shown in
Fig. ESI-2.† Hence the ion transport in the bulk of SE is
different. Intuitively, also the effective ionic conductivity in
their respective cathode composites will also be lower. Thus, the
ion transport across the interface will not be the same in both
cases. This adds an extra kinetic limitation for LPS compared to
LPSCl. The other reason for differences in ion transport across
the interface can come from a more porous LPS–SE and its
cathode composite compared to LPSCl, which will be discussed
later. This highly porous nature creates hurdles in achieving
sufficient contacts, and thus even with lower operating pressure
values, the effects get emphasized. This could explain the poor
electrochemical performance of LPS compared to LPSCl.
(b) Also, for the in situ SEM experiments, the pellet is
mechanically broken into 3 pieces, leaving some sort of
mechanical shock in the battery which could explain the poor
17146 | J. Mater. Chem. A, 2022, 10, 17142–17155
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performance in the electrochemistry inside the SEM compared
to those cycled with full pellets with LPSCl outside the SEM in
the same in situ cell as shown in Fig. ESI-3.†
In situ SEM: imaging and chemical analysis
Solid electrolyte. Fig. 3(a) depicts the backscattered electron
(BSE) images of LPS–SE evolution during cycling. One can see
the presence of pre-existing cracks and some dark spots in
pristine LPS. These pre-existing cracks seem to form an inter-
connected network, and thus a dened path exists through
which cracks can grow. Our theoretical calculations, based on
the LPS thickness and surface area approximate a 72% com-
pacity for LPS which agrees with the pristine LPS image,
revealing the poor compacity. The presence of dark spots is
a common observation in the literature for LPS; however, they
have been attributed to voids.39 We do not think of this as void,
since the secondary images reveal these dark spots to have
a solid form and shape as shown in Fig. ESI-5(a).† The EDX of
such dark spots in the LPS presents the complete absence of
sulphur, and phosphorus but the presence of oxygen (refer to
the EDX map in Fig. ESI-5(a)).† Since we are not able to detect Li
with our EDX analysis, we cannot strike out the fact that there
could also be Li metal inside the SE. It could also be a possible
impurity associated with oxygen such as Li2O. Another peculiar
feature of pristine LPS is that it possesses a layered morphology
as shown in its cross-section image in Fig. ESI-5(b).† This
feature of LPS also makes it more prone to crack formation,
since this layered morphology denes cleavage planes. During
LPS rst charge, the analyses show the apparition of a big and
relatively sharp crack of about 11 mm. Thus, LPS displayed in
this region in Fig. 3(a) shows crack formation and growth, as
wide as
13 mm within the 1st charge interval. In addition, the
pre-existing cracks widen and become more visible as the
charging progresses. Electro-chemo-mechanical stress is
created during battery charging. This stress could be due to
plating (Li deposition) or the volume expansion of NMC
3%40
or of the lithium anode41 that exerts stress on the SE or the
expansion of SE42 due to its decomposition. This stress is then
exerted on LPS, that is on pre-existing cracks, interconnected
networks of cracks etc. causing faster growth of cracks. Thus,
the intrinsic nature of LPS with its layered morphology (Fig. ESI-
5(b)†) is prone to generating sharp, huge and fast propagating
cracks.
Fig. 3(b) depicts the BSE images of LPSCl evolution during
cycling. The pristine material surface seems more compact
from the SEM images, in good agreement with our theoretical
calculations of compacity
89%. However, the surface of LPSCl
seems more uneven/rough compared to that of LPS. This
roughness could be due to large particles of LPSCl (50–150 mm)
compared to those of LPS (0.01–7 mm). During the cycling, an
approx. 12 mm uneven/blunt crack is visible by the end of the 5th
charge which grows to
33 mm by the end of the 15th charge.
Unfortunately, we do not have a 1st charge SEM image of LPSCl
to compare the crack growth with LPS. However, the crack width
at the 5th charge of LPSCl (12 mm) is comparable to the crack
width by the end of the 1st charge of LPS (
13 mm), thus,
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Fig. 3 Backscattered electron (BSE) images of solid electrolyte evolution during cycling of (a) b-Li3PS4 and (b) Li6PS5Cl. These images show the
crack formation and evolution.
validating the point that the crack grows (widens) at a much
faster rate in LPS than in LPSCl. The gures ESI-6 and ESI-7,†
show the growth of cracks in LPSCl from 0 min up until the 5th
charge at the anode and cathode interface respectively. These
BSE images conrm that LPSCl indeed shows slow crack growth
and the new cracks are formed at or near the pre-defect area.
The areas in the LPSCl that are compact seem to remain
untouched irrespective of the interface. The following are the
key observations:
(1) Compacities and the surfaces of the two SEs. The difference
in terms of compacity could come from the differences in
particle size of the two SEs. LPS is ner (0.01–7 mm), while LPSCl
is composed of a mix of different particle sizes (50–150 mm).
These particle size differences also lead to a rough surface in
LPSCl and a smoother surface in LPS. Thus, when the two SEs
are pressed at the same pressure, LPSCl compacts more as ner
particles ll in the voids le by large ones. This is not possible
in the case of LPS.
(2) Nature of the cracks and their growth. The cracks in LPS
seem sharper/more dened, while those in LPSCl are blunt/
uneven. Also, the crack growth is much faster in the former
case, than in the latter case. The faster crack growth in LPS
could also be explained based on higher porosities. There's
a high possibility that during Li plating, Li depositions could
take place inside these porosities at the anode interface, and
exert mechanical stress on SE, causing elongation of neigh-
bouring pre-existing cracks. Such local stress-induced inside
the surface aws of SE are reported to cause transgranular
cracks.43 LPS is a glass-ceramic-based SE that shows fractures
associated with typical glassy materials.1 Fractures associated
with glassy materials are classied as brittle fractures. Brittle
fractures give rise to sharp cracks that are known to expand and
grow much faster (speeds—up to 2100 m s1) than ductile
cracks, seen in LPSCl. Ductile cracks grow slower and give blunt
cracks. The cracks that propagate in a brittle glassy material will
continue to grow once initiated and can serve as one of the
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Journal of Materials Chemistry A
plausible explanations for faster short circuits with LPS than
with LPSCl.
(3) First cracks, then dendrites. The intuition about cracks in
SEs is that they could be induced by dendrite penetration and
they grow with their growing propagation. In situ X-ray computed
tomography44 coupled with X-ray diffraction36 studies with a Li–
LPSCl–Li symmetry cell have revealed that cracks travel ahead of
dendrites which very much aligns with our in situ SEM observa-
tions. Cracks seem to grow and propagate ahead of creped Li or
Li dendrites. Also, every crack is expanding simultaneously,
rather than individual dendrites propagating through the SE.
From our observations, we believe it's the porous structure of the
SE that determines this fate of cracks being induced rst and
then dendrites. The generation of electro-chemo mechanical
stress during battery cycling is now a known fact. The way this
generated stress gets distributed is determined by the porous
nature of SE. More porous SE (LPS in this case) will better
distribute this stress, than the compact one (LPSCl in this case).
This could also explain the faster expansion of pre-existing cracks
in LPS. The expanded cracks in turn will serve as a path for
dendrites and nally the battery short circuits as evident with the
potential drop at 3.75 V in the case of LPS. Thus, also according
to our observations, in compliance with previous observations
it’s cracks rst, and then dendrites follow the cracks.
Anode interface (Li/SE interface). Fig. 4(a) depicts the
evolution of the BSE images of the LPS/Li interface during the
rst charge. Good contact between LPS–Li is visible at 0 min. By
the end of the 1st charge, this interface experiences an approx-
imately 9 mm contact loss. In addition, the pre-existing cracks
present on the LPS surface also seem to sharpen/widen and are
more clearly visible.
Similarly, for LPSCl, an initial good contact at 0 min shown
in Fig. 4(b), experiences approx. 36 mm contact loss by the end of
the 5th charge. Unfortunately, we couldn't carry out imaging at
the 1st charge during LPSCl cycling, and hence no direct
comparison with the LPS 1st charge could be made. However,
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Fig. 4 Anode interface: (a) and (b) backscattered electron (BSE) images at the lithium interface for LPS and LPSCl solid electrolyte respectively
showing the loss of contact. (c) Li dendrite morphologies observed in LPS (secondary electrons SE) and (d) LPSCl (black outlined, backscattered
electrons BSE).
approximately 8 mm contact loss at the same position aer the
2nd cycle, as shown in Fig. ESI-5(c),† shows that contact loss is
still lower when compared with LPS. The presence of certain
structures that create spacing between LPSCl–Li is visible by the
end of the 5th charge. These structures perhaps still keep LPSCl
and Li in contact even with the complete loss seen. Also, there is
a possibility that deeper in the battery, contact between the SE
and anode is still present allowing the cycling to continue. The
contact loss between SE/Li could be attributed to a combination
of processes occurring in the battery.
(1) Plating (during charging). Plating will induce a loss of
contact at the interface as Li ions get deposited at the SE/Li
interface. This deposition puts stress on the SE/Li interface
causing contact loss. This could be one of the reasons for
contact loss in both SEs. However, in the case of LPSCl, as the
battery discharges (stripping), the Li ions move back to the
cathode, thus, the possibility of recovering this contact loss. But
since the contact loss remains permanent, this highlights the
irreversibility32 of the process. With every cycle, a residual
contact loss is le which keeps adding to the contact loss of the
previous cycle and this grows which could also explain the
capacity fade with each cycle and huge irreversibility in the
capacity values of LPSCl. Also, some areas experience higher
contact losses than others indicating the non-uniform Li
deposition/plating at this interface.
(2) Volume expansion/volume stress induced during cycling. The
stress exerted from the volume expansion of active materials
during charge in systems such as NMC–sulphide SE–Li–In can
reach as high as 1–1.25 MPa.24 In our case, the axial screw on the
top of the current collector cannot compensate for such pres-
sure and the loss of contact becomes inevitable. While the SE/Li
interface experiences loss of contact, a contact gain between Li/
CC (current collector) is possible as the anode is forced towards
the CC during charging and away during discharging. The
17148 | J. Mater. Chem. A, 2022, 10, 17142–17155
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reverse is true for the cathode. This generated stress has been
known to strain the NMC particles,24 another leading reason for
the capacity fade.
The other striking difference between the two SEs is the
number of and the nature of morphologies (structures) of
deposited Li at the anode interface. Fig. 4(c) shows the
morphology of the deposited Li at the anode interface in the
case of LPS. Two kinds of morphologies are visible. A thick bre-
like morphology labelled as 1 and a spherical morphology
labelled as 2. Fig. 4(d), shows the observed morphologies at the
LPSCl/Li interface. At least 3 kinds of morphologies, labelled as
bre-like (
0.6 mm), globular (
2.6 mm) and thick cylindrical
structures (
4.6 mm), were seen during the in situ analysis.
Mind you, these are only the surface observations and we do not
strike out the possibility of more such structures beneath the
surface in contact with SE. As can be seen in Fig. 4(d), these
formed morphologies are buried deep down the Li/SE interface,
and hence no EDX chemical analysis was possible. However, the
backscattered electron (BSE) images reveal that the formed
structures are not purely Li metallic structures. The BSE signal
is proportional to the atomic number of the species. Thus,
a brighter area's signal possibly comes from high atomic
number (Z) elements in the system meaning probably the
presence of S or P and we assume that this could correspond to
degradation products such as Li2S which is widely reported at
the anode interface45 while slightly grey areas could be Li
depositions/dendrites either still in the metallic state or covered
by a layer of decomposed SE, Li2S, Li3P or Li2O.
As already highlighted, the lithium plating and stripping
processes are non-uniform. Thus, different regions especially in
the case of the LPSCl/Li interface, experience local depositions
giving rise to different morphologies of these deposited Li.
Local depositions occur, due to surface inhomogeneities at the
Li/SE interface, such as defects, impurities or irregularities on
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the Li surface, surface roughness or any surface aws etc. They
are considered hotspots for Li depositions. They alter the
topography and possibly affect the morphologies of the depos-
ited Li. Considering that similar Li metal foil was used in both
the experiments and a similar cleaning process was used, we
expect that the Li surface impurities and rigorousities/surface
roughness on both surfaces will remain constant. Thus, differ-
ences at the SE/Li interface come from differences in the
surfaces of the two SEs. SE particle size affects the surface
roughness. As explained earlier, LPS has a smoother surface
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than LPSCl. Higher surface roughness and higher topographical
variations give a more inhomogeneous deposition, leading to
void formation, resulting in more observed dendrite morphol-
ogies which have already been highlighted by the Masahiro
Tatsumisago group.20 This could explain why we observe so
many different morphologies with LPSCl than with LPS.
Cathode interface. Fig. 5 depicts the modications observed
at the cathode interface during the in situ cycling for both the
SEs. Fig. 5(a) shows the 0 min secondary electron (SE) image of
a secondary NMC particle surrounded by LPS and the carbon
additives in the cathode. By the end of the 1st charge, an
approximately 22 nm thick surface layer/lm on NMC,
Fig. 5 Secondary electron (SE) images of the cathode composite showing the cathode interface in (a) LPS and (b) LPSCl (c) backscattered
electrons (BSE) images show the delamination of the cathode from LPSCl with increasing cycle.
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Journal of Materials Chemistry A
a possible cathode electrolyte interphase (CEI) is seen. The EDX
analysis on this region, marked with a red cross (c) as shown in
Fig. ESI-8(a),† presents an S/P atomic ratio of approx. 3 as
opposed to the expected value of 4 obtained from the LPS-ref.
The obtained values have been tabulated (ESI†). The position of
this secondary NMC particle in the entire cathode composite of
LPS is shown in ESI-9(a).† Similarly, Fig. 5(b) shows the cathode
interface evolution of LPSCl. A similar kind of surface layer on
NMC in contact with SE is visible by the end of the 15th charge.
This layer has an approximate thickness of about 170 nm. The
EDX analysis of this surface layer, marked with the blue cross
(c) and corresponding atomic ratios of elements tabulated
below, as shown in Fig. ESI-8(b),† presents an S/P atomic ratio of
3.3 as opposed to the expected value of 5 obtained from refer-
ence LPSCl. The lower atomic ratio of S/P (3 in the case of LPS,
as opposed to 4 and 3.3 in the case of LPSCl, as opposed to 5),
reveals a higher “P”, compared to S thus, highlighting the
possibility of forming a “P” rich compound at this interface. The
position/location of this secondary NMC particle with the
formed surface layer in the bulk of the cathode composite of
LPSCl is shown in ESI-7(b).† We also found a similar kind of
surface lm/layer on the side of cathode composite that was
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Journal of Materials Chemistry A
close to the current collector side, during the post-mortem of an
ex situ cycled cell made with LPS–SE as shown in Fig. ESI-10(d)
and (e).† These observations conrm the formation of such
a surface lm/CEI to be a bulk phenomenon and not just
surface observations. A study on NMC622/LPSCl13 by time-of-
ight secondary ion mass spectrometry (ToF-SIMS) coupled
with XPS, studied the nature of this interface with cycling. They
found decomposed products at this interface that are mostly
composed of phosphates and sulphate like species, whereas
transition metal compounds such as TMS, TMP, and TMCl
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can be neglected. With NMC being the available oxygen source,
they found that the formation of Li2SO4 or Li3PO4 at this
interface is plausible. They also showed that the amount of
Li3PO4 formed was much higher than that of Li2SO4. This is in
very good agreement with our conrmed atomic ratios of S/P.
Also, since Li2SO4 and Li3PO4 are both insulating in nature, this
formed CEI will indeed be insulating. We also observed a higher
reactivity and charging effect of this formed CEI with an elec-
tron beam, highlighting and conrming the possibility of the
insulating nature of this formed interphase. Similarly, the S/Cl
ratio is lower (3.3), than the expected value (5), highlighting
lower “S” and the possibility of the formation of compounds
like LiCl. A study on interfacial degradation of Li6PS5Cl against
LiCoO2 (LCO) via in situ electrochemical Raman microscopy
conrmed the formation of P2Sx (x $ 5) and LiCl46 during
charging.
The cathode composite also comprises other interfaces such
as C/SE and C/NMC, apart from NMC/SE. The C/NMC interface
is a stable one, similar to the one found in conventional liquid
electrolyte-based batteries. However, the NMC/SE as discussed
already and the C/SE18 are known to be detrimental to battery
performance. They lead to the degradation of SE at higher
Fig. 6 Post mortem of a LPS-based battery: (x) a piece of the LPS battery used for post mortem analysis. (a) Backscattered electron (BSE) image
shows the formation of voids on the LPS surface in contact with the Li anode and (a0 ) the associated magnified image. (b) A secondary electron
(SE) image of the LPS surface shows the presence of dendrites inside the solid electrolyte and (b0 ) associated magnified BSE image.
17150 | J. Mater. Chem. A, 2022, 10, 17142–17155
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voltages, forming a layer of decomposed products, known as an
“interphase”. The VGCF/thiophosphate interface however is
known to form decomposed products that are redox-active.12
These redox-active decomposed products are known to improve
the initial capacity. However, increasing cycles lead to capacity
fade, which is the case with our LPSCl. The formation of a space
charge layer, at NMC/sulphide SE, which occurs due to differ-
ences in chemical potentials has also been reported but seems
to have negligible impact.47 The formation of poorly conducting
decomposition products (interphase) and poor or small contact
areas is known to be more detrimental and increase interfacial
resistance. Thus, in this case, we would relate the formation of
this insulating CEI to being the leading cause of capacity fade in
the case of LPSCl. A stable interphase (SEI-anode interphase/
CEI-cathode interphase) is the one that is formed during the
initial cycles and does not grow with the increasing cycle.
However, in the case of unstable interphase, this keeps thick-
ening with increasing cycles,48 which is the case with both SEs
studied here. This is a big problem for battery cycling.
Fig. 5(c) shows the cathode-LPSCl interface at lower magni-
cation. The cathode composite seems less compact at 0 min.
We expect less compacity in the cathode composite since
materials of different crystallinities and ductilities are pressed
together at one dened pressure. As NMC is a highly crystalline
material, a higher pressure would be required to form
a compact composite. Also going higher in pressure means
more mechanical damage and hence an optimum of 3 tons was
selected for the fabrication of the cathode composite. The areas
marked as A1, A2 and A3, expand from
0.1 mm,
1.85 mm, and

0.24 mm at the 0 min to
1.72 mm,
21.94 mm and
18.88 mm,
respectively by the end of the 15th charge. Also, complete
delamination of the cathode (the electrode itself) takes place by
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Paper Journal of Materials Chemistry A

the end of the 15th charge. In the present scenario, since LPSCl
acts as a better barrier for dendrite penetration due to its better
compacity, compared to LPS, the generated electro-chemo-
mechanical stress during cycling is exerted upon the cathode
causing delamination of the cathode from the SE layer
(mechanical failure) whereas, in the case of LPS, due to the high
porosity of SE, this stress is transferred throughout the SE,
causing crack growth (mechanical failure) and in turn causing
a dendritic short circuit (electrical failure).
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localized stripping thus forming such voids. A dark black area
with a thickness of
6 mm (Fig. 6(b0 )), is visible inside the crack
present in the SE (Fig. 6(b)) and considering the high difference
in atomic number with LPS (white compound) the black phase
is probably lithium. Since the mechanical strength of the two
SEs, (
20 GPa)1 is almost similar, the mechanical strength
offered to block the dendrites should practically be the same.
Also, the electronic conductivities of the two SEs are almost
similar, as shown in Fig. ESI-2.† The electronic conductivity of
SE being the reason for dendrite penetration in LPS can also be

Post mortem analyses of in situ cycled batteries by SEM eradicated.43 The other ways that dendrites can thus propagate
are via grain boundaries, pre-existing or newly formed cracks,
To further our understanding obtained from the surface
voids/pores etc. For LPS as already stated, the poor compacity
observations via in situ cycling and to validate/conrm our
and thus high porosity could majorly serve the path for dendrite
observations, post mortem investigation of the in situ cycled
propagation. Thus, the post mortem conrms that the dendritic
batteries at different interfaces was carried out by SEM. Fig. 6
short circuit is indeed the cause of the sudden potential drop in
shows the post mortem images recorded on the LPS in contact
the case of LPS.
with lithium. Fig. 6(x) shows the general view of the investigated
Fig. 7 shows the images obtained from postmortem inves-
piece on which a part of the lithium remains (upper part of the
tigation of the LPSCl in situ cycled battery. A piece of Li surface
piece) in contact with the SE. In Fig. 6(a), the presence of
which was in contact with LPSCl was used for post mortem
a phase on top of the LPS surface which has a black contrast on
investigation as shown in Fig. 7(y). This represents the general
the BSE images (see also Fig. 6(a0 )) indicating a low atomic
view of the analysed piece. On this backscattered image (Z-
number compound, is visible. Its morphology (Fig. 6(a0 ) and (b))
dependence contrast) three colours (white, grey and black) are
looks like “lace” with the presence of round holes. Considering
visible indicating the presence of at least 3 different phases. The
the Z—information and the observed morphology, this phase
black color represents the Li foil. By investigating further
corresponds to deposited lithium on the LPS surface and the
(Fig. 7(a) and (a0 )), the grey area formed on top of the Li, seems
holes to voids which are a common observation29 induced
like it’s composed of a lot of small grains. Their analyses by EDX
during plating/stripping. However, the voids seen on the LPS
reveal the presence of a high sulphur content (S) with an atomic
surface are questionable since the LPS battery fails during the
ratio of S/P
14 (LPSCl atomic ratio S/P ¼ 5). The deviation
1st charge and no stripping (discharge) has been carried out.
from the expected ratio of LPSCl indicates the formation of
One of the possible ways to explain this void formation can be
decomposition products rich in sulfur, most probably Li2S or
found in Fig. 2(a). The continuous potential increase and drop
Li2Sn. The formation of the interphase between Li metal/
that occurs aer the battery short circuit could give rise to

Fig. 7 Post mortem of the LPS-based battery. (y) A piece of Li surface in contact with LPSCl used for postmortem analysis. (a) The backscattered
secondary electron (BSE) image shows the formation of reduced SE on the Li surface and (a0 ) associated magnified image. (b) BSE image of the Li
surface with Li plated structures and (b0 ) the associated magnified image of the plated Li.

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Journal of Materials Chemistry A Paper

sulphide SE is now commonly known in the literature. This Postmortem of an ex situ cycled battery with LPS by SEM
occurs due to the intrinsic chemical instability of sulphide SEs
To further conrm our observations made from in situ and
with the Li metal anode. This interphase comprises Li2S, Li3P
post mortem of the in situ cycled battery, we also carried out
and LiX in the case of Li6PS5Cl. But in the case of Li6PS5Cl, this
postmortem of an ex situ cycled cell outside the SEM with our
interface is known to be stabilized aer a few hours of
ASSB reference cell (pmma-matrix). ESI-1(a)† shows the 1st
contact.6,49 The ionic and electronic conductivity of the formed
charge electrochemical curve of LPS obtained with the pmma
interphase at the Li/SE interface has been known to be an
reference cell, cycled outside the SEM. The observations such
important factor in improving the short-circuiting tolerance of as sharp cracks (ESI-10(b)†), the formation of anode inter-
all-solid-state Li–metal batteries. Suyama et al. showed that by phases (ESI-10(c)†), Li plated structures (ESI-10(f)†) and CEI/
increasing the Li3P content in the interphase, the cell can cycle
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surface layers (ESI-10(d) and (f)†) are all coherent from the
longer without short-circuiting.23 So, could there be differences
observations made during the in situ experiment. This indeed
in total ionic and electronic conductivities of formed inter-
conrms the reliability of the surface observations made from
phases between the two sulphide SE? Or differences in the total
in situ SEM experiments. We believe that open surfaces can
amount of formed Li3P between b-Li3PS4 and Li6PS5Cl? This
indeed give fast reactions since the surface remains open and
could be another possible explanation for the different short-
exposed; however from our post-mortem analysis of the in situ
circuiting behaviours between the two SEs. In other words, this cell/ex situ cell we do not believe this behaviour to be different
could explain why it's easier to have a dendrite short circuit in b- from the bulk.
Li3PS4, than in LPSCl. This hypothesis however needs to be
To summarize our discussion, Fig. 8 provides a schematic
veried further in this case.
summary of various failure modes, observed in the two SEs via
Further investigation of the lithium surface is presented in
in situ SEM. We believe that these failure modes are the pieces
Fig. 7(b) and (b0 ). In Fig. 7(b) also three phases are present: (i)
of the same puzzle and hence are linked together, as has been
the black one at the bottom corresponding to Li foil (ii) the grey
shown in recent studies.50 They could be categorized into either
one discussed previously, corresponding to degradation prod-
of the following 3 interlinked broad modes of failure (mecha-
ucts, and (iii) the white one whose composition is on par with nism of failure):
the solid electrolyte. The morphology of lithium (Fig. 7(b0 )) (1) Electrical failure comprises dendrite short circuits or
shows a lot of reliefs and is composed of lament-like struc-
mechanically induced short circuits or an increase in the
tures. It is very different from the original lithium surface and
impedance value.
more consistent with plated structures. Li plated structures are
(2) Mechanical failure could be cracks in SE, loss of contact
formed, with depositions of dead Li-ions during the ion trans-
at the interface, the delamination phenomenon or the global
port thus, highlighting the capacity fade and extremely poor
volume expansion/contraction of the cell during cycling, etc.
capacity by the end of the 15th charge as shown in Fig. ESI-4.†
(3) Electro(chemical) failure is a joint term to describe
chemical and electrochemical failures together. It comprises

Fig. 8 Schematic summarizing all the observed failure modes observed in the LPS vs. LPSCl solid electrolytes.

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failures associated with the intrinsic instability of two chemical
compounds, e.g. Li metal in contact with thiophosphate SEs and
also describes the degradation associated with the application
of electrochemical potentials, e.g. the formation of the CEI etc.
Such evolutions have been observed separately in previous
studies but they were all observed during our experiments
showing the complexity of such systems. X-ray CT coupled with
SEM studies on LPS highlighted that the main mode of failure
associated with LPS kind of SE is a chemo-mechanical failure.42
LPS expands during its chemical decomposition with Li metal
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upon cycling, leading to the formation of small cracks. Li metal
then penetrated through these small cracks. In our case, we
believe the intrinsic nature of b-Li3PS4 lies at the core of its
failure. The poor compacity of the LPS–SE separator (72%), even
poorer compacity of the cathode composite (51.75%), the
interconnected network of porosities, pre-existing cracks, and
layered morphology of LPS that denes the fracture planes are
at the core. The electro-chemo-mechanical stress, generated
during the 1st charge (Li deposition), is exerted on the poorly
compact LPS–SE. Since LPS is poorly compact, generated stress
is distributed throughout the SE, causing the simultaneous
growth of pre-existing cracks. There's a high probability that Li
depositions could occur inside the porosities of LPS. This
creates higher stress in SE leading to faster crack growth. Since
the fracture planes seem to be dened due to layered
morphology, cracks grow faster and sharper. Later on, these
cracks serve as a path for dendrites. Also, faster crack propa-
gation occurs due to its glassy nature. In short, LPS clearly
shows electrochemically induced (plating) mechanical failure
(cracking in SE), collectively electro-chemo-mechanical failure
leading to short circuit aka electrical failure (dendrites).
In LPSCl, upon 1st charge, due to electrical plating,
mechanical stress is generated at the anode interface. Since this
SE is more compact, the generated stress cannot spread in the
SE but gets exerted upon the electrodes. Similarly, volume
expansion from NMC keeps building up. This generated
mechanical stress keeps on adding up until there's complete
delamination of the SE/cathode interface and huge contact loss
at the SE/anode interface. Dendrites formed at the anode
interface do not penetrate inside SE, and thus we believe that
LPSCl acts as a better barrier compared to LPS, in preventing
dendrite propagation. This ability to act as a better barrier
possibly comes from the good compacity of SE, due to large
particles and also a good particle size distribution (PSD). Also,
the nature of fracture with LPSCl is ductile, and hence the
cracks propagate at a slower rate compared to LPS. The higher
surface roughness due to the large particle size of SE could be
one plausible explanation for the many different dendrite
morphologies observed. Thus, the main mode of failure could
be a chemo-mechanical failure for LPSCl.
Conclusions
An understanding of the failure mechanisms in all-solid-state
batteries using promising solid electrolytes is crucial for their
development. Hence we performed a thorough chemical and
morphological investigation using in situ and operando SEM
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Journal of Materials Chemistry A
analysis on two sulphide based solid electrolytes namely b-
Li3PS4 and Li6PS5Cl to fully comprehend and categorize the
different modications observed.
We separate the evolutions as parts of three main inter-
connected failure modes:
 (1) Electrical failure with the formation of lithium
dendrites propagating across the SEs as in the case of LPS
leading to short-circuit.
 (2) Electro-chemical failure with the formation of degra-
dation products, a SEI and CEI, in both cases.
 (3) Mechanical failure with the apparition of cracks and
their expansion in both solid electrolytes as well as the delam-
ination of the cathode composite as in the case of LPSCl.
All these failure modes are interlinked and should be studied
as a whole to fully grasp the origin of the performance limita-
tion. Among them, we believe that mechanical failure is at the
core of the capacity losses since these are irreversible in nature.
We also highlighted that the key factor determining the differ-
ences in the failure between the two SEs lies in their respective
intrinsic natures.
Throughout this work and in our discussions, we emphasize
the role of surface roughness, size of SE particles etc. However,
this doesn't seem to be a direct comparison since the two above
mentioned SEs are different. To perform a direct comparison
and validate the role of SE particle size and its impact on
dendrite morphology, the formation of thick structures and
their origin, compacity/porosity, dendrite and crack propaga-
tion etc. by keeping the SE constant will be the focus of our
future work.
Author contributions
Conceptualization, data curation, formal analysis, investiga-
tion, methodology, visualization and the writing of the original
dra were carried out by Neelam Ghanshyam Yadav. Nicolas
Folastre, Mickael Bolmont, and Arash Jamali aided in the
development of the in situ cell used during the experiment.
Mathieu Morcrette and Carine Davoisne, the corresponding
authors were responsible for project administration, supervi-
sion, validation of the research output and reviewing the written
manuscript. The above descriptions are accurate and have been
agreed upon by all authors.
Conflicts of interest
There are no conicts to declare.
Acknowledgements
The authors would like to thank the French ministry (MESRI)
and the French National Research Agency (STORE-EX Labex
Project ANR-10-LABX-76-01) for nancial support. We would
also like to thank the “cellule énergie” of CNRS for the funding
to develop the in situ cell used during this study.
J. Mater. Chem. A, 2022, 10, 17142–17155 | 17153

Journal of Materials Chemistry A
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