REVIEW

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Insights into Influencing Electrode Calendering on the

Battery Performance
Mozaffar Abdollahifar,* Heather Cavers, Sören Scheffler, Alexander Diener, Mark Lippke,
and Arno Kwade

main concern for the LIBs since their in-

As the demand for lithium-ion batteries (LIBs) continuously grows, the ception in 1991. At the time they could
necessity to improve their efficiency/performance also grows. For this reason, achieve specific energy of 100 Wh kg−1 ,
optimization of the individual production steps is critical. Calendering is a for about $1000/kWh, and currently up
crucial production step whereby electrode coatings are compacted to targeted to 350 Wh kg−1 (800 Wh L−1 ), for about
$200/kWh,[1,2] with the outlook to further
densities. This process affects the porosity, adhesion, thickness, wettability, upgrade the specific energy to more than
and charge transport properties of the electrodes, as well as the homogeneity 400 Wh kg−1 (1100 Wh L−1 ) for the near
of the coatings. Optimal calendered electrodes improve volumetric energy future.
density, cyclic stability, and rate capability of the cells and also enhance the In order to increase energy density,
structural stability of the active material, which affects electrode safety and most research studies on LIBs have con-
centrated on various anode and cath-
polarization. This article outlines the fundamental processes and
ode active materials, suitable binders
mechanisms, as well as how modeling, simulation, and tomography can be and electrolytes, particularly for lithium-
used to optimize these processes. Additionally, the influence of calendering nickel-manganese cobalt-oxides (NMC)
on a wide range of anode and cathode active materials is discussed. This and silicon (Si)/carbon composite active
review serves to give a deeper understanding into the calendering materials.[3,4] However, electrode and cell
process-structure-performance relationships, and how they can be optimized manufacturing development are also crit-
ical for enhancing the energy density,
to improve the performance of LIBs. and other performance parameters such
as cycling stability and rate capability
of LIBs.[5] Currently, the manufacturing
[1,6–14]
1. Introduction of LIB electrodes involves slurry mixing, all the way to
cell building and welding processes (Figure 1a). Calendering
In recent years, due to their high energy density the demand for (Figure 1b) is a standard and low-cost (about 5% of the to-
rechargeable lithium-ion batteries (LIBs) has increased exponen- tal cost)[1] process in electrode manufacturing, which can in-
tially for recently emerging electric vehicles (EVs) and hybrid elec- crease the cell volumetric energy density and enhance the
tric vehicles (HEVs), and it will continue to dominate the EV mar- bonding strength between the active materials/conductive car-
ket, at least for the next 15 years. Despite their inherently high en- bons/binders and the current collector by reducing the porosity
ergy density, further improving the energy density has been the from 50-–70% down to 20–40%. Moreover, cells for different ap-
plication like EVs and HEVs need different densities and, thus,
calendering degrees. The impact of calendering parameters (line
M. Abdollahifar, H. Cavers, S. Scheffler, A. Diener, M. Lippke, A. Kwade
load, speed, and temperature) should be considered based on
Institute for Particle Technology
Technische Universität Braunschweig the material formulation, slurry solids content, and drying proce-
Volkmaroder Str. 5, 38104 Braunschweig, Germany dure. For instance, with increasing rolling temperature, the elec-
E-mail: [email protected] trode’s porosity and compaction resistance are decreased, and a
M. Abdollahifar, H. Cavers, S. Scheffler, A. Diener, M. Lippke, A. Kwade higher adhesion strength is achieved.[15] Higher line load dur-
Battery LabFactory Braunschweig (BLB) ing calendering could increase the energy density of cells, but
Technische Universität Braunschweig
Langer Kamp 19, 38106 Braunschweig, Germany the effective surface area and tortuosity for diffusion of Li-ions
will decrease, resulting in an adverse impact on the power den-
The ORCID identification number(s) for the author(s) of this article sity of cells.[16] Calendering to a certain level could improve the
can be found under https://doi.org/10.1002/aenm.202300973 wettability of electrodes, due to the arrangement of particles and
© 2023 The Authors. Advanced Energy Materials published by the increase in divergence within the pore networks.[17] However,
Wiley-VCH GmbH. This is an open access article under the terms of the calendering beyond an ideal level reduces wettability, because of
Creative Commons Attribution-NonCommercial-NoDerivs License,
which permits use and distribution in any medium, provided the original
reduction in porosity and average pore diameter.[18] Hence, the
work is properly cited, the use is non-commercial and no modifications calendering process should be optimized to achieve electrodes
or adaptations are made. with an overall optimum structure delivering sufficient electri-
DOI: 10.1002/aenm.202300973 cal and ionic conductivities, adhesion and mechanical properties

Adv. Energy Mater. 2023, 13, 2300973 2300973 (1 of 34) © 2023 The Authors. Advanced Energy Materials published by Wiley-VCH GmbH
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Figure 1. a) Schematic illustration of electrode production to cell production chain. b) Schematic illustration of the calendering process and its effect
on the electrode porosity and structure of a typical double-sided electrode. The blue and black particles are active materials and conductive carbons,
respectively, and the yellow shapes represent the binder. c) SEM cross-sectional images of a typical single-layer anode electrode (composition: 90 wt%
graphite (Gr) active material, 4 wt% conductive carbon, and 6 wt% binder), before (left) and after (right) calendering. The electrodes manufactured
and calendered at Battery LabFactory Braunschweig (BLB).

in order to deliver a battery with a maximum volumetric energy 2. Electrode Calendering Process
density and a longer cycle life.
This review aims to outline the fundamentals of the calender- Calendering is one of the important process steps in the produc-
ing process, and demonstrate how this process could be a per- tion chain of electrodes (Figure 1a) for LIBs, as it determines the
formance enhancing step in LIB fabrication. The following sec- final electrode microstructure. After mixing, coating, and drying,
tions will start with the calendering process and related mech- the porous coating undergoes mechanical compaction, reducing
anism. Afterward, discussions about the simulation, modeling the coating porosity and improving the volumetric energy den-
and tomography studies are systematically reviewed based on sity by reducing the coating thickness (Figure 1b). Typical scan-
the porous electrode theory and electrode structures. Finally, ning electron microscope (SEM) images of electrodes before and
the influence of calendering on the mechanical and electro- after calendering are demonstrated in Figure 1c. Aiming to im-
chemical behaviour of LIBs and other battery electrodes are prove the surface and bulk uniformity of the electrodes, the typi-
discussed. cal calendering process consists of a two-roll compaction process

Adv. Energy Mater. 2023, 13, 2300973 2300973 (2 of 34) © 2023 The Authors. Advanced Energy Materials published by Wiley-VCH GmbH
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scrap and complicating ongoing process steps, such as cutting

and packaging. Those electrode defects may be reduced by us-
ing a heated calendering process. Heating the rolls reduces the
needed line load,[15] and a lower line load reduces the spring back
of the electrode[20] and the shear stress between the current col-
lector and the coating. Overall, a well-designed and intelligent
process control is necessary to reach desired product properties
and quality.[5]

2.1. State-Of-The-Art
Figure 2. Schematic view of the in gap circumstances, including the roll
force FN , the electrode thickness before (𝛿El,𝜌0 ) and after (𝛿El,𝜌i ) the calen- The effect of the calendering process differs between anodes
dering, the in-gap width (𝛿 Γ ), the roll radius rR , and the inlet and outlet and cathodes and depends on the used electrode chemistry. As
strings SIn and SOut . ZC describes the compaction zone and ZR the relax-
the calendering process affects the particle network as well as
ation zone of the coating.
the pore network, it strongly influences the electrical, electro-
chemical, and mechanical properties of the electrodes. Regarding
in which the electrode is drawn in the calender gap where the the mechanical characterization, Haselrieder et al. introduced a
force, FN , is applied. Typically, the force, FN , is normalized by the method based on nano-indentation and reported that the calen-
coating width, wC , and referred to the line load qL (Equation (1)). dering process mainly reduces the plastic deformation energy
of the electrode while preserving the elastic deformation energy,
FN which is important for the ongoing process step and the cy-
qL = (1)
wC cling capability.[21,22] Furthermore, analyzation methods based on
nano-indentation or micro-manipulation[22] can characterize the
Within the roller gap particle rearrangement and, for high line mechanical behavior of active material and correlate the results
loads, particle breakage occur,[19] resulting in plastic deforma- with the calendering process.[22–25] A good electrochemical per-
tion. formance is critical for battery cells in practical applications. The
Additionally, an elastic deformation mainly of the active ma- effect of calendering differs significantly from anodes to cath-
terial occurs, leading to a fast elastic recovery (spring back) of odes, but also from the used material composition. On the an-
the electrode directly after leaving the roller gap. Besides the line ode side, a moderate compaction rate has been reported to be
load, the gap width, 𝛿Γ , and the circumferential speed, v0 , are the beneficial as it may reduce irreversible capacity loss while im-
main control parameters (Figure 2). proving cyclability.[21,22,26,27] Conversely, higher compaction rates
The rolling radius, rR , the electrode geometry (width: wC and were reported to reduce the cell performance due to increased
thickness: 𝛿El,𝜌0 ), and gap width, 𝛿 Γ , define the electrode’s catch- diffusion resistivity.[21,22,28,29] As the calendering process lowers
ment area within the gap through the contact area, AΓ . The con- the porosity, it affects the wettability. For graphite anodes, com-
tact area and the calendering speed define the dwell-time of the parable results have been shown for the effects of wettability
coating within the roller gap. According to Equations (3) and on the cell performance, and moderate compaction improves
(4), the contact area depends on the roller radius, increasing the the wettability due to a positive alignment of the graphite par-
roller size leads to a larger contact area and a higher dwell-time. ticles. In contrast, higher compaction has a poor wetting abil-
Higher dwell-time means more time for particle rearrangement, ity due to the progressive reduction in porosity and pore size
heat transfer, and a smoother compaction process with less shear distribution.[18]
stress. By ignoring the relatively small curvature within the roll In contrast to anodes, cathode active materials (CAMs) typi-
gap, the contact area, AΓ , can be calculated through the coating cally show poor electrical conductivity. Therefore, for cathodes,
width wC and the inlet and outlet strings SIn and SOut (Equa- calendering has a significant effect on cell performance, as af-
tion (2)). ter calendering the electrical conductivity of cathodes can be im-
( ) proved due to a denser particle arrangement and a better bonding
AΓ = wC × SIn + SOut (2) between the conductive additive and the active material. Studies
for the CAMs, such as lithium cobalt oxide (LCO), lithium iron
√ phosphate (LFP), NMCs and lithium–nickel–cobalt–aluminum–
( ) oxides (NCAs) have shown that by calendering the electrochem-
Sin = rR × 𝛿El,𝜌0 − 𝛿Γ (3)
ical performance is improved due to a reduction in the electrical
resistance.[30–33] However, ongoing reduction in porosity by cal-
√ ( ) endering results in an ionic limitation through the increase in
Sout = rR × 𝛿El,𝜌i − 𝛿Γ (4) tortuosity and diffusion resistance. Additionally, with increasing
calendering load, particles’ cracks are more likely to happen. Hut-
The different deformation behavior of the current collector and tner et al.[19] investigated the relationship between the moisture
the coating not only compression, but also strain perpendicu- uptake and the calendering process observing a higher moisture
lar to the compression, and the occurring electrode spring back, uptake for higher calendering loads, and addressed this to an in-
may lead to different electrode defects,[17] resulting in electrode creased surface area due to particle breakage.

Adv. Energy Mater. 2023, 13, 2300973 2300973 (3 of 34) © 2023 The Authors. Advanced Energy Materials published by Wiley-VCH GmbH
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Balancing electrical and ionic conductivity while identifying ( )B

qL = A × 𝜌C,i − 𝜌C,0 (6)
the ideal electrode porosity is the main challenge and goal of
the calendering process. From cell testing with varied C-rates, This approach turns out to be a quadratic correlation with B
the literature shows that the strongest calendering degree does = 2, and simultaneously small values for A (A < 1 gcmmm
3N
), which
not equate with the best electrochemical performance. Rather,
a good balance between compaction and porosity, which is re- means, in general, that doubling the coating density requires a
sponsible for the lithium-ion transport via diffusion, is neces- quadruple line load. Considering this, and according to Equa-
sary to achieve the best electrochemical performance in terms tion (6), the increase of the coating density is theoretically always
of specific energy[21] or for a percentage comparison between possible using line loads going up to infinity. In a real compaction
specific energy at different C-rates and initial specific energy.[34] process of composite structure, this is not possible due to limit-
Regarding the long-term cycling of cells with calendered elec- ing side factors like raw material density and breakage strength
trodes, it is much harder to separate the influence of the calen- of the particles.[22]
dering process step from other parameters, for example, mate- An improved empirical modeling approach was developed by
rial aging. Haselrieder et al.[21] demonstrated the best cycle sta- Meyer et al. in several publications.[15,36,37] The authors predict
bility for the electrode with a compaction degree of 10%, whereas coating density as a function of applied line load during calender-
the electrodes with a compaction degree of 5% and 26% per- ing, using double-sided NMC cathode and Gr anode electrodes.
formed worst. Schilcher et al.[35] investigated the long-term elec- In their first publication,[36] they varied the production speed of
trochemical performance of lithium manganese oxide (LiMn2 O4 , the calender line used, resulting in an accurate correlation be-
LMO) cathodes with six different coating densities (from 1.63 to tween coating density, 𝜌C , and applied line load, qL . By plotting
2.35 g cm−3 ). Here, the coating density of 1.82 g cm−3 showed the coating density against line load, defining the initial coating den-
best long-time stability, and the two electrodes with the highest sity, 𝜌C,0 , of the electrode after the coating and drying process, as
coating densities of 2.35 and 2.12 g cm−3 displayed accelerated coating well as maximal density, 𝜌C,max , at minimal calender roll
cell aging, resulting in a faster decrease of accessible specific ca- gap, they obtained an exponential fit (Equation (7)). Furthermore,
pacity. they introduced an electrode-dependent compaction factor called
The following sections take a closer look into the different in- compaction resistance, 𝛾 C , which works as a damping factor in
teractions between the calendering process and their influence this model approach:
( )
on material-related properties. ( ) q
𝜌C = 𝜌C,max − 𝜌C,max − 𝜌C,0 exp − L (7)
𝛾C

2.2. Empirical Modeling A considerable advantage of this exponential fit is the conver-

gence of the coating density up to a maximum value defined by
The first attempts to model the calendering process step from material specific properties, such as raw material density and
empirical data were shown by Haselrieder.[22] The line load was porosity value in cubic close packing.
considered as a function of the compaction degree, Π, (Equa- In a further publication, Meyer et al.[37] investigated cathodes
tion (5)), which itself is defined as 1 minus the ratio of the height with different active materials and coating thickness variation of
of the electrode after the compaction process, 𝛿 E,a , to the height NMC111-cathodes. The authors aimed for a proportionality fac-
of the initial electrode thickness, 𝛿 E,initial :[21] tor, p, between the initial coating density and the maximum coat-
ing density after compaction. They assumed that p would be sim-
ilar to the ratio between a simple cubic packing (scp; 47.64%) and
𝛿E,a
˙ = 1− (5) a cubic close packing (ccp; 25.95%), which would be 0.54. The re-
𝛿E,initial sults from electrode compaction show that p tends to be around
a value of 0.4. The author explained this with the structural rear-
It was shown that in the area of 0 ≤ Π ≤ 0.25, a poten- rangement effect, whereby the additives are forced between the
tial fit could be used to describe the correlation between line active material particles and, therefore, fill space that the active
load and compaction degree. Further, Haselrieder showed that material particles are not capable of occupying due to their larger
higher line loads are required to achieve same density when size. This leads to a decreased porosity of the electrode coating. As
using electrodes consisting only of active material and binder, mentioned in their previous publication,[36] different active ma-
compared to three-component electrodes (active material, binder, terials used can lead to a specific active material-dependent com-
conductive agent). This phenomenon can be explained with paction factor when maintaining a constant mass loading of the
the binder’s mainly elastic deformation behavior and, there- electrodes under investigation. Furthermore, a linear correlation
fore, higher spring back of the electrode after passing the cal- was shown between the compaction resistance of electrodes with
ender roll gap. In addition, Haselrieder correlated the required constant active material and increasing mass loading. With these
line load for compaction with the resulting coating density for two findings, Meyer et al.[37] replaced the compaction resistance
LiCo1/3 Ni1/3 Mn1/3 O2 (NMC111)-cathodes and for spherical Gr factor, 𝛾 C , with a combination of the mass loading, MC , and a ma-
(meso-carbon micro-beads, MCMB)-anodes. Haselrieder chose a terial specific mass dependency factor, μ. Using the correlation
potential fit for the description of the required line load, qL , (Equa- between initial and minimal coating density with the proportion-
tion (6)) for increasing the coating density from initial density ality factor, and replacing the compaction resistance, Equation (6)
after the coating process, 𝜌C,0 , to the coating density after calen- was adapted by using the coating porosity, 𝜖, instead of coating
dering, 𝜌C,i , whereby two form factors A and B are used[22] density, 𝜌, resulting in Equation (8):

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( ( ))
q The authors led this dependency of the compaction resistance
𝜀C = 𝜀C,0 p + (1 − p) exp − L (8)
𝜇MC back to the higher hardness and modulus of elasticity of Si, com-
pared to the comparatively weak Gr particles. Furthermore, it
Hereby, it has to be considered that in addition to mass loading was shown from micro manipulation measurement that the Si-
or electrode thickness, respectively, the thickness of the current rich electrodes tend to have higher deformation work at constant
collector, for both anode and cathode production, plays an im- indentation depth, as well as a lower ratio of plastic to elastic
portant role regarding the correlation between achieved coating deformation behavior, which supports the assumption of a Si-
density and required line load. Just from the geometrical point dependent increase of the compaction resistance.[25]
of view, a thicker current collector would be equivalent to higher The modeling of the calendering behavior of electrodes for
mass loadings with otherwise the same conditions. LIBs from experimental data has made steady progress over
Besides active material and mass loading, the temperature of the last years. For future applications, the usage of new cell
the calender rolls plays a major role in the compaction behav- chemistries, or improved active material will simultaneously re-
ior of electrode coatings, especially of cathodes, due to the ther- quire further development of the modeling work, particularly re-
moplastic deformation behavior of the commonly used binder garding mechanical behavior of active materials. Furthermore,
polyvinylidene fluoride (PVDF).[15,38] Due to this, Meyer et al.[15] new inline measurement techniques are required, like the direct
investigated the calendering behavior of NMC111-cathodes with roll gap measurement system developed by Diener et al.[20] which
varied carbon black (CB) and binder contents at different roll can be used for a stronger linkage of the interactions between ma-
temperatures. It was shown based on a comparison of electrodes chinery, process parameters, and product.
with different mass loadings that the compaction resistance de-
creases with the rising temperature of the calender rolls. It was
also shown that a linear relationship for the influence of the roll 2.3. Electrode Defects
temperature between glass temperature and melting tempera-
ture of the thermoplastic binder can be assumed for the mass- From the view of the production side, electrodes for LIBs are
dependent factor, μ. This led to a modification of the calculation a multilayer product consisting of different materials with
of the compaction resistance, 𝛾 C , from the specific mass depen- specific material properties and deformation behavior. Due to
dency factor μ and the mass loading, MC , by taking the theoretical this, dissimilar elastic and plastic deformation of the electrode
mass dependent factor at a roll temperature of 0 °C, the roll tem- layers takes place. The compaction does not only occur in the
perature, TR , and a recipe dependent temperature coefficient 𝜉 vertical direction between the calender rolls, the electrode is also
(Equation (9)) into account. deformed lengthwise and crosswise according to the direction
of the production line. Here, it is important to mention that the
( )
𝛾C = 𝜇0 ◦ C − 𝜉 × TR × MC (9) thickness of the current collector and its material stiffness play-
ing a major role regarding the total amount of deformation. The
Implementing Equation (9) into Equation (7) led to a fit from behavior of the electrode’s different layers (active material layer
empirical modeling of the dependency between applied line load and current collector) leads to wrinkles (Figure 3a) at the edge of
and coating density or, respectively, coating porosity that cov- the electrode coating, as the copper or aluminum foil protruding
ers the influence of mass loading, roll temperature, and coating from beneath the coating are not mechanically deformed in the
recipe:[15] same way as the coated area.[39–41] When the current collector
is thicker, its material properties have a higher influence on
( ( )) the overall compaction behavior of the electrode and, therefore,
qL
𝜀C = 𝜀C,0 × p + (1 − p) exp − ( ) (10) the importance of the current collector increases. It can be as-
𝜇0 ◦ C − 𝜉 ⋅ TR ⋅ M C sumed that the wrinkles are relatively smaller for thicker current
collectors with otherwise the same conditions. Those wrin-
New active materials, such as Si or NMC811, have recently kles can be mainly responsible for imprecise electrode cutting
been employed to enhance the gravimetric and volumetric energy and, therefore, impede an accurate stacking process during cell
density of electrodes or cells. These new materials come along assembly.[40] Furthermore, the wrinkles resulting from the differ-
with material-specific influences on the production process, as ent material deformation behaviors from the same applied stress
shown by Meyer et al.[36] for NMC111 and Gr, and by Meyer et can lead to inner mechanical tension, leading to a corrugation
al.[37] for NCA and different NMC materials. According to these of the electrode as depicted in Figure 3b. The corrugation of the
material dependencies, Scheffler et al.[25] investigated the calen- whole electrode also influences the stacking and packing process
dering behavior of Gr–Si-blend anodes with varied Si content, in- in the cell assembly.[17,34] For a non-symmetric electrode coating
creasing required line loads with increasing Si content to achieve profile, this inner tension also leads to a lengthwise arc-like shape
the same coating density as a Gr reference electrode. In parallel, of the electrode (Figure 3c).[41] The first attempt to quantify the
the compaction resistances using the modeling approach from corrugation of the electrode after compaction was made by Mayr
Meyer et al.[36] increases with higher Si mass fractions. It was et al.[42] using two measurement systems within the calendering
shown that the correlation between compaction resistance and system. For this, they implemented an inline measurement
Si mass fraction, wSi , can be described with Equation (11) with system for the electrode thickness (confocal sensors) and an
𝛾C, wSi = 1 = 170.0 ± 6.4 N mm−1 : inline measurement system for the electrode topography, cross-
( ) 0.4 wise to the direction of production (laser triangulation sensor).
𝛾C = 𝛾C,G + 𝛾C, wSi = 1 − 𝛾C,G ⋅ wSi (11) Using the data from the electrode topography, the authors were

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Figure 3. Electrode defects occurring from calendering; a) wrinkles; b) electrode corrugation; c) arc-like electrode; d) inhomogeneous coating thickness;
e) cracks of active material particles; f) electrode foil tear. Reproduced with permission.[41] Copyright 2018, De Gruyter.

able to show an overall corrugation of the electrode itself with a particles break as shown in Figure 3e.[19,41] Huttner et al.[19]
peak-valley-value of 3.22 μm and a corrugation of 1.36 μm of the investigated the calendering behavior of NMC622 cathodes,
coating edge for an NMC cathode with a porosity of 30% after focusing on particle breakages using BET surface measurement
calendering. Further development of inline sensor-based product and moisture analysis of the electrodes. They found that with
control systems should cover an overall concept of the measure- increased coating density, the moisture content rises linearly
ment of the electrode corrugation, the electrode thickness, and over the specific surface area of the electrode coatings in a range
potential electrode defects. Combining these inline measure- from 2.6 to 3.2 g cm−3 . Furthermore, they showed that the
ment devices with the modeling of the dependencies between specific discharge capacity of the investigated electrode with
process parameters and product properties, an agile closed-loop a coating density of 3.2 g cm−3 decreased, which lead back to
process control can enhance electrode quality, and decrease the breakage of the active material particles, causing them to
production scrap resulting from the calendering process.[42] become more electrochemically inactive due to the breakage and
An unpredictable electrode defect that cannot be covered by lost contacts within the coating.
using this inline measurement technology is an inhomogeneous In general, if the internal stresses in the electrode coating,
coating thickness (Figure 3d), resulting from failure during the or between coating and foil, or the external stresses like ten-
electrode coating process. Certainly, this electrode defect leads sion in the direction of production, exceed the tear tension of
to an inhomogeneous stress distribution during compaction, the electrode itself, this forces electrode tearing (Figure 3f). The
which results in an inhomogeneous density of the electrode appearance of tears during production leads to production stop
coating, leading to local capacity gradients of a battery cell.[41] and production scrap. In all cases, electrode tears have to be
Applying normal and shear stress to the coating during calender- prevented.[41]
ing forces the active material particle in the coating to collide. If An overview of the impact on the further production process
the stress between the particles exceeds their breaking strength, of a battery cell caused by the different possible electrode defects

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trodes via AC impedance and electrochemical impedance based

on symmetrical cells, as shown by Landesfeind et al.[46] For the
cathode, the authors showed monotonically increasing tortuosity
for porosity ranges between 0.52 and 0.29. However, the anode’s
tortuosity decreases at first when the coating is compacted from
porosity of 0.55 to 0.43. The tortuosity undergoes a substantial
increase afterward, when the electrode is further compacted to
porosity of 0.41.[45]

3. Modeling, Simulation, and Tomography

Experimental methods to investigate the influence of calender-
ing on the morphology and properties of electrodes can be costly
in terms of raw materials, physical resources, and time. More-
Figure 4. Schematic representation of the effective (LP,eff ) and ideal
(LP,ideal ) pore length. over, a direct monitoring of the microstructure changes during
calendering is hardly or even not possible. Use of models and nu-
merical simulation methods offer a far less expensive alternative.
presented, was given by Günther et al.[17] The authors divided the Modeling approaches can characterize everything from the me-
electrode defects into three classifications: chanical behavior of individual particles[47] to macro-scale mod-
els, focusing on global parameters in the electrode, such as parti-
a) Rejects, electrode useless for process cle distribution, porosity or tortuosity.[24,45,48–53] Experimental ap-
b) May lead to rejection during the process proaches, such as X-ray computed tomography (CT) can be used
c) Defect harmless for process to characterize the electrode microstructure and can be combined
with models.[54] Numerical models can help to better understand
They declared that electrode corrugation is the most impact- the complex factors that contribute to the electrode microstruc-
ful electrode defect, mainly impacting the stacking and packag- ture. This understanding is critical for optimizing the fabrication
ing process. Additionally, a tear of the electrode affects the laser process, and to predict resulting performance of LIBs. Available
cutting of the electrode to sheets, as well as the stacking and elec- software tools and modeling approaches are still somewhat lim-
trical contacting of the electrode sheets.17 ited, due to the non-linearity, and complexity of LIBs.[55] However,
Overall, calendering is a critical step during electrode manu- much research has been done in recent years to improve the rel-
facturing, and it can control the electrode film’s adhesion, thick- evance of modeling approaches, which can be used toward im-
ness, and porosity. It also controls the electrode tortuosity (𝜏), provement of LIB performances. In the following chapter, exam-
which is used to relate electrolyte conductivity and diffusivity due ples of modeling approaches will be given, demonstrating how
to the microstructure of the electrode.[43] It is the ratio between these methods can be key to forming connections between the
the lithium-ion diffusion path through the coating and the coat- fabrication steps and battery performance.
ing thickness. In other words, it can be defined as the ratio be-
tween the effective pore length, LP,eff, and the ideal pore length,
LP,ideal , using a cylinder as pore geometry (Equation (12)).[44] the 3.1. Microstructure
schematic representation is shown in Figure 4.
Modeling of electrode microstructures can be used to predict
LP,eff compaction behavior depending on the electrode compositions.
𝜏 = (12)
LP,ideal This was demonstrated by Meyer et al.,[37] who used a Heckel-
based model equation, supplemented by a predictive model, to
As the electrode undergoes plastic deformation during calen- predict the lowest achievable coating porosities after calendering
dering, the pores and the pore structure experience a change, as for different theoretical packing structures with varying particle
already discussed. Froboese et al.[44] introduced a method to de- size distributions and mechanical characteristics. Knowledge of
termine the pore size distribution of electrodes based on mer- the microstructure is also important for investigating tortuosity, a
cury intrusion. Thus, they can also calculate an electrode’s tor- critical parameter for understanding Li-ion diffusion properties.
tuosity based on porosity data. The authors investigated a Gr- Usseglio-Viretta et al.[45] compared three different approaches for
based anode at five different coating densities between 0.84 and determination of the tortuosity factor (namely microstructure ho-
1.58 g cm−3 . The authors show a rising tortuosity with rising mogenization supplemented by mathematically complemented
coating density for a compression rate up to 31%. The tortuos- carbon binder domains, macro-homogeneous model fitting, and
ity decreases again for the strongest calendered electrode, with a direct experimental measurements), and found that they were in
compression rate of 47%. Simultaneously, the error bars from a good agreement for Gr and NMC electrodes. Forouzan et al.[56]
double determination increase significantly, forcing the authors used shifted-force Lennard–Jones potential functions and gran-
to assume strong destruction like particle detachment or particle ular Hertzian force to simulate particle interactions and evalu-
cracks in the coating and, therefore, a non-homogenous electrode ate the particle arrangement resulting from processing param-
coating.[44] Francois et al.[45] investigated anode and cathode elec- eters. Lippke et al.[57] modeled the structure formation during

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Figure 5. a) Demonstrates a computational workflow, starting with the slurry (coarsed grain molecular dynamics, CGMD, simulation), to the dried elec-
trode (CGMD simulation), to the calendered electrode (discrete element method, DEM, simulation) and finally the assessment of the electrochemical
performance (with continuum finite element method, FEM, models). Reproduced with permission.[61] Copyright 2021, Elsevier. b) Demonstrates granu-
lar and colloidal dynamic simulations of the slurry, drying and calendering phase of electrodes, including cross-sections of the middle of electrodes. The
AM particles are shown in red, the carbon-binder domain (CBD) phase in blue and the pore phase with the white region. Reproduced with permission.[65]
Copyright 2020, American Chemical Society. c) Demonstrates the workflow for generating a 3D computational finite element mesh from a combination
of 3D image data and an analytical CBD “binder bridge” algorithm. Reproduced with permission.[66] Copyright 2020, The American Society of Mechanical
Engineers.

drying using the discrete element method (DEM) by using surro- advantage that can be compensated for by employing the SPH
gate models for relevant fluid effects and could predict the coat- model in a DEM-style environment. They used a similar model in
ing porosity for different mass loadings. As most electrode mi- another study[60] to investigate the effects of AM particle shape,
crostructural simulations focus on spherical particles, Becker et size, orientation, and stiffness on the resulting microstructure
al.[58] Modeled the influence of particle shape on the mechani- after calendering. Ngandjong et al.[61] also employed a DEM
cal compression and resulting transport properties of electrodes type model to investigate multiple processing steps, including
for non-spherical particles, using a novel random close packing slurry preparation, drying, calendering, and eventually, the elec-
algorithm. trochemical processes in the electrode, as demonstrated in Figure
As each process step can be highly dependent on one another, 5a. Lombardo et al.[62] used a physics-based 3D model to mimic
many microstructure investigations include simulations of mul- carbon-binder domain (CBD) migration during drying, and the
tiple process steps. For example, Nikpour et al.[59] proposed a impact of the drying process on the final microstructure after cal-
multi-phase smoothed particle model, derived from smoothed endering. In a study by A. Shodiev et al.[63] the calendering and
particle hydrodynamics (SPH), to simulate the drying and cal- electrolyte wetting steps were investigated with a 3D-resolved lat-
endering steps of electrode production. They found in previous tice Boltzmann method (LBM) to understand the influence of the
manufacturing models that DEM can have unstable interfaces electrolyte microstructure on the electrolyte wetting processes.
while trying to maintain liquid- and solid-type behavior, a dis- Another study by Lombardo et al.,[64] used 3D modeling to in-

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Figure 6. Schematic overview of both modeling approaches for the inactive material: a) Bond approach and b) carbon-binder domain (CBD) particle
approach. Active material and current collector in gray, inactive material in its respective form in black.

vestigate the dispersion, drying, and calendering steps on the investigation of mechanical properties goes hand-in-hand with
electrode microstructure, and their influence on electrochemi- microstructural investigations or other electrode properties (e.g.,
cal performance. In an investigation of the structure of the CBD tortuosity, porosity, etc.). One of the most important applications
and AM in the electrode, Srivastava et al.[65] used the open-source for understanding the mechanical properties of the coating is to
molecular dynamics software LAMMPS to simulate the colloidal understand the mechanical stress induced in the coating in re-
and granular dynamics, and investigate a strategy to engineer the sponse to the calendering process itself.
electrode mesostructures through control of the CBD cohesion Different approaches exist for the mechanical simulations dur-
and the adhesion strength between the AM and CBD phases. ing the calendering process, which mainly differ in the represen-
Their approach is demonstrated in Figure 5b. This strategy was tation of the CBD (Figure 6): In some instances, the CBD was
shown to have the potential to control transport properties in the simulated by Sangros et al.[24,68,69] and Ge et al.[70] using solid-
electrode (including electronic and ionic conductivity and active state bridges (bonds), while, for example, Ngandjong et al.[61,62]
material surface area availability). used CBD adhesive surrogate particles. Both approaches were
Tomographic imaging can be an essential technique for in- demonstrated to be capable of depicting the mechanical behav-
vestigating electrode microstructures. Westhoff et al.[52] used 3D ior of the electrode correctly. The solid-state bridge approach of
reconstructions from tomographic imaging of the microstruc- Sangros et al.[68] was also used for the modeling of heat conduc-
ture of electrodes with different calendering densities to inves- tion in electrodes in the context of calendering by Lippke et al.[71]
tigate multi-layer cathodes and correlate the microstructure with Sangrós Giménez et al.[24] proposed a DEM approach to de-
the electronic resistivity. As the microstructure of the CBD can scribe the mechanical properties of NMC cathodes with the
be difficult to resolve separate from the CAM, due to the differ- elasto-plastic Thornton–Ning contact model, to model mechan-
ences in attenuation of these materials, Lu et al.[53] employed a ical behavior of the NMC particles, and a dissipating bond model
dual-scan superimposition X-ray CT technique to produce 3D re- for the CBD, capturing the viscoelastic response of the electrodes
constructions of both the NMC and the CBD to give a detailed during calendering and quantifying the elastic recovery. The re-
overview of the microstructural inhomogeneities before and after sulting porosity evolution for the calendered electrodes from
calendering, including the slurry phase. In a study by Trembacki their study is demonstrated in Figure 7. A study by Zhang et al.[72]
et al.,[66] 3D reconstructions with X-ray CT, combined with a developed DEM simulations based on the Edinburgh elasto-
binder bridge algorithm (to estimate the mesostructured of the plastic adhesion (EEPA) contact model to analyze electrode mi-
CBD), were used with finite element effective property simu- crostructure responses to calendering. In addition, combinations
lations to analyze heterogeneity and trends (such as tortuosity of both approaches exist, as shown by both Schreiner et al.[73] and
and effective conductivity) across the electrodes, to determine Ge et al.,[70] who demonstrated that a combination of the EEPA
the influence of calendering on the performance. Alternative ex- and bonding contact models facilitated an effective description of
perimental techniques can be combined with modeling to un- electrode behavior. In multiple studies, Schreiner et al.[73,74] also
derstand the microstructure, as shown by Malifarge et al.,[67] used DEM to investigate the influence of calendering on the elec-
who used X-ray diffraction to evaluate the proportion of oriented trode parameters, such as compaction resistance, elastic spring
anisotropic particles in the electrode. back, and initial particle cohesion. DEM simulations were also
used in another study by Sangrós Giménez et al.[69] to gain infor-
mation about the mechanical integrity of calendered electrodes
3.2. Mechanical Properties and the development of mechanical stress within the structure
due to lithiation, as well as estimate the adhesion strength of
Understanding the mechanical properties of electrodes can help the electrode. Ge et al.[70] carried out similar works to Sangros
to predict the influence of calendering on the electrode. Often and compared the tortuosity of the virtual electrode with X-ray

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properties relations for the ionic and electric conductivity and

applied them in the P2D framework of the Doyle–Newman elec-
trode model, allowing them higher accuracy in predicting opti-
mal porosities than with the classical P2D model.
The influence of calendering on the electrochemical perfor-
mance was also investigated by Lenze et al.[79] using a P2D
physico-chemical battery model, based on the work by Legrand et
al.[80] In a coupled multi-level model approach, Schmidt et al.[81]
and Thomitzek et al.[82] combined a P2D model for simulating
the battery cell, with a process chain model in order to analyze
process–structure–property relationships and analyze the influ-
ence of tolerances in the manufacturing process on the process-
ing parameters. They demonstrated that uncertainties in the cal-
endering performance produce broad porosity distributions and
that mass loading and thickness deviations have the highest im-
pact on cell performance. Ngandjong et al.[61] were able to couple
Figure 7. a) Demonstrates porosity evolution for electrodes subjected to
their calendering simulation with preceding drying simulation
calendering processes. Reproduced with permission.[24] Copyright 2019,
Elsevier. and with electrochemical simulations were able to depict the in-
fluence of the calendering degree on the electrochemical perfor-
mance.
tomography data. Stershic et al.[75] investigated the particle con-
Nelson et al.[47] used geometric characteristics of NMC parti-
tact distribution within NMC electrodes using fabric tensors and
cles subjected to calendering or ball milling, extracted from X-
compared DEM data with X-ray tomography,[75] although their
ray nanotomography measurements, applied as computational
modeling approach had shortcomings, likely due to the inade-
domains in multi-physics transport models to investigate the Li
quate consideration of the CBD.
concentration gradients within an NMC particle during the in-
These studies demonstrate that the complexity of a real-world
tercalation process. They found that the calendering step sig-
electrode requires combinations of multiple approaches (both in
nificantly decreased the time needed for the intercalation pro-
modeling and with experimental techniques, such as X-ray to-
cess, and ball milling further reduced it. Modeling can also
mography) in order to accurately describe the mechanical behav-
be used to investigate macroscale Li distribution, as demon-
ior of the electrode microstructure.
strated by Kespe and Nirschl et al.[48] who mapped the spatial
Li distribution within solid microstructures for different par-
3.3. Electrochemical Properties ticle arrangements, demonstrating that Li accumulated in re-
gions with higher specific surface areas. The Li distribution
The link between microstructure and electrochemical perfor- within electrodes subjected to calendering at different charge
mance is well-known, as properties such as porosity or tortuosity states was investigated by Ngandjong[61] using DEM models, cou-
can have direct implications on charge transfer processes. This pled to a course-grained MD model and a 4D-resolved finite el-
link is still perhaps not fully understood, and modeling processes ement method (FEM) model to predict the electrochemical per-
offer a way to gain deeper insight into the connection between formance. Also, Chouchane et al.[83] investigated the influence of
electrode microstructure, properties and electrochemical perfor- the spatial distribution of CBD within NMC electrodes using 3D
mance, especially in the case of electrodes subjected to the calen- modeling approach. They found that having the inactive material
dering process, which alter the microstructure. phase spread on the active material as film results in poorer per-
Simple electrode parameters, such as porosity, have been use- formance than agglomerate-like morphology due to a loss in ac-
ful for predicting the electrochemical performance of electrodes. tive surface area. Shodiev et al.[84] showed the significant effect of
The porous electrode theory (PET) model, developed by Newman heterogeneities in porosity in electrodes on the ionic impedance
et al.[76] has been shown by Smekenset et al.[55] to reliably predict and tortuosity factors and consequently, the overall capacity. It
material and battery manufacturing parameters and for interpret- became apparent that the optimal electrode structure requires a
ing the performances of LIBs, based on given manufacturing pa- decreasing porosity from the separator side to the current collec-
rameters. tor side. In the study by Lu et al.[53] they simulated the discharge
Investigation of capacity fading can also be supplemented with of the reconstructed cathode (from X-ray CT) at various C-rates.
modeling approaches. Purewal et al.[77] used a coupled chemical- This simulation is demonstrated in Figure 8.
mechanical degradation model to address calender loss and vari- The surface free energy of electrodes will influence the wet-
able discharge rate and describe capacity fade over different oper- tability, which can strongly influence the transport properties
ating conditions. The impact of calendering on LIB performance and resulting performance. The Owens–Wendt–Rabel–Kaelble
was also investigated by Lenze et al.[51] using pseudo-2D (P2D) (OWRK) model was adopted by Davoodabadi et al.[85] to calculate
model simulations. They demonstrated a correlation between ca- the surface free energy (SFE) of electrodes subjected to calender-
pacity losses during cycling and the electrode morphology with ing, and processed using solvent- or water-based methods. They
calendering parameters. For investigations of electron and ion demonstrated that the SFE decreases with increasing degree of
transport in electrodes with different compression ratios, Laue calendering, corresponding to lower electrolyte wettability. The
et al.[78] used a 3D micro-structural model to derive electrode wettability was also investigated by Davoodabadi et al.[86,87] to in-

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Figure 8. Calendering effect on electrode microstructure and electrochemical performance obtained by X-ray nano-computed tomography and modeling.
a) Experimental setup; b) photograph of the alignment; c) X-ray radiograph before the compression; d−f) images of the electrode microstructural
evolution with different calendering stages; g−i) graphical representation of the mass flux within the calendered pores structures; j) the pore size
distribution associated with the calendering steps; k) establishing the microstructural parameters according to the calendering steps determined by
the 3D reconstructions; l) A comparison of electrochemical performance between electrodes with three different mass loadings and whether they are
calendered or uncalendered. Reproduced with permission.[53] Copyright 2020, Springer Nature.

vestigate the effect of the manufacturing parameters on wettabil- without having to undergo costly processing steps. Modeling ap-
ity, by using calendered and uncalendered electrodes with several proaches would also be invaluable for comprehending the influ-
electrolytes, among other approaches. They assess the wettabil- ence of calendering on the electrode microstructure and how it
ity using a solid permeability coefficient (SPC) for porosities be- influences charge transport properties, especially at the critical
tween 30% and 55%, showing that the SPC value decreases for electrode/electrolyte interface at the nanoscale. There is an inti-
decreasing coating porosities. Thus, the wettability deteriorates mate interplay between processing, electrode structure and per-
with a more substantial calendering degree as the pores size of formance, and the resulting mechanical properties, charge trans-
the electrode shrinks, additionally to the overall decreasing free port properties and electrochemical performance are thus closely
volume to take up the liquid electrolyte. related. Using modeling approaches can bring a deeper under-
The studies discussed in this chapter have shown that model- standing of the relationship between these properties.
ing can be invaluable in planning of calendering processes and
predicting the results of cell performance. Application of model- 4. Performance of Calendered LIB Electrodes
ing to process steps, especially calendering, can serve not only to
better understand the results, but also to predict mechanical and Calendering improves electrode adhesion and density, and in-
electrochemical properties of electrodes subjected to calendering, creases the electrical conductivity between particles. Neverthe-

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less, higher electrode density results in lower porosity, thus, process. They employed micron-sized carbon fibers to stabilize
obstructing electrolyte diffusion. Therefore, the electrode den- the thick electrode structure and to improve the electrode kinet-
sity and porosity should be optimized before using the cells.[88] ics. The cell assembled with cathode and anode electrodes pos-
For instance, calendering could reduce the electrode porosity sessing porosities of 38% and 48%, respectively, showed a high
from 60% to about 20% and 25% for Gr and NMC electrodes, energy density of 441 Wh L−1 at a rate of 0.1C, and better cy-
respectively.[36] Change in porosity and density of electrodes seri- cling stability with different C-rates. El Baradai et al.[94] increased
ously affect the cell’s electrochemical performance. In the follow- the reversible capacity from 85 to 315 mAh g−1 and electronic
ing sections, the effect of calendering on the mechanical and elec- conductivity from 70 to 600 S m−1 , and reduced porosity from
trochemical performance of anode and cathode electrodes will be 70% to 34% by calendering high porous bio-sourced printed elec-
discussed. trodes. However, the specific capacity for the calendered elec-
trode is significantly lower than the pristine electrode. Baunach
et al.[95] studied the influence of drying temperature on the in-
4.1. Performance of Calendered Anodes ternal electrode structure and demonstrated that adhesion force
is strongly dependent on drying temperature: drying at higher
The AAMs play a critical role in LIBs, as these materials’ phys- temperatures decreases adhesion force. Subsequent calendering
ical and chemical properties directly affect the electrochemical improved adhesion, but ultimately did not eliminate the drying
performance of batteries. In addition to material choice, anode influence. Liu et al.[96] developed a method for manufacturing Gr
microstructure and, thus, density and porosity are essential to anode electrodes with a solvent-free technique to enhance adhe-
achieve a battery with high energy density and cycle life stability. sion strength through dry-spraying of PVDF, as an adhesion en-
The following sections will address the influence of calendering hancer layer on the copper current collector, before Gr coating.
on the mechanical and electrochemical properties of the most The mechanical strength of electrodes and electrochemical per-
frequently used anode materials (e.g., Gr, Si, Si/carbon compos- formance (rate and cycling) are expressively enhanced using this
ites). fabrication method. In high energy density LIBs, lithium plating
on the Gr anode surface under fast-charging conditions results in
permanent loss of lithium from the cathode, instability of cathode
4.1.1. Graphite structure, and thus capacity fading, which is the critical challenge
that restricts fast-charging of LIBs.
Graphite (Gr) from synthetic or natural sources possesses a high Kazyak et al.[97] made a conducting solid electrolyte (Li3 BO3 -
degree of graphitization has been used as an AAM in commercial Li2 CO3 ) as an artificial solid electrolyte interphase (SEI) on cal-
LIBs,[89] owing to its favorable features such as low cost and rel- endered Gr electrodes (porosity of about 32%) using an atomic
atively natural abundance, high electrical conductivity (1 × 105 layer deposition technique. After the calendering step, the de-
(parallel to basal plane), 3 × 102 (orthogonal to basal plane)), position was conducted with a substrate temperature of 200 °C
exceptional cycle life, and theoretical capacity of 372 mAh g−1 . (Figure 9a). This protective layer enabled an excellent cycle life
Besides many parameters such as the electrolyte conducting with 4C charging (15 min) without lithium plating, and for the
salt, type of Gr, binder, and conductive carbons, and their per- calendered electrode a capacity retention of 80% after 500 cycles
centages, electrode microstructure also plays a key role in high- in full-cell pouch cells, with an areal capacity of 3 mAh cm−2 ,
performance batteries. Electrode microstructure depends on the was achieved. Furthermore, CE was improved, and with a re-
drying and calendering processes, leading to a preferred orien- duction in cell polarization, the energy efficiency of the charg-
tation and internal pore structure.[90,91] Additionally, the CB and ing process was enhanced. Klein et al.[98] investigated a similar
Gr network becomes denser after calendering, leading to higher full-cell study with electrolyte optimization. They demonstrated
electronic conductivity, owing to better contact points between that adding electrolyte additives strongly depends on the bench-
the conductive additives and active material as they form a denser mark system’s quality. In other words, the type of compression
network after compression.[92] As one of the first reported calen- technique (calendered or hand-pressed Gr electrodes) before cell
dering studies, Haselrieder et al.[21] investigated different com- assembly could affect the benchmark system’s electrochemical
pression rates of 5–26% on the Gr electrodes. The electrodes with performance. Although both compression techniques exhibited
a compression rate of 10% delivered a good cycling life perfor- similar electrode porosity (about 40%, and about 53% for an un-
mance (200 cycles at 1C), even better than the uncalendered elec- pressed electrode) and similar visible surface appearance, the cal-
trode. The calendering of Gr electrodes at pressures of 0.1–0.3 endered electrodes performed better in the LIB full-cell. Dang et
tons cm−2 increases the reversible capacity and meaningfully en- al.[99] fabricated a low-tortuous Gr electrode, with high electrolyte
hances cyclability. The improved cyclability was attributed to bet- infiltration, by a freeze-drying method. The calendering does not
ter adhesion to the current collector.[26] However, at higher com- affect the electrochemical behavior of the freeze-dried electrode
pression rate (pressures about 4–8 tons cm−2 ), calendering of Gr except slightly decreased the CE of the first cycles from about 92%
electrodes has negative effects on the reversible capacity, and the to 90.5%. However, this method for drying electrodes at the in-
first cycle Coulombic efficiency (CE), owing to the low ion dif- dustry level is not economical.
fusion within the liquid paths and also particle break-up at the Electrode production was investigated by Billot et al.,[100] with
highest compression rate.[31,93] a focus on the binder amount, the electrode thickness, and cal-
Singh et al.[12] manufactured thick (250–350 μm) single-sided endering process, which are influential factors on the adhesion
Gr anodes and lithium–nickel manganese-cobalt-oxide (NMC) strength, a crucial parameter for the life span and the produc-
cathodes with different porosities obtained from the calendering tion of LIBs. They demonstrated that in the calendering process,

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Figure 9. a) Schematic processes of the electrode fabrication, including coating a single-ion conducting solid electrolyte (Li3 BO3 -Li2 CO3 ) via calendering
and atomic layer deposition for Gr electrodes. Also, discharge capacity cycling of NMC532/Gr pouch cells with and without Li3 BO3 -Li2 CO3 coating at 4C
fast-charge cycles. Reproduced with permission.[97] Copyright 2022, John Wiley & Sons. b) Schematic representation of the thickness changes and the
shear forces generated depending on the roll diameter. The larger roll diameters lead to higher adhesion. Reproduced with permission.[100] Copyright
2020, John Wiley & Sons. c) Cycling performance of fabricated Si-based electrodes before or after calendering (1 ton cm−2 ) at 480 mA g−1 , with a Si mass
loading of about 3 mg cm−2 . d) Schematic illustration of the breaking-restoring of the particle/binder bonds after the calendering-maturation processes.
e) The effects of the electrode porosity on the first coulombic efficiency of Si-based anodes. Reproduced with permission.[112] Copyright 2017, Elsevier.

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with a decrease in the shear stresses by increasing the roll diame- can have difficulties to withstand calendering processes,[109] but
ter from 200 and 400 mm, the adhesive strength is affected posi- this is not the case for nano Si. The Obrovac group[110] prepared
tively, and significantly increased it by 19%. The shear stress is de- a bulk quantity of layered amorphous Si powder by a chemical
creased by increasing the roll diameter, because of the layer thick- delithiation technique. Layered Si powders obtained from this
ness reduction in the longitudinal direction (Figure 9b). Overall, method have large amounts of open volume between the Si lay-
larger roll diameters lead to higher adhesion strengths.[35] Jang et ers that can accommodate volume changes during (de)lithiation.
al.[101] used heat treatment on the fabricated Gr electrode, made Compared to the bulk crystalline Si, the cycled layered amor-
with a pore-formation agent, polytetrafluoroethylene (PTFE). Af- phous Si electrodes exhibited a lower volume expansion during
ter the heat treatment, the PTFE particles were depolymerized to lithiation and enhanced cycling stability. The layered amorphous
form micro-sized pores. The porosity of the electrodes was fixed Si structure may become damaged during the calendering pro-
to 30%, from about 50%, by calendering. The electrodes showed cess. However, the calendered electrodes showed similar cycling
improved wetting ability, ionic diffusion rate, tortuosity, and elec- stability but higher volumetric energy density than the uncalen-
trode surface area, and ionic resistance and ionic polarization in dered electrodes. Yuca and Çolak[111] studied the neutralization of
the electrode were decreased. The fabricated electrode displayed polyacrylic acid (PAA) by NaOH, as a binder, and subsequent cal-
a specific capacity of about 200 mAh g−1 , whereas a typical elec- endering process during Si electrode fabrication. The electrode
trode only showed 140 mAh g−1 at a high current density of 3C. loading was 1 mg cm2 . The first cycle CE increased from about
The drawback of this work, compared to a standard Gr electrode, 70 to 75% after neutralization and calendering, and also the cy-
could be low electrode density and poor cycling life, because of cling life stability after 100 cycles was enhanced for calendered
the use of 40 wt% PTFE in the electrode, which is not pointed out electrodes from 862 to 1370 mAh g−1 . Karkar et al.[112] manufac-
in the paper. tured Si (46 wt%) electrodes with an extra maturation step[113]
Recently, our group[102] developed a novel electrode production in an atmosphere with high humidity of about 80% R.H for 2–
process (twin-screw extrude with the integration of manufactur- 3 days after calendering and before post-drying and cell assem-
ing steps of coating, drying, and calendering into one continu- bly. This maturation makes an important change in the electrode
ous line), which is based on Gr anodes with a solid mass content structure and improves the interface connection of active materi-
of more than 50 wt%. This advanced electrode processing was als/conductive carbons/binder together with the current collector
enabled by selecting new binder materials, machinery design, (Figure 9c–e), therefore, enhancing its mechanical strength with
and process parameters. Due to the binder being exposed to high better electrochemical behavior.[113] Applying the maturation step
mechanical/shear stresses within the twin-screw extruder (with after calendering has a major advantage that restores the particle-
a short-time for mixing) and calender gap, the binder type is a binder cohesive bridges and makes a robust calendered electrode
crucial parameter for a high-performance electrode. By applying even with high active mass loading (3 mgSi cm−2 ) and low poros-
this low solvent process design, the Gr electrodes with a density ity (30%). The electrode exhibited a capacity of about 1800 mAh
of about 1.3 g cm−3 were achieved, which is higher than the ref- g−1 (5.4 mAh cm−2 ) after 50 cycles, with an improved CE. With
erence electrode made with the wet-coating method after drying decreasing porosity, the capacity retention and initial CE were in-
(1.0 g cm−3 ); thus, a following calendering step after drying may creased. The CE increased from 75% to about 90% for the elec-
not require for the twin-screw extrude with corrected calendering trodes with porosities of 75% and 30%, respectively (Figure 8e).
of wet electrode process. An improved electrochemical result for matured calendered
Si/carbon electrodes were also obtained by Vanpeene et al.[114]
Wang et al.[115] prepared a Si structure with high stability at a
4.1.2. Silicon pressure of over 100 MPa (the mechanical stress during calen-
dering could be up to 80 MPa)[35,93] by depositing a dense Si shell
Si anodes, with ten times the theoretical capacity of graphite (using a Si layer of about 200 nm) onto each Si particle cluster.
anodes, have attracted considerable research attention for next- The fabricated particles meaningfully advance mechanical stabil-
generation LIBs comparing the specific capacity of 4212 mAh ity, and the structure of these particles remained undamaged af-
g−1 for Li4.4 Si to Gr anode with only 372 mAh g−1 .[103] Besides, ter the calendering process (Figure 10a1 –a4 ). The calendered elec-
Si is the second-most abundant element in the earth’s crust, and trodes demonstrated a high initial CE of about 90% and a high
it is environmentally benign and has low electrochemical poten- volumetric capacity of more than 2000 mAh cm−3 . The excellent
tial. However, Si has a huge volume change during (de)lithiation, electrochemical performance can be attributed to the porous in-
a common drawback in Si-alloy anodes, leading to severe parti- ner structure providing void space to accommodate the volume
cle pulverization and the formation of unstable solid-electrolyte expansion during the cycling with an excellent calendering capa-
interphase, leading to increasing internal resistance and rapid bility of the Si particles
capacity decay.[104–106] Many nano-engineering approaches effec- The significant volume change of Si anodes could be relatively
tively solve several problems related to the volume expansion of accommodated by common and costly methods to fabricate
Si anodes.[107,108] However, the practical application of these fancy Si nanostructures and Si/carbon composites with void spaces
anodes is challenging due to limitations such as low mass load- in the particle structure. Thus, a low tap density and large
ing and calendering incompatibility, which can result even in a surface area result in lower energy density and CE upon cycling,
lower volumetric energy density than state-of-the-art Gr anodes. because of increased SEI formation reactions. To solve this
Specifically, during calendering, the structure of the anode can issue, Lee et al.[116] developed a milling method for producing
easily collapse under high pressure, damaging the porous fea- micron-sized Si secondary particles with a high tap density
tures. Certainly, Si is usually a hard and brittle material, and thus (0.81 g cm−3 ) and a low surface area. The fabricated electrodes

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Figure 10. Pressure-resistant property test and SEM images (Scale bar is 2 μm) taken after calendering on a1 ) uncoated, a2 ) 100 nm Si coating, and
a3 ) 200 nm Si coating on the Si nanoparticles cluster. a3 ) The fraction of unbroken spheres after different calendering pressures. Reproduced with
permission.[115] Copyright 2018, American Chemical Society. b1 ,b2 ) Cycling performance and CE of the SiO/ poly(9,9-dioctylfluorene-co-fluorenone-
co-methyl benzoic ester electrode after calendering with different porosities at 100 mA g−1 . Electrode: 90% SiO and 10% poly(9,9-dioctylfluorene-
co-fluorenone-co-methyl benzoic ester) binder. Electrolyte:1.2 m LiPF6 in ethylene carbonate/diethyl carbonate (3/7 w/w) with 30 wt% fluoroethylene
carbonate (FEC). Reproduced with permission.[118] Copyright 2015, American Chemical Society. c1 –c3 ) Top surface and cross-sectional SEM images
of Si-iron-manganese alloy electrode and electrode/electrolyte wettability results after different pressing pressures. Reproduced with permission.[119]
Copyright 2017, Springer Nature.

showed a density of 1.4 g cm3 after calendering, and exhibited Zhao et al.[118] optimized the porosity and density of SiO (with
a volumetric capacity of 598 mAh cm−3 and excellent cycling about 10% carbon coating)/ polymer composite electrodes using
stability, maintaining more than 95% of the initial capacity after a calendering process. The electrodes were calendered from a
500 cycles, with a high CE of 99.7%. Wang et al.[117] investigated porosity of 63% to 43%. The calendered electrode with a density
Young’s modulus (E) and hardness (H) of Si/PVDF composite 1.19 g cm3 (porosity of 47%) enhanced cycling performance and
electrodes at various state of charges (SOCs) and cycle numbers energy density compared to the uncalendered and the other cal-
using nano-indentation for the both (un)calendered electrodes. endered electrodes. The calendered electrodes achieved an areal
The calendered electrodes have lower porosity (about 50%), capacity of ≈3.5 mAh cm2 at a 0.1C rate, which was an improve-
thus for every SOC they have larger E and H values than the ment of about 1 mAh cm2 compared to the uncalendered elec-
uncalendered electrodes (about 70%). Their data displayed that trode. CE, a critical value for long-term cycling, was improved
mechanical integrity is vital to advancing the electrochemical from 99.33% to 99.76% for the electrode with 47% porosity; re-
performance of calendered electrodes. sults are shown in Figure 10b1 ,b2 .

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Alaboina et al.[119] fabricated a calendered anode electrode, Si– an areal capacity of about 2.5 mAh cm−2 and a specific capacity of
Iron–Manganese (Si–Fe–Mn, 80–18–2 wt%) alloy + Gr compos- about 680 mAh g−1 , which was around 85% of the value for un-
ite. The calendered electrodes were discussed in terms of poros- calendered electrodes. However, the cycling stability was similar
ity, electrolyte wettability, and long-term cycling (Figure 10c1 –c3 ). to the uncalendered electrodes, with 90% capacity retention after
Both specific capacity and CE are reduced by increasing of the 200 cycles.
calendering stress, due to reduction in the core active pores of Fei et al.[130] developed a method to coating reduced graphene
the electrodes. Cao et al.[120] used the mechanofusion process oxide (RGO)/ SiO micro-particles of 3–10 μm on the current col-
to synthesize Si-alloy/Gr anode composite materials. The cal- lector without using any binder or conductive carbon. The un-
endered electrodes resulted in an energy density improvement calendered SiO/RGO electrode layers were loosely packed. How-
of about 10% with specific capacity of about 950 mAh g−1 at ever, the electrode layers became much denser after calendering,
1C during 50 cycles. Du et al.[109] demonstrated that the energy and the electrode thickness was reduced to half of the uncalen-
density and cycling performance of Si-alloy electrodes could be dered electrode. The calendered electrodes showed a specific ca-
enhanced if the alloy is combined with Gr and calendered to pacity of about 1000 mAh g−1 over 100 cycles, with a first CE at
a porosity of about 20%. The calendered electrodes prepared about 70%. Li et al.[131] manufactured the spherical granules of
with mixed Si/Gr using PVDF as a binder demonstrated a bet- SiOx /Gr/carbon composites using a spray drying process. The
ter cycle life, due to the stronger mass loading film.[121] How- obtained granule particles possessed enhanced electrical conduc-
ever, calendering of Si-based anode electrodes prepared with non- tivity (518 S m−1 ) and maintained structural integrity during cal-
PVDF binders (carboxymethyl cellulose / styrene-butadiene rub- endering and following (de)lithiation processes. The calendered
ber (CMC/SBR), alginate, polyimide) considerably reduces their electrode anodes with a density of about 1.4 g cm−3 showed a bet-
cycling stability, mainly because of the low porosity in the elec- ter initial CE (83%) and a low volume expansion of about 14%,
trode after calendering.[122–124] good cycling stability, and outstanding rate capability (about 90%
of the original charge capacity remained at 5C). Nevertheless, the
capacity retention of calendered anodes without a pitch coating is
4.1.3. Si/Carbon Composites much lower than that of the uncalendered electrode anode with a
pitch coating. Hence, the carbon derived from the pitch is critical
In order to solve the above mentioned challenges of Si anodes in the Si/Gr composite anodes of LIBs.[132–134]
for practical applications, many efforts have been carried out Fabrication of porous structures is a well-known approach to
to achieve first high CE, a stable SEI, long-term cycle life and, overcoming the pulverization of Si-based anodes. Nevertheless,
of course, high volumetric energy density. For instance, fabri- low mass loading and the poor mechanical strength (calender-
cating Si/carbon composites with different techniques to ob- ing incompatibility) of these porous particles are challenging for
tain a variety of morphologies and structures, with unique ma- high volumetric energy density batteries. Additionally, the uncal-
terial and electrochemical performance, have been frequently endered porous electrodes need more electrolytes, hence lower-
reported.[3,125,126] Electrode calendering, which can improve the ing the cell energy density. However, some studies[104–107] devel-
volumetric energy density of batteries, is a vital process for oped unique approaches to fabricate high-performance calender-
preparing high-quality electrodes for practical applications. Re- compatible porous Si structures as anodes of LIBs. Son et al.[135]
garding calendering studies, Kierzek et al.[127] synthesized a prepared a macro-porous design for a carbon coated Si/Gr com-
Si/carbon composite that consisted of Si and Gr micro-particles posite anode (Figure 11), consisting of an ultrathin Si layer. This
embedded in a pitch coke matrix via a heat treatment at 1100 °C. robust macroporous matrix can resist high pressure and preserve
Besides the calendering study, the effects of PVDF and CMC as its porous architecture during electrode calendering. The calen-
binders for the preparation of the electrodes were investigated. dered composite electrodes, with a density of 1.6 g cm−3 and the
Calendering the electrode mass up to 30% of the initial film active material content of more than 95 wt%, displayed an areal
thickness was possible without electrode damage (for electrodes capacity of over 3.6 mAh cm−2 (and reversible capacity of 665
with a gravimetric capacity of about 500 mAh g−1 ). However, mAh g−1 ) with an excellent first CE of about 91%, and a lower
a volumetric capacity of 670 mAh cm−3 was calculated for the electrode swelling of 40%. Additionally, the calendered electrodes
calendered electrode, which is higher than the commercial Gr- showed stable cycle life and retained a high energy density of
based anodes (about 450 mAh cm−3 ).[128] Calendering was per- about 930 Wh L−1 over 100 cycles, with mitigated electrode ex-
formed to 100% (uncalendered), 60%, 40%, and 30% of the ini- pansion (Figure 10b). Recently, Müller et al.[136] investigated the
tial film thickness, which shows no effect on the cycling per- effect of carbon coating and calendering on Si/Gr composite par-
formance of anodes containing 12% Si in the composite. All ticles produced in pilot scales of about 1 kg, which were manufac-
anodes showed similar and very high CE. Therefore, calender- tured via scalable fluidized bed granulation.[132] The carbon coat-
ing improved the packing density to 1.35 g cm−3 without re- ing improved the stability of composite particles and their electri-
ducing the specific capacity, but increased the volumetric energy cal conductivity. The carbon-coated and uncoated electrodes were
density. calendered to densities of approximately 1.0–1.45 g cm−3 (the
Li et al.[129] synthesized a porous Si/carbon composite, us- density for uncalendered electrodes was about 0.8 g cm−3 ). The
ing an electrochemical etching technique, with pores of up to calendered carbon-coated Si/Gr composites, even for the high-
50 nm in diameter. They showed that after calendering some est density (1.45 g cm−3 ), showed a superior electrochemical per-
large porous Si/carbon particles were broken, but the structural formance. However, Si nanoparticles were detached during cal-
integrity of particles remained unchanged. The calendered elec- endering for the non-carbon coated composites, resulting in a
trode exhibited a good electrochemical cycling performance with quicker degradation at higher electrode densities. Therefore, af-

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Figure 11. a) Effect of carbon coating on the calendering capability of the porous structure of Si-coated macroporous carbon/Gr composites. b) Volu-
metric energy densities of electrodes for full-cell cycling. Cross-sectional SEM images of the electrodes after calendering for c) Si coated macroporous
carbon/Gr composites (Si@MPC-G), inset before calendering, d) about 5 wt% carbon coated on Si@MPC-G (C/Si@MPC-G), insets before calendering.
All electrodes: active material/CB/CMC)/SBR: 95/1/2/2. The areal capacities are 3.6 mAh cm–2 . Electrolyte: 1.3 m LiPF6 in ethylene carbonate/diethyl
carbonate (3/7 v/v) with 10% fluoroethylene carbonate (FEC). Reproduced with permission.[135] Copyright 2020, John Wiley & Sons.

ter calendering, the positive impact of carbon coating on Si/Gr chanical resilience of carbon nanotube/Si/carbon particles was
composites was more noticeable. measured by in situ atomic force microscopy (AFM) and SEM.
Jia et al.[137] manufactured a high porosity calender-compatible Xu et al.[138] produced Si/graphene/carbon nanotube (CNT) com-
carbon-nanotube/Si/carbon microspheres. These porous parti- posites with a 3D, spherical porous structure using in situ growth
cles can tolerate pressure over 200 MPa, similar to pressures of spheres of graphene and CNTs around Si particles. The par-
for industrial electrode calendering. The electrodes with a load- ticles have high electrical conductivity and mechanical strength,
ing of 3 mAh cm−2 exhibited a specific capacity of 750 mAh which can be compatible with the high-pressure calendering pro-
g−1 , and about 92% capacity retention over 500 cycles. The both cess over 100 MPa. In contrast, the particles in the compressed
(un)calendered electrodes exhibited similar cycling stability. Over electrode preserved their spherical shape. The calendered elec-
120 cycles, the electrodes calendered to 1.2 and 1.4 g cm−3 trodes after five cycles showed a volume expansion of about 18%
demonstrated capacity retentions of 96 and 91%, with volumet- after lithiation, suggesting an ability to withstand the stress cre-
ric capacity densities of 844 and 980 mAh cm−3 , respectively. ated during cycling. The lithiated electrode with a calendered
The end-of-life swelling of the calendered electrodes was esti- density of 0.64 g cm−3 exhibited a volumetric capacity of about
mated from electrode thickness changes before and after cycling, 1000 mAh cm−3 . Additionally, these anodes demonstrated a re-
which were about 34% and 45% after 120 cycles for the elec- versible capacity of 900 mAh g−1 after 700 cycles (90% capacity
trodes calendered to 1.2 and 1.4 g cm−3 , respectively. The me- retention).

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Wu et al.[139] manufactured a Si/3D carbon composite anode (Si, germanium, and tin), and conversion- (transition metal ox-
material with good electronic and ionic conductivity using a pro- ides, such as Fe3 O4 , Co3 O4 , CuO, etc.) mechanism active mate-
ton exchange technique. This porous structure withstands the rials, that need more porosity, because of having significant vol-
high-pressure calendering process, while providing space for vol- ume expansions during dis(charging) processes. Hence, for ev-
ume change of the Si nanoparticles during the (de)lithiation pro- ery electrode, the optimum condition of calendering should be
cesses. This porous structure also provides many ion diffusion determined based on the selected active material.
channels and reduces lithium ion diffusion path, thus showing
higher lithium ion transfer numbers. The calendered electrodes
4.2. Performance of Calendered Cathodes
showed an excellent cycling performance of 1600 mAh g−1 , with
capacity retention of 75% at 2 A g−1 after 1000 cycles, and an ex-
Calendering of cathodes serves a somewhat different role from
traordinary rate capability of 1056 mAh g−1 at 10 A g−1 .
the calendering of anodes, as CAM are typically more limited
SiO2 -based anode materials could also be used in LIBs, ow-
in intrinsic conductivity, which must be thus compensated by
ing to their high theoretical capacity, better cycling stability than
strong interactions between the CAM and the conductive carbon
pure Si, abundance, and environmental friendliness. Neverthe-
network. From work in electrochemical impedance spectroscopy
less, low CE and irreversible capacity losses during cycling are
(EIS) and modeling it has been seen that a variety of parame-
the main challenges in using this anode material for commer-
ters, including the intrinsic properties of the CAM, the structure
cial cells. Buga et al.[140] investigated the effects of the amount of
of the oxide particles and the interface between the oxide parti-
carbon and also calendering process on the porous SiO2 /carbon
cle and the carbon network all have a significant influence on
composites. The optimized calendered electrode showed the best
the performance.[61,65,70,75,146–149] For this reason, it is important
cycling stability, with a specific capacity of 715 mAh g−1 , higher
to better understand the properties of different CAMs and how
CE, and the lowest charge transfer resistance during 200 cycles.
the calendering processes of cathodes based on these CAMs im-
Table 1 shows the comparison of some calendered anode elec-
pact the electrode morphology, material properties, and electro-
trodes reported.
chemical performance.

4.1.4. Lithium Titanium Oxide 4.2.1. Lithium Iron Phosphate

Spinel lithium titanium oxide (Li4 Ti5 O12 , LTO) is an anode ma- Lithium iron phosphate (LiFePO4 , LFP) is an attractive CAM
terial of LIBs with a specific capacity of 175 mAh g−1 . LTO is for commercial applications due to its low cost, low toxicity,
well-known for its low reactivity with common electrolytes, in- high stability, high safety and theoretical capacity (170 mAh g−1 ),
tense volume changes, and high voltage plateau of 1.55 V (vs and long-term cyclability.[150–155] However, despite its many ad-
Li/Li+ ).[141–143] The effect of calendering on the LTO anode has vantages, LFP still suffers from intrinsic limitations because of
been investigated. For example, Acharya et al.[144] investigated its poor electrical conductivity and sluggish Li+ transport.[150,151]
the influence of calendering on the charging rate of LTO elec- Common methods to overcome these challenges are fabricating
trode anodes. LTO was coated on an aluminum foil current nanoparticles,[156] using specialized conductive coatings,[151] use
collector, the electrodes were calendered with thickness reduc- of blended cathodes,[157,158] or implementing 3D foam current
tions from 10% to 42%. For the electrode with a 42% thickness collectors.[150,156] These methods can add costs or extra process
reduction, the thickness was changed from 175 μm (uncalen- steps, resulting in less cost-effective production. By calendering
dered electrode, 1.05 g cm−3 ) to 100 μm (1.76 g cm−3 ), and it the LFP electrodes during electrode production, the mechanical
demonstrated good capacity retention at 5C, although it exhib- contact between the CAM, the binder and the conductive addi-
ited faster capacity fade compared to the uncalendered and 10% tive improves, and thus the electrochemical performance is im-
calendered electrodes. Gockeln et al.[145] studied the influence of proved.
two electrode fabrication methods: lamination and doctor blade Work by Lu et al.[159] on LFP cathodes, with Gr and CB as the
techniques for LTO/carbon composites. They studied the effect conductive additives, and a PVDF binder, investigated the impact
of lamination pressures (varied from 1.5-3.3 MPa) on the mi- of calendering on the electrode properties and electrochemical
crostructure, and resulting electrochemical performance of the performance. In this study, the LFP cathodes before and after cal-
electrodes. The laminated electrodes demonstrated higher spe- endering had porosities ranging from 34% to 55% and demon-
cific capacities than both (un)calendered blade-caste electrodes, strated significantly different resistances of 40 and 1.5 Ω, respec-
however, the cycling stability was similar for laminated and cal- tively. Oladimeji et al.[28] showed a similar effect of calendering on
endered electrodes. LFP cathodes with PVDF and CB, where the charge transfer resis-
Overall, anode electrodes have volume expansion during lithi- tance measured by EIS was improved from 182.4 to 157.8 Ω after
ation process, therefore, for the most cases the anode electrodes calendering. Kannan et al.[155] demonstrated the improvement
should have more porosity than cathode electrodes, and calender- in electrochemical performance of LFP cathodes, based on LFP,
ing may take more optimization, the calendering degree strongly carbon (conductive carbon (3%) and super P (3%)), and PVDF,
depends on the type of anode active material, binders and elec- after calendering with multiple different separator types. Bom-
trode thickness and compositions. For instance, the electrodes mel et al.[30] showed that both the contact resistance and the elec-
with intercalation mechanism active materials (Gr and titanium trochemical performance could be improved by calendering LFP
oxides) can be calendered to higher densities, with relatively cathodes. Sousa et al.[152] demonstrated an improvement in dis-
lower porosities, compared to the electrodes made with alloy- charge capacity after calendering for rates up to 5C (from 27.4

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 Table 1. Literature comparison of composition, and electrochemical performance of anode electrodes before and after calendering (Cal.).

Anode Electrode composition [ wt%] Density [g cm3 ] Porosity [%] First cycle capacity before/after Cycling life before/after Cal. Ref.
before/after Cal. before/after Cal. Cal.

Adv. Energy Mater. 2023, 13, 2300973

Graphite (Gr) Gr: CA: PVDF: (88:4:8) 0.96/1.36 56/38 Similar 2.5 mAh cm2 at 0.05C similar, 2 mAh cm−2 after 300 cycles at [21]
1C
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Gr: CA: PVDF: (92:2:6) - NA/40 NA/340 mAh g−1 at 0.1C similar, 330 mAh g−1 after 15 cycles at [96]
1C
Gr: CA: CMC:SBR: - - Similar about 310 mAh g−1 at similar, 300 mAh g−1 after 120 cycles at [99]
(92.5:3.5:1.5:2.5) 0.1C 0.1C
Gr: CA: PAA: PTFE: (90:2:8:40) - 50/30 Similar about 300 mAh g−1 at NA/240 mAh g−1 after 120 cycles at 2C [101]
0.1C
Silicon Si nanoparticle: CA: PAA - - Similar about 1750 mAh g−1 at 862/1370 mAh g−1 after 100 cycles at [111]
(75:10:15) 0.1C 0.1C
Si:graphite:CB: polyimide: (43.3: - NA/20-25 Similar about 2240 mAh g−1 at similar, 1680 mAh g−1 after 50 cycles at [110]

2300973 (19 of 34)

24.2:19.3:13.2) 0.2C 0.2C
SiO SiO/C :Polymer: (90:10) 0.83/1.28 63/43 Similar about 3 mAh cm−2 at 2/3 mAh cm−1 after 120 cycles at 0.1C [118]
0.1C
Si;Fe–Mn alloy Si-alloy: Gr: CA: polyamide: - - similar, 600 mAh g−1 at 0.1C similar, 600 mAh g−1 after 100 cycles at [119]
(15:76:1:8) 0.1C
Si-alloy/graphite Si-alloy/ Gr: CA: lithium 0.98/1.25 NA/35 similar, 950 mAh g−1 at 0.1C similar, 950 mAh g−1 after 50 cycles at [120]
polyacrylate (LiPAA): 0.1C
(75:5:25)
Si/carbon /Gr Si/C: CA: CMC:SBR: (80:5:12:3) 0.5/1.3 - similar, 600 mAh g−1 at 0.2C similar, 600 mAh g−1 after 30 cycles at [127]
0.2C
Si/C/Gr: CA: CMC:SBR: NA/1.6 60/27 similar, about 660 mAh g−1 at NA/630 mAh g−1 after 50 cycles at 0.5C [135]
(94:1:2:2) 0.5C
Si/C/Gr: CA: CMC:SBR: 0.8/1.45 63/33 similar, about 600 mAh g−1 at similar, about 540 mAh g−1 after 120 [136]
(90:4.6:3.6:1.8) 0.5C cycles at 1 mA cm–2
Si:Gr: CMC: CA + KOH: 0.6/1.5 70/30 Similar about 3500 mAh g−1 at similar, 1400 mAh g−1 after 50 cycles at [112]
(73.2:11:7.3:8.5) 90 mA g−1 600 mA g−1
Si/carbon/CNT CNT/Si/C: CA: polyimide: 0.8/1.8 - NA/660 mAh g−1 at 0.5C NA/1300 mAh g−1 after 1500 cycles at [137]
(80:5:15) 1 mA cm–2
CNT/Si/C: CA: PVDF: (80:10:10) NA/0.64 - NA/1600 mAh g−1 at 0.2 A g−1 NA/1000 mAh g−1 after 700 cycles at 2 A [138]
g–1
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Figure 12. LFP cathodes: a,b) SEM images, c,d) cross-sectional SEM images, e,f) comparative rate capability and charge/discharge curves of
Li/SPNE/LFP cells measured at 70 °C. Reproduced with permission.[161] Copyright 2022, Springer Nature.

mAh g−1 to over 80 mAh g−1 ), for LFP cathodes prepared us- ode, compared to 47 mAh g−1 for the uncalendered). Calendering
ing screen-printing methods and an LFP-based ink. Besnard et was also applied to LFP-based ASSBs by Helmers et al.[162] and
al.[157] explored the impact of calendering on both pure LFP cath- they showed that direct calendering led to an increase in elec-
odes and blended NMC/LFP cathodes, and for both of them, it trical conductivity, but decrease in ionic conductivity, while cal-
was demonstrated that the conductivity experienced only a slight endering during the extruder process led to increase ionic con-
increase (0.3 to 0.6 S m−1 in the case of the LFP electrode mix- ductivities. Yang and Joo et al.[150] also demonstrated that highly
ture) after calendering while the contact resistance significantly structured cathodes (in this case, LFP on a NiCrAl-alloy foam)
decreased (from 36 to 0.8 Ω cm2 for LFP cathodes). There is, how- also benefit from calendering as the cathodes showed significant
ever, a trade off in electrode properties, as shown by the work of improvements in the kinetics after pressing. Besides ASSB ap-
Yu et al.[160] where the increase in cathode density after calen- plications, Napolskiy et al.[163] applied calendering to novel LFP
dering led to a decrease in capacity. However, in both cases the cathodes that use CNTs as the conductive additive and demon-
energy density must be considered, which is improved upon cal- strated that high compression rates resulted in low porosity and
endering. For example, in the case of Yu et al., the density was poor rate performance due to poorer electrolyte wettability. How-
increased from 1.55 to 2.2 g cm−3 , corresponding to an improve- ever, they also demonstrated that the C-rate performance could be
ment in volumetric energy density of about 42%, while the loss improved by increasing the roll temperature and found that high
in specific capacity (≈111 mAh g−1 to ≈ 87 mAh g−1 ) by going to C-rate performance and good cycling stability could be achieved
higher densities was only about 22%. with a compression rate of 10% and roll temperature of 100 °C.
Calendering can also play a role in improving performance
for novel LFP cathode types. Erabhoina et al.[161] demonstrated
for all-solid-state batteries (ASSBs) based on LFP cathodes, com- 4.2.2. Nickel–Manganese–Cobalt-Oxides
posed of LFP, CB, PEO. and LiTFSI, that the density and homo-
geneity of the cathode could be increased after calendering, as Nickel manganese cobalt oxides (NMC) are by far the most popu-
demonstrated in Figure 12, resulting in an increase in the dis- lar CAM for high energy and high power LIB applications. These
charge capacity delivered (82 mAh g−1 for the calendered cath- materials possess many advantages, including high energy den-

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Figure 13. a) Schematic interpretation of charge transport processes in NMC cathodes with different porosities after calendering, where blue spheres
= AM, black spheres = CB, flakes = Gr and gray wires = binder. Green lines demonstrate electric pathways. In the SEM cross-sections, the red color
illustrates the CBD. Reproduced with permission.[166] Copyright 2016, Elsevier. b) In situ electrode compression experiment using X-Ray nano-CT and
the microstructural evolution. E–G) Reconstructed virtual slices showing the microstructural change of the AM_L electrode under 7% (E), 15% (F), and
22.5% (G) compression, following a DSS procedure to include the deformation of CBD. Red arrows indicate the particle deformation. Structural self-
arrangement (from top to bottom) via particle rotation and deformation (H). Yellow arrows indicate the compression of CBD. Details of the cylinders to
characterize particle orientation are introduced later. I–K) Reconstructed virtual slices overlaid with color-map showing the change of the inter-particle gap
under 7% (I), 13.5% (J), and 24% (K) compression of the AM_S electrode. Comparison of the particle size distribution between AM_S and AM_L (L). The
standard deviation for AM_S and AM_L is 1.8 and 3.1 mm, respectively. The insets display the morphology of the color-coded particles, highlighting the
average size difference. Reproduced with permission.[169] Copyright 2020, Elsevier. c) The adhesion strength, 𝜎 Z , of cathodes with different compositions
at constant mass loading (280 g m−2 ) and roll temperature (25 °C). Reproduced with permission.[15] Copyright 2020, John Wiley & Sons. d) The capacity
retention of NMC cathodes with different densities after calendering at different C-rates. Reproduced with permission.[182] Copyright 2017, Elsevier.

sity, high power density, high specific capacity, high rate capabil- responding to a density increase from 2.25 to 2.95 g cm−3 , re-
ity, and good thermal stability.[19,164,165] In the cathode, NMC is in- sulted in a significant decrease in the electrode resistivity. Haar-
tegrated into a conductive carbon network, composed of binders mann et al.[168] also investigated the impact of calendering on
and conductive carbon, and in order to maximize the many ad- NMC622 cathodes (PVDF (2.25%) and CB (1.5%) and Gr (0.75%))
vantageous properties of NMC, the morphology of the electrode with varying solids content in the dispersion (65 vol%, 70 vol%,
must be optimized. 75 vol%, and 80 vol%). They found that the electrical resistance
One of the most essential steps in cathode production is to en- was highest for both the highest and lowest solid contents, and
sure that the CAM has good contact with the conductive carbon could be significantly reduced for all solids contents by calender-
network to enable efficient electron transfer. Bockholt et al.[166] ing.
demonstrated this with cross-sectional SEM images where the 51–High compaction can increase the ionic resistance, there-
contact between NMC and the carbon network was improved af- fore, it may negatively impact the electrochemical performance.
ter calendering (from a porosity of 45% to 35% and 25%) to es- A detailed X-ray nano-CT study by Lu et al.[169] explored the in-
tablish efficient electrical pathways. In another study, Bockholt et terplay between electrode thickness, porosity and density after
al.[167] also demonstrated that intensive dry-mixing of the NMC compression for NMC electrodes up to 24%. Their results are
cathode materials mixture could result in loss in electrical con- demonstrated in Figure 13b. They found that for electrodes com-
tact within the electrode coating, due to coating of most of the posed of larger particles, calendering can worsen pre-existing
conductive additive onto the CAM surface. These contacts could microstructural heterogeneities, leading to limited C-rate perfor-
be re-established by calendering, resulting in strong cycling sta- mance, while for electrodes composed of smaller particles, the
bility, with no capacity loss after 400 cycles at 1C, and improved deformation due to calendering was much more homogeneous,
C-rate performance up to 5C. This is schematically demonstrated the tortuosity lower, and thus these electrodes showed a higher
in Figure 13a, including SEM cross-sectional images, for NMC rated capacity. In general, in this study, the performance at high
cathodes produced with different densities after calendering. Im- C-rates was worse for the NMC cathodes after calendering. How-
proved C-rate performance was also observed by Parikh et al.[16] ever, the highest cathode porosity in this study was only 35.4%
after reduction of the porosity from 50% to 35%, an effect at- (uncalendered), which likely contributed to the limited rate capa-
tributed to shortened Li+ diffusion lengths. In a study by West- bility.
phal et al.,[23] calendering of NMC cathodes (composed of CB The mechanical challenges of NMC when compacted were
(5%) and PVDF (5%)) with line loads of up to 468 N mm−1 , cor- compensated for by Kim et al.[170] through combining a high-

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mechanical-strength single-crystalline NMC with a polycrys- load efforts due to the elastic deformation of PVDF, thus, lower
talline NMC. They found that particles with low mechanical PVDF contents lead to higher achievable porosity. However, ad-
strength found in the upper layer of the cathode can be fractured hesion strength increased with PVDF content and decreased with
during calendering. By creating a double-layer cathode with high porosity until ≈30%, whereby it increased again. This relation-
mechanical strength, single-crystalling NMC making up the up- ship is demonstrated in Figure 13c. Diener et al.[20] evaluated
per layer, this fracturing effect was completely prevented. A study the deformation behavior of NMC622 cathodes during calender-
by Klemens et al.[171] examined the influence of calendering on ing, whereby they directly measured the deformation using a
cathodes containing a porous, structured NMC111 and a com- direct-gap detection method, demonstrating again the influence
pact NMC111. The found that the porous NMC111 cathodes re- of the inactive components in NMC cathodes. They found that
quired a higher compaction factor, but the resistivity was reduced the spring back effect was lowered with higher binder content
by 95%, while it was just 78% for the compact NMC111, although (1.5 wt% to 4.0 wt% PVDF), due to plastic deformation, and
this could be improved with higher coating drying rates. Müller with higher mass loadings (20.1 to 35.4 mg cm−2 ), due to the
et al.[172] also investigated the influence of calendering on cath- space for particle rearrangement. A study by Primo et al.[180] ex-
odes based on porous structured NMC111, and found that the amined the influence of both calendering pressure and tempera-
porous NMC111 is capable of withstanding pressures up to 40% ture and found that while the porosity and mechanical properties
porosity without damaging the CAM pore structure. mainly depend on the applied pressure, the electrodes’ conduc-
Kuchler et al.[173] analyzed the 3D microstructure with X-ray tivity mainly depends on the temperature, likely due to deforma-
tomography to determine the influence of calendering on NMC bility of PVDF increasing with temperature. This is reinforced by
cathodes and found that significant changes in the morphology the fact that the correlation between conductivity and calendering
already occur for compaction loads of 300 MPa or higher, al- temperature was better for measurements taken after electrolyte
though no information about the line load was given. A study by infusion, due to polymer swelling effects.
Daemi et al.[174] took the X-ray tomography investigation a step Control of the porosity of the cathode coating can be crit-
further and used 4D visualization to image battery electrodes un- ical for minimizing the cell impedance, as was observed by
dergoing compression in situ, and map the strain evolution and Trask et al.[181] who calendered a Li1.2 Ni0.15 Mn0.55 Co0.1 O2 cath-
particle displacement. They found that strain was seen as concen- ode with PVDF (4%) and conductive carbon, C45 (4%), reduc-
trating throughout the point of the electrode where compression ing the porosity from ≈56% to 34.5% and drastically reducing
was applied and propagating toward the bottom, with this effect the cell impedance measured by EIS. Kang et al.[182] also showed
attributed to the high displacement of small particles fragments. reduced cell impedance of NMC111 cathodes after calendering
The content of inactive material in the cathode (namely binder from densities of 1.9 g cm−3 to 2.6, 3.0, and 3.2 g cm−3 , how-
and conductive carbon) can strongly influence the impact of ever the rate capability of these cathodes was significantly worse
calendering.[175] A study by Zheng et al.[176] investigated the im- at 3.2 g cm−3 , as demonstrated in Figure 13d, and evidence of
pact of calendering on a Li[Ni1/3 Co1/3 Mn1/3 ]O2 -based cathode crushing of the NMC particles was seen. Similar behavior was ob-
with varying contents of PVDF and acetylene black (CB). They served in a study by Stein et al.[183] where the calendered NMC111
found that with low levels of inactive material (2% PVDF and cathodes initially showed improved discharge capacities and rate
1.6% CB), calendering could significantly reduce bulk electric capabilities, however, for long-term cycling, the capacity fading
resistances within the coating, without changing the charge- was higher. This is likely due to the particle crushing phenomena,
transfer resistance, however, with high levels of inactive mate- whereby the cracking of particles initially increases the electro-
rial (8% PVDF and 6.4% CB), the charge-transfer resistance in- chemically active surface area, but causes more SEI growth and
creased after calendering. This is due to the strong decrease in particle breakage with further cycling. Particle breakage caused
porosity accompanying the calendering of cathodes with high by calendering can lead to higher moisture uptake, which can be
inactive material contents. Another study by Lenze et al.[177] in- detrimental to the electrochemical performance, as observed by
vestigated the influence of CB contents (4% and 5.88%) on the Huttner et al.[19] for NMC622 cathodes. The influence of calen-
performance of NMC cathodes after calendering. They found dering on tortuosity can also be used to explain the detrimen-
that low CB contents show lower discharge capacities above C- tal electrochemical performance, as electrodes with higher den-
rates of 0.2C, even after calendering to a volume reduction of sities typically possess higher tortuosities, which in turn inhibits
up to 22 %. The impact that calendering has on the inactive ionic conductivity within the electrode due to longer ion diffusion
material in the cathode must also be considered, as demon- distances.
strated in a study by Grissa et al.[178] where they observed PVDF Calendering can also be used to enable thicker cathodes
degradation in Li[Ni0.5 Mn0.3 Co0.2 ]O2 cathodes (PVDF (2%) and with higher energy densities. In a study by Du et al.,[184] thick
CB (2%)) calendered to 27% and 21.2% porosity with a two-roll NMC532 based cathodes (with mass loadings up to 25.4 mg
press at 80 °C. Investigation of the morphology of NMC cath- cm−2 ) produced using aqueous methods showed crack forma-
odes by Rajendra et al.[179] using X-ray microtomography showed tion in the coating after drying, and demonstrated that the
a significant impact on the conductive carbon domain, suggest- cracks in the coating could be reduced or removed by calender-
ing that this region is permanently deformed by calendering ing, which was accompanied by reduction in the internal resis-
(with 2 MPa calendering pressure). Another study by Meyer et tance of the electrode. Hu et al.[185] investigated calendering of
al.[15] investigated the impact of calendering at different temper- LiNi0.7 Mn0.22 Co0.08 O2 cathodes with thicknesses of 132 μm be-
atures on LiNi1/3 Mn1/3 Co1/3 O2 cathodes with NMC:PVDF:CB ra- fore calendering (areal loading of 22.41 mg cm−2 ) and found that
tios of 94:3:3, 92:4:4 and 90:5:5, and found that increasing cal- reduction of the porosity from 60 % to 40% with calendering im-
endering temperatures lead to decreasing porosities and line proved the rate capability and capacity retention. Singh et al.[186]

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employed calendering to reduce the cathode thickness 10%, in or- and electrochemical performance, more rigorous electrochemi-
der to enable the cycling of NMC111 cathodes at 0.5C with thick- cal studies are necessary, especially for up-scaled processes. That
nesses up to 320 μm (loading weight of ≈72 mg cm−2 ). Another being said, a few points regarding calendering of cathodes can
study by Singh et al.[187] studied the impact of calendering on already be stated:
NMC111 cathodes (composed of C65 (3%), Gr (3%), carbon fibers
(1%) and PVDF (3%)) with a 300 μm thickness (≈71 mg cm−2 ), 1) Calendering can be a critical step to ensure electronic transfer
reducing the porosities from 44% to 38% and increasing the process in the cathode coating, due to the limited intrinsic
volumetric energy density at C/5 by 19%. They found that the electrical conductivity of most CAMs.
NMC cathode with the lowest porosity demonstrated the best 2) High calendering strengths can result not only in highly
performance, however, this study modified the cathode and an- dense cathodes, which are accompanied by charge transfer
ode porosities simultaneously, so definitive statements about the limitations, but also in particle breakage, which can lead to
influence of calendering on the cathode cannot be given. How- higher moisture uptake, more active sites for electrolyte side
ever, it can be stated that there is always a tradeoff between en- reactions and pulverization of the CAM during cycling.
ergy and power density, as Heubner et al.[188] showed in their 3) The amount and distribution of the inactive components in
study of NMC622 cathodes with thicknesses ranging from 129 the cathode (namely binder and conductive additive) influ-
to 212 μm and porosities from 34% to 43%. They demonstrated ence the effectiveness of calendering.
that while energy density increases with increasing thickness and
decreasing porosity after calendering, the charge transfer resis-
tance also increases, leading to poor C-rate performance. They 4.2.3. Lithium–Nickel–Aluminum-Oxides
also observed the deformation and cracking of particles using
high line loads (1000 N mm−1 ). Hu et al.[185] investigated cal- Lithium nickel (cobalt or manganese) aluminum oxides (NCA
endering of LiNi0.7 Mn0.22 Co0.08 O2 cathodes with thicknesses of and NMA) are common CAMs for LIB applications due to
132 μm before calendering (areal loading of 22.41 mg cm−2 ) and their high theoretical capacity and good cyclability at room
found that reduction of the porosity from 60% to 40% with calen- temperature.[192] However, Ni-rich cathodes can be subject to ex-
dering improved the rate capability and capacity retention. Some treme capacity fading owing to CAM particle cracking and break-
select electrochemical results from the literature for cathodes be- age during long-term cycling.[193] Compaction of the cathodes via
fore and after calendering are shown below in Table 2. The lim- calendering can improve the electronic percolation network and
ited entries and information displayed in this table reflect the volumetric energy density, however, for NCA, over-compaction
need for more electrochemical-based calendering studies, as well can destroy the mechanical properties, facilitate particle cracking
as standards for which metrics to report. and restrict electrolyte wetting.[193] It is vital to optimize the cal-
Calendering has also been employed for producing cathodes endering approach for this material.
containing non-traditional cathode binder materials (such as Lu et al.[194] investigated the impact of calendering on
CMC), demonstrating its utility for enabling novel production LiNi0.8 Co0.15 Al0.05 O2 (NCA) cathodes, prepared with Gr, CB and
processes (e.g., aqueous based). In a study by Loeffler et al.[189] PVDF, with varying thicknesses and demonstrated that improved
NMC111 cathodes were produced using aqueous dispersions coating uniformity could be achieved after calendering. Bobrikov
with CMC (5%) and Super C45 (5% and 7%, corresponding to et al.[192] also studied Lix Ni0.8 Co0.15 Al0.05 O2 (NCA) cathodes to
mass loading of 7.5 and 3.3 mg cm−2 , respectively) and the im- investigate the impact of calendering on the abnormal phase-
pacts of calendering were investigated. They found that calender- separated structural behavior of NCA during the initial charge
ing of the high energy density cathode, using calendering forces cycle. It was demonstrated that stronger compaction partially
which corresponded to density changes from 1.49 g cm−3 to 1.66 suppresses the phase separation of NCA and causes partial de-
and 1.88 g cm−3 , respectively, led to lower capacity fading at 1C struction of the NCA agglomerates, which improves the ion
after 70 cycles. transport characteristics. A study by Sarawutanukul et al.[193] on
The application of calendering can also serve to improve LiNi0.88 Co0.09 Al0.03 O2 (NCA) employed calendering processes to
the properties of NMC cathodes produced using non-traditional optimize the electrode properties. They observed a decrease in
methods. In a study by Sliz et al.[190] screen-printed NMC523 NCA crystallite size after calendering, which can contribute to an
and NMC88 cathodes, where NMP was replaced with DMF, were accumulation of strain on the particle and decrease the capacity
produced and it was found that calendering reduces the rough- retention capabilities. However, they showed that with optimal
ness and improves the long-range electrical contact in the coat- compaction degree (of 17.54%) and particle rearrangement, high
ing. Xiong et al.[191] produced NMC532 cathodes with an oriented C-rates and high capacity retention could be achieved.
pore structure using a NH4 HCO3 foaming agent and showed im- From a study by Haselrieder et al.[195] a high power lithium
proved C-rate performance after calendering (with capacity reten- manganese spinal (Li(Li-Mn-Al)2 O4 ) that was sensitive to me-
tion of 67.6% at 5C). chanical stresses could be enabled by blending it with NCA
Although the influence of calendering on NMC cathodes has (LiNi0.8 Co0.15 Al0.05 O2 ), allowing it to be subjected to calendering,
been studied more than any other cathode material, the majority which improved the specific discharge capacity for C-rates up to
of these investigations were done at the lab scale, which must be 6.5C. A study by Meyer et al.[37] investigated the influence of cal-
taken into consideration when thinking of upscaling the process. endering on two different NCA cathodes. They found that the
Additionally, many of these studies had limited electrochemi- cathode containing a blend of NCA with smaller NCA particles
cal investigations and to better understand the interaction be- had a more distinct porosity decrease at low line loads compared
tween calendering processes, resulting electrode microstructure to the NCA cathode with larger NCA particles. The breaking

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 Adv. Energy Mater. 2023, 13, 2300973
Table 2. Comparison of cycling capacities before and after calendering for select NMC cathode examples from the literature.
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Anode Electrode composition [wt%] Density [g cm−3 ] Porosity [%] before/after First cycle capacity ratio Cycling capacity ratio before/after Ref.
before/after Cal. Cal. before/after Cal. Cal.

Gr NMC/C45/CMC: 88/7/5 1.49/1.66 and 1.88 – ≈131/≈134 mAh g−1 (1.88 g ≈122/≈127 mAh g−1 (1.88 g cm−3 ) [189]
cm−3 ) at 1C after 70 cycles at 1C
Li NMC/PVDF/CB: 94/3/3 1.9/3.0 ≈60/≈39 ≈132/≈126 mAh g−1 after at 0.1C ≈19/≈87 mAh g−1 at 1C and 0/≈87 [182]
mAh g−1 at 4C
Li NMC/PVDF/C65/Gr: - 32.5/18.8 ≈173/≈168 mAh g−1 after at 0.2C ≈78/≈74 mAh g−1 at 3C and [169]
94.5/3/1.67/0.83 ≈127/≈126 mAh g−1 at 5C

2300973 (24 of 34)

Li NMC/PVDF/Super P: 96/2/2 - 60/40 ≈202 at 0.1C for both ≈180 /≈200 mAh g−1 at 0.1C after [185]
24 cycles and ≈100/≈165 mAh/g
at 2C
Li NMC/CB/Gr/PVDF: 2.6/2.8 and 3.2 33.86/30.20 and 20.55 - ≈60 and ≈45 mAh g−1 at 1C after 30 [19]
95.5/1.5/0.75/2.25 cycles; ≈160 mAh g−1 at 0.1C
after 65 cycles for both (2.8 and
3.2 g cm−3 )
- NMC/CB/PVDF: 90/6/4 2.06/2.73 and 2.21/2.74 - ≈117 mAh g−1 and ≈115 mA g−1 ≈92 and ≈88 mAh g−1 at 5C; ≈117 [167]
after 27 cycles and ≈108 mAh g−1 at 1C after 430
cycles
Li NMC/CB/Gr/PVDF: - 50.6/40 and 67.7/40 ≈140/≈145 mAh g−1 and ≈20/36.67 mAh g−1 and [171]
89.29/3.57/3.57/3.57 ≈150/≈150 mAh g−1 at 0.5C 55.34/85.36 mAh g−1 at 5C
Gr NMC/CB/PVDF: 90.2/5.88/3.02 Calendering degree - - ≈99/≈80/≈122 mAh g−1 at 2C; [177]
0%/10%/22% ≈10/≈7/≈27 mAh g−1 at 5C
Li NMC/CB/PVDF: 96/2/2 - 21.2 and 27.0 162 mAh g−1 at 0.1C for both ≈115 and ≈140 mAh g−1 at 0.1C for [178]
both
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strength of this blended NCA was also slightly lower than NCA ability to withstand calendering stress. It was shown that the
without the small particles, despite the fact that the smaller NCA structural integrity of the LNO particles was maintained with
particles possessed higher densities. Sim et al.[196] studied the 100 MPa of compaction, but experienced breakage after 500 MPa.
effects of calendering on LiNi0.9 Mn0.05 Al0.05 O2 (NMA) cathodes A real mechanical benefit was difficult to see from Al doping,
and proposed that calendering could reduce the pulverization of however, after cycling at C/5 for 5 cycles, capacity retention of
NMA particles for repeated electrochemical cycling, resulting in 95.5% was seen, compared to 77.6% for the undoped LNO. Sim-
an overall improvement in capacity retention. ilar improvements in capacity retention were observed for dop-
ing with tungsten (W), along with improvements in the ability to
withstand compaction pressures.
4.2.4. Lithium Cobalt Oxide Due to its extensive limitations, LNO has not been widely stud-
ied, as transition metal-doped LNO materials (such as NMC) of-
Lithium cobalt oxide (LiCoO2 , LCO) was a popular CAM due to its fer much better performances.[203,205] However, more popular Ni-
high tap density, high ionic conductivity, high discharge plateau rich CAMs still suffer similar limitations to LNO, so it is crucial
voltage, and high theoretical capacity.[197,198] To enable the high to better understand how mechanical processing can improve the
voltages of LCO, however, the material will be subjected to volt- electrochemical performances of these materials.
ages beyond 4.2 V, where it can undergo side reactions and loss
of Co and O, leading to particle breakage and ultimately limiting
the long-term cycling stability.[198] 4.2.6. Lithium–Manganese Oxide and Lithium–Nickel–Manganese
In a study by Fa and Fedwik,[199] LCO cathodes were subjected Oxide
to calendering, and showed that the specific capacity could be im-
proved by compaction with 27 MPa and further improved with Lithium manganese oxide (LiMn2 O4 , LMO) is a well-known
compaction at 54 MPa. An improvement in the C-rate capabil- CAM due to its theoretical capacity (148 mAh g−1 ), low-cost and
ity was also observed. In a study by Ebner et al.,[43] calendering environmentally friendliness.[35,206] However, for long-term cy-
of non-spherical LCO particles was compared to NMC particles, cling LMO possesses limited cycling stability- due to Jahn-Teller
and significantly higher tortuosity anisotropy was observed from distortions,[207] structural fatigue and particle cracking. Addi-
LCO, however, not much difference in the particle alignment tional loss of active Mn can lead to capacity fading and reduced
for LCO was seen after calendering for pressures of 30, 60, and electrical conductivity.[35] Due to the limitations of LMO, it is of-
200 MPa. Lim et al.[201] studied calendered LCO particles with ten combined with Ni (LiMnx Niy O4 , LMNO) to improve cycling
packing densities of 2.2 to 3.6 g cm−3 . They observed that with stability.[208,209] Calendering offers an additional industry accessi-
increasing packing density, the porosity, contact resistance, SEI ble method for improving cycling performance.
resistance, and charge transfer resistance all decreased while the Schilcher et al.[35] studied the influence of the calendering step
specific surface area and tortuosity increased. The discharge ca- on the electrode structure and electrochemical performance of
pacities were also improved (from 140 to 148 mAh g−1 ) at 0.1 C LMO cathodes. They observed that an improvement in the elec-
for densities of 2.2 and 3.6 g cm−3 , respectively, and these positive trochemical performance for LMO cathodes was seen for com-
effects are enhanced at 1C. paction rates up to about 25%, corresponding to optimal densi-
Although calendering cannot address all the challenges of LCO ties around 2.0 g cm−3 and a line load of 158 N mm−1 . Beyond
cathodes, it can offer one possible solution to improve cycling that, the particle breakage was too large, and more severe capacity
performance. When combined with additional strategies, such as fading was observed. Lenze et al.[177] also investigated calender-
CAM coatings, the electrochemical performance can be further ing of LMO cathodes and showed significant improvements in
optimized. the specific discharge capacity up to 5C for 15% and 30% calen-
dering rates, especially for LMO cathodes with a CB: binder ratio
> 1. If the long term cycling stability challenges of LMO can be
4.2.5. Lithium Nickel Oxide solved, its high C-rate performance makes it a promising candi-
date for LIBs. He et al.[210] successfully applied calendering to a
Despite its low operating voltage than other transition metal ox- lithium-rich, manganese layered oxide (Li1.2 Mn0.54 Ni0.26 O2 ) cath-
ides, lithium nickel oxide (LiNiO2 , LNO) is a good CAM can- ode, a material associated with electrode compacting problems
didate due to its high-temperature stability, low self-discharge, and high capacity loss in long term cycling, by infusing a near-
high specific capacity, and certainly, a low-cost cathode compared zero-strain 𝛼-LiAlO2 to the grain boundaries.
to Co-containing CAM.[201–203] One of the major challenges of
LNO is the anisotropic volume change during charge/discharge,
which can result in micro crack formation and eventual particle 5. Calendering of Lithium–Sulfur Battery Electrodes
pulverization.[202,203]
Fan and Fedkiw et al.[199] studied the impact of calendering Lithium–sulfur batteries (LSBs) have been considered promis-
of LNO cathodes on the electrochemical performance and com- ing high-energy-density secondary battery system with an energy
pared to LCO and LMO cathodes. They found that while the ca- density of 2572 Wh Kg−1 (2835 Wh L−1 ),[211] which is about four-
pacity of LNO could be improved for compaction up to 27 MPa, fold higher than those of state-of-art LIBs. Although LSBs are
the rate capability was much more limited than LMO and LCO well-known for practical high-energy density batteries, their volu-
cathodes. In a study by Hamam et al.,[205] LNO and 3% Al-doped metric energy density is not competitive with LIBs due to the high
LNO were subjected to mechanical testing to determine their electrode porosity of most sulfur cathodes, which hinders their

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commercialization. Additionally, the practicality of LSBs is hin- the calendering process showed that electrodes have lower dis-
dered by many problematic issues, such as short cycle life and low charge voltage and capacity, because of poor electrolyte wetting
sulfur content/loading, poor safety, and a high self-discharge rate in the low porosity, resulting in decreasing energy density.
because of the shuttling of polysulfide intermediates between the Feng et al.[221] developed a method to fabricate sulfur-rich sec-
cathode and anode.[212–214] After the formation of polysulfides ondary particles by a scalable production, using hail-inspired
in the first cycles, the initial electrode structure/morphology is nano-storm technology, and evaluated the calendering com-
changed. Due to dependence of the electrochemical performance patibility and conductivity of these composites. They used an
of LSBs on the electrode conditions, the design of the macrostruc- electrode microenvironment model to understand the role of
ture of the electrode is a controlling factor for the bulk produc- calendering-compatibility of the active material. A high areal ca-
tion of electrodes. The calendering process is one critical step pacity of 12 mAh cm−2 at 1 mA cm−2 is obtained with a super
that determines the macroporous structure, electrolyte/sulfur ra- high loading of 14 mg cm−2 in the coin cell tests. However, pouch
tio, mechanical properties, and bulk density and conductivity of cells with various sulfur loadings also delivered a high specific
the electrodes.[215–224] Some studies showed interesting results capacity of about 1300 mAh g−1 for ten cycles. Besides the dry-
for calendered electrodes of LSBs. ing study of LSB electrodes, Titscher et al.[218] investigated calen-
For instance, Kim et al.[215] have optimized electrode pro- dered electrodes with sulfur loadings of about 3 mg cm−2 , with
cessing conditions, such as mixing conditions and calender- different compression grades of about 5% to 50% (electrode den-
ing at different temperatures. The mild mixing conditions sity about 0.6–0.9 g cm−3 ). All calendered and uncalendered elec-
and high-temperature calendering helped to produce favorable trodes showed similar specific capacity at 0.05C to 1C. Neverthe-
pore structures and enhance electrochemical performance. Both less, the manufactured electrode with 50% compression exhib-
(un)calendered electrodes demonstrated a capacity of 1000 mAh ited higher energy density.
g−1 at 0.1C. Also, stable capacity retention of 700 mAh g−1 after Xue et al.[219] introduced Lix Mo6 S8 as an interlayer when they
200 cycles at 0.5C, and higher rate capability for the calendered developed sulfur cathode electrodes for LSBs. Interestingly, the
electrode was achieved. Zhai et al.[216] developed a 3D electrode Lix Mo6 S8 interlayer, with its high electronic and ionic conductiv-
made of sulfur/nitrogen-doped porous graphene/CNT skeleton, ities and extra capacity contribution, could enhance the volumet-
and used calendering of this electrode in order to obtain a high ric energy density of the calendered electrode (4 mg cm−2 ) at a
volumetric energy density of 850 Wh L−1 , which is over threefold pouch-cell level. Their results exhibited that the cell with Celgard
higher than that of the uncalendered electrode (275 Wh L−1 ). The polypropylene separator (PP)@Lix Mo6 S8 and a high sulfur load-
electrode with a compression of 30% showed a high rate capabil- ing cathode has an areal capacity of about 3 mAh cm−2 at 1 mA
ity, over 40% capacity retention at 2C, mainly ascribed to the en- cm−2 , with an outstanding retention of 93.1% over 100 cycles.
hanced conductivity from 6.4 to 11.8 S cm−1 , and well-maintained Remarkably, the volumetric energy density of calendered elec-
macropores in the electrode. The results could be attributed to trode (85 μm) with PP@ Lix Mo6 S8 is about fivefold higher than
low sulfur content in the electrode (only about 22 wt%), which the PP separator at 1 mA cm−2 . These results suggest that this
is far from the average loading of 50% in the literature.[225] interlayer facilitates the redox kinetics of the cathode electrodes
However, Lu and co-workers[217] designed electrodes with 4 mg with high density. Some of their results are shown in Figure 14a.
cm−2 , and studied the effects of electrode porosity on the elec- Gröbmeyer et al.[220] deeply investigated the effect of calendering
trochemical performance of the electrodes using the calender- on the two types of electrodes manufactured by KS6 (Gr, 26 m2
ing process. The optimized electrode delivered a high energy g−1 ) and Super C65 (62 m2 g−1 ) conductive carbon. The uncalen-
density of over 1300 Wh L−1 . For an area of 1 cm2 of the dered sulfur/Super C65 electrodes exhibited a rough surface with
uncalendered electrode (120 μm thick) about 11 μL of elec- huge cracks formed during solvent evaporation. However, calen-
trolyte was necessary, whereas, only 4.7 μL was required for dering of electrodes makes a smooth surface without material ag-
the same area of the calendered electrode (60 μm thick). Con- glomerates, removes the large cracks, and makes good contrasts
trolling electrode porosity can decrease the electrode volume between the sulfur and the conductive carbon. The KS6 with a
and electrolyte amount needed for full electrode wetting. There- 2D structure generates a better percolation path via encapsulat-
fore, increasing the electrolyte/sulfur/conductive carbon contact ing the sulfur particles completely, to enhance the accessibility of
(three-phase contact between active material-conductive carbon- sulfur particles by the electrons. Also, the internal electrode resis-
electrolyte)[226] improves the battery performance and delivers a tance when KS6 is employed was reduced by 68% after calender-
higher specific energy density electrode. Additionally, they used ing, resulting in a better electrochemical performance than the
Li2 S6 as an electrolyte additive to increase the wettability of elec- electrode made by Super C65 (the internal electrode resistance
trodes when the thick electrode is used, resulting in enhancing decreased by 38%), which contacts the sulfur particles in a net-
cycling stability (≈80% for 200 cycles) even with a dense and high- work of a few micrometers.
loading electrode. Liu et al.[227] used La0.8 Sr0.2 MnO3 (6.5 g cm−3 ) Niesen et al.[222] developed sulfurized poly(acrylonitrile) cath-
as a sulfur host for high volumetric capacity cells. The calendered ode materials and made electrodes with 90 wt% active material
electrodes (pressed at 0.2 MPa) with a sulfur loading of 6.2 mg content, with an areal loading of 2.7 mAh cm−2 . With increas-
cm−2 and electrolyte/sulfur ratio of 7 μL mg−1 exhibited a cath- ing in density from 0.8 to 1.0 g cm−3 via calendering, no change
ode density of 1.69 g cm−3 and porosity of 21%, in an excellent can be seen in the cells’ rate performance and the long-term cy-
volumetric energy density about 2700 Wh L−1 , compared to un- cling test (which demonstrated a decay of ∼8% (0.05% per cy-
calendered one (0.98 g cm−3 , 55%, 1787 Wh L−1 ). The volumetric cle) after 400 cycles). Chien et al.[223] doubled the capacity density
energy is comparable to the Ni-rich oxide cathode (1800–2160 Wh of the sulfur-carbon composite electrodes with sulfur-loading up
L−1 ) of LIBs. However, further increasing comperssion during to 3.5 mg cm−2 by calendering at 50 °C. The Cai group[224] opti-

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Figure 14. a) Effect of calendering on sulfur/carbon (weight ratio of 6/4) cathodes with different separators: polypropylene@Lix Mo6 S8 (PP@Lix Mo6 S8 ),
PP@carbon (PP@C), and pristine PP at 0.25 and 1 mA cm−2 , and also SEM images of sulfur/carbon electrodes before (105 μm) and after (85 μm)
calendering. Cathode electrode composition: 90% sulfur/carbon composite, and 10% PVDF. Reproduced with permission.[220] Copyright 2019, Else-
vier. b) The (dis)charge curves of sulfur/carbon (weight ratio of 80/20) cathodes with sulfur loading of 5 mg cm−2 under different porosities, and
the results obtained from the developed analytical model showed the correlations between the porosity of the cathode electrodes and energy densi-
ties. The electrode: sulfur/carbon composite/CB/carboxymethyl cellulose/styrene-butadiene rubber with a weight ratio of 76/18/3/3. Reproduced with
permission.[225] Copyright 2019, Springer Nature.

mized electrode porosity, and sulfur loadings of 2.5-5 mg cm−2 , 6. Calendering of the Other Type of Battery
to increase volumetric energy density to 500 Wh kg−1 without Electrodes
sacrificing the sulfur utilization, which is restricted by the elec-
tronically accessible surface area of the carbon matrix. A typi- Jiang et al.[228] studied the calendering process on carbon-coated
cal two-plateau discharge behavior of an LSB at ≈2.4 and 2.1 V Na3 V2 (PO4 )3 (NVP), as a most promising cathode of sodium-ion
was observed when the porosity was higher than 55%, with an batteries,[229,230] to explore the limitations in external ionic con-
initial discharge capacity of about 1100 mAh g−1 . By reducing ductivity. They used two different sizes, 80 and 800 nm, for NVP,
the porosity to 40%, the initial discharge capacity is only 250 and the results showed a similar performance at high C-rates.
mAh g−1 , signifying that electrodes with higher porosity obvi- The fast Na+ diffusion in the NVP/carbon composite structure
ously provide more reaction sites, and hence has a higher sulfur suggests that NVP/carbon should be produced in a denser form
utilization rate. Based on their cell assembly and the results, elec- (larger particles) to increase the tap density. They also showed
trodes with a porosity of 50–60% were recommended for a prac- that the performance of the NVP/carbon electrodes depends
tical high-energy LSB design (Figure 14b). Table 3 reports stud- on more external electronic and ionic conductivities, which are
ies regarding calendering effect on the some selected elctrodes unfavorably affected by calendering and high areal loading.
of LSBs. To make a thicker sulfur cathode, the active material After calendering, more than 50% of the electrode thickness
particles should be hard enough during calendering to achieve was reduced, which reflects the main drawback of using nano-
a robust electrode and, thus, efficient conduction of ions and sized particles. The calendered electrodes demonstrated a signif-
electrons. icant drop in rate performance, and at 20C, dropped from 85%

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 Adv. Energy Mater. 2023, 13, 2300973
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Table 3. Literature comparison of electrode composition and electrochemical performance of sulfur electrode cathodes of LSBs before and after calendering (Cal.).

Electrode composition [wt%] Density [g cm3 ] Porosity [%] First cycle capacity [mAh g−1 ] Cycling life ratio before/after Ref.
before/after Cal. before/after Cal. before/after Cal. Cal.

Sulfur:CB: poly(ethylene oxide): poly(vinyl pyrrolidone) 0.6/1.1–1.7 - Similar about 1000 at 0.1C ≈500/700 mAh g−1 after 150 [215]
(68:23:8:1) cycles
Nitrogen-doped graphene (NG);sulfur:CNT (53:22:25) - - Similar about 1100 at 0.5C ≈400/900 mAh g−1 after 180 [216]
cycles
Ketjen black/sulfur composite (80 wt% S): CB: CMC:SBR - 64/29 Similar about 1100 at 0.1C ≈750/900 mAh g−1 after 200 [217]

2300973 (28 of 34)

(80:10:6:4) cycles
carbon/sulfur composite (60 wt% S): CMC:SBR (90:5:5) - - Similar about 1100 at 1C ≈200/700 mAh g−1 after 400 [219]
cycles
Sulfur:CB:PVDF (60:30:10) - - Similar about 700 at 1C ≈180/450 mAh g−1 after 400 [220]
cycles
Co2 O3 /sulfur/carbon composite: CB: polyacrylic acid - ≈72/30 N.A./1350 at 1C ≈300/500 mAh g−1 after 110 [221]
(80:10:10) cycles
sulfurized poly (acrylonitrile) composite: CB: CMC:SBR 0.8/1.2 56/33 Similar about 1200 at 1C ≈similar 1100 mAh g−1 after [222]
(90:5:2:3) 400 cycles
Carbon/sulfur composite (78 wt% of sulfur): CB: CMC:SBR - 70/55 Similar about 1000 at 1C ≈similar 1100 mAh g−1 after [224]
(78:18:3:3) 400 cycles
Sulfur: Ketjen black: CB: carbon nanofibers: poly(ethylene 0.6/1.5 70/26 Similar about 1000 at 0.1C ≈similar 820 mAh g−1 after [223]
oxide): poly(vinylpyrrolidone) (65:21:3.5:3.5:5.4:1.6) 100 cycles
Sulfur/La0.8 Sr0.2 MnO3 : CB: CMC:SBR (80:13:4.2:2.8) 0.98/1.69 55/21 Similar about 800 at 0.1C NA/600 mAh g−1 after 120 [227]
cycles
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(uncalendered) to 60% (calendered) because of a decreasing The following conclusions can be generally applied to anode
porosity and increased tortuosity, which hinders ionic diffusion. and cathode electrodes:
The effects of calendering on Zn|MnO2 batteries were also in-
vestigated on both Zn and MnO2 electrodes.[231,232] Calendering 1) Calendering firmly controls electrode density and porosity;
reduces the layer thickness of both electrodes and the microp- higher electrode density increases the volumetric capacity
ore surface area of the MnO2 cathode, which is a drawback for of cells. Lower electrode porosity decreases the electrolyte
discharge capability and cycling life. The batteries with a calen- amount required for complete electrode wetting, which is crit-
dered MnO2 cathode showed about 40% lower discharge capaci- ical in view of cost and gravimetric capacity density. The elec-
ties than the uncalendered electrodes for identical discharge con- trode porosity can strongly control the CE and cycle life of bat-
ditions. However, if only a calendered Zn anode was used with tery cells, especially since increasing the density can increase
the uncalendered MnO2 , the discharge capacity was increased by the ionic resistance.
about 25%. 2) Calendering may also decrease the internal electrical resis-
Douard et al.[233] studied the effect of electrode porosity on the tance of electrodes, increasing the conductive additive-active
electrochemical performance of MnO2 symmetric supercapaci- material contact, enhancing the electronic conductive path-
tor devices in neutral aqueous electrolytes by electrode calender- ways, and improving the rate capability.
ing. For whatever the mass loading (2–12 mg cm2 ), reducing the 3) Calendering affects the electrode tortuosity and wettability,
porosity from 70% (pristine electrode) to 50% (calendered elec- which are critical for a high-performance and safe cell, in-
trode) enhanced the areal and volumetric capacitances. Reduc- fluencing electronic pathways, ionic pathways, and determin-
ing the porosity for electrodes with high-mass loadings by calen- ing the electrolyte filling step. For instance, in the sulfur elec-
dering could reduce the charge transfer resistance and increase trodes, because of the insulating nature of sulfur, and conse-
the double-layer capacitance. Additionally, the electrode wetting quent need for high electrolyte-sulfur-conductive carbon con-
property depends on the electrode loading and porosity. The cal- tact in the electrode, low porosity increases the electrochemi-
endered electrodes showed stable capacitance values compared to cal polarization and lowers sulfur utilization.
uncalendered ones, which proposes a faster wetting of the denser 4) Calendering of electrodes smooths out the electrode’s surface,
electrodes. removes large cracks, and enhances the contact between the
active materials and the conductive additives. This allows for
an optimization of the conductive network inside the compos-
7. Conclusions and Outlook ite electrode, thus increasing the overall electrical conductivity
of the electrode.
In this review, the foundation of calendering processes and their 5) The line load, the roll temperature, and the roll diameters in
underlying mechanisms were outlined. The link between the the calendering affect the adhesion strengths, and all three
calendering process and the material-dependent structural re- need to be optimized for target electrode compositions.
sponse, and resulting performance is a crucial one. It was demon- 6) The calendering processing is critical for improving the struc-
strated how understanding this link can help to optimize calen- tural stability of the active material and CBD in the electrode.
dering processes for a wide variety of AMs and applications, as 7) Dispersing conductive additive nano particles in the electrode
well as allow calendering to be used to optimize material proper- after calendering also is a critical factor for having a better
ties of electrodes. electrochemical performance.[234]
Modeling and simulations can be a more accessible, cost- 8) Optimizing the calendering process for a given electrode com-
effective way to gain detailed understanding of microstructure, position is critical. Calendering electrodes without any opti-
mechanical and electrochemical effects in the electrode, resulting mization can lead to the following drawbacks: i) pore collapse
from the calendering process. Connecting modeling approaches after calendering, resulting in poor electrolyte wetting abil-
with experimental investigations is an important step to better ity and ion diffusion; ii) damage of the hollow microstructure
understand the process-structure-performance relationship. for some porous nanostructured active materials (like porous
Calendering of cathodes can be key step in the production pro- Si composites), in which case a gentle calendering process
cess to enable the necessary electron transfer reactions. However, should be applied; iii) reduction of the three contact phases
knowledge of the microstructure and properties of the electrode, of electrolyte-active material-conductive additives,[226] making
especially the CBD region and the CAM, is a necessary first step electrolyte less accessible to the active materials, reducing the
to choosing the appropriate calendering parameters to apply. specific surface area of the electrode, and increasing the elec-
Anode electrodes, because of volume changes during trode tortuosity, and thus poor electrochemical performance
(de)lithiation processes, should be very carefully calendered. The of the electrode; and iv) in some cases, damage of the current
calendering degree strongly dependents on the type of anode ac- collector if the calendering condition is not optimized for the
tive material, binders, and electrode compositions. For example, electrodes.
the electrodes with intercalation mechanism active materials 9) The optimal calendered electrodes may have a less SEI forma-
(graphite and LTO) can be calendered to higher densities, with tion than uncalendered electrodes, as the electrode porosity
relatively lower porosities, compared to the electrodes made is reduced (the possibility of contacting active materials with
with alloy- (Si, germanium, and tin), and conversion- (transition electrolyte would be less). On the other word, with optimized
metal oxides) mechanism active materials. Therefore, for every calendering condition, the particle positions are altered, thus,
electrode, the optimum condition of calendering should be changing in their shapes and structure should be minimum.
determined based on the chosen active material. Therefore, no effect on the atom scale can be concluded for

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the optimal calendered electrode. However, applying a very Received: March 31, 2023
high compaction degree on the electrodes to fabricate elec- Revised: May 6, 2023
trodes with high-density could damages particles and change Published online: May 26, 2023
their morphology particularly for porous particles.

Calendered electrodes are mainly tested in half-cells, and many

[1] Y. Liu, R. Zhang, J. Wang, Y. Wang, iScience 2021, 24, 102332.
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Mozaffar Abdollahifar received his doctorate in chemical engineering and energy storage materials
from National Taiwan University (NTU) in 2018, focused on the supercapacitor electrodes and cath-
ode materials of lithium-ion batteries (LIBs). After a postdoctoral stay at the NTU (2 years), in 2021,
he was appointed as research scientist in the Institute for Particle Technology (iPAT), and the Battery
LabFactory Braunschweig (BLB) of Technische Universität Braunschweig. His research interests are
including battery materials, battery process engineering, battery recycling, supercapacitor materials,
and nanomaterials.

Heather Cavers completed her B.Sc. in chemistry at the University of Manitoba, Winnipeg, Canada,
after which she obtained her M.Sc. and her doctorate in Materials Science and Engineering (2021)
from Christian-Albrecht University of Kiel, Germany. Her thesis topic was regarding aspects of the
chemistry of silicon/sulfur lithium-ion battery full-cells. She is currently working as a Post Doc at the
Institute of Particle Technology (iPAT), Technische Universität Braunschweig, Germany. Her research
expertise includes materials science, electrochemistry, and novel lithium-ion battery materials.

Arno Kwade worked 9 years as a process engineer in industry after finishing his doctorate in the field of
ultrafine milling in stirred media mills at Technische Universität Braunschweig in 1996. Since 2005 he
is leading as professor at Technische Universität Braunschweig the Institute for Particle Technology
with research focus on developing process-structure-property relationships for processes in which
particles are mechanically stressed and formulated, from milling and mechanochemical synthesis
over mixing to production and calendering of electrodes for lithium-ion and all-solid-state batteries.
Today he is also chairman of the Battery LabFactory Braunschweig (BLB) and the Centre of Pharmaceu-
tical Engineering (PVZ).

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