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A Review of Lithium‐Ion Battery Electrode Drying: Mechanisms and

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DOI: 10.1002/aenm.202102233

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A Review of Lithium-Ion Battery Electrode Drying:

Mechanisms and Metrology
Ye Shui Zhang,* Nicola E. Courtier, Zhenyu Zhang, Kailong Liu, Josh J. Bailey,
Adam M. Boyce, Giles Richardson, Paul R. Shearing, Emma Kendrick,* and Dan J. L. Brett*

$34.2 billion (USD) which is expected to

Lithium-ion battery manufacturing chain is extremely complex with many grow at a compound annual growth rate of
controllable parameters especially for the drying process. These processes 13.0% from 2020 to 2027.[1] The manufac-
affect the porous structure and properties of these electrode films and influence turing of these batteries has largely been
performed in the same way since their initial
the final cell performance properties. However, there is limited available drying
commercialization by Sony in the 1990s.[2]
information and the dynamics are poorly understood due to the limitation of In general, the electrode manufac-
the existing metrology. There is an emerging need to develop new methodolo- turing process consists of mixing, coating,
gies to understand the drying dynamics to achieve improved quality control of drying, calendering, post-drying, and cell
the electrode coatings. A comprehensive summary of the parameters and vari- assembly steps, as shown in Figure 1. The
ables relevant to the wet electrode film drying process is presented, and its con- common composites for typical LIB elec-
trodes consist of active materials (AM)
sequences/effects on the finished electrode/final cell properties are mapped.
with particle sizes of ≈10–20 µm, con-
The development of the drying mechanism is critically discussed according to ductive additives with particle sizes of
existing modeling studies. Then, the existing and potential metrology tech- ≈100 nm, and binder (polymeric or water-
niques, either in situ or ex situ in the drying process are reviewed. This work is soluble).[3] The active components of the
intended to develop new perspectives on the application of advanced tech- negative and positive electrodes (graphite,
and LiCoO2 for the original LIBs, respec-
niques to enable a more predictive approach to identify optimum lithium-ion
tively) are mixed separately into a slurry
battery manufacturing conditions, with a focus upon the critical drying process. containing a conductive additive, such as
carbon black (CB) and a polymeric binder,
(polyvinylidene fluoride, PVDF) in a sol-
1. Introduction vent such as N-methyl-2-pyrrolidone (NMP). The carbon binder
domain (CBD) promotes mechanical integrity and electron
Lithium-ion batteries (LIBs) are ubiquitous within portable transport, whereas the pores left by evaporated solvent are filled
applications such as mobile phones and laptops, and increas- with electrolyte, promoting lithium-ion transportation, both
ingly used in e-mobility due to their relatively high energy being directly linked to the performance of the battery through
and power density. This has led to an exponential increase in mass transport limitations.[4] The slurry is then tape-cast onto
batteries being manufactured with a current market size of a current collector (CC) (Cu for the negative electrode, and Al

Y. S. Zhang, Z. Zhang, J. J. Bailey, A. M. Boyce, P. R. Shearing, D. J. L. Brett N. E. Courtier, G. Richardson

Electrochemical Innovation Lab Mathematical Sciences
Department of Chemical Engineering University of Southampton
University College London Southampton SO17 1BJ, UK
London WC1E 7JE, UK K. Liu
E-mail: yeshui.zhang@ucl.ac.uk; d.brett@ucl.ac.uk WMG
Y. S. Zhang, N. E. Courtier, Z. Zhang, K. Liu, J. J. Bailey, A. M. Boyce, University of Warwick
G. Richardson, P. R. Shearing, E. Kendrick, D. J. L. Brett Coventry CV4 7AL, UK
The Faraday Institution J. J. Bailey
Quad One School of Chemistry and Chemical Engineering
Harwell Science and Innovation Campus Queen’s University Belfast
Didcot OX11 0RA, UK Belfast BT7 1NN, UK
E-mail: e.kendrick@bham.ac.uk E. Kendrick
Y. S. Zhang School of Metallurgy and Materials
School of Engineering University of Birmingham
University of Aberdeen Birmingham B15 2TT, UK
Aberdeen AB24 3UE, UK
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/aenm.202102233.
DOI: 10.1002/aenm.202102233

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Figure 1. a) Electrode and battery manufacturing process; b) the challenges of LIB manufacturing process and the strategies to achieve desirable
products.

for the positive electrode), the resulting coating is then dried improving performance and reducing the propensity for
to produce a cohesive film which adheres to the CC. The dried failure. Porosity is required such that ionic diffusion of lithium-
electrode is then calendered to reduce the electrode thickness, ions in the electrolyte occurs, along with electronic conductivity
increasing 3D connectivity, electronic conductivity, and maxi- between the active components through the conductive addi-
mizing the volumetric energy density.[3] tive, to ensure that electrons can move from the redox-active
To achieve consistency within cell electrodes, a homogenous, sites in the active components to the CCs as the battery charges
defect-free coating is required, with target weights realized and discharges. The microstructure is important in optimizing
throughout the layer. This enables homogenous current den- the electronic and ionic conductivity through the correct elec-
sities and lithium transport between the anode and cathode, trode architectures. The distribution of the microporous phase,

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formed by the CB and binder, which partially fills the pores In this review, the DP is reviewed and the specific stages and
between the electrode particles (AM), improves the mechanical mechanisms of this process discussed, with a critical discus-
stability of the electrode and improves the electrical contact to sion about the drying mechanism and models, which have been
the CCs.[4] The microstructure is controlled through the mixing, used to understand drying dynamics. The effect of different
coating, and, most importantly, the drying and subsequent cal- parameters and variables upon the architecture and resultant
endering processes. physical and electrochemical properties of the electrodes is
Although the wet processing of electrodes has developed into reviewed and the possible defects and how these can be charac-
a mature technique in the electrode manufacturing industry,[5] terized are considered. Finally, the metrology currently utilized
there remain unresolved issues with the process, especially to measure the influence of the drying parameters/variables on
coating inconsistency and microstructure defects occurring in the electrode is discussed as well as future improvements and
the drying process (DP).[6] The DP is affected by the previous opportunities to apply advanced metrology for the analysis, con-
slurry mixing step and also correlated to the subsequent cal- trol, and modeling of film drying.
endering process. Researchers assert that the properties of the
electrode layer, such as its microstructure and morphology, are
strongly dependent on the manufacturing process, especially 2. Drying Mechanism
upon the drying protocol.[6b,7] Hawley and Li[6b] have reviewed
the current state of electrode manufacturing for LIBs and criti- A typical phase change process during electrode drying is sum-
cally discussed the key slurry properties that can be adjusted to marized in Figure 2. The slurry phase becomes a semi-slurry
optimize wet slurry fabrication. The authors noted that the elec- as the solvent evaporates followed by further removal of solvent
trochemical performance of the electrode is not solely affected to form a condensed layer of coating, and finally resulting in
by slurry rheology, but that the drying parameters also play an a compacted solid film coating. The process and mechanisms
important role in determining the electrochemical properties can be explained through multiple stages which relate to the
of the finished electrode. The optimal coating rate is sensitive morphological and physical changes in the coating shown in
to the specific drying mechanisms. Solvent elimination plays a Figure 2; a) aggregation, b) film consolidation, c) film shrinkage,
key role in next-generation smart electrode manufacturing.[6b] and d) pore emptying, segregation, and bonding. These stages
To better control the properties of the electrode, it is imperative are controlled through the solvent extraction mechanisms and
to improve understanding of the drying dynamic,[8] and thus processes as shown in Figure 3. The different processes and
provide the means for manufacturing tailored electrode archi- mechanisms are critically discussed, and potential models are
tectures that can unlock the further potential of LIBs.[6b] compared in later section.
At the same time, the cost of drying is also an important
factor that must be taken into account to optimize electrode
manufacturing.[3] Wood et al.[9] calculated the possible cost 2.1. Aggregation
reduction in LIB manufacture based on electrode processing
cost, energy consumption, electrode thickness, and energy Aggregation is where the particles, solvent, and binder coalesce
consumption for electrolyte wetting and solid electrolyte inter- to form the semi-solid coating. The rheological properties of
phase (SEI) layer formation. The energy consumption during the initial inks are extremely important here, as once the shear
electrode processing is determined by the solvent type, disper- from the coating deposition is removed, the inks must form
sion of the solid loading, drying temperature, air flow rate, and a stable network structure with no flow, this coat weight then
drying time. The authors discuss doubling the thickness of the remains homogenous with no defects for the subsequent DP.
electrode to reduce the cost of CCs and separators.[9] However, Liu and Mukherjee[20] developed a morphology-detailed mes-
they note that this would also lead to an increase in energy con- oscale model to understand the influence of variables, such as
sumption in the DP. It has been reported that around 29% of active particle morphology and size, volume fraction, solvent
total energy consumption for manufacturing LIBs comes from evaporation, and interactions between the composites. The ini-
the stringent requirements on the facilities needed for the tial aggregation or film structure model was extrapolated to give
electrode slurry mixing and coating processes.[10] Another 47% further insight into the drying mechanism. The authors pro-
of the total process energy derives from the electrode DP, in posed both spontaneous aggregation and evaporation-induced
terms of NMP evaporation and recovery.[11] As noted in ref. [12], aggregation regimes. In this model, spontaneous aggregation
improving the electrode manufacturing process to reduce both could be improved with low evaporation rates, which increases
cost and energy consumption is a significant challenge. the interfacial area compared to evaporation-induced aggrega-
Various aspects of the electrode manufacturing process have tion. This regime could be a potential strategy to optimize the
been the subject of recent studies; these include works on the DP in terms of high-quality microstructure.
effects of mixing sequences on the electrode components,[13]
mixing tools,[13a,14] coating,[15] drying,[7a,b,8,16] calendering[17]
and post-drying.[18] To effectively control electrode manufac- 2.2. Film Consolidation
turing will require a series of advanced analytical techniques
which could be compatible with in situ and/or ex situ character­ In the second stage of the DP, a semi-slurry is formed, at this
izations,[5d,17k,19] particularly in the DP. The influence of drying point the film consolidates and a surface layer forms on the
parameters/variables on the properties of the finished electrode top of the coating. A top-down film consolidation mechanism
is extremely complex. was summarized by Jaiser et al.[8] The consolidation layer of

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Figure 2. Typical electrode drying process from a) slurry phase to b) form a semi-slurry, following with the c) further removal of solvent and d) end up
with a compacted solid film of coating (yellow lines indicate the binder, pink particles indicate active material particles, black dots indicate the conduc-
tive carbon and light blue color indicates the solvent).

the electrode is rapidly formed on the surface of the electrode, drying is complete. During the film shrinkage and solvent evap-
even at low density of slurry, with no sedimentation. The con- oration stages of drying, the functional additives are mobile and
solidation layer grows as the solvent evaporates and the con- frequently distribute throughout the film.[16e]
solidation layer area expands until it approaches the substrate.
As the solvent evaporates, binder migration can occur with the
solvent, once the shrinkage of the film stops the migration will 2.4. Segregation and Bonding
also stop. Sedimentation does not occur significantly in the
battery electrode slurry because of its high viscosity. However, In the final stages of the DP, the polymer forms a strong adhe-
increased temperatures reduce the viscosity of the electrode sive bond to the substrate, and the final solvent is removed,
slurry, which can instigate a low level of sedimentation.[21] such that a cohesive strength also forms between all of the par-
ticles in the final solid electrode film. Potential segregation of
the film can occur and the driving force for this increases with
2.3. Film Shrinkage/Pore Emptying temperature and mass flow rate of the solvent evaporation.[21]
Consequently, reduced drying time also leads to a reduced
In the third stage of the DP, the binder has a low level of sol- time-to-fixation/time-for-segregation. It has been reported[16a,22]
vent remaining in it, and the final shrinkage of the coating that the higher degree of polymer entangling would benefit the
occurs and the final stage of pore emptying. Jaiser et al.[16e] adhesion strength, and that entanglement may increase with
hypothesized that during the film shrinkage regime, the solid decreasing drying time. The time-to-fixation is also related to
constituents in the wet film will contact each other to finally the targeted loading, such that the higher the targeted loading,
form a connected solid layer during shrinkage. The porous the thicker the wet film and more solvent used. Therefore, the
structure will form as the backbone of the dry film. The liquid time-to-fixation will increase with the increment of the abso-
menisci are pinned and play an important role in microstruc- lute amount of solvent. The term “bonding” is used to describe
ture evolution since the capillary forces work at the three-phase the process that affects the strength of adhesion of the coating
boundary. Film shrinkage will compete with pore disappear- to the substrate, which includes the wetting of the substrate
ance and the gas–liquid interface regresses from the pore until and thermal activation. The increased temperature leads to

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Figure 3. A summary of the latest three stages of drying mechanism. Reproduced with permission.[26] Copyright 2020, Wiley.

increased wetting since the surface tension is reduced, based phase of drying is much longer than the first phase and
on the Eötvös rules.[21] Thermal activation here describes the more complex.[16i,23a] Susarla et al.[16i] used a continuum-level
increased diffusion velocity and overcoming of activation mathematical model to describe the physical phenomenon of
energy along with the increased temperature. These two effects the cathode DP to study solvent removal during the second
boost the interactions between the binder and substrate. phase. The mathematical model also took into account mass
and heat transfer due to the phase change of the solvent.
The finding reveals that most of the solvent (≈90%) removal
2.5. Solvent Evaporation occurs in the first phase and this process is finished in
less than the half of the total drying period. Stein et al.[23a]
Solvent evaporation controls the different stages of the DP describe the two phases of drying subject to the thickness
and hence the morphology of the film. During the electrode, of the electrode coating. The first phase was described as
DP is generally classified into two phases according to sol- a linear process with a constant evaporation rate to form a
vent concentration, drying rate and moisture content.[16a,i,23] compact skeleton of the AM, such that the electrode dimen-
The first phase is a surface phenomenon as the solid particles sions at this stage have no significant difference to the final
are suspended in a pool of the solvent where the evaporation dimensions. The rest of the solvent occurs during the second
rate has the dominant contribution to the drying rate and phase of drying and the re-distribution of conductive additive
is constant until a porous structure is formed. The second and binder occur at this stage.

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2.6. Comprehensive Drying Mechanism remoistening of the cell components post-drying.[5d] For lab-
based electrode slurry drying, the conventional air-drying
Often the drying mechanisms use the same principals to method is to cast the slurry on the CC and dry in an ambient
describe the complete process rather than breaking it down environment or similar mild temperatures. Alternatively, high
into different mechanisms. In this respect, Westphal and throughput drying methods could revolutionize the LIB elec-
Kwade[21] summarized the DP, including the first drying stages trode manufacturing process. There is significant scope to
of film consolidation, and the second drying stage of pore emp- improve the process, and some examples of alternative methods
tying. The further solvent evaporation drives the re-distribution are suggested from the electrocatalyst as well as the battery
of active and inactive materials and forms a porous network of industry. Inert gas flow (for air sensitive materials) is for new
the coating. The following stage is the segregation that occurs battery materials such as the high nickel NMC, or the sulfide
by retreating of the liquid–gas interface in the network. The solid-state electrolyte are air sensitive. The materials react
narrow pores of the AM backbone and the retreating liquid– with the atmosphere, wither the water or the carbon-dioxide
gas interface may potentially impede the segregation. The last to form residuals on the surface and to degrade the materials.
stage is the inactive materials segregate toward the surface of Therefore, modifying the deposition and DP to remove these
the coating, leading to a depletion of inactive material at the contaminants may be required. The inert gas may quicken the
interface between the coating and substrate.[8,21] Font et al.[24] DP as the heavier gas displaces the solvent during drying.[27,28]
suggest a similar drying mechanism where the DP initiates Rotational drying can also speed up the manufacturing, but
with film shrinkage during which the solvent evaporates from is limited to electrodes of a particular size and shape, and as
the surface of the coating, causing shrinkage until the particles such is not currently possible with reel to reel coatings. A well-
of the AM contact each other and stop the coating thickness dispersed is loaded onto the electrode substrate on the inverted
from further reductions. The second stage is the pore emp- rotator, then rotated at speed until the film is completely dry.[27]
tying in which the residual solvent in the pores between AM Spray drying method can achieve high speed that has been
particles evaporates. Jaiser et al.[16e] developed a more detailed widely applied in many industries as a coating method, such as
model to describe the drying mechanism of the electrode based catalysts, drug carriers, sensors, electronic materials, and bat-
on previous work.[7a,25] As previous, the first stage of solvent tery electrodes.[29] Examples where this has been used are in
evaporation, driven by capillary forces, leads to film shrinkage silicone-based anodes,[29a] LiMn2O4 cathode,[29b] and Cu6Sn5/C
and consolidation. Once a solid film is formed from the solid composite powders.[29c] The residual water in the electrode can
interconnected particles, film shrinkage terminates. Further cause unwanted side reactions that influence cell performance.
evaporation of the solvent causes the liquid phase to recede into So, the second DP is essential for controlling the water level of
the porous electrode structure, with subsequent pore emptying. the manufactured electrode to less than 100 ppm. The cost of
All proposed drying descriptions suggest that the movements drying is significantly affected by the entire electrode manufac-
of the components in the solvent evaporation stage play a more turing process which could be reduced by attaching additional
important role in the formation of the electrode microstructure heating systems, such as IR, microwave, dielectric heating, and
compared to the pore-emptying stage.[16c,f ] laser drying.[3,30]

3. Parameters and Variables That Affect Battery 3.2. Drying Rate

Performance
Solvent evaporation in the industrial electrode DP involves
There are several parameters and factors that affect the quality a huge expenditure of energy that is a decisive cost factor for
of the electrode that impact upon the final battery performance, manufacturing battery electrodes.[9,16e,31] The drying rate is
e.g., the drying rate, binder types, temperature, drying proce- determined by the drying temperature and the air flow rate/
dures, and formulation. The effects of these factors are dis- velocity.[7a,16i] Typical drying rates in industrial coating processes
cussed in this section. are in the range of 25–50 m min−1. A fast drying time of 1–2 min
may be required in some particular cases. It should be noted
that the capital cost for industrial electrode coating is inversely
3.1. Drying Methodologies proportional to the drying rate.[16e] The optimized drying rate
during the electrode manufacturing process will promote the
As discussed previously, the drying and method of drying the balanced binder distribution of electrode film. However, the
inks and pastes is paramount for establishing the microstruc- higher drying rate will result in an uneven distribution of sol-
ture of the electrodes, cohesion of the film, and adhesion to uble and dispersed binder throughout the electrode, potentially
the CC.[3,19b] Prior to deposition, the components of the elec- accumulating at the surface.[8,16a–c] This binder migration can
trode slurry also require to be well dispersed, and the active also lead to electrode delamination,[7a,b,16c,g] due to the reduction
components stabilized within a binder and conductive additive in adhesion strength at the CC-electrode interface. In electrode
matrix, which translates into the electrode upon drying.[3] The suspensions with low solid loadings, the AM particles can move
most common electrode drying method at the industrial scale within the solvent for much longer and can collide and form
is to dry the electrode slurry by large belt dryers with infrared agglomerates due to cohesive interaction. Cohesive interaction
radiators or hot air fans which are installed in the coater and resulting from capillary pressure due to the surface tension of
where possible upstream of the dry-room. This is to avoid the liquid menisci between particles can cause the formation of

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cracks.[32] In the case of suspensions with a very low (10 wt%) during aqueous electrode processing. The water-based slurry
solid content, Scheepers et al.[32] found that the drying tempera- has excessive particle agglomeration, more hydroxyl groups on
ture has no significant effect on crack formation. the coating surface, and high surface tension compared with
High temperatures have been reported to potentially lead to NMP-based slurry.[11] The agglomerate formation for electrodes
greater binder migration, which can cause electrode delamina- prepared by an aqueous process is due to the weak van der
tion and result in a high resistance.[7a,b,16c,g] Electrode adhesion Waals attractions, or strong electrostatic interactions caused
is strongly dependent upon the drying temperature and that by surface charges.[13i,39] The strong hydrogen bonding and
higher temperatures result in lower adhesion strength between electrostatic forces promote agglomeration. Therefore, there
the copper CC and the coating layer, as shown for graphite and is a need to add extra dispersant to supply an electrostatic
LiFePO4-based electrodes.[7a,b,33] Greater segregation of inactive barrier.[6b] The inferior wetting of aqueous slurry on the CC
components is observed, which reduces the adhesion strength leads to high surface tension and lower adhesion strength that
and increases the electrical resistance and elasticity. However, can potentially reduce the cycle life of the cell.[6b,40] In addition,
the thickness of the coatings needs to be also considered, and the aqueous cathode slurry is basic, which could potentially cor-
in the case for graphite,[13] it was observed that the adhesion rode the aluminium CC, and can promote metal dissolution.
strength decreases as the drying temperature increases from Moreover, electrodes made from water-based solvents can lead
80 to 110 °C with mass loadings up to 8.1 g cm−2 and adhesion to more cracking without optimum drying protocols[11,40b,41] and
strength decreases when the mass loading is over 10.5 g cm−2. it has been reported that the challenges induced by aqueous
This could be explained as the shorter time-to-fixation is processing are more serious for slurries containing nickel-
indicative of faster polymer entanglement and subsequently rich AM.[42] Susarla et al.[16i] compared the energy demand for
less time for segregation. Adhesion strength was shown to be drying water-based solvent coatings and concluded that it is
independent of mass loading, although increasing the drying nearly ten times less than for organic-based solvent coatings.
temperature from 110 to 130 °C resulted in increasing segre- Li and Wang[16a] investigated binder concentration distribu-
gation. This situation is thought to be caused by the reduced tions in dried water-based (carboxymethyl cellulose, CMC)
time-to-fixation as the temperature increases with relatively and organic-based (PVDF) LiCoO2 electrode sheets and the
low mass loading. The situation for higher mass loading is the electrode properties in terms of physical, electrical, and elec-
opposite.[21] trochemical properties. The experimental results showed the
electrode made of organic-based binder had a nonuniform dis-
tribution of the electrode components, and to an extent worse
3.3. Binder Types than that for the electrode made of water-based binder. They
also predicated the binder distribution in the dried electrode
As mentioned previously, typical electrodes are manufactured based on theoretical calculations of migration-controlled drying
by applying a thin coating onto a CC, wherein the coating kinetics, indicating that the organic-based binder has higher
slurry is a mixture of AM, conductive carbon, binder, and nonuniform distributed electrode constituents compared with
solvent. The most widely used organic-based binder is PVDF the water-based electrode layer. This resulted in the electrode
and NMP.[7b,8,13b,f,16a] To effectively restrict the volume change, prepared with organic-based binder having weaker CC adhe-
a novel dual crosslinked binder has been synthesized from sion and higher electrical resistance.
crosslinking esterification reaction of poly(hydroxyethyl meth- Apart from the conventional electrode manufacturing pro-
acrylate) (PHM) and polyacrylic acid (PAA) to fabricate Si cess, a self-healing silicon microparticle anode for high-energy
anode. As one of the most widely used organic-based binder,[34] LIBs has been investigated,[43] which relies on the ability to
NMP is a costly solvent in the electrode manufacturing pro- repair damage spontaneously that is an important survival
cess and it is reprotoxic and treated as a restricted substance in feature in nature because it increases the lifetime of most
the EU.[35] Aqueous solutions/water-based binder could poten- living creatures. The authors highlighted this feature is highly
tially reduce the cost of electrode manufacturing and energy desirable for rechargeable batteries because the lifetime of
consumption.[9] Water-based processing has been commercial- high-capacity electrodes (e.g., silicon anodes) is shortened by
ized for graphite anode manufacturing[12] and researchers have mechanical fractures generated during the cycling process.[43]
extended the approach to the manufacture of cathodes.[36] The A novel water-based conductive binder PF-COONa is reported
coating manufacturing and capital cost on equipment for both by Liu et al.[44] for high-performance silicon anodes in LIBs,
water-based and NMP-based electrode drying has been calcu- which can form strong chemical bond with the Si particles
lated in $ kW h−1. The findings showed that the total costs for and ensures the electrode mechanical integrity and electronic
electrode manufacturing contribute to 8–9% of the total battery conductivity.
pack cost.[11] The authors estimated that a two-times reduction
of capital equipment cost could be expected in drying and sol-
vent recovery steps for using water-based solvent compared with 3.4. Thickness and Mass Loading
NNP-based solvent.[37] The solvent recovery step requires less
capital investment, and it is environmental friendly compared The formulation, mass, and mass balance of the electrodes
with the polymeric-based solvent recovery.[6b,11,38] However, directly relate to battery performance. The gravimetric and vol-
although there are advantages for using water-based solvents umetric energy density of LIBs can improve through improved
during electrode manufacturing, there are also disadvantages/ manufacturing factors, such as a reduction in the amount of
challenges related to process ability and cell p ­erformance inactive material, reduction of pore volume, thinner separator,

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less CC, and hence thicker electrode layers.[9,17g,45] For example variables are mainly based on the mechanism models which
with thicker electrode, the ratio of active component to CC is use the physical or chemical equations to describe the drying
higher, less electrode cutting is required and a lower number dynamics. Few attempts have been made to utilize interpretable
of electrodes in the stack which results in lower manufacturing machine-learning methodologies to analyze parameters for the
costs.[4] Another method of increasing the energy density is to electrode DP.
reduce the inactive components in the electrode formulation In order to improve the qualities of LIBs with high energy
(binder and conductive additive) in the electrode. The decrease density, a quality planning strategy to identify the interac-
of the active-to-inactive material ratio will lead to an increase tions between process and product along the whole battery
of electrical resistance and an optimum ratio is required for production chain was proposed by Westermeier et al.[48] Sev-
improved electrode and cell performance.[46] Westphal and eral active parameters/variables (temperature, number of
Kwade[21] found the resistance, adhesion strength and elas- heating cycles, etc.) and passive parameters/variables (mois-
ticity stay constant with an inactive material ratio higher than ture content, thickness difference, adhesion, etc.) from the
12 wt%. Zheng et al.[46] investigated the cooperation between DP were identified and analyzed based on the failure mode
AM, binder, and conductive carbon in a LIB cathode. The and affect the data analysis solution; then, drying parameters
authors reported the total inactive material amount and binder- with a significant effect on the cell quality could be chosen
to-conductive additive ratio significantly affect the porosity, con- for quantifications by experiments or data-driven models.
ductivity, specific capacity, first Coulombic efficiency, and rate With the rapid development of cloud-computing platforms
capability of the electrodes. However, Westphal and Kwade.[21] and artificial intelligence, data-driven solutions are becoming
found higher mass loading leads to greater segregation of inac- powerful tools to conduct sensitivity analyses of battery
tive materials within the electrode and poor adhesion, which production. Several studies have been carried out through
can be solved with lower drying temperatures. designing suitable data-driven models such as neural net-
works,[49] decision trees,[50] and support vector machines[51]
to predict and analyze the interdependencies of parameters
3.5. Modeling of Drying Parameters and Variables for battery manufacturing processes, such as mixing and
coating. However, to our best knowledge, no attempt has
As a consequence of the complexity of the DP, involving coupled been applied for parameter analysis of the DP. Note that the
mechanical and chemical mechanisms, numerous parameters DP will also generate numerous parameters and data, so
are variables, is required to describe the system, as discussed designing the effective data-driven models to analyze the cor-
in Sections 3.2–3.5. These parameters/variables play a direct relations and importance of drying parameters is a recom-
and vital role in affecting the properties of dried intermediate mended research direction.
products; which, in turn, further determine the properties of
final manufactured batteries.[26] Understanding the individual
or combined effects of these parameters/variables on the fin- 3.6. Coating Defects and Influences on the Electrode and
ished electrodes is of great importance to the optimization and Battery Performance
improvement of the dried intermediate product qualities. The
main approach to analyze interdependencies among the various Coating defects are caused by inhomogeneities in the ink, or
drying parameters and variables is still based on trial and error. due to the limitations between the coating and the DPs. Pin
In light of this, reliable and flexible models to achieve effective holes, cracks, delamination, and inhomogeneities can in gen-
analyses of drying parameters/variables and predict dried inter- eral be controlled by the speed of the coating and of drying.
mediate product properties are urgently required. Figure 4 shows the cause and effect for the different defects.
To date, several modeling techniques have been adopted to
perform analysis of different drying parameters/variables. To 1) Binder migration and delamination, can be controlled through
uncover how the DP affects the distributions and interactions of drying conditions (Figure 4c). High temperature leads to
components in the electrode composite, Liu and Mukherjee[20] binder migration to the surface of the electrode reducing ad-
proposed a mesoscale morphology model to analyze the particle hesion, and causing inhomogenous distribution of the bind-
morphology properties as well as solvent evaporation dynamics, er and delamination of the electrode.[8,24] The heterogenous
while their effects on the constituent phase distribution of distribution of binder will also affect the electrochemical per-
LIBs electrode were also explored. The results illustrate that formance, including the internal resistance and associated
better aggregation with conductive additive particles could be rate capability as the binder acts as a barrier for lithium-ion
obtained with smaller isometric active particles. Through con- insertion.[6b,16b,c,g,23a,52]
sidering more forces on the mesoscale particles, such as contact 2) Component segregation, Figure 4e. Component segregation of
friction and solvent-caused damping force, a dynamic particle the binder and conductive additive in an electrode leads to
packing model was proposed to forecast the microstructure of binder and CB concentrations that decrease from the top to
slurries and dried films.[47] As the DP can easily cause spatial the bottom of the coating.[21] The segregation increases as the
in-homogeneities within the electrode component distribu- drying temperature and the amount of solvent used increase.
tion, further leading to the reduced battery performance, Font CB was shown to be more concentrated at the top surface
et al.[24] constructed an electrode drying mathematical model region of the coating and decreases linearly from top to bot-
to predict and track the binder distribution evolution. Existing tom at a low drying rate.[16h] Component segregation reduces
modeling techniques for prediction of drying parameters/ the adhesion strength between the electrode coating and the

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Figure 4. Schematic diagrams of the electrodes with coating defects. a) Slurry phase of coating; b) components sedimentation; c) delamination of
coating from current collector; d) coating cracking and delamination; e) components segregation; f) desirable dried electrode coating with homog-
enous distribution of components.

CC/substrate, as well as inducing a substantial increase in greater cracking issues, particularly at faster drying rates.[26]
the electrical resistance and elasticity. Figure 4d is a model of cracking of the electrode coating.
3) Film shrinkage and cracking. Shrinkage of the electrode film
is normally caused by that solvent evaporation from the po- The parameters which influence the properties of the LIB
rous structure influences the evolution of the microstructure electrodes during the DP and the corresponding consequences
and re-distribution of the components, such as the binder.[16e] are summarized in Figure 5. During the DP, a series of param-
Shrinkage leads to drying stress development, consequent- eters affect electrode properties, including the drying rate,
ly causing coating cracking, curling, and delamination. binder types, and formulation. The drying rate is controlled
Water-based solvents and thicker electrodes tend to have by the temperature, pressure, radiation intensity, and airflow,

Figure 5. Summary of the parameters/variables which can affect the electrode formation during the DP and corresponding issues and consequences.

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depending on the type of drying method. The types of binder binder type, and formulation, as shown in Figure 5. To opti-
directly correlate with the drying time, as the slurry made mize the DP during electrode manufacture, all of the param-
from water-based binder would take a relatively shorter time eters should be considered.[16d,i] In order to control the DP,
to dry out the coating comparing with the slurry made from metrology measurements are needed to understand the effect
an organic-based binder. There are different defects generated of the input variables upon the outputs. Section 4 details the
by different drying conditions, such as binder migration of metrology tools currently available to study the electrodes in
the electrode coating, delamination of the coating layer from greater detail.
the CC, electrode film shrinkage, and the component segrega-
tion of the coating. Correspondingly, these defects will affect
the microstructure of the formed electrode, adhesion strength 4. Electrode Drying Metrology
between the electrode coating and the CC, cell capacity, resis-
tivity, and cycling performance. Various types of metrology have been applied in the DP to
The drying mechanisms during the DP are complex and study the drying mechanism, which are all based on different
the electrochemical performance of the formed electrodes are principles and have different resolutions as shown in Table 1.
dominated by different drying parameters, such as drying rate, These are very powerful techniques that have been applied to

Table 1. Summary of metrology applied in electrode drying process or emerging and potential metrology that can be applied in the LIB electrode
drying process.

Metrology Type Scale Environment Ex situ applications In situ applications

[70c,92]
AFM Scanning probe microscopy nm–µm Inert/ambient Surface morphology, roughness; Morphology[56b] and mechanical
Morphology,[56a,c] mechanical,[57] elec- property[56d]
trical,[58] functional properties[59]
Cantilever deflection Scanning probe microscopy µm or over 25 ± 1 °C and 20% of N/A Drying stress development[60]
method relative humidity
EDX Spectroscopy % Vacuum Element composition and distributio N/A
n[16f,23a,27,80a]
Fluorescence-based Microscopy mm Ambient Drying mechanism, liquid Microstructure change[16b]
imaging/microscopy distribution[16e]
MIP Quantitative nano Vacuum Pore size distribution[6b] N/A
[27]
Optical interferometric Optical metrology nm–cm Ambient Surface morphology and thickness N/A
profilometry
Raman spectrometer Quantitative µm Ambient SEI formation,[93] structural character- Binder distribution;[16c] phase transi-
ization of carbon materials[79a] tion and Lithium-ion intercalation into
graphite;[94,95]
SEM/TEM Electron microscopy nm–µm Vacuum Surface morphology and micro Cryo-SEM for microstructure
structure;[12,16a,f,23a,27,70c,80,96] CB evolution;[16b] structure and
distribution;[16h] particle and surface morphology[79,148,149]
morphology[78]
TGA/TG-MS Thermogravimetry µg Ambient/programmed N/A Drying rate, binder distribution[16a]
heating
X-ray CT/Radiography Tomographic nm–cm Ambient N/A Particle distributions[85]
XRD/SAXS/CV-SANS/ X-ray scattering nm Ambient Microstructure of the particles[70] Crystallographic evolution;[70a,71,72,97]
neutron CT structural change;[77] structure evalua-
tion,[78] electrolyte[98]
QCM Mass measuring metrology ng Ambient N/A BF4− intercalation into graphite;[97b] SEI
thickness and viscoelastic properties[99]
FTIR Spectroscopy % Ambient N/A SEI evolution and oxygen-containing
groups evolution[95,100]
IR Thermal imaging Thermography µm Ambient N/A Surface temperature[63e]
MSDWS Spectroscopy µm Ambient N/A Particles movement in colloidal slurry/
suspension[68a,b,d,69]
Ultrasound acoustic Acoustic metrology ns Ambient N/A Physical dynamics;[101] lithium plating
technique on anode;[102] electrodes lithiation and
delithiation[103]
XPS Spectroscopy ppm Vacuum Chemical composition;[70b,96,97] binder Chemical features (qualitative and
distribution[52a] quantitative)[56c]

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Figure 6. a) The reviewed metrology grouped by the capability of measuring the different key parameters during the electrode drying process. b) An
example of cathode characterized by X-ray CT and the resolved pores, NMC as active material (AM)) and the carbon binder domain (CBD). Reproduced
with permission.[55] Copyright 2020, Nature. c) Examples of micrograph of LIBs cathode dried at 120 °C scanned by a Zeiss EVO 10 scanning electron
microscope. d) An example of AFM analysis for NMC622 cathode coating dried at 100 °C. e) Raman spectra for a typical LIB cathode composite mate-
rial, NMC622, PVDF, and C65, recorded between 100 and 3500 cm−1 (514 nm) with a laser power of 10 mW. f) An example of interferometry result for the
surface roughness analysis of NMC622 coating which was dried at room temperature. g) An example of the surface temperature profile of a cathode
coating obtained by IR thermal camera. h) An example of in-line ultrasound acoustic measurement of cathode coating drying at 40 °C.

LIB electrodes DP. Some of them have been introduced in the also included in this section, as a guidance for the researchers
LIB electrode DP either as ex situ or in situ methods to inves- to find the most relevant and suitable method to assist the
tigate the electrode microstructure evolution or component research. These include in situ/operando characterization
distributions. methods to characterize LIBs in terms of electrochemical reac-
Although some of the metrology have been briefly reviewed tions and degradation mechanisms. A variety of spectroscopy
for characterizing the morphology of LIB electrodes after DP and microscopy techniques for elucidation of chemical and
ex situ,[53] as shown in Figure 6a. There are very limited details physical properties.[54]
about the existing metrology, such as capability of the methods
for carrying out in situ investigation, resolutions, and tar-
geting applications for investigation of LIB electrode DP. As 4.1. Metrology for Characterizing LIB Electrodes
listed in Table 1, we were not only summarizing the existing
metrology which have been used in the LIB electrode DP, but Most of the metrology measurements current are based upon
also including the emerging metrology that has potential to be ex situ measurements.
introduced in the DP to support the in-depth understanding of Atomic force microscopy (AFM) has been widely used as a
drying dynamics. tool to measure the surface roughness and morphology of coat-
The reviewed metrology is grouped according to its capa- ings (Figure 6d). Although highly sensitive, it is not expected
bility and types as shown in Table 1 and Figure 6a. The out- that AFM techniques can be integrated into drying metrology
look of each method for investigating the LIB electrode DP is measurements due to the high sensitivity of the machine to

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vibrations. Advanced AFM systems not only probing surface X-ray diffraction (XRD) is a powerful technique to charac-
properties such as morphology,[56] but also mechanical (e.g., terize the crystallinity of materials and it has been widely used
elastic modulus),[57] electrical (e.g., conductivity, permittivity),[58] to characterize electrode materials.[70–72] Conventional synchro-
functional properties[59] (e.g., piezoelectric response), etc.[56a] tron or neutron scattering can obtain information for the non-
Cantilever deflection is an in situ method which could offer equilibrium phase behavior of colloids that the synchrotron
improved quality control upon coatings and DPs.[60] Here, beams are horizontally emitted from the source.[73] There are
stress development of the electrode during drying can be limited applications of using conventional synchrotron or neu-
measured, using a cantilever, laser, position sensing detector, tron scattering in colloidal suspension DP which is intrinsically
and data recording system.[61] This is significantly larger scale settled horizontally to the ground due to the gravity, such as
(microscale depending on the size of the laser spot) compared spry DP,[74] sessile drops,[25] or dip coating.[75] Synchrotron X-ray
to AFM (nanoscale or microscale). beams have been used to vertically pass through thin films to
Interferometry has the highest sensitivity among several phase- probe the structural change of colloidal suspensions, which
sensitive methods which is a powerful tool for nondestructive 3D requires special design of the setup.[76]
observations. It can measure surface roughness and thickness Vertical small-angle X-ray scattering (SAXS) has been devel-
and quantitatively visualize the salt concentration distributions oped as an in situ tool to investigate drying behavior of charge-
that arise in electrolytes during battery operation.[62] Figure 6f is stabilized colloidal silica.[77] It has been reported that the
an example of interferometry result for the surface roughness solidification of the colloidal particles perform ordering at the
and defect analysis of cathode coating which was dried at room beginning stage of the drying, and then followed by an imme-
temperature. As a technique with fast data acquisition ability, diate aggregation which was driven by capillary pressure and
interferometer could be further applied as an in situ method to thermal motion of the particles. The further application of
investigate the surface evolution of the LIB electrode during DP. this metrology has been extended to fuel cell electrode related
Infrared (IR) thermal imaging as a temperature mapping study. Kusano et al.[78] used contrast-variation small-angle neu-
method has been used to study operational LIBs.[63] The IR tron scattering (CV-SANS) to perform a structural evaluation of
thermal images can be obtained with a noncontact IR thermal a catalyst ink for polymer electrode fuel cell electrodes during
camera to detect the thermal radiation and convert it to elec- the DP. This technique shows the great potential to investigate
trical signals for processing thermal images or videos.[64] the structural change of the crystallographic compositions in a
Although the IR thermal imaging results could be affected nanoscale resolution during LIB electrodes during DP.
by the radiation from object, atmosphere, and surrounding Raman spectroscopy has been used to quantitatively analyze
object,[65] this may be resolved by altering the position of the IR the binder distribution in LIB anodes during the freeze–drying
camera by 45°.[66] It has been reported that thermal sensitivities process.[16c] The coating was taken out of the drying oven at
of 0.03–0.09 °C within the temperature range of 0–120 °C could different drying stages for freeze–drying, and subsequently
be achieved,[63b,d] and the spatial resolutions of 0.1–0.3 mm underwent Raman analysis to quantify the binder concen-
could be attained.[63f,67] Figure 6g is an example of the surface tration through the cross-sections of the coating. Drying at
temperature profile of a cathode coating obtained by IR thermal 150 °C resulted in a higher concentration of the binder
camera, which could be used to learn about solvent evaporation at the surface of the coating compared with that at room
and surface temperature variation. temperature.[16c] Applications of Raman technique have been
Mercury intrusion porosimetry (MIP) has been used to reviewed in more detail.[79] The spatial resolution of Raman
measure the pore size distribution of the dried anode film. This spectrometers coupled with an optical microscope can approach
is a quantitative technique which is capable of analyzing a large microscale. Figure 6e demonstrates the Raman spectra for typ-
volume (marco or over) of the LIB electrode to obtain a more ical LIB cathode composite materials, NMC622, PVDF, and C65,
representative porous structure in both nano- and microscale which proves the capability to study binder distribution for both
resolutions. LIBs cathode and anode.
Light-based methods are difficult to use in black slurries, as Scanning electron microscopy (SEM) with associated add-
the light waves are absorbed by the slurry components. But can ons is a powerful technique which has been widely applied to
be used for polymeric coatings. Multi-speckle diffusion wave characterize the electrode, especially for the microstructure
spectroscopy (MSDWS) is a technique based on light scattering of the electrode materials and distribution of the elements in
which has been developed to study colloidal material proper- the different components, as shown in Figure 6c.[16a,f,23a,27,70c,80]
ties during DP by measuring the size, molecular weight, and Li and Wang[16a] used SEM to characterize the microstructure
relaxation of the particles.[68,69] Fluorescence-based imaging/ of graphite electrodes, and map the binder concentration dis-
microscopy has been used to image the latex particle migration tribution in electrodes formed from different types of binders
within graphite electrode slurry during the DP,[16b] this demon- (water-based and organic-based). Stein et al.[23a] used SEM with
strated the vertical particle distribution of the coating through energy-dispersive X-ray spectroscopy (SEM-EDX) to analyze
the characterization of the fluorescent light intensity. Jaiser the microstructure of electrodes by scanning their top and the
et al.[16e] further developed the electrode drying mechanism bottom to study the mechanism of the DP due to solvent evapo-
model of electrode coating by imaging the fluorescent light of ration. Transmission electron microscopy (TEM) can inves-
the coating at different drying times with a single-lens reflex tigate structural and compositional information with atomic
camera equipped with a macro object lens. This could be fur- resolution.[81] Kusano et al.[78] used TEM micrographs to sup-
ther developed to incorporate with more advanced metrology to port their assumption that there is significant structural change
able acquiring more dynamic information simultaneously. of electrodes during the DP, especially cracking.

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The energy-selective back (ESB) detector is able to identify the ­ icrostructure of electrodes is important for understanding the
m
light elements but also the same element with different phases, structural heterogeneity and its corresponding effects on battery
especially for carbons, such as graphite, diamond, and amor- performance. X-ray CT has been applied in situ to determine
phous carbon.[82] The further application of this detector was the microstructure evolution during battery degradation.[55,63e,89]
investigated by Pfaffmann et al.,[16h] they introduced a novel As the porosity of LIB electrode is normally formed during the
technique to enhance the contrast of fluorine-rich regions by drying stage during solvent removal. X-ray CT has great poten-
using the ESB detector to easily distinguish the CB in graphite tial to study the porosity evolution during the DP.
electrodes. The authors then use this technique to investigate High-throughput X-ray CT can indirectly track the lithium dif-
the CB distributions in cross-sections of graphite electrodes to fusion during the degradation process and the neutron CT can
find out the influences of the drying temperature on the CB directly identify lithium diffusion during electrode wetting by
distributions during electrode DP.[52a] an electrolyte.[90] Lu et al.[55] have developed a full microstruc-
Thermogravimetric analysis (TGA) can be used to quantify ture-resolved 3D model based on an X-ray nano CT dual-scan
the areal distribution of binder residue in the manufactured superimposition technique to accurately correlate the micro-
electrodes made of different binders (organic-based and water- structure and performance, which can be used to investigate
based) through selective analysis of different parts of the the microstructure evolution, porosity, and tortuosity as shown
electrode.[16a] TGA is the most simplest and easy access technique in Figure 6b, which could also assist electrode manufacturing
to study the thermal dynamic change of LIB electrode slurry monitoring and control. Dynamic lithium distribution upon
according to the different thermal stability of the composition. dendrite growth and shorting revealed by operando neutron
Quartz crystal microbalance (QCM) is one of the common imaging has been studied,[91] to observe the dynamic distribution
bulk acoustic wave sensors capable of monitoring mass change of Li flowing from the anode to cathode during charge which is
with nanogram resolution. The oscillating frequency shift can be induced by the internal short circuit due to Li dendrite growth.
converted to mass change on the sensor surface using the Sau-
erbrey equation.[83] As a sensitive mass sensing metrology, there
is potential to apply QCM in the LIB electrode DP to monitor 4.2. Summary of Electrode Metrology
the solvent evaporation in a nanoscale resolution to correlate it
with the microstructural evolution or fluid dynamics during DP. Various techniques have been used to characterize electrodes
Ultrasound acoustic-based technique has been widely applied and investigate the influence of DP (to LIB electrodes DP or
as a battery diagnostic tool to study the battery during opera- electrochemical power source electrode systems or other sim-
tion. The application of ultrasound acoustic technique provides ilar viscoelastic slurry DP) on their properties. Some of the
the potential to further apply in LIB electrode DP for drying techniques are ex situ methods, the measurement made after
dynamic studies, as the most dominant change during DP is drying, such as AFM, fluorescence-based imaging/micro­
physical change such as the solvent evaporation, density and scopy, optical interferometry, SEM, TEM, EDX, XRD, and
porosity of the electrode coating, etc. Figure 6h is an example MIP.[6b,16a,e,f,23a,27,70c,78,80,92] Some of the techniques have been
of in situ ultrasound acoustic measurement of cathode coating successfully used as in situ methods to study the evolution
drying at 40 °C, which the time-of-flight change corresponds to of the electrode during DP in terms of binder and particle
the physical properties change of the electrode slurry coating. distributions, microstructure, drying rate, and drying stress
The technique is scalable and simple and has significant development.[16a–c,h,60,78,85] The techniques used for ex situ anal-
potential for future applications as an in situ method for LIB ysis of the electrode after drying are typically used to investigate
electrode drying dynamic study as recently demonstrated.[84] the macrostructure and microstructure of the electrode. Table 1
X-ray photoelectron spectroscopy (XPS) is a powerful surface is a summary of the reviewed metrology which either applied
chemistry characterization technique, which can quantify the in electrode DP, or emerging and potential metrology that can
surface elemental compositions of coatings with a depth of be applied in the LIB electrode DP. Each of the technique may
≈5 nm.[52a,70b] Zang et al.[52a] studied the migration of styrene only be suitable for one electrode or both, depending on the
butadiene latex during the drying of coating suspensions using individual equipment running environment and feasibility of
XPS. the experimental setup.
X-ray radiography has been used to study the dynamic drying Possible advanced metrology tools which could be applied
behavior of electrode slurries consisting of SiOx, CB, and to the DP are QCM, IR-imaging, X-ray CT, Raman, and ultra-
CMC in a water-based binder solution.[85] The authors took a sound. QCM could be used to support the investigation of
horizontal slice of the radiograph through the base of a volume ­solvent evaporation rate during LIB electrode DP in a nanoreso-
reconstruction of a dried drop consisting of SiOx and SUPER lution. IR thermal imaging allows the investigation of surface
C45 in a solution of CMC and deionized water. A series of X-ray temperature changes to help optimize heat pulsing effects and
radiographs were taken during the electrode slurry DP for cal- process temperature. MSDWS could be used to monitor par-
culating the spatial distribution of AM. Nonuniform distribu- ticle movement in electrode slurry. X-ray CT is capable for char-
tion of active particles formed very quickly, and heating could acterizing 3D microstructure evolution. Raman spectroscopy
boost the uniformity of active particles distribution in the early could help to identify binder distribution throughout the elec-
stage of slurry drying. trode coating as an in situ method with further development.
Different scales of X-ray computed tomography (X-ray CT) Ultrasound acoustic technique may be able to acquire physical
have been applied extensively to characterize the microstruc- dynamics of the electrode for a long period, as the signal
ture of the electrodes after drying.[45,86–88] Mapping the 3D responses are very quick.

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5. Challenges and Future Perspectives diffusion of the gases was modeled according to Fick’s law. The
transport equations were coupled to an equation for the con-
5.1. Drying Mechanism Models and Insights servation of energy. The solvent evaporation rate was expressed
as a function of saturation, temperature, and porosity. The cap-
In the field of electrode drying, continuum-level mathemat- illary pressure also depended on temperature via the surface
ical modeling can test hypotheses and identify the key phys- tension.[16i] However, notably, this work does not consider the
ical mechanisms that influence the DP and the quality of the process of binder migration and so conclusions drawn from
final electrode. The goal is to establish a model that accurately this model are unable to take into account or explain the influ-
describes how properties of the slurry and drying conditions ence of binder migration on film properties, such as adhesion.
control each part of the DP. Once such a model has been estab- A summary of the latest three-stage drying mechanism is
lished, the ultimate aim is to provide a fast and reliable method illustrated in Figure 3. Here, two 1D, continuum-level models of
to predict the optimal drying conditions for different types of the DP are compared.[24] Each of these models is valid only for
electrode slurry. part of the DP (either the initial film shrinkage stage or the sub-
From previous work as discussed above in Section 2 and sequent pore emptying stage) and involves a subset of the phys-
Figure 3, it is known that the drying mechanism follow sev- ical mechanisms that have been shown to play an important
eral stages. Each of these stages can be modeled, and measure- role in the dynamics of electrode drying. As a result of these
ments based upon the metrology for in situ drying can be used limitations, neither model can wholly explain the experimental
to parameterize these models. evidence for a three-part DP presented in ref. [16d]. The optimal
drying strategies proposed by Susarla et al.[16i] and Font et al.[24]
1) As the solvent at the surface evaporates, more solvent is trans- appear not to be consistent as the first suggests increasing,
ported upward toward the surface. The removal of solvent while the second suggests decreasing, the drying rate during
from between the AM particles causes them to consolidate. a multi-stage DP. However, the conclusions from the work of
2) The final aspects of stage one are when the pore volume be- Susarla et al.[16i] are drawn only from a model of the pore emp-
gins to empty. This is observed from a change in the film tying stages of drying, while those of Font et al.[24] apply only
surface. Often the end of stage one is where any film shrink- to the initial film shrinkage stage. Therefore, these conclusions
age stops, however in some cases further consolidation par- are not necessarily contradictory and each may explain part of
ticularly for small particles sizes occurs until the solvent in the proposed three-stage optimal drying protocol.[16d]
surface porosity is also removed. However, neither of these existing models[16i,24] can be relied
3) After the pore empties, a second constant rate solvent evapo- upon to predict the whole optimal LIB electrode DP. The three-
ration is observed, with transport toward the surface via cap- stage procedure determined in the experimental study man-
illary action. Large pores therefore empty preferentially to ages to reduce the total drying time while maintaining good
smaller pores. mechanical properties in the final dry electrode coating (in par-
4) Finally, the remaining solvent evaporates and is transported ticular adhesion between the electrode film and CC), thereby
in the gaseous phase through the electrode microstructure increasing the efficiency of the drying step.[16d] There is a need
to the surface. This drying phase can be faster and does not to create a more comprehensive and more reliable model to
result in any particle or binder movement. understand the electrode drying mechanism, therefore to predi-
cate the optimal drying protocol for different compositions and
Cardinal et al.[104] proposed a 1D model that included formulations for LIB manufacturing.
Brownian diffusion, sedimentation, and evaporation to study In summary, the key mechanisms to consider in models of
the drying of a model system comprised of monodisperse LIB electrode drying are the consolidation of the active parti-
silica particles in water. Buss et al.[80d] proposed a 1D model cles, the convection/evaporation of the solvent, the advection
for the transient concentration profiles of particles and soluble and diffusion of inactive material (both the binder and con-
polymer in a drying suspension, that involved sedimentation, ductive additives), and the development of stress/cracking. In
evaporation, and diffusion. They studied a model system of contrast to the drying of other particulate coatings, the process
poly(vinyl alcohol) (PVA), silica particles, and water. Routh and of sedimentation appears to have a negligible effect on elec-
Zimmerman[105] derived a governing equation for the evolution trode drying performed at industrially relevant drying rates.
of particle volume fraction. They obtained numerical solutions Therefore, knowledge of the electrode structure, solid content,
for various Peclet numbers and an asymptotic solution for large pore size (solvent content) can be applied to estimate transport
Peclet numbers. speeds and mechanisms. For example, capillary transport can
Recently, Susarla et al.[16i] proposed a 1D model for sol- be expressed by Darcy’s law (permeability multiplied by the gra-
vent removal during the electrode DP has been discussed in dient of capillary pressure).[107] A review of past and remaining
Section 2. They used an established volume-averaging tech- challenges in pore network modeling in drying technology is
nique proposed by Whitaker[106] to develop a macroscopic presented by Metzger.[108] Many other industries also require
model. The porous structure formed from the AM is assumed insight into dehydration of porous materials, and a comprehen-
to be in a continuum and each dependent variable is averaged sive review is available for food.[109] This highlights that many
over a small representative volume. The model variables were of techniques and methods are applicable to electrode manu-
temperature, partial pressure of vapor, and liquid saturation of facturing and there are significant opportunities to translate
the pore network. Convective transport of the liquid solvent, gas- methodologies from other industrial practices. There are many
phase solvent, and air was modeled via Darcy’s equation, while opportunities for improved control and monitoring of this

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Figure 7. A summary of techniques that are used to study the electrode DP and the potential techniques that could be introduced to study the process.

DP. Models can incorporate measured parameters to provide or drying stress development, however the drying dynamic
insight in real time changes in the process. One example to information acquired is very limited due to limitations of the
improve the DP would be to control the initial DP through sol- different techniques.[16a–c,h,60,78,85] Figure 6 and Figure 7 sum-
vent transport in the electrode through lower solvent contents marize the techniques that have been used to study electrode
in the slurry and monitoring the process through in situ meas- DP and the prospective techniques that could be introduced in
urements—optimizing the drying temperatures and air flow. the DP to study drying dynamics. As summarized in Figure 5,
Then hasten the process in the final stage with a fast drying there are various parameters/variables during the DP that can
method (IR-drying, e.g.) to remove the final solvent in the vapor lead to different defects of the final electrodes to subsequently
phase. Often the metrology is not used during the DP due to affect the cell performance. Therefore, the early-stage charac-
the difficulties in incorporating these tools into the drying area. terizations of the electrode post-drying could be indicative of
Significant opportunities are around the integration of meas- the final cell performance. Figure 6a illustrates the reviewed
urement techniques, particularly to measure film thickness, metrology grouped by the capability of measuring the different
coat weight, and also incorporate optical techniques into the key parameters (solvent evaporation/drying rate; film thick-
drying area to monitor and control the DP. ness/morphology/structure; components distributions/surface
temperature) during the electrode DP. The drying dynamics
of wet electrode slurry coatings are complex and still poorly
5.2. Discussions and Perspectives of Electrode understood. Ex situ metrology does not provide real time data,
Drying Metrology and significant opportunities are available to expand current in
situ monitoring. There is an emerging need to introduce and
There are three primary methods that have been used to study develop more advanced metrology techniques to study the DP.
the electrode DP.[6b] Electrochemical performance of the elec- The in-depth understanding of the effects of drying para­
trodes which has the benefit of directly correlating the drying meters/variables on electrode formation by directly observing
parameters with electrochemical performance of LIBs. How- the DP will not only help understand the mechanism of the
ever, it is not a way to guide the manufacture to optimize the DP, but also contribute to the next generation of electrode
DP with an understanding of the drying mechanism. Experi- design for LIBs to achieve the electrode quality control in the
mental studies using different metrology/characterization tech- early stage of LIB manufacturing.
niques, as discussed in Section 5, or computer simulations,
which require preliminary experimental results. Simulations
and modeling are a faster way to evaluate the drying scenario 6. Conclusion
and provide insight into the DP.[16i] Parameters such as col-
loidal stability, heat, and mass transfer coefficients can provide In this review, the DP of Li-ion battery electrodes has been
useful data for the early stage of electrode manufacturing.[20,47] considered and the effect of different parameters/variables on
Current in situ characterization examples include microstruc- the architecture and properties of resultant electrodes were
ture evolution, drying rate, binder and particles distribution, discussed. A critical review of different drying mechanisms

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Ye Shui Zhang is a Faraday Institution Research Fellow at University College London, UK since
January 2018 and has been appointed as a lecturer in Chemical Engineering at University of
Aberdeen, UK in Dec 2021. She has completed her B.Sc. from University of Birmingham in 2012
and M.Sc. (Engineering) from The University of Sheffield in 2013. She finished her Ph.D. in
September 2017 at University of Leeds. Her research interests cover broad area of chemical engi-
neering, including energy storage materials, lithium-ion battery manufacturing, pyrolysis-catalysis
of waste, high-temperature quartz crystal microbalance, carbon nanotubes synthesis, and circular
economy of plastics.

Emma Kendrick is a professor of Energy Materials. Kendrick has worked in industry and aca-
demic extensively on energy materials and devices; batteries and fuel cells, and has 70 papers
and 21 patent family applications in this field. Her recent book chapter on Advanced Battery
manufacturing is being published by the RSC. Her research over the last 20 years has focused on
translation of novel functional materials to industry relevant device demonstrators, new battery
materials, and chemistries to cell demonstrators. Her enthusiasm for new technology develop-
ment, mainly batteries, extends to the industrial and academic fields.

Dan J. L. Brett is a professor of Electrochemical Engineering at University College London. His

research is in the area of electrochemical engineering and technology. This includes electro-
chemical energy conversion and storage (fuel cells, batteries, supercapacitors, electrolyzers),
electrochemical sensors, electroanalysis, hybrid vehicles, and microgeneration technologies. He
specializes in developing novel diagnostic techniques for the study of high- and low-temperature
fuel cells and their materials.

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