Particuology 57 (2021) 56–71

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Particuology
journal homepage: www.elsevier.com/locate/partic

Invited review

Advanced electrode processing of lithium ion batteries: A review of

powder technology in battery fabrication
He Liu a,b , Xinbing Cheng c , Yan Chong c , Hong Yuan a,b , Jia-Qi Huang a,b,∗ , Qiang Zhang c,∗
a
School of Materials Science & Engineering, Beijing Institute of Technology, Beijing 100081, China
b
Advanced Research Institute of Multidisciplinary Science, Beijing Institute of Technology, Beijing 100081, China
c
Beijing Key Laboratory of Green Chemical Reaction Engineering and Technology, Department of Chemical Engineering, Tsinghua University, Beijing
100084, China

a r t i c l e i n f o a b s t r a c t

Article history: Lithium ion batteries have achieved extensive applications in portable electronics and recently in elec-
Received 4 October 2020 tronic vehicles since its commercialization in 1990s. The vast applications of lithium ion batteries are not
Received in revised form only derived from the innovation in electrochemistry based on emerging energy materials and chem-
16 December 2020
ical engineering science, but also the technological advances in the powder technologies for electrode
Accepted 17 December 2020
processing and cell fabrication. Revealing the effects of powder technology on electrode microstruc-
Available online 12 January 2021
ture evolution during electrode processing is with critical value to realize the superior electrochemical
performance. This review presents the progress in understanding the basic principles of the materials
Keywords:
Lithium ion batteries
processing technologies for electrodes in lithium ion batteries. The impacts of slurry mixing and coating,
Composite electrode processing electrode drying, and calendering on the electrode characteristics and electrochemical performance are
Powder technology comprehensively analyzed. Conclusion and outlook are drawn to shed fresh lights on the further devel-
Slurry coating and drying opment of efficient lithium ion batteries by advancing powder technologies and related advanced energy
Electrode calendering materials.
© 2021 Chinese Society of Particuology and Institute of Process Engineering, Chinese Academy of
Sciences. Published by Elsevier B.V. This is an open access article under the CC BY license (http://
creativecommons.org/licenses/by/4.0/).

Introduction to LiNi1−x−y Cox Mny O2 (x = 1/3, y = 1/3: NCM111; x = 0.3, y = 0.2:

The rechargeable batteries have achieved practical applications
in mobile electrical devices, electric vehicles, as well as grid-scale
stationary storage (Jiang, Cheng, Peng, Huang, & Zhang, 2019; Wang
et al., 2020b). Among various kinds of batteries, lithium ion bat-
teries (LIBs) with simultaneously large energy/power density, high
energy efficiency, and effective energy retention rate after long-
term cycles are considered as the best-performing energy storage
systems, especially for the recently emerging electric vehicles (Cai
et al., 2020; Tian et al., 2019; Wang et al., 2019a).
Since Sony Corporation manufactured the first-generation com-
mercial LIBs in 1990s, extensive efforts have been devoted to
boost the battery cycling performance mainly on the innovation in
materials electrochemistry and processing technology (Armand &
Tarascon, 2008; Liang et al., 2019; Liu et al., 2020a). Great progress
has been achieved in materials innovations from LiFePO4 , LiCoO2 ,
∗ Corresponding authors.
E-mail addresses: jqhuang@bit.edu.cn (J.-Q. Huang),
zhang-qiang@mails.tsinghua.edu.cn (Q. Zhang).
NCM532; x = 0.2, y = 0.2: NCM622; x = 0.1, y = 0.1: NCM811) for the
cathode, graphite to silicon/graphite hybrid for the anode, liquid
non-aqueous electrolyte to the solid-state electrolyte (Hao, Yang,
Luo, Tian, & Shan, 2018; Lu et al., 2020; Ou, Zou, Jin, Wu, & Wang,
2020). The mixing state and microstructures of cathode, anode,
binder, and conductive particles are highly dependent on powder
technology in the battery manufacture processing (Li & Taniguchi,
2019; Liu et al., 2019a; Liu et al., 2020b). This is a very impor-
tant factor to determine the cycling performance of the electrodes.
More efforts are requisite to optimize the powder processing dur-
ing electrode fabrication and to reveal the relationship between
the processing condition and the microstructures of the electrodes
as well as the battery performance (Kwade et al., 2018). Advanced
electrode processing technology can enhance the cyclability of bat-
teries, cut the costs (Wood, Li, & Daniel, 2015), and alleviate the
hazards on environment during manufacturing LIBs at a large scale
(Liu et al., 2020c; Wood et al., 2020a; Zhao, Li, Liu, Huang, & Zhang,
2019).
The fabrication of commercial LIBs includes electrode manufac-
turing, cell assembly, formation and inspection (Scheme 1). The
electrodes can be obtained via slurry mixing and coating, dry-

https://doi.org/10.1016/j.partic.2020.12.003
1674-2001/© 2021 Chinese Society of Particuology and Institute of Process Engineering, Chinese Academy of Sciences. Published by Elsevier B.V. This is an open access article
under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
H. Liu et al. Particuology 57 (2021) 56–71

Scheme 1. The fabrication process of commercial LIBs, in which powder issues involved in the electrode manufacturing process are highlighted in this review.

ing, and calendering. Afterwards, the cell is assembled through

electrode and separator slitting, winding, electrolyte filling, and
packaging. The remaining stages are cell formation and quality
check (Hawley & Li, 2019a). Among them, electrode manufacturing
involves particle technology issues and electrode microstructure
evolution, which can significantly determine the electrochemical
performances (Daniel & Besenhard, 2012; Li, Daniel, & Wood, 2011).
Therefore, electrode fabrication process is emphasized in the fol-
lowing discussions with focus on the powder technologies.
Typically, four main steps are involved for electrode process-
ing of commercial LIBs, including slurry mixing, coating, electrode
drying, and calendering. Firstly, the dry electrode components
(active materials, conductive agents, and binders) are mixed with
solvents to obtain a liquid slurry with uniformly distributed par-
ticles (Väyrynen & Salminen, 2012). Then the obtained liquid
slurries are coated on metallic foil current collectors and smoothed
to be uniform electrode films. The as-obtained films are subse-
quently heated to adequately remove solvent out of electrode
films. Finally, the film is compressed by two metal rollers to a
proper thickness with superior and uniform porosity. During these
steps, the distributions of active materials, ionic and electronic
agents are determined by the powder technology with many oper-
ation parameters, including the ingredient and features of raw
materials (active and electronically conductive particles, binders,
and solvents), composition ratio, mixing steps, coating procedure
(thickness and rate), temperature program of drying electrode
films, and degree for calendering electrodes (Baunach et al., 2016,
Hawley & Li, 2019b, Jeon, Biswas, Patton, & Wujcik, 2020). The ratio-
nal optimization of these parameters can be realized by deeply
Fig. 1. The schematic to illustrate the connection of two spherical solid particles in
understanding the correlation among the materials processing,
the liquid slurry (Bitsch et al., 2014).
electrode microstructures, and battery performance. It is believed
that intelligent modifications to the powder technologies can effec-
tively extend the lifespan of batteries even with similar electrode Slurry preparation
components.
In this review, we summarize the recent progress in the Liquid slurry is the most frequently used platform to fabri-
materials processing technologies of LIBs with focus on pow- cate the electrode materials mainly owing to its low cost and
der technology to achieve better electrode microstructures and high processibility (Väyrynen & Salminen, 2012). The formulation
enhanced electrochemical performances at a cell scale. The review and properties of electrode slurries determine the quality of the
is organized in the order of electrode manufacturing procedure. resulted electrode film. A uniform electrode film can be achieved
In slurry preparation part, the features of raw materials, mix- only when the electrode slurry is stable with a low extent of
ing sequence and procedure, and solid content of dispersions agglomeration and sedimentation. The connection and interactions
are discussed. Some aqueous systems are also discussed con- between the solid particles and solvents as well as inside the solid
sidering their features of cost effectiveness and environmental particles can strongly affect the slurry features, such as viscosity
benignity. Later, the impacts of coating and drying methods on and sedimentation stability, etc. Capillary forces can regulate the
electrode microstructure and electrochemical performance are formation and determine the strength of the interactions among
discussed. The relations between calendering parameters and elec- solid particles (Fig. 1) (Bitsch et al., 2014). The dispersibility of
trode thickness, porosity, density, and active surface area are also solid particles can be characterized by the three-phase contact
included. Finally, the emerging challenges for future development angle (QS,B ), which is defined as the angle between the secondary
of advanced electrodes of LIBs are explored, especially from the phase (S, herein refered as the liquid phase) and the surface of solid
perspective of powder technologies. particles surrounded by the bulk solvents (B). Two general circum-

57
H. Liu et al.
stances can be classified by QS,B : if QS,B > 90◦ , the secondary phase
cannot effciently wet the solid particles, leading to the formation of
droplets; If QS,B < 90◦ , the secondary phase can effectively wet the
surface of solid particles, rendering the formation of liquid bridges
between solid particles. The corresponding network structure of
the slurry is defined as pendular states, which is preferable for the
well-dispersed slurry. Thus, it is important to figure out the rela-
tionship between the solid particles and solvents in the electrode
slurries.
Non-aqueous system
The solvents adopted for electrode fabrication can be organic
solvent-based (non-aqueous) or water-based (aqueous) systems
(Yan et al., 2018). Actually, organic solvents systems rather than the
water-based ones are frequently adopted due to the high reactivity
with active materials and agglomeration tendency of water-based
systems. Additionally, all water must be completely removed from
the electrode materials after the drying process considering the
highly reactive nature and narrow voltage window of water, lead-
ing to a rigid requirement of water contents (below 10–20 ppm) for
working Li ion batteries (Chen, Li, Shen, & Zhang, 2018; Xiao et al.,
2020b).
In the typical non-aqueous systems, N-methyl-2-pyrrolidone
(NMP) is extensively utilized as the solvent to obtain a stable slurry
of active materials with polyvinylidene fluoride (PVDF) and carbon
as the binder and conductive agent, respectively. Variations in each
component and their properties, including the particle size, specific
surface area, and electronic/ionic conductivity severely determine
the rheological properties, stability, and dielectric characteristics
of resulted dispersions (Kanhere et al., 2019; Wang, Zhao, & Takei,
2019). Small particle sizes result in low porosities, but lead to a high
stiffness of the electrode film (Mayer et al., 2020). Electrode parti-
cles with nanometer size exhibit obvious advantages in improving
the performance of LIBs (Guo, Hu, & Wan, 2008; Zhang, Cheng, &
Zhang, 2016). Nanometer-sized electrode materials present bet-
ter kinetics for ion and electron transport due to the dramatically
shortened diffusion pathway and fast diffusion rates along the
largely existing grain boundaries (Okubo et al., 2007). The larger
surface area of nanomaterials also contributes to the high-rate
capacity of LIBs due to the greatly reduced specific current density
of the active material. Additionally, the nanoparticles can quickly
absorb and store large amounts of lithium ions without deteriorat-
ing the electrode (Chan et al., 2008). Nevertheless, nanoparticles
with high surface areas also risk severe parasitic reactions with
electrolytes, pronounced agglomeration, and low packing density,
leading to a low initial Columbic efficiency, large contact resistance,
and poor volumetric energy density of electrodes (Pomerantseva,
Bonaccorso, Feng, Cui, & Gogotsi, 2019). Therefore, the influence
of particle size on electrode performance is much complicated
depending on the type of active materials and processing parame-
ters (Li et al., 2011).
Besides the features of raw materials, the flow behavior of the
electrode slurry is greatly determined by the mixing sequence
and procedure (Wenzel, Nirschl, & Nötzel, 2015). Mixing sequence,
namely the order of introducing the mixed materials into the slurry,
also has large impacts on the features of slurry and the electro-
chemical performance of as-obtained electrodes (Bauer & Nötzel,
2014; Bockholt, Haselrieder, & Kwade, 2016; Kuratani et al., 2019;
Westphal et al., 2017). Kim et al. reported that the highest dis-
charging capacity and cycling stability can be achieved by firstly
dry mixing LiCoO2 (LCO) and carbon black (CB) and subsequently
adding PVDF solution in NMP to form a slurry (Kim, Jeon, Chung,
& Chang, 1999). However, some other researchers declared that
the dry mixing process of active materials and conductive agents
before adding binder solution can reduce the slurry viscosity and
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Particuology 57 (2021) 56–71
stability, and the long-range electrical network of active materi-
als (Bauer, Nötzel, Wenzel, & Nirschl, 2015; Bockholt et al., 2016a;
Bockholt, Indrikova, Netz, Golks, & Kwade, 2016).
Wang et al. comprehensively investigated the effects of mix-
ing sequence on the slurry features, electrode microstructure,
conductivity, and discharge rate performance of NCM cathodes
(Wang, Dang, Meyer, Arsenault, & Cheng, 2020). In sequence 1, the
PVDF/NMP solution was firstly mixed with the conductive agents
(CB) and then mixed with NCM powder. In contrast, NCM powder
was dry mixed with CB followed by adding the binder solution in
sequence 2. Several conclusions are reached in sequence 1: (1) Mix-
ing CB with a binder solution before addition of NCM can promote
the formation of gel-like slurries. (2) Porous CB/PVDF clusters rise
on NCM surface after drying the slurries, forming interconnected
conductive network linking NCM particles electronically. Addition-
ally, the porous structure facilitates the transport of Li ions. The
higher electronic and ionic conductivities are superior to achieve
high-rate capability. (3) The mixture of CB and NCM promotes the
strong binding between the CB and NCM particles, resulting in a
reduced CB ratio in the CB/PVDF cluster and liquid slurries. (4)
The CB nanoparticles were distributed along the PVDF chains form-
ing porous carbon-binder-domains between the NCM particles for
sequence 1 after drying the slurries, while a PVDF shell covered the
NCM particles for sequence 2. Therefore, the ionic and electronic
conductivities of electrodes in sequence 1 were increased from 0.05
to 0.11 mS cm−1 , 115.93 to 173.17 mS cm−1 , respectively. The elec-
trodes obtained by sequence 1 had better rate performance at 5 C,
while the compact layer of CB/PVDF between the NCM particles
obtained by sequence 2 may block ionic transport.
Mixing procedure is another important factor to determine the
particle state in the working electrodes (Li, Armstrong, Daniel,
Kiggans, & Wood, 2013). Lee et al. investigated the role of two
different mixing steps on the rheological properties of electrode
slurries (Fig. 2(a) and (b)) (Lee, Ryu, Han, Ahn, & Oh, 2010). Dur-
ing the multi-step procedure, the solvents are added into solid
mixtures stepwise, while for the one-step procedure the total
amounts of solvents are added at once. An increased viscosity of
the slurry is achieved when only a portion of the solvent is added
at the beginning in the multi-step procedure. This results in higher
shear forces during mixing, destroying the CB agglomerates more
effectively. Therefore, compared with the one-step procedure, the
multi-step procedure renders the slurry fluid feature and more
uniform dispersion of solid components, leading to the homoge-
neously distributed active materials and conductive agents without
agglomeration. As a result, the electrodes fabricated from the multi-
step procedure exhibit an enhanced electrochemical performance
in cycling stability and rate capability, due to the significantly
reduced electrode polarization induced by the reduced contact
and charge transfer resistances during lithiation/de-lithiation pro-
cesses (Fig. 2(c)). Besides the experimental work, the superiority of
multi-step mixing procedure was also reconfirmed by multiscale
modeling (Fig. 2(d)) (Liu et al., 2014a). Larger conductive interfa-
cial area ratios are obtained with a stepwise mixing procedure,
demonstrating its significant role in forming desirable electrode
structures. Additionally, a high-quality electrode microstructure
can be obtained at different mixing sequences when different
temperature conditions are applied. Therefore, mixing procedure,
active particle size/morphology, and temperature condition syn-
ergistically act on the electrode microstructures, and an optimum
combination of these factors contributes to a superior electrode
microstructure with improved performance.
The dry mixing of raw materials as the first step critically
determines the structural and electrochemical properties of the
manufactured electrodes. Different dry mixing strategies with var-
ious mixing techniques can regulate the conductivity, packing
density, and viscosity of the resulted electrode powders. Bock-
H. Liu et al.
Fig. 2. The schematics for different mixing steps: (a) one-step process, (b) multistep process, and (c) corresponding discharge capacities in the Li/LCO batteries obtained by
the two different mixing steps (Lee et al., 2010). (d) 3D schematics map illustrating the relation between particle morphology, conductive interfacial area ratio, and mixing
parameters (Liu, Battaglia, & Mukherjee, 2014). A stepwise mixing sequence and cubic active nanoparticles with a small size prefer to generate larger conductive interfacial
area ratios and form desirable microstructures with desired electronic diffusion pathways.
holt et al. proved that different dry mixing techniques, such as
rotary drum mixer (RDM), Nobilta (NOB), Eirich intensive mixer
(EIR), and planetary mixer (PM), generate notable differences in the
powder, suspension, and electrode properties of NCM electrodes
(Bockholt, Haselrieder, & Kwade, 2013). There are large carbon
black agglomerates in the bulk phases when using RDM with a low
mixing intensity. Consequently, the lowest electrical conductivity
is observed for this sample. In contrast, powder mixtures by EIR and
PM methods present a ten-time higher powder conductivity con-
tributed from the more evenly and finely distributed carbon black
fragments. The carbon black interacts with the binder after wet
mixing with binder slurries to form a conducting and binding net-
work among NCM particles. While the mixtures obtained by highly
intensive NOB mixing exhibits a reduced powder conductivity. This
is attributed to a separated deposition of conductive additives and
binder (Bauer et al., 2015). In the high intensity mixer, the carbon
black is deposited on the NCM forming a tight layer. Subsequently
adding the binder does not lead to conductive carbon black-binder
domains, but an isolating polymer shell surrounding the carbon
coated particles. This configuration suppresses the electric conduc-
tivity massively. It also leads to a higher packing density and lower
viscosity of resulted mixtures. As a result, a pouch cell assembled
with this electrode affords the worst discharge rate performance. A
newly 3D mixer collaborating with a multi-step mixing procedure
is verified to be more effective in mixing cathode slurries (Liu et al.,
2014a).
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Particuology 57 (2021) 56–71
The solid content of dispersions is a significant factor affecting
the rheological properties of slurries, which is multiply determined
by the component features, ratio, mixing methods, and sequences.
Ouyang et al. probed the roles of solid contents on the rheolog-
ical property of slurries and electrode structures (Ouyang et al.,
2020). With the unique long-chain structures, PVDF molecule can
alter its configuration once contacting the solid particles in slurry,
and its bridging role alters along with the solid content of the
slurries. The optimized content varies for different systems, below
which particle sedimentation easily occurs. Additional yield stress
will generate in the slurry above the optimized content, lead-
ing to inhomogeneous distribution of electrode ingredients. The
most suitable solid content of the slurry in this study is optimized
to be in the range from 63.9% to 66.3% after extensive experi-
ments.
Non-aqueous systems have large advantages in the practi-
cal applications and much experience have been accumulated in
the commercialized products. Slurry mixing is generally consid-
ered as the core technology of a battery plant. Great progress
has been achieved in the hands-on experience, while under-
standing the mechanism of the slurry preparation relatively
falls behind. More efforts are required to investigate the dis-
tribution of slurry components and fluid mechanics to achieve
an improved electrochemical performance of electrodes materi-
als.
H. Liu et al. Particuology 57 (2021) 56–71

Aqueous system

Though the organic solvents are very mature in the industrial

electrode processing, cost, environmental, and safety concerns still
exist. Recently, aqueous system has been considered to fabricate
electrodes due to its environmental benignity and cost effective-
ness (Jeschull, Brandell, Wohlfahrt-Mehrens, & Memm, 2017; Tsai,
Tsai, Tung, Hsieh, & Li, 2013). Besides, the aqueous solvent also has
the advantages of lower drying thermal budget (Wood et al., 2018),
environmentally friendly manufacturing and recycling process (Li
et al., 2020). Nevertheless, challenges remain in aqueous slurry
systems considering the large differences between water-based
and NMP-based systems, including poor wetting and adhesion
behaviors on metal current collectors, excessive secondary particle
agglomeration, Li leaching from cathodes and the resulted corro-
sion, structural change issues in aqueous cathode slurries, and more
rigorous drying process (Wood et al., 2018). All these issues must be
addressed to realize the replacement of non-aqueous systems with
the aqueous ones through the whole manufacturing and recycling
process of LIBs.
Along with the replacement of the frequently adopted toxic
NMP solvent by water, the extensively adopted PVDF binder
is substituted by the relatively cheap carboxymethyl cellulose
(CMC) binder, which mainly contains hydroxyl (–OH) and carboxyl
(–COOH) functional groups to determine the gelation of the slurry
(Carvalho et al., 2016; Li, Chen, & Chen, 2017). The strong elec-
trostatic force and hydrogen bonding in water systems result in
easy powder agglomeration. Additional pretreatments, including
physical (such as ball milling, ultrasonication, high-speed shear
mixing, grinding, etc.) and chemical (chemical functionalization,
surfactants, oxidation treatment, etc.), are required to disperse con-
ductive carbon material in aqueous slurries by reducing the surface
energy of carbon particles and improving their wetting features
(Léonard & Job, 2019; Lu et al., 1996; Starke, Seidlmayer, Dolotko,
Gilles, & Pettinger, 2017). The adding of extra dispersants is no pre-
requisite for a stable and homogeneous aqueous slurry. CMC is a
polyelectrolyte, which acts as an effective dispersant for the par-
ticle dispersion in aqueous slurry, while PVDF plays a comparable
role in the non-aqueous slurry. Additional additives, such as poly-
acrylic acid (PAA), usually improve the flowability of the slurry
(Li, Lee, & Peng, 2006; Li, Armstrong, Kiggans, Daniel, & Wood,
2012), but sometimes may have detrimental impact on electrode
adhesion (Bauer, Çetinel, Müller, & Kaufmann, 2019) or even cell
performance (Li et al., 2006).
In aqueous system, the features of raw materials also play key
roles in determining slurry and electrode properties. For the sil-
icon anode, the size of the silicon particles not only influences
slurry features during electrode processing, but also determines the
long-term cycling performances (Andersson, Hernández, Edström,
& Mindemark, 2020). The smaller particles lead to higher viscosities
of slurry especially at small shear rates (Fig. 3(a)-(c)).
Different from the non-aqueous systems, the aqueous slurries
usually have a high surface tension, which causes poor wettabil-
ity on current collectors and results in easy electrode delamination
(Du et al., 2017; Qi et al., 2015; Tsai, Jhang, Hsieh, & Li, 2016). This Fig. 3. SEM images of Si particles with the sizes in (a) ␮m and (b) nm; (c) Rota-
problem can be effectively handled by reducing the surface tension tional viscometry measurements on slurries with Si, carbon black, and sodium
carboxymethyl cellulose (Na-CMC), indicating the smaller particles lead to higher
of slurries and enhancing the surface energy of current collectors
viscosities of slurry especially at small shear rates (Andersson et al., 2020).
(Meng et al., 2020). The former one can be realized by employing
co-solvent or multi-solvent slurries, for instance an ethanol–water
system. The latter one can be achieved through physical treatments, cathodes. For NCM532 cathode, aqueous processing can regulate
e.g. plasma treatment or corona discharge treatment. The surface the surface chemistry of the NCM532 particles as Li ions in active
energy of aluminium (Al) current collectors can be enhanced by material can be leached into the aqueous solution and transition
two-fold after corona discharge treatment (Li, Rulison, Kiggans, metals will migrate to occupy Li sites (Hamam, Zhang, Liu, Johnson,
Daniel, & Wood, 2012). & Dahn, 2020; Liu et al., 2015), which has been observed for
Another critical issue associated with aqueous processing sys- many cathode materials (Hawley et al., 2020; Wood et al., 2020b).
tems is Li leaching from cathodes, particularly for the high-nickel Therefore, a cation mixture layer usually covers on the surface of

60
H. Liu et al.
NCM532. Immersing NCM532 powder in water for 1 h results in
the enrichment of Li2 CO3 and LiOH on its surface compared with
the counterpart exposing to ambient air for 1 year (Bichon et al.,
2019). However, the situation is much worse in the Ni-rich NCM622
or NCM811 as compared to NCM532 (Wood, Li, et al., 2020). This
drives the pH values of slurries to as high as 12, leading to dam-
ages to the electrode particles and severe corrosion of Al current
collectors (Kukay et al., 2021).
The introduction of trace phosphoric acid proves to be effective
in suppressing the change in surface chemistry, thus decreasing
the content of LiOH and Li2 CO3 (Kazzazi et al., 2018; Pedaballi & Li,
2020). With 1% H3 PO4 additive in the aqueous slurry, enhanced
cycling stability can be achieved relative to the conventional
NMP-based electrode owing to the superior electrode/electrolyte
interfacial behaviors (Xu et al., 2019). Surface coating on the NCM
electrode is another method to suppress the dissolution of transi-
tion metal ions (Hofmann, Nagler, Kapuschinski, Guntow, & Giffin,
2020; Loeffler et al., 2016). A similar phenomenon occurred for
Si/carbon/CMC composite electrodes (Tranchot, Idrissi, Thivel, &
Roué, 2016). The electrodes obtained from acidic slurries can better
withstand the high mechanical stresses of Si electrodes generated
during cycling, thus maintaining the structural integrity of the elec-
trode and leading to a higher capacity retention (Zou, Ji, Pang, Xu, &
Lu, 2020). The effect is induced by the formation of covalent bonds
between Si particles and CMC chains in the acidic environment.
Therefore, it is of great significance to understand the interfacial
chemistry in the aqueous systems (Yan et al., 2019a). An overlooked
issue of Si aqueous slurry is its decomposition and H2 evolution dur-
ing slurry preparation and battery manufacturing at a large scale,
which is caused by extra oxidation of Si particles, adversely impact-
ing the Coulombic efficiency and capacity (Hays, Key, Li, Wood, &
Veith, 2018).
The aqueous slurry system presents obvious advantages
in materials processing and could totally innovate the whole
engineering processes. Though it cannot wholly replace the non-
aqueous systems now, the aqueous slurry can be a potential system
for the future electrode processing after effectively handling the
problems of water residue and system compatibility. In fact, aque-
ous processing has been successfully commercialized for graphite
anodes and LiFePO4 cathodes (Li, Armstrong, et al., 2012; Li et al.,
2017b). Many researching teams, including Oak Ridge National Lab-
oratory (ORNL) (Wood, Wood, et al., 2020) and Helmholtz Institute
Ulm (HIU) (Bresser, Buchholz, Moretti, Varzi, & Passerini, 2018;
Kuenzel et al., 2018), and companies have conducted significant
work to handle the main challenges associated with water-based
high-capacity cathodes. Therefore, all water-based processing of
LIBs is hopeful in the near future to achieve a green and sustainable
LIB manufacturing system.
Comparison of electrode performance in two systems
One concern remains after handling these issues in aqueous sys-
tems: Is the electrochemical performance of electrodes obtained
from water-based systems comparable to the NMP-based ones? A
positive answer can be given with aqueous-processing low-voltage
cathodes, such as LiFePO4 , NCM111, NCM532. Comparison of the
cycling performance of LiFePO4 /graphite pouch cell with two pro-
cessing systems proves that both cells exhibit a same capacity
retention of 83.7% at the 668th cycle (Fig. 4(a)) (Wood et al., 2018).
Considering the higher rates (0.33 C vs. 0.2 C) were applied in the
water-based cells, one could expect that the long-term cyclability
of water-based cells surpasses the NMP ones. The rate perfor-
mance and cycling stability of cells with aqueous-based NCM111
are also comparable with these of the NMP-system (Hofmann,
61
Particuology 57 (2021) 56–71
Kapuschinski, Guntow, & Giffin, 2020). In NCM532/graphite pouch
cell, the discharge rate performance of water- and NMP-based elec-
trodes is almost identical, with a capacity retention of 86% at 1 C (1
C = 1.5 A) (Fig. 4(b)) (Wood et al., 2018). Strategies including reg-
ulating the pH value of water-based slurries and adopting novel
aqueous binder can further boost the electrochemical performance
of aqueous-based NCM (Ibing et al., 2020; Zhang et al., 2019a).
Notably, differences between two systems also need to be con-
sidered. On one hand, aqueous-processed thick cathodes (> 4 mA h
cm−2 ) easily undergo destructive cracking during drying, while this
is not observed for the NMP-based cathodes (Sahore et al., 2020). On
the other hand, switching cathode processing from non-aqueous
system to aqueous system can severely change the pore structure
of the cathodes, leading to the different wetting behaviors of elec-
trolytes and finally changing the discharging rates (Davoodabadi
et al., 2019).
The situation becomes complicated when it comes to the high-
capacity Ni-rich cathodes, such as NCM622 and NCM811. It is
widely accepted that the amount of Li ions leached from NCM cath-
odes increases with increasing nickel content (Hamam et al., 2020;
Hofmann, Kapuschinski, Guntow, & Giffin, 2020; Wood, Li, et al.,
2020), while the influence of Li dissolution on electrode structure
and electrochemical performance varies with different research
groups. Wood et al. revealed that only 3 wt.% Li ions dissolution was
detected in NCM811 under typical aqueous processing conditions,
which has minor surface modification of electrodes without chang-
ing the bulk structure (Wood, Li, et al., 2020). In addition, the slight
Li ions dissolution into the water can be recovered onto the elec-
trode surface during drying. This leads to a slightly higher discharge
capacity (around 5 mA h g−1 ) of water-based NCM811 compared
with the NMP-based counterpart at the first cycle. The reversible
Li+ /H+ -exchange mechanism was also confirmed by Hofmann et al.,
which is evidenced by the increased discharge capacity during
the initial five formation cycles (Hofmann et al., 2020b). How-
ever, water-processed pouch cells exhibited slightly lower capacity
retention after 1000 cycle (∼70% vs. ∼76%) and inferior discharge
rate performance at high rates of 3 C (136 mA h g−1 vs. 160 mA h
g−1 ) compared to the NMP-based cells. The lower discharge capac-
ity is caused by the formulation differences (the distribution of
conductive agents and binders in the electrodes) in two systems
rather than water exposure. While some others contributed this
gap to the detrimental effects of water on the Ni-rich electrodes,
especially for NCM622 and NCM811 cells (Hofmann et al., 2020b).
Water-based cells also show a higher cathode/electrolyte interfa-
cial impedance, lower initial discharge capacity (3–10 mAh g−1 ),
lower initial Coulombic efficiency (1–3%), higher polarization, and
increased capacity fade during cycling relative to the NMP-based
cells (Hofmann et al., 2020b). The slightly inferior performance can
be assigned to the degradation of the active materials, the formation
of barrier layers by water or CO2 contaminants, and the increased
side-reactions of aqueous processing electrodes.
The mild effect becomes fatal when LiNi0.8 Co0.15 Al0.05 O2 (NCA)
cathode with high water sensitivity is manufactured in aqueous-
system (Hofmann et al., 2020a). Water exposure of NCA renders
the generation of large amounts of highly resistive surface species
and water-induced leached species, which not only leads to the
degradation of electrode structure at the surface, but also heav-
ily impedes the insertion and extraction of Li ions. Consequently,
negligible performance of cells with water-based NCA electrode is
achieved with a very high polarization. This indicates that there
are big challenges in aqueous processing of highly water-sensitive
electrodes. Suppressing the formation of water-induced species
through modification of the particle surface may provide a solution
to conquer the challenges.
H. Liu et al.
Fig. 4. Comparison of the electrochemical performance of pouch cells with electrodes obtained from different processing systems: (a) long-term cyclability of LiFePO4 /graphite
pouch cell; (b) discharge rate performance of NCM532/graphite pouch cell (Wood et al., 2018).
Slurry coating
The slurries are coated on the metal foil current collectors to
achieve working electrodes. Many techniques have been employed
to fabricate electrode films (Hawley & Li, 2019a, Lalau & Low, 2019;
Lee et al., 2020; Yu et al., 2017; Zhang, Yuan, & Li, 2018; Liu, Chen,
Liu, Chu, & Tiu, 2017), including spray coating, spin coating, dip
coating, comma bar coating, ink-jet printing, electrophoretic depo-
sition, doctor blading, and slot die coating, and so on. The last
two methods are adopted most frequently. (1) During doctor blad-
ing operation, the foil substrate is mainly used with the coating
roller directly contacting the slurry tank, and the contacted excess
slurry is coated on the foil substrate by ensuring that the sub-
strate can contact the coating roller and the doctor blade. Therefore,
the distance between the substrate and the doctor blade will be
determined, eventually forming a uniform coating on the substrate
surface. (2) The slot die coating process is a high-precision wet coat-
ing technology. During fabrication, the slurry is squeezed along the
gap of the coating mould and ejects to the foil substrate under a con-
stant pressure and a certain flow rate. Compared with other coating
methods, slot die method has many advantages, including the faster
coating speed, higher coating accuracy, and uniform thickness in a
closed-loop. The slurry component, coating method, and parame-
ters have significant effects on the electrochemical performance of
electrodes.
Garofalo et al. tested the effect of four frequently adopted
coating methods on the process characteristics and the resulted
electrochemical performances (Garofalo, Lawler, Walczyk, &
Koratkar, 2018): doctor blade, Mayer rod, slot die, and low vol-
ume low pressure (LVLP) spray. The coated materials are graphene
oxide (GO) slurry and GO can be uniformly coated on the cop-
per foil surface with all four methods. Batteries with electrodes
obtained by different coating methods vary considerably in specific
capacity at different discharge rates, of which Mayer rod method
shows the best performance, with specific capacities of 400, 280,
100, and 40 mA h g−1 at 0.05, 0.1, 0.5, and 1.0 C, respectively
(1.0 C = 372 mA g−1 ). Based on the overall considerations of the
adhesion, deposition consistency, usability, cleanability, and elec-
trochemical performance, doctor blading was verified as the most
suitable method for laboratory applications, while the Mayer rod
method exhibited great potential for high volume fabrication.
Slot die coating is one of the predominant methods in manu-
facturing LIB electrodes. The advantages of this prevailing method
compared to routine roll coating are precise dosing, closed feed sys-
tem, and easy scalable process parameters (Kraytsberg & Ein-Eli,
2016). The as-resulted electrodes have an even thickness without
62
Particuology 57 (2021) 56–71
Fig. 5. The coating stability window for a slot-die coating machine. The coating
process is stable when the capillary number is located in the area below the border
line (Kraytsberg & Ein-Eli, 2016).
coating defects. To this end, the hydrodynamic features of slurries
and the coater parameters should be balanced. A stable coating
process can be achieved when the capillary number (Ca = (V)/,
affected by the slurry viscosity , substrate speed V, and slurry sur-
face tension ) is located in the area below the border line (Fig. 5)
(Kraytsberg & Ein-Eli, 2016). Therefore, small  and V, large  are
preferable to obtain a stable coating process (relatively low capil-
lary number). However, the substrate speed is determined by the
coater productivity. In this respect, the viscosity of slurries needs
to be as low as possible.
Besides the industrial slurry coated methods, some other
approaches are proposed to produce next-generation electrodes
with advanced performances or functionality, including sintering,
extrusion, and freezing. However, these methods usually involve
complicated processing and are poorly suitable for industrial pro-
duction at large scales. Deploy electrophoretic deposition (EPD)
recently arises as an alternative method for electrode coating (Ha,
Islam, & Robinson, 2012, 2015; Lee, Woo, Kakati, Kim, & Yoon,
2018). In this approach, the electrode thickness and mass load-
ing of the obtained electrodes can be efficiently regulated through
changing the colloidal electrolyte components, applied voltage, and
deposition time. However, most of electrodes obtained by EPD
are still thin and with a low loading of active materials. NCM111
electrodes prepared by the EPD approach can reach an electrode
thickness of about 60 ␮m with a mass loading of 15 mg cm−2 , cor-
responding to a high density active material of 90 wt.% (Lalau &
Low, 2019). The electrode thickness and loading can be further
H. Liu et al.
improved to 150 ␮m and 30 mg cm−2 by replacing the 2D Al foil
current collector to 3D mesh Al current collector. The obtained elec-
trode presented open pore frameworks throughout the thick film,
leading to a high Li-ion diffusion coefficient (1.10×10−12 cm2 s−1 ),
low ohmic resistance (2 ), solid electrolyte interphase (SEI) resis-
tance (81 ), and charge transfer resistance (23 ), indicating a
high potential to achieve superior rate performance.
During electrode coating, the properties of obtained electrode
are mainly affected by the coating methods and operating con-
ditions. Large trial-and-errors are conducted to obtain optimized
operating conditions, which requires large amounts of time, man-
power, and money. Therefore, more theoretical researches are
required to clearly understand the relations between coating meth-
ods and operating conditions to achieve the superior electrode
structure and thickness with an optimum economy.
Electrode drying
The solvent in the coated film has to be removed from the
composite electrode slurry composed of active particles, conduc-
tive additives, binders, and solvents. The drying process can be
determined by many factors, including the evaporation kinet-
ics of the solvent, the flow properties and solid content of the
slurry, the diffusion and sedimentation properties of particles,
and the particle-particle interactions. The evaporation of sol-
vents during drying renders redistribution of particulate phases in
slurries. Therefore, the drying process can profoundly affect the
microstructures of electrode and hence the electrochemical per-
formance. Much efforts have been devoted to reveal the relation
between the electrode microstructure and the drying conditions.
The microstructure features during the drying process can be inves-
tigated via small-angle X-ray scattering (Kim et al., 2013), diffusing
wave spectroscopy (Lee et al., 2013), cryogenic scanning elec-
tron microscope (Buss, Roberts, Crawford, Peters, & Francis, 2011),
fluorescence microscopy (Lim, Ahn, & Yamamura, 2013), Raman
spectroscopy (Hagiwara, Suszynski, & Francis, 2014), and model-
ing (Buss et al., 2011). The formation of dried film is a competitive
process of particle diffusion, film evaporation and sedimentation.
Comprehensively understanding the manner how the suspension
of slurries transforms into a porous film can present direction on
engineering uniform electrode films.
The solvent adopted in the slurry is a decisive factor for elec-
trode drying behaviors (Sahore et al., 2020). Solvent properties,
such as viscosity, boiling point, and evaporation rate, have large
impacts on the kinetics of electrode drying, further determine the
evolution of the electrode microstructures. Additionally, the drying
process can also change the distribution of particles in the slurries
with different solvents. Non-uniform distributions of active mate-
rials are frequently observed when the LCO slurry is prepared with
organic solvent, while water-based preparation leads to a relatively
uniform distribution of electrode materials (Li & Wang, 2011). The
theoretical calculation considering a migration-controlled kinet-
ics implied that the electrodes obtained from organic-based slurry
have higher electrical resistance (Zhang, Shen, Cheng, & Zhang,
2019).
Solvent evaporation rate also has large impact on the redis-
tribution of each component in the slurries and hence the
electrode microstructures. Two distinct evaporation phases can be
found upon drying electrode slurries coating on current collectors
(Fig. 6(a)) (Stein, Mistry, & Mukherjee, 2017). In the first phase, sol-
vent evaporates from surface with a constant evaporation rate until
the electrode thickness ceases to change. During this step, the par-
ticulate framework of relatively large active particles is formed. In
comparison, smaller conductive additive and binder rearrange in
the framework in the second phase, eventually leading to the dried
63
Particuology 57 (2021) 56–71
electrode film. Later, the effects of drying sequence on electrode
structures and electrochemical performance were investigated by
drying the same electrode slurries with different procedures: the
single-stage and two-stage process. The electrode film was directly
dried at a specified temperature (70 ◦ C or 120 ◦ C) in the single-stage
drying process, while an initial drying at room temperature for
16 hours is involved in the two-stage drying process before dry-
ing at high temperatures in the oven. Consequently, a two-stage
drying process at 70 ◦ C performs better than the single-stage one
at 120 ◦ C in galvanostatic cycling performance (Fig. 6(b)), since the
former process renders the formation of large active material parti-
cle framework and redistribution of smaller particles successively,
which favors to construct a desired additive network surrounding
the active materials. Instead, the single-stage process undergoes
simultaneous rearrangement of various phases. Notably, binder
migration is a general problem for the drying of battery slurries.
The faster the drying process is carried out, the more uneven binder
distribution occurs. To realize high coating speed at limited dryer
length, two-step or even multi-step drying is applied with low dry-
ing rates at the beginning and high dying rates at the end of the
drying process. This further indicates the superiority of multi-step
drying process in fabricating electrodes.
The latex particle migration behaviors during drying electrode
slurries with different concentrations of active materials (graphite)
were investigated using real-time fluorescence microscopy
(Fig. 7(a)-(f)) (Lim et al., 2013). The microstructures of graphite slur-
ries are highly dependent on the amount of CMC chains absorbed on
graphite surface, which ultimately determines the migration state
of latex particles. A consolidation layer of segregated latex particles
distributes on the surface of 1 wt.% graphite slurries (Fig. 7(a)-(c)).
In contrast, latex particles are well-dispersed among the graphite
particles in 5 wt.% graphite slurries (Fig. 7(d)-(f)). This indicates that
the migration of latex particles can be suppressed by CMC chains
when above the entanglement concentration of CMC, leading to a
more uniform electrode film.
Stress generated from the shrinkage of coating slurry layers
during electrode drying could lead to film defects such as curl,
crack, and delamination. The cantilever deflection method has been
developed to detect the in-plane stress of electrode during drying
(Kim, Sung, Hur, Ahn, & Lee, 2010; Price et al., 2014). Lim et al.
investigated the stress evolution of anode slurry upon the dry-
ing processes (Lim, Kim, Ahn, & Lee, 2015). The result indicated
that polymerized styrene butadiene rubber (SBR) in a graphite/SBR
slurry can fill the voids generated between the graphite particles
when increasing SBR concentrations, while CMC is adsorbed on the
surface of graphite inducing the agglomeration of graphite particles
(Xiao et al., 2020a). Based on the stress generated during drying,
a processing map was proposed illustrating the roles of CMC and
SBR concentration on the mechanical strength of the electrode film
(Fig. 7 (g)) (Lim et al., 2015). The stress releases to a free state in
region I (the top graph on the right side of Fig. 7(g)), indicating
that the film in this CMC/SBR concentration region has an infe-
rior mechanical strength. Similarly, the film in region II exhibits
a slightly better mechanical strength. In contrast, the maximum
stress maintained without relaxation in region III (the bottom graph
on the right side of Fig. 7(g)), indicating that the film in this region
presents sufficient mechanical strength. Therefore, large amounts
of SBR are necessary in the composite slurry to boost the mechanical
strength of resulted films with a low content of CMC.
The dynamic behavior during drying the slurry drops at the
edges decides the smoothness of the obtained electrode. Higa et al.
calculated the spatial distribution of electrode particles by an X-
ray radiography-based procedure (Fig. 7(h)) (Higa et al., 2017).
The electrode particles promptly become non-uniformly dispersed
within the slurry drops. A coffee ring effect is observed at the end
of the drying process with active particles settling into a ring shape
H. Liu et al. Particuology 57 (2021) 56–71

Fig. 6. (a) The schematics illustrating drying behaviors of slurry materials coated on a substrate, which includes a two-phase model of thickness decrease and component
rearrangement. The adopted electrode materials are NCM with BET surface area of 0.3–0.8 m2 /g, an average particle size of 8–12 ␮m, and a density of 2.2 g/cm3 purchased
from Targray, with a weight proportion of 70% NCM, 20% Super C-65, and 10% PVDF. (b) Galvanostatic cycling of cells with NCM electrodes drying at different procedures
(Stein et al., 2017).

and rare particles leaving in the center of the dried slurry drop as
a consequence of evaporation from the curved drop surface. Simi-
larly, the edge of a slurry coating film also involves a curved surface,
as the coating layer transitions from the uniform bulk thickness to
zero thickness. Therefore, the uneven distribution of active mate-
rial particles should also occur at the edges of the dried electrode
films. This leads to non-uniform current distribution across the
electrode surface during battery operation. Heating immediately
after slurry is coated onto metal foil current collectors can effec-
tively promote the coating uniformity of slurries, and the active
material particle distributes more uniformly with the increasing
heating power. Additionally, a more concentrated slurry can pro-
mote the uniformity of coating electrode films. It should be noted
that this study is qualitative, considering that the slurry drop (about
3 mm across) is not large enough for the centers to dry into a uni-
form film.
Both the distribution of electrode components and electrode
structure are highly dependent on the electrode drying process.
This further determines the electron and ion diffusion behaviors,
and ultimately the rate performance of electrodes. A uniform elec-

64
H. Liu et al. Particuology 57 (2021) 56–71

Fig. 7. Migration behaviors of latex particles during drying process: (a, d) optical microscopes, (b, e) atomic force microscopes, (c, f) cross-sections SEM images of latex
particles for (a − c) 1 wt.% and (d − f) 5 wt.% graphite slurries (Lim et al., 2013). (g) Processing window map to dry the electrode slurry coated on a substrate. Symbol ×, , and
 indicate poor, less, and good mechanical strength of the film, respectively (Lim et al., 2015). (h) Optical images of horizontal slices of dried slurry at varied heating powers
(Higa et al., 2017).

trode with desired structures can be obtained by optimizing the
equipment design and drying procedure.
Electrode calendering
The calendering step plays a significant role during the fab-
rication of electrodes, since it generates remarkable changes in
the thickness, porosity, density, and active surface area of elec-
trode materials (Davoodabadi et al., 2018; Xu, de Vasconcelos,
Shi, Li, & Zhao, 2018), finally affecting the long-term cycling per-
formance (Meyer, Bockholt, Haselrieder, & Kwade, 2017; Zheng,
Tan, Liu, Song, & Battaglia, 2012). After calendering, the contacts
within the electrode particles and between the electrode particles
and current collectors become compact, hence rendering a small
electron resistance, improvement in electrolyte phase transport,
electrical and thermal conductivity (Ott, Völker, Gan, McMeeking, &
Kamlah, 2013). Besides, this step can reduce the electrode thickness
with the same mass loading of active materials, which is benefi-
cial to improve the volumetric energy density of practical batteries
(Parikh, Christensen, & Li, 2020; Zhai et al., 2017). Unfortunately,
the high compression loads during calendering can reduce the elec-
trode porosity and the effective surface area that Li ions can reach,
which presents adverse impact on the power density of batter-
ies (Parikh et al., 2020). Therefore, a proper level of calendering
is preferred to achieve superior conductive and mechanical prop-
erties simultaneously (Ren et al., 2020). Moderate calendering rates
between 8% and 14% are acceptable for high capacity retention after
long-term cycles (Haselrieder, Ivanov, Christen, Bockholt, & Kwade,
2013).
Several simulation researches are conducted to probe the
physico-chemical features of electrode during calendering (Lenze
et al., 2017). Giménez et al. quantitatively investigated the evolu-
tion of structural and mechanical properties of NCM cathode during
the calendering process with a novel discrete element method.
These features include the porosity and thickness of electrodes, the
active surface area and coordination number of electrode particles,
the contact areas between electrode particles and current collec-
tors, and the mechanical stress within the structures. Particularly,
this model is able to capture the viscoelastic response of NCM cath-
odes after removing the calendering pressure. The relative elastic

65
H. Liu et al.
Fig. 8. (a) Schematic of the calendering process and corresponding SEM images; (b) Evolution of porosity at different calendering degrees. The electrode composites include
90 wt.% NCM powder, 4 wt.% carbon black, 2 wt.% conductive graphite, and 4 wt.% PVDF (Sangrós Giménez, et al., 2019).
recovery ranged from 10.25% to 17% depending on the calendering
degree (Fig. 8) (Sangrós Giménez, Finke, Schilde, Froböse, & Kwade,
2019), which agrees well with the experimental results (Deswita,
Djodi, & Kartini, 2018). Further studies were conducted to uncover
the effects of calendering degree on the electrical and ionic con-
ductivities as well as adhesion strength of NCM cathode (Sangrós
Giménez, Schilde, Froböse, Ivanov, & Kwade, 2020).
As mentioned above, calendering generates complicated influ-
ences on the electrode microstructures, and the combined effects
dictate the electrochemical performance (Sangrós Giménez, Finke,
Nowak, Schilde, & Kwade, 2018; Zhao, Han, Zhang, & Zhang, 2020).
Malcolm et al. found that the calendered NCM electrode exhibit
superior performance during the initial few cycles but poorer
capacity retention during the following cycles compared to the
uncalendered counterpart (Stein et al., 2017). The better initial
performance of calendered electrode is assigned to the syner-
getic effects of reduced electrode thickness and porosity as well as
enhanced electrochemical active area caused by crack formation,
which shortens the diffusion length and leads to a smaller charge
transfer resistance (Liu et al., 2019c). However, the enhanced elec-
trochemical active area also contributes to the generation of more
SEI. The preexisting fractures of active particles generated by calen-
dering can propagate during cycling. Consequently, the calendered
cell fades more rapidly hereafter. Therefore, the impacts of calen-
dering of electrode structures must be comprehensively considered
66
Particuology 57 (2021) 56–71
to obtain an optimized electrode with high initial capacity, long
lifespan, and high energy density.
The proper electrode structural regulation is beneficial to
improve the volumetric capacity and energy density of batteries,
while excessively calendering leads to the decrease in ion and
electron transfer efficiency, and the electrochemical performance.
Clearly analyzing the mechanical properties of electrode materials
during calendering is necessary to obtain an optimized electrode
structure.
Dry processing techniques
Another solution to reduce the cost and adverse impact on
environment is reducing the dosage of solvents during the man-
ufacturing process or even solvent-free fabrication of electrodes
(Cho, Eom, & Cho, 2010). In this regard, dry processing technique is
an alternative option (Bockholt et al., 2016a; Wu, Zheng, Hendrick-
son, & Plichta, 2019). The dry mixture of powders containing active
materials, binders, and conductive agents can be directly printed on
the current collectors or form standalone electrodes via calender-
ing or hot rolling with controllable electrode thickness and density
(Fig. 9(a)) (Ludwig, Zheng, Shou, Wang, & Pan, 2016). Another great
advantage of dry mixing method is the abandon of solvent dry-
ing process. The simplified process also makes it easier to control
the microstructures of resulted electrodes. Different binder dis-
H. Liu et al.
Fig. 9. Dry painting methods for electrode manufacturing: (a) electrostatic spraying deposition method (Ludwig et al., 2016) and (b) room temperature dry roll-to-roll
manufacturing technique (Kirsch et al., 2019).
tribution behaviors were observed for dry painted electrodes and
conventional slurry coating electrodes. Compared with the forma-
tion of fixed polymer layers covered on the LiCoO2 surface, the
dry painting process constructs conductive binder agglomerates
around LiCoO2 particles, resulting in a lower interfacial impedance
and superior discharge rate and cycling performance (Ludwig et al.,
2016). The feasibility of this dry coating method has also been
demonstrated in preparing NCM cathodes with superior electro-
chemical performance (Al-Shroofy et al., 2017; Liu et al., 2017b). Hu
and coworkers proposed a scalable dry roll-to-roll manufacturing
process to fabricate free-standing electrodes using compressible
holey graphene as conductive matrix (Fig. 9(b)) (Kirsch et al.,
2019). This solvent- and binder-free technique operating at room-
temperature and low pressure renders much reduced energy input
and is less time consuming.
Notably, superior dry mixing methods and advanced dry pow-
der painting techniques (Ludwig et al., 2016; Zhou et al., 2020) need
to be exploited to guarantee the mixing uniformity of electrode
materials and afford a high bonding strength between powders
and current collectors. The satisfactory achievements obtained
from dry electrode processing stimulate this technique to be more
competitive in developing advanced electrodes (Ludwig et al.,
2017). Further exploring advanced dry coating methods toward
large-scale electrode production is imperative considering their
economic and environmental superiority.
Conclusion and outlook
High energy/power density, long service life, and enhanced
safety are the permanent pursuits for practical LIBs, which requires
not only the progress in the electrode materials electrochemistry,
but also the advances in the materials processing technologies. The
composition ratios, mixing sequences, coating methods of elec-
trode slurries, the drying and calendering procedures of electrode
films during electrode processing can strongly determine the dis-
tribution of active materials, ionic and electronic agents, and the
microstructures of electrodes, finally acting on the electrochem-
ical performance of practical batteries. By deeply understanding
the correlation between the fabrication parameters and electrode
67
Particuology 57 (2021) 56–71
microstructures as well as battery performance, the optimized
technologies can be achieved to further enhance the electrochem-
ical performance in working LIBs. Several points are proposed for
the future development of advanced electrodes of LIBs:
1) The granularity of electrode materials determines the ion and
electron transfer kinetics within the electrodes. Electrode par-
ticles in nanometer size present better kinetics for ion and
electron transport. However, there are large interfacial resis-
tance and severe side reactions in a working cell. Elaborately
synthesizing electrode materials with hierarchical structures
through advanced powder technologies is an efficient route to
regulate the dispersion of electrode particles in the slurries and
the redistribution of electrode components inside the films dur-
ing coating and drying.
2) The dispersion and restacking of energy particles are highly
dependent on the distribution of electrode particles in the slurry.
However, rare researches are conducted on the particle arrange-
ment inside electrodes. More attentions are requested at the
microscopic level with specific shape and interfaces of a working
particle rather than merely focus on the electrodes. Rationally
designing electrode materials with specific particle size and
initial agglomeration state from the perspective of practical
applications can maximize the functions of particles in energy
storage devices. This indicates that equalized distribution of
electrode particles may possibly not be essential, while spe-
cific arrangement of electrode particles favors the formation of
compact electrode structures.
3) The volume of the electrode materials is highly dependent on
the state of charge-discharge of working batteries. It requires
full consideration of the battery design to avoid the harm to the
battery performance caused by size changes of electrode mate-
rials during battery cycling. It is imperative to reveal the particle
expansion and shrinkage during cycling and their roles on the
cell performance both on the materials and device levels.
4) Compared with the extensive focus on the electrode processing
in LIBs, few attentions are paid on the electrode fabrication of
solid-state batteries and Li metal batteries (Li et al., 2019). The
slurry preparation of cathodes and anodes with solid-state elec-
H. Liu et al.
trolyte particles is a critical issue in solid-state batteries (Wang,
Zhang, et al., 2019). The design of perfect protecting layers on Li
metal anode is also a crucial subject for Li metal batteries (Liu
et al., 2019a; Liu et al., 2019b; Yan, Zhang, Huang, Liu, & Zhang,
2019). Revealing the particle issues in these processes plays vital
roles in improving electrode performance of next-generation
batteries.
5) There is lacking of fundamental knowledges on the underlying
processes during slurry coating, electrode drying, and calender-
ing. Consequently, the theoretical relations between electrode
processing parameters and ultimate electrochemical perfor-
mance are still not clearly known, though some companies
already achieved much (unpublished) knowledge on the slurry
processing by many trial-and-errors. The electrode process
technologies strongly depend on the operational experiences.
Elaborate electrochemical characterization and simulation of
the electrode processing is helpful to gain deep insight into the
relations between the slurry features, deposition methods, dry-
ing and calendering mechanism, and electrode structures, which
can present new insights for the low cost and high performance
of LIBs.
6) Powder technology is a result of the interactions between
multiple objects. Efficiently integrating the advantages from
interdisciplines of chemistry, physics, materials, energy, and
engineering science is the key to accelerating the update of bat-
tery technologies from the direction of particle science. More
attentions are required to focus on the particle technologies,
especially the solid–liquid interface.
Sustainable development of LIBs with full-life-cycle involves
a set of technical process, including screening of raw materials,
synthesis of battery components, electrode processing and battery
assembly, battery cycling and recycling. This review intends to call
more attention to the electrode processing, not merely to the mate-
rials synthesis, which is imperative for the commercial applications
of LIBs. Besides adopting the electrode materials with low cost, the
advance in processing technologies of electrode slurries can largely
cut the cost of LIBs as well. It is beneficial to make more efforts
into engineering innovation to improve the processing capacity of
electrode fabrication.
Declaration of Competing Interest
The authors report no declarations of interest.
Acknowledgements
This work was supported by National Natural Science Founda-
tion of China (Grant Nos. 21805161, 21808121, and 21825501),
National Key Research and Development Program (Grant No.
2016YFA0202500), China Post-Doctoral Science Foundation (Grant
Nos. 2020M670155 and 2020T130054), and the Tsinghua Univer-
sity Initiative Scientific Research Program.
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