Journal of Energy Storage 25 (2019) 100862

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Journal of Energy Storage

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Electrode manufacturing for lithium-ion batteries—Analysis of current and T

next generation processing⋆
⁎
W. Blake Hawleya,b, Jianlin Lia,b,
a
Oak Ridge National Laboratory, Energy and Transportation Science Division, 1 Bethel Valley Road, Oak Ridge, TN 37830, USA
b
University of Tennessee, Bredesen Center for Interdisciplinary Research and Graduate Education, 418 Greve Hall, 821 Volunteer Blvd., Knoxville, TN 37996, USA

A R T I C LE I N FO A B S T R A C T

Keywords: As modern energy storage needs become more demanding, the manufacturing of lithium-ion batteries (LIBs)
Slurry represents a sizable area of growth of the technology. Specifically, wet processing of electrodes has matured such
Electrode processing that it is a commonly employed industrial technique. Despite its widespread acceptance, wet processing of
Electrode drying electrodes faces a number of problems, including expensive and dangerous solvent recovery, cut-off waste,
Electrode architecture
coating inconsistencies, and microstructural defects due to the solvent drying process. This review considers
Roll-to-roll manufacturing
each of these issues and discusses which electrode slurry properties should be considered when optimizing wet
slurry fabrication. Simultaneously, methods to replace traditional wet processing of electrodes are being ex-
tensively researched. Some of these novel electrode manufacturing techniques prioritize solvent minimization,
while others emphasize boosting energy and power density by thickening the electrode and, subsequently,
creating an organized pore structure to permit faster ion diffusion. This review contemplates the advantages and
disadvantages of each of these approaches and provides a comprehensive outlook on the future of electrode
manufacturing.

1. Introduction improving electrode fabrication lies largely in the ability to sig-

Since their inception in 1991, lithium-ion batteries (LIBs) have
emerged as a sophisticated energy storage formulation suitable for
applications such as cellular phones, laptop computers, and handheld
power tools. Recently, LIBs have received widespread acceptance as the
most suitable power source for many alternative fuel vehicles, including
fully-electric battery electric vehicles, that could play a meaningful role
in combatting anthropogenic climate change. As such, the incentive to
optimize LIB technology has escalated considerably. The United States
Department of Energy (DOE) has a stated goal of reducing the cost of an
LIB suitable for use in an electric vehicle to $80 per usable kWh within
the next ten years [1]. To achieve this goal, electrode materials de-
velopment, refined understanding of engineering fundamentals, and
ingenuity in the fabrication process are imperative [2]. While several
studies have been dedicated to materials discovery, notable progress
has been made on the engineering front as well [3]. The incentive for
nificantly increases the volume ratio of active materials in LIBs, re-
sulting in higher energy density and lower cost.
The electrode manufacturing procedure is as follows: battery con-
stituents, which include (but are not necessarily limited to) the active
material, conductive additive, and binder, are homogenized in a sol-
vent. These components contribute to the capacity and energy, elec-
tronic conductivity, and mechanical integrity of the electrode. It is
important that the mass ratios between ingredients be such that the
optimal combination of properties is attained [4]. Moreover, the se-
lection of solvent will dictate which binders are suitable, as well as
whether additional additives will be required. The resulting suspension
is referred to as the electrode slurry, which is then coated onto a metal
foil, i.e. Al and Cu foils for positive electrodes and negative electrodes,
respectively. On a lab scale, coating is usually achieved with com-
paratively primitive equipment such as the doctor blade, while at the
industrial level, the state-of-the-art is the slot-die coater [5,6]. The

⋆
This manuscript has been authored by UT-Battelle, LLC under Contract No. DE-AC05-00OR22725 with the U.S. Department of Energy. The United States
Government retains and the publisher, by accepting the article for publication, acknowledges that the United States Government retains a non-exclusive, paid-up,
irrevocable, world-wide license to publish or reproduce the published form of this manuscript, or allow others to do so, for United States Government purposes. The
Department of Energy will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan (http://energy.gov/
downloads/doe-public-access-plan).
⁎
Corresponding author at: Oak Ridge National Laboratory, Energy and Transportation Science Division, 1 Bethel Valley Road, Oak Ridge, TN 37830, USA.
E-mail address: lij4@ornl.gov (J. Li).

https://doi.org/10.1016/j.est.2019.100862
Received 18 June 2019; Received in revised form 23 July 2019; Accepted 25 July 2019
Available online 31 July 2019
2352-152X/ © 2019 Elsevier Ltd. All rights reserved.
W.B. Hawley and J. Li
Fig. 1. Flowchart illustrating the electrode fabrication process.
coating is then dried and compressed down to the desired thickness in a
step called calendering or pressing. The remaining stages are electrode
slitting, winding, packaging, and assembled cell formation and in-
spection (see Fig. 1). The literature suggests two major goals for elec-
trode fabrication research: (1) to gain fundamental understanding of
how each stage in the manufacturing process impacts the resulting
electrode morphology and capability, and (2) to investigate methods by
which the individual steps may be accelerated or made more affordable
to meet rising consumer demands.
While materials are the most expensive component in battery cost,
electrode manufacturing is the second most expensive piece, accounting
for between 20 and 40 percent of the total battery pack cost, with be-
tween 27 and 40 percent of this cost coming from electrode preparation
[7–10]. Models, such as the battery performance and cost (BatPaC)
model, have been developed to provide an assessment of cost factors
and design limitations of LIBs [11–14].
The challenges associated with electrode production are stage-spe-
cific. Mechanistically, the biggest challenge associated with slurry
preparation is imparting stability to the active material and conductive
additive particles from deleterious colloidal activities, namely ag-
glomeration and sedimentation. It is equally important that the slurry
be processable, i.e. that it may be cooperative with the coating step.
Although mixing is a relatively inexpensive task [8], the time required
for sufficient slurry dispersion constrains throughput. Coating and
drying, by contrast, are much quicker actions, but can be three to ten
times as expensive as mixing [8,15]. Modern coating processes have
reached speeds of 50 m min−1, though there is desire to escalate the
speed further; industrial drying can take place in the span of just one to
two minutes [16]. The most pertinent issue with drying is the lack of
fundamental knowledge of the underlying processes taking place in the
electrode film [17], though progress has been made in recent years.
This lack of understanding has led to extreme variations in electrode
microstructure and performance.
In this review, the literature associated with slurry characterization,
coating, and drying is considered, as these three operations represent a
great opportunity for savings in manufacturing time and costs. They
also have a significant impact on electrode microstructure, which will
ultimately determine the electrochemical viability of the device (see
Fig. 2). This analysis is carried out in the sections titled “Desirable
Slurry Properties” and “Drying Process Insights.” A brief summary of
the influence of the calendering stage is described in “Calendering In-
fluence on Morphology.” Novel cathode production methods are being
developed in an effort to make more reproducible and favorable
morphologies at lower costs. These possibilities are explored in the
section titled “Next Generation Electrode Processing.”
2
Journal of Energy Storage 25 (2019) 100862
2. Desirable slurry properties
The two most paramount features of a viable electrode slurry are
that it is stable and processable. Given that electrode slurries contain
active particles that are substantially larger than molecules comprising
the solvent and that are responsive to Brownian motion, they may be
approximated as colloidal suspensions [19]. The stability of a slurry is
evaluated by its ability to combat detrimental naturally-occurring
phenomena, specifically agglomeration and sedimentation. Agglom-
eration can take place due to relatively weak van der Waals attractions
or, more rarely and harmfully, relatively strong electrostatic interac-
tions due to surface charges [20]. Water-based slurries provide an en-
vironment conducive to agglomeration due to comparatively strong
hydrogen bonding and electrostatic forces; because of this, they often
require the addition of a dispersant, which supplies an electrostatic
barrier. Aqueous slurries also suffer from poor wettability onto current
collectors, though strategies have been developed to increase the sur-
face tension of current collectors and decrease the surface energy of
slurries [21,22]. Additionally, the basicity of aqueous cathode slurries
commonly leads to corrosion of the aluminum current collector
[23,24]. This complication is particularly serious for aqueous suspen-
sions containing nickel-rich active materials [25]. Among the best
methods to prevent corrosion are the addition of phosphoric acid (thus
dropping the slurry’s pH) [24,26–30] or preventing direct contact be-
tween active material and aluminum through a metal oxide coating on
the active material [31] or a carbon coating on the current collector
[23,32].
Despite these drawbacks, aqueous processing is desirable since it
eliminates the need for solvent recovery, leads to operation and capital
investment cost savings, is environmentally benign, allows for easier
manufacturing plant siting and permitting, and cuts life-cycle CO2
emissions [33,34]. In fact, water-based processing has already been
commercially adopted for graphite anodes [3]. Lately, several studies
have been dedicated to finding suitable dispersants and optimizing
their concentration to enable water-based processing for cathodes
[35–47].
Steric hinderance is generally achieved in colloidal suspensions
through inclusion of an adsorbing polymer, i.e. the binder. Adsorbed
binder layers have been measured at 32 nm thick on active material
particles and at 9.5 nm thick on carbon black particles [48]. However, a
thick binder coating on the active material surface has been demon-
strated to increase electrical resistance [49], therefore providing in-
centive to not drastically increase the slurry solid content. Depending
on the molecular weight (MW) of binder selected and the strength of
particle-binder interactions, dangling ends of binder can form en-
tangled networks in a phenomenon called bridging flocculation. These
volume-spanning networks are beneficial in promoting sedimentation
W.B. Hawley and J. Li
Fig. 2. Scheme describing the relationships between (a) electrode processing, (b) structure, and (c) electrochemical properties [18].
resistance in the slurry. Gravitational settling of the active material
particle clusters can lead to coatings with an inhomogeneous distribu-
tion of particles. Another way to combat sedimentation includes den-
sity-matching the solvent with the particles in solution, though active
materials are generally far denser than the usable solvents, so this idea
is rather unrealistic. An additional suggestion is to heighten the visc-
osity of the solution to limit mobility of the particles, though this will
negatively impact the coating procedure [50]. A cartoon exhibiting the
morphology of particles due to a dispersant, thickening agent, and
3
Journal of Energy Storage 25 (2019) 100862
bridging network is displayed in Fig. 3.
Slurry blending is executed via one of three main mechanisms:
hydrodynamic shear mixing, ball-mill mixing, or ultrasonic homo-
genization. Shear mixers come in many varieties, such as planetary
mixers and Rushton turbines, and represent the most common in-
dustrial equipment [51–53]. Energetic ball-mill mixing has been de-
monstrated to degrade high-MW aqueous binders [54], meaning it may
be a technique best reserved to dry blend active materials and con-
ductive additives. Ultrasonic homogenization has received increasing
W.B. Hawley and J. Li
interest, since it is capable of producing better dispersions at lower
energy inputs than shear mixers [55,56] and is compatible with high-
performance conductive additives like carbon nanotubes [57,58].
However, there are scalability issues associated with ultrasonication,
since high-power systems have yet to sufficiently proliferate intensity of
cavitation. In addition to the equipment used, the order in which
components are added to the suspension is important. Dry-blending of
active materials and conductive additives [59–61] and sequential in-
corporation of solvent or solids [62–64] have both been shown to im-
prove contact between the active material and conductive additive,
which subsequently aids the electrochemical performance (see Fig. 4).
A detailed review of slurry preparation is presented by Kraytsberg and
Ein-Eli [65].
From a processability perspective, the ideal electrode slurry would
be capable of being coated at high speeds with few defects. Among the
most common industrial coating instrumentation is the slot-die coater,
in which the slurry is transferred through a slot gap onto a moving
substrate. Slot-die coating is a favorable slurry application technique in
that it is capable of operating at speeds demanded by industry and is
proficient in achieving even coating thicknesses with precision. Ding
et al. have contributed a comprehensive overview of the theory of the
slot-die coating technique [66].
Despite the effectiveness of slot-die coating, some defects may still
4
Journal of Energy Storage 25 (2019) 100862
Fig. 3. Stabilization methods due to a (a) dis-
persant, (b) thickening agent, and (c) bridging
polymer. Reprinted from Ceramics
International, 40, W. Bauer and D. Notzel,
Rheological properties and stability of NMP
based cathode slurries for lithium ion batteries,
4591–4598, Copyright (2014) with permission
from Elsevier [50].
Fig. 4. 3D phase map showing the effect of mixing sequence
and active particle shape (cubical, spherical, and polyhedral)
on conductive interfacial area. Empty shapes indicate small
particle size and filled shapes indicate large particle size. Blue
shapes indicate constant-temperature mixing and red shapes
indicate increased-temperature mixing. The one-step proce-
dure combined active material, conductive additive, binder,
and solvent at once. The two-step procedure added binder into
a mixture of the other components halfway through the total
mixing time. Multi-step-1 combined half of the active material
and half of the conductive additive in two identical steps prior
to adding binder, while Multi-Step-2 added all of the active
material at once and added half of the conductive additive in
two identical steps. Reprinted (adapted) with permission from
Z. Liu, V. Battaglia, P. P. Mukherjee, Mesoscale Elucidation of
the Influence of Mixing Sequence in Electrode Processing,
Langmuir, 30, 15102-15113. Copyright (2014) American
Chemical Society [64] (For interpretation of the references to
colour in this figure legend, the reader is referred to the web
version of this article).
arise, namely agglomerates, pinholes, metal particle contaminants, or
exaggerated non-uniformity [67]. These can occur due to insufficient
mixing, insufficient degassing of the slurry, or hardware malfunctions.
These defects have been observed inline by mounted laser caliper sys-
tems [68] and X-ray radiography [69]. Agglomerates and pinholes have
been shown to diminish coulombic efficiency during cycling, while
pinholes, metal contaminants, and non-uniformity all cause poor rate
capability [67].
Among the best methods to appraise the stability and processability
of an electrode slurry (and, therefore, the effectiveness of the homo-
genization procedure) is by characterizing its flow behavior via
rheology. Liu et al. have introduced basic rheology concepts in the
context of LIB electrodes [70]. It is widely acknowledged that the most
influential rheological feature of a slurry is its viscosity, which is im-
pacted by a number of constituent properties, including particle size,
shape, roughness, and charge; thermodynamic and hydrodynamic
forces; and solid fraction.
It is simplest to model electrode slurries as suspensions with a bi-
modal particle size distribution, with the active material particles being
substantially larger than the conductive additives. In this approxima-
tion, it can be reasonably predicted that the mass fraction of conductive
additives will contribute more to the slurry’s viscosity than that of ac-
tive materials [71]. This is because the smaller conductive additive
W.B. Hawley and J. Li
particles have a much larger specific surface area than the larger active
materials; thus, an incremental increase in the number of conductive
additive particles will generate extra particle-particle interactions than
an equivalent incremental increase in the number of active material
particles. These interactions contribute to the stress in the suspension
and, ultimately, its viscosity [19].
Realistically, this approximation is too simple, given that active
materials and conductive additives each exist in three size classes:
primary particles, aggregates, and agglomerates. Aggregates are col-
lections of primary particles which are held together by strong elec-
trostatic forces, and agglomerates are collections of aggregates which
are held together by weaker van der Waals interactions [65]. It is of
utmost importance that the mixing process disperse these agglomerates.
It has been shown that a higher slurry solid content can lead to a better
dispersion of conductive additive agglomerates, which leads to im-
proved electrochemical performance [49]. Schilde et al. attribute this to
a higher shear stress being generated in the slurry during mixing, which
also improves process time and energy efficiency [72]. Another ad-
vantage of an increased slurry solid fraction is the reduction of drying
time. Since industrial dryers have a finite length and there is desire to
increase production speed, it is imperative that the solvent fraction be
minimized so that it may be completely removed, as demonstrated by
Nguyen et al.’s pilot scale study [73].
A proper basis for the argument that viscosity is the paramount
feature of a slurry is the fact that coating instruments have limitations; a
slurry that is too thick is challenging to pump and apply homo-
geneously to the current collector. If the slurry were thinned out, the
slot-die coater would be capable of faster operation [74–76], though
slurries that are too thin may trickle during the coating operation and
lead to coating thickness variations [77]. Similarly, a lower viscosity
can strengthen the efficacy of vacuum pressure, which helps limit
variations in coating thickness and air bubble formation [5,78]. In
addition to the mechanical improvements, a low-viscosity slurry may be
loaded with more active materials and remain within the operational
window of the equipment. This presents two distinct advantages: (1)
the ability to construct a more energy dense electrode, and (2) a re-
duction in the amount of solvent necessary. In the case of N-methyl-2-
pyrrolidone (NMP)-based electrodes, the second advantage can be
monumental, since it is a hazardous chemical that is expensive to re-
cycle [79]. BatPaC simulations have estimated that the energy input
needed to recover NMP is roughly 45 times greater than the energy
required to vaporize it [13]. It should be noted that a trade-off is ob-
served if extra active materials are added, since this will increase the
viscosity of the slurry and reduce the maximum line speed and poten-
tially diminish the effectiveness of vacuum pressure. In summary, by
considering the slurry viscosity, the manufacturer can obtain an ex-
cellent combination of coating throughput, defect management, active
material density, and solvent minimization.
Tagawa and Brodd state that the viscosity of an electrode slurry
should range from 10 to 20 Pa s [80], though it is insufficient to report a
single value of viscosity without the context of shear rate. This is be-
cause the shear rate applied in a rheometer can be correlated to a
coating instrument’s coating speed. Consideration of the entire viscosity
curve as a function of shear rate allows for analysis of the low shear
viscosity (LSV), which is a gauge of how stationary the slurry will be
after it has been coated (Fig. 5). According to Bitsch et al., increasing
the LSV will produce sharper edge contours of the coating and thus
reduce waste generation. To attain a higher LSV, they added 1-octanol,
which is immiscible with water, to an aqueous anode slurry. This
strategy had negligible impact on high shear viscosity (HSV) and
electrochemical achievement [81].
Another rheological property of interest is the yield stress (σ0),
which represents the minimum force needed to induce flow in the
slurry. σ0 is a function of the cohesiveness of the microstructure present
in the slurry; once σ0 is surpassed, the suspension will flow. The optimal
method to measure σ0 is controversial; several experiments do not
5
Journal of Energy Storage 25 (2019) 100862
directly measure σ0 but instead derive general trends from the LSV of
the viscosity profile [36,45,82]. Others obtain values by fitting stress vs.
strain data to models, in particular the Herschel-Bulkley model
[43,83–85]. Bauer and Notzel identified the yield point as the transition
point in the stress vs. strain curve [50] (Fig. 5). Despite the ambiguity in
how measurements are completed, a mild σ0 (roughly 1–50 Pa) can help
resist sedimentation and only becomes problematic when it interferes
with the pumping and coating operations.
Viscoelasticity, though it is reported far less often than viscosity in
the literature, is also an important rheological consideration.
Viscoelasticity refers to the relationship between the viscous (or liquid-
like) and elastic (or solid-like) behavior of a material. Small amplitude
oscillatory shear techniques, like amplitude sweeps and frequency
sweeps, can reveal the viscoelastic character of the sample. In ampli-
tude sweeps, the frequency of oscillation is held constant while the
applied strain is increased (usually logarithmically), while a frequency
sweep does the inverse. The outputs of these tests are the storage
modulus, G’, and the loss modulus, G’’. G’ is a measure of the amount of
energy from the perturbation that is stored and is therefore a quanti-
fication of the elasticity of the material. G’’, then, is a measure of the
amount of energy that is dissipated as heat and is a quantification of the
viscous nature of the material.
At low strain in an amplitude sweep, the value of G’ will remain
relatively constant, indicating that the network structure is intact. This
region of cohesive network structure is referred to as the linear vis-
coelastic regime (LVR), and the constant value of G’ is referred to as the
equilibrium storage modulus, G’0, and is a descriptor of the strength of
the network. When G’ decreases to a value of 5–10 percent below G’0,
the network structure is disrupted. The strain at which this occurs is
referred to as the critical strain (γc) (Fig. 5). More commonly reported,
however, is the frequency sweep, where the relative magnitudes of G’
and G’’ are compared and the sensitivity of G’ to angular frequency is
evaluated. Generally, the more independent G’ is of frequency, the more
elastic is the slurry (Fig. 5). Frequency sweeps have been utilized to
differentiate between LiFePO4 (LFP) powders that had been dispersed
(D-LFP) or had gelled (G-LFP) in water. The G-LFP samples had G’ that
were less dependent on frequency than the D-LFP samples, and the
magnitude of G’ for the G-LFP samples was substantially greater than
that of the D-LFP samples [86–88]. This was ascribed to extra hydrogen
bonding (and thus agglomeration) resulting from the surface functional
groups [87]. It was also determined that the hydroxyl group present in
carboxymethyl cellulose (CMC), a thickening agent used in aqueous
slurries, promotes powder agglomeration [88]; however, the carbox-
ylate group present in CMC promotes powder dispersion [36]. In ad-
dition to indicating the stability of particles in the slurry, viscoelastic
characterization of a slurry is an indicator of its processability. Speci-
fically, a mildly elastic behavior has been shown to widen the opera-
tional window for slot-die coaters [89–92], though this finding is
system-specific and has yet to be examined for electrode slurries.
It must be emphasized that the slurry elements will dictate what
flow response is preferred. Specifically, the choice of organic (typically
NMP) or aqueous solvent will decide the particle arrangement more
conducive to an optimal slurry. Investigations executed using an or-
ganic solvent routinely call for weakly flocculated slurries whose binder
forms a volume-spanning network to prevent active material sedi-
mentation [82,83,85,86,93–96]. However, many studies performed on
aqueous-based systems reach a contradicting conclusion: that bridging
should be avoided and the best way to impart stability is through
electrostatic, or at least, electrosteric, measures
[35,39–41,43,45–47,97]. Tables 1 and 2 recap the rheological signature
of NMP-based and aqueous-based slurries from the literature, respec-
tively.
It seems that three factors must be considered when determining
whether a network structure will be beneficial: (1) the density of the
slurry, (2) the size of the active materials, and (3) the potential for
agglomeration. Regardless of surface charge, two forces act on colloidal
W.B. Hawley and J. Li Journal of Energy Storage 25 (2019) 100862

Fig. 5. Plots of commonly measured rheological properties for cathode slurries.

(a) Viscosity curves should be considered in two regions: the LSV, which should
be high in order to form sharper coating edges, and the HSV, which should be
low in order to facilitate faster, more consistent coating. (b) The yield stress can
be measured in several ways; in this plot, it is taken as the stress value corre-
sponding to the plateau region in a stress vs. strain curve. (c) In an amplitude
sweep, G’ remains constant within the LVR until the network structure is
broken at the critical strain, γc. (d) In a frequency sweep, the relative magni-
tudes of G’ and G’’, as well as the sensitivity of G’ to ω can provide information
on the solid-like or liquid-like response of the slurry.

particles: Brownian (FB) and gravitational (Fg). These forces may be Fg =

4
(ρ − ρm ) πr 3g
calculated according to Eqs. (1) and (2).17 3 p (2)
−23
FB =
kB Tabs In Eq. (1) and (2), kB is the Boltzmann constant (1.381 × 10 J K-
r (1) 1
), Tabs is the absolute temperature in Kelvin, r is the radius of the

6
W.B. Hawley and J. Li
Table 1
A summary of rheology of slurries using organic solvent. In this table, CB stands for carbon black, and B stands for binder. A * represents a slurry in NMP and a **
represents a slurry in tetrahydrofuran.
Slurry Constituents Mixing Procedure
Cathode Slurries
LFP and LiNiMnCoO2 Pre-mixed LFP or NMC and CA at 2800 rpm for 10 min, then
(NMC), CB, PVDF (B)* dispersed in a pre-mixed binder solution at 2000 rpm for
30 min. Solid loadings were 20 and 30 vol%.
LiNi0.5Mn1.5O4, CB, carbon Mixed slurry in dissolver mixer for 15 min at 2000 rpm,
nanofibers, PVDF (B)* passed slurry through three-roll-milling system to ensure
deagglomeration; examined slurry for industrial pilot scale
coating line
Li1.1V3O8, CB, PMMA (B)** Blended all constituents using a magnetic stirrer for 12 h.
Solvent concentration was varied from 0.002–0.01 mL mg−1.
LiCoO2 (LCO), CB, PVDF Pre-mixed LCO and CB for 1 h, mixed entire mixture for 2 h, at
(B)* 3000 rpm, agitated at 5 s−1 for 0 – 7 days. Solid loading was
70 wt%.
LCO, CB, PVDF (B)* Pre-mixed LCO and CB for 1 h, mixed entire mixture at
3000 rpm for 2 h and 7 more days, respectively. Solid loading
was 70 wt%.
Anode Slurries
Graphite, PVDF (B)* Solid loading was 40 wt%. Compared eight different kinds of
graphite.
particle, ρp and ρm are the densities of the particle and the suspending
medium, respectively, and g is the acceleration due to gravity (9.81 m s-
2
). As seen in Eq. (2), the density gradient partially governs the rate of
sedimentation. However, since NMP and water have similar densities,
the first factor is inconsequential. For nano-sized active materials, such
as LFP, sedimentation does not occur as rapidly as it would for micron-
sized active materials like lithium transition metal oxides, such as NMC
(LiNixMnyCo1-x-yO2). Therefore, the network structure is not as im-
portant for LFP-containing slurries. The third factor becomes particu-
larly relevant for aqueous-based slurries, as discussed.
Despite the information gained from rheological characterization of
slurries, Morelly et al. recently argued that it is not a reliable predictor
of battery performance [98]. This is evident in several studies, parti-
cularly the results of Hintennach and Novak who studied the influence
of surfactant chain length on agglomeration of titanium dioxide (TiO2).
Longer surfactant chains aided in dispersing the TiO2 particles, but the
suspension viscosity that resulted in the highest discharge capacity was
different for every surfactant [99]. In Bitsch et al.’s work, two similarly
performing electrodes were obtained whose slurries had distinct flow
responses. The slurry including secondary fluid had a higher LSV and
G’ > G’’, but behaved about the same as the slurry with no secondary
fluid, which displayed limited shear thinning and G’ < G’’ [81]. To
better predict electrochemical performance, the drying procedure,
which is known to have a strong impact on electrode architecture, must
be considered.
3. Drying process insights
Once the electrode slurry is coated, the solvent must be evaporated
from the film in a drying step. Electrode drying is a complex process
since it involves mass transfer in the solid, liquid, and vapor phases, as
well as heat transfer. During drying, there are three competing physical
7
Journal of Energy Storage 25 (2019) 100862
Comments Reference
High-MW PVDF (900,000-1,300,000 g mol−1) with LFP yielded [50]
viscosity of 10.8 Pa s (γ̇ = 50 s−1); low-MW PVDF
(370,000-450,000 g mol−1) had a viscosity of 1.0 Pa s (γ̇ = 50 s−1);
σ0 increased with binder MW. Slurries with coarse NMC powders
were much less viscous than LFP slurries. Inclusion of CB increased
viscosity; pre-mixing stage caused a decrease in viscosity for NMC
slurries (6.1 Pa s to 1.7 Pa s, γ̇ = 50 s−1).
Slurry mixed with 44 wt% solids and 52 wt% solids achieved nearly [73]
identical viscosity curves (at γ̇ = 0.1 s−1, μ =100 Pa s, and at
γ̇ = 100 s−1, μ =3 Pa s) and viscoelastic moduli (G’ > G’’ at low
frequency, crossover occurs between 0.1–0.8 Hz) due to reduction of
binder fraction. Reduced binder still allowed for good adhesion and
cyclability (fade of about 0.08 mA h g−1 per cycle). Lower solvent
content enabled industrially-acceptable drying times (˜3 min).
Low-concentrated slurry displayed Newtonian behavior; high- [82,85]
concentrated slurry had high σ0. Best slurry concentration
(0.006 mL mg−1) had distinct but mild σ0 (< 3 Pa).
Sample becomes more Newtonian as mixing time rises. LSV falls to [83]
10 Pa·s (γ̇ = 0.01 s−1) for the seven-day agitated sample; LSV is
200 Pa s (γ̇ = 0.01 s−1) for seven-day unagitated sample. G’ < G’’
for two-day agitated sample while G’ > G’’ for two-day unagitated
sample. Network structure degrades under low-agitation post-mixing.
LSV (γ̇ = 0.01 s−1) of seven-day slurry was about 15 Pa s (50 Pa s for [94]
freshly mixed case). HSV (γ̇ = 200 s−1) of seven-day slurry was about
1.5 Pa s (2.5 Pa·s for freshly mixed case). Both slurries were shear
thinning. Both slurries had G’ < G’’, though both moduli were
greater for freshly mixed case.
Viscosities of carbon particles varied by six orders of magnitude. All [95]
slurries were shear thinning. Viscosity was correlated to amount of
polymer adsorbed on graphite.
processes – evaporation of the solvent, diffusion of the binder, and se-
dimentation of the particles [100]. There are three primary methods by
which drying is studied in the literature. The first is to vary drying
parameters, such as the length or intensity of the drying process, and to
assess the resulting electrochemical performance of the electrode. Al-
though this approach delivers the most direct judgement of whether a
given procedure yields a viable electrode, it provides no insight into the
underlying drying mechanisms. Furthermore, it is difficult to attribute
discrepancies in output solely to a variation in drying parameters since
electrode manufacturing is an interconnected, complicated process.
More revealing are experimental methods that examine electrode
morphology; some of these include cryogenic scanning electron mi-
croscopy (cryo-SEM) [101–103], fluorescence microscopy (FM) [104],
X-ray photoelectron spectroscopy (XPS) [105], Raman spectroscopy
[106], energy-dispersive X-ray spectroscopy (EDX) [107], and energy
selective backscattering (ESB) [108]. Cryo-SEM and FM may be used in-
situ to monitor microstructure changes in real time, though they are
strictly qualitative approaches. Additionally, cryo-SEM requires ex-
pensive sample preparation, and FM requires a stand-in binder for
styrene butadiene rubber (SBR) latex [104]. Alternatively, XPS and
Raman can be utilized to obtain quantitative metrics of binder dis-
tribution, though they must be used post-mortem. Further, Raman re-
quires an unrealistically high binder concentration to enact [106]. ESB
has been demonstrated to be superior to EDX in its ability to distinguish
between carbon black, binder, and graphite in negative electrodes,
though this technique will require fine-tuning to be applied to cathode
materials containing heavier elements [108].
The third class of drying investigations employ computer simula-
tions. Given the specialized equipment and amount of time and labor
needed to carry out laboratory experiments to examine electrode
drying, simulation work is incredibly valuable in that it allows for re-
latively fast drying scenario evaluation. However, many of these studies
W.B. Hawley and J. Li Journal of Energy Storage 25 (2019) 100862

Table 2
A summary of rheology of slurries using aqueous solvent. In this table, AM stands for active material, CA stands for conductive additive, B stands for binder, D stands
for dispersant, and T stands for thickener.
Slurry Constituents Mixing Procedure Comments Reference

Cathode Slurries
LFP, CB, CMC (B)
LCO, graphite, polyacrylic latex
(B), PAA-NH4 (D)
LFP, CA, xanthan gum (B), PEI (D)
LFP, CB, PVA and polyethylene
glycol (B), CMC and HPMC (T)
LFP, graphite and CB, PBA-latex
(B), PSSA (D)
CMC solutions with a degree of substitution (DS) of 0.7 and
1.28 were compared. Solid loading was 40 wt%.
Slurries with varying PAA-NH4 content (0.001 to 0.1 wt%)
were blended by ball-milling with Y2O3-stabilized ZrO2
media for 24 h.
PEI was blended in water for 2 min. LFP and CB were added
in two subsequent 15 min blending stages. For slurries
containing xanthan gum, LFP and CB blending stages were
only 10 min, then xanthan gum was added and blended for
10 min. Xanthan gum concentration ranged from 0–2.0 wt
%.
A high energy mixer sheared the electrode slurry for
10 min. The concentration of surfactant Triton X-100
varied from 0.1–1.5 wt%.
Slurries were mixed by ball milling with Y2O3-stabilized
ZrO2 mixing media for 2-3 days. Solid loading was 40 wt%.
PSSA content varied from 0-4.0 wt%.
Both slurries were shear thinning with viscosity at γ̇ = 100 s−1 [39]
about 0.05 and 0.2 Pa·s for DS = 1.28 and 0.7, respectively.
LSV (γ̇ = 0.1 s−1) of the 0.1 wt% PAA-NH4 slurry was 1.5 Pa·s and [40]
for 0 wt% PAA-NH4 was 8.5 Pa s. The 0 wt% PAA-NH4 is shear
thinning while slurries with PAA-NH4 are Newtonian. Viscosity
decreases with increasing PAA-NH4 content. Best discharge
capacity was with a PAA-NH4 content of 0.01 wt%.
Suspensions including all constituents had no reductions in [43]
viscosity beyond PEI fraction of 1.5 wt%. Shear thinning behavior
at low shear rates (below γ̇ = 150 s−1) was strong, but above
γ̇ = 150 s−1, the suspension was Newtonian. Electrochemical
cycling data showed addition of PEI improved cathode
performance.
All slurries had shear thinning behavior, though as concentration [45]
of surfactant increased, LSV and HSV decreased. At γ̇ = 10 s−1,
viscosity of 1.5 wt% surfactant slurry was < 0.1 Pa·s, while slurry
with 0.1 wt% surfactant slurry was 2 Pa s. Gains in discharge
capacity are minimal beyond 1.0 wt% Triton X-100.
At high shear rate (γ̇ = 800 s−1), viscosity heightened between 0- [47]
1.0 wt% PSSA; declines between 1.0-3.0 wt%; remains
comparatively constant from 3.0–4.0 wt%. Viscosity (γ̇ = 800 s−1)
at 3.0 wt% PSSA is 0.2 Pa·s and for 1.0 wt% PSSA is 0.8 Pa s.
Electrochemical performance was optimized at PSSA fraction
=2.0 wt%.

Anode Slurries
Graphite, CMC (T), SBR (B)
Graphite, CMC (B), styrene-
butadiene copolymer latex
(T), PAA (D)
Slurries with a solid loading of 35 wt% were ultrasonicated
for 3 min, then allowed to rest for 12 h.
Slurries with a solid loading of 35 wt% were ultrasonicated
for 3 min.
Relative viscosity declines as CMC concentration increases from [35]
0.3 wt% to 1.5 wt%. At γ̇ = 100 s−1, apparent viscosity of 0.3 wt%
solution was 0.2 Pa s and apparent viscosity of 1.5 wt% solution
was 1.0 Pa s.
Sample with CMC concentration =0.9 wt% and PAA [41]
concentration =0.6 wt% was order of magnitude less viscous than
sample with no PAA and CMC concentration = 1.5% (20 Pa s and
200 Pa s at γ̇ = 100 s−1, respectively). Discharge capacity
retention after 500 cycles for PAA-containing electrode was 86%
and for PAA-less electrode was less than 65%.

Fig. 6. Step-by-step progression of the wet slurry drying process. Reprinted from Journal of Colloid Science, 494, S. Jaiser, L. Funk, M. Baunach, P. Scharfer, W.
Schabel, Experimental investigation into battery electrode surfaces: The distribution of liquid at the surface and the emptying of pores during drying, 22–31,
Copyright (2017), with permission from Elsevier [115].

use simplifying assumptions, such as one-dimensional drying, distinct to a higher internal resistance within the electrode
binder and solvent phases, colloidal stability, and values for heat and [17,100,104–107,110–118] because binder acts as a barrier for Li-ion
mass transfer coefficients [17,109–111]. insertion. In addition to the binder, movement of carbon black to the
Despite the flaws in drying investigations, there is unity among surface has been noted during drying [108,119].
researchers on some fundamentals of the drying process. First, there is A further point of agreement in the literature is that high tem-
general consensus on the existence of binder migration, which refers to peratures exacerbate the problem of inactive material inhomogeneity
the upward diffusion of binder to the surface of the coating during [106,110,117,120,121]. High temperatures lead to an escalated rate of
drying. This weakens the mechanical integrity of the coating and leads diffusion of solvent to the coating surface. Coatings dried at 150 °C had

8
W.B. Hawley and J. Li Journal of Energy Storage 25 (2019) 100862

three times as much binder at the surface layer than on the substrate 4. Calendering influence on morphology
layer, while a coating dried at room temperature was more uniform
[106]. Westphal and Kwade varied drying temperature and mass A dry electrode’s microstructure may be described with a number of
loading in graphite anodes and used adhesion strength as a measure of metrics that can be loosely correlated with its performance. One of
binder allocation. They found that as mass loading is increased, the these metrics is the tortuosity, which is the ratio of the average diffu-
optimal adhesion strength was observed at lower drying temperatures sion length across the electrode to the straight path length. Values of
[120]. Font et al. obtained similar results suggesting that greater drying tortuosity for porous electrodes in the literature vary from 2.5 to 30
rates led to greater binder migration. They explain that this is due to a [127–129], indicating (1) that experimental methods for measuring
faster upward binder convection and, since the total drying time is tortuosity may not yet be perfected, (2) that there are a multitude of
shorter, there is less time for the binder to redistribute itself via factors to consider when optimizing tortuosity, and, most obviously, (3)
Brownian motion [110]. that there is need for major advancement.
It has been seen empirically that drying does not advance in a Tortuosity has conventionally been believed to scale according to
single, constant-rate step. Initially, the top layer of solvent recedes in a the Bruggeman relationship, which is written in Eq. (3).
proceeding frequently called “film shrinkage.” Once this layer of liquid
has been evaporated, the solvent must be removed from where it has τ = ε −α (3)
been trapped between the solids in a stage called “pore emptying” (see
In Eq. (3), ε is the porosity and α is the Bruggeman constant, defined
Fig. 6). As drying proceeds, pore emptying becomes increasingly chal-
as 0.5. Despite its prevalence in the literature, the Bruggeman re-
lenging, since less free solvent is able to diffuse to the surface. These
lationship is far too simple to account for the complexities of electrode
underlying phenomena have provided reason as to why drying takes
manufacturing and the diversity of electrode materials used [130]. For
place in three distinct regions, which are (1) a short region of increasing
instance, tortuosity is traditionally measured in the through-plane (i.e.
drying rate, (2) a longer region of constant drying rate, and (3) a
perpendicular to the current collector) direction, while less developed
comparatively short region of decreasing drying rate. Simulations have
methods exist for quantifying the in-plane (i.e. parallel to the current
suggested that up to half of the drying time is devoted to withdrawing
collector) tortuosity [131,132]. Most tortuosity models also assume that
the final 10 percent of solvent, which highlights how difficult it is to
path lengths have constant cross-sectional areas, which is impractical
complete pore emptying [17].
[133]. Many experimental approaches have been developed to calcu-
The existence of these drying regions was elucidated through a
late tortuosity, including impedance measurements and tomographic
number of trial-and-error studies. Jaiser et al. initially exposed anode
imaging, though it is not our intention to review them at this time
coatings to high-drying rate (HDR) and low-drying rate (LDR) steps to
[129,131–135]. Similarly, research has been dedicated to determining
determine the best spacing between them. In this work, they discovered
the effects of material properties on tortuosity, such as particle shape
that the intermediate drying stage is most sensitive to HDR [122]. They
[131], size distribution [134], and binder content [136], though these
later established the characteristic solvent volume fraction, a system-
lie outside of the scope of this publication.
specific parameter that signal the transition from film shrinkage to pore
Calendering of electrodes has a noticeable impact on porosity and
emptying. In most scenarios, the characteristic solvent volume fraction
tortuosity. Unsurprisingly, an increase in compaction pressure leads to
was able to reliably predict the onset of the HDR-sensitive intermediate
a reduction in electrode thickness and an increase in electrode density
stage [123]. They were also able to define a second characteristic sol-
[137]. It follows that a strong calendering intensity will also increase
vent fraction, after which the drying rate may be increased again at the
the tortuosity of the electrode, since particles occupy less volume and
end of the drying process to accelerate production. Using these three
are thus closer together [134]. Calendering also has the effect of in-
drying regions, the first with an HDR, the second with an LDR, and the
creasing the aspect ratio of particles, which allows for more particles to
third with an HDR, and two characteristic solvent volume fractions,
be packed into a fixed volume element; however, this comes with the
they were able to maintain the adhesion obtained by a two-step drying
trade-off of increased tortuosity.
procedure (the first with an HDR and the second with an LDR) while
In terms of electrochemical performance, it had been observed that
reducing the drying time by 40 percent [116].
un-calendered graphite anodes yielded superior cycling performance
During drying, stress develops due to the shrinking coating liquid
due to a less perturbed microstructure [138]. However, the opposite
and causes cracking, curling, and delamination of the coating, parti-
had also been reported, with compressed electrodes showing a lower
cularly for aqueous slurries. A processing window map for systems
irreversible capacity loss, which was believed to occur due to less ex-
using CMC and SBR has been generated and determined that at a CMC
posed surface area [139]. Shim and Striebel observed that anodes
concentration of 0.5 wt%, the stress development proceeds in-
subjected to a moderate compaction pressure demonstrated the lowest
dependently of the SBR concentration [124]. This is a helpful finding
capacity loss [137]. They proposed that there exists an optimal ca-
for slurry processing, since it is of interest to minimize additives to
lendering intensity where the ohmic resistance and tortuosity, which
realize the most energy dense electrode. Cetinel and Bauer were able to
decrease and increase with increasing pressure, respectively [140], are
formulate NMC slurries with solid contents as high as 50 vol% with a
minimized.
CMC concentration of 0.5 wt%, while at a CMC concentration of 2.0 wt
Two techniques are used primarily to elucidate electrode micro-
%, the solid content did not surpass 30 vol% [125].
structure: focused ion beam-scanning electron microscopy (FIB-SEM)
As mentioned, aqueous processing presents engineering, environ-
and X-ray computed tomography (XCT). Researchers using FIB-SEM
mental, and economic advantages in the drying process. Wood et al.
have experienced difficulty separating phases due to poor contrast be-
concluded that the drying and solvent recovery costs can be cut in half
tween the cutting plane and solid behind pore openings, though
by switching traditional NMP solvent with water, though the biggest
Hutzenlaub et al. have demonstrated success distinguishing between
gains lie in equipment investment cost [33]. For a given solid loading in
active material, binder, and pore space [141]. Shearing et al. used XCT,
the slurry and areal loading in the dried electrode, the drying time of an
a non-destructive imaging technique, at multiple length scales on
aqueous slurry is expected to take longer than that of an NMP-based
porous LIB electrodes and discovered good agreement between por-
slurry, though it has been demonstrated that water-based slurries can
osity, tortuosity, and pore connectivity [142]. Still, conclusions are
generally achieve higher solid loadings (60 wt%) than NMP-based
difficult to reach from these techniques, as electrode morphologies are
slurries (45 wt%) due to a smaller viscosity contribution from the
still very heterogeneous. Features of heterogeneous electrodes are: (1)
binder [126]. Wood et al. found that this reduction in solid loading
locally poor connectivity of active material [143], (2) more rapid
from NMP-based to water-based suspensions could reduce the dwell
dendrite formation, and (3) non-uniform current flow [144].
time necessary for drying by 27 percent [33].

9
W.B. Hawley and J. Li
Fig. 7. SEM images showing similarity in microstructure between cathodes made with PVDF (a and b) and EB-cured acrylated polyurethane (c and d). Republished
with permission of Electrochemical Society, Inc., from Electron Beam Curing of Composite Positive Electrode for Li-Ion Battery, Z. Du, C. J. Janke, J. Li, C. Daniel, D.
L. Wood III, 163, 13, 2016; permission conveyed through Copyright Clearance Center, Inc [146].
5. Next generation electrode processing
Based on this discussion, drying protocols currently used in-
dustrially seem to have unavoidable constraints on drying speed if
electrode microstructure is to be preserved. Therefore, innovations in
the drying process are necessary to strengthen productivity. Currently,
a scalable method of reducing solvent content in electrode slurries is the
utilization of extruders, which require 50 percent less solvent than
standard planetary mixers [145]. Another pathway to solvent reduction
is the implementation of curable technology, such as ultraviolet and
electron beam (EB) curing, which can be utilized to cross-link low-MW
polymers. This is advantageous in the drying stage since less solvent (or
none at all) is present in the slurry, but the cohesion and adhesion will
not suffer since these polymers will be cross-linked after coating. Du
et al. have demonstrated this promising strategy on a laboratory scale
and an industrial scale (coating speeds of 150 m min−1) with acrylated
polyurethane oligomers in water. The cathodes they synthesized
achieved comparable electrochemical performance to those made with
the conventional NMP/PVDF chemistry [146] (Fig. 7).
Another solution under development is the elimination of solvent
from manufacturing entirely. One such dry coating technique is elec-
trostatic spray deposition (ESD) (see Fig. 8). Al-Shroofy et al. used ESD
to dry coat a cathode consisting of NMC111, carbon black, and PVDF.
After dry mixing the solids, an electrostatically charged spray gun was
employed to spray them onto an electrically grounded aluminum foil.
Although their dry coated electrodes were slightly less capable than the
wet coated control electrodes at high discharge rates, the dry coated
electrodes showed superior cycle life, particularly after 200 cycles.
Their ESD setup was able to produce an electrode sheet that was
18 mm × 25 mm in one minute, so the scalability of this procedure is
still in question [147]. A similar dry coating method proposed by Wang
et al. produced LCO cathodes with superior rate capability and cy-
clability and lower cell polarization compared to a wet-coated electrode
10
Journal of Energy Storage 25 (2019) 100862
[148].
An intriguing and potentially more energy-efficient technique than
ESD is the solvent-less, binder-less, room temperature dry roll-to-roll
manufacturing (DR2R) technique introduced by Kirsch et al [149].
DR2R mixes holey graphene, a compressible carbon material [150],
with active material, then presses the mixture at a pressure of about
20 MPa. Pressing takes place between two aluminum sheets; one to
prevent adherence to the die and the other to use as a current collector,
though the authors demonstrate that this technique is capable of gen-
erating freestanding electrodes. Kirsch et al. show that pressing at
20 MPa for only 10 s can create an LFP cathode (11.6 mg cm−2) with no
structural changes and comparable rate capability with a traditionally
produced cathode [149]. DR2R has the potential to be a far more en-
ergy and time-efficient procedure than traditional, wet slurry coating,
though the manufacture of holey graphene is elaborate in that it must
be synthesized in a tube furnace at 430 °C for 10 h with a yield ranging
from only 70–80 percent [151] (Fig. 9).
Another opportunity exists in the thickening of electrodes to achieve
more energy and power-dense cells. Thick electrodes also allow for
faster assembly times [152] and cost effective processing, since fewer
expensive inactive materials (namely current collectors and separators)
are necessary. It has been suggested that doubling the cathode thickness
from 50 μm to 100 μm could reduce cell cost by up to 25 percent [153].
Within thin electrodes with micron-sized active particles, it is specu-
lated that the rate-limiting step is the solid state diffusion of ions
through the host material [154]. However, as electrodes are thickened,
ion diffusion lengths become longer and mass transport becomes in-
creasingly restrictive, particularly at high C-rates [152]. Physically,
thick electrodes are limited by cell polarization and inaccessibility of
active materials [155]. In LCO-based cathodes, this problem is espe-
cially deleterious as the stoichiometric lithiation limit is reached [156].
It has been demonstrated that mass transport resistance can become the
rate limiting factor in electrodes that are 106 μm thick [157].
W.B. Hawley and J. Li Journal of Energy Storage 25 (2019) 100862

Fig. 8. Electrostatic spray deposition coating process for an LIB cathode. Reprinted from Journal of Power Sources, 352, M. Al-Shroofy, Q. Zhang, J. Xu, T. Chen, A. P.
Kaur, Y.-T. Cheng, Solvent-free dry powder coating process for low-cost manufacturing of LiNi1/3Mn1/3Co1/3O2 cathodes in lithium-ion batteries, 187–193, Copyright
(2017), with permission from Elsevier [147].

Material modifications have been proposed as a means to boost
discharge performance as the intercalation limit is reached [158],
though engineering controls, in particular the management of tortu-
osity, could supply a more pragmatic alternative. The consequence of
the aforementioned research is the understanding that minimizing
tortuosity should be a priority in modern electrode engineering if en-
ergy density goals are to be met. This has led to the origination of a
number of novel electrode manufacturing practices that deviate from
orthodox wet slurry processing. Specifically, the design of three-di-
mensional (3D) electrode architectures featuring pathways of near-unit
tortuosity have been demonstrated to improve cell capacity at realistic
charge and discharge rates. Creating organized, straight, narrow pore
channels eliminates the trade-off between tortuosity and porosity (see
Eq. (3)) that is characteristic of random electrode microstructures
[159].
Manipulated electrode architectures have been researched for mi-
crobattery applications [160–164] and have served as the template for
techniques utilized in larger cells. Bae et al. combined coextrusion with
a sintering approach similar to that used by Lai et al. [160] to fabricate
electrodes they had modeled with dual-scale porosity. Their procedure
passed electrode suspensions through feedrods, creating straight,
narrow, cylindrical channels, and assembled them into an electrode.
The non-active materials were removed via sintering to maximize en-
ergy density. SEM images revealed that three passes through the ex-
truder created an aligned, low-tortuosity pore structure; these elec-
trodes were capable of an impressive 7 mA h cm−2 at a discharge rate of
2C [165]. Cobb and Solberg found that using a coextrusion approach
can cut the inactive materials in a pouch cell assembly by greater than
40 percent [166].
An alternative method of pore alignment is freeze casting.
Currently, at least for electrode manufacturing, this idea has only been
applied to water-based electrode slurries. However, when considering
the industrial desire to administer aqueous processing, this is hardly a
setback. In freeze casting, slurry is coated onto a moving substrate like
in traditional wet slurry processing; once cast, the substrate is cooled
below the freezing point of the solvent. If cooled sufficiently quickly,
the ice forms thin crystals that organize the slurry ingredients into the
spacing between the crystals. The ice is then sublimed, leaving straight
pores. Additive-free structures can be created by sintering the resulting
electrode, though this is not a requirement. The noteworthy parameters
in freeze casting are the freezing rate, slurry composition, and sintering
temperature (if applicable). Behr et al. observed a decline in pore

Fig. 9. Dry roll-to-roll manufacturing technique for an LIB electrode. Reprinted (adapted) with permission from D. J. Kirsch, S. D. Lacey, Y. Kuang, G. Pastel, H. Xie,
J. W. Connell, Y. Lin, L. Hu, Scalable Dry Processing of Binder-Free Lithium-Ion Battery Electrodes Enabled by Holey Graphere, ACS Appl. Energy Mater. 2 (2019)
2990–2997. Copyright (2019) American Chemical Society [149].

11
W.B. Hawley and J. Li
channel spacing with increasing cooling rate and an inhomogeneous
crystal thickness for all formulations. They argue that this is detri-
mental to battery performance, since thinner crystals would reach a
lower state of charge and would be drained more quickly [167]. The use
of a co-solvent, like sucrose or ethanol, could assist in controlling ice
crystal thickness [168]. Delattre et al. similarly found that for Li-
Ni0.8Co0.15Al0.05O2 cathodes faster cooling rates led to lower pore
spacing and increasing tortuosity. Although they were able to obtain a
tortuosity value around 2.0 for a cooling rate of 7.5 °C min−1, the area
specific capacity of this cathode had fallen 67 percent when the dis-
charge rate was increased from C/10 to 1C [135].
One scalability concern with coextrusion and freeze casting is that
they require high temperatures for sintering. One pore alignment
strategy that has been employed at room temperature is laser struc-
turing [169–172]. In this approach, a laser ablates microchannels
within the coated electrode to facilitate faster ion transport. Smyrek
et al. obtained a capacity retention of about 50 percent at a discharge
rate of 3C in their laser-structured 100 μm thick NMC cathode, which
was better than the 35 percent retention demonstrated by the ca-
lendered 100 μm thick NMC cathode [171]. Pfleging et al. exhibited
marginally better cyclability for laser-structured NMC cathodes when
compared with unstructured cathodes [170]. Using laser-induced
breakdown spectroscopy, Smyrek et al. elucidated increasing lithium
concentrations around the microchannels during cycling [172]. This
result exposes the effectiveness of laser-structuring in expediting ion
diffusion.
Although the initial results of laser structuring are promising, one
drawback is the need of specialized equipment. A solution to this is to
create pore matrices through alignment via a magnetic field [173–175].
The principle of this approach is to include an additive that is re-
sponsive to a low-strength magnetic field, then to use this field to align
a pore structure within the electrode. Sander et al. added sacrificial
pore-forming agents in the form of magnetic microrods and magnetic
emulsion droplets that were later sintered out. Using this method, they
obtained 310 μm thick LCO cathodes capable of delivering three times
the discharge capacity of a conventionally manufactured LCO cathode
at 2C [173]. Billaud et al. used a similar strategy, though instead of
using sacrificial additives they coated graphite flakes with electro-
chemically inert superparamagnetic iron oxide nanoparticles (SPIONs)
to produce thick anodes. Using SPIONs, the magnetic field strength
required to orient the graphite flakes was only 100 m T for a loading of
3.2 mA h cm−2. The aligned anodes demonstrated three times the spe-
cific charge of an unaligned electrode at 2C [174]. Li et al. produced
LCO cathodes with a tortuosity of 1.93 that were 400 μm thick. This
approach was preferable to that proposed by Sander et al. in that it did
not require sintering of the electrode, though Li et al. did utilize ul-
trasonic homogenization as a means of preparing the slurry, which is
not yet a feasible large-scale mixing method. Additionally, their elec-
trodes demonstrated a capacity retention of only about 20 percent at a
discharge rate of 2C, indicating room for improvement [175].
Another method utilizing a sacrificial pore-forming agent is the
micro-templating technique demonstrated by Singh et al. [149]. So-
dium bicarbonate (NaHCO3) is dissolved in NMP, then slurry con-
stituents are added and mixed. After coating, drying, and calendering
the electrode, it can be washed with DI water, which reacts with
NaHCO3 to form NaOH and CO2 which are easily removed, leaving
behind an interconnected pore structure. The authors utilized a low
solid loading in the slurry (25 wt%), meaning a significant amount of
NMP was necessary to fabricate these electrodes. While the rate per-
formance of the micro-templated electrodes was significantly better
than the baseline, the highest mass loading tested was 7.5 mg·cm−2, a
loading far lower than that of other successful techniques [149].
Among the thickest electrodes reported in the literature were fab-
ricated according to a filtration technique used by Zolin et al, reaching
an areal capacity of 20 mA h·cm−2 [176]. Though filtration has been
demonstrated as a successful technique to produce electrodes
12
Journal of Energy Storage 25 (2019) 100862
[177–179], these studies have necessitated the use of cellulose fibril
binders in a high weight percent that ultimately could not be attached
to a current collector. By first filtering a binder-less slurry, solvent was
rapidly dried from the sample. Second, a small amount of binder so-
lution was added, such that the final binder content in the electrode was
as low as 1 wt%. This technique was successful due to small punctures
made in the current collector with protruding edges. These burrs al-
lowed for successful filtration and achieved adhesion through me-
chanical interlocking. To enable adhesion between the initial binder-
less slurry and the current collector, the authors used carbon nanofi-
bers. Though these materials are relatively expensive, Zolin et al. report
that manufacturing thick cathodes in this manner still saves the man-
ufacturer roughly 23 percent compared to standard processing
(NMC111/graphite cell, 50 Ah with 400 cm2 active surface area) [176].
The thickest NMC111 cell assembled (20 mA h cm−2) demonstrated 90
percent capacity retention after 100 cycles (charge and discharge at C/
10, 2.5–4.2 V) and delivered 15 percent specific discharge capacity at
1C [176]. These performance metrics need to be improved for this
technique to be adopted industrially; two avenues of improvement
could be integrating an organized pore structure (i.e. reducing cell
tortuosity) and, as the authors suggest, the development of an electro-
lyte with higher ionic conductivity.
Manipulation of electrode architecture on both the macro- and
micro-scale was achieved by Li et al. by combining an additive manu-
facturing extrusion process with exposure to an electric field [180]. In
the additive manufacturing procedure, a base coating was applied to
the current collector, followed by a digitally structured layer. After
printing, a 10 kV electric field was applied to the electrode, aligning the
active materials in the direction parallel with the field (similar to
magnetic alignment discussed previously). Though the authors con-
ceded that the printing process takes longer than state-of-the-art slot-
die coating, the drying process proceeded much more quickly due to a
heating substrate at the end of the extruder. Cycling these electrodes
against a lithium anode, the authors found that their LiMn2O4 cathode
produced with both macro- and micro-control showed 21 percent, 16
percent, and 7 percent higher areal capacity than cathodes with no
structuring, cathodes with macro-structuring, and cathodes with micro-
structuring, respectively [180].
A final interesting innovation with the goal of thickening electrodes
is the development of a semi-solid electrode. Semi-solid cathodes are
prepared without binder and are pre-mixed with electrolyte [181],
which replaces the volume that would be occupied by binder. Chiang
et al. claim to have created semi-solid cathodes that are between 35 and
75 vol% active material and with a thickness ranging from 250 μm to
2 mm. These cathodes are capable of areal specific capacities of
7 mA h cm−2 at C/4 and 2 mA h cm−2 at 5C [182]. These cathodes will
require coating methods not commonly seen in battery processing,
since Chiang et al. claim the viscosity of the semi-solid cathode ranges
between 1000–100,000 Pa s at 1000 s-1; this is too viscous for slot-die
coating.
6. Conclusions and outlook
It is a compelling time in the history of LIB electrode fabrication,
given that industry has accepted wet slurry processing as a relatively
cost effective avenue of production. As the global LIB manufacturing
capacity is rising rapidly, a significant investment has been made in wet
slurry processing equipment. Despite this, slurry formulation, coating,
and drying are still insufficiently understood, particularly given the
large number of combinations of slurry ingredients, to state definitively
that wet slurry processing has been optimized. Furthermore, to meet
the U.S. DOE cost target for LIBs, continuous cost cutting from electrode
manufacturing is mandatory. This lies in reducing inactive components,
developing solvent-free processing, and acquiring better understanding
of slurry properties, deposition methods, drying mechanisms, and
electrode properties. Specifically, the following areas need to be
W.B. Hawley and J. Li
considered:
• Viscosity, the most readily reported and critical rheological feature
of a slurry, must be considered in the context of the shear rate, since
a higher LSV can minimize scrap and lead to a more stable coating
and a lower HSV makes the coating operation faster and less prone
to defects
• The optimal slurry microstructure is dependent on how susceptible
the particles are to agglomeration and sedimentation
•
Viscoelasticity measurements correlate with the strength of a brid-
ging network and are therefore a descriptor of sedimentation re-
sistance, though little can be said definitively about the impact of
viscoelasticity on coating
• Rheology can, to a limited extent, be a general indicator of coating
homogeneity and therefore electrochemical performance, but em-
pirical evidence suggests that it alone is not a reliable predictor
• Some slurry characteristics, such as appropriate binder concentra-
tion, must be informed by findings from the drying process
•
To strike a balance between production speed and microstructure
preservation, the drying rate must be varied according to how sen-
sitive the underlying mechanism is to the drying rate
• To realize more cost effective, less hazardous production, it is in the
interest of the producer to (1) supplant the toxic solvent NMP with
water, (2) minimize the amount of solvent used, or (3) replace wet-
coating approaches with dry-coating techniques
•
Novel deposition methods are needed for high speed coating
• A scalable procedure to manipulate the pore alignment in electrodes
that is applicable to a variety of anode and cathode materials is
essential to enhance energy and power density of LIBs
• Tailored electrode architectures are an effective way to boost power
density and possibly to enable fast charging, but their effect on cycle
life needs to be verified
Acknowledgements
This research at Oak Ridge National Laboratory (ORNL), managed
by UT Battelle, LLC, for the U.S. Department of Energy (DOE) under
contract DE-AC05-00OR22725, was sponsored by the Office of Energy
Efficiency and Renewable Energy (EERE) Vehicle Technologies Office
(VTO) (Deputy Director: David Howell; Applied Battery Research (ABR)
Program Manager: Peter Faguy). The authors thank Linxiao Geng
(ORNL) for his assistance in revising the manuscript.
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