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Technical and Economic Analysis of Solvent-Based Lithium-Ion Electrode

Drying with Water and NMP

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DOI: 10.1080/07373937.2017.1319855

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 Drying Technology
An International Journal

ISSN: 0737-3937 (Print) 1532-2300 (Online) Journal homepage: http://www.tandfonline.com/loi/ldrt20

Technical and economic analysis of solvent-based

lithium-ion electrode drying with water and NMP

David L. Wood, Jeffrey D. Quass, Jianlin Li, Shabbir Ahmed, David Ventola &
Claus Daniel

To cite this article: David L. Wood, Jeffrey D. Quass, Jianlin Li, Shabbir Ahmed, David Ventola &
Claus Daniel (2018) Technical and economic analysis of solvent-based lithium-ion electrode drying
with water and NMP, Drying Technology, 36:2, 234-244, DOI: 10.1080/07373937.2017.1319855

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 DRYING TECHNOLOGY
2018, VOL. 36, NO. 2, 234–244
https://doi.org/10.1080/07373937.2017.1319855

none defined

Technical and economic analysis of solvent-based lithium-ion electrode

drying with water and NMP
David L. Wood IIIa, Jeffrey D. Quassb, Jianlin Lia, Shabbir Ahmedc, David Ventolab, and Claus Daniela
a
Oak Ridge National Laboratory, Energy and Transportation Science Division, National Transportation Research Center, Knoxville, TN, USA;
b
Babcock & Wilcox MEGTEC, De Pere, WI, USA; cArgonne National Laboratory, Chemical Sciences and Engineering Division, Argonne, IL, USA

ABSTRACT ARTICLE HISTORY

Processing lithium-ion battery (LIB) electrode dispersions with water as the solvent during primary Received 5 December 2016
drying offers many advantages over N-methylpyrrolidone (NMP). An in-depth analysis of the Accepted 4 April 2017
comparative drying costs of LIB electrodes is discussed for both NMP- and water-based dispersion KEYWORDS
processing in terms of battery pack $/kWh. Electrode coating manufacturing and capital equipment Coatings; energy analysis;
Downloaded by [Oak Ridge National Laboratory] at 07:59 03 January 2018

cost savings are compared for water vs. conventional NMP organic solvent processing. A major heat and mass transfer;
finding of this work is that the total electrode manufacturing costs, whether water- or NMP-based, porous media; transport
contribute about 8–9% of the total pack cost. However, it was found that up to a 2 � reduction in phenomena
electrode processing (drying and solvent recovery) cost can be expected along with a $3–6 M savings
in associated plant capital equipment (for a plant producing 100,000 10-kWh Plug-in Hybrid Electric
Vehicle (PHEV) batteries) using water as the electrode solvent. This paper shows a different
perspective in that the most important benefits of aqueous electrode processing actually revolve
around capital equipment savings and environmental stewardship and not processing cost savings.

Introduction adding to the poor understanding of the cost

contributions of these steps to LIB manufacturing, as
Conventional electrode processing in lithium-ion
well as adding to the difficulty of meeting the ultimate
battery (LIB) manufacturing represents a significant
cost target and realizing widespread electric vehicle
$/kWh cost due to complex slurry mixing (formulation
commercialization.
chemistry) procedures, high energy consumption from
In addition to the processibility and economic issues
electrode drying, and N-methylpyrrolidone (NMP)
with LIB coatings, drying is also critically important to
solvent recovery. In addition, the costly processing aids
obtain high-integrity electrodes and has been addressed
of NMP and polyvinylidine fluoride (PVDF) are needed
in This Journal by Baunach et al.[2] They found that the
to manufacture the electrode slurries. Processing with
drying temperature used in an NMP/graphite anode
water instead of NMP offers the following advantages:
system strongly impacted the dried coating’s ability to
(1) elimination of solvent recovery, (2) processing aide
withstand the 90° peel test without flaking or cracking.
(solvent) cost savings, (3) substantial capital equipment
Lower drying temperatures were found to give both
savings, (4) environmental friendliness (green chemical
better binder distribution and coatings with superior
engineering), and (5) easier battery manufacturing plant
current collector adhesion and particle cohesion.
siting and permitting. To meet the Department of
This paper will focus on the solvent (primary) drying
Energy, Vehicle Technologies Office and United States
and recovery aspects of LIB electrode manufacturing at
Advanced Battery Consortium ultimate pack cost target
industrial scale. Due to the high boiling point of NMP
of �$125/kWh at ≥350 Wh/kg, low-cost,[1] advanced
(204.3 vs. 100°C for water) and the extremely low vapor
electrode processing methods are needed to offset the
pressure of NMP (1.0 mm Hg at 40°C vs. 55.3 mm Hg
inherently high cost of active materials. Little has been
for water), a great deal of drying energy is needed for
published in the open scientific literature on this topic,

CONTACT David L. Wood III wooddl@ornl.gov Oak Ridge National Laboratory, Energy and Transportation Science Division, National Transportation
Research Center, 2370 Cherahala Blvd., MS-6479, Knoxville, TN 37932, USA.
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/ldrt.
Notice: 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 nonexclusive, paid-
up, irrevocable, world-wide license to publish or reproduce the published form of this manuscript, or allow others to do so, for the 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).
© 2017 Taylor & Francis

removing the liquid during electrode coating formation.
However, use of NMP does offer a significant advantage
over water in terms of heat of vaporization on a mass
basis (510 vs. 2260 kJ/kg for water). This paper will
cover how these competing physical properties of
NMP and water contribute to electrode manufacturing
drying energy consumption. It is also a follow-up study
to the recent Oak Ridge National Laboratory (ORNL)
study from Wood et al.[3] In that study, it was estimated
that switching from NMP to water for LIB electrode
processing could save as much as 10.5% on the pack
production cost, reducing the cost of NMP-based
materials, and drying of $54.7/kWh—usable
($38.3/kWh—total), down to $2.09/kWh—usable
($1.46/kWh—total) for that of water.
Downloaded by [Oak Ridge National Laboratory] at 07:59 03 January 2018
In addition, NMP as a volatile organic compound
(VOC) must be recovered by a chemical process such
as condensation or vacuum distillation because it is
toxic, flammable, and explosive, which adds significant
cost to the overall handling of NMP during electrode
coating. Water may simply be released into the atmos-
phere, adding a substantial environmental benefit to
aqueous electrode processing. The LIB electrode coating
lines that utilize NMP must also be designed to prevent
a fire or explosion, increasing the capital cost of a
battery plant.
Comparison with BatPaC, TIAX, and ORNL cost
estimations
Several important studies have been done, which
consider the pack-level cost implications of LIB
electrode processing. BatPaC,[4] Argonne’s spreadsheet-
based performance and cost model for automotive
battery packs, has been widely used to project battery
costs. For a 10 kWh 60 kW PHEV battery with
LiNi0.6Mn0.2Co0.2O2/graphite chemistry, the battery
pack is estimated to cost ~$2,930, when produced at a
plant capacity of 100,000 packs per year. Electrode
processing, which includes materials preparation, elec-
trode coating and drying, NMP recovery, calendering,
interprocess material handling, and slitting contributes
$240 to the cost of the battery pack. More specifically,
the drying and NMP recovery contribute $54 (1.8%)
and $24 (0.8%), respectively, to the cost of the battery,
which is equivalent to $7.8/kWh, or about 15% of the
electrode processing costs given by Wood et al.[3] This
substantial difference is believed to be due to the fact
that low volumes were used in the latter work as com-
pared with the much higher volume of 100,000 packs
in the former work.
TIAX analysis[5] has suggested that the cathode
(LiNixCoyAl1-x-yO2 or “NCA”) coating and drying
DRYING TECHNOLOGY 235
processes contribute 19–22% of the electrode prep-
aration cost, where the electrode preparation represents
between 27 and 40% of the processing costs, and the
processing cost ranges from $60 to 80/kWh toward
the cost of a PHEV battery with NCA cathode material.
In other words, the electrode coating and drying were
estimated at about 8.8% of the processing costs, and
the processing costs at $80/kWh represent about 20%
of the pack cost at ~$400/kWh. Therefore, the coating
and drying costs estimated by TIAX are 8.8 of 20%, or
about 1.8% of the total pack cost, and are in relatively
good agreement with the BatPaC modeling. Son has
also reported performance benefits of non-NMP dry-
electrode coating, which led to lower measured area-
specific impedance and faster rate capability.[6] Jaffe
estimates that the cost of large format batteries will level
off just under $200/kWh by 2017.[7]
Manufacturing benefits and technical barriers
of water-based electrode processing
The benefits of switching from an organic solvent to
water for any chemical process are quite advantageous,
but it is particularly advantageous in LIB production
because expensive NMP ($1.5–3.0/L in bulk quantities)
is used as the electrode slurry processing aide. Other
economic benefits have been estimated as well, includ-
ing up to a 10% reduction in total capital costs, up to
85% reduction in waste management expenses, at least
65% reduction in solvent costs, and ~10% reduction
in pack cost per Wh.[8] Facility construction benefits
consist of complete reduction in VOC emissions, lower
drying energy consumption and thermal budget, and
simpler siting and permitting. An interesting environ-
mental benefit was also calculated by Zackrisson et al.
who determined significantly lower life-cycle CO2
emissions in producing a 10 kWh battery pack could
be attained (4,400 kg for NMP-based processing vs. only
3,400 kg for aqueous processing).[9]
Aqueous electrode processing presents three major
challenges, though, related to both processability and
cell performance. First, the water-based slurries have a
much higher surface tension than their NMP based-
counterparts and do not properly wet the Al and Cu
current collector foils (whose surface energies are only
~35–40 mN/m). The surface tension of water is
72.8 mN/m, compared with only 41.0 mN/m for NMP
(at 25°C), and the composite water-based slurries with
active material, conductive carbon black additive, and
polymer binder may be as high as 65 mN/m. The
second problem is excessive particle agglomeration
(between active material secondary particles, between
carbon black secondary particles, or between active
 236 D. L. WOOD ET AL.
material and carbon black secondary particles), which
is caused by attractive interactions between colloidal
particles. This situation may result in inhomogeneous
distribution of electrode components and poor
electrochemical performance if not properly handled
with dispersants, thickening agents, optimal mixing
protocols, and coating parameter optimization.
Third, processing the active materials in water leaves
additional chemisorbed and physisorbed water and
hydroxyl groups on the particle surfaces, which must
be removed through an optimized “secondary” drying
protocol (adsorbed water removal after a discrete
coating roll has been made and just prior to cell
assembly). ORNL has solved all three of these
problems over the past 5 years, in particular for the
Downloaded by [Oak Ridge National Laboratory] at 07:59 03 January 2018
cathode, and now uses both anode and cathode aqueous
electrode processing for LIBs as a standard operating
procedure.[10–17]
Problems and performance concerns with
water-based electrode processing
If not handled properly, water-based electrodes may
have certain problems and performance limitations.
One is metal dissolution in water during processing.
For example, when LiFePO4 is exposed to water for
one day, the solvated concentration of Li ions is 9.4 �
0.9 mg/L, and this value continues to increase with
exposure time. The active material solubility in water
affects the shelf life of aqueous slurries, and dissolved
Li could lead to lower cell capacity if these ions are
not intercalated back into the active cathode. It has been
shown, however, that de-intercalated Li via air or water
exposure can re-intercalate into the active cathode
material, such as LiFePO4.[18]
Two additional concerns are inferior wetting of
aqueous slurries onto current collectors, resulting from
high surface tension of the slurry, and lower adhesion
strength of the electrode to the current collector from
waterborne binders than PVDF, which affects cycle life.
Furthermore, drying the aqueous slurry is more
challenging, and the likelihood of forming cracks is
higher if the drying protocol is not optimized. Water-
borne binders are typically more hydrophilic than
PVDF, so aqueous processed electrodes more readily
adsorb moisture. Assuming that the secondary drying
protocol and cell assembly time are the same (for
water-based and NMP-based slurries), the aqueous pro-
cessed electrodes tend to have higher moisture content
in the assembled cells, which also affects long term
performance.
The following important questions related to LIB
electrode drying will be addressed in detail based on
real-world electrode manufacturing equipment and
processes:
. What are the cost drivers related to energy consump-
tion during drying of lithium-ion electrodes?
. What is the actual energy consumption and proces-
sing cost benefit in switching from NMP to water?
. How are the coating and drying processes simplified
in switching from NMP to water (process flow
diagram (PFD) comparison)?
. How do lithium ion cells manufactured with water-
based electrode processing compare in performance
to NMP processed ones?
Background
The drying of aqueous and solvent-based LIB coatings is
a critical operation in the production of battery electro-
des from cost, electrode quality, and electrode perfor-
mance standpoints. This unit operation often requires
the largest equipment and the greatest amount of energy
in the entire coating process. Often the drying
equipment design and operating conditions affect the
throughput and quality of the product, and it is impor-
tant to understand and characterize the drying process
to produce quality product in an efficient manner.
The drying process can be divided into three
periods: heat-up, constant-rate, and falling-rate regimes.
Figure 1 shows a typical drying curve for a coated web.
Most of the solvent or water is removed during the
constant-rate period. During this period, the solvent
reaches the surface of the coating relatively unimpeded
and the major resistance to mass transport is in the gas-
phase boundary layer at the surface of the coating. The
falling-rate period follows the constant-rate period and
typically accounts for only a small fraction of the total
water or solvent removed. However, the falling-rate per-
iod can represent a significant portion of the overall
drying time needed to achieve the final properties of
the dried product. During the falling rate period, the
solvent is partially impeded from reaching the surface
of the coating as the major resistance to mass transport
is within the porous volume of the coating phase:
Experimental trials are often necessary to access drying
time requirements in the falling rate period.[19]
To calculate the rate of drying in the constant-rate
period, one needs to know the sources of heat to the
coating, the rate of heat transfer between the air and
the coating surface, the temperature of the air and coat-
ing surface, and the properties of the coating, web, and
air. A generalized equation [Eq. (1)] that expresses the
balance between heat and mass transfer for two-sided
drying is included in Fig. 2. Knowing these various
parameters for a given dryer configuration, one can

Figure 1. Typical drying curve showing heat up, constant rate, and falling rate periods.
Downloaded by [Oak Ridge National Laboratory] at 07:59 03 January 2018
Figure 2. Simplified heat and mass balance for drying of aqueous or solvent-based coating on a web material.
calculate the resulting drying performance for a given
coating operation.
Detailed cost study and unit operations
modeling
The following sections deal with the tradeoffs between
manufacturing LIB electrodes with water and NMP
from a chemical engineering unit operations viewpoint.
A focus is placed on solvent drying and recovery, and
capital vs. operating costs. Two different anode slurry
chemistries were evaluated: a 32% solids water-based
graphite anode with latex binder and a 32% solids
NMP-based graphite anode with PVDF binder.
Operating savings for NMP vs. water
In analyzing the operating costs of the LIB electrode
coating process, one must take into consideration both
the electrode drying requirements as well as any emis-
sion control requirements associated with the solvents
used in the overall process. For water-based electrodes,
the analysis is limited to the drying step. For NMP, both
drying and solvent recovery play important roles in the
overall process. The following sections provide an
overview of the key process steps as well as an
indication of the operating costs difference between
DRYING TECHNOLOGY 237
water-based and NMP-based coating processes for LIB
electrode production.
Electrode drying
The electrode drying process is a complex one that
requires both a heat and mass transfer model to predict
both the drying physics as well as an overall mass
and energy balance for the system. The drying process
can be modeled using tools described in Section
“Background”. A typical drying curve for an anode-
based electrode is shown in Fig. 3a. Using the results
of the drying model, the resulting operating costs for
the system can be determined using a mass and energy
model as depicted in Fig. 3b. The results of a typical
(baseline) low-solids-content LIB anode drying process
are shown in Table 1. Actual operating costs for the
drying portion of both the water-based and NMP-based
electrode productions are similar in magnitude. How-
ever, the costs associated with the recovery of the
NMP result in a significant overall operating costs
difference between the two systems. The total energy
consumption for this anode baseline case is 25.7% lower
for the water-based approach than the NMP-based
one. This difference is much less significant than that
predicted by Wood et al., where they suggested as much
as an 8.1� lower combined anode and cathode drying
cost for the water-based approach.
 238 D. L. WOOD ET AL.
Downloaded by [Oak Ridge National Laboratory] at 07:59 03 January 2018
Figure 3. (a) Schematic of a typical drying process for both a water-based anode and an NMP-based anode. (b) Schematic of a
typical mass and energy balance model for the drying process of an electrode. Note: NMP, N-methylpyrrolidone.
Solvent recovery
A closer look at the NMP recovery process has been
initiated by setting up a process model. Figure 4 shows
a PFD where the evaporated solvent from the dryer is
recovered first in a condenser, then a zeolite wheel,
and then finally scrubbed out of the exhaust. The NMP
condensate contains water and other hydrocarbons,
and is separated by vacuum distillation. For a LIB plant
using 4.1 M kg/year of NMP with 96% recycle rate, the
dryer heat load is ~130 kW. The largest energy demand
of ~3,800 kW is at the air heater. It is notable that this
value is relatively low because of the heat recovery step
in the air-to-air heat exchanger in which 2,700 kW of
heat is recovered.[20] The main driver behind the heat
demand is the large air flow rate required in the dryer
to ensure that the NMP concentration is always
maintained far below the flammability limits, typically
an order of magnitude lower. The simulated case limited
the NMP concentration at 1,150 ppmv.
Capital equipment savings for NMP vs. water
The primary unit operations affected by NMP and water
are slurry mixing, electrode coating and drying, and
emission control from the drying process. Because
NMP is classified as a combustible liquid (not a flam-
mable liquid) with a high boiling point (204°C), the
design of the slurry mixers does not require explosion
proof features or components. Therefore, the same
mixer design can be used for water and NMP
processing, and no capital cost differences exist for
slurry mixing. This same logic applies to the electrode
 DRYING TECHNOLOGY 239

Table 1. Summary of operating energy requirements for the Table 2. Summary of capital costs for NMP–solvent recovery
drying process of a typical electrode. equipment.
Item Units Anode–NMP Anode–water Capacity Estimated cost (industry)
Web width Mm 730 730 NMP storage tank 560 m3 $560,000
Line speed m/min 12 12 Main blower 152,000 Nm3/h $190,000
Web material Copper Copper Make-up air blower 15,200 Nm3/h $36,500
Web caliper μ 20 20 Air-to-air heat exchanger 6,800 m2 $460,000
Web weight g/m2 177 177 Filter 20 m2 $14,000
Coating Anode slurry Anode slurry Air heater 3,800 kW $20,000
Dry coat weight g/m2/side 110 110 Condenser 3,400 m2 $1,380,000
Dry coating specific heat cal/g · °C 0.3 0.3 Chiller 1,200 kW $950,000
% Solids by weight % 32 32 Chilled water pump 5,700 L/min $25,000
Solvent type NMP Water Distillation column 13 L/min $1,000,000
Solvent weight g/m2/side 235 235 Zeolite wheel (operating) 120 kg-NMP/day $425,000
Web throughput m2/min 8.7 8.7 Scrubber 14,200 Nm3/hr $225,000
Web heat load kcal/m2 1.98 1.98 Total system cost $5,285,500
Dry coating heat load kcal/m2 7.70 7.70 NMP, N-methylpyrrolidone.
Solvent heat load kcal/m2 74.61 262.63
Total product heat load kcal/m2-web 84.29 272.31
Dryer operating heat load kW 650 823
Total dryer heat load kcal/m2-web 1,067 1,351 Electrode drying
Downloaded by [Oak Ridge National Laboratory] at 07:59 03 January 2018

Solvent condensation kW 458 Although NMP is a combustible liquid, there remains a

heat load
Solvent condensation kcal/m2-web 751 concentration range of NMP vapor in air that could
heat load lead to an explosion. The lower explosive limit (LEL)
NMP, N-methylpyrrolidone. is 1.3 vol%, and the upper explosive limit is 9.5 vol%.
In the drying chamber, the concentration of NMP must
coating and drying system with one exception to the be monitored to insure that it remains at or below 25%
drying chambers, which relates to the emission control of the LEL which is 0.325 vol%. Instruments called LEL
and solvent recovery equipment; NMP requires con- monitors are required in each dryer zone to measure the
trols, and water does not. Section “electrode drying” concentration in real time. In addition, the associated
describes this advantage in more detail. control logic to insure a safe operating condition is also
required. The cost of LEL monitors and control logic is
relatively modest for a production line, and a rough
estimate of $75,000 savings for a production line using
water in place of NMP can be made.

Solvent recovery
The major capital savings for water compared with
NMP processing are the elimination of the entire emis-
sion control and solvent recovery system described in
Section “solvent recovery”. The following units are not
required for water but are for NMP: (1) condenser,
(2) zeolite wheel, (3) scrubber, (4) NMP storage tanks,
and (5) chillers and heaters to support NMP recovery.
For a high-volume production scenario, the total
savings by eliminating solvent recovery equipment is
between $3 and 6 M, which is a significant savings
in capital investment for any factory. Details of the
capital costs are listed in Table 2. Therefore, the
solvent recovery capital cost savings dwarf the electrode
drying capital cost savings by almost two orders of
magnitude.

Coating and drying parametric study

During the drying of LIB electrodes, several key process
Figure 4. Schematic of a typical process for the drying and variables play an important role in how the electrode
recovery of NMP. Note: NMP, N-methylpyrrolidone. material dries. These variables can affect the time
 240 D. L. WOOD ET AL.
required to dry as well as the quality of the dried
material. Some of these variables include the humidity
of the supply air, the solids loading of the coating,
and the electrode layer thickness. In addition, these
variables can be dependent on the solvent used in the
coating process. To better understand these interac-
tions, a parametric study was conducted using a drying
model developed for LIB electrode materials and the
solvents of NMP and water. The model is based on
the details listed in Section “background” and is a
first-order approximation of the drying rate. The
model has been validated based on empirical data from
pilot and field trials for various LIB electrode materials.
However, experimental trials are often necessary to
access the actual drying characteristics of specific
materials.[19] Although the model is somewhat simpli-
Downloaded by [Oak Ridge National Laboratory] at 07:59 03 January 2018
fied, the relative relationships derived from the model
are valid. The following sections present the results of
this study.
Supply air dew point ( 60°C to þ25°C)
The moisture level in the supply air used to dry the LIB
electrode material can have an effect on the rate at
which water is dried from a LIB electrode coating,
which is a result of the partial pressure of water in the
air near the drying surface. Figure 5 shows the relation-
ship between supply air humidity and the dryer resi-
dence time or required drying time for a constant LIB
electrode coating. If NMP-based slurries are manufac-
tured outside of a dry room with an ambient dew point
of 20°C, but water-based slurries are manufactured in a
Figure 5. Relationship between supply air humidity and resulting dryer residence time for water-based LIB electrode coating.
Note: LIB, lithium-ion battery.
dry-room environment (dew points less than 40°C),
the residence time in the dryer may be reduced from
45 to 38 s (a 16% reduction). The water-based electrode
can be readily dried out. For example, when dried with
supply air with an ambient dew point of 10°C which is
easy to achieve, it only takes 41 s to dry the electrode.
Reducing the dew point in the supply air can only
reduce the drying time by a few seconds but induces
extra cost and energy consumption in preparing the
supply air.
Slurry solids loading (30–65%)
The slurry solids loading in the LIB electrode material
can have an effect on the rate at which water or NMP
is dried from a LIB electrode coating, which is a result
of the change in the amount of water or NMP that is
needed to be dried from the coating. Figure 6 shows
the relationship between slurry solids loading and the
dryer residence time or required drying time for a con-
stant LIB electrode coating. With same solids loading in
the slurry and same areal loading in the dry electrode, it
requires longer dwell time to dry the water-based elec-
trode. However, the water borne binder solutions could
have lower viscosity than the PVDF-NMP solution,
which allow higher solids content in the water-based
slurry and enable a shorter dwell time. For example,
ORNL has shown that the solids loading for a water-
based LiNi0.5Mn0.3Co0.2O2 (NMC532) cathode slurry
may be raised up to 60%, whereas NMP-based slurries
are typically 45%.[21] Similar rheological properties were
maintained for high coating quality between the two
 DRYING TECHNOLOGY 241
Downloaded by [Oak Ridge National Laboratory] at 07:59 03 January 2018

Figure 6. Relationship between slurry solids loading and resulting dryer residence time. Note: LIB, lithium-ion battery; NMP,
N-methylpyrrolidone.

slurries. If this same difference in slurry solids Electrode layer thickness (50–200 µ)
loadings was applied to the graphite anode data in
The electrode layer thickness of the LIB electrode material
Fig. 6, a dwell time of 38 s for the water-based slurry
can have an effect on the rate at which water or NMP is
would be realized as compared with a dwell time of
dried from a LIB electrode coating, which is a result of
52 s for the NMP-based slurry (a 37% longer residence
the change in the amount of water or NMP that is needed
time).

Figure 7. Relationship between LIB electrode layer thickness and resulting dryer residence time. Note: LIB, lithium-ion battery; NMP,
N-methylpyrrolidone.
 242 D. L. WOOD ET AL.

to dry as well as the distance of the solvent must travel
through the coating to reach the surface and evaporate.
Figure 7 shows the relationship between electrode layer
thickness and the dryer residence time or required drying
time for varying thickness LIB electrode coating. As coat-
ing thickness increases to obtain higher energy-density
electrodes, there will be a penalty for using a water-based
slurry. For example, there is only a 4 s longer dwell time at
100 g/m2 areal loading for water-based anode slurries, but
this difference increases to 11 s when the coating areal
loading is tripled to 300 g/m2.
Performance comparison between NMP and
water-based processing
Downloaded by [Oak Ridge National Laboratory] at 07:59 03 January 2018
graphite/LiFePO4 pouch cells were validated.[22]
Figure 8 shows the rate performance and long-term
cyclability of 1.5-Ah pouch cells with NMC532 and
graphite electrodes via NMP- and water-based proces-
sing, and the electrode information is listed in
Table 3. Celgard 2325 was used as the separator and
the electrolyte is 1.2 M LiPF6 in ethylene carbonate/
diethyl carbonate (3/7 wt). The cells were cycled
between 2.5 and 4.2 V, and electrodes were assembled
into 1.5-Ah pouch cells. The cells went through four
formation cycles at C/20/-C/20 before the rate test fol-
lowed by long-term cyclability test. As shown in
Fig. 8a, the electrodes via NMP- and water-based pro-
cessing demonstrate identical and comparable rate per-
formance. The capacity retention is 86% when

As the interest level in manufacturing LIB electrodes (in
particular cathodes) via water-based slurries has grown
over the last 6–7 years, two of the three main problems
associated with its implementation (slurry wetting and
agglomeration) were solved by ORNL, but one concern
of battery makers and automotive Original Equipment
Manufacturer (OEMs) has remained: does aqueous pro-
cessing significantly add to the adsorbed (chemisorbed
and physisorbed) moisture prior to the secondary dry-
ing step and result in higher capacity fade during
long-term cycling? This issue has also been recently
addressed by ORNL in which both the residual elec-
trode moisture level (via Karl Fisher titration) and
long-term cycling performance of graphite/NMC and
discharged at 1C (1C ¼ 1.5 A) at 25°C. The comparison
in long-term cyclability is shown in Fig. 8b. The pouch
cells with NMP-based processed electrodes (red curve)
were cycled at 0.2C/ 0.2C at 25°C, and the temperature
was increased to 30°C at 548th cycle. The temperature
increase resulted in 4% capacity increase. The pouch
cells with water-based electrodes were cycled at 0.33C/
0.33C at 30°C. Although the water-based processed
electrodes showed faster capacity fade at the beginning
which could be ascribed to the nonoptimized formation
protocols, the capacity fade slowed down after the first
50 cycles. Both cells demonstrated identical capacity
retention of 83.7% after 668 cycles. Considering the
water-based processed electrodes were cycled at higher

Figure 8. Electrochemical performance comparison in pouch cells with NMC532 and graphite electrodes via NMP- and water-based
processing (a) rate performance at 25°C and (b) long-term cyclability. Comparable rate performance and long-term cyclability were
observed from both cells. Note: NMP, N-methylpyrrolidone.

Table 3. Electrode information of NMC532 and graphite via NMP- and water-based processing.
Electrode Electrode composition Areal loading (mg/cm2) Porosity (%)
NMC532 (NMP based) NMC532/carbon black/5130 PVDF ¼ 90/5/5 wt 13.2 37
Graphite (NMP based) Graphite/carbon black/9300 PVDF ¼ 92/2/6 wt 7.6 33
NMC532 (water based) NMC532/carbon black/CMC/ Latex ¼ 90/5/1/4 wt 13.3 36
Graphite (water based) Graphite/carbon black/CMC/ SBR ¼ 92/2/2/4 wt 7.4 34
CMC, carboxymethyl cellulose (Mw ¼ 250 k); NMP, N-methylpyrrolidone; PVDF, polyvinylidine fluoride; SBR, styrene-butadiene rubber.

C rate, their long-term cyclability is comparable or even
better than the NMP-based processed one. The capacity
retention after 886 cycles is 79.5%. More detailed results
will be discussed in a future publication.
Conclusions and recommendations
An in-depth analysis of the comparative drying costs of
LIB electrodes is discussed for both NMP-based and
water-based dispersion processing in terms of pack
$/kWh. Electrode coating manufacturing and capital
equipment cost savings are compared for water vs.
conventional NMP organic solvent processing. A major
finding of this work is that the total electrode manufac-
turing costs, whether water- or NMP-based, contribute
Downloaded by [Oak Ridge National Laboratory] at 07:59 03 January 2018
about 8–9% of the total pack cost. However, it was
found that about a 2� reduction in electrode processing
(drying and solvent recovery steps) cost can be expected
along with a $3–6 M savings (for a plant producing
100,000 10-kWh PHEV batteries) in associated plant
capital equipment. This study is meant to be a more
realistic, industrial scale, follow on to an earlier one
based on low-volume cell production and a smaller scale
pilot coating line published in 2015 by Wood et al. This
follow-up paper offers a different conclusion that the
most important benefits of aqueous electrode
processing actually revolve around capital equipment
savings and environmental stewardship and not
processing cost savings.
Funding
Parts of this research at the Oak Ridge National Laboratory,
managed by UT Battelle, LLC, for the U.S. Department of
Energy (DOE) under contract DE-AC05-00OR22725, and
Argonne National Laboratory, managed by UChicago
Argonne, LLC, Operator of Argonne National Laboratory
under contract no. DE-AC02-06CH11357, were sponsored
by the Office of Energy Efficiency and Renewable Energy
(EERE) Vehicle Technologies Office (VTO) (Deputy Director:
David Howell) Applied Battery Research subprogram
(Program Manager: Peter Faguy).
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