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The Influence of Different Post-Drying Procedures on

Remaining Water Content and Physical and
Electrochemical Properties of Lithium-Ion Batteries
Fabienne Huttner,* Wolfgang Haselrieder, and Arno Kwade

Consequently, LIBs are believed to be

The post-drying of electrodes and separators for lithium-ion batteries just before the most promising energy storage tech-
cell assembly aims at reducing the water content in the cells below a critical nology for various applications. The
value. This is important as the remaining water can lead to cell degradation and manufacturing know-how for small LIBs
has already been transferred to the produc-
thus cause a safety risk. In addition, it can impede the formation of an effective tion of larger cells, and LIBs have entered
solid electrolyte interface. Nevertheless, the post-drying of lithium-ion battery the market of electric vehicles and station-
electrodes and separators is still poorly investigated. Considering this, three ary energy storage yet. Nevertheless, the
different post-drying procedures are investigated on pouch cells and compared process chain of the manufacturing of
with the non-post-dried state. The remaining water contents are measured via LIBs is very long and complex, and is sub-
jected to various internal and external influ-
coulometric Karl Fischer Titration and correlated to the resulting electrochemical
ences. Therefore, to meet the increasing
performance. Surprisingly, the most intensely post-dried cells show the worst demands on battery lifetime, safety, reli-
electrochemical performance despite reaching the lowest water content. In ability, cycling capability, and specific
contrast, the mildest post-dried cells, which show the highest water content, energy and power, a highly reproducible
achieve the best electrochemical performance. Further analyses show that manufacturing process of LIBs and strin-
extreme post-drying can cause irreparable damages within the electrode struc- gent quality control are essential.[4,5,7]
In this regard, one of the quite critical
tures. Therefore, a good electrochemical performance is not only guaranteed by
pollutants in LIBs is water.[7–10] There are
low remaining water content but also, in particular, by gentle post-drying. several ways for water to get inside the bat-
tery cells. As the electrodes add the highest
mass to the cells, they can increase the
water contamination in the cells consider-
1. Introduction ably, depending on their material system and structure.[11] The
water, in turn, gets into the electrodes through various paths.
In the course of the current global energy transition, electro- Partially, it is already brought into the electrode structures by
chemical energy storage techniques are believed to be a key factor the initial materials, which store water from their surrounding
for the development and establishment of e-mobility and station- atmosphere.[7,9,12,13] In addition, water can be added during
ary energy storages. Within this context, lithium-ion batteries the liquid processing of the coatings.[7] At industrial scales, elec-
(LIBs) show clear benefits compared with other battery systems. trodes for LIBs are produced by coating a slurry with organic sol-
Among others, they provide an outstanding cycling stability for vents as N-methyl-2-pyrrolidone (NMP) or water onto a current
various applications and can also be designed for both high- collector. In a first drying step, the solvents are removed from the
power and high-energy applications. In addition, considerable slurry to produce a solid porous electrode structure.[4,14] After
research work on LIBs has been accomplished in the last coating and drying, there can still remain several thousand
decades, and the properties of the battery cells and their compo- ppm of water in the electrodes.[7] Furthermore, water can get into
nents are already well understood. Originating in the 1990s, the cell components by their remoistening in the surrounding
manufacturing processes are well established nowadays with atmosphere after the drying process during further processing,
high throughput for small LIBs, commonly applied in consumer storage, transport, or cell assembly.[15,16] In fact, the water
electronics.[1–6] absorption of the electrodes depends mostly on their active sur-
face, atmospheric humidity, and the temperature.[16] Comparable
F. Huttner, Dr. W. Haselrieder, Dr. A. Kwade mechanisms to the ones occurring in the electrodes take place in
Institute for Particle Technology the used separators. Depending on their material system, sepa-
Technische Universität Braunschweig rators can adsorb large quantities of water.[7] But as they claim
Volkmaroder Straße 5, 38104 Braunschweig, Germany only small mass of the cells, their impact on the cell’s water con-
E-mail: fabienne.huttner@tu-braunschweig.de
tamination is lower, respectively. Finally, water can be introduced
The ORCID identification number(s) for the author(s) of this article during cell assembly by adding the electrolyte which contains,
can be found under https://doi.org/10.1002/ente.201900245. even in its best quality, more than 20 ppm.[9,11] Thus, the water
DOI: 10.1002/ente.201900245 contamination of the cells depends on the material system and

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structure, the process conditions during manufacturing, further
processing, and cell assembly, and on the conditions of transport
and storage.
The remaining water content in the cells is problematic as it
undergoes unwanted side reactions with the conducting salt
LiPF6, which is commonly used in organic electrolytes for
LIBs.[9,16–20] These reactions lead to the formation of gaseous
hydrogen fluoride (HF) and further acidic decay products[16]
LiPF6 þ H2 O ! 2HF þ LiF þ POF3 (1)
These unwanted side reactions cause various problems. The
loss of conductive salt leads to a decline of the electrolyte conduc-
tivity and, correspondingly, to an increasing electrical resistance
and a decreasing cell capacity.[16] The acidic products can further
cause decomposition of the active materials,[1,7,16,20] e.g., by
leaching of manganese in NMC cathodes.[16] In addition, these
compounds can hinder the formation of an effective solid elec-
trolyte interface (SEI) or attack an already existing SEI.[5,7,17,21,22]
However, according to Langklotz et al., small contents of water
seem to improve the formation and the stability of the SEI.[16]
Nevertheless, the gaseous products released during the decom-
position of the electrolyte increase the pressure in the battery cell
and thereby the risk of explosion.[17]
Thus, the water contamination in the cells and consequently
the water content of the single cell components has to be
adequately low. The water contamination of the electrolyte
in LIBs and its consequences have already been well studied
and are considered carefully during manufacturing.[7,17–19]
However, to our knowledge, little focus has been set on the water
contamination of electrodes and separators. These cell compo-
nents can, depending on their material system and structure,
adsorb large amounts of water. Claiming the majority of the cell
mass, they can dramatically increase the water contamination
within the cells. As it is quite difficult to manufacture, transport,
and store electrodes and separators under continuous dry,
defined, and consistent conditions, they need to be post-dried
before being assembled into battery cells to guarantee a constant
low level of water. At industrial scale, this is realized by large belt
dryers with infrared radiators and drying fans that are installed
upstream of the dry rooms.[4,14,23,24] To avoid the remoistening of
the cell components after post-drying (PD), the whole cell assem-
bly then takes place in large dry rooms with dew points at 37  C
or lower.[23,25]
According to Schünemann et al., post-drying is a process with
the highest energy expenditure within the process chain of cell
manufacturing.[23,26] Furthermore, the installation of dry rooms
Table 1. Different post-drying procedures and conditions for the electrodes and separators.
Post-drying procedure (Short cut) Post-drying device
Non-post-dried – –
Argon-post-dried Vacuum lock of argon-glove box
Medium-term-vacuum-post-dried Vacuum oven
Long-term-vacuum-post-dried Vacuum oven
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is one of the costliest single investments of facilities for battery
cells and in operation they cause a high energy consumption.[23]
Therefore, a better understanding of the post-drying and its opti-
mization offers a high potential to save costs. Although this proc-
essing step has a great impact on safety and electrochemical
performance of the cells, to our knowledge, post-drying is still
not fully investigated and adequately understood. On the one
hand, the necessary reduction of the residual amount of water
to maintain a good and safe cell performance is still not deter-
mined; on the other hand, the influence of post-drying on the
properties of the electrode structures and the electrochemical
performance is not extensively examined. This is why the process
of post-drying of LIB electrodes and separators is addressed in
this study.
2. Results and Discussion
To better understand the process of post-drying, the influence of
three different post-drying procedures on remaining water
content, electrochemical performance, and physical and
structural properties of electrodes are investigated in comparison
with the non-post-dried state. For a good comparability, the post-
drying procedures are conducted with the same type of post-
drying, namely, a combination of vacuum and Argon-purging.
To produce clear and measurable differences, the intensity of
post-drying is varied widely by raising the temperature and
the duration of the process, starting with Argon-post-drying,
followed by medium-term-vacuum-post-drying, and ending
with long-term-vacuum-post-drying (Table 1). As material sys-
tem, a NCM622-cathode (95.5 wt% NCM622, 1.5 wt% C65,
0.75 wt% SFG6L, 2.25 wt% [polyvinylidene fluoride] PVDF) with
27 mg cm2 mass loading and an accordingly balanced graphite-
anode (94 wt% SMGA5, 2 wt% C65, 2 wt% CMC, 2 wt% SBR)
with 14.9 mg cm2 mass loading are chosen (Table 2). Separion
S240P30 serves as separator. The influence of the post-drying pro-
cedures on the remaining water content is analy-
zed and correlated with the resulting electrode structures and
final electrochemical performance, which is tested in one compart-
ment pouch cells. To better state the differences in electrochem-
ical performances, the electrodes are additionally characterized
regarding mechanical and electrical properties.
2.1. Remaining Water Content
Figure 1 maps the remaining water content of the entire
electrode–separator assemblies (ESAs) which result from the
Post-drying conditions
Automatic purging for 15 min at 20  C (3 drawing vacuum/inerting)
Electrodes: 18 h at 120  C in vacuum Separators: 4 h at 60  C in vacuum
3 manual drawing vacuum/inerting before cell assembly
Electrodes: 96 h at 120  C in vacuum Separators: 4 h at 60  C in vacuum
3 manual drawing vacuum/inerting before cell assembly
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Table 2. Materials and recipes for electrode manufacturing.

Material (function) Material type Supplier Mass content [wt%]

Anode
Graphite (active material) SMGA-5 – 94.00
Carbon black (conductive agent) C-NERGY Super C65 Imerys 2.00
Carboxymethyl cellulose (binder) CMC Sunrose MAC500LC Nippon Paper 2.00
Styrene—butadiene rubber (binder) SBR, Zeon Binder BM-451B Zeon 2.00
Deionized water (solvent) – – Solvent content in suspension: 54.00
Cathode
LiNi0.6Co0.2Mn0.2O2 (active material) NCM622 BASF 95.5
Carbon black (conductive agent) C-NERGY Super C65 Imerys 1.50
Graphite (conductive agent) TIMREX SFG6L Imerys 0.75
Polyvinylidene fluoride, PVDF (binder) Solef 5130 Solvay 2.25
N-Methyl-2-pyrrolidone, NMP (solvent) Electrochemical grade BASF Solvent content in suspension: 25.00

1600 (1417 ppm). Medium-term-post-drying in vacuum even leads

Calculation according to mass ratio
to a water content reduction of 84% (to 225 ppm), and
cathode : separator : anode
1400 long-term-post-drying in vacuum to a reduction of 90%
= 4.8 : 1.1 : 4.1
specific water content / ppm

(average of 3 samples each) (to 136 ppm). These results are quite interesting, showing that
1200
the short post-drying in argon at room temperature already leads
1000
to a remarkable reduction of the water content.
In Figure 2, the remaining water content of the single cell
800 components cathode, separator, and anode is shown. As the
water contents of the aluminum (cathode) and copper (anode)
600 current collectors are smaller than 20 ppm in the undried condi-
tion, it is assumed that the detected water originates almost
400 entirely from the coating materials, namely, active materials,
binder, and additives.[7] According to Langklotz et al., the water
200

0
Non-PD Argon-PD Medium- Long-
vac.-PD vac.-PD 3000
post-drying procedure / - cathode
separator
Figure 1. Specific water content of entire ESAs resulting in different anode
2500
specific water content / ppm

post-drying procedures. Measured via coulometric KFT in dry room

(TD ¼ 30  C), measuring time 10 min. Calculated with weight of the
entire electrode (coating þ current collector).
2000

1000
three different post-drying procedures (determined without elec-
trolyte) compared with an ESA with non-post-dried components.
As the remaining water content of the entire cells is of interest, 500
the water content is calculated with the weight of the entire elec-
trodes (coating þ current collector), and computed without the
arresters of the electrodes. The remaining water content of
the single components is calculated in accordance with their 0
Non-PD Argon-PD Medium- Long-
mass ratios in the entire cells. As the mass ratio of the three com- vac.-PD vac.-PD
ponents namely cathode: separator: anode is 4.8:1.0:4.2, it is the post-drying procedure / -
cathode which constitutes most of the cell mass, closely followed
Figure 2. Specific water content of the single-cell components resulting in
by the anode. The separator only corresponds to a little part of the different post-drying procedures. Measured via coulometric KFT in dry
cell mass (11 wt%). Figure 1 shows that already by post-drying room (TD ¼ 30  C), measuring time 10 min. Average of three samples
with argon, the water content can be massively reduced by each. Calculated with weight of the entire electrode (coating þ current
77% (to 326 ppm) compared with the non-post-dried state collector).

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release of electrodes is based on an equilibration process.[16] The
reduction of water which can be achieved by post-drying depends
on the properties of the active material (surface area, heat of
adsorption), temperature, atmospheric humidity, and pressure.
As post-drying of electrodes in ovens is usually conducted under
reduced pressure, the post-drying procedures of this work are
conducted in vacuum atmosphere. The impact of the vacuum
is very complex as it influences the reduction of the water content
on the one hand and the structural properties of the electrodes
on the other hand.[16] However, this is not the focus of the
present study.
Altogether, the results point out that an intensification of the
post-drying process leads to the reduction of remaining water
content in all the three components. In the following, the initial
water content and the release of water under post-drying will be
considered in detail for each component.
The separator Separion constitutes the most hydrophilic com-
ponent with 2646 ppm in the condition “Non-PD” (see Figure 2).
The high hydrophilicity is attributed to its open porosity on the
one hand and mainly to the coating of inorganic and nanoparticle
ceramics on the other hand.[27,28] Although it was post-dried and
stored under the same conditions for both “vac.–PD” processes,
the separator contains a bit more water in the “Medium-vac.-PD”
ESA (482 ppm) than in the “Long-vac.-PD” ESA (423 ppm). This
is due to the fact that the separator could adsorb more water dur-
ing the cell assembly of the “Medium-vac.-PD” cells, as the anode
and the cathode caused a higher contamination of the argon
atmosphere of the glovebox with water.
The separator shows a very high water release for all post-
drying procedures applied. However, it still contains a relatively
high amount of water compared with the other two components.
This indicates that the separator contains a large amount of
weakly bound water, but also a remarkable amount of chemically
and more strongly bound water which cannot be removed by the
chosen post-drying parameters. However, since the hydrophilic
separator only constitutes a small part of the cell mass, the
remaining water content of the ESAs achieve very low levels.
Even when only post-drying in argon, the separator increases
the remaining water content of the ESA by just 15%.
The anode also adsorbs high amounts of water, containing
2412 ppm in the condition “Non-PD” (see Figure 2). This can
be explained by the hydrophilic binder CMC[12,29–31] and by
the aqueous processing of the slurry, which introduces additional
water into the electrode.[7] A further reason could be the water
adsorption of graphite and especially its surface coating, which
is applied to achieve capacities around 360 mAh g1. According
to Fu et al., active hydrophilic sites at the surface of graphite exist,
which adsorb water when exposed to a humidity higher than
1000 ppm.[13] Compared with the separator, the anode shows
an even greater water release after all post-drying procedures,
indicating a higher amount of weakly bound water. However,
there is still a certain amount of chemically bound water remain-
ing in the anode even after long-term-vacuum-post-drying
(177 ppm).
Compared with the aforementioned two components, the
cathode adsorbs only small amounts of water. Under the condi-
tion “Non-PD”, only 304 ppm are measured (see Figure 2).
Among others, one reason for this could be the strong hydropho-
bicity and low surface energy of the binder PVDF.[32] According
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to Stich et al., nickel-cobalt-manganese-oxide (NCM) cathodes
show a low specific surface area in combination with lower
hydrophilicity and lower bonding strength of water in compari-
son with other electrode materials.[7] Under post-drying, the
cathode still releases water and reaches a rather low water content
of 39 ppm after long-term-vacuum-post-drying. This shows that
the majority of the low water content is weakly bound and can be
released by intensifying the post-drying procedure.
2.2. Electrochemical Performance
Figure 3 shows the electrochemical long-term performances
and the C-rate capabilities of the one-compartment pouch cells
(graphite-anode with 14.9 mg cm2 mass loading, NCM622-
cathode with 27 mg cm2 mass loading, separator: Separion,
see Table 2) resulting from the different post-drying procedures.
The C-rates at discharge of the different cycling steps are shown
in detail in Figure 4. The cell capacity of the pouch cells is nor-
malized to the mass of the cathode active material NCM622. This
is due to the fact that the lithium ions in LIBs are provided by the
cathode-active material, hence this is a limiting factor for the cell
capacity. In addition, the normalization of the cell capacity
regarding the mass of the cathode-active material enables a direct
comparison to the material information of the manufacturer or
to other scientific works.
To be able to compare the post-drying procedures, the cell
assembly was conducted under argon atmosphere in a glove
box for all procedures. As the argon atmosphere already leads
to a remarkable water release of the cell components (compare
“Argon-PD” in Figure 1), it was not possible to assemble cells in
the “Non-PD” state in the argon glove box. Non-post-dried cells
were also assembled under normal atmosphere for testing but
the process was not successful. Therefore, the electrochemical
Argon-PD (326 ppm)
Medium-vac.-PD (225 ppm)
180 Long-vac.-PD (136 ppm)
NCM
specific discharge capacity / mAh g-1
160
140
Cycling Cycling Cycling
120
100
80
60
40
1. C-rate 2. C-rate 3. C-rate
test
20 test test
0
0 50 100 150 200
cycle no. / -
Figure 3. Specific discharge capacities of one-compartment pouch cells
resulting from different post-drying procedures with indication of
the remaining water content in the entire ESAs. Average of three
samples each.
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Argon-PD (326 ppm)
Medium-vac.-PD (225 ppm)
Long-vac.-PD (136 ppm)
180
0.2C
0.1C
NCM
160
specific discharge capacity / mAh g-1
140
1C
120
100
80
60
2C
40
3C
20 5C
0 influence the total deformation work and the elastic deformation
0 5 10 15
cycle no. / -
Formation C-rate test
Figure 4. Detailed presentation of the specific discharge capacities of the
first 25 cycling numbers shown in Figure 3. Indication of the C-rate at
discharge of the different cycling steps and the remaining water content
of the ESAs. Average of three samples each.
performance can only be compared between the post-dried ESAs.
Regarding Figure 3 and 4, the “Argon-PD” ESAs achieve the best
results both in C-rate capability and in long-term
performance. The “Medium-vac.-PD” ESAs, however, provide
a reduced performance, showing lower specific discharge capac-
ities at the beginning and in general a distinct declining, also
more pronounced than for the argon-post-drying. However, none
of the ESAs deliver performances comparable to those found in
literature, which can be explained by the low content of carbon
black (1.5 wt%).[33] In literature, higher discharge capacities are
achieved by adding 5–15 wt% of conductive additives, but this
was not a focus of the present study.
Regarding the corresponding residual water content of the dif-
ferent post-drying procedures (see Figure 1), the electrochemical
properties in Figure 3 might appear rather surprising. As
explained earlier, water is seen as a really critical impurity in
LIBs.[7–10] According to that, the best electrochemical perfor-
mance would be expected to be one of the ESAs with the lowest
remaining water content, ergo “Long-vac.-PD”s. However, the
post-dried ESAs with the highest water content (326 ppm,
“Argon-PD”) show the best performance. Hence, a good electro-
chemical performance cannot be in general guaranteed by a low
remaining water content. Instead the process conditions and
their intensity seem to significantly influence the physical and
structural properties of the cell components, and therefore have
a great impact on the electrochemistry.
To understand the influence of the different post-drying pro-
cedures, the physical properties of the cell components have to be
studied in more detail. As the separator Separion is known to be
resistant to high temperatures up to 240  C and is post-dried
equally for both “vacuum-PD” procedures, it is assumed that
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the electrodes must be responsible for the great differences in
electrochemical performance. Consequently, the following
analyses are performed only for anode and cathode.
0.1C
2.3. Micro Compression
The micro compression measurements give information about
1C
the strength and the elasticity (or plasticity, respectively) of the
electrode coating. Whereas the total deformation work Wtot
indicates the strength of the coating, the ratio of elastic to total
deformation work Wel/Wtot shows which amount of the total
deformation work is elastic and returns to its original form when
discharged. A sufficient elasticity of the coating is important to
prevent irreversible damages during processing and operation of
the battery cells and consequently contributes to a longer
lifetime.
The results depict that different post-drying processes
20 25
percentages (see Figure 5 and 6). In particular, great differences
Recovery Cycling can be observed with regard to the cathode. For a better compar-
ison, a joint presentation of the electrodes is chosen. This leads to
a loss of the anode’s resolution, which has to be considered in the
interpretation of the measurements.
In Figure 5, the median value of the total deformation work
Wtot,50 and its mean absolute deviation resulting in the different
post-drying procedures are shown for anode and cathode.
Regarding the anode, a slight decrease of the total deformation
work can be observed with intensifying the post-drying
conditions (by 14% from 967 nJ at “Non-PD” to 830 nJ at
“Long-vac.-PD”). In contrast, the cathode subjected to the
argon-post-drying process shows a high increase of the total
deformation work. It is conspicuous that the mean absolute devi-
ation of this post-drying procedure is higher than that of the
others. This could indicate that argon-post-drying causes a more
inhomogeneous water release than the other post-drying proce-
dures, which can be explained by its short duration. However,
post-drying of the cathode with applied underpressure in an oven
7000
anode
6000
cathode
deformation work Wtot,50 / nJ
5000
median value of total
4000
3000
2000
1000
0
Non-PD Argon-PD Medium- Long-
vac.-PD vac.-PD
post-drying procedure / -
Figure 5. Dependence of the median value (with mean absolute deviation)
of total deformation work Wtot,50 on different post-drying procedures.
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0.90
0.75
deformation work (We/Wtot)50 / nJ
median value of ratio elastic/tot.
0.60
0.45
0.30
0.15
0.10
0.05
0.00
Non-PD Argon-PD Medium-
vac.-PD
post-drying procedure / -
Figure 6. Dependence of the median value (with mean absolute deviation)
of the ratio of elastic to total deformation work (We/Wtot)50 on different
post-drying procedures.
in general and its intensification result in a noticeable decrease of
the total deformation work.
In Figure 6, the median value of the ratio of the elastic defor-
mation work to the total deformation work (We/Wtot)50 is plotted
for anode and cathode after different post-drying procedures. For
the anode, the results show that the intensification of post-drying
also slightly decreases the percentage proportion of elastic defor-
mation work (by 18% from 0.11 nJ at “Non-PD” to 0.09 nJ at
“Long-vac.-PD”). With regard to the cathode, post-drying with
applied underpressure in an oven reduces the percentage propor-
tion of elastic deformation work. However, the “Argon-PD”
cathode outlies again, showing a higher percentage of elastic
deformation work compared with the other post-drying
procedures.
Altogether, the measurements show that intensifying the post-
drying procedure of the anode impairs its mechanical properties,
leading to a decrease in the total deformation work on the one
hand and a decrease in the proportions of the elastic deformation
work on the other hand. Therefore, with intensifying post-drying,
the strength of the coating declines (see Figure 5) and the plas-
ticity increases (see Figure 6). Consequently, the post-drying pro-
cedures must cause an irreversible damage or change within the
electrode structure. The reason for this is related to the structural
change of the carboxymethyl cellulose/styrene—butadiene
rubber (CMC/SBR) binder matrix. The thermal range of applica-
tion of SBR is from 50 to þ100  C.[34,35] At temperatures above
100  C, the elastomer decomposes to low molecular com-
pounds.[35] According to Rao et al., prolonged heat treatment
of CMC at 120  C leads to its degradation, characterized by a loss
of viscosity.[36] This phenomenon presumably occurs during
post-drying also due to depolymerization.[36] The depolymeriza-
tion processes can damage the CMC/SBR binder network and
decrease its flexibility and binding strength,[37] thus causing
an embrittlement of the binder matrix. Furthermore, because
of their hygroscopic nature, CMC and CMC-hydrogels show a
high volume increase, so-called swelling, when exposed to
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humidity or water.[30,38–41] When adding CMC to SBR, the blend
anode also shows a pronounced swelling behavior.[42] In accordance
cathode with that, drying of aqueous films containing CMC as binder
leads to shrinkage of the binder matrix, which is expected to
induce stress into the solid structure.[30] Subsequently, also when
post-drying the already solid electrode structures, the vaporiza-
tion of the remaining water could cause further shrinkage of
the CMC/SBR binder matrix of the anode. The binding ability
of CMC is based on the formation of polymeric 3D networks
in which the particles are mechanically enclosed.[43,44] The
shrinkage in conjunction with the embrittlement of the binder
network during post-drying could lead to an irreparable damage
of the CMC/SBR binder network within the anode. The loss of
contact surfaces and the decrease in the strength of the binder
matrix would therefore cause a reduction in cohesion, strength,
Long- and elasticity of the whole composite structure.
vac.-PD This explanatory approach is consistent to the measurements
of the anode’s mechanical behavior under micro compression
(see Figure 5 and 6). As a result, the decrease in the total defor-
mation work after argon-post-drying could be explained by the
high release of water and the volume shrinkage involved, causing
a slight loss of strength of the whole coating. As “Argon-PD”
is performed at room temperature and short exposition, embrit-
tlement is unlikely. Compared to “Argon-PD”, the “Medium-
vac.-PD” anode requires the same total deformation work but
shows a lower elastic amount. This indicates a beginning embrit-
tlement of the binder network. The loss of viscosity of CMC was
observed to be time-depending.[36] Therefore, in addition to the
shrinkage caused by the water release, the higher embrittlement
of the “Long-vac.-PD” anode is responsible for the decreasing
elasticity. As a consequence, the loss of contact surfaces and
the decline of strength of the binder matrix would be responsible
for the decrease of elasticity, as the micro compression measure-
ments cause greater irreversible damages on the coating.
Regarding the cathodes, the decrease of strength (due to lower
total deformation work) and elasticity of the samples “Medium-
vac.-PD” and “Long-vac.-PD” (see Figure 5 and 6) could be
explained by degradation of the binder PVDF, as well. The bind-
ing ability of PVDF is also based on the formation of polymeric
3D networks, in which the particles of the active material are
mechanically included.[43] The maximum temperature for
PVDF under continuous load is around 150  C and its heat
deflection temperature according to ISO 75 HDT/A (1.8 MPa)
is 115  C. Taking into account that the oven-post-drying is per-
formed not only at 120  C but also in vacuum, it is quite possible
that the PVDF binder already starts creeping by thermal activated
processes (diffusion creep) during post-drying.[45] The creeping
mechanisms could lead to the rearrangement of the carbon black
particles and therefore damage the integrity of the carbon-black
binder network. The outlying “Argon-PD” cathode is more
difficult to explain. One possible explanation could be that during
post-drying in vacuum, both remaining water and solvent (NMP)
are reduced. Within the complex binder-composite structure,
this could lead to a structure with higher strength and elasticity.
The remaining water and NMP are reduced by post-drying in
vacuum, but “Argon-PD” at room temperature does not cause
diffusion creep. Thus, at “Argon-PD”, the positive influence of
the reduction of water and NMP on the strength and elasticity
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of the cathode is not overlapped by the negative impact of
diffusion creep.
2.4. Specific Electrical Resistance
The specific electrical resistances of the anodes resulting from
the different post-drying procedures are shown in Figure 7.
As the anode has a low specific electric resistance in general,
the differences are not very exposed in absolute values.
However, the “Argon-PD” anode achieves the lowest specific
electric resistance, whereas the “vac.-PD” procedures lead to
an increase in the property with increasing duration of post-
drying. Thus, the reduction of remaining water decreases the
specific electric resistance of the “Argon-PD” anode. Possibly,
at the anodes “Medium-vac.-PD” and “Long-vac.-PD“, the posi-
tive effect of the water reduction is shattered by the increasing
degradation of the CMC/SBR binder matrix explained earlier.
Therefore, as the binder matrix is loaded with carbon black as
conducting agent, its degradation comes along with the simulta-
neous damage of the electric percolation pathways.
In Figure 8, the specific electrical resistances after different
post-drying are shown for the cathode. Considering the
cathodes “Argon-PD” and “Standard-vac.-PD”, the reduction of
the remaining water and the solvent NMP during post-drying
causes a lower specific electrical resistance. The cathode
“Standard-vac.-PD” achieves the lowest value, which could be
explained by the higher reduction of water (see Figure 2) and
probably NMP as well. The cathode “Long-vac.-PD” has the high-
est specific electrical resistance. This could be the result of the
diffusion creep explained earlier, which leads to the damage
of the electric pathways.
2.5. Scanning Electron Microscopy
In Figure 9, scanning electron microscopy (SEM) images of
embedded cross-sections of the anode after different post-drying
procedures are shown. In comparison to the state “Non-PD”
3.0
Anode
2.5
resistance / *cm
specific electrical
2.0
1.5
1.0
0.5
0.0
Non-PD Argon-PD Medium-
vac.-PD
post-drying procedure / -
Figure 7. Dependence of the specific electrical resistance of the anode on
different post-drying procedures. Average of ten samples each.
Energy Technol. 2019, 1900245
www.entechnol.de
1800 Cathode
1500
resistance / *cm
specific electrical
1200
900
600
300
0
Non-PD Argon-PD Medium- Long-
vac.-PD vac.-PD
post-drying procedure / -
Figure 8. Dependence of the specific electrical resistance of the cathode
on different post-drying procedures. Average of ten samples each.
(see Figure 9a), an increase in compression of the microstructure
can be observed with rising post-drying intensity (see
Figure 9b–d). For the “Long-vac.-PD” anode (see Figure 9d),
the compression within the coating is so high that a remarkable
deformation of the surface occurs. These observations support
the aforementioned explanation, according to which the water
release during post-drying leads to a shrinkage of the binder
CMC. As discussed earlier, the shrink behavior of CMC
together with the embrittlement of the CMC/SBR binder net-
work at higher temperatures leads to irreparable damages of
the microstructure. As the preparation of the samples
for SEM was conducted under normal atmosphere, remoisten-
ing of the coatings must have occurred before the SEM
images were taken. Nevertheless, a visible compression and
deformation of the coating can be observed. This confirms
that the post-drying causes irreversible changes in the
microstructure.
The SEM images of the cathodes are shown in Figure 10.
Here, the microstructural changes are marginal—only when
comparing the “Non-PD” state (see Figure 10a) to the highest
post-drying intensity, namely “Long.-vac.-PD” (see Figure 10d),
a slight change can be observed. Also in these cases, the post-
drying leads to a small compression in parts of the microstruc-
ture. This is in accordance with the observations discussed
earlier, which stated that high post-drying intensities cause
creeping of the PVDF binder, leading to slight changes in the
microstructure.
To quantify the observed binder network changes, pore mer-
cury intrusion measurements were conducted for all post-drying
procedures to detect possible differences in the pore radius dis-
tribution. Further information on the measurement principle is
given by Froböse et al.[3] and Haselrieder et al.[46] The results
Long- show that there is no detectable change in the pore radius
vac.-PD distribution for both anode and cathode. However, it has to be
considered that pore mercury intrusion can only detect near-
surface pores, which is why structural changes within the coating
cannot be measured by this method.
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Figure 9. SEM images of embedded cross-sections of the anode resulting from different post-drying procedures, 1000 magnification. a) Non-PD,
b) Argon-PD, c) Medium-vac.-PD, and d) Long-vac.-PD.

Figure 10. SEM images of embedded cross-sections of the cathode resulting from different post-drying procedures, 1000 magnification. a) Non-PD,
b) Argon-PD, c) Medium-vac.-PD, and d) Long-vac.-PD.

3. Conclusions
For a better understanding of the process step of post-drying of
LIB electrodes, three different post-drying procedures were
investigated and compared with the non-post-dried state. The
post-drying procedures were conducted with the same type
of post-drying, namely, a combination of vacuum and Argon-
purging but with widely varying intensities (low: Argon-
post-drying; medium: medium-term-vacuum-post-drying; high:
long-term-vacuum-post-drying). It was shown that different
post-drying procedures have a great impact on mechanical
and electrical properties of the electrodes and, therefore,
significantly influence their structure and their achievable
electrochemical performance.
As water is seen as a critical impurity in LIBs,[7–10] the best
electrochemical performance would have been expected for
the ESA with the lowest remaining water content, ergo “Long-
vac.-PD”. Surprisingly, the cells with the highest water content
after post-drying (326 ppm, “Argon-PD”) showed the best perfor-
mance. On the one hand, these results showed that a good elec-
trochemical performance can already be achieved with a water
content of 326 ppm. On the other hand, it became clear that
an adequate electrochemical performance cannot be automati-
cally guaranteed by reducing water content as much as possible.
Further analyses showed that during post-drying, the occur-
ring processes and their influence are very complex and difficult
to identify and to evaluate as they overlap each other.
Concerning the anode, structural and electrical properties
were negatively affected with intensifying the post-drying condi-
tions. A possible explanation for this was found in the shrink
behavior of the binder CMC when releasing water in conjunction
with the embrittlement of the CMC/SBR binder network at
higher temperatures. These two processes could have led to
irreparable damages of the anode’s CMC/SBR binder network.
Consequently, the loss of contact surfaces and the decrease in the
strength of the binder matrix would have caused a reduction of

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cohesion, strength, and elasticity of the whole composite
structure and the damage of electric percolation pathways.
Regarding the cathode, the argon-post-drying procedure led to
the best properties above all, which was explained by the reduc-
tion in remaining water and solvent NMP. Both mechanical and
electrical properties declined with intensifying the post-drying
conditions. A possible reason was found in the thermally acti-
vated diffusion creep of the binder PVDF, which could have
led to the rearrangement of the carbon-black particles and, there-
fore, damage of the integrity of the carbon-black binder network
and the electric percolation pathways.
The damage of the electric percolation pathways in both ano-
des and cathodes led to a decrease in the achievable electrochem-
ical performance. Therefore, the structural changes caused by
post-drying can overlap and significantly reduce the positive
effects of the achieved water release on the electrochemical per-
formance. This is why, in general, a good performance cannot be
guaranteed by only adjusting a low remaining water content.
Instead, the type of post-drying and its intensity seem to have
a high impact on the electrochemistry.
4. Experimental Section
As explained earlier, there already exist several works concerning the neg-
ative impact of water in battery cells.[17–20] Nevertheless, there is hardly any
information about a critical value of remaining water in battery cells or
about the influence of post-drying on the cell properties. Taking this into
consideration, these questions are addressed in this study. Three different
post-drying procedures were designed to investigate the impact of varying
post-drying conditions and the consequences of different remaining water
content. The remaining water contents were measured via coulometric
Karl Fischer Titration and correlated with the electrochemical performance
of the cells. To understand the resulting differences, the cell components
were then analyzed in detail with regard to their physical and structural
properties. As the separator Separion added only small amount of mass
to the battery cell and was known to be resistant to high temperatures up
to 240  C,[47] attention was devoted to the electrodes during further
analyses in this study.
Materials and Electrode Composition: For the electrodes, common mate-
rials and recipes were used (Table 2).[4] To identify an impact of the dif-
ferent remaining water content, electrodes with a high mass loading were
produced, namely, cathodes with 27 mg cm2 and accordingly balanced
anodes with 14.9 mg cm2 mass loading. This complied a slight oversizing
of the anode’s capacity (ccathode/canode ¼ 1/1.2), which was chosen to avoid
the risk of lithium plating.[48] For the anode, a copper foil with a thickness
of 10 μm served as substrate (Sumitomo Electric Hartmetall GmbH,
Germany). The cathode’s suspension was coated on an aluminum foil
of 20 μm thickness (Hydro Aluminium GmbH, Germany).
Electrode Manufacturing Processes: For the manufacturing of the anode,
a TURBULA T 2 F mixer (Willy A. Bachofen AG Maschinenfabrik,
Switzerland) was used to prepare a dry powder mixture of the components
SMGA-5, C65, and CMC. The mixing time was set to 15 min at a tip speed
of 49 min1. The dry powder mixture was then dispersed in the dissolver
DISPERMAT CA60 (VMA-GETZMANN GmbH, Germany), using a 50 mm
tooth disk. As an acting solvent, deionized water was filled in 1 L vessel.
The dry powder mixture was added under cooling to 15  C and a tip speed
of 1.31 m s1 using a vibratory channel with a slant of 60%–80%. The
slurry was then dispersed over 60 min with a peripheral speed of 9 m s1
under cooling to 15  C. SBR was added during the concluding degassing,
which was conducted for 20 min with a tip speed of 1.31 m s1 and under
cooling to 15  C. The final solids content of the slurry was 46 wt%.
The cathode was manufactured using a planetary mixer PMH10
(NETZSCH GmbH und Co. Holding AG, Germany). A high-speed stirrer
with double butterfly setup and a cross-beam low-speed stirrer were used
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as mixing tools. In addition, a baffle rotating along the mixing vessel wall
was installed. First, the dry components (NCM 622, C65, SFG6L, and
binder PVDF) were mixed in the planetary mixer at stirrer tip speeds of
5.03 m s1 (high-speed stirrer) and 0.53 m s1 (low-speed stirrer). Next,
the solvent (N-methyl-2-pyrrolidon) was added to a solids content of
82.5 wt% of the slurry (kneading step). This slurry was then dispersed
for 60 min with a high-speed stirrer tip speed of 4.19 m s1; the tip speed
of the low-speed stirrer was set to 0.53 m s1. The planetary mixer moved
with a speed of 100 rpm. To reach the coating window of the used con-
tinuous coating machine LabCo (Kroenert GmbH & Co. KG, Germany),
the dispersed slurry was then diluted to a solid content of 75 wt% for
30 min with the same tip speeds as used during dispersion.
For coating and drying, the aforementioned pilot-scale continuous con-
vective coating and drying machine LabCo was utilized. The target mass
loading of the electrodes was adjusted by a reverse-roll comma-bar and
detected inline behind the three-segment drying section by the ultrasonic
measurement USM-200 (MESYS AG, Switzerland). The anode was coated
and dried with a speed of 1 m min1; the drying temperature of the three
individual adjustable drying segments of 2 m length each was set to 65  C,
and airflow to 40% diffuse/40% diffuse/60% direct. The cathode was
coated and dried with a speed of 2 m min1; the temperatures of the
drying segments were set to 60  C/80  C/100  C. While the anode stayed
uncalendered, the cathode sheets were calendered to a coating density of
3.0 g cm3 in a calender GKL 400 (SAUERESSIG GmbH und Co. KG,
Germany).
Post-drying Procedures: To identify the influence of post-drying, three
different post-drying procedures were chosen and compared with the
non-post-dried state (Table 1). For a good comparability, all post-drying pro-
cedures were conducted with the same type of post-drying, namely, a com-
bination of vacuum and Argon-purging. To produce clear and measurable
differences, the intensity of post-drying was varied extensively by raising the
temperature and the duration of the process. The argon-post-drying proce-
dure (automatic purging with 3 drawing vacuum/inerting for 15 min at
20  C) showed the lowest intensity regarding the duration as well as
temperature and pressure. The medium-term-vacuum-post-drying already
represented a significantly higher post-drying intensity (18 h at 120  C in
vacuum, followed by 3 drawing vacuum/inerting). Finally, the highest
intensity was achieved by long-term-vacuum-post-drying (96 h at 120  C
in vacuum, followed 3 drawing vacuum/inerting) by extremely extending
the duration of post-drying.
For the two oven-post-drying procedures, temperature up to 120  C and
vacuum were considered as the set-up represented common post-drying
conditions.[7,49] As the used separator Separion was known to be resistant
to high temperatures up to 240  C,[47] the attention was focused on the
electrodes in this study. This was why the separators were post-dried
equally for both vacuum-post-drying procedures according to the
manufacturer recommendations.
The vacuum-post-dryings were conducted in a vacuum oven (Model VD
115, BINDER GmbH, Germany) with a negative pressure of 1  102 mbar
which was flange mounted to an argon-glove box (GS Glovebox
Systemtechnik GmbH,Germany; O2/H2O < 0.1 ppm). The argon-post-drying
was performed in a pre-switched vacuum lock of the argon-glove box.
Determination of Water Content According to Karl Fischer: The remaining
water in the cells caused cell degradation on the one hand and inhibited
the formation of an effective SEI on the other hand.[17–20] Therefore, it was
very important to investigate whether there was some kind of a critical
value of remaining water content for LIBs and how the remaining water
influenced the physical and electrochemical properties. For this reason,
the remaining water content xw of electrodes and separators in the
non-post-dried state and after the different procedures of post-drying were
measured by KFT. Therefore, the Karl Fischer Titrator AQUA 40.00 with
headspace module (ECH Elektrochemie Halle GmbH, Germany), placed
in a dry room with a dew point of TD ¼ 30  C, was used. The operating
principle applied was as follows: The headspace vials were automatically
pierced by a double cannula and transported into the oven, where the sam-
ple was heated up to the set temperature. The air above the electrolyte
acted as carrier gas and was continually titrated to dryness within the
closed loop. The carrier gas was pumped into the headspace vial through
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www.advancedsciencenews.com
the cannula and the moisture was transported, which was emitted by the
sample during heating, from the headspace vial into the measuring cell
where it was titrated. Including the sample’s weight, the water content
of the sample was then calculated as a function of the electricity consumed
during titration.
In this study, for each analysis, a threefold determination was per-
formed and averaged. For the calculation of the water remaining in the
electrodes, the measured water content was related to the complete
weight of the electrode, namely, coating and current collector. During each
post-drying experiment, samples with weights of about 0.2 g for separators
and 0.7–0.8 g for anodes and cathodes were taken, rolled, and put into
headspace vials. The vials were closed as quickly as possible with crimp
caps and measured by KFT on the same day to prevent the exchange of
humidity with the surrounding area. The measuring time for all compo-
nents accounted for 10 min, and the measuring temperature of cathodes
was set to 120  C, of anodes to 100  C, and that of separators to 80  C.
These temperatures were chosen on the basis of previous study, consid-
ering the thermal stability of the used materials and the possible oxidation
of the copper current collector.[7]
Electrochemical Characterization: The electrochemical rate-capability
tests were conducted with one compartment pouch cells in laboratory size
[55 mm (anode)  50 mm (cathode)]. After post-drying, the cell compo-
nents were directly transferred into the argon glove box for the cell
assembly. As separator, the ceramic separator Separion S240P30
(LITARION GmbH, Germany) with a thickness of 28 μm was chosen.
LP57 (BASF SE; Germany) with 1 m LiPF6 and 2 vol% vinylene carbonate
(VC) served as electrolyte. The electrochemical measurements were per-
formed at room temperature of 21  C with a battery testing machine
(Series 4000, Maccor, Inc., USA). The test procedure was constituted in
Table 3. The upper and lower cut-off voltages were set to 4.2 and 3.0 V,
respectively.
Micro Compression: The total deformation energy of anodes and cath-
odes and its elastic and plastic amounts were measured via micro com-
pression measurements (UNAT, ASMEC GmbH, Germany) using a flat
punch indenter with 100 μm diameter.[14,50] At first, a reference sample
of the test series was measured path-controlled to determine the force
which was needed to indent the coating by a defined compression of
10%. All samples were then compressed force-controlled until the deter-
mined maximal force was reached. For each sample, 80 measuring points
were applied with a compression rate of 2.8 mN s1 during loading and
unloading (for more details and complete procedure, see Barth et al.[51,52],
Fischer-Cripps[53] and Bockholt[24]). With the resulting force-displacement-
diagrams, the different types of deformation work (plastic (Wpl), elastic
(Wel), and total (Wtot) deformation work with Wtot ¼ Wel þ Wpl) and their
Table 3. Electrochemical test procedure.
Cycling step Charge and discharge parameters (3–4.2 V)
Formation 3 0.1 C/0.1 C (Ch./Dis) only CC
1. C-rate test 3 0.2 C/0.2 C (Ch./Dis) CCCV in Ch.
3 0.2 C/1 C (Ch./Dis) CCCV in Ch.
3 0.2 C/2 C (Ch./Dis) CCCV in Ch.
3 0.2 C/3 C (Ch./Dis) CCCV in Ch.
3 0.2 C/5 C (Ch./Dis) CCCV in Ch.
Recovery after 1. C-rate test 2 0.1 C/0.1 C (Ch./Dis) CCCV in Ch.
Cycling 50 1 C/1 C (Ch./Dis) CCCV in Ch.
Recovery before all further C-rate tests 2 0.1 C/0.1 C (Ch./Dis) CCCV in Ch.
Further C-rate tests 3 0.2 C/1 C (Ch./Dis) CCCV in Ch.
3 0.2 C/2 C (Ch./Dis) CCCV in Ch.
3 0.2 C/3 C (Ch./Dis) CCCV in Ch.
Recovery after all further C-rate tests 3 0.1 C/0.1 C (Ch./Dis) CCCV in Ch.
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relations was calculated. The median Wx,50 or (Wx/Wy)50, respectively, was
often used as a characteristic value of the sum distribution of all measured
values.
Specific Electrical Resistance: The specific electrical resistance of the
electrodes after the different post-drying procedures was measured by
an in-house developed test method. This method gave a characteristic
for the electron transport kinetic as a function of the conductance or
the ohmic resistance, correspondingly. The electron transfer through
the composite-coating layer and the current collector was therefore char-
acterized by inducing a direct current of 1 mV while measuring the voltage
drop. The specific electrical volume resistance was calculated in consider-
ation of the measured voltage drop and the samples’ dimensions. For
each experiment, ten samples were measured and averaged. For the mea-
surement, each sample was placed on a conductive brass disk and a brass
piston with a diameter of 10 mm. To ensure a planar, homogenous elec-
trical contact, the sample was then pressed slightly by a mechanical testing
machine increasing the nominal stress up to a maximum of 0.4 MPa.
Further information is given by Haselrieder et al.[46] and Westphal et al.[54]
Scanning Electron Microscopy: The structural changes of the electrodes
caused by the different post-drying procedures were also investigated by
non-destructive imaging techniques using SEM. Therefore, cross-sections
of the post-dried electrodes were embedded in resin and sputtered with
gold. The SEM images were subsequently taken with the Helios G4 CX
microscope (FEI Deutschland GmbH, Germany). This microscope pro-
vided an electron beam parameter space of 0.8 pA to 100 nA and an elec-
tron beam resolution of 0.6 nm at 30 kV (with scanning transmission
electron microscopy, STEM) and 1.0 nm at 1 kV. The chamber achieved
a vacuum <2.6  106 mbar (after 24 h pumping).
Acknowledgements
The authors gratefully thank the German Federal Ministry for Education
and Research (BMBF) for the financial support (FKZ 03XP0080B). The
authors would like to thank Julian Mayer, Christiane Schilcher, Tanja
Boll, Jan-Michael Kröhnke, and Louise Niemeyer for the experimental
support and the fruitful discussions.
Conflict of Interest
The authors declare no conflict of interest.
Keywords
electrochemical performance, Karl Fischer titration, lithium-ion batteries,
post-drying, water content
Received: February 26, 2019
Revised: April 18, 2019
Published online:
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