Hysteresis Behavior in The Sorption Equilibrium of Water in Anodes For Li-Ion Batteries

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Article
The hysteresis behavior in the sorption
equilibrium of water in anodes for Li-ion batteries
Jochen C. Eser, Birthe Deichmann, Tobias Wirsching,
Peter G. Weidler, Philip Scharfer, and Wilhelm Schabel
Langmuir, Just Accepted Manuscript • DOI: 10.1021/acs.langmuir.0c00704 • Publication Date (Web): 09 May 2020
Downloaded from pubs.acs.org on May 11, 2020
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Page 1 of 43 Langmuir
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10 The hysteresis behavior in the sorption equilibrium
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14 of water in anodes for Li-ion batteries
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19 JOCHEN C. ESERa*, BIRTHE DEICHMANNa, TOBIAS WIRSCHINGa, PETER G. WEIDLERb,
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21 PHILIP SCHARFERa, WILHELM SCHABELa
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24 a) Institute for Thermal Process Engineering – Thin Film Technology
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Karlsruhe Institute of Technology
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29 Kaiserstraße 12, 76131 Karlsruhe, Germany
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31 E-mail: jochen.eser@kit.edu
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34 b) Institute of Functional Interfaces
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36 Karlsruhe Institute of Technology
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39 Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany
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42 KEYWORDS: DESORPTION, DRYING, HYSTERESIS, LI-ION BATTERY, MOISTURE
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ABSTRACT: A hysteresis in the sorption equilibrium influences the production process of many
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48 multi-component material systems. Electrodes for Li-ion batteries consist of several materials,
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50 some of which exhibit a hysteresis in their sorption equilibrium with water. The moisture content
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52 ad- and absorbed in the electrodes of the Li-ion battery turned out to be an issue for its
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electrochemical performance and is reduced in the post-drying process. During this process, the
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57 hysteresis in the sorption equilibrium needs to be overcome, in order to achieve a low residual
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Langmuir Page 2 of 43
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6 moisture content of the electrode. Modelling the post-drying process requires a description of the
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8 sorption equilibria of water in the components of the battery. This paper builds on previous
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11 research about the sorption equilibria and examines the hysteresis behavior of typical graphite
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13 anodes, with the active material graphite, carbon black as conductive additive and sodium
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15 carboxymethyl cellulose (CMC) as well as styrene butadiene rubber (SBR) as polymeric binders.
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17 Moreover, mechanisms for the occurrence of the hysteresis are presented and it is shown, how
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sorption equilibria during drying can be described by applying models from the literature on the
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22 materials of battery electrodes. Theoretical deliberations on hysteresis mechanisms are validated
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24 investigating graphite anodes of different material compositions and their materials.
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28 INTRODUCTION
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30 In their process chain, electrodes for Li-ion batteries are subjected to many individual process
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32 steps. An energy intensive process step is the post-drying process 1 which is often designed
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empirically and has hardly been addressed scientifically. In this process, moisture ad- and absorbed
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37 in the electrodes is removed to a certain amount. If the electrodes have reached their sorption
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39 equilibrium with the dryer conditions, an unwanted remoistening takes place in the dry room
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41 during further cell processing. This remoistening happens, since the electrodes aim for the sorption
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equilibrium with the gas phase in their vicinity. The activity of water aW in the electrode is given
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46 as a ratio of the partial pressure of water pW in the gas phase and the saturation vapor pressure at
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48 the temperature of the electrode pW*(TElectrode) resulting in aW = pW/pW*(TElectrode). It therefore
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50 adjusts according to the relative humidity rH of the dry room, which is determined by the dew
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point TD and the saturation vapor pressure pW*(TDry room) of water depending on the temperature of
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55 the dry room: rH = pW*(TD)/pW*(TDry room).
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6 A reduction of the temperature from dryer to dry room is thus accompanied by an increase of the
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8 water activity of the gas phase, even if the dew point of the dry room and the dew point at the exit
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11 of the dryer are the same. Typical dew points of dry rooms in the battery production chain are
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13 around TD = -50 °C. 2 Provided that the sorption equilibrium was not showing any hysteresis, the
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15 electrode could be stored in the dry room instead of undergoing an energy intensive post-drying
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17 process. This is illustrated in Figure 1.
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Dry room conditions
22 Ambient conditions
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Dryer conditions
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Water mass loading X W / ppm
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27 n
28 De sorp tio
29 on
30 ing o rpt i
31 Dr y yS
a r
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ec ond
33 S
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35 ois t en ing
36 R em
37 tion
38 S or p
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44 Water activity aW / -
45 Figure 1. Schematic representation of the post-drying process. The drying process starts at a high
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47 water activity wherefore the activity is reduced and the layer is dried. Due to a decrease in the
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49 temperature after the drying process, the electrode starts to resorb.
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52 Yet, previous investigations have shown that the electrodes do show a hysteresis 3 and therefore
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55 need to be dried. Another advantage of high drying temperatures is the acceleration of the slow
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3
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6 mass transport kinetics at low mass loadings. Kinetic effects will, however, not be addressed in
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8 this paper.
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11 In order to remove the moisture cost-efficiently, the process understanding needs to be improved
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13 by modelling. Although first efforts can be found in the literature, 4 the mechanisms of heat and
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15 mass transfer of water in electrodes for Li-ion batteries are not completely understood. Of
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17 particular interest is the anode, as it contributes the most moisture to the cell. 4 Especially water-
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borne binder systems play a key role. 3,5,6
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22 Concerning the hysteresis in the sorption behaviour of water in electrodes for Li-ion batteries,
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24 three challenges need to be addressed. Firstly, relevant mechanisms that cause the hysteresis of
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26 moisture sorption in the components of a Li-ion battery need to be identified. Secondly,
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sorption/desorption and hysteresis scanning loops need to be distinguished. Between drying and
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31 post-drying, the electrodes undergo further process steps. Thus, the course of desorption is unlikely
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33 to follow the whole path of the primary desorption isotherm but starts at a fluctuating relative
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35 humidity instead. This is why the desorption isotherm needs to be modelled depending on the
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sorption isotherm. Thirdly, Figure 1 displays that an unwanted remoistening takes place during
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40 further cell processing due to an increase of water activity. A modelling of the secondary sorption
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42 isotherm depending on the primary sorption and desorption needs to be found. Provided that the
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44 electrodes are dried to a very low moisture content in the post-drying process, the remoistening
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runs on the primary sorption isotherm.
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49 The phenomenon of hysteresis in ad/ab- and desorption in general has long been observed in the
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51 water sorption 5,6 and an explanation for the hysteresis behavior has been sought. 7,8 Over the years,
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53 various theories have been employed to explain hysteresis. It is particularly difficult to evaluate
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55 the predominant mechanism in the sorption of moisture in battery electrodes, since a whole variety
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6 of different electrodes with different active materials, structure and material composition is
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8 reported in literature. For carbon electrode materials, graphite is deployed just like diamond or
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11 carbon nanotubes. 9 Besides, surface modifications or carbon composite electrodes are reported,
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13 for example to address a volume change during (de)lithiation. 10,11 Chen et al. reported a new
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15 strategy to wrap Ni-incorporated and N-doped carbon nanotube arrays on porous Si and received
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17 a high reversible capacity as well as an excellent cycling stability. 12
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In the most common case for anodes of Li-ion batteries, however, natural or synthetic graphite
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22 particles are employed, which are incorporated in a network of solvent- or water-based polymeric
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24 binders. 13,14 In the following, we focus on anodes that contain synthetic surface modified graphite
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26 particles, on which the moisture tends to adsorb and water-based polymeric binders, some of which
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rather show a volume uptake of the moisture and a high swelling behavior like CMC.
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31 The following paragraphs will give a brief overview about the theory on adsorption and absorption.
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33 Adsorption
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35 An established model to describe the physical adsorption on solid sorbents is the BET equation
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named after Brunauer, Emmett and Teller. 15
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⋅ ⋅
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41 =
1− ⋅ 1+ −1 ⋅
(1)
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45 In the BET equation, Xi is the loading of the sorbent, ai is the activity of the sorbate and kBET as
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47 well as Xm are parameters fitted to the measurement data.
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49 The latter fit parameter of the BET-equation, which describes the loading with a monolayer of a
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52 sorbate, also allows an experimental determination of the surface area of a sorbent in m2 per g dry
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54 mass.
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5
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= ⋅ ⋅
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8 (2)
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11 In equation (2), NA is the Avogardo-constant, the molar mass of the adsorptive and
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14 AAdsorbate is the area occupied by an adsorbed sorbate molecule. For water, a literature value is given
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16 as AWater = 12.5 Å2. 16
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18 Furthermore, Brunauer et al. developed under some assumptions an extension of the model to
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material systems with a finite number of adsorbate layers and isotherms of different shape, which
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23 is displayed in equation (3). 17,18
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⋅ ⋅
=
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26 1−
27 " "
1+ !⋅ − !$ ⋅ %&' − ! ⋅ " − ! + 1 ⋅ % + ! ⋅ $ ⋅ %('
2 2
(3)
⋅
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" "
1+ −1 ⋅ + ⋅ − $⋅ − ⋅ $ ⋅ %('
29 %
30 2 2
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32 In equation (3), (2n-1) is the number of layers of adsorbate, that can fit in the walls of a pore.
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34 Moreover, g is an additional temperature-dependent fit parameter that is associated with the heat
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36 of adsorption in the last layer of adsorbate. 17,18
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39 The temperature-dependence of the fit parameters g and kBET can be presented in the following
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41 form.
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44 - 3
= exp , 1 ; " = exp , 1
./ ⋅ 0 ./ ⋅ 0
45 (4)
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48 In equation (4), E is the difference of the heat of adsorption in the first adsorbed layer and the heat
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50 of liquefaction. Q is the difference of the heat of adsorption in the last adsorbed layer and the heat
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53 of liquefaction.
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55 In case of the physical adsorption on solid sorbents, capillary condensation has been identified as
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57 the cause of hysteresis for many material systems. Various mechanisms were considered to explain
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6 the observation in detail, such as an incomplete wetting of pores during adsorption, ink-bottle
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8 shaped pores or a delay in forming the meniscus in the capillaries. 19,20 Cohan described how the
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11 partial pressures at which adsorption (pA) and desorption (pD) take place behave in a cylindrical
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13 pore with open ends. 18 He stated that these considerations also apply to closed capillaries with
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15 constrictions. 20
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17 4 %6789: 4;
, 1 =
4∗ 0 4∗0
18 (5)
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In this equation, pA is the partial pressure of adsorption, pD the partial pressure of desorption and
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23 p*(T) the saturation vapor pressure at a given temperature T. The exponent nCohan equals two, if
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25 the corresponding requirements of ideal wetting behavior in a cylindrical or cylindrical constricted
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27 pore are fulfilled. 18,19
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In his model conception of capillary condensation, Cohan does not consider the pore structure or
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32 the pore network and regards only single cylindrical pores. In the view of recent literature, Cohan’s
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34 model is thought to be an oversimplification. 21 Nevertheless, for some material systems, it
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36 provides a straightforward way to determine the primary desorption from the adsorption isotherm.
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The exact form of the hysteresis of adsorption exists in various shapes. The international union of
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41 pure and applied chemistry (IUPAC) has identified several different types of adsorption hysteresis
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43 loops depending on the pore and particle structure. A narrow pore size distribution between equal-
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45 sized particles shows a different hysteresis form than slit-like pores between platelet-shaped
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particles. 22,23
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50 With every of the forms of hysteresis, a so called low pressure or open hysteresis may occur,
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52 meaning that the hysteresis may be observed to the lowest attainable pressures. 22 Although an
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54 open hysteresis can also be enabled by chemisorption, 24 it is in case of physisorption associated
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56 with the swelling of a non-rigid pore structure or with the irreversible uptake of molecules in pores
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6 of approximately the same width as that of the adsorbate molecule. 20,22 Moreover, the presence of
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8 permanent gases is also thought to be a reason for the irreversibility of adsorption. 20 Furthermore,
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11 an intercalation of polar molecules accompanied by the expansion and contraction of a sorbent
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13 might result in a hysteresis over the complete range of activity, which has been observed during
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15 the sorption of polar sorbates in montmorillonite clays. 21,25
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17 Even though capillary condensation is unlikely to be the only hysteresis mechanism involved, it
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will play a role during the sorption in the materials inside the electrode of a Li-ion battery.
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22 Absorption
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24 A considerable amount of moisture in typical graphite anodes is, however, not adsorbed on the
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26 particles but absorbed in the binder carboxymethyl cellulose (CMC). 3 This cellulosic binder is a
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29 derivative of cellulose. In anodes for Li-ion batteries, usually its sodium salt is employed.
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31 Cellulose is a material that has been extensively studied by researchers in the field of drying of
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33 wood. Since there is not even agreement in literature on the explanation of hysteresis in the
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35 sorption of water in cellulose, the description of hysteresis in whole electrode structures is even
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more complex.
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40 Although different results have been acquired in the latest years, 26 early considerations assume a
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42 superposition of several mechanisms as a reason for the sorption in cellulosic materials. Kollmann
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44 suggests that a saturation of hydroxyl groups occurs at low activities following a theory proposed
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by Urquhart. 27 He assumes that a hysteresis is observed since unsaturated hydroxyl groups try to
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49 saturate each other during drying and are no longer available for the sorption of water molecules
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51 during sorption. This mechanism is succeeded by capillary condensation in the range of higher
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53 activities. 28 The idea of superimposing several processes in order to explain the hysteresis in the
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sorption of water in cellulosic materials has remained to this day. 29,30 In addition to this, some
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6 recent studies attribute hysteresis behavior in cellulosic materials only to capillary
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8 condensation, 31,32 whereas other studies relate the hysteresis to structural changes when their glass
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11 transition temperature is exceeded. 33
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13 The latter follows a theory developed by Vrentas and Vrentas. 34,35 They explained the hysteresis
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15 behavior of the sorption of a solvent in polymers with structural changes due to an exceeding of
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17 the glass transition temperature of mixtures of solvents and polymers and used a modified Flory-
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Huggins approach in order to model the sorption isotherms. 36
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23 = < ⋅ exp 1 − < + = ,? 1 − < @
+ ⋅ A$ (6)
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In this equation, ai is the activity of the solvent, φi is the volume fraction of the solvent, χi,j is the
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29 Flory-Huggins interaction parameter and F is defined by equation (7). The parameter k equals one
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31 in case of absorption and deviates from one in case of desorption according to equation (9). 33,36
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33
⋅ 1−B @
⋅ CD ,E −D ,E,F G I0F 0
A= H JH − 1J 0 < 0F
34
./ ⋅ 0 IB 0F
35 (7)
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38 In equation (7), is the molar mass of the solvent, B is the mass fraction of the solvent, cp,S and
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40 cp,S,g are the heat capacities of the polymer and the polymer in the glassy state and Tgm is the glass
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42
transition temperature of the mixture of polymer and solvent. A correlation for the concentration-
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45 dependent glass transition from the glass transition temperatures Tgi and Tgj of two materials is
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47 given in the equation by Fox. 37
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49 &'
B 1−B
0F =H + J
50
0F 0F?
(8)
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52
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54 If T > Tgm, F equals zero. In this case, equation (6) represents the Flory-Huggins approach. The
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56 rate of change of Tgm with change in penetrant mass fraction can be obtained from Pierlot. 38
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9
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6 According to the model by Vrentas and Vrentas, the parameter k can be calculated as follows.
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8 0;
C0; − 0F@ G − 0; ⋅ ln , 1
9 0F@
=
0
10 (9)
11 C0 − 0F@ G − 0 ⋅ ln , 1
12 0F@
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14 The fit parameter TD should not be confused with the dew point and represents according to the
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16 model a temperature which produces the same structure for an absorption sample which is
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18 equivalent to the desorption structure at temperature T. It can be adapted to measurement data and
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Tg2 is the glass transition temperature of the polymer. 33
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23 Salmén and Larsson showed experimentally that the hysteresis of chemically modified cellulosic
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25 materials varies with its softening behavior. 34 Hill and Beck were the first to apply the theory to
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27 their experimental results of the sorption of water in cellulose. 33
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29
By contrast, instead of equation (6), variations of the BET-equation are employed to describe the
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32 primary sorption of water in cellulosic materials, especially in literature about food processing
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34 technology. 39
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36 Regardless of the predominant mechanism for the hysteresis, neither of the here mentioned models
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38 of sorption isotherms are able to predict hysteresis loops. Still, a way to describe a secondary
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41 desorption from the sorption and desorption isotherm needs to be found.
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43 In literature about the adsorption on solid sorbents, this is done by applying the density functional
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45 theory. 32,40 A more straightforward semi-empirical approach is proposed by Zhang et al. 41, who
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47 considered a model suggested by Mualem. 42,43
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50 Though originally having been derived for the theory of capillary condensation, the equation
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52 proposed by Zhang et al. primarily mediates between given ad-/ab- and desorption isotherms. We
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54 propose a different empirical equation following a similar approach, in order to describe the
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56 hysteresis behavior in electrodes for Li-ion batteries.
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6 During post-drying of the electrodes, desorption occurs from the upper inflection point of the
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8 isotherm XU until the course of the primary desorption branch is reached. Consequently, the
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11 desorption loops with loading XDes are located between the primary sorption X1.Sorp and desorption
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13 X1.Des and can be described by equation (10).
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15
X'.STUV XYZ[
XOPQ = X'.OPQ. + X'.STUV − X'.OPQ ⋅, 1
16
XW
(10)
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18
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20 At high activities, the loading approaches the value of the primary sorption isotherm, whereas it
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22 approaches the value of the primary desorption isotherm for low activities.
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24 The only parameter in this equation for the secondary desorption branch, which is not part of the
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26 modelling of the primary sorption or desorption, is the parameter nDes. Empirical investigations
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show that !; = 2 is in good agreement with experimental results.

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35 EXPERIMENTAL SECTION
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37 In this paper, graphite anodes used in Li-ion batteries were investigated consisting of graphite
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39 particles, carbon black as conductive additive and Na-CMC as well as SBR as binders. Details
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42 about the materials and the experimental setups can be found in a former publication. 3 Table 1
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44 summarizes the latter.
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46 Table 1. Overview of experimental setups
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48 Method 1 Method 2 Method 3
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50 Measurement setup
Magnetic suspension Magnetic suspension
Hydrosorb
51 balance balance
52 Gas phase Saturated gas flow Pure vapor Pure vapor
53
Measurement
54 Gravimetric Gravimetric Pressure
principle
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11
1
2
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6 Method 1 and 2 are gravimetric measurement methods with a high resolution at sufficient sample
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8 masses and differ in the adjustment of the gas phase activity. Method 1 is operated at
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11 atmospheric pressure and the dew point of the gas phase is adjusted by mixing a dry and a
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13 saturated gas flow, providing for the opportunity to adjust low activities at low temperatures.
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15 Results of the measurements are compared to method 3, an acknowledged standard device for
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17 sorption isotherms.
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20
In contrast to previous investigations, however, the drying temperature was decreased to
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22 T = 90 °C in all setups to prevent the binders from being damaged. Frequent repetition of
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24 experiments or excessively long drying times lead to changes in the phase equilibrium of the
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26 anode, which may be attributable to material changes in the binder when using high temperatures
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over long periods.
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31 Measurements of the glass transition temperature were done by differential scanning calorimetry
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33 with a DSC 204 from Netzsch.
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RESULTS AND DISCUSSION
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40 It has been shown previously that the anode of the Li-Ion battery shows a hysteresis in its sorption
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42 equilibrium. 3 The aim of this paper is to further evaluate this hysteresis behavior of anodes for Li-
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44 ion batteries.
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Graphite represents the biggest mass fraction among the materials in the anode of the Li-ion
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49 battery. Its sorption isotherm represents most likely type IV from the IUPAC classification and
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51 its hysteresis behavior at a temperature of T = 30 °C is displayed in Figure 2.
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12
1
2
3
4
5
6 1200
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8 Method 1 Adsorption [3]
9 Method 1 Desorption
10 1000
Mass loading XW / ppm
13
14 800 Method 3 Adsorption [3]
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17 600 Fit Adsorption eq. 3
18 Fit Desorption eq. 5
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21 400
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23
24
200
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27 Water-graphite, 30 °C
28 0
29 0 0.2 0.4 0.6 0.8 1
30
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33 Figure 2. Hysteresis behavior of the sorption of water on graphite particles at T = 30 °C measured
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35 by three different experimental setups. Measurement values were fitted by using equation (3) for
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38 the adsorption and equation (5) for the desorption. Values of the adsorption isotherm are taken
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40 from a former publication. 3
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43 Graphite shows a hysteresis in its phase equilibrium. The reason for the hysteresis is assumed to
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45 be capillary condensation. Measurement data were fitted by using equation (3) for the adsorption
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47 and equation (5) for the desorption. The fit parameters are presented in Table 2. Deviations
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50 between measurement and model are visible in the range of highest activity, since the model cannot
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52 reproduce the exact course of the entire isotherm. For the post-drying process, this range of activity
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54 plays a minor role.
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56 Table 2. Fit parameters for the adsorption and desorption of water in graphite.
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13
1
2
3
4
5
6
E / J mol-1 Xm / ppm n/- Q / J mol-1 nCohan
7
8 1. Adsorption 6000 125 5 10000 -
9
10 1. Desorption 6000 125 5 10000 1.5
11
12
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14 The course of the hysteresis reminds most of type H3 according to the IUPAC classification, which
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16
is associated with plate-like particles. 22 This plate-like structure can be confirmed from SEM-
17
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19 pictures. Based on this is a possible model concept of the water adsorption in the graphite particles
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21 displayed in Figure 3.
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34 Figure 3. Possible model concept of the water adsorption on the graphite particles. The particles
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exhibit a plate-like structure that causes slit-like pores in which the water adsorbs.
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14
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6 Just like graphite, carbon black also shows a hysteresis in its phase equilibrium. Figure 4 presents
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8 the measurement data, which remind of a type V isotherm according to the IUPAC classification
9
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11 that is associated with weak interactions between sorbate and sorbent. 17
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13 1000
15
800
18
20
Method 3 Adsorption [3]

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22 600 Method 3 Desorption
23 Fit Sorption eq. 3
24
25 Fit Desorption eq. 5
26 400
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29
30 200
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33 Water - carbon black, 30 °C
34
0
35
36 0 0.2 0.4 0.6 0.8 1
37 Water activity aw / -
38
39 Figure 4. Hysteresis behavior of the sorption of water on carbon black particles at T = 30 °C
40
41
42
measured with three different setups. Measurement values were fitted by using equation (3) for the
43
44 adsorption and equation (5) for the desorption. Values of the adsorption isotherm are taken from a
45
46 former publication. 3
47
48
49 Measurement data of the adsorption of water on carbon black were again fitted by using equation
50
51 (3) for the adsorption and equation (5) for the desorption isotherm. Deviations are visible in the
52
53
54
desorption branch especially at low activities. The corresponding fit parameters are presented in
55
56 Table 3.
57
58
59
60
15
1
2
3
4
5
6 Table 3. Fit parameters for the adsorption and desorption of water in carbon black.
7
8
9
E / J mol-1 Xm / ppm n/- Q / J mol-1 nCohan
10
11
1. Adsorption -800 298 7 -50 -
12
13 1. Desorption -800 298 7 -50 1.7
14
15
16
17 By and large, graphite and especially carbon black do not contribute to the sorption equilibrium of
18
19
20
the anode with water to a large extent. By contrast, the binder CMC is responsible for the main
21
22 water uptake in the anode. 3 Therefore, this binder has been tested for its hysteresis behavior.
23
24 An estimation of the inner surface or the pore volume, respectively, can be done by Argon
25
26 sorption at T = 87 K. The surface area of CMC particles determined from experiments accounted
27
= 1.5 _@ /".
28
29
for a low value of ,\]\
30
31 Entirely different are the results from experiments with water sorption and desorption, which are
32
33 displayed in Figure 5. Films of CMC take up a huge amount of water. Moreover, the phase
34
35 equilibrium of water in CMC is temperature-dependent and exhibits a hysteresis, which is also
36
37
38
temperature-dependent. At T = 30°C, the hysteresis is quite distinct while it almost disappears at
39
40 T = 90 °C. In Figure 5, the experimental values are compared to the model developed by Vrentas
41
42 and Vrentas.
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
16
1
2
3
4
5
6 1
7
8 Sorption 30 °C
9
10
Desorption 30 °C
11 0.8 Sorption 60 °C
Mass loading XW / gW gCMC-1
12
Desorption 60 °C
13
14 Sorption 90 °C
15 0.6
Desorption 90 °C
16
17 Fit Sorption eq. 6
18
Fit Desorption eq. 6
19 0.4
20
21
22
23
0.2
24
25
26 Water-CMC
27
28 0
29 00.4 0.2 0.6 0.8
31
Figure 5. Hysteresis of water sorption in a layer of CMC at different temperatures and compared
32
33
34 to the desorption model of equation (6). Measurement values were recorded using method 2.
35
36
37 Figure 5 shows that the model by Vrentas and Vrentas can describe the hysteresis behavior.
38
39 Deviations emerge especially in the desorption at high activities and high temperatures. The former
40
41 might be explained by additional capillary condensation. In the post-drying process, though, values
42
43
at high activities play a minor role. An improved adaption for higher temperatures might succeed
44
45
46 by a different temperature-dependence of the parameter k in equation (9) from the fit parameter
47
48 TD.
49
50 The model requires a set of fit parameters which are given in Table 4. The glass transition
51
52 temperature of pure water was taken from the literature as Tg,w = 135 K. 44
53
54
55 Table 4. Fit parameters of the hysteresis of water sorption in CMC.
56
57
58
59
60
17
1
2
3
4
5
6
Δcp / J kg-1 K-1 Tg,CMC / K- χ/- TD / K
7
8 1. Sorption 380 550 0.3 -
9
10 1. Desorption 380 550 0.3 220
11
12
13
14 The validity of two of these fit parameters, Tgm and Δcp, was verified by measurements with
15
16
17 differential dynamic scanning calorimetry (DSC). For this purpose, CMC particles were loaded
18
19 with moisture at different water activities. In DSC measurements, the glass transition temperature
20
21 is visualized by a step. 45 Yet, not all samples showed a very pronounced step. The results are
22
23 displayed in Figure 6 and compared to the used model from equation (8) given by Fox. In addition,
24
25
26
available data from the literature for the glass transition temperature of cellulose with varying
27
28 water content is displayed. 46,47
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
18
1
2
3
4
5
6
7
600
8 Measurement values CMC
9
Glass transition temperature Tg / K
10 500 Fit Fox equation

11
12 Cellulose Szczesniak et al.
13
14 400 Cellulose Hancock & Zografi
15
16 Pure water Hancock & Zografi
17
18
300
19
20
21 200
22
23
24
25 100
26 Water-CMC
27
28
29
0
30 0 0.2 0.4 0.6 0.8 1
31 Mass fraction xW / -
32
33
Figure 6. Glass transition temperature of CMC loaded with water as a function of the water
34
35
36 content. Measurement values are compared to the model by Fox 37 and values from the literature
37
38 from cellulose. 46,47
39
40
41 In Figure 6, the measured data for CMC is in decent accordance to the used fit parameters and the
42
43 model by Fox. 37 The glass transition temperature from the fit therefore seems to be in a reasonable
44
45
range.
46
47
48 With DSC measurements, also the heat capacity can be determined. The difference in heat capacity
49
50 at the step of glass transition turned out to be in the range of Δcp = 200 J/(kg K), which is lower
51
52 but in the same order of magnitude as the fit parameter from Table 4. A reduction of the fit
53
54
55
parameter, however, results in a flattening of the isotherms at low activities.
56
57
58
59
60
19
1
2
3
4
5
6 In conclusion, modelling the primary sorption and desorption isotherm of the phase equilibrium
7
8
of water in CMC is reduced to only two unknown fit parameters χi,j and TD.
9
10
11 In the production process of electrodes for Li-ion batteries, it is particularly important for the
12
13 description of the phase equilibrium to also be able to describe secondary desorption isotherms.
14
15 Thus, the moisture content during varying conditions in the production process can be reproduced.
16
17
In Figure 7, measurement values of scanning hysteresis loops at T = 30 °C are compared to the
18
19
20 model description from equation (10).
21
22
23 0.5
24 Desorption 1
25
26 Desorption 2
Mass loading XW / gW gCMC-1
27 0.4
28 Desorption 3
29
Desorption 4
30
31 0.3 Sorption
32
33 Desorption
34
35
Dry mass
0.2
36
37
38
39
0.1
40
41
42 Water-CMC, 30 °C
43
44 0
45 0 0.2 0.4 0.6 0.8
47
48 Figure 7. Hysteresis scanning loops of the sorption of water in a layer of CMC at T = 30 °C.
49
50
51 Measurement values were recorded using method 1 (diamonds) and 2 (circles) and are compared
52
53 to the model from equation (10). Also, the measurement value is marked, which was recorded after
54
55 the desorption at T = 30 °C and the dew point of the dry gas flow.
56
57
58
59
60
20
1
2
3
4
5
6 Figure 7 shows that the measurement values approach the primary desorption isotherm at lower
7
8 activities. There is a decent accordance of the scanning hysteresis loops to their model description.
9
10
11 Furthermore, the measurement value is marked, which was recorded after the desorption at
12
13 T = 30 °C and the dewpoint of the dry gas flow. With thick layers of CMC, the decrease in mass
14
15 at particularly low dew points becomes extremely slow. At low temperatures, thick layers have
16
17 not reached their equilibrium after days. If the material system shows an open hysteresis cannot
18
19
20
be answered conclusively from this measurement. The low dew point of the dry gas stream, which
21
22 is below the measurement range of the chilled mirror hygrometer, as well as kinetic effects can
23
24 affect deviations of the measurement and the exact equilibrium value.
25
26 The other binder, SBR, shows a more pronounced glass transition in DSC measurements. The
27
28
29
experiments covered a range of activity from almost zero to aW = 0.32. However, the glass
30
31 transition temperature of dry and moisture loaded SBR was in all experiments below room
32
33 temperature, suggesting that no hysteresis would appear according to the model by Vrentas and
34
35 Vrentas assuming an absorption of water in a film of SBR. The data of the measurement is
36
37
displayed in Figure 8.
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
21
1
2
3
4
5
6
7
300
8
Water - SBR
9
Glass transition temperature Tg / K
10 250
11
12
13
14
200
15
16
17 150
18
19 Measurement values
20
21
100
Fit Fox equation
22
23
Yoshio et al.
24 50
25
26 Pure water Hancock & Zografi
27
28
0
29 0.0 0.2 0.4 0.6 0.8 1.0
30 Mass fraction xW / -
31
32
33
Figure 8. Glass transition temperature of SBR loaded with water measured with DSC as a function
34
35 of the water content. Measurement values are compared to a fit of the equation by Fox 37 as well
36
37 as a value from the literature with a similar SBR. 48
38
39
40 In agreement with these considerations and the DSC measurements, a hysteresis in the phase
41
42 equilibrium of water in films made of a SBR dispersion, which is displayed in Figure 9, could not
43
44
45
be detected between T = 30 °C and T = 90 °C. However, there are indications that adsorption also
46
47 plays a role in addition to absorption.
48
49 Although microscope images of the films suggest a complete film formation of the particles and
50
51 therefore a volume uptake by the film, the surface area determined from the phase equilibrium
52
53
54
according to equation (2) results in a value of around ABET = 30 m2/g which is quite similar to a
55
56 value obtained assuming a close packing of SBR particles. Even though an absorption particularly
57
58
59
60
22
1
2
3
4
5
6 at a higher range of water activity is probable, it is presumed that the adsorption of water on and
7
8 in between the SBR particles predominates for the range of low water activity. In this range, which
9
10
11 is especially important for the post-drying process, measurement values, as shown in Figure 9, can
12
13 be described by a fit from equation (3). The required density of SBR for the calculation of the
14
15 surface area of a close packing was taken as aE b = 1040 "/_e from manufacturer information,
16
17 which agrees with values from the literature. 49 The diameter of the SBR particles is in the range
18
19
20 of dSBR = 150 nm.
21
22
23 0.06
24
25 Sorption 30 °C
26 Desorption 30 °C
0.05
Mass loading XW / gW gSBR-1
27
28 Sorption 60 °C
29
0.04
31
32 Sorption 90 °C
33
Desorption 90 °C
34 0.03
35 Fit sorption eq. 3
36
37
38 0.02
39
40
41
42 0.01
43 Water-SBR
44
45
0.00
46
47
0.0 0.2 0.4 0.6 0.8
49
50
51 Figure 9. Phase equilibrium of the sorption of water in a film made of SBR particles. Measurement
52
53 values at three different temperatures measured with two different setups, method 1 (diamonds)
54
55 and 2 (circles), are compared to the fit from equation (3).
56
57
58
59
60
23
1
2
3
4
5
6 As it has already been pointed out, Figure 9 shows the absence of a hysteresis in the phase
7
8 equilibrium with water in the considered temperature and concentration range. Deviations between
9
10
11 sorption and desorption are rather attributable to measurement inaccuracies. The fit parameters
12
13 according to equation (3) are given in Table 5. A fit from Flory-Huggins, displayed in equation
14
15 (6), would be particularly suitable to fit the range of high activity.
16
17 Table 5. Fit parameters for the sorption equilibrium of water in SBR according to equation (3).
18
19
20
E / J mol-1 Xm / kg kg-1 n/- Q / J mol-1
21
22
Sorption 5241 0.00725 9 11045
23
24
25
26
27
Just as the binder CMC, the anode shows a temperature-dependent sorption equilibrium. It also
28
29 has a hysteresis, which is additionally temperature-dependent. This is depicted in Figure 10.
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
24
1
2
3
4
5
6
7 15000
8
9
Sorption 30 °C
10
Desorption 30 °C
11 12000
12
Sorption 60 °C
13
15 9000
16 Sorption 90 °C
17
19
6000
20
21
22
23
24 3000
25
26 Water-anode variation 1
27
28 0
29 0.0 0.2 0.4 0.6 0.8
31
32
33
Figure 10. Hysteresis behavior of water sorption in an anode at three different temperatures. The
34
35 sorption equilibrium and the hysteresis are temperature-dependent. Measurement values were
36
37 recorded using method 2.
38
39
40 The width of the hysteresis decreases with increasing temperature. The phase equilibrium shows
41
42 a distinct similarity to the equilibrium of its binder CMC. The comparison of the equilibrium of
43
44
45
the anode to the found models of the sorption equilibria of its materials is therefore a logical step.
46
47 In Figure 11, the measurement values at T = 60 °C from Figure 10 are compared to the mass
48
49 weighted addition of the equilibria of the materials of the anode. The equilibrium of the binder
50
51 CMC is described by the parameters from Table 4, the equilibria of the particles with parameters
52
53
54
from Table 2 and Table 3 and the equilibrium with SBR from Table 5. The advantage of
55
56
57
58
59
60
25
1
2
3
4
5
6 superimposing the equilibria of the materials to describe the equilibrium of the electrode takes
7
8 effect as soon as changes in the material composition of the electrodes are carried out.
9
10
11
12
13 Sorption
14
15 Desorption
16 12000
Sorption
17
18 Desorption
19
20
21 8000
22
23
24
25
26
27 4000
28
29
30
31 Water-anode variation 1, 60 °C
32 0
33
0 0.2 0.4 0.6 0.8
34
36
37 Figure 11. Hysteresis behavior of the sorption of water in an anode at 60 °C. Measurement data
38
39 are compared to the addition of its materials. CMC is described by the model by Vrentas and
40
41
42
Vrentas with fit parameters from Table 4, the data of the equilibria of the particles are taken from
43
44 Table 2 and Table 3 and the equilibrium with SBR from Table 5.
45
46
47 Figure 11 shows a decent accordance between the measurement values and the addition of the
48
49 equilibria of the materials. Yet, the model description of the desorption from Figure 11 only
50
51 represents a primary desorption isotherm. Scanning isotherm loops are particularly important when
52
53
54
describing the moisture desorption in the post-drying process of electrodes for lithium-ion batteries
55
56 and the moisture loading in the entire electrode production chain.
57
58
59
60
26
1
2
3
4
5
6 When scanning the hysteresis loops, it becomes visible that individual desorption branches
7
8 approach the primary desorption curve. More information is provided in the supporting
9
10
11 information in Figure S12. Curves of mass loading of moisture in the electrode production also
12
13 run on hysteresis loops of the phase equilibrium after coating and drying.
14
15 The applicability of this model is not confined to this specific anode. An anode with a different
16
17 binder content has also been investigated. A secondary desorption isotherm as well as the
18
19
20
corresponding model is also displayed in the supporting information in Figure S13.
21
22
23
24 CONCLUSION
25
26
The sorption equilibrium of water in a graphite anode of a Li-ion battery has been investigated. It
27
28
29 shows a hysteresis, which is caused by different mechanisms. While capillary condensation is
30
31 assumed to cause the hysteresis in the particles graphite and carbon black, exceeding the glass
32
33 transition temperature is suspected to cause the hysteresis in the sorption equilibrium with the
34
35
binder Na-CMC.
36
37
38 The relevance of this hysteresis in the sorption equilibrium for the residual moisture content in the
39
40 production process of electrodes for Li-ion batteries is pointed out. In order to achieve a low
41
42 residual moisture content, the hysteresis needs to be overcome. Since especially the binder Na-
43
44 CMC shows a low pressure hysteresis, low activities need to be attained in the post-drying process.
45
46
47 It was discovered that the experimental data of the hysteresis loops approach a curve that can be
48
49 described from the equilibria of the materials of the anode for a wide range of water activity and
50
51 temperature. Individual hysteresis loops are modelled based on data from the sorption and
52
53 desorption isotherm. This approach to describe the desorption isotherm is required in order to
54
55
56
model the post-drying process of electrodes for Li-Ion batteries and their moisture loading in the
57
58
59
60
27
1
2
3
4
5
6 electrode production chain. With the help of these models, it is possible to determine the
7
8 equilibrium moisture loading, which is going to adjust in the electrodes, as long as the electrodes
9
10
11 are given enough time or the diffusion of water in the anode is rapid enough.
12
13
14
15
16
17
18
19
20
21
22 AUTHOR INFORMATION
23
24
25 Corresponding Author
26
27 * JOCHEN C. ESER
28 Institute for Thermal Process Engineering
29 Karlsruhe Institute of Technology
30
Kaiserstraße 12, 76131 Karlsruhe, Germany
31
32 E-mail: jochen.eser@kit.edu
33
34
35
36 Author Contributions
37
38
The manuscript was written through contributions of all authors. All authors have given approval
39
40
41 to the final version of the manuscript. ‡These authors contributed equally.
42
43
44 Funding Sources
45
46 The authors thank the BMBF for the financial support within the ProZell Cluster-Project Roll-It
47
48
49 (03XP0080A).
50
51
52
53 ACKNOWLEDGMENT
54
55 The authors thank Andreas Roth, Gerrit Schöne and Sabrina Herberger from KIT-TVT for
56 support in experiments.
57
58
59
60
28
1
2
3
4
5
6 ABBREVIATIONS
7
8 CMC, Carboxymethyl cellulose, DSC, Differential scanning calorimetry, IUPAC, international
9
10 union of pure and applied chemistry, SBR, styrene butadiene rubber
11
12
13
14 References
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51 (34) Salmén, L.; Larsson, P. A. On the origin of sorption hysteresis in cellulosic materials.
52 Carbohydrate polymers 2018, 182, 15–20.
53 (35) Engelund, E. T.; Thygesen, L. G.; Svensson, S.; Hill, C. A. S. A critical discussion of the
54 physics of wood–water interactions. Wood Sci Technol 2013, 47, 141–161.
55 (36) Vrentas, J. S.; Vrentas, C. M. Hysteresis Effects for Sorption in Glassy Polymers.
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11 carboxymethyl cellulose, guar, locust bean, tragacanth and xanthan gums. Carbohydrate
12 polymers 2012, 89, 592–598.
13 (40) Landers, J.; Gor, G. Y.; Neimark, A. V. Density functional theory methods for
14 characterization of porous materials. Colloids and Surfaces A: Physicochemical and Engineering
15 Aspects 2013, 437, 3–32.
16 (41) Zhang, X.; Zillig, W.; Künzel, H. M.; Zhang, X.; Mitterer, C. Evaluation of moisture
17 sorption models and modified Mualem model for prediction of desorption isotherm for wood
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materials. Building and Environment 2015, 92, 387–395.
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21 Water Resour. Res. 1973, 9, 1324–1331.
22 (43) Mualem, Y. A conceptual model of hysteresis. Water Resour. Res. 1974, 10, 514–520.
23 (44) Hancock, B. C.; Zografi, G. The Use of Solution Theories for Predicting Water Vapor
24 Absorption by Amorphous Pharmaceutical Solids: A Test of the Flory–Huggins and Vrentas
25 Models. Pharmaceutical Research 1993, 10, 1262–1267.
26 (45) Schabel, W. Trocknung von Polymerfilmen. Ph. D. thesis, Karlsruhe Institute of
27 Technology, Karlsruhe, 2004.
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30 and the Water Content of Amorphous Pharmaceutical Solids. Pharmaceutical Research 1994,
31 11, 471–477.
32 (47) Szcześniak, L.; Rachocki, A.; Tritt-Goc, J. Glass transition temperature and thermal
33 decomposition of cellulose powder. Cellulose 2008, 15, 445–451.
34 (48) Yoshio, M.; Brodd, R. J.; Kozawa, A. Lithium-ion batteries: Science and technologies;
35 Springer: New York, NY, 2009.
36 (49) Bitsch, B.; Dittmann, J.; Schmitt, M.; Scharfer, P.; Schabel, W.; Willenbacher, N. A novel
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39 Journal of Power Sources 2014, 265, 81–90.
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32 Schematic representation of the post-drying process. The drying process starts at a high water activity
33 wherefore the activity is reduced and the layer is dried. Due to a decrease in the temperature after the
34 drying process, the electrode starts to resorb.
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Hysteresis behavior of the sorption of water on graphite particles at T = 30 °C measured by three different
33 experimental setups. Measurement values were fitted by using equation (3) for the adsorption and equation
34 (5) for the desorption. Values of the adsorption isotherm are taken from a former publication. 3
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17 Possible model concept of the water adsorption on the graphite particles. The particles exhibit a plate-like
18 structure that causes slit-like pores in which the water adsorbs.
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32 Hysteresis behavior of the sorption of water on carbon black particles at T = 30 °C measured with three
33 different setups. Measurement values were fitted by using equation (3) for the adsorption and equation (5)
34 for the desorption. Values of the adsorption isotherm are taken from a former publication. 3
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32 Hysteresis of water sorption in a layer of CMC at different temperatures and compared to the desorption
33 model of equation (6). Measurement values were recorded using method 2.
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33 Glass transition temperature of CMC loaded with water as a function of the water content. Measurement
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32 Hysteresis scanning loops of the sorption of water in a layer of CMC at T = 30 °C. Measurement values were
33 recorded using method 1 (diamonds) and 2 (circles) and are compared to the model from equation (10).
34 Also, the measurement value is marked, which was recorded after the desorption at T = 30 °C and the dew
point of the dry gas flow.
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32 Glass transition temperature of SBR loaded with water measured with DSC as a function of the water
33 content. Measurement values are compared to a fit of the equation by Fox 37 as well as a value from the
34 literature with a similar SBR. 48
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Phase equilibrium of the sorption of water in a film made of SBR particles. Measurement values at three
33 different temperatures measured with two different setups, method 1 (diamonds) and 2 (circles), are
34 compared to the fit from equation (3).
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36 150x120mm (150 x 150 DPI)
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32 Hysteresis behavior of water sorption in an anode at three different temperatures. The sorption equilibrium
33 and the hysteresis are temperature-dependent. Measurement values were recorded using method 2.
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32 Hysteresis behavior of the sorption of water in an anode at 60 °C. Measurement data are compared to the
33 addition of its materials. CMC is described by the model by Vrentas and Vrentas with fit parameters from
34 Table 4, the data of the equilibria of the particles are taken from Table 2 and Table 3 and the equilibrium
with SBR from Table 5.
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Hysteresis Behavior in The Sorption Equilibrium of Water in Anodes For Li-Ion Batteries

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Hysteresis Behavior in The Sorption Equilibrium of Water in Anodes For Li-Ion Batteries

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is published by the American Chemical Society. 1155 Sixteenth Street N.W.,

show that !; = 2 is in good agreement with experimental results.

Method 3 Adsorption [3]

10 500 Fit Fox equation

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