science technique

Effect of polymer membrane production method on

properties of gel electrolytes for lithium-ion batteries
Monika Osiska-Broniarz*, Agnieszka Martya, Boena Rydzyska, Maciej Kopczyk
Institute of Non-Ferrous Metals, Branch in Poznan, Central Laboratory of Batteries and Cells,
Poznan, Poland
Please cite as: CHEMIK 2014, 68, 5, 459467

Introduction
For several years now, lithium-ion batteries have been used as
a main power supply source for electronic consumer products. The
advantages of lithium-ion batteries include high cyclic lifetime and no
memory effect, which allows relatively long-term use of such power
supply sources without need to replace them. Typical secondary
lithium-ion cells supply almost all mobile electric devices, from mobile
phones, through laptops and tablets, to toothbrushes [1, 2].
Liquid electrolytes, used commonly in lithium-ion batteries,
provide relatively high ion conductivity, however, their volatile
fumes may lead to the violent explosion of a battery.
For many years, numerous scientific studies have been
conducted regarding finding a suitable solid electrolyte that would
allow complete elimination of liquid phase from lithium-ion cell.
Previous results of research on polymer electrolytes have not yet
led to their practical application [36].
Gel polymer electrolytes as a combination of liquid and polymer
electrolytes seem to be an alternative. The polymer membrane
is activated by soaking in a liquid electrolyte, which involves the
introduction of lithium ions to specially prepared porous membrane
capable of retaining liquid phase in numerous single pores [7].
Activated polymer membrane exhibit qualities of stable gel,
combining properties of liquid and solid electrolytes [8].
Research conducted worldwide is aimed more and more often
to search for new manufacturing technologies and novel materials,
both polymer and inorganic ones, which could be used as fillers
that could improve transport properties of lithium ions. Many gel
polymer electrolytes have higher and higher conductivity, almost
equal to the conductivity of liquid electrolytes this is especially
true for composite gel polymer electrolytes [912].
There are no papers in the literature that would allow direct
comparison of the methods used for production of gel polymer
electrolytes with application of specific polymers, commonly used for
that purpose, prepared at the same time under similar conditions.
Gel polymer electrolytes have been produced all over the world
for many years. The most well-known, and widely described in
scientific publications, method used for their production is twostep method, so called Bellcore process. This method is, of course,
a proper one, but due to the use of harmful reagents (i.a. dibutyl
phthalate, diethyl ether), it is dangerous to both human health and
the natural environment. There are also many other techniques for
polymer membrane production that allow the elimination of harmful
reagents. However, they do not always allow the maintenance of the
physical, chemical and electrochemical parameters of membranes
prepared using the two-step method [5, 13].
This paper presents results of research on gel polymer electrolytes
for ion-lithium cells produced using various methods. The polymer
membranes for gel polymer electrolytes were produced using
four different methods over the course of conducted research.
Corresponding author:
Monika Osiska-Broniarz, Ph.D., (Eng.), e-mail: monika.osinska@claio.poznan.pl

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The criterion for selection of polymer membrane production

technology as a part of conducted studies was the reduction of
membrane preparation time and the possibility of elimination of
solvents harmful to human health and the natural environment used
in the manufacturing process.
Conducted research was aimed to compare parameters of PVdF/
HFP polymer membranes and determination of the most optimal,
ecological manufacturing method that would allow application of
such gel polymer electrolytes in high-energy, safe lithium-ion cells.
Experimental part
Polymer membrane preparation
Polymer membranes for gel polymer electrolytes were prepared
using four production methods, significantly different from one
another. In the course of conducted research polyvinylidene fluoride/
hexafluoropropylene copolymer (PVdF/HFP, Kynarflex 2751,
Atofina) was used it was an only component of each produced
polymer matrix.
The first prepared polymer membrane was produced using the
most prevalent method in the scientific literature, i.e. two-step
method involving modification of two-step Bellcore process [5, 14,
15]. In the course of conducted studies, the PVdF/HFP copolymer
was dissolved in acetone (Chempur, analytical grade). Subsequently,
butyl phthalate (DBP, pure, Merck-Schuchardt) was added as
a plasticiser to the system. Such prepared mixture was stirred for
several hours. Then, the solution was poured onto a flat surface
and left there for the solvent to slowly evaporate. The subsequent
step involved the extraction of the plasticised polymer membrane
in diethyl ether (Chempur, analytical grade) in order to wash off
dibutyl phthalate from the membrane and generate micropores in
the membrane. The ready membrane was dried in a vacuum at
60C for 24 hours.
The next method used for membrane production was inversephase process [13, 16, 17]. Two, different solvent systems were
used. In the first system, the copolymer was dissolved using a mixture
of two solvents, significantly different from each other in terms of
evaporation temperature, i.e. the mixture of N-Methylpyrrolidone
(NMP, pure, Merck-Schuchardt) and acetone (C3H6O, analytical
grade, Chempur). The other system, used for production of polymer
membranes by means of inverse-phase method, was a mixture
of solvents, of which only one was a solvent of PVdF/HFP. The
studies involved use of mixture of solvents: dimethyl formaldehyde
(DMF, analytical grade, Chempur) and glycerol (C3H8O3, analytical
grade, POCH-Gliwice). The systems described above with use
of two different solvent systems were stirred for several hours
until homogeneous mixtures were obtained. Such mixtures were
then poured onto a smooth surface and then slowly dried utilizing
the evaporation temperature differences of individual solvents,
which allowed the formation of pores in the structure of polymer
membrane. Polymer membranes were dried until their weight was
constant at 60C and 120C, respectively.

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Table 1
List of components and methods used in polymer membrane
production that were used during execution of current works
Acronym

Polymer membrane
composition

Production method of polymer

memebrane

BEL

100% PVdF/HFP

modified two-step method (Bellcore)

GL

100% PVdF/HFP

method using mixture of solvents: DMF

and glycerol

NA

100% PVdF/HFP

method using mixture of solvents: NMP

and acetone

PW

100% PVdF/HFP

method using steam

Physical and chemical characterization of polymer membranes

FT-IR spectra measured using molecular absorption spectroscopy
were used to confirm the removal of solvents used in the course of
the membrane production. Measurements were performed using
Bruker Equinox 55 infra-red spectrometer.
The research also included X-ray diffraction analysis of individual
polymer membranes using Philips PW1050 powder diffractometer.
Obtained diffractograms allowed the determination of membrane
composition and degree of crystallinity of polymer membranes
produced by different methods. The degree of crystallinity specifying
qualitative content of crystalline phase in tested membrane was
determined based on the mathematical dependence between area
of material crystalline phase and total area under the diffraction
curve, which includes crystalline and amorphous phase of the
studied membrane. The degree of crystallinity was determined
based on following mathematical dependence.

Electrochemical characterization of gel polymer electrolytes

In order to activate polymer membranes, membrane samples in
the form of discs of known diameter and thickness were immersed
in electrolyte LP30, which is 1M lithium salt solution, lithium
hexafluorophosphate (LiPF6, 99.99%, Aldrich) in a 1:1 mixture
of diethyl carbonate (EC 99%, Aldrich) and dimethyl carbonate
(DMC 99%, Sigma-Aldrich). The time of polymer membrane
activation excited was 1 hour.
Determination of the specific conductivity for gel polymer
electrolytes was carried out using electrochemical impedance
spectroscopy (EIS) in a wide temperature range. The measurement
system involved two-electrode Swagelok-type cells, in which
between two steel electrode gel polymer electrolyte of known
diameter and thickness were placed. The values of specific
conductance of gel electrolytes were determined from Nyquist
plot and the mathematical dependence between resistance value
and electrolyte geometry, =l/R*A, where l is a electrolyte
thickness, cm; A- electrolyte surface area, cm2; R- electrolyte
resistance determined from the Nyquist plot.
The measurements involved the use of PARSTAT 2263
measurement device and Votsch climatic chamber that allows control
over measurement temperature with an error up to 0.2C.
The measurement of anodic stability was carried out using
cyclic voltamperometry in measurement cell Li/gel electrolyte/
Pt, where metal lithium was used as a reference electrode and
counter electrode, while platinum electrode was used as a working
electrode. The measurements were carried out from the rest
potential to 6 V at 25C using PARSTAT 2263 measurement device
with necessary software.
Results and Discussion
Figure 1 presents FT-IR spectra for polymer membranes
prepared with four, significantly differing from each other, production
techniques. The measured spectra of individual membranes confirm
complete removal from their structure of solvents and chemical
compounds used in the production process. The correct course
of polymer membrane production process has been also confirmed
by X-ray diffraction analysis.

area of crystalline phase

degree of crystallinity = *100%

area of crystalline phase+area of amorphous phase

Furthermore, membranes were subjected to the analysis of

topographic structure using Scanning Electron Microscopy (SEM)
that allows identification of the morphological structure and
determination of mean size of pores formed during the production
of polymer membranes. Measurements were carried out using
ZEISS EVO40 measurement apparatus.
The quantity of adsorbed solvent that can be retained inside
the structure of the polymer membrane was determined based on
the measurement of weight change of the membrane soaked in
the liquid medium as a function of time. For tests, a fragment of
each of produced membranes of known weight was used prior
to tests it was additionally dried at 60C for 24 hours. The amount of
absorbed liquid phase was determined using following mathematical
dependence:
m m

t
0
membrane weight increase =
*100%

m0

m0- dry membrane weight; mt- membrane weight after the specified time

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Fig. 1. FT-IR spectra of polymer membranes

Figure 2 presents diffractograms of produced membranes.

Polymer membrane (BEL), which was produced using one of
the most widely spread membrane production methods, has
diffractogram containing reflexes for 2 angles at approximately
27 and approximately 39 corresponding to the structure of
PVdF-HFP (data card PDF4+ 000421650). The application of
membrane production method from PVdF/HFP copolymer using
individual solvents causes changes in the intensities of reflexes or
even their elimination occurring for 2 angles at approximately 27
and approximately 39. Furthermore, the degree of crystallinity
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The other method of gel electrolyte production, used in the

course of conducted research, included dissolving of PVdF/HFP
copolymer in acetone (C3H6O, analytical grade, Chempur). The
homogeneous mixture was poured onto glass plate, which was
then placed in the vessel filled with steam. The entire system was
heated up to approximately 120C for 6 hours, in order to interfere
with the evaporation process and form a porous membrane
structure [5, 13].
All polymer membranes that were prepared using
aforementioned methods (Tab. 1) were dried at 60C for 24 hours
prior to scientific measurements. All polymer membranes and all
gel polymer electrolytes were characterized in detail in terms of
physicochemical and electrochemical properties.

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has been also determined (see Tab. 2) its values are very similar
to each other. It proves that there is no direct effect of used
polymer membrane preparation technique on the value of degree
of crystallinity.

Fig. 2. X-ray diffractograms for polymer membranes produced using

different methods

Moreover, an analysis of liquid phase absorption kinetics on

polymer membranes was carried out (Fig. 4). Based on the weight
changes of membrane immersed in liquid solvent of density similar
to the density of liquid electrolyte, the absorption properties of
dry composite membranes have been evaluated. The amount of
electrolyte that can be absorbed by polymer membrane is a very
important parameter characterizing gel polymer electrolytes.
This is the amount of absorbed electrolyte by membrane, and
the actual amount of lithium ions contained there, determines ion
transport in the cell, which has a direct effect on the parameters
of the entire lithium-ion cell. It has been observed that the largest
absorption capacity of liquid phase is exhibited by polymer
membrane produced using glycerol-GL (approximately 400%) and
the second is membrane produced using two-step procedure BEL
(approximately 230%). The lowest liquid phase absorption capacity
is exhibited by membranes produced using NMP and steam NA,
PW (approximately 50%). The maximum saturation of pores of
tested membranes occurs after approximately 0.51 hour from the
start of the activation process.

Table 2
Degree of crystallinity for polymer membranes produced using
different methods.
Polymer membrane acronym

Degree of crystallinity

PW

12.11

NA

11.01

GL

11

BEL

10

Images of topographic surface of polymer membranes produced

using various methods, obtained by means of scanning electron
microscopy (SEM) are shown in Figure 3. The membrane produced
using modified Bellcore method BEL (Fig. 3a) has a porous structure,
in which the diameter of individual micropores is below 2m. The
membrane produced using glycerol (Fig. 3b) has high porosity
and the diameter of individual pores is in range of approximately
1015 m. Polymer membranes produced using NMP or steam
(Fig. 3c and 3d, respectively) show a very homogeneous structure.
No micropores were observed in these structures.

Fig. 4. Measurements of absorption capacity of dry polymer

membranes immersed in propylene carbonate (PC)

The next stage of research which was carried out involved the
determination of temperature dependence of specific conductance
of gel polymer electrolytes (Fig. 5 and 6). It was found that the
highest values of specific conductance in the studied temperature
range are shown by gel polymer electrolyte with polymer membrane
produced using glycerol (GL), which at 25C has conductivity of value
equal to 0.51*103S/cm. For gel electrolytes, containing polymer
membrane produced using one of the most popular methods
modified Bellcore method (BEL), the specific conductance of this
electrolyte is 5 times lower than for electrolyte with GL membrane
it equates to =0,12*103S/cm at 25C. Gel electrolytes with
NA and PW polymer membranes at 25C have very low specific
conductance, 0.84*106 S/cm and 0.69*105 S/cm, respectively.

Fig. 3. Surface images of polymer membrane cross-sections

taken using

SEM for membranes obtained using following methods:

a) Bellcore process; b) using mixture of solvents: DMF and glycerol;
c) using mixture of solvents: NMP and acetone; d) using steam
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Fig. 5. Arrhenius curves determined for individual polymer electrolytes

as a function of temperature. Temperature range: 1080C

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Fig. 6. Specific conductance values for investigated polymer

electrolytes at 25C

Linear voltamperometry curves of gel polymer electrolytes

with polymer membranes produced using different techniques
are presented in Figure 7. One can observe significant difference
in values of oxidation current and in the range of decomposition
voltage for the investigated systems. Definitely, the most stable gel
electrolyte is electrolyte produced using activation of GL membrane
and the second is gel electrolyte with BEL polymer membrane. Gel
polymer electrolytes with NA and PW membranes have significantly
lower decomposition voltage range and higher values of oxidation
current in comparison to the electrolytes produced by activation of
GL and BEL membranes.

Fig. 7. Plots of anodic stability of gel polymer electrolytes. Potential

measurement range: from resting potential to 6V, scan rate 10mV/s

Summary
The carried out studies led to the observation of the effect of
the polymer membrane production method on the properties of gel
polymer electrolytes based on PVdF/HFP copolymer. The inversephase method for polymer membrane production using a mixture
of solvents: DMF and glycerol allows production of the most porous
structure of polymer membrane and at the same time obtaining
highest liquid phase capacity, i.e. 400% in relation to dry membrane
weight. Gel polymer electrolytes with GL membrane have also
higher specific conductance in the investigated temperature range
in relation to other studied gel polymer electrolytes. It is also
worth noting that the production of polymer membranes using
the inverse-phase method in DMF-glycerol solvent system, after
activation in liquid electrolyte, allows an increase in ion transport
capability. Application of such solvent system also allows reduction
of the amount of harmful solvents used in production and shortening
of the duration of the production process.
This work has been carried out under research activities no. DS 3787/E
138/ S /2013 funded by the Ministry of Science and Higher Education.

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*Monika Osiska-Broniarz, Ph.D., Eng. is a graduate of the Faculty
of Chemical Technology, Poznan University of Technology. She has obtained
a degree of the doctor of chemical sciences in 2006. Currently, she works as
a researcher in the Institute of Non-Ferrous Metals, Branch in Poznan, Central
Laboratory of Batteries and Cells. She constantly broadens her knowledge in the
field of novel materials and technological solutions that can be applied in lithiumion or lithium-air batteries and fuel cells.
e-mail: monika.osinska@claio.poznan.pl, phone: +48 61 2797 803

Agnieszka Martya, Ph.D. has received a degree of the doctor of chemical

sciences in 2004 from the Faculty of Chemistry, Adam Mickiewicz University in
Poznan. Currently she serves as the Head of the Structure Laboratory at the
Advanced Materials Department of the Institute of Non-Ferrous Metals, Branch
in Poznan, Central Laboratory of Batteries and Cells. She focuses her scientific
interest on: catalytic materials, fuel cells and photovoltaics

Boena Rydzyska, Ph.D. Eng. has graduated from the Faculty of Chemical
Technology, Poznan University of Technology in the field of Inorganic Chemical
Technology (1997). She works as a researcher at the Laboratory of Reserve
Batteries of the Institute of Non-Ferrous Metals, Branch in Poznan. Specialty
chemical power sources.

Maciej Kopczyk, Ph.D., Eng., Assoc. Prof. of the IMN is a graduate of

the Faculty of Chemical Technology, Poznan University of Technology. For
many years he has been serving as the Director of the Institute of Non-Ferrous
Metals, Central Laboratory of Batteries and Cells. Scientific interests: chemical
technology, electrochemistry and chemical power sources.

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Conductivity values of individual gel polymer electrolytes are

very well correlated with liquid phase absorption capacity of polymer
membranes used for their production. The higher the amount of
absorbed liquid electrolyte by given polymer membrane, the higher
the value of specific conductance of gel polymer electrolyte.