Beruflich Dokumente
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Burak aglar
Wissenschaftliche Schriftenreihe
des Fraunhofer ICT
Band 61
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ISBN (Print): 978-3-8396-0794-7
D 90
Zugl.: Karlsruhe, Univ., Diss., 2014
Druck: Mediendienstleistungen des
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Dissertation
by
Burak alar
Supervisor:
Co-supervisor:
Date of Submission:
28.02.2014
Date of Examination:
16.05.2014
DECLARATION
I declare that this dissertation is the product of my own work and it has not been
submitted before for any degree or examination elsewhere. All the sources and
contributions to this work have been indicated or acknowledged particularly.
Burak alar
ACKNOWLEDGEMENT
ACKNOWLEDGEMENT
The time that was dedicated to this work was not only for scientific purpose. It was a
challenge to exist and to be successful far away from my country, family and friends. In this
period, I have received a considerable support from many people.
I would like to thank to Prof. Dr.-Ing. Peter Elsner for supervising my work. He was always
kind and his suggestions, corrections and contributions were valuable to finish my thesis. I
also would like to thank to Prof. Dr. rer. nat. Oliver Kraft for co-supervising my thesis and
giving me the chance to share my work with him. I am also grateful to chairman, Prof. Dr.Ing. Peter Gratzfeld for giving his time to the preparation and the organization of my exam.
I am greatly appreciated for endless help and patience of my mentor, Dr. rer. nat. Peter
Fischer. His meticulous attitude at work is a great example for my future career. I never
forget the support of Dr. Jens Tbke and Dr. Karsten Pinkwart who believed me and gave
me an opportunity to finish my thesis and to take responsibility in the activities of my
department.
Dr. Christof Hbner was a lighthouse in the ocean of my Ph.D. journey. He gave an
important support to shape my thesis and not to lose my goal. Irma Mikonsaari, Carolyn
Fischer, Shyam Sathyanarayana, Ganiu Olowojoba and Patrick Weiss were more than
colleagues to me. They were always ready to help me and their support made my thesis real.
Dr. Duygu Karabelli and Onur Cagri Temiz were my fellows and great personalities who
inspired me and made my life better. All my colleagues from applied electrochemistry and
polymer departments deserve great thanks for all their friendship and help.
Thanks to European Communitys Seventh Framework Program (FP7/2007-2013) under
grant agreement no. 238363, my work received a financial support.
CONTACT project
partners, Dr. Pertti Kauranen and Mikko Karttunen from VTT Research Centre, Finland,
Dipl.-Ing. Justin Richards from Wolfsburg and Dr. Thorsten Hickmann from Eisenhuth GmbH
played a crucial role for my scientific progress and I would like to give my deepest regards to
them.
Finally, my family and my friends in Turkey deserve a sincere thank because I always felt
their support and love deep in my heart.
-IV-
ABSTRACT
ABSTRACT
Redox flow batteries gained considerable attention in the last decades due to their high
energy efficiency, long operational-life and distinct power/energy output design. They were
initially used as storage systems for renewable energies, as back-up systems or as
uninterruptable power sources. All-vanadium type batteries use only vanadium species as
the electrolyte for redox reactions, preventing the cross-contamination related cell-failures.
Bipolar plates are one of the main components of redox flow batteries and require high
electrical conductivity, good mechanical stability and good corrosion resistance. However,
graphite blocks, carbon-carbon composites or metals are used as a bipolar plate material.
They have high-cost of production, low corrosion stability and require further treatments such
as corrosion protection coatings for metallic bipolar plates. Conductive composite bipolar
plates have been widely used and studied as alternative materials for fuel-cell applications,
but redox flow battery literature is very limited for these materials. This study aims to develop
thermoplastic-based bipolar plates via injection molding and to evaluate their potential to be
used in all-vanadium redox flow battery applications. Polypropylene (PP) and polyphenylene
sulfide (PPS) were chosen as matrix materials due to their chemical stability. Synthetic
graphite was used as primary conductive filler. To improve the electrical and mechanical
properties of bipolar plates, multi-wall carbon nanotubes (MWCNTs) were utilized with
different concentrations. To optimize filler dispersion and to promote the flow characteristics
of composites, titanate-based coupling agent and Montan wax were used for PPS- and PPbased composites respectively. The electrical, mechanical, rheological and electrochemical
properties of the produced bipolar plates were examined. Microscopic images were used to
visualize the dispersion of fillers in the polymer matrix. All-vanadium redox flow cell tests
were carried out in laboratory scale to study the behavior of bipolar plates in their real
working media. The substitution of graphite with the same amount of MWCNTs increased the
electrical conductivities in the through-plane (up to 20 S/cm for PPS) and in-plane directions
(up to 50 S/cm for PP) as well as improving the flexural strength values (over 100 MPa for
PPS). According to capillary rheometer results and the calculated specific energy input of
twin-screw extruders, both Montan wax and the coupling agent positively influenced the
processing of highly-filled composites by decreasing overall viscosities. Titanate-based
coupling agent also made a positive contribution to the electrical properties of PPS-based
bipolar plates. Cyclic voltammetry measurement and calculated diffusion coefficient and
heterogeneous rate constants showed that samples containing MWCNTs had faster reaction
kinetics for vanadium species. Bipolar plates with higher CNT fillings (3 wt. % for PP) and
titanate coupling agent (3 wt. % for PPS) exhibited lower hydrogen evolution potentials in
-V-
ABSTRACT
corrosion measurements but Montan wax addition seemed to be protective against acidic
corrosion. For the PP matrix: 77 wt. % graphite, 3 wt. % CNT and 1 wt. % wax; for the PPS
matrix: 70 wt. % graphite, 2.5 wt. % CNT and 3 wt. % coupling agent were found to be the
optimum filler concentrations for the investigated ranges. The produced bipolar plates were
compared with commercial plates in battery cell-tests and encouraging results (energy
efficiency of 80 % at 50 mA/cm2 for PP) were obtained for further implementation of the
developed bipolar plates in all-vanadium redox flow batteries.
-VI-
TABLE OF CONTENTS
TABLE OF CONTENTS
ACKNOWLEDGEMENT ......................................................................................................... IV
ABSTRACT ............................................................................................................................. V
LIST OF ABBREVIATIONS ..................................................................................................... X
LIST OF SYMBOLS .............................................................................................................. XII
LIST OF TABLES ................................................................................................................. XIV
LIST OF FIGURES ................................................................................................................ XV
1.
INTRODUCTION ........................................................................................................... 1
1.1.
Motivation ...................................................................................................................... 6
1.2.
Objectives ...................................................................................................................... 6
2.
BACKGROUND ............................................................................................................. 7
2.1.
2.2.
Polypropylene .......................................................................................................... 33
3.1.2.
3.1.3.
Graphite ................................................................................................................... 34
3.1.4.
3.1.5.
3.1.6.
Montan wax.............................................................................................................. 37
TABLE OF CONTENTS
3.2.1.
3.2.2.
3.3.2.
3.3.3.
3.3.4.
3.3.5.
3.3.6.
3.3.7.
Corrosion measurements......................................................................................... 51
3.3.8.
4.1.2.
4.1.3. Cyclic voltammograms and calculated diffusion coefficient and heterogeneous rate
constants ................................................................................................................................ 58
4.1.4.
4.2.1.
4.2.2.
4.2.3.
4.2.4.
4.2.5. Cyclic voltammograms and calculated diffusion coefficient and heterogeneous rate
constants ................................................................................................................................ 72
4.2.6.
TABLE OF CONTENTS
-IX-
LIST OF ABBREVIATIONS
LIST OF ABBREVIATIONS
ADL
BPP
Bipolar plate
CAES
CB
Carbon black
CCVD
CF
Carbon fiber
CNT
Carbon nanotubes
CV
Cyclic voltammetry
CVI
DSC
EESS
EMI
Electromagnetic interference
EPDM
Ethylene-propylene-diene monomer
EV
Electrical vehicles
FE-SEM
GDL
HEV
LCP
L/D
MWCNT
OCV
Open-circuit-voltage
PE
Polyethylene
PECVD
PEI
Polyetherimide
PF
PHEV
-X-
LIST OF ABBREVIATIONS
PHS
PI
Polyimide
POAMA
PP
Polypropylene
PPS
Polyphenylene sulfide
PS
Polystyrene
PSU
Polysulfone
PTFE
Polytetrafluoroethylene
PVC
Polyvinylchloride
PVDF
Polyvinylidene fluoride
RES
RFB
RHE
SEI
SOC
State of charge
SWCNT
VRFB
-XI-
LIST OF SYMBOLS
LIST OF SYMBOLS
Epa
V (volt)
ap
s-1
ap
Pa (pascal)
Applied force
N (newton)
Co
mol.cm-3
Epc
V (volt)
Chiral angle
Chiral vector
Xc
Crystallinity
Tc
Crystallization temperature
Concentration
mol.lt-1
Current
ampere
Deflection
mm
mm
Do
Diffusion coefficient
cm2.s-1
Pdischarge
mW.cm-2
Electrical conductivity
S/cm
Electrical resistivity
ohm.cm
Electrochemical energy
Joule
Faraday constant
C.mol-1
si
Flexural modulus
Pa (pascal)
Flexural-strain parameter
El
Formal potential
V (volt)
(degree)
-XII-
LIST OF SYMBOLS
Hcold
J/g
Hc
Heat of crystallization
J/g
Hm
Heat of fusion
J/g
cm.s-1
mm
Mmax
N.m
Tm
Melting temperature
ip
Peak current
ampere
Ep
Peak potential
V (volt)
Resistance
ohm
Scan rate
V/s
rpm
mm
V (volt)
cm2
Test pressure
Pa (pascal)
Temperature
kg/h
cm
Torque of extruder
Unit vector
J.mol-1.K-1
Voltage
V (volt)
mm3.s-1
wt. %
Weight percentage
mm
-XIII-
LIST OF TABLES
LIST OF TABLES
Table 1 Standard for polymeric composite bipolar plates, Department of Energy, USA ....... 17
Table 2 Comparison of aspect ratio and electrical conductivity of carbon-based conductive
fillers ....................................................................................................................................... 25
Table 3 Physical properties of polypropylene (Borflow HL508FB) ......................................... 33
Table 4 Physical properties of polyphenylene sulfide (Ryton V-1) ....................................... 33
Table 5 Physical properties of primary synthetic graphite (KS5-75TT) .................................. 34
Table 6 Physical properties of MWCNTs (NC7000) .............................................................. 35
Table 7 Properties of Ken-React KRTTS titanate coupling agent ....................................... 36
Table 8 Physical and chemical properties of Licowax OP Montan wax ................................. 37
Table 9 Production scheme of PP-based bipolar plates ........................................................ 38
Table 10 Twin-screw extruder process parameters for the production PP-based bipolar
plates ...................................................................................................................................... 40
Table 11 Injection molding process parameters for the production PP-based bipolar plates 41
Table 12 Production scheme of PPS-based bipolar plates .................................................... 41
Table 13 Specific energy input (SEI) and torque values of twin screw extruder for the
production of PPS-based composites .................................................................................... 43
Table 14 Cathodic and anodic peak potentials for V4+/V5+ side in cyclic voltammetry analysis
at 20 mV/s scan rate (PP-based bipolar plates) ..................................................................... 60
Table 15 Diffusion coefficients and heterogeneous rate constants of PP-based bipolar plates
for the redox reaction of V4+/V5+ (Calculated from data of cyclic voltammetry and equations
25 and 26) .............................................................................................................................. 60
Table 16 Differential scanning calorimetry (DSC) analysis results of produced PPS-based
composites ............................................................................................................................. 71
Table 17 Cathodic and anodic peak potentials for V4+/V5+ side in cyclic voltammetry analysis
at 20 mV/s scan rate (PPS-based bipolar plates) .................................................................. 73
Table 18 Diffusion coefficients and heterogeneous rate constants of PPS-based bipolar
plates for the redox reaction of V4+/V5+ (Calculated from data of cyclic voltammetry and
equations 25 and 26).............................................................................................................. 74
-XIV-
LIST OF FIGURES
LIST OF FIGURES
Figure 1 Classification of the energy storage technologies (discharge time vs. system power
rating) according to their applications....................................................................................... 2
Figure 2 Schematic drawing of all-vanadium redox flow battery ............................................. 7
Figure 3 Redox flow battery cell stack with 4 individual cells .................................................. 8
Figure 4 Redox flow battery test-cell components; a) Steel plate, b) Isolation plate, c) Flowthrough graphite electrode (bipolar plate), d) Flow frame, e) Graphite felt, f) Membrane, g)
Graphite electrode (bipolar plate), h) Steel plate.................................................................... 12
Figure 5 Graphite felt electrodes for the redox reactions of vanadium species ..................... 12
Figure 6 Demonstration of four oxidation states of vanadium element in H2SO4 solution.
From left to right: V5+, V4+, V3+ and V2+ ................................................................................... 13
Figure 7 FAP-0 Fuma-SEP membrane ................................................................................. 13
Figure 8 Bipolar plates (Schunk FU4369) and copper current collector ................................ 14
Figure 9 Flow frames made of polyvinylchloride (PVC) ......................................................... 15
Figure 10 End-plates (made of steel) .................................................................................... 15
Figure 11 (a) Unstructured and injection molded bipolar plates, (b) commercial bipolar plates
with self-made flow channel patterns ..................................................................................... 18
Figure 12 Samples of metallic bipolar plates. (Left: diamond-like carbon coated titanium,
chromium, tungsten and vanadium metallic bipolar plates. Right: stainless steel-based
metallic bipolar plates)............................................................................................................ 20
Figure 13 Graphical explanation of the percolation theory (Electrical conductivity of the
composite matrix vs. total conductive filler concentration). Composite starts to be electrically
conductive after concentration, C1 which is percolation threshold ......................................... 22
Figure 14 a) Hexagonal and b) rhombohedral structure of graphite ...................................... 23
Figure 15 Chirality of carbon nanotubes. The structure of carbon nanotubes is named as
armchair, zig-zag or chiral according to rolling-up direction (chiral vector) and angle (chiral
angle) ..................................................................................................................................... 24
-XV-
LIST OF FIGURES
-XVI-
LIST OF FIGURES
Figure 32 a) Capillary rheometer machine Gttfert, Rheograph 2002 and b) die samples with
different length and diameter.................................................................................................. 48
Figure 33 Three-electrode-setup with working and counter electrode of produced bipolar
plates and reference electrode of mercury/mercurous sulfate (Hg/Hg2SO4). Electrolyte is 1.6
M VOSO4 in 2 M H2SO4 / 0,05 M H3PO4................................................................................. 50
Figure 34 The self-prepared corrosion measurement setup with schematic explanation
(Fraunhofer ICT, Wolfsburg) .................................................................................................. 51
Figure 35 All-vanadium RFB Cell-Test Setup for galvanostatic charge-discharge analysis .. 52
Figure 36 Galvanostatic charge-discharge test output-graph (power vs. time) for the
calculation of energy efficiency and discharge power density ................................................ 53
Figure 37 Through-plane and in-plane electrical conductivity of PP-based bipolar plates with
different MWCNT and Montan wax concentrations ................................................................ 54
Figure 38 FE-SEM picture of cryo-fractured PP-4 sample (Magnification of 10000x) ........... 55
Figure 39 Flexural strength values of PP-based bipolar plates with different MWCNT and
Montan wax concentrations.................................................................................................... 56
Figure 40 Photo of bipolar plates after injection molding to visualize the effect of Montan wax
to the flow behavior of composites ......................................................................................... 57
Figure 41 Cyclic voltammetry results of PP-based bipolar plates at 20 mV/s scan rate (Effect
of MWCNT and Montan wax concentrations to the reversibility of vanadium redox reactions)
............................................................................................................................................... 58
Figure 42 Corrosion measurement of PP-based bipolar plates in 2M H2SO4 solution and at
scan rate of 5 mV/s (Effect of MWCNT and Montan wax concentrations to the chemical
stability of produced bipolar plates) ........................................................................................ 61
Figure 43 Energy efficiency values of PP-based PP-4 (a, b and c) and Schunk bipolar plates
vs. current density .................................................................................................................. 63
Figure 44 Discharge power density values of PP-based PP-4 (a, b and c) and Schunk
bipolar plates vs. current density ............................................................................................ 65
Figure 45 Through-plane and in-plane electrical conductivities of PP-based bipolar plates
with different MWCNT and titanate coupling agent concentrations ........................................ 66
Figure 46 FE-SEM picture of cryo-fractured PPS-6 sample (Magnification of 5000x) .......... 67
-XVII-
LIST OF FIGURES
Figure 47 Flexural strength and modulus values of PPS-based bipolar plates with different
MWCNT and titanate coupling agent concentrations ............................................................. 69
Figure 48 Capillary rheometer results of composite materials with different MWCNT and
titanate coupling agent concentrations ................................................................................... 70
Figure 49 Cyclic voltammetry results of PPS-based bipolar plates at 20 mV/s scan rate
(Effect of MWCNT and titanate coupling agent concentrations to the reversibility of vanadium
redox reactions)...................................................................................................................... 73
Figure 50 Corrosion measurement of PPS-based bipolar plates in 2M H2SO4 solution and at
scan rate of 5 mV/s (Effect of MWCNT and Montan wax concentrations to the chemical
stability of produced bipolar plates) ........................................................................................ 75
Figure 51 Energy efficiency values of PPS-based PPS-6 (a, b and c) and Schunk bipolar
plates vs. current density........................................................................................................ 76
Figure 52 Discharge power density values of PPS-based PPS-6 (a, b and c) and Schunk
bipolar plates v. s. current density .......................................................................................... 77
-XVIII-
INTRODUCTION
1.
INTRODUCTION
Energy has always been a crucial point in our life since primitives until the industrial world of
21st century. Especially, after the industrial revolution and due to increasing human
population, energy consumption and storage gained critical role. Limited sources of fossil
fuels, questionable safety of nuclear power plants, and negative contribution of those energy
sources to environment, global warming and fluctuations in energy prices due to economic
crisis directed us to reliable, economically and environmentally friendly energy options.
Renewable energy sources (RES) such as solar and wind energies were accepted as
promising green energy sources [1, 2]. However, fossil fuel based energy dominates the
worlds electricity generation, constructing solar panels or building on and off-shore wind
turbines fascinated many entrepreneurs,
governments. This green-attend was also statistically revealed and researches showed that
in 2012 installed solar photovoltaic and wind capacities in the world grew 41 % and 18.9 %
respectively [3]. The increasing dependence and investments to RES brought the questions
of stability and quality of electricity which is generated by these facilities. When the sun is
blocked by clouds or the wind does not blow, RES turn into unreliable and costly choice. At
this point, electrical energy storage systems (EESS) were thought to be a solution to convert
the electrical energy from power plants into form which can be used later when it is needed
[4]. EESS give a chance to regulate contingencies in power plants, to store electricity in offpeak times instead of high-demand period of a day, to stabilize power quality in the grid and
also provide fuels to the electrical or hybrid vehicles [5]. Through these storage systems,
both utilities and customers started to benefit from improved power stability and quality,
diminished losses in transmission lines, reduced costs and positive contributions to
environment by lower emissions [6]. There are several concerns for the installation of EESS
depending on their applications. The capital and life-cycle costs with safety regulations are
the most important ones but EESS also should have long calendar life (> 15 years) and
require minimum maintenance. EESS can be classified according to their way of electrical
energy storage. Capacitors and supercapacitors typically store electricity directly in electrical
charges, pumped hydro and compressed air energy storage techniques use potential energy
and flywheels deposit electricity in the form of kinetic energy. Probably electrochemical
storage units are the biggest group of EESS for both stationary and mobile applications. In
this case, electrical energy is stored in the form of electrochemical species and reversible
reactions make electricity conversion possible. This type of energy storage covers the first
examples of lead-acid batteries to high-temperature sodium-sulfur batteries or recently
developed redox flow batteries to widely known lithium-ion batteries and fuel cells [5]. In
-1-
INTRODUCTION
Figure 1, the electrical energy storage systems are shown depending on their discharge time
and power capacities. This categorization gives information about the application of these
systems. When high-power flywheels and supercapacitors are used in power quality
management or as uninterruptable power sources due to their fast-response times, systems
like pumped hydro or compressed air (CAES) are developed for bulk power management.
Batteries where stored energy is used in minutes to hours are reliable choices for loadleveling and peak-shaving applications as well as grid supports.
Figure 1 Classification of the energy storage technologies (discharge time vs. system power
rating) according to their applications. [7]
Pumped hydroelectric storage (PHS) is widely used large-scale EESS. However, large
volume of reservoir, long storage period, high efficiency and relatively low capital cost per
unit of energy; the high cost of construction, geographical obstacles (finding suitable largeareas) and environmental disadvantages (deforestation of the area) are main constraints
which limit the number of PHS in the world [4]. CAES uses off-peak electricity to deposit
compressed air in underground reservoirs and this air is used in combustion turbines to
generate electricity when the demand increases [8]. CAES are one of the biggest energy
storage units similar to PHS with a power rating of 50-300 MW, estimated efficiency of 70 %
and long-lifetime (approximately 40 years), but fossil fuel dependent electricity production
and similar geographical issue like PHS, make them less attractive [4]. Electrochemical
-2-
INTRODUCTION
INTRODUCTION
life (>10000 cycles) and longer lifetime (>15 years) are promising properties for large-scale
applications like; remote area power control units, uninterruptable power sources and load
leveling. RFBs employ different redox couples as energy source such as; iron/chromium,
bromine/polysulfide, vanadium/bromine or all-vanadium. Besides sharing similar advantages
with other RFB types, all-vanadium redox flow battery outshines because of eliminated
cross-contamination risk due to employed vanadium electrolyte in both half-cells [11, 12].
Composite materials were always part of renewable energy sources and energy storage
systems either by taking role in the production of devices or components of energy storage
mediums (i.e. wind turbine blades, electrode materials of batteries). Composites are made of
two or more components and the individual properties of these constituent materials are
used to achieve to the overall structural improvement. It is believed that composites were
always in our life and probably, straw-reinforced clay was the first example of it which was
used to protect clay from cracking, a long years before todays world of composites [13].
Changing of the human needs in historical perspective caused a transition from pure metals
to composites. A chosen continuous matrix such as; polymer, ceramic or metal was used as
a host for reinforcing materials. Polymers with low strength and stiffness, metals with high
ductility and ceramics with high strength and stiffness were combined with several
reinforcements to improve their mechanical, electrical and thermal properties. Those
reinforcing materials had spherical, fibrous, platelet or irregular geometries and as well as
their shape, the interaction with matrix material was a key point to achieve desired properties
[14]. Composite systems with improved fracture toughness, fatigue strength, thermal stability,
ductility and stiffness were started to be used for diverse applications. Especially lightweight
composites (polymer- carbon fiber) were found as a promising candidate for the substitution
of metallic automobile parts and for the production of aircraft components which makes the
weight reduction and fuel-saving possible [15]. By introduction of metals, their alloys
(aluminum, titanium, and nickel aluminide), ceramics (silicon carbide, silicon nitride) and
finally carbon fiber/carbon matrix materials, operating temperatures of composites were
extended over 2000 and those composites were started to be used in critical aerospace
applications [13]. In the second part of 20th century, the world of composites met with
nanomaterials, however their discovery or first examples go back to centuries ago, those
new materials dropped the scale from micro to the 10-9 of 1 meter. This transition brought
many changes in the properties of materials due to improved surface area and surface
characteristics of nanomaterials. The definition of nanomaterial was enhanced by the
discovery of nanotubes, nanofibers, fullerenes and nanowires. Due to their high aspect ratio
(the ratio of longest dimension to the shortest dimension), nanofibers and nanotubes were
-4-
INTRODUCTION
accepted as -theoretically- high reinforcement fillers [16]. Polymers which are mainly
insulators (except intrinsically conductive polymers) were started to be used as binders for
the production of carbon based composites. Mixing polymer matrix with conductive fillers
such as carbon black, carbon nanotubes, graphite, graphene, carbon fibers, metal particles
or intrinsically conductive polymers like polyaniline, polypyrole was accepted as alternative
way of material production for the mediums where it is problematic to use metals. This
approach brought ease of shaping, low density, corrosion resistance and wide range of
electrical conductivities compared to metallic conductors. The electrical resistivity of these
composites takes place between insulators (1015 .m) and metals (10-7 .m) which are
suitable for electromagnetic interference (EMI) shielding, electronic equipment or semiconductors for dissipation of static electricity [17]. Researchers in the field of fuel cells and
batteries took advantage of improved the electrical properties of CPCs to replace the
electrode materials of these systems which are made of metal, graphite or carbon/carbon
based composites. However, CPCs have lower stiffness compared to metals or less
electrical conductivity than pure graphite sheet; economically optimized production methods
of CPCs (injection molding i.e.), corrosive protection of polymer matrix, porous free medium
and ease of structuring of final product created a new market for polymers and conductive
fillers [18]. Bipolar plates of redox flow batteries which are responsible of cell integrity and
electron transfer inside the battery are one of the recently focused application and research
area of CPCs [19, 20].
In this study, thermoplastic polymers: polypropylene (PP) and polyphenylene sulfide (PPS)
were used as a matrix material. To achieve desired electrical, mechanical and
electrochemical properties, these matrices were filled with graphite, carbon nanotubes
(CNTs) and additives (Montan wax and titanate-based coupling agent) via twin-screw corotating extruders. Bipolar plates were produced by injection molding. CNTs were examined
as potential secondary filler inside the graphite-thermoplastic matrix to improve the electrical
and mechanical properties. Contribution of additives to the flow behavior of composites was
studied with rheological tests. The produced bipolar plates were tested in all-vanadium redox
flow
battery
single-cell.
Corrosion
measurements
were
performed
to
evaluate
-5-
INTRODUCTION
1.1.
Motivation
The production of polymeric composite bipolar plates is widely studied topic for fuel cells [21,
22]. However, application of bipolar plates to all-vanadium redox flow batteries requires
similar properties like high electrical conductivity and good mechanical stability, the
differences in working battery media and structural design of bipolar plates make these two
application areas apart. Understanding the production of bipolar plates is a key issue to be
able to improve composite properties. On the contrary to common production methods such
as dry mixing and compression molding [23-25], the combination of twin-screw extruder and
injection molding makes production of bipolar plates more time and cost efficient due to short
cycle times. Processing of highly-filled composites has an obstacle of increased viscosities
which make mixing and production steps critical. Suitable additives and proper feeding
methods -especially for extruder- should be developed to overcome this problem. To obtain
satisfactory single-cell performance, the electrical conductivity should be increased without
making a sacrifice of mechanical properties. Carbon nanotube based hybrid composites are
more successful to answer this request rather than single filler graphite-composites [26].
Finally, proper filler-polymer ratio and suitable surface finishing should be adjusted to
produce porous free and corrosive resistant bipolar plates.
1.2.
Objectives
To produce bipolar plates for all-vanadium redox flow batteries which are chemically
stable in battery media and meet minimum threshold requirements in galvanostatic
charge-discharge tests
-6-
BACKGROUND
2.
BACKGROUND
2.1.
Redox flow battery is a secondary type, so called rechargeable battery which uses potential
difference between redox couples to convert chemical energy into the electrical energy or
vice versa. The battery is divided into two half-cells by ion-exchange membrane which is also
used to transport necessary anionic and cationic species for redox reactions. Electrolytes are
deposited outside of the cell into separated tanks and are pumped into the core of the
battery. During the battery is charged, species are oxidized at the negative electrode (anode)
and reduced at the positive electrode (cathode) and reverse reactions occur during
discharge. The schematic diagram of redox flow cell is shown in Figure 2.
Anode: An - e- An+1
Cathode: C
m+1
+ e- C
(1)
m
(2)
-7-
BACKGROUND
The operation of redox flow battery is realized by circulating electrolyte into two half-cells. To
scale-up the system, it is necessary to connect several cells in parallel by using bipolar
plates and/or to increase the size of electrodes [27]. Schematic drawing of connected 4 cells
into stack is shown in Figure 3.
Figure 3 Redox flow battery cell stack with 4 individual cells. [27]
Redox flow systems have several advantages against other electrochemical storage
batteries such as: low working temperatures, high overall energy efficiencies of 85-90 %,
large number of charge/discharge cycles, long-life expectancy (>10 years) and high chargedischarge rates. All these aforementioned characteristics of RFBs make them promising
candidates for large-scale energy storage applications. One of the most important features of
redox flow battery is the ability of distinguishing power and energy concepts in the
development of the system. When the power of the battery is determined with the size of
electrode surface area and number of cells in the stack, energy capacity can be improved by
increasing electrolyte volume or its concentration [11].
Redox flow batteries are generally categorized depending on their anolyte and catholyte
which are used in redox reactions.
-8-
BACKGROUND
The Iron/Chromium system was one of the first studied types of redox flow batteries. During
1970s and 80s much attention paid by Lewis Research Center of NASA. The battery
contains an aqueous solution of ferric/ferrous redox couple at the positive electrolyte
(Fe2+/Fe3+) and chromic-chromous couple (Cr2+/Cr3+) at the negative electrolyte.
Fe2+ Fe3+ + e2+
3+
Cr Cr + e-
(3)
(4)
The iron/chromium redox flow battery uses graphite felt or carbon fiber electrodes for redox
reactions. As reduction of chromium is slow, trace amount of gold and lead are used as a
catalyst on the negative electrode but not for iron reactions. The system has a relatively low
open-circuit potential (0.90 and 1.20 V) [28]. For the operation of this type of redox battery,
crossover of iron to the chromium side and vice versa should be eliminated [11].
In the bromine/polysulfide system, the positive electrolyte is sodium bromide, and the
negative electrolyte is sodium polysulfide. These chemical species are highly available, cost
effective and possess high-solubility in aqueous media which makes possible the reduction
of electrolyte volume to store required amount of charge [28].
At the positive electrode, three bromide ions are combined to form the tribromide:
-
(5)
At the negative side, the sulfur in the solution is transferred between polysulfide and sulfide:
2-
2-
2S2 S4 + 2e-
(6)
It should be taken into account that during cell operation it is possible to face with crossover
and mixing of electrolytes in the system which causes the precipitation of sulfur species on
membrane and formation of H2S and Br2 [11].
Zinc/bromine gained an attention because of its high energy density, low cost reactants,
highly reversible redox couples and relatively large cell voltage (~1.8V at open circuit).
Unfortunately, material corrosion, high-self discharge rates and dendrite formation during
zinc deposition on charge, are reported as main disadvantages. The electrochemical
reactions are as follow:
-
(7)
-9-
BACKGROUND
(8)
Zinc/bromine redox flow battery (RFB) differs from other types as in one of its half-cell
reactions dissolution and formation of electrodeposited solid phase of zinc takes place. As
energy storage capacity depends on the thickness and structure of zinc layer; decoupling of
power and energy concept is not acceptable for zinc/bromide RFBs [27, 28].
To overcome energy density limitation of redox flow batteries, recently, researchers started
to focus on non-aqueous alternatives which avoid the decomposition of water at extreme
potentials. These systems contain organic solvents (acetonitrile i.e.) which are used to
dissolve redox species such as; metal-ligand complexes. These complexes provide wider
working potential window due to their higher solubility. Ionic liquids are also used as a
supporting electrolyte to improve the conductivity of electrolyte. When cation exchange
membranes are widely used for aqueous RFBs, anion exchange membranes are preferred
for non-aqueous alternatives because anion of supporting electrolyte has crucial role as a
charge carrier [29]. As it is understood, main research in the field of non-aqueous RFB is
focused on the development of suitable redox couples and supporting electrolyte to deal with
low conductivity of electrolyte and high cost drawbacks [30].
2.2.
All-vanadium redox flow battery (VRFB) consists two electrolyte tanks filled with the
electrolyte of V2+/ V3+ and V4+/ V5+ in sulfuric acid solution. These electrolytes are pumped
through the battery stack and via redox reactions electricity is generated. In the core of the
battery, two half-cells are divided by ion-exchange membrane which transfers protons that
are necessary for redox reactions and keeps vanadium species in their original half-cells.
Electron transfers occur on the surface of electrode materials which are highly porous and
electrons are transferred to the surface of bipolar plates [31]. Finally, bipolar plates direct
these electrons through the following cell or if it is the last cell via current collector through
out of the stack. During charge and discharge states, following reactions occur in related
half-cells:
Negative half-cell:
2+
Discharge
Charge
(9)
-10-
BACKGROUND
Positive half-cell:
Charge
+
Discharge
2+
(10)
-11-
BACKGROUND
Figure 4 Redox flow battery test-cell components; a) Steel plate, b) Isolation plate, c) Flowthrough graphite electrode (bipolar plate), d) Flow frame, e) Graphite felt, f) Membrane, g)
Graphite electrode (bipolar plate), h) Steel plate.
All VRFBs benefit from four different valance states of vanadium element (Figure 6). In the
positive half-cell, V4+/V5+ and in the negative half-cell V2+/V3+ species are used for redox
reactions.
Figure 5 Graphite felt electrodes for the redox reactions of vanadium species.
-12-
BACKGROUND
Electrolytes are generally prepared by dissolution of vanadium salts (i.e. V2(SO4)3 or VOSO4)
in sulfuric acid (H2SO4) with varying concentrations and in some cases further species are
added such as: phosphoric acid (H3PO4) [33]. Sulfuric acid was selected as supporting
electrolyte due enough solubility of all four oxidation state of vanadium. However, V2O5, V2O3
and VCl3 are also tried as vanadium source for the preparation of electrolyte; their high cost,
low stability or low solubility limit their usage [37].
BACKGROUND
Bipolar plates (Figure 8) are components which are supposed to possess high electrical
conductivities. The role of the bipolar plate is to transfer electrons which are produced by
redox reactions through the next cell or to the current collector. These materials should have
good mechanical stability and good chemical resistance against acidic electrolyte of VRFB.
Their weight is also an important issue for large-scale applications and always alternative
materials are studied to decrease the weight and the cost.
Figure 8 Bipolar plates, Schunk FU4369 (left) and copper current collector (right).
The detailed explanation about bipolar plates will be given in the following section. Bipolar
plates are combined in the last cell of the stack with current collectors which are made of
metals (i.e. Copper) to direct the electrons out of the stack. For improved electron transfer;
the contact resistance between bipolar plate and current collector should be decreased.
Another important point to take care is the leakage of the battery which happens due to
untightened cell-structure or damaged bipolar plates. In such a scenario, electrolyte may
destroy the current collector which disturbs the electron transfer and as a result decreases
cell performance. In VRFB, the flow management of the electrolyte should be understood
and optimized for better cell performance. Flow frames (Figure 9) are used to direct the
electrolyte homogenously inside the cell. These frames are generally made of polypropylene
(PP), polyvinylchloride (PVC), polyethylene (PE) or polyvinylidene fluoride (PVDF) based
polymers which can withstand against acidic solutions. They are located around the bipolar
plates and electrodes for an optimum interaction with the electrolyte.
Pipes, electrolyte reservoir tanks and pumps are important to reserve vanadium electrolyte at
optimum temperatures and to circulate it between tanks and stack at previously determined
velocity. Steel end plates are used to pack cell components together and to give them
mechanical stability (Figure 10).
-14-
BACKGROUND
BACKGROUND
battery in Australia and USA. In 1993, VRFB was started to be used by Mitsubishi
International Corporation (MIC) and KashimaKita Electric Power Corporation for loadleveling and photovoltaic-development applications. Mitsubishi has installed 20 kW allvanadium redox flow battery in 1997 at Kashima Kita power station (Japan). In Austria,
Cellstrom GmbH started to market an allvanadium battery for distributed energy and voltage
output moderation from photovoltaic and wind based renewable energies. In 2004, VRB
Power Systems marketed VRFB as remote area power supply [40]. Redox flow batteries
were also used for stand-alone Intelligent Transportation System (ITS) applications along
motor- and expressways. In 2005, it was published that the Austrian National Motor- and
Expressway Operator, ASFINAG built a 1 kW pilot system with integration of wind turbines
and photovoltaic cells. This system was designed as an alternative to diesel generators and
lead-acid batteries and showed reliable and cost effective performance as a power supply
[41].
BACKGROUND
standard for bipolar plates of redox flow batteries does not exist but the necessity of similar
characteristics such as high electrical conductivity, good mechanical property and good
electrochemical stability facilitates its adaption to VRFBs.
Bipolar plates which are used in VRFBs require different properties compared to ones that
are used in fuel cells. In fuel cells, hydrogen i.e. is used as a fuel source and water is
generated as by-product. The transportation of materials is realized by channels which are
machined on the surface of bipolar plates. In the case of VRFBs, these channels, with
different designs, are used to direct electrolyte and to optimize its interaction with the
surface of graphite felt [Figure 11]. Like gas permeability, thermal conductivity is also another
important characteristic for fuel cell bipolar plates.
Table 1 Standard for polymeric composite bipolar plates, Department of Energy, USA.
Properties
Electrical conductivity
Thermal Conductivity
Flexural Strength
Flexibility
Tensile Strength
Corrosion Resistance
Threshold Values
>100 S/cm
>10 W/(m.K)
>25 MPa
3-5 % deflection in mid-span
>41 MPa
<1 A/cm2
BACKGROUND
energy or power output), the production methods, manufacturer company and the amount of
components, bipolar plates have an important portion in the total cost of VRFB stacks [43,
44]. Post treatments, high production temperatures, coatings etc. increase the production
costs. As well as their cost, the weight of bipolar plate is also subjected to optimization.
Especially, when large scale applications are considered, graphite block or metallic based
bipolar plates have drawbacks against lighter conductive composite based bipolar plates.
(a)
(b)
Figure 11 (a) Unstructured and injection molded bipolar plates, (b) commercial bipolar plates
with self-made flow channel patterns.
The increasing demand for redox flow batteries and fuel cells for stationary and mobile
applications made the development of cell components essential. The studies on bipolar
plates are mostly focused on their price, mechanical/chemical durability and the electrical
conductivity. Bipolar plates from graphite were used in earlier decades. The high weight of
graphite blocks was one of the obstacles. When their thickness is diminished, the structure
started to be porous and very brittle which causes mechanical weakness. Metals were
proposed as alternative solution with ability of producing thin and mechanically stable plates
but their chemical resistance was an important problem to be solved. Carbon-based layer
depositions were examined to protect metallic bipolar plates without increasing contact
resistances. This attitude became successful but still, the cost of coating step and their
corrosive resistance is widely studied. Carbon-carbon based composites which are produced
by chemically infiltrated carbons into carbon fiber based matrices, showed superior electrical
and mechanical properties but on the other hand production costs, high temperature
treatments and the difficulty of plate machining interrupted their expansion. Polymer-based
-18-
BACKGROUND
conductive composites recently gained a lot of interest due to their low production cost, ease
of machining, short production cycles, mechanical stability and chemical resistance. The
main attention was given to increase their electrical conductivity which is examined by
addition of conductive fillers such as; carbon black, graphite, carbon nanotube and carbon
fibers into polymer matrices [22, 45]. The detailed information and examples of these above
mentioned bipolar plates are given in the following sections.
(11)
2H+ + 2e- H2
(12)
-19-
BACKGROUND
Corrosion process (Equations 11-12) involves oxidation and reduction reactions. In a simple,
acidic corrosion of metallic bipolar plate, oxide of metal is produced in anode and hydrogen
evolution occurs in the cathode. Besides, given reactions, depending on the acidic solution
and composition of metal, other side reactions take place [47]. If bipolar plate starts to
corrode during the operation of energy storage systems, the formation of an oxide layer on
the surface of the metal increases the contact resistance of bipolar plate which directly
affects the cell efficiency. In further steps, the deterioration of metallic plates causes
poisoning of the membrane by stacked metal complexes inside the pores. Some metals are
able to resist against corrosion over a large voltage range such as; tantalum (Ta), titanium
(Ti), hafnium (Hf) and niobium (Nb) which are not economically feasible for fuel cell or redox
flow applications [22]. To be able to use metallic bipolar plates their electrochemical stability
should be improved. Coating technology is used since decades to protect the surfaces that
are vulnerable against corrosive attacks. For the metallic bipolar plates development of
several coatings is a wide research topic. These coatings should possess low contact
resistance, good mechanical stability, pinhole-free structure and low production cost [47].
Figure 12 Samples of metallic bipolar plates (Left: diamond-like carbon coated titanium,
chromium, tungsten and vanadium metallic bipolar plates. Right: stainless steel based
metallic bipolar plates).
Conductive coatings are classified as carbon- and metal-based. Carbon-based coatings
include conductive polymers, diamond-like coatings (Figure 6) and graphite while metalbased coatings are noble metals, metal-nitrides and metal-carbides. As an example for latter
case, stainless steel (316 SS) was coated with titanium nitride (TiN) and both electrical
conductivity and corrosion resistance results were found to be improved. In another study,
Chromium nitride/chromium-coated 316L SS via physical vapor deposition (PVD) showed
lowered interfacial contact resistance [48]. Carbon coatings which are prepared by plasmaassisted chemical vapor deposition (PE-CVD) for stainless steel substrates or pyrolyzed
-20-
BACKGROUND
carbon-polymer composite sprayed on the surface of SS 316L type stainless steel bipolar
plates were found to be promising alternatives to overcome aforementioned obstacles [22].
BACKGROUND
this conductive filler (until C1) the composite keeps behaving like an insulator due to the lack
of contact between fillers. After a certain amount of filler concentration (which is percolation
threshold, C1) the composite starts to be conductive material. When percolation threshold is
reached, electrical conductivity of the composite increases rapidly until the matrix becomes
saturated with those fillers. When the matrix is saturated, it is hard to disperse more filler due
to lack of polymer to wet/disperse more fillers. At this point, poor filler-polymer interactions
and porous structure in the composite negatively influence the mechanical stability of the
material. The percolation threshold depends on; the aspect ratio and particle shape of fillers,
processing method of composites and the electrical resistivity of polymer matrix itself. To be
able to reach percolation values at lower filler concentrations, fibers and nanotubes are
favorable choices due to their high aspect ratios compared to fillers like carbon black and
graphite [18].
Filler
Matrix
BACKGROUND
filler ratio, the overall composite viscosity increases. Finding a balance between the amount
of filler and processability of composites require the optimization of filler type, process
parameters and proper choice of matrix material. In the following paragraphs filler types,
advantages of different polymer matrices and process techniques are discussed.
a)
b)
BACKGROUND
graphite have different bulk properties which originate from the order of crystallites. When
those crystallites are in a long-range order, the bulk properties of graphite become more
anisotropic. Synthetic graphite simply orientates graphitic structures in a random pattern. It is
also possible to obtain synthetic graphite by introduction of heteroatom such as; nitrogen,
oxygen and sulfur or by intercalating species between graphene layers which contributes to
the degree of disorder [53].
Carbon nanotubes (CNTs) gained a considerable attention after their invention in 1991 by
Iijima [54]. CNTs are simply formed by wrapping graphene layers into tubular shapes. CNTs
can be classified single-wall or multi-wall depending on the number of graphene layers they
are made of. The electrical properties of CNTs depend on how the graphene layers are
wrapped (chirality) and the diameter [55]. CNTs can be semiconductor or metal due to
different chirality (Figure 15).
(13)
Where n and m are the number of steps of along the zig-zag carbon bonds and
and
are unit vectors. When chiral angle is 0 , it is called zig-zag and at 30 the structure is
named as armchair. CNTs show unique material properties like elastic modulus of 1 TPa
-24-
BACKGROUND
which is close to diamond (1.2 TPa), 10-100 times higher strength than stainless steel,
thermal stability up to 2800 and electric-current-carrying capacity which is 1000 times
higher than copper wire. However, these outstanding characteristics were found highly
promising for applications from electronic to polymer industries, they belong to individual
carbon nanotubes and the understanding of real contribution of CNTs to the composites and
solving the problems related with their dispersion and distribution are still one of biggest
challenges and obstacles in view of the commercialization of CNT-based products. Carbon
nanotubes are obtained by using several different production methods. Arc-discharge, laser
ablation and chemical vapor deposition (CVD) and its derivatives like plasma-enhanced
chemical vapor deposition (PECVD) are very well-known techniques to produce single- or
multi-wall CNTs [56].
Besides graphite and carbon nanotubes many other carbon-based conductive fillers such as;
carbon black, carbon fiber and expanded graphite are used for the production of bipolar
plates. Individual properties of some of those fillers are given in table 2. Although these
conductive fillers are used alone to achieve desired properties, hybrid systems (combination
of 2 or more fillers) are also accepted as an advantageous way for improving electron
transfer inside the matrix.
Table 2 Comparison of aspect ratio and electrical conductivity of carbon based conductive
fillers. [49, 57, 58]
Property
Graphite
SWCNTa
MWCNTb
Carbon
Black
Carbon
Fiber
Aspect Ratio
Electrical
Conductivity
(S/cm)
Close to 1c
100-10000
100-10000
6-440
400-1000
1 x 103-
5 x 102-
10-100
600
1 x 10
1 x 10
Hybrid systems use fillers with different geometries to decrease the resistivity between
conductive units and to increase the overall electrical conductivity of the composite. This
approach also gives a chance to decrease the total filler ratio as conductive fillers are used
more efficiently [59].
-25-
BACKGROUND
2.6. Additives
Using additives to increase the electrical and mechanical properties of final products, to
optimize the flow behavior of composites or to improve dispersion/distribution of fillers is
another highly studied and applied technique. Some carbon based fillers i.e. carbon black
and carbon nanotubes tend to agglomerate and it is necessary to de-bond them which is
another step to the production. Carbon black particles aggregate due to high surface area
and oxide containing polar functional groups such as; carboxyl, carbonyl or hydroxyl. It is
also similar in the case of CNTs which are attracting each other via weak van der Waals
forces. These inter-particle interactions must be overcome in order to be able to disperse
fillers homogenously inside the matrix. Coupling agents are used for inorganic fillerreinforced polymers. Coupling agents have two different groups (tail and head). When one
group reacts with surface of filler, other groups links this filler to the polymer by physical or
chemical interactions. There are commercialized, titanate, silane and zirconium based
coupling agents. Xu et al. studied the effect of coupling agent on the electrical properties of
CB filled PP/PVDF matrix and explained the reaction mechanism of titanate coupling agent
(Figure 16).
-26-
BACKGROUND
employed silane coupling agents to improve the electrical and mechanical properties of
polypropylene and polyimide based MWCNT filled composites. These improvements were
explained with increased filler-polymer interaction and improved filler dispersion [61]. Similar
to coupling agents waxes are also used to improve composite properties. Especially as
internal and external lubricants for the production of polyvinyl chloride (PVC) based products.
Treffler et al. studied this effect with different waxes (long chain ester waxes, oxidized
polyethylene waxes and polyethylene/polypropylene waxes). It was discussed that the
structure and polarity of lubricants are very important for processing PVC. For instance,
lubricants with high polarity and short carbon chains are favorable to penetrate between the
molecular chains to decrease the viscosity and montanic acid ester waxes reduced pressure
formation in the extruder without changing rheology [62].
2.7.1. Thermosets
Thermoset resins are covalently bonded three-dimensional materials which are cross-linked.
This polymer network is formed by chemical interactions of linear polymer chains or
clustering of monomers. The polymerization of thermosets occurs in two steps; first,
monomers are partially polymerized into linear chains and secondly, crosslinking is formed
by chemical additives, heat or electromagnetic radiation. This crosslinking process is the
main difference of thermoset resins compared to thermoplastics. Due to this property,
thermosets cant be re-melted or dissolved completely in solvents once they are cross-linked
[63]. Phenolic resins, epoxies, polyester and vinyl ester are very well-known thermoset resins
and epoxy is highly-desired for the production of bipolar plates. Thermosets are able to
dissolve/wet higher amount of conductive fillers compared to thermoplastics due to their low
viscosities. The preparation method i.e. solution mixing is another factor which simplifies the
control of the overall viscosity of thermoset composite. As previously discussed, chemical
stability is an important property for bipolar plates. The cross-linked structure of thermoset
resins increases chemical resistance of the composite compared to thermoplastic-based
-27-
BACKGROUND
ones [64]. On the other, the period which is necessary for crosslinking and the removal of
solvent during the molding of thermoset composites makes the overall process time longer
and the production step costly.
In the literature and in company portfolios, many thermoset-based bipolar plates are studied
and presented. To overcome difficulties related with the production cycle-times and to benefit
from individual properties of different thermoset resins, researchers examined the effect of
process parameters, filler properties and combination of different conductive fillers. The
electrical conductive pathway and mechanical properties of composites highly depend on the
particle size and aspect ratio of conductive fillers. Luo et al. examine the effect of graphite
particle size on the composite properties. It was found that by increasing particle size,
porosity and the electrical resistance decreases due to low aspect ratio of filler which
requires less polymer to be wetted and well-established conductive pathway because of
larger particles. On the other hand, bending strength decreases because when the
mechanical stress is concentrated on the conductive fillers, those particles cant withstand
under the pressure as well as the polymer does [65]. The effect of particle shape to the
electrical conductivity was discussed in the work of Heo et al. Spherical and flake type
graphite containing phenolic resin composite was prepared with 85 wt. % filler content. The
results showed that the composite with flake type graphite have higher electrical
conductivities compared to spherical one. The point-to-point interaction of spherical graphite
particles gave a chance to the penetration of phenolic into filler-filler contact areas but in the
case of face-to-face interacted and tightly connected flake type graphite, filler-filler contact
resistance was decreased [66]. Taherian et al. proposed the effect of compression molding
pressure on the composite properties. Pressures of 15 bar and 740 bar were studied to
prepare
graphite-phenolic
resin
composites.
Increased
molding
pressure
caused
-28-
BACKGROUND
conductive fillers is a key point to benefit from their individual properties. Functionalization of
conductive fillers was employed especially for small-scale trials or specific applications to
improve filler-polymer interaction. Especially, these studies were focused on the carbon
nanotubes because of their highly agglomerated structure. In one study, poly(oxyalkylene)amines (POA) bearing maleic anhydride (MA) was grafted onto MWCNTs to increase
MWCNT-vinyl ester interfacial bonding [69]. Besides the mechanical strength, electrical
conductivity of POAMA grafted MWCNT filled vinyl ester composite due to better dispersion
of CNTs. Sun et al. revealed that Fenton/UV treatment is an optimal oxidation process to
introduce hydroxyl and few carboxyl groups on the side-walls of CNTs without harsh
damages. Phenolic composites which were prepared with 3 wt. % treated-CNTs and with
approximately 83 wt. % graphite showed superior electrical and bending properties to
untreated-CNT filled system [70].
2.7.2. Elastomers
Elastomers are started to be studied recently for the production of bipolar plates. However,
their research area is not as wide as thermosets and thermoplastics; they show high
chemical resistance and good mechanical properties which are promising characteristics for
bipolar plates. In redox flow batteries and fuel cells, elastomers are used as a gasket
material which has a crucial role to supply tightness and to give mechanical stability when
cell-components are stacked together. Elastomers are usually thermoset but when their
chemical crosslinking is replaced with physical-crosslinking they become thermoplastic.
Thermoset like elastomers exhibit elastic and viscoelastic characteristics and once they are
cross-linked, they cant be reprocessed or recycled. Thermoplastic elastomers exhibit
reversible deformation. They generally consist two phases. One phase which is continuous
shows elastic behavior and the other phase which is dispersed represent the physical
crosslinking. These physical crosslinks disappears with increasing temperature. On the
contrary of thermosets, thermoplastic elastomers can be processed similar to thermoplastics
which bring technological advantages [71]. Elastomeric bipolar plates consists one phase
matrices such as polyurethane elastomer, two-phase vulcanized thermoplastic elastomers
(i.e. vulcanized ethylene-propylene rubber phase dispersed in a thermoplastic polypropylene
matrix or blend of polyvinyl ester and a polyurethane elastomer) or silicone elastomer which
is composed of vinyl polydimethyl siloxane and contains dimethylhydrogen siloxane as the
curative [7274].
-29-
BACKGROUND
2.7.3. Thermoplastics
The main difference between thermoset and thermoplastic resins is their chemical structure.
While thermosets are cross-linked, thermoplastics have linear polymer structure and they
dont need any curing during composite production. This property of thermoplastics makes
them remoldable and reformable. Pure thermoplastic resins or their composites can be
reprocessed several times due to the reversibility of physical softening and melting [75]. The
lack of chemical reaction of crosslinking decreases cycle times and also the process
becomes easier to monitor. If working temperatures increase, the modulus retention of
thermoplastics decreases because of no-chemical bonds. Thermoplastics are supposed to
be dried properly prior to the processing to prevent the releasing of gases or water vapor
during production otherwise structural defects and the decrease in mechanical properties are
observed. In the literature, the pyramid of excellence is used to classify thermoplastic
family. The bottom part of this pyramid consists commodity thermoplastics such as;
polyethylene (PE), polypropylene (PP), polystyrene (PS). In the center of the pyramid
engineering thermoplastics are located. They are chemically more stable and processed at
higher temperatures compared to base thermoplastics i.e. polyphenylene sulfide (PPS),
polysulfone (PSU), polyetherimide (PEI). The top of the pyramid consist thermoplastics like
liquid crystal polymer (LCP), polytetrafluoroethylene (PTFE), polyimides (PI) etc. Which are
suitable for high-tech applications and they are differ from the rest of the pyramid with
superior prices [76].
Thermoplastic resins such as; polypropylene, polyethylene, polyvinylidene fluoride (PVDF),
liquid crystalline polymer, polyphenylene sulfide and fluoropolymers are used with the
research and commercial purposes for the production of bipolar plates. Thermoplastics
become more suitable for mass production and automated processes by using injection
molding instead of compression molding. Employing injection molding brings the low cost
production, short cycle times, high dimensional tolerance and the possibility of combination
of different resins in one-step. When the production of bipolar plates is taken into account,
the high electrical conductivity of the composite depends on the amount, type and effective
dispersion of conductive fillers. Increased wt. % of filler causes higher viscosities and as a
result improper flow behavior during injection molding. Mainly thermosets show better
carbonaceous filler-polymer interaction due to their polar backbones and this eases to reach
higher electrical conductivities with comparatively lower filler ratios. The thermoplastics which
are chosen for mass-production generally have non-polar structure which influences fillerpolymer interaction negatively and proposes the necessity of high filling ratios [64].
-30-
BACKGROUND
Mixing methods and processing techniques highly affect the orientation and distribution of
fillers as well as their interaction with polymer matrix. The electrically conductive polymer
composites are produced by combination of different mixing methods (melt, solution or dry
mixing) and processing methods (i.e. compression molding, injection molding or wet-lay
process). Inadequate mixing and processing methods may damage filler-filler interactions,
cause degradation of polymer (if proper temperature control is not realized) and terminate
with irregular shape of final product [18].
Depending on melt flow rate of polymer, its solubility and particle form (i.e. powder or pellet)
proper mixing methods should be selected. The electrical conductivity of polypropylenegraphite based polymer composite was studied with solution and melt-mixing techniques and
it was reported by Dweiri et al [77] Due to better dispersion and distribution of conductive
fillers, solution mixing was found to be more effective method for higher electrical
conductivities. This conclusion rises from better penetration of resin between conductive
fillers in a liquid form compared to melted state of the same polymer. However, solution
mixing can give better properties; volume of material which is produced is generally smaller
than melt mixing or dry mixing methods. In solution mixing it is also necessary to evaporate
the solvent which adds one more step to the production process.
The electrical conductivity of composite bipolar plates deviates in the through-plane and inplane directions due to the orientation of conductive fillers during production process.
Especially injection molded bipolar plates show higher in-plane electrical conductivities
compared to the through-plane. High injection speeds and applied shear at dies orientates
the filler in the direction of injection. However, compression molding provide random
orientation to conductive fillers in the cooling step, this effect is not significant for injection
molding. A considerable attention is given to optimize the mold temperature, holding
pressure or injection speed to surpass above mentioned disadvantage [78].
As well as process optimization, intrinsic properties of thermoplastic have also significant
influence on the properties of bipolar plates. The effect of crystallinity of PP and the
concentration of MWCNT were studied by Liao et al. [26] Melt mixed components were
compression molded. 4 phr MWCNT was substituted with graphite at 80 wt. % graphite and
20 wt. % PP composition and in-plane electrical conductivity of higher than 500 S/cm was
achieved. It was also concluded that low crystallinity polymer system had a better interaction
with MWCNTs because of CNTs better distribution in non-crystalline areas. This caused to
higher electrical conductivities and better filler-polymer interactions.
-31-
BACKGROUND
The contact resistance between bipolar plate and porous electrode was thought to be one
the major problems which causes ohmic losses inside the cell and decreases the cell
performance. In 2008, Qian et al [19] came up with an idea of adhesive bonding of graphite
felt electrode to bipolar plate. Carbon-based adhesive conductive layer (ADL) was prepared
by mixture of phenol formaldehyde resin (PF), carbon black and graphite powder. Graphite
felt sheet was heat bonded on the surface of bipolar plate by controlling the thickness of ADL
layer. Impermeable bipolar plate-electrode assembly was successful to decrease the surface
area resistivity almost 300 m.cm2. This decrease had also positive influence on the energy
efficiency which was increased to 81 % at a current density of 40 mA cm-2.
For fuel cell applications PP or PVDF are widely used due to their chemically inert nature or
PPS for high-temperature stability. VRFB literature consist thermoplastic elastomers, PP and
rubber blends and PE based thermoplastic as matrix material. In early study of M. SkyllasKazacos [79] PP was mixed with thermoplastic elastomers styrene-ethylene-butylenestyrene (SEBS) and different types of rubbers (buthyl rubber, nitrile rubber etc.). Carbon
black and graphite fiber were used as conductive fillers. These components were melt mixed
and pressure molded. By using 35 wt. % CB and 5 wt. % graphite fiber, volume resistivity as
low as 0.36 .cm were achieved. To produce bipolar plates with a thickness less than 1mm,
PP matrix was modified with rubber based polymers and satisfactory mechanical stability
was obtained by addition of ethylene-propylene-diene monomer (EPDM) rubber. In a similar
study, Haddasi-Asl et. al [80] examined the mixture of high-density polyethylene (HPDM) with
EPDM to have impermeable bipolar plates. The ratio was 40-20 wt. % HDPE to EPDM. The
rest of the matrix was the combination of 20 wt. % CB and 20 wt. % Graphite fiber. Bipolar
plates with less than 1 mm thickness and 0.23 .cm volume resistivity were successfully
produced.
-32-
EXPERIMENTAL
3. EXPERIMENTAL
3.1. Materials
3.1.1. Polypropylene
Polypropylene homopolymer (Borflow HL508FB) was purchased from Borealis A/S,
Denmark. This product was developed for fiber applications. Due to its high melt flow rate
(800 g/10 min) it is used for melt blown applications and microfibers at high spinning speeds.
It possesses controlled rheology, easy processability, optimal product consistency and it is
suitable for electrostatic charging. Physical properties are given in Table 3.
Table 3 Physical properties of polypropylene (Borflow HL508FB).
Grade
Density
(g/cm3)
Melting
temperature (C)
Molecular weight
distribution
800
0.9
156-160
Narrow
Melt flow
rate1
(g/10min)
Density
g/cm3
Ash
(wt. %)
5000
1.3 1.4
0.8
Particle Size2
35
Mesh
60
Mesh
99.8
99.5
-33-
Color
Off
white
EXPERIMENTAL
3.1.3. Graphite
TIMREX KS5-75TT primary synthetic graphite (Figure 17) was purchased from TIMCAL
Graphite & Carbon, Switzerland and used as a primary conductive filler for the production of
bipolar plates. KS5-75TT shows medium toughness and good lubricating properties.
According to datasheet, this graphite grade exhibits low friction coefficient and high electrical
conductivity. Physical properties are shown in Table 5.
Table 5 Physical properties of primary synthetic graphite (KS5-75TT).
Physical Properties
Metric
Comments
3
Bulk density
Particle size
Ash content
0.410 g/cm
70 m
0.04 %
1.55 ohm.cm
1.60 ohm.cm
1.80 ohm.cm
2.25 ohm.cm
140 W/m.K
0.2 %
45 g/100 g
Electrical resistivity
(pressure 2.5 t/cm3)
Thermal conductivity
Moisture content
DBP absorption
Scott
d90
Typical
Particle size 80 m,
Particle size 42 m,
Particle size 15 m,
Particle size 10 m,
Typical
Dibutylphthalate
Unit
nanometers
microns
%
%
2
m /g
kg/m3
Value
9.5
1.5
90
10
*
250-300
60
-34-
Method of Measurement
TEM
TEM
TGA
TGA
HRTEM
BET
EXPERIMENTAL
100 m
200 m
Figure 18 FE-SEM image of as received MWCNTs, NC7000 from Nanocyl S.A. (50 x
magnification).
-35-
EXPERIMENTAL
Figure 19 Chemical structure and photo of Ken-React KRTTS titanate coupling agent.
Ken-React KRTTS is used in diverse application areas such as production of resin-based
lacquers, coatings, adhesives and processing of thermosets and thermoplastics. The product
is selected for adhesion promotion, coupling and dispersing of fillers (inorganics, organics,
pigments, fiber etc.), to adjust rheological properties of resins and composites. Some wellknown benefits are dispersion of carbon black in printing inks and viscosity reduction in
thermoplastics. The specified properties of Ken-React KRTTS are given in Table 7.
Table 7 Properties of Ken-React KRTTS titanate coupling agent.
Property
Method
Physical form
Color
Liquid
8-16 (Gradner)
ASTM D2849
Viscosity
@ 25 C/77 F
40-200 cP
Specific gravity @ 25
C/77 F
0.93-0.95
ASTM D1298
180-230 F
Approx. 300 F
6-8
ASTM D56
-36-
ASTM E70-52T
EXPERIMENTAL
Value
Solid
Slight yellow
Relative Density
Melting point
1.02 g/cm3
62 C
Vapor pressure
Water solubility
Octanol-water partition coefficient
(Log Kow)
Granulometry
Flammability
7.9x10-5 Pa (25 C)
5 mg/L
Structural formula
2
61 m (median diameter)
Non-flammable
R-CH2-COOCH2CH2CH(CH3)OCOR / R-CH2COO R1
where R is generally an even-numbered saturated
alkyl chain and R1 is alkyl chain of long chain fatty
alcohols (esterified)
-37-
EXPERIMENTAL
Polypropylene wt. %
Graphite wt. %
CNT wt. %
Wax wt. %
PP-1
20
80
PP-2
20
79
PP-3
20
78
PP-4
20
77
PP-5
19
77
PP-6
17
77
-38-
EXPERIMENTAL
Figure 22 Schematic representation of twin screw extruder in the 1st step. Polymer was fed
from main feeder and MWCNTs were fed from side feeder.
In the second step, produced CNT masterbatch was mixed with graphite. Masterbatch was
fed into main-feeder and graphite was introduced by side feeder from the position of L/D 40.
The illustration of extruder and temperature profile for 2nd step was given in Figure 23. The
feeding of graphite is also as crucial as CNTs. As CNT-masterbatch increases the viscosity
inside the extruder, graphite should be fed from a point where it does not influence the
viscosity negatively and possess good dispersion of the second filler before the composite
reaches the exit-die. Montan wax was mixed with PP via SOMOS dry air dryer for
10 minutes and fed from main feeder like pure-PP. The scheme of the extruder for the
addition of wax was also given in figure 23. This time, due to brittleness of the composites,
output of the extruder was a chunk of material instead of strand. The materials which come
up from the die were directly cooled in the water-bath and dried 3 hours at 80 C in Heliomat
4T 2M WINsystem Turbo dryer before processed in injection molding machine.
Figure 23 Schematic representation of twin screw extruder in the 2nd step. Polymer-CNT
masterbatch as well as Montan wax was fed from main feeder and graphite was fed from
side feeder.
As in the case of PPS-based bipolar plates, specific energy input (SEI) value of extruder was
also calculated for PP-based composites. All process parameters were given in Table 10.
Equation 14 which was specially prepared for Leistritz HP 27 x 52D extruder was used to
-39-
EXPERIMENTAL
calculate SEI and obtained results were also presented in Table 10. Screw design for
preparation of CNT-masterbatch and graphite/wax addition step is given in Appendix A.
Table 10 Twin-screw extruder process parameters for the production PP-based bipolar
plates.
Samples
Pressure
CNT-MB*
bar
26
PP-1
30-40
PP-2
50-65
PP-3
75-115
PP-4
100-125
PP-5
118-126
PP-6
50-60
*MB: Masterbatch
Melt
Temp.
C
225
Throughput
rate
kg/h
10
Screw
speed
rpm
1000
235
241
250
260
254-257
252-267
5
5
5
5
5
5
300
300
300
300
300
300
2Mmax I
n
9550
Em
Torque
SEI
(kWh/kg)
%
39
1.10
18
21
27-29
36-40
39-41
23-24
0.30
0.36
0.47
0.64
0.68
0.41
(14)
Where; Mmax is max. Torque for one-screw shaft (128 N.m), I is torque (%), n is the screw
speed (rpm), E is the gear drive efficiency (it is taken 0.95) and m is the throughput rate
(kg/h).
EXPERIMENTAL
Bipolar plates with dimensions: 150 mm x 150 mm x 3 mm were produced. All process
parameters are given in table 11.
Table 11 Injection molding process parameters for the production PP-based bipolar plates.
Samples
Units
PP-1
PP-2
PP-3
PP-4
PP-5
PP-6
Feeding
50
50
50
50
50
50
Zone-1
200
200
200
200
200
200
Zone-2
210
210
210
210
210
210
Zone-3
220
220
220
220
220
220
Zone-4
230
230
230
230
230
230
Die
Mold Temperature
240
130
240
130
240
130
240
130
240
130
240
130
Injection Speed
cm/s
80
80
80
100
100
80
Injection Pressure
bar
1600
1600
1800
1925
1936
1470
Holding Pressure
bar
1100
1000
1200
1800
1600
1000
Holding Time
Temperature Profile
PPS wt. %
Graphite wt. %
CNT wt. %
Titanate wt. %
PPS-1
27.5
72.5
PPS-2
27.5
71.25
1.25
PPS-3
27.5
70
2.5
PPS-4
24.5
72.5
PPS-5
24.5
71.25
1.25
PPS-6
24.5
70
2.5
-41-
EXPERIMENTAL
-42-
EXPERIMENTAL
Temperature profile was 60-315-320 , at feeding, mixing and output respectively. Granules
were collected into water-bath and dried in vacuum-oven overnight. To compare
processability of composites, specific energy input (SEI) of twin-screw extruder was
calculated with equation 13 and given in table 13. In this case, Mmax (max. torque for onescrew shaft) was taken 90 Nm and E (gear drive efficiency) was 0.96.
Table 13 Specific energy input (SEI) and torque values of twin screw extruder for the
production of PPS-based composites.
Samples
*Torque (%)
SEI (kWh/kg)
PPS-1
15
0.35
PPS-2
14
0.32
PPS-3
16
0.37
PPS-4
7.5
0.17
PPS-5
0.16
PPS-6
7
0.16
*It should be taken into account that due to high viscosity of the composites twin-screw
extruder was operated without a die.
Figure 27 Demag Ergotech 100/420 120 El-Exis S type injection molding machine.
-43-
EXPERIMENTAL
(a)
(b)
Figure 28 a) Through-plane electrical conductivity test setup with Keithley 2400 Multimeter
and Fluke 87V True RMS multimeter, b) sandwiched bipolar plate between two gold coated
copper-electrodes.
Injection molded bipolar plates were grinded almost 0,1 mm from each side with FEPA
P#220-800-1200 grade silicon carbide grinding papers respectively to take out the polymerrich layer which increases the resistance. Grinding process brings the roughness to the
surface of bipolar plates. Gas diffusion layers (GDL) from SGL Carbon, Germany (35 AA)
-44-
EXPERIMENTAL
were used to decrease the contact resistance and during the measurement bipolar plate is
sandwiched between two GDLs. Sample size was 10 mm x 10 mm x 3 mm. To have
reproducible results 1 MPa pressure was applied. Measurements were done in two steps
(Figure 29) and the through-plane conductivity of bipolar plate was calculated as follow:
1
R
(16)
l
RA
(17)
Where; R is the resistance in ohm (calculated from applied current, I and voltage drop across
the specimen, V) is the resistivity (ohm.cm), is the electrical conductivity (S/cm), l is the
thickness of the sample (cm) and A is the surface area (cm2) in which the pressure is
applied.
Arrangement-1:
Rtotal-1 =2xRcopper electrodes + 2xRcopper-GDL + RGDL
-45-
EXPERIMENTAL
Arrangement-2:
Rtotal-2 =2xRcopper electrodes + 2xRcopper-GDL + 2xRGDL + 2xRGDL-Bipolar plate + RBipolar plate
For the 1st arrangement, it was assumed that resistivity of copper electrode and the contact
resistance between electrode and GDL are too small compared to the resistivity of GDL and
they were neglected. In the 2nd arrangement, as well as the first assumptions, it was
accepted that using GDL paper between bipolar plate and copper electrode decreases GDLbipolar plate contact resistance and this value can be neglected as well.
The in-plane electrical conductivity setup (Figure 30) was prepared according to the principle
of ISO 3915 standard. Sample dimension was 70 mm x 10 mm x 3 mm. The current was
applied by Keithley Model 2400 sourcemeter from both sides of the sample and the voltage
drop was measured with Fluke 87V True RMS multimeter. An electrode with span length of
10 mm was located in the middle of the sample and voltage drop was recorded. For lower
contact resistance between specimen and electrodes, samples were painted with conductive
silver paint.
As surface grinding did not bring a significant improvement for in-plane measurement,
samples were tested as they were produced. Equations 1 to 3 were also used for the
calculation of the in-plane electrical conductivity. In this case; I is span length of electrode
which measures voltage drop (cm) and A is the cross-sectional area of specimen (cm2).
Figure 30 In-plane electrical conductivity test setup with Keithley 2400 Multimeter and Fluke
87V True RMS multimeter.
EXPERIMENTAL
speed was applied by Universal testing machine (Figure 31) Inspekt Table 50kN (Hegewald
& Peschke, Germany). Data interpretation was explained in Appendix D.
3FI
(18)
2bh2
f is the flexural-stress parameter, F is the applied force (Newton), l is the span (mm), b is the
width of the specimen (mm) and h is the thickness of the specimen (mm).
Flexural strain f =
600sh
I2
(19)
f is the flexural-strain parameter, s is the deflection (mm), l is the span (mm) and h is the
thickness of the specimen (mm).
Deflection si =
fi I2
6h
(20)
-47-
EXPERIMENTAL
Flexural modulus Ef =
f2 -f1
f2 -f1
(21)
Flexural modulus was calculated in MPa, by using flexural stresses (f) at different
deflections (s).
(a)
(b)
Figure 32 a) Capillary rheometer machine Gttfert, Rheograph 2002 and b) die samples with
different length and diameter.
Apparent viscosity (Pa.s) was defined as the ratio of apparent shear stress (
ap),
in pascals
32Q
(22)
D3
Where; D is the diameter of capillary die bore (mm), Q is the volume flow rate (mm3/s)
Apparent shear stress
ap
pD
4L
(23)
-48-
EXPERIMENTAL
p is the test pressure (Pa), L is the length of die (mm) and D is the diameter of the die (mm).
Hm +Hcold
(Hf 1-Wf )
(24)
Cold crystallization is an exothermic reaction and the heat of cold crystallization (Hcold) was
subtracted from heat of fusion. Heat of fusion of 100 % crystalline PPS was taken from
literature as 146.2 J/g [81]. Wf was defined as weight fraction of fillers. The interpretations of
heating and cooling spectra were given in Appendix E.
EXPERIMENTAL
(H2SO4) prior to the measurements. Before the measurement, electrolyte was purged with
nitrogen (N2) and during the measurement nitrogen source was located in to 3-electrode
arrangement by preventing the disturbance of the electrolyte. 2 minutes open-circuit-voltage
(OCV) measurement was done for each sample. For negative half-cell (V2+/V3+), samples
were cycled 10 times at positive potentials with 20 mV/s to increase cyclic performance of
the reduction of V3+ (without starting oxygen evolution on the electrode surface).
ip =2.99105 n(na )
1/2
A(C 0 )D1/2
0 v
(25)
Where; ip is the peak current (amperes), n is the number of electrons involved in the rate
determining step, is the charge transfer coefficient, A is the electrode surface area (cm2),
Co0 is the bulk concentration of oxidant (mol/cm3) and v is the scan rate (V/s). A plot of ip vs.
v1/2 gives a straight line with a slope proportional to Do.
-50-
EXPERIMENTAL
na F
RT
Ep -E0I
(26)
F is the faraday constant (96485 C/mol), R is the universal gas constant (8,314 J/mol.K), T is
temperature in Kelvin, Ep is the peak potential and E0l is the formal potential (the mean
average of cathodic peak potential (Epc) and anodic peak potential (Epa)). A plot of lnip vs. (EpEl) have a slop of (naF/RT) and an intercept proportional to k0.
EXPERIMENTAL
In corrosion measurement, similar to cyclic voltammetry trials, current density (A/cm2) vs.
potential (V) graph for a certain potential window was used to obtain Tafel plot which gives
information about cathodic and anodic current densities of different bipolar plates.
W=
t1
Wout
Win
(27)
V t I t dt
(28)
t2
-52-
EXPERIMENTAL
Pdischarge =
1
t
t1
(29)
V t I t dt
t2
Figure 36 Galvanostatic charge-discharge test output-graph (power vs. time) for the
calculation of energy efficiency and discharge power density.
-53-
-54-
addition of fillers, and after a certain amount the polymer matrix loses its capability of wetting
[84]. All these scenarios cause a porous and inhomogeneous structure of bipolar plates
which shows lower electrical conductivities than expected. In order to improve the flow
behavior of the composite and to optimize filler dispersion, Montan wax was studied as an
additive.
Figure 37 Through-plane and in-plane electrical conductivity of PP-based bipolar plates with
different MWCNT and Montan wax concentrations.
Different concentrations were processed in order to understand its effect on the electrical
properties. The additions of wax did not improve the electrical conductivity of bipolar plates.
Probably, the addition of 1 wt. % wax was not enough to change filler-filler interactions, or the
mixing of wax was not homogenous for PP-5. A sample with 3 wt. % wax (PP-6) showed
even lower conductivity values at the same total filler concentrations. It is known that the
addition of wax with high melt flow rates decreases the overall viscosity of the composite. At
the same time, this reduces applied shear stress (Table 10) by the extruder due to the
lubricating effect of the wax. The less the applied shear, the poorer may be the filler
dispersion [85], and as a result electrical conductivity tends to decrease.
-55-
1 m
-56-
Figure 39 Flexural strength values of PP-based bipolar plates with different MWCNT and
Montan wax concentrations.
Any further improvement was achieved by increasing CNT content or adding 1 wt. % Montan
wax due to already densely filled polymer matrix. The dramatic decrease of sample PP-6
(with 3 wt. % Montan wax) can be explained by the substitution of wax with PP. It is probable
that decreased resin concentration and also brittle structure of wax due to its high crystallinity
and short polymer chains decreased the mechanical strength of the composite. However,
any standard for redox flow battery bipolar plates exist, according to Department of Energy
(USA) [26] minimum flexural strength value should be 25 MPa for fuel cell applications. In
this aspect, produced bipolar plates fulfill mechanical strength requirements. According to
calculated SEI values (Table 11) 3 wt. % wax addition decreased the work which was done
by the extruder from 0.64 kWh/kg to 41 kWh/kg compared to S-4 sample. Also figure 40
shows that bipolar plates with wax (PP-5 to PP-6), exhibited improved mold filling in injection
molding where produced plates have better edge-shapes. These observations can be
accepted as a proof for improved the flow behavior of composite.
-57-
Figure 40 Photo of bipolar plates after injection molding to visualize the effect of Montan wax
to the flow behavior of composites.
heterogeneous rate constants (k0). Cyclic voltammogram in figure 41 contains the data which
was obtained at 20 mV/s for the comparison of different bipolar plates. Individual results of
each sample at different scan rates were given in Appendix B.
As it was discussed in previous chapter, reversibility of electrochemical reactions depends on
several criteria. The deviation or change of the peak potentials at different scan rates is one
of those points which should be considered [88]. For the redox reaction between V4+ and V5+,
all samples showed this deviation with increased scan rate (Appendix B).
Anodic peak
Cathodic peak
Figure 41 Cyclic voltammetry results of PP-based bipolar plates at 20 mV/s scan rate (Effect
of MWCNT and Montan wax concentrations to the reversibility of vanadium redox reactions).
At high scan rates, if reaction kinetics is not fast enough, the concentration of the conversion
of chemical species cant be maintained as it is proposed in Nernst equation [88]. As a result,
the reaction starts to be irreversible. Another parameter is the separation of peak potentials
which should be smaller than 59 mV/(n), where n is the number of electrons which is
transferred during redox reactions. This is 1 in the case of our reactions. As it is seen in
table 14, all samples possess peak potential separations far from 59 mV which is the sign of
irreversibility. On the other hand, both conversion peaks are seen during the reactions which
-59-
makes the conclusion of irreversibility is quite unsure. This kind of reactions can be named
as quasi-irreversible.
However, only graphite filled sample (PP-1) exhibited high peak potential separation, the
addition of CNT, made the redox reactions more reversible. The higher electrical
conductivities and increased surface area of electrode due to CNTs were considered for the
explanation of this improvement.
Table 14 Cathodic and anodic peak potentials for V4+/V5+ side in cyclic voltammetry analysis
at 20 mV/s scan rate (PP-based bipolar plates).
Samples
PP-1
0.59
1.72
PP-4
0.78
1.42
PP-5
0.75
1.49
PP-6
0.83
1.37
Higher diffusion coefficient [89] and reaction rate constants (Table 15) are also indicators of
favorable surface of electrode for the conversion reactions of redox species. However, lowaddition of wax did not make a significant change (PP-5), increased amount of wax was
found to be not-promising for surface reactions. Especially, lower peak current densities of
PP-6 indicated that the reaction kinetics is slower compared to other bipolar plates. Lowviscous wax tends to flow easily and covers the conductive fillers which hinder their
electrochemical activity.
Table 15 Diffusion coefficients and heterogeneous rate constants of PP-based bipolar plates
for the redox reaction of V4+/V5+ (Calculated from data of cyclic voltammetry and equations
25 and 26).
Samples
Do (cm2/s)
ko (cm/s)
PP-1
5.89E-08
3.88E-04
PP-4
1.61E-07
4.64E-04
PP-5
9.34E-08
4.64E-04
PP-6
6.71E-08
4.12E-04
While the produced bipolar plates had a role for the redox reactions in (+) half-cell,
unfortunately, the conversion between V2+/V3+ was not reversible in any plate surface.
However, the samples were pre-treated at (+) potentials for the introduction of oxide groups,
-60-
still there was no peak for the redaction of V3+ to V2+. In the literature, this irreversible
behavior was found related with the surface preparation method. It was explained that
surface preparation with alumina powder had a negative effect on reversibility compared to
sandpaper usage [90]. However, in our study, the preparation was done by sandpaper; the
reason can be irreversible character of the reaction on the surface or the early start of
hydrogen evolution which hinders the redox reaction.
hydrogen and oxygen evolution starts on the surface. These reactions can cause
deterioration of electrode and bipolar plate surfaces and also have an impact on the total
balance of the battery electrolyte. To interpret Tafel plot, it should be known that at cathodic
branch if the current density is higher, it shows start of hydrogen evolution on the surface at
less negative potentials. The same is valid with less positive potentials for the oxygen
evolution in the anodic branch.
Polymer binders show good chemical stability compared to metals in acidic operation media
of VRFB. The introduction of carbon-based conductive fillers and additives may change the
stable structure of overall composite. Corrosion measurements of PP-based bipolar plate aim
to explain the effect of MWCNT and Montan wax addition on the electrochemical behavior of
composite material. The Tafel plot (Figure 42) shows that the current density of anodic and
cathodic sides first increased by addition of 3 wt. % MWCNT (PP-4) compared to PP-1 and
then increasing concentration of Montan wax decreased again the current densities
especially at anodic side. It is described in the literature that the lower the current density the
better the corrosion protection of the sample [91].
When conductive filler ratio is low (PP-1) fillers were better covered and shielded by polymer
against corrosive attacks. Also, added Montan wax was successful to wet and to make fillers
less susceptible against corrosion. Sample with 3 wt. % Montan wax (PP-6) had more
positive corrosion potential compared to PP-5 and PP-1 which is the indication of the
necessity of more energy or voltage to induce corrosion on this sample [92]. Anodic peak
currents for PP-4 and PP-5 which start at 0.4 V and 0.15 V respectively and seen as
stretched bump, can be attributed to the surface oxide layer formation due to hydroquinonequinone redox couples [93] or other carbon-based structures. If cathodic currents are
compared, sample PP-4 shows higher cathodic current which is the indication of early start of
hydrogen evaluation on the surface. Decreased corrosion stability of CNT-added samples
can be explained by surface grinding as well. Grinding leads to high surface area CNTs in
contact with the acidic medium. The carbon rich surface give rise to acidic carbon corrosion.
On the other hand, it is also known that CNT addition increases the real surface area which
is challenging to measure. If this effect is considered, cathodic and anodic current densities
of CNT added samples are expected to decrease simultaneously.
As a conclusion, all produced bipolar plates can be employed in a certain potential window in
which they are corrosion free but also the further effect of the oxide layer formation should be
examined with long-term cell-test and corrosion measurements.
-62-
Figure 43 Energy efficiency values of PP-based PP-4 (a, b and c) and Schunk bipolar plates
vs. current density.
-63-
Prepared cells with the produced bipolar plates showed higher energy efficiencies (> 80%) at
lower current densities. By increasing current densities, efficiency results tend to decrease
because the battery is forced to transfer more electrons at a unit time. This may cause the
increase of the internal resistances which will decrease the energy efficiencies. However,
current density of 75 mA/cm2 was achieved with the produced bipolar plates and obtained
energy efficiency values were comparable with commercial plate. The deviation between
three measurements could be originated from the diversity of the preparation of test cells.
Especially, small differences in the compression of the felt (normally 10 % compression) or
the changes in bipolar plate-copper plate contacts may influence the results. Nevertheless,
obtained energy efficiency values showed the charge-discharge consistency of bipolar
plates. Their capability of working at higher current densities is a sign for good electrical
conductivity especially in the through-plane direction.
Figure 44 Discharge power density values of PP-based PP-4 (a, b and c) and Schunk
bipolar plates vs. current density.
The reason why prepared cells could not operate up to 100 mA/cm2 can`t be described
exactly. The stability of membrane and graphite felt, the reaction behavior of redox species
-64-
and the conditions of bipolar plate surface at high current densities could have affected the
electron generation and transfer. If bipolar plate surface starts to be oxidized, the internal
resistivity increases which is described as ohmic resistance and given energy, to charge
the battery, is used to overcome this barrier meanwhile the overall energy efficiency
decreases.
Superior discharge power density values (Figure 44) are indicators of favorable surface
structure for vanadium redox reactions and increased reaction rates. As cell-tests were
performed under same conditions and with same cell-components, main difference
originated from bipolar plate itself. However, main redox reactions take place on graphite felt
(electrode) BPPs are still responsible of a part of those reactions due to similar carbon-based
structure. It can be concluded that surface grinding of polymer composites and higher
surface area of CNTs create more possibility for the conversion of vanadium species on the
surface of the produced bipolar plates. According to short-term cell-test results, if it is
considered that 50 mA/cm2 is the threshold value for the operation of VRFB, produced PPbased bipolar plate showed better performance compared to commercial plate.
-65-
4.2.
Polyphenylene sulfide is chemically stable polymer which will not be affected from the
corrosive attacks of acidic working media of VRFB. Its high melt flow rate was thought to be
effective solutions to avoid processing difficulties. PPS in powder form pre-mixed with fillers
prior to the melt-mixing in order to increase the homogeneity of the composite. Conductive
fillers were graphite and carbon nanotubes which were used for PP-based bipolar plates.
Titanate-based coupling agent was employed to improve the filler-polymer interaction which
leads to better filler dispersion and higher mechanical stability.
-66-
standard threshold for bipolar plate production. The electrical conductivity increases in both
directions by the substitution of graphite with CNTs and by addition of the coupling agent.
Samples from PPS-1 to PPS-3 prove the positive contribution of CNTs to the electrical
conductivity of highly-filled matrices which was discussed in previous chapters. CNTs act as
bridges between graphite particles due to their high aspect ratio [26]. This phenomenon was
also visualized by FE-SEM pictures of cryo-fractured samples. CNTs are seen as dispersed
in polymer matrix which fills the gap between graphite particles. It is also observed that
graphite particle size decreased during processing (Figure 46).
CNTs decrease the inter-particle resistance between the graphite particles. The relatively low
anisotropic behavior obtained in the electrical conductivity measurements can be attributed
to the low-anisotropy of the chosen graphite-type. The main challenge of using CNTs is the
necessity of breaking up their agglomerates; otherwise it is hard to benefit from their unique
electrical properties [94].
1 m
-67-
easily in the twin-screw extruder and injection molding machine while giving a chance for
better wetting of the conductive fillers by the polymer. In parallel to this effect, the decreased
overall viscosity helped the dispersion of fillers, especially CNTs, more uniformly inside the
matrix. As a result of this, the in-plane and through-plane electrical conductivities of the
composite PPS-6 reached up to 70 S/cm and 20 S/cm respectively. These values are almost
3 times higher compared to the sample PPS-3 which has the same conductive filler amount
but no titanate coupling agent. On the other hand, it should be noted that decreased viscosity
of composite means less applied shear by the extruder-screws. This may negatively affect
the electrical conductivities due to lower dispersion/distribution quality of conductive fillers. It
is concluded that high filling ratios (>70 wt. %) of composites shadows this effect and positive
contribution of coupling agent comes forward.
-68-
Samples
PPS wt. %
Graphite wt. %
CNT wt. %
Titanate wt. %
PPS-1
27.5
72.5
PPS-2
27.5
71.25
1.25
PPS-3
27.5
70
2.5
PPS-4
24.5
72.5
PPS-5
24.5
71.25
1.25
PPS-6
24.5
70
2.5
Figure 47 Flexural strength and modulus values of PPS-based bipolar plates with different
MWCNT and titanate coupling agent concentrations.
-69-
sample without CNTs (PPS-1) (Figure 48). Higher surface area of CNTs gives a chance for
more filler-polymer interaction which increases the composite viscosity. Beside increased
viscosity, Lafdi et al. showed that chemically or physically developed filler matrix interaction
is beneficial for the mechanical properties [86]. In this perspective, capillary rheometer
results correlate well with flexural strength values for the samples PPS-1 and PPS-3.
Apparent viscosity results showed that the contribution of titanate-based coupling agent to
composites was more like a lubricant effect than coupling of fillers and polymer matrix. By
addition of coupling agent to sample PPS-3, apparent viscosity decreased (PPS-6). It was
already discussed in the literature that bonding or linking between filler and polymer should
exhibit higher viscosity values due to hindered behavior of polymer chains [84]. In our case,
titanate-based additive may have decreased the resistance between filler-filler and fillerpolymer system which makes the flow of composite easier.
Figure 48 Capillary rheometer results of composite materials with different MWCNT and
titanate coupling agent concentrations at 320 C.
-70-
Tm (C)
Hm (J/g)
Hcold (J/g)
Tc (C)
Hc (J/g)
Xc (%)
pure-PPS
282.01
43.70
17.81
218.60
49.91
42.07
PPS-1
283.96
8.15
9.39
251.19
13.66
43.61
PPS-2
283.59
9.40
4.72
251.02
15.01
35.10
PPS-3
283.53
9.23
8.50
251.39
16.55
44.08
PPS-4
283.50
7.31
7.72
251.61
12.51
41.96
PPS-5
282.82
8.58
11.26
251.18
12.91
55.40
PPS-6
282.55
8.71
10.07
250.77
12.58
52.44
In the literature, it has been shown that the comparison of heat of fusion (Hm) and
crystallinity of composite (Xc) are useful indicators to study the interaction between the fillers
and the polymer [99]. Well-established polymer filler interaction restricts the movement of
polymer chains during the melting process and increases the necessary heat which should
be given to the sample. As the crystallinity of composite was calculated by using heat of
-71-
fusion it would be also possible to get indirect explanation about polymer-filler interaction by
interpreting crystallinity results.
The slight difference in the heat of fusion of the samples without additive can be attributed to
the measurement and interpolation sensitivity because their melting temperatures are also
close to each other. Unexpectedly, the samples with additive didnt show any increase in the
heat of fusion compared to their reference samples without additive. The reason could be the
high carbon content and purity of conductive fillers that were used in this study. In the
absence of functional groups like hydroxyl, carboxylic and so on, its not favorable to obtain
strong interaction between the filler and the polymer. DSC analysis is made with samples in
the weight of mg. Such low amounts can bring filler and polymer concentration deviations.
When small changes occur in the homogeneity of composite from specimen to specimen,
this could directly affect the calorimetric behavior. In this case, it should be also taken into
account that PPS-4, PPS-5 and PPS-6 have 3 wt. % lower PPS content than the other
samples. However, some of the samples showed higher crystallinity than pure PPS,
according to above-mentioned points, it would be scientifically more accurate to propose that
titanate-based coupling agent actually increased the filler-filler interaction which is the sign of
the higher electrical conductivities but did not bring improvement to filler-polymer interaction.
(30)
n=1, is the number of electrons transferred during redox reaction of V4+ and V5+
-72-
All bipolar plates can be classified as quasi-reversible for redox reaction between V4+ and
V5+. To evaluate the difference between reaction kinetics of bipolar plates, their diffusion
coefficients and heterogeneous rate constants were calculated and given in Table 18.
Anodic peak
Cathodic
Figure 49 Cyclic voltammetry results of PPS-based bipolar plates at 20 mV/s scan rate
(Effect of MWCNT and titanate coupling agent concentrations to the reversibility of vanadium
redox reactions).
Table 17 Cathodic and anodic peak potentials for V4+/V5+ side in cyclic voltammetry analysis
at 20 mV/s scan rate (PPS-based bipolar plates).
Samples
PPS-1
0.49
1.90
PPS-3
0.78
1.48
PPS-6
0.80
1.41
-73-
Do (cm2/s)
k0(cm/s)
PPS-1
2.46E-08
3.73E-04
PPS-3
7.92E-08
3.10E-04
PPS-6
9.13E-08
4.62E-04
The highest diffusion coefficient and rate constant can be found with sample PPS-6. Higher
rate constant indicates that following the application of potential, the equilibrium between
oxidation and reduction is re-established quickly. Diffusion coefficient as well as higher peak
currents indicates improved redox reactions on the surface of PPS-6 compared to other
composites. For the reactions of negative half-cell of the battery, oxidation peaks of V2+ to V3+
are seen at potentials around 0 V for all produced bipolar plates but the reduction peak is
insignificant. The reduction of V3+ could be masked by the hydrogen evaluation which starts
at closer potentials. According to general outcome of cyclic voltammogram, CNT-filled bipolar
plates with titanate-based coupling agent exhibit higher peak current densities. This can be
attributed to their higher electrical conductivity and to the high surface area of the CNT filler.
vanadium redox flow battery. Three independent cell-tests were operated from the same
composite (PPS-6), thats why terms PPS-6a, PPS-6b and PPS-6c were used. Cell-tests for
commercial material (Schunk) were also repeated three times with fresh bipolar plates but
this BPP possessed very low standard deviation. Energy efficiency values (Figure 51)
showed that at lower current densities, carbon nanotube filled bipolar plate (PPS-6) shows
performance as high as the commercial plate. Unfortunately, increasing current density
decreases energy efficiency due to increased ohmic loss inside the battery [82]. Ohmic loss
for VRFB is related to the contact resistance between the graphite electrode and the bipolar
plate, the individual electrical resistivity of the electrode and the bipolar plates and the ionic
resistivity of the proton exchange membrane and electrolyte [19]. If it is considered that the
only difference between the cells was the bipolar plate then ohmic loss can be related to the
intrinsic electrical resistivity of the plate and its contact resistance with the graphite electrode.
Figure 51 Energy efficiency values of PPS-based PPS-6 (a, b and c) and Schunk bipolar
plates vs. current density.
Its was shown that Schunk FU 4369 bipolar plate has lower through-plane electrical
resistivity than PPS-6 which facilitates electron transfer even at higher current densities
-76-
Figure 52 Discharge power density values of PPS-based PPS-6 (a, b and c) and Schunk
bipolar plates v. s. current density.
Figure 52 shows that the vanadium redox flow test cell which was prepared with PPS-6
bipolar plate reaches 50 mW/cm2 discharge power density which can be accepted as
minimum threshold value for VRFB and also possess higher discharge power densities
-77-
compared to Schunk bipolar plate. Higher power density can be attributed to elevated
reaction rate on the surface of electrode and also to higher discharge voltage value.
However, redox reactions occur on the porous electrode surface, still small amount of those
reactions may happen on the bipolar plate surface which was also shown by 3-electrode
setup analyses. As, porous graphite electrode was the same in both setups; the difference
may came from the surface properties of bipolar plates itself. Grinding of polymer layer could
make the surface of PPS-6 bipolar plate, more favorable compared to Schunk FU 4369 to
electrochemical changes. As a result, redox reactions of vanadium species may be
enhanced on carbon-fillers of produced bipolar plate.
Developed PP and PPS-based bipolar plates were characterized by electrical, mechanical,
rheological, electrochemical analysis and finally, chosen samples (PP-4 and PPS-6) were
compared with commercial bipolar plate in VRFB single-cell test. PPS-6 exhibited higher inplane and through-plane electrical conductivities than PP-4 at lower conductive filler
concentrations (72.5 wt. % total). This result can be explained by better dispersion of
conductive fillers via pre-mixing and improved filler-filler interaction by titanate-based
coupling agent. On the other hand, 22.5 % more binder concentration of PPS-6 compared to
PP-4 increased the mechanical strength of bipolar plate. Cyclic voltammetry experiments and
corrosion tests showed that PP-4 and PPS-6 have similar peak potential separations,
heterogeneous rate constants and corrosion current densities of anodic and cathodic
branches. These results can be attributed to the similar carbon structure in both composites
which are mainly responsible of surface reactions. Outcomes of single-cell tests exhibited
that PP-4 was able to operate at higher current densities, however its electrical conductivity
is lower than PPS-6. As previously discussed, it is possible to have deviations between celltests due to cell-assembly and the effect of internal resistances. Although, the reversibility of
electrochemical reactions and carbon corrosion of bipolar plates were found similar in
analysis which takes couple of hours, the electrochemical durability of PP-4 in cell-tests
which take 2 to 3 weeks, was considered as the main reason for its superior performance.
All in all, produced bipolar plates possessed promising results compared to commercial
bipolar plate. Especially at lower current densities either they were equally good as
commercial opponent or better with respect to energy efficiency and discharge power
density.
-78-
CONCLUSION
5. CONCLUSION
The literature sources and the commercial background of bipolar plates for fuel-cell
applications have longer history compared to redox flow batteries. As all-vanadium redox
flow batteries have different operation principles compared to fuel-cells, it is very important to
understand the effect of the battery media on the produced bipolar plates. Bipolar plates
should be developed by considering the electrical, mechanical and electrochemical
thresholds and to be evaluated in similar conditions to the battery atmosphere.
In this study, injection molding was chosen as the production method of bipolar plates. Its
advantages include lower dimensional tolerance, shorter cycle time and lower production
cost compared to compression molding. The parameters of a twin-screw co-rotating extruder
and an injection molding machine were examined to maintain proper processing of highlyfilled polymer composites, which was accepted as one of the main challenges for the
presented work. Polymer binders with high melt flow rates and different additives were
employed to decrease the melt flow resistance of composite. Carbon nanotubes were used
as a secondary filler in addition to low-anisotropic synthetic graphite, to obtain the desired
electrical conductivities in both through-plane and in-plane directions. The influence of the
concentration of carbon nanotubes and the additives on the mechanical properties was also
studied. This was found to be important for the application of bipolar plates because they
should be capable of withstanding the applied clamping pressures when battery stacks are
prepared. As redox reactions of VRFB are highly dependent on the surface properties and
the necessity of the chemical resistance originates from the acidic nature of the electrolyte
solution, the behavior and stability of bipolar plate surfaces were investigated with cyclic
voltammetry tests and corrosion measurements. Finally, a galvanostatic charge-discharge
analysis was carried out in a VRFB single-cell test and the results were used to forecast the
potential of these bipolar plates in future VRFB applications.
It was proved that carbon nanotubes are promising fillers for hybrid systems (graphite-CNT),
which had higher electrical conductivities than single-filler (only graphite) composites. For
both PP- and PPS-based composite plates, the substitution of graphite with the same
amount of CNTs improved the electrical properties drastically. Either the dispersion of CNTs
into the polymer matrix which is located between the graphite fillers or the decrease of fillerfiller contact resistances via bridging graphite particles gave rise to the production of
electrically-highly conductive polymer composites. However, the addition of Montan wax to
the PP matrix did not improve the electrical properties. Titanate-based coupling agent was
found to be an effective additive to improve overall composite conductivity. The in-plane
-79-
CONCLUSION
conductivity value of 70 wt. % graphite and 2.5 wt. % CNT filled PPS composite was
increased with the addition of 3 wt. % coupling agent from 28 S/cm to 67 S/cm. This outcome
was attributed to improved filler-filler interaction via the coupling agent.
Carbon nanotubes also had a positive influence on the mechanical properties of bipolar
plates due to their high mechanical strength. However, this could only be exploited where
proper CNT-matrix interaction was established. As CNTs were well-dispersed in the PP
matrix by the preparation of a CNT-PP masterbatch prior to addition of graphite into the
extruder, the composite with 78 wt. % graphite and 2 wt. % CNT showed almost 17 % higher
flexural strength (48 MPa) compared to sample without CNTs. However, samples with added
Montan wax showed improved the flow behavior of the composite as shown by the
decreased specific energy input of the extruder and also led to better mold filling in the
injection molding step. The mechanical properties were negatively affected when the
concentration reached up to 3 wt. %. A similar behavior was also observed in PPS
composites with an added coupling agent. It was concluded that these results could originate
from the decreased amount of polymer binder, the intrinsic brittle character of Montan wax or
the lubricating nature of the coupling agent.
Cyclic voltammetry tests were used to calculate the diffusion coefficient and the
heterogeneous reaction rate constants, which in turn were used to compare the reversibility
and the tendency of the surface of bipolar plates to the redox reactions of vanadium species.
The CNT filled composite plates showed comparatively more reversible reaction kinetics and
increased amount of conversions on their surface, which were shown by smaller peak
potential separations and higher peak current densities respectively. These observations
were also correlated closely with diffusion coefficients and reaction rate constants. However,
the main conversion of vanadium species takes place on the graphite felt. It was concluded
that the higher surface area of carbon nanotubes increased the probability of the redox
reactions compared to single graphite filled composites. Corrosion measurements showed
higher anodic and cathodic current densities for PPS bipolar plates with coupling agent and
PP bipolar plates without wax compared to their counter samples. However the interaction of
the titanate-based coupling agent with the acidic media was not completely understood and
the decreased PPS concentration may also have increased the chance of interaction of
conductive fillers with the electrolyte. In the case of PP-based bipolar plates, wax addition
could have supplied protection to conductive fillers which have a tendency to be oxidized
after exposure to acidic solutions.
-80-
CONCLUSION
The VRFB cell test for the evaluation of bipolar plates and the comparison of their
performance with that of commercial plates gave satisfactory results. The produced bipolar
plates showed higher energy efficiencies (>75 % for PP-based and >70 % for PPS-based) at
a current density of 50 mA/cm2 and superior discharge power densities (80 mW/cm2 at
75 mA/cm2) compared to the commercial product. Comparatively lower through-plane
electrical conductivity and the increased ohmic resistance due to high current densities were
found to be the main reasons for the deviation of energy-efficiency values for the produced
bipolar plates. In particular, better discharge power densities were attributed to the increased
surface area resulting from grinding of the polymer-rich skin layer, which favored the
vanadium redox reactions. These promising outcomes may raise the possibility of using
those bipolar plates in real applications and depending on further long-term tests and
electrochemical stability tests, the materials can be commercialized.
This study, which covered the production and the evaluation of highly-filled polymer
composites from the earliest stages, made an important contribution to our understanding of
bipolar plates. Graphite- and carbon-nanotube-filled thermoplastic-based bipolar plates were
successfully developed and tested, and it was clearly proved that the produced bipolar plates
have significant potential for use in VRFB applications.
-81-
SUMMARY OF ACHIEVEMENTS
6. SUMMARY OF ACHIEVEMENTS
The twin-screw extruder and injection molding were combined for the production of
bipolar plates. This cost and time effective production technique was optimized for
processing of highly-filled polymer composites.
The titanate coupling agent and Montan wax were proved as effective flow promoters
for highly-filled polyphenylene sulfide and polypropylene resins respectively. Titanate
coupling agent improved also the electrical conductivity of PPS-based composites.
The carbon nanotubes were found as promising secondary filler for graphite filled
thermoplastic composites to obtain superior electrical and mechanical properties
compared to single-filler systems.
-82-
FUTURE WORKS
7. FUTURE WORKS
The presented study covers the development and analysis of bipolar plates from the first
steps. The processing of highly-filled resins by extruders and injection molding machine is
already a challenging task. Due to viscosity or feeding problems of incorporating high amount
of fillers in to polymers, there is not much room to optimize process parameters. As it was
experienced, the concentration, dispersion and distribution of secondary filler -MWCNTs in
our study- is highly important for bipolar plate properties. The preparation of CNT-polymer
masterbatch is possible to be improved by using another screw design or feeding point in
extruder. On the other hand, the shortening/destructing effect of screw speed on CNTs
should be online or offline tested with microscopic images or with electrical conductivity
measurements to be sure that electron transfer on CNTs is not shattered.
When production advantages of injection molding (shorter cycle-life, low cost, low
dimensional tolerance) are combined with comparatively higher electrical conductivities of
compression molded bipolar plates; injection-compression molding method seems promising
approach to produce superior bipolar plates. The negative particle-orientation effect of
injection die especially on the through-plane electrical conductivity can be minimized with
compression step where fillers tend to randomly orient. Also by this technique, highly-filled
composites can be packed by compressing pressure. This avoids the necessity of high
injection and holding pressures which are one of the main challenges for the production of
bipolar plates.
The electrochemical stability in a battery media is a long-running property. However our celltests and corrosion measurements give valuable information about the behavior of the
produced bipolar plates in working media, it will be highly useful to design long-term cell-tests
which cover several months of cell-operation and to do more corrosion measurements by
taking specimens from different parts of bipolar plates. These tests would allow us to have
concrete ideas about the stability of our bipolar plates.
As bipolar plates are commercial materials and the contribution of their cost is crucial for
overall feasibility of vanadium redox flow applications; cost-calculation study is a good
opportunity to foresee the potential place of bipolar plates in the market. However such
studies require specific turnout (x number of BPPs produced/year) and established up-scale
production units, the calculation can be realized roughly to estimate the cost of the
production for internal purposes.
-83-
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redox
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Electrochemistry
LIST OF PUBLICATIONS
Carbon
Nanotube/Epoxy
Suspensions:
Influence
of
Processing
Parameters Proceedings of the society for the advanced materials and process
engineering (SAMPE) conference 2013, Paris, France. March, 2013.
7. Olowojoba G, Sathyanarayana S, Caglar B, Kiss-Pataki B, Mikonsaari I, Hbner C,
Elsner P. Influence of process parameters on the morphology, rheological and
dielectric
properties
suspensions
of
three-roll-milled
Polymer2013;54(1):188198.
(Peer-reviewed).
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multiwalled
DOI:
carbon
nanotube/epoxy
10.1016/j.polymer.2012.11.054
-93-
APPENDIX A:
-94-
-95-
-96-
-97-
-98-
APPENDIX C:
Time[h]
DataSet
Line
Command
U[V]
I[A]
Ah[Ah]
Wh[Wh]
0.0213
191
131
Charge
0.0526
0.99853
0.0000
0.0000
0.0379
192
131
Charge
0.3179
0.99975
0.0167
0.0052
0.0546
193
131
Charge
0.3211
0.99975
0.0333
0.0105
0.0713
194
131
Charge
0.3240
0.99975
0.0500
0.0159
0.0879
195
131
Charge
0.3263
0.99975
0.0666
0.0213
0.1046
196
131
Charge
0.3287
0.99944
0.0833
0.0267
0.1213
197
131
Charge
0.3312
0.99975
0.1000
0.0322
0.1379
198
131
Charge
0.3344
0.99975
0.1166
0.0378
0.1546
199
131
Charge
0.3365
0.99975
0.1333
0.0434
3.6921
414
132
Pause
1.5330
0.00000
3.6697
4.0212
3.6921
415
132
Pause
1.5335
0.00000
3.6697
4.0212
3.7005
416
132
Pause
1.5281
0.00000
3.6697
4.0212
3.7088
417
132
Pause
1.5279
0.00000
3.6697
4.0212
3.7089
418
133
discharge
1.5289
0.01184
3.6697
4.0212
3.7089
419
133
discharge
1.4617
-0.97364
3.6697
4.0212
3.7255
420
133
discharge
1.4449
-1.00005
3.6530
3.9971
3.7422
421
133
discharge
1.4388
-1.00005
3.6364
3.9731
3.7589
422
133
discharge
1.4339
-1.00005
3.6197
3.9491
3.7755
423
133
discharge
1.4295
-1.00005
3.6030
3.9253
3.7922
424
133
discharge
1.4258
-1.00005
3.5864
3.9015
3.8089
425
133
discharge
1.4231
-1.00005
3.5697
3.8777
3.8255
426
133
discharge
1.4201
-1.00005
3.5530
3.8540
3.8422
427
133
discharge
1.4176
-1.00005
3.5364
3.8304
-99-
APPENDIX D:
Name
S-2_79G-1CNT-1
S-2_79G-1CNT-2
S-2_79G-1CNT-3
S-2_79G-1CNT-4
S-2_79G-1CNT-V1
S-2_79G-1CNT-V2
fM
43.10
44.26
42.33
44.37
47.02
49.19
MW
med
MINI
MAXI
s
s2
V
ANZ
fM
45.05
44.31
42.33
49.19
2.58
6.66
5.73
6.00
fM
0.34
0.37
0.36
0.39
0.35
0.36
fM
0.36
0.36
0.34
0.39
0.02
0.00
4.76
6.00
s
0.498
0.517
0.504
0.557
0.517
0.509
b
10.0
10.0
10.0
10.0
10.0
10.0
s
0.52
0.51
0.50
0.56
0.02
0.00
4.05
6.00
b
10.0
10.0
10.0
10.0
0.00
0.00
0.00
6.00
-100-
h
3.0
3.0
3.0
3.0
3.0
3.0
d1
10.0
10.0
10.0
10.0
10.0
10.0
d2
10.0
10.0
10.0
10.0
10.0
10.0
Lv
51.0
51.0
51.0
51.0
51.0
51.0
h
3.0
3.0
3.0
3.0
0.00
0.00
0.00
6.00
d1
10.0
10.0
10.0
10.0
0.00
0.00
0.00
6.00
d2
10.0
10.0
10.0
10.0
0.00
0.00
0.00
6.00
Lv
51.0
51.0
51.0
51.0
0.00
0.00
0.00
6.00
APPENDIX E:
-101-