DEVELOPMENT OF ASYMMETRIC POLYSULFONE MEMBRANE FOR

THE APPLICATION IN TROPICALIZED LEAD ACID BATTERY

WAN AHMAD HAFIZ BIN WAN HASSAN

A thesis submitted in fulfilment of the

requirements for the award of the degree of
Master of Engineering (Gas)

Faculty of Chemical and Natural Resources Engineering

Universiti Teknologi Malaysia

SEPTEMBER 2004
 UNIVERSITI TEKNOLOGI MALAYSIA
PSZ 19:16 (PIND. 1/97)
BORANG PENGESAHAN STATUS TESIS‹
JUDUL : DEVELOPMENT OF ASYMMETRIC POLYSULFONE MEMBRANE
FOR THE APPLICATION IN TROPICALIZED LEAD ACID BATTERY

SESI PENGAJIAN: 2003/2004-II

Saya WAN AHMAD HAFIZ BIN WAN HASSAN

(HURUF BESAR)
mengaku membenarkan tesis (PSM/Sarjana/Doktor Falsafah)* disimpan di Perpustakaan Universiti
Teknologi Malaysia dengan syarat-syarat kegunaan seperti berikut :

1. Tesis adalah hakmilih Universiti Teknologi Malaysia.

2. Perpustakaan Universiti Teknologi Malaysia dibenarkan membuat salinan untuk tujuan
pengajian sahaja.
3. Perpustakaan dibenarkan membuat salinan tesis ini sebagai bahan pertukaran di antara institusi
pengajian tinggi.
4. ** Sila tandakan (9)

SULIT (Mengandungi maklumat yang berdarjah keselamatan atau kepentingan

Malaysia seperti yang termaktub di dalam AKTA RAHSIA RASMI
1972)

9 TERHAD (Mengandungi maklumat TERHAD yang telah ditentukan oleh

organisasi/badan di mana penyelidikan dijalankan).

TIDAK TERHAD

Disahkan oleh

(TANDATANGAN PENULIS) (TANDATANGAN PENYELIA)

Alamat Tetap: Lot 1553, Kampung Gong

Prof. Dr. Ahmad Fauzi bin Ismail
Maksom, Alor Lintah,
Nama Peyelia
22000 Jertih
Terengganu Darul Iman.

Tarikh: 25th September 2004 Tarikh: 25th September 2004

CATATAN : * Potong yang tidak berkenaan.

** Jika tesis ini SULIT atau TERHAD, sila lampirkan surat daripada pihak berkuasa/organisasi
berkenaan dengan menyatakan sekali sebab dan tempoh tesis ini perlu dikelaskan
sebagai SULIT atau TERHAD.
‹ Tesis dimaksudkan sebagai tesis bagi Ijazah Doktor Falsafah dan Sarjana secara
penyelidikan, atau disertai bagi pengajian secara kerja kursus dan penyelidikan, atau
Laporan Projek Sarjana Muda (PSM).
 25th September 2004
Librarian
Perpustakaan Sultanah Zanariah
Universiti Teknologi Malaysia, Skudai
Johor Darul Takzim

Sir,

CLASSIFICATION OF THESIS AS RESTRICTED

MASTER IN ENGINEERING (GAS) THESIS
DEVELOPMENT OF ASYMMETRIC POLYSULFONE MEMBRANE FOR THE
APPLICATION IN TROPICALIZED LEAD ACID BATTERY (AUTHOR: WAN
AHMAD HAFIZ BIN WAN HASSAN)

Please be informed that the above mentioned thesis entitled “DEVELOPMENT OF

ASYMMETRIC POLYSULFONE MEMBRANE FOR THE APPLICATION IN
TROPICALIZED LEAD ACID BATTERY ” be classified as RESTRICTED for a
period of three (3) years from the date of this letter. The reasons for this
classification are

(i) The materials of this research are advanced discovery that is considered
new in Malaysia.
(ii) The materials of this research are in the process of patent filing.
(iii) The materials of this research possess high commercial value and
potential.

Thank you.

Sincerely yours,

PROF. DR. AHMAD FAUZI ISMAIL

Gas Engineering Department
Faculty of Chemical and Natural Resources Engineering
Universiti Teknologi Malaysia
Ext. 35592; email: afauzi@utm.my
 “I hereby declare that I have read this thesis and in my opinion
this thesis is sufficient in term of scope and quality for the award of
degree of Master of Engineering (Gas)”.

Signature :
Name of Supervisor : Prof. Dr. Ahmad Fauzi Bin Ismail
Date : September 25th, 2004
BAHAGIAN A – Pengesahan Kerjasama*

Adalah disahkan bahawa projek penyelidikan tesis ini telah dilaksanakan melalui
kerjasama antara _____________________ dengan _______________________

Disahkan oleh: -

Tandatangan : ……………………………. Tarikh : ……………………..

Nama :……………………………..
Jawatan :……………………………..
(Cop rasmi)

* Jika penyediaan tesis/projek melibatkan kerjasama

BAHAGIAN B – Untuk Kegunaan Pejabat Sekolah Pengajian Siswazah (SPS)

Tesis ini telah diperiksa dan diakui oleh:

Nama dan Alamat : Prof. Madya Dr. Mohamed Kheireddine Aroua

Pemeriksa Luar Jabatan Kejuruteraan Kimia,
Fakulti Kejuruteraan, Universiti Malaya,
50603 Kuala Lumpur

Nama dan Alamat : Prof. Madya Dr. Rahmat Mohsin

Pemeriksa Dalam I Jabatan Kejuruteraan Gas,
Fakulti Kejuruteraan Kimia dan Kejuruteraan
Sumber Asli, Universiti Teknologi Malaysia,
81310 Skudai, Johor Darul Takzim

Pemeriksa Dalam II :

Nama Penyelia lain :

(jika ada)

Disahkan oleh Timbalan Pendaftar di SPS:

Tandatangan : ............................................... Tarikh : ..................................

Nama : GANESAN A/L ANDIMUTHU

 ii

I declare that this thesis entitled “Development of Asymmetric Polysulfone

Membrane for the Application in Tropicalized Lead Acid Battery” is the result of my
own research except as cited in the references. The thesis has not been accepted for
any degree and is not currently submitted in candidature of any other degree.

Signature :
Name of Author : Wan Ahmad Hafiz bin Wan Hassan
Date : September 25th, 2004
 iii

Dedicated to ma and abah,

you are the wind beneath my wings.
 iv

ACKNOWLEDGEMENT

It is indeed a pleasure for me to express my appreciation and gratefulness to

all those people and organizations who have contributed to this study.

First and foremost, I would like to show my sincerest gratitude to my

supervisor, Professor Dr. Ahmad Fauzi Ismail for his supervision, motivation,
encouragement and insightful comments throughout the duration of this study. His
mentoring led to my growth and development in areas that extend beyond science.

Special thanks also goes to all of the Membrane Research Unit (MRU) team
members for their continuous assistance, encouragement and moral support
throughout my study especially to the lecturers, research officers as well as the
postgraduate students. They have been like none other than the second family to me.
Thank you guys.

I also would like to express my gratefulness to Universiti Teknologi Malaysia

(UTM) for generously awarding me the financial support through its industrial
technology development (PTP) scholarship.

To my beloved family, thank you for the continuous support and advice
during this study. My appreciation also goes to all the people who have contributed,
directly or indirectly towards the establishment of this study. Above all, I thank Allah
the Almighty for His grace, mercy and guidance throughout my life.
 v

ABSTRACT

The objectives of this research are to develop asymmetric polysulfone membrane for
the application in lead acid battery and to investigate the effect of fabrication
conditions on the performance of the membrane-assisted lead acid battery and its
morphology. The function of the membrane is to prevent electrolyte losses by
minimizing the rate of vaporized electrolyte disposed into the atmosphere. Lead acid
batteries in tropical countries normally face the problem of water decomposition,
caused by the combine factors of the charge-discharge process and the heat
accumulation caused by hot tropical climate and heat generated from engine
compartment. This causes unpleasant setbacks such as corrosion of parts inside the
car bonnet and having to top up the electrolyte whenever it reduces. The membrane
will be functioning as a water-retaining device when applied onto the battery vent
holes by delaying the permeation of hydrogen, oxygen and traces of water vapor
during charge-discharge processes. Effects of polymer concentration and casting
shear rate were investigated in order to produce the most suitable membrane. The
prepared membranes were tested on lead acid battery during charging process to
evaluate their performance in retaining electrolyte as well as minimizing pressure
build up. Results showed that decreasing polymer concentration in casting solution
decreases compactness of the polymer matrixes in the membrane structure, therefore
decreases pressure build-up in battery casing during charging process. Increasing
shear rate resulted in a decrease of skin layer thickness and in turn, lowers the
pressure build-up during battery charging process. Membrane with 13 wt/wt %
Polysulfone (PSF) and 87 wt/wt % of N-N-dimethylformamide (DMF) and at shear
rate of about 233.33 s-1 was found to be the most suitable membrane to be applied on
the maintenance free battery. At room temperature, the electrolyte losses of a
membrane-assisted lead acid battery is about 6.67 grams per hour, while for
conventional battery is about 26.67 grams per hour. During charging process at
temperature about 80oC, membrane assisted lead acid battery can save up to 40% of
electrolyte losses compared to the conventional battery. Membrane characterization
using Scanning Electron Microscopy (SEM) and Raman Spectroscopy were also
carried out to investigate the structure of the membrane and to differentiate the
components of the permeated electrolytes from both membrane-assisted and
conventional batteries. Based on SEM images, it can be observed that the membrane
cast at the shear rate of about 233.33s-1 has the most suitable skin layer thickness.
The membrane is permeable enough to minimize the pressure build up inside the
battery and sufficiently selective enough to minimize the electrolyte losses. In the
Raman spectrometer analysis, it was proven that with the application of membrane,
the intensities of hydrogen and oxygen gases in the permeated vaporized electrolyte
had been suppressed to about 50-60% and 10-30% respectively. Therefore this
research is considered as a revolutionary step in the establishing a new age of
maintenance free battery with the application of membrane technology into lead acid
battery.
 vi

ABSTRAK

Objektif penyelidikan ini adalah untuk membangun membran polisulfona asimetrik

bagi aplikasi pada bateri asid plumbum dan mengkaji kesan keadaan pembikinan
terhadap prestasi bateri asid plumbum berbantu membran serta morfologinya .
Fungsi membran adalah untuk menghalang kehilangan elektrolit dengan
meminimumkan kadar pembebasan elektrolit teruwap ke atmosfera. Bateri asid
plumbum di negara tropikal sering mengalami masalah kehilangan air yang terurai
disebabkan oleh gabungan faktor proses cas-nyahcas dan pengumpulan haba
disebabkan oleh cuaca panas tropika serta haba terjana daripada bahagian enjin. Ini
mengakibatkan kesan sampingan seperti karatan alatan bahagian enjin serta terpaksa
menambah air suling apabila takat elektrolit berkurang. Membran ini akan berfungsi
sebagai peralatan penahan air apabila digunakan pada lubang bateri dengan
memperlahankan kebolehtelapan hidrogen, oksigen dan wap air ketika berlakunya
proses cas-nyahcas. Kesan kepekatan polimer serta kadar tuangan telah dikaji bagi
menghasilkan membran yang paling sesuai untuk tujuan ini. Membran yang terhasil
diuji pada bateri asid plumbum ketika proses pengecasan bagi menilai prestasi
membran menghalang kehilangan air serta mengurangkan peningkatan tekanan
dalaman bateri. Keputusan bagi ujikaji menunjukkan pengurangan kepekatan polimer
dalam larutan tuangan mengurangkan kepadatan matriks polimer dalam struktur
membran, oleh itu menurunkan peningkatan tekanan dalaman bateri ketika proses
pengecasan. Peningkatan kadar tuangan menyebabkan pengurangan ketebalan
lapisan kulit membran dan ini mengakibatkan pengurangan peningkatan tekanan
dalaman bateri. Membran dengan formulasi 13 berat/berat % polisulfona (PSF) dan
87 berat/berat % N-N-dimetilformamida (DMF) dan kadar tuangan sebanyak 233.33
s-1 didapati paling sesuai bagi aplikasi pada bateri bebas penyelenggaraan. Pada suhu
bilik, kehilangan air bagi bateri berbantu membran adalah sebanyak 6.67 gram per
jam manakala bagi bateri konvensional adalah sebanyak 26.67 gram per jam. Ketika
proses pengecasan pada suhu 80oC pula, bateri berbantu membran mampu
mengurangkan 40% daripada kehilangan air berbanding dengan bateri konvensional.
Pencirian membran menggunakan kemikroskopan elektron imbasan (SEM) dan
spektroskopi Raman juga telah dijalankan bagi mengkaji struktur membran serta
membandingkan komponen elektrolit teruwap dari bateri berbantu membran dan
konvensional. Berdasarkan imej SEM, didapati membran yang dituang pada kadar
tuangan sebanyak 233.33 s-1 menghasilkan ketebalan lapisan kulit paling sesuai.
Membran ini cukup telap untuk meminimumkan peningkatan tekanan dalaman bateri
serta mempunyai kememilihan yang sesuai untuk mengurangkan kehilangan air.
Analisis Raman pula telah membuktikan bahawa dengan aplikasi membran,
keamatan gas hidrogen and oksigen dalam elektrolit teruwap telah dapat dikurangkan
sebanyak 50-60% dan 10-30%. Oleh itu, penyelidikan ini dianggap sebagai langkah
revolusi dalam pembangunan bateri bebas penyelenggaraan dengan penggunaan
teknologi membran dalam bateri asid plumbum.
 vii

TABLE OF CONTENTS

CHAPTER PAGE
TITLE PAGE i
DECLARATION ii
DEDICATION iii
ACKNOWLEDGEMENT iv
ABSTRACT v
ABSTRAK vi
TABLE OF CONTENTS vii
LIST OF FIGURES xii
LIST OF TABLES xv
NOMENCLATURE xvi
LIST OF APPENDICCES xvii

1 INTRODUCTION

1.1 Lead Acid Battery

1.1.1 History of Lead Acid Battery Development 1
1.1.2 Lead/acid battery: The General Chemistry 1
1.1.2.1 Operation of a Lead Acid Battery Cell During
Discharge 3
1.1.2.2 Operation of a Lead Acid Battery Cell During
Charge/Recharge 4
1.1.3 Types and Characteristics of Lead Acid Battery 5
1.1.3.1 Starting, Lighting and Ignition (SLI) Battery 6
1.2 Malaysian Motor Trade Scenario 7
 viii

1.3 Malaysian Battery Market 7

1.4 Influence of Water Decomposition In Lead Acid Batteries 9
1.5 Problem Statement 11
1.6 Research Objectives 12
1.7 Scopes of Study 13

2 LITERATURE REVIEW

2.1 Membrane Separation Technology

2.1.1 Definition of Membrane Separation Processes 14
2.2 Membrane Separation Process Types
2.2.1 Development of Gas Separation Membrane 16
2.2.2 The Principles of Gas Permeation 18
2.3 Solution Diffusion Mechanism 22
2.4 Asymmetric Membranes 24
2.4.1 Formation of Asymmetric Membranes 26
2.4.1.1 Composite Structure Process 26
2.4.1.2 Phase Inversion Process 27
2.5 Types of Phase Inversion Processes 28
2.5.1 Dry-wet Phase Inversion 28
2.6 Membrane Formation Processes 30
2.6.1 Phase Inversion Factors 31
2.6.2 Rheological Factors 32
2.7 Previous Methods in Overcoming Water Losses 34
In Lead Acid Batteries
2.7.1 Valve Regulated Lead Acid Batteries with 35
Immobilized Electrolyte
2.7.2 Suppression of Hydrogen Evolution and Oxygen 38
Reduction Effect
2.7.3 The Use of Additional Electrolyte Volume in 39
Lead Acid Battery
 ix

3 RESEARCH METHODOLOGY

3.1 Research Design 41

3.2 Experimental Methods 43
3.2.1 Membrane Preparation 43
3.2.1.1 Materials 43
3.2.1.2 Casting Solution Preparation 44
3.2.1.3 Asymmetric Membrane Preparation 45
3.3 Membrane Permeation Cell Test 48
3.4 Lead Acid Battery Charging Simulation Test 49
3.4.1 Preliminary Screening Membrane-assisted 49
Lead Acid Battery Charging Test
3.4.2 Membrane-assisted Lead Acid Battery Charging Test 50
3.4.3 Membrane-assisted Lead Acid Battery Charging Test 52
With Heat Supply
3.5 Vaporized Electrolyte Composition Measurement Using Raman 53
Spectroscopy
3.5.1 Selection of Analytical Instrument 53
3.5.2 Raman Spectrometer 54
3.5.3 Experiment Set-up 55
3.6 Scanning Electron Microscopy (SEM) Analysis 56

4 RESULTS AND DISCUSSION

4.1 Analysis on The Resultant Membrane 57

4.1.1 Gas Permeation Test Results 57
4.1.2 Preliminary Screening Membrane-assisted 59
Lead Acid Battery Charging Test Analysis
4.1.2.1 Effect of Membrane Formulation on The 60
Performance of Membrane in Retaining
Electrolyte Level
 x

4.1.3 Membrane-Assisted Lead Acid Battery 62

Charging Test Analysis
4.1.3.1 Effect of Shear Rate on The Performance of 64
Asymmetric Polysulfone Membrane in
Minimizing Electrolyte Losses
4.1.3.2 Effect of Shear Rate on The Performance of 67
Asymmetric Polysulfone Membrane in Minimizing
Pressure Build Up

4.1.4 Membrane-Assisted Lead Acid Battery Charging Test 73

with Heat Supply Analysis
4.1.4.1 Effect of Water Bath Temperature on Electrolyte 73
Losses of Lead Acid Battery During Charging
4.1.4.2 Effect of Water Bath Temperature on Pressure 75
Build Up in Lead Acid Battery During Charging
4.2 Vaporized Electrolyte Composition Measurement Using Raman 78
Spectroscopy
4.3 Membrane Characterization Using Scanning Electron 84
Microscopy (SEM)
4.3.1 Effect of Polymer Concentration on Membrane 84
Morphology
4.3.2 Effect of Shear Rate on Membrane 87
Morphology

5 CONCLUSIONS AND FUTURE WORK

5.1 Conclusions 90
5.2 Recommendations for Future Work 92

REFERENCES 94
 xi

PUBLICATIONS 102

APPENDICES 103
Appendix A-B
 xii

LIST OF FIGURES

FIGURE NO. TITLE PAGE

1.1(a) Cell operation during charge state 3

1.1(b) Cell operation during charge/recharge 4
2.1 Membrane-based gas separation process 18
2.2 Mechanism for gas separation using (a) porous 20
membrane and (b) nonporous membrane
2.3 An asymmetric membrane structure 25
2.4 Steps involved in the formation of asymmetric flat 29
sheet membranes using dry/wet phase separation
process
2.5 Cross section of a recombinator 34
2.6 Valve regulated lead acid battery with immobilized 36
electrolyte
3.1 Research design 42
3.2 Monomer unit of a Polysulfone (PSF) 44
3.3 Apparatus for polymer solution preparation 45
3.4 Pneumatically-controlled casting machine 46
3.5 Gas permeability testing rig 48
3.6 Schematic drawing and cross section of battery cap 51
3.7 Membrane-assisted lead acid battery charging test 51
3.8 Membrane-assisted lead acid battery charging test with 53
heat supply
3.9 Vaporized electrolyte composition measurement with 56
Raman Spectrometer
4.1 Permeation rate for five different membranes 59
 xiii

4.2 Effect of shear rate on the performance of asymmetric 66

Polysulfone membrane in minimizing electrolyte losses
4.3 Minimization of electrolyte losses with comparison to 67
the conventional lead acid battery
4.4 Effect of casting shear rate on the pressure build up 69
inside battery casing
4.5 Effect of casting shear rate on the flow rate profile of 71
vaporized electrolyte
4.6 Total electrolyte losses during membrane-assisted lead 74
acid battery charging test with heat supply
4.7 Minimization of electrolyte losses with comparison to 75
the conventional lead acid battery
4.8 Effect of water bath temperature on pressure build up in 76
a lead acid battery during charging
4.9 Effect of water bath temperature on the flow rate profile 77
of vaporized electrolyte
4.10(a) Raman spectrum for vaporized electrolyte 80
(conventional battery) sample taken at 100 minutes of
charging process
4.10(b) Raman spectrum for vaporized electrolyte (membrane- 80
assisted battery) sample taken at 120 minutes of
charging process
4.11 Overall hydrogen intensities for vaporized electrolyte 82
gas samples for conventional and membrane-assisted
lead acid batteries.
4.12 Overall oxygen intensities for vaporized electrolyte gas 83
samples for conventional and membrane-assisted lead
acid batteries
4.13 Scanning electron micrographs of membrane cross 86
section at different polymer concentration
4.14 Scanning electron micrographs of membrane cross 89
section at different shear rate
 xiv

LIST OF TABLES

TABLE NO. TITLE PAGE

1.1 Types, characteristics and applications of lead acid 6

battery
1.2 Characteristics of starting, lighting and ignition (SLI) 7
battery
1.3 Losses of water in the lead acid battery 11
3.1 Comparison on Raman Spectrometer and Gas 54
Chromatography
4.1 Casting solution formulations 58
4.2 Preliminary screening of membrane for membrane- 61
assisted lead acid battery test result
4.3 GS6 membranes prepared with different shear rate 63
4.4 Total and average rate of electrolyte losses during 65
membrane-assisted lead acid battery charging test
 xv

NOMENCLATURE

A - Surface area of flat sheet membrane (m2)

C - Concentration (cm3(STP)/cm3)
D - Diffusion coefficient (cm2/s)
I Current (Ampere)
k - Mass transfer coefficient
l - Membrane thickness (cm)
lr - Pore length (cm)
p - Pressure (cmHg)
po - Atmospheric pressure (cmHg)
p - Mean pressure (cmHg)

∆p - Transmembrane pressure (bar)

P - Permeability coefficient (cm3(STP).cm/cm2.s.cmHg)
P /l - Pressure-normalized flux or permeability
(cm3(STP)/cm2.s.cmHg)
Q - Volumetric flow rate (L/h)
S - Solubility coefficient (cm3(STP)/cm3.cmHg)
T - Temperature (K)
V - Permeation velocity of product
α - Selectivity (dimensionless)
γ& - Shear rate (s-1)
i - Component i
j - Component j
T - Total
 xvi

LIST OF APPENDICES

APPENDIX PAGE

A Membrane-assisted Lead Acid Battery Charging Test 103

Results
B Raman Spectrum for Vaporized Electrolyte During 116
Charging Process
 CHAPTER 1

INTRODUCTION

1.1 Lead Acid Battery

1.1.1 History of Lead Acid Battery Development

Practical lead acid batteries began with the research and inventions of
Raymond Gaston Plante in 1860. In Plante’s fabrication method, two long strips of
lead foil and intermediate layers of coarse cloth were spirally wound and immersed
in a solution of about 10% sulfuric acid. The early Plante cell had little capacity,
since the amount of stored energy depended on the corrosion of one lead foil to lead
dioxide to form the positive active material, and similarly the negative electrode was
formed by roughening of the foil (on cycling) to form an extended surface. But since
then, there had been so much improvement on the traditional Plante cell, on the
aspect of it’s design, capacity, and even practicality, in order to suit so many
applications related to the portable power source.

1.1.2 Lead Acid Battery: The General Chemistry

A lead acid battery is a device, which converts the chemical energy contained
in its active materials directly into electric by means of an electrochemical oxidation-
reduction (redox) reaction (Linden, 1995). This type of reaction involves the transfer
of ions from one material to another through an electric circuit. A cell, the basic
electrochemical unit, is a circuit where ions are transferred during charging and
discharging state. Each cell must consists of three major components such as:
 2

i) The anode or the negative electrode

The reducing or fuel electrode, which gives up electrons to the external circuit and is
oxidized during the electrochemical reaction.

ii) The cathode or the positive electrode

The oxidizing electrode, which accepts electrons from the external circuit and is
reduced during the electrochemical reaction.

iii) The electrolyte

The ionic conductor that provides the medium for transfer of electrons, as ions,
inside the cell between the cathode and anode. The electrolyte is typically a liquid,
such as water or other solvents, with dissolved salts, acids or alkalis, to impart ionic
conductivity. Some batteries use solid electrolytes, which are ionic conductors at the
operating temperature of the cell.

Physically the anode and cathode are electronically isolated in the cell to
prevent internal short-circuiting, but are surrounded by the electrolyte. In practical
cell designs a separator material is used to separate the anode and the cathode
electrodes mechanically. The separator, however, is permeable to the electrolyte in
order to maintain the desired ionic conductivity. In some cases the electrolyte is
immobilized for a non-spill design. Electrically conducting grid structures or
materials may also be added to the electrodes to reduce internal resistance.
 3

1.1.2.1 Operation of a Lead Acid Battery Cell During Discharge

The operation of a cell during discharge is shown schematically in Figure

1.1(a). When the cell is connected to an external load, electrons flow from the anode,
which is oxidized, through the external load to the cathode, where the electrons are
accepted and the cathode material is reduced. The electric circuit is completed in the
electrolyte by the flow of anions (negative ions) and cations (positive ions) to the
anode and cathode, respectively. The discharge reaction can be written as below,
whereas lead (Pb) as the anode material and lead oxide (PbO2) as the cathode
material. And finally we get the overall reaction for discharge as in Equation 1.3:

At negative electrode: anodic reaction (oxidation, loss of electrons)

Pb → Pb2+ + 2e (1.1)
At positive electrode: cathodic reaction (reduction, gain of electrons)

PbO2 + 4H+ + 2e → Pb2+ + 2H2O (1.2)

Overall reaction: (discharge)

Pb + PbO2 + 2H2SO4 → 2PbSO4 + 2H2O (1.3)

Electron Flow

LOAD
_ +
C
A A
N T
O H
Flow of cations
D O
E D
E
Flow of anions

Figure 1.1(a) Cell operation during discharge state

 4

1.1.2.2 Operation of a Lead Acid Battery Cell During Charge/Recharging

During recharge of a rechargeable secondary battery such as lead acid

battery, the current flow is reversed and oxidation takes place at the positive
electrode and reduction at the negative electrode, as shown in Figure 1.1(b). As the
anode is, by definition, the electrode at which oxidation occurs and the cathode the
one where reduction takes place, the positive electrode is now the anode and the
negative is the cathode.

At negative electrode: cathodic reaction (reduction, gain of electrons)

Pb2+ + 2e → Pb (1.4)

At positive electrode: anodic reaction (oxidation, loss of electrons)

Pb2+ + 2H2O → PbO2 + 4H+ + 2e (1.5)

Overall reaction: (charge/ recharge)

2PbSO4 + 2H2O → Pb + PbO2 + 2H2SO4 (1.6)

_ Electron flow
+
DC Power
_ C +
A A
T N
H Flow of anions O
O D
D E
E
Flow of cations

Figure 1.1 (b) Cell Operation During Charge/Recharge

 5

Nevertheless there is another side reaction that occurs during charging of lead
acid battery instead of the primary reduction-oxidation (redox) reaction as mentioned
above. During the final stage of charging, whenever the cell nearly approaches full
charge, or when most of the lead sulfate (PbSO4) has been converted into lead (Pb)
and lead oxide (PbO2 ), the cell voltage will become greater than the gassing voltage.
At this point and onwards, overcharge reactions occurs, and as a result, hydrogen and
oxygen is produced at anode and cathode. The reaction, known as the gassing
reaction is shown as below:

At negative electrode

2H+ + 2e → H2 (1.7)
At positive electrode
1
H2O → O2 + 2H+ + 2e (1.8)
2
Overall reaction
1
H2O → H2 + O2 (1.9)
2

This gassing reaction, however, is said by battery researchers to be the main

factor to the water decomposition in lead acid batteries.

1.1.3 Types and Characteristics of Lead Acid Batteries

Lead acid batteries were designed in many configurations to suit many

applications that require portable and dependable power source. As listed in Table
1.1, there are four main types of lead acid batteries and by far, the automotive
starting, lighting and ignition (SLI) type is the most popular and the widest in use.
The factor that causes its popularity is due to the blooming of the motor industry,
which apparently translates to the demand of SLI batteries. In this research work, the
emphasize has been given to SLI batteries since it is the most commercialized type
and has the most advancement in its design and technology. Most significant of the
 6

Table 1.1: Types, characteristics and applications of lead acid battery (Linden, 1995)

Type Characteristics Applications

Automotive Popular, low cost secondary
Starting, lighting battery, moderate specific-
and ignition (SLI) energy, high rate, and low
temperature performance;
Traction (motive Designed for deep 6-9 hour
power) discharge, cycling service
Stationary Designed for standby float
service, long life, VRLA
designs
Portable Sealed, maintenance free, low Portable tools, small
cost good float capability,
moderate cycle life
Automotive SLI, golf
carts, lawn mowers,
tractors, aircraft, marine
Industrial trucks, material
handling, electric vehicles,
special types for
submarine power
Emergency power,
utilities, telephone, UPS,
load leveling, energy
storage
applications and devices,
and portable electronic
equipment

advances are the use of the lighter weight plastic containers, the improvement of
shelf life, the dry charge process and the maintenance free design (Linden, 1995).

1.1.3.1 Starting, Lighting and Ignition (SLI) Battery

The design of lead acid batteries is varied in order to maximize the desired
type of performance. Tradeoffs exist for optimization among such parameters as
power density, energy density, cycle life, “float-service life” and cost. A starting,
lighting and ignition (SLI) battery whose main function is to start an internal
combustion engine discharges briefly but at a high current. Once the engine is
running, a generator or alternator system recharges the battery and then maintains it
on float at full charge or slight overcharge. Other characteristics for starting, lighting
and ignition (SLI) are tabulated in Table 1.2.
 7

Table 1.2: Typical characteristics of a starting, lighting and ignition (SLI) battery
Characteristics and unit SLI Figures
Chemistry
Anode Pb
Cathode PbO2
Electrolyte H2SO4 (aqueous solution)

Cell voltage (typical), V:

Nominal 2.0
Open circuit 2.1
Operating 2.0-1.8
End 1.75

Operating temperature, oC -40 to 55

Energy density (at 20 oC)

Wh/kg 35
Wh/L 70

Discharge profile (relative) Flat

Power density High

Self discharge rate (at 20 oC) 20-30 (Sb-Pb)

% loss per month

Calendar life, years 3-6

Cycle life, cycles 200-700

Advantages Low cost, ready availability, good high-rate,

high and low temperature operation, good float
service

Limitations Relatively low cycle life, limited energy

density, poor charge retention and storability,
hydrogen evolution

Major cell types available Prismatic cells:

30-200 Ah at 20h rate
 8

1.2 The Malaysian Motor Trade Scenario

The Malaysian motor trade has started during mid 1960's where all motor
vehicles found on the roads were imported. Since then, the Malaysian motor trade
has not changed a lot where most of vehicles were imported from Europe and due to
the colonial background, the majority of the motor vehicles were British origin. In
the late 1960's, Japanese cars were slowly introduced to the Malaysian roads and
began gaining popularity because of their low price and fuel consumption. At the
same year also, the government of Malaysia approved the setting up of car assembly
plants and within ten years almost every European, Japanese and Australian make
was assembled in Malaysia by eight industrial groups producing more than fifty
variants.

Under the scenario of economic success, Malaysia went through an economic

boom in the 1970's and the early 1980's making it one of the fastest growing markets
in Asia. Manufacturing goods is increasingly becoming an important feature of the
country's economy, with so many companies inside and outside the country
constructing their plants here, including the manufacture of Proton Saga automobile
in 1984. Due to the low price and good dependability, Proton Saga and its variants
have gained their popularity among the Malaysian people and the sales has boomed
where more than 1 million Proton cars were sold throughout the nation.

1.3 Malaysian Battery Market

In keeping up with the development of motor vehicle trade in Malaysia, the

sales of lead/acid batteries grew at almost the same pace. The first company to set up
its lead/acid battery manufacturing plant in Malaysia was the Chloride Group, which
was built in Kuala Lumpur in the year 1959. This is followed by the commissioning
of a new lead/acid battery plant by Century Batteries. Many battery manufacturing
companies have been setup since then, where lead acid battery demand seems to
increase year by year due to growth in manufacturing and car population and also by
lead acid battery life expectancy.
 9

Battery and various other manufacturing industries were enjoying the

emerging economic bloom during the ‘80s. Investments were pouring from inside
and outside of the country due to the Malaysian economic and its stability. Today,
there are about twelve major battery manufacturers of lead/acid batteries of many
varieties such as starting, lighting and ignition battery (SLI), storage battery,
stationery battery and others (Ibrahim, 1988). Famous foreign brand names such as
Yuasa, Yokohama and Century are setting up their manufacturing plants here,
seemingly that the market for these batteries are secured here. This phenomenon
occurs also as a respond to the growth of lead acid battery industry that concentrates
not only for domestic market but also for the export-based production (Wong, 1992).
As presented in many review articles concerning lead acid battery industry, a very
positive future is forecast for the battery manufacturing industry globally, as well as
in Europe and Asia (Billard, 1992; da Silva, 1997; Hawkes, 1997).

As more and more companies are manufacturing their products here, the
competition of becoming the best seller in the country has begun to be stiffer. Each
company is working hard in producing new items that are not only relatively low in
price, but offers better performance than other normal products. Normally the
product that they are developing is the maintenance free battery, which needs no
topping up of deionised water whenever the electrolyte level goes low.

1.4 Influence of Water Decomposition In Lead Acid Batteries

It is aforementioned that the main reason for the decomposition of water

inside the lead acid battery is caused by electrolysis due to overcharging. However,
water decomposition is not solely caused by this factor, as there are few other factors
that cause water losses. Table 1.3 summarizes the estimation of other influences of
water decomposition in lead acid battery.

a) Through electrolysis due to overcharging

The electrolysis phenomenon occurs normally whenever the battery is

charged. The basic electrode processes in the positive and negative electrodes
 10

involve a dissolution-precipitation mechanism and not some sort of solid-state ion

transport or film formation mechanism (Ruetschi, 1978). As the sulfuric acid in the
electrolyte is consumed during discharge, producing water, the electrolyte can be
considered an “active material” and in certain battery designs can be the limiting
material.

As the cell approaches full charge and the majority of the PbSO4 has been
converted to Pb and PbO2, the cell voltage on charge becomes greater than the
gassing voltage and the overcharge reactions begin, resulting in the production of
hydrogen and oxygen (gassing) and the resultant loss of water (Linden, 1995).

b) Antimony content of the grids and cyclic durability

During the construction of lead acid batteries, specifically alloy production,

antimony is added into the lead paste to harden it because pure lead is too soft
(Linden, 1995). The objective of antimony addition into the lead paste is to make
sure that the lead alloy stays attached to the grid. There is also another literature cited
that explains antimony content in the alloy have a stabilizing effect on the active
materials under cyclic stress (Kiehne, 1989).

It is understood that during charging, high over voltage slows down reactions
at the electrodes substantially, as some single steps of the reaction are impeded
effectively. Thus the system is in an unstable condition and any substance that
facilitate these partial
 11

Table 1.3: Losses of water in the lead acid battery (Kiehne, 1989)

Factors affecting water losses in Estimated quantity of water losses per day
lead acid battery (eg. Traction battery, one cycle per day,
charging coefficient 1.10)
Electrolysis
Due to overcharging 3.4 g
Due to self-discharge 0.06 g
Diffusion of water by gassing 0.07 g
Evaporation 0.01 g
Water in acid vapor < 2 x 10-4 g
Diffusion of water by the gas by < 0.1 g
circulation pumps
Corrosion of the positive grid < 0.2 g

reaction steps can in some cases accelerate the gassing process and therefore greatly
influence the water decomposition process (Kiehne, 1989).

c) Through heat build up and evaporation

It is a well-known fact that the climate for Malaysia is hot and humid
throughout the year. As the sequence, battery electrolyte will evaporate easily as the
battery casing absorbs heat whenever the car is parked outdoor in the scorching sun.
In addition to that, in certain car bonnets such as Proton cars, place their battery too
close to the engine, and this will add up to the heat build up due to the hot climate.
These two factors are considered to be the main reasons why batteries in tropical
countries need to be topped
with deionised water frequently. On average, the temperature measured inside the
battery is between 60 to 80oC, and at this point, evaporation occurs.

1.5 Problem Statement

The lead acid battery especially in tropical countries has a critical water
decomposition problem, which seems to be deteriorating its life cycle and
performance. The combination factor of overcharging and hot weather contributed to
the water losses in lead acid battery. This is causing the electrolyte level to decrease.
 12

Whenever the electrolyte level goes down, the acid concentration becomes stronger
and this leads to a corrosion problem where the strong acidity will attack the
connector between grid and terminal and to a certain extent, the connector will break.
Another subsequent to the water decomposition problem is the consumer has to top
up the electrolyte level every time it goes lower than the minimum level. These are
some of the problems faced in the flooded starting, lighting and ignition (SLI)
batteries that seems need some review in its design to improve the performance.

Some manufacturers introduced the so-called “maintenance free” batteries

that uses gelled electrolyte in their products. However, it is a disappointment that this
immobilized electrolyte fails to operate in hot engine condition as reported in oriental
cars, where the temperature inside the booth compartment can reach up to 60 oC to
80oC. Therefore, it is thought that the application of gas separation membrane would
be ideal in solving the water decomposition problem in lead acid batteries. The
membrane, which acts as a selective barrier, retains electrolyte level by controlling or
minimizing the rate of vaporized electrolyte disposed into the atmosphere. Hydrogen
and oxygen gases formed during overcharging will be vented minimally as to
balance the pressure build up inside the battery. The membrane skin layer thickness
needs to be adjusted in order to suit the battery operating conditions.

1.6 Research objectives

Based on the aforementioned background and the problem statement, therefore

the main objectives of this research are as follows:

a) To develop gas separation membrane for the application on tropicalized lead

acid battery.
b) To investigate the effect of fabrication conditions on the performance of the
membrane-assisted lead acid battery and its morphology.
 13

1.7 Scopes of Study

In order to achieve the aforementioned objectives, the following scopes have

been drawn:

a) To develop the optimum casting solution and casting condition in fabricating

the most suitable gas separation membrane for application on lead acid
battery.
b) To measure and analyze the performance of the membrane assisted lead acid
battery during the lead acid battery charging process.
c) To quantitatively measure the composition of vaporized electrolyte of both
conventional and membrane assisted lead acid batteries using Raman
Spectroscopy.
d) To determine structure of asymmetric membranes by using scanning electron
microscopy (SEM).
 CHAPTER 2

LITERATURE REVIEW

2.1 Membrane Separation Technology

2.1.1 Definition of Membrane Separation Processes

Membranes have gained an important place in chemical technology and are

used in a broad range of applications. The key property that is exploited is the ability
of a membrane to control the permeation rate of a chemical species through it. In
separations applications, the objective is to allow one component from a mixture to
permeate freely, while hindering permeation of other components.

Membrane is mainly utilized for separation and it may be categorized both by

its structure and function, which describes how and under what conditions they
perform. In general, a membrane process requires two essential uniform bulk phases
(two liquid phases, two gas phases or a liquid and a gas phase) separated by a third
phase - the membrane, which is physically and or chemically distinctive from both of
them (Winston Ho and Sirkar, 1992). The membrane acts as a selective barrier and
restricts the transport of various chemical species in a rather specific manner due to
its properties and the force field applied. In a membrane process, the two bulk phases
may be miscible or immiscible to each other and the membrane, which is an
interphase between the two bulk phases, is either a homogeneous phase or a
heterogeneous collection of phases. It can be gaseous, liquid, or solid, or
combination of these phases (Winston Ho and Sirkar, 1992).
 15

For a solid membrane, the two bulk phases can be a combination of miscible
or immiscible liquid phases and gaseous phases. For example, gas 1/ solid
membrane/ gas 2 (gas separation), liquid 1/solid membrane/gas (vapor) 2
(pervaporation), and liquid 1/solid membrane/miscible liquid2 (dialysis,
electrodialysis, reverse osmosis, ultrafiltration and microfiltration), gas 1/solid
membrane/liquid 2 and etc (Winton Ho and Sirkar, 1992)

For a liquid membrane, the two bulk phases can be any combination of
gaseous phases, immiscible liquid phases and a solid phase. The bulk liquid phases
must also be immiscible with the liquid membrane phase. For example, gas 1/liquid
membrane/gas 2, gas 1/liquid membrane/liquid 2, liquid 1/liquid membrane/gas 2
and liquid1/liquid membrane/liquid 2.

For membrane separation process, the bulk phases are mixtures. A membrane
process permits selective separation and controlled transfer of mass or energy
between two bulk phases interposed by the membrane. The membrane is selective to
one of the species in the mixture due to the differences in mobility or solubility of
species in the membrane. Therefore, one of the species in the mixture is allowed to
be exchanged in preference to others causing one bulk phase, either the permeating
stream or the retained phase to be enriched in that species while the other is depleted
of it.

The movement of any species across the membrane is caused by one or more
driving forces which arise from a gradient of chemical potential, electrical potential,
or even the temperature gradient. A gradient in chemical potential may be due to a
concentration gradient or pressure gradient or both.
 16

2.2 Membrane for Gas Separation

2.2.1 Development of Gas Separation Membrane

Gas separation has become a major industrial application of membrane

technology only during the past 15 years, but the study of gas separation has a long
history. It was J. K. Mitchell of Philadelphia, who attributed the first scientific
observation that different gases permeate through membranes at unequal rates,
reported this phenomenon in 1831 (Lacey, 1972). In his observations, balloons made
of Indian rubber (natural rubber) were put into gas atmospheres of different
composition blew up with different velocities, depending on the nature of the gas:
hydrogen filled balloons are faster than air, but the fastest gas was carbon dioxide.
Mitchell noted that carbon dioxide was absorbed by rubber expanded in volume and
hence, porosity was induces in the solid sample, which provided a way of penetration
of carbon dioxide molecules (Paul and Yampol' skii, 1994).

However, systematic studies on gas separation particularly began with Sir

Thomas Graham, who over a period of 20 years measured the permeation rates of all
the gases then known through every diaphragm available to him. This was no small
task because his experiments often had to start with synthesis of the gas. Graham
gave the first description of the solution-diffusion model, and his work on porous
membranes led to Graham’s law of diffusion.

Sir Thomas Graham, about three and a half decades after the founding of
J.K.Mitchell’s work, was said to have fathered gas separations via membranes,
discussed the mechanism of permeation in strikingly modern terms and demonstrated
experimentally that mixtures of gases can be separated by means of rubber
membranes (Lacey, 1972). Subsequently, further evidence of the separation
possibilities is contained in a statement made by Graham in his pioneer paper “On
the Molecular Mobility of Gases” in 1863 (Hwang and Kammermeyer, 1975). In this
treatise, which resulted in the formulation of Graham’s Law, the author mentioned
“the partial separation of mixed gas”. Only a few years later, 1866, Graham
published another paper dealing with the use of “colloid septa” for the separation of
 17

gases (Hwang and Kammermeyer, 1975). Through the remainder of the 19th and the
early 20th centuries, the ability of gases to permeate membranes selectively had no
industrial or commercial use and value. The concept of the perfectly selective
membrane was, however used as a theoretical tool to develop physical and chemical
theories, such as Maxwell’s kinetic theory of gases.

From 1943 to 1945, Graham’s law of diffusion was exploited for the first
time, to separate U235F6 from U238F6 as part of the Manhattan Project. Finely
microporous metal membranes were used. The separation plant, constructed in
Knoxville, Tennessee, represented the first large scale of gas separation membranes
and remained the world’s largest membrane separation plant for the next 40 years.
However, this application was unique and so secret that it had essentially no impact
on long-term development of gas separation.

In the 1940’s to 1950’s, Barrer, van Amerongen, Stern, Meares and others
laid the foundation of the modern theories of gas permeation. The solution-diffusion
model of gas permeation developed then is still the accepted model for the gas
transport through membranes. However, despite the availability of interesting
polymer materials, membrane fabrication technology was not advanced enough at
that time to make useful gas separation membrane systems from these polymers.

The development of high flux anisotropic membranes and large surface area
membrane modules for reverse osmosis applications in the late 1960’s and early
1970’s provided the basis for modern membrane gas separation technology. The first
company to establish a commercial presence was Monsanto, which launched its
hydrogen-separating Prism membrane in 1980. The company had the advantage of
being a large chemical company with ample opportunities to test pilot and
demonstration-scale systems in its own plants before launching the product. The
economics were compelling, especially for the separation of hydrogen from
ammonia-plant purge-gas streams. Within a few years Prism systems were installed
in many such plants (Baker, 2000).
 18

2.2.2 The Principles of Gas Permeation

Through looking back at the history of the establishment of gas separation by

using polymeric membranes, we know that the basic concept had been found almost
a century ago, when Sir Thomas Graham found the solution-diffusion theory.
However, during the early stages, not many industrial applications were done based
on this concept. Only after the initiation of Loeb and Sourirajan in producing
cellulose acetate membrane for reverse osmosis in 1960’s has made the theory
attracting so many attention for the researchers and the industry to look into the
matter more seriously.

In the 1940’s till the 1950’s, van Amerongen has been said to be the man who
initiated the present knowledge concerning the mechanism of gas permeation
through polymeric membranes. This is followed by a research by Rogers and also in
a monograph edited by Crank and Park. A typical schematic membrane process for
gas separation is shown in Figure 2.1 (Spillman and Sherwin, 1990).

High Pressure High Pressure

Feed Retentate

Low Pressure
Permeate
Fast Permeating Gas
Slow Permeating Gas

Figure 2.1 Membrane-based gas separation process

 19

In gas separation, a gas mixture at an elevated pressure is passed through

across the surface of a membrane that is selectively permeable to one component of
the feed mixture whereby the membrane permeate is enriched in this species. The
opposite side of the membrane is held at a lower pressure. The pressure difference
across membrane provides the driving force for the diffusion of gas across the
membrane and it is controlled by compressing the feed gas and or evacuating the
low-pressure side of the membrane.

Membrane process for gas separation works on the principle of differences in

the relative transport rates of the feed components in a gaseous mixture. Components
that diffuse more rapidly become enriched in the low pressure permeate stream,
while the slower components are concentrated in the retentate or the residue stream,
which remains on the high pressure. As gaseous mixture passes along a membrane,
the partial pressure decreases for the faster permeating component and increases for
the slower permeating component.

Both porous and non-porous membranes can be used as selective gas

separation barriers. In Figure 2.2 illustrated the mechanism of gas permeation for
both porous and non-porous membranes (Raymond and Gregory, 1992). As shown in
Figure 2.2(a), in porous type membrane, there are three mechanisms of separation.
Gases are separated on the basis of their molecular size by small pores through the
membrane under the driving force of a hydrostatic pressure difference via viscous
flow figure. If pores are relatively large, i.e., from 0.1 to 10µm, gases permeate the
membrane by convective flow, and no separation occurs. If the pores are smaller
than 0.1µm, then the pore diameter is the same size as or smaller than the mean free
path of the gas molecules. Diffusion through such pores is governed by Knudsen
diffusion, and the transport rate of any gas is inversely proportional to the square root
of its molecular weight. This relationship is called the Graham’s Law of diffusion.
Finally, if the membrane pores are extremely small, on the order of 5 to 20Å, then
the gases are separated by molecular sieving. Transport through this type of
membrane is complex and includes both diffusion in the gas phase and diffusion of
adsorbed species on the surface of the pores (surface
 20

Convective Flow

• Knud

en Diffusion

Molecular Sieving

(a)

Solution Diffusion
Mechanism

(b)

Figure 2.2 Mechanism for gas separation using (a) porous membrane and

(b) non-porous membrane

diffusion). These very small pore membranes have not been used on a large scale,
but ceramic and ultramicroporous glass membranes with extraordinarily high
selectivities for similar molecules have been prepared in the laboratory.
 21

Although these microporous membranes are topics of considerable research

interest, all current commercial gas separations are based on the non-porous polymer
membranes as shown in Figure 2.2(b). Separation through non-porous polymer
membranes occurs by solution-diffusion mechanism. These membranes contain no
holes or pores in the conventional sense. They rely on the principle that gases
dissolve in and diffuse through solid material.

The transport of gases through a nonporous polymeric membrane is a

complex process that can be described by the following equation:

Ji = DiKiG (pio – pil) (2.1)

l

where is Ji the flux of component i [g/(cm2.s)], pio and pil are the partial pressure of
component i on the either side of the membrane, l is the membrane thickness, Di is
the permeate diffusion coefficient, and KiG is the Henry’s Law sorption coefficient
[g/(cm3.pressure)]. In gas permeation it is much easier to measure the volume flux
through the membrane than the mass flux, so Equation 2.1 is usually recast as:

ji = DiKi (pio – pil) (2.2)

l

where is ji the volume (molar) flux expressed as [cm3 (STP) of component i/(cm2.s)],
pio and pil are the partial pressure of component i on the either side of the membrane,
l is the membrane thickness, Di is the permeate diffusion coefficient, and Ki is the
sorption coefficient with the unit [cm3 (STP) of component i /(cm3 of
polymer).(pressure)]. The product DiKi can be written as Pi which is called the
membrane permeability and is a measure of the ability of the membrane to permeate
gas. The ability of a membrane to separate two gases i and j is measured by the ratio
of their permeabilities called the membrane selectivity:
 22

αij = Pi (2.3)
Pj

Permeability can be expressed as product of two terms. One the diffusion

coefficient Di which reflects the mobility of the individual molecules in the
membrane material and the other one is Ki, gas sorption coefficient which reflects the
number of molecules dissolved in the membrane material. Thus equation 2.3 can be
written as:

αij = Di Ki (2.4)
Dj Kj

The ratio Di / Dj is the ratio of the diffusion coefficients of the two gases and
can be viewed as the mobility selectivity, reflecting the size differences of the two
molecules. The ratio Ki / Kj is the ratio of the sorption coefficients of the two gases
and can be viewed as the sorption or solubility selectivity, reflecting the relative
condensabilities of the two gases.

2.3 Solution-Diffusion Mechanism

Gas transport through nonporous membrane is determined predominantly by

solution-diffusion mechanism (Pinnau and Koros, 1992). In essence, solution
diffusion mechanism describing gas transport through non-porous membrane
involves a combination of Fick’s Law of diffusion and Henry’s Law of solubility.
Gas diffusion through non-porous membranes can be described by Fick’s law, which
is stated as:

dc
J = −D (2.5)
dx
 23

where J is diffusion flux of penetrate gas or amount of penetrate gas permeate

through membrane area in unit time, D is diffusion coefficient and dc/dx is local
concentration gradient of penetrate gas at a given position in membrane (Stern,
1972).

On the other hand, according to Henry’s law, we have:

c = Sp (2.6)

where c is the concentration and pressure, p of penetrate gas at membrane interface

can be related by solubility coefficient, S. The solubility coefficient is estimated as
reciprocal of Henry’s law constant (Stern, 1972).

Both equations (equation (2.5) and equation (2.6)) are then combined and
integrated to give:

∆pΑ
Q = DS (2.7)
l

where Q is volumetric flow rate of penetrate gas permeate through membrane, A and
l is membrane effective area and thickness, while ∆p is pressure difference across
membrane (Stern, 1972).

Hence, permeability of gases through membrane depends on diffusivity and

solubility coefficients that vary with permeate and membrane material. A common

way of expressing permeability is given by:

P = DS (2.8)

where P is permeability coefficients. Unit of permeability is Barrer (1 Barrer = 10-10

cm3(STP).cm/cm2.s.cmHg).
 24

2.4 Asymmetric Membranes

Asymmetric membranes layered structures in which the porosity, pore size or

even membrane composition changes from the top to the bottom surface of the
membrane. Usually asymmetric membranes have a thin, selective skin layer
supported on a much thicker, highly permeable microporous substrate. Because the
selective skin layer is very thin, membrane fluxes are high. The microporous
substrate provides the strength required for handling the membrane. The importance
of asymmetric membrane was not recognized until Loeb and Sourirajan prepared the
first high flux, asymmetric reverse osmosis membranes by what is now known as the
Loeb-Sourirajan’s technique. Hindsight makes it clear that some of the membranes
produced in 1930’s and 1940’s were also asymmetric but the importance of
asymmetric was not realized at that time. Loeb and Sourirajan’s discovery was a
critical breakthrough in the membrane technology. Their reverse osmosis membranes
were an order of magnitude more permeable than the symmetric membranes
produced previously with the same materials. For a number of years the Loeb-
Sourirajan technique was the only method of making asymmetric membranes, but the
demonstrated benefits of the asymmetric structure encouraged the development of
other methods. Improvements in asymmetric membrane preparation methods and
properties were accelerated by the availability in the late 1960’s of the scanning
electron microscope (SEM), which allowed the effects of changes in the membrane
formation process on the structure to be assessed easily (Baker, 2000).

Symmetric or asymmetric membranes can be differentiated depending on

whether or not the morphology of the membrane is the same across the entire
thickness of the membrane. Symmetric (homogeneous) membrane have a uniform
density across the thickness, while asymmetric membrane posses a significantly
higher void volume.

As shown in the Figure 2.3 below, we can observe that an asymmetric

membrane consists of a very thin and dense polymer layer (0.1µm to 1µm) on a
highly porous thick sub-layer (100µm to 200µm) (Strathmann, 1986).
 25

0.1µm~1µm

100µm~200µm

Skin Layer

Sublayer

Figure 2.3 Asymmetric membrane structure

The separation characteristics of asymmetric membranes are determined by

the nature of the skin polymer or pore size and the mass transport rate mainly by the
thickness, since the mass transport rate is inversely proportional to the thickness of
the actual barrier layer or the skin layer. The highly porous sub-layer serves only as a
support for the very thin and fragile skin and has no, or very little, effect on the
separation characteristics and mass transfer rate of the membrane.

Asymmetric membranes made from glassy polymers are widely used in

industrial gas separations (Kesting and Fritzsche, 1993). These membranes have a
very thin, dense skin integrated with a porous supporting layer. The thickness,
porosity and pore size of the dense skin layer determine the permeability and
permselectivity of the asymmetric membrane at a given operating pressure and
temperature. The membrane suitable for gas separation must have a small enough
porosity and pore size so as to increase membrane selectivity, and a thin skin layer
for improved gas permeability. In addition, the sub-structure of the asymmetric
membrane should have good mechanical strength with negligible gas transport
resistance. Asymmetric membranes having different structures can be prepared by
 26

the selection of suitable membrane making procedures (Wang et al., 1995). In

general, surface defects of asymmetric membranes could be repaired using the well-
known technique developed by Henis and Tripodi based on surface coating using
highly permeable materials such as silicon rubbers.

Furthermore, the skin layer density is somewhat greater than that of the
substructure, and whose depth (everything else being equal) does not vary
appreciably with total membrane thickness. Because of its greater density, the skin
layer offers greater resistance to material transport that that provided by a
substructure layer of equivalent thickness. Indeed, where the difference in density
between the two layers is great, the gas transport resistance of the entire membrane is
approximately equal to that of the dense skin layer alone.

2.4.1 Formation of Asymmetric Membranes

The industrial and commercial importance of asymmetric membranes has

forced researchers to gain their efforts on studies of the formation mechanisms. In
the preparation of asymmetric membranes, there are two techniques that have been
developed. One utilizes the phase inversion process and the other one leads to a
composite structure (Strathmann, 1986).

2.4.1.1 Composite Structure Process

For the formation of the composite membrane, a homogeneous solid polymer

film, which is the actual selective membrane barrier, is deposited or coated onto the
surface of a suitable active micro-porous substrate. The early composite membranes
were made by casting a thin film of cellulose esters on a water surface from a very
dilute solution; after the solvent evaporated, the thin film was lifted off onto a
substrate (Strathmann, 1986). Normally, these composite membrane were prepared
for the application of reverse osmosis membranes but were rather impractical for
large scale production, since the solvent needed to dissolve the polymer often also
attacks the microporous substructure. Only after the usage of the recently developed
 27

interfacial polymerization technique, yields a better result for the formation of

composite membranes.

2.4.1.2 Phase Inversion Process

Phase inversion is a process whereby a polymer is transformed in a controlled

manner from a liquid to a solid state. The process of the solidification is very often
initiated by the transition from one liquid state into two liquids (liquid-liquid
demixing). At a certain stage during demixing, one of the liquid phases (the high
polymer concentration phase) will solidify so that a solid matrix is formed. By
controlling the initial stage of phase transition the membrane morphology can be
controlled, i.e. porous as well as nonporous membranes can be prepared. The
resultant membranes have a skin layer, which integrally bonded in series with a thick
porous substructure. The skin and the substructure are composed of the same
material. The skin layer, which contains the effective separating layer, is one of the
key elements in determining the membrane permeability and selectivity. To have a
high performance air separation membrane, this skin layer has to be as thin as
possible and must contain minimum defects (Chung et al., 1997).

The concept of phase inversion covers a range of different techniques such as

solvent evaporation, precipitation by controlled evaporation, thermal precipitation,
precipitation from the vapor phase and immersion precipitation (Wijmans and
Smolders, 1986). But most of the industrial and lab-scale application of the phase
inversion membranes are prepared by immersion precipitation.

Immersion precipitation, which was firstly introduced by Loeb and Sourirajan

in 1960’s, has been studied and exploited most for the production of skinned
membranes. According to Koenhen, the gelation at increased polymer concentration
on the top layer formed the skin layer, whereas liquid-liquid phase separation by
nucleation and growth is understood responsible in forming the porous sublayer
(Koenhen, 1977). The key feature to the immersion precipitation is the immersion of
 28

the cast polymer film into the non-solvent coagulation bath. The membrane formed
though polymer precipitation as a resultant of the solvent loss and an increase in
polymer concentration in the top layer of the polymer solution.

2.5 Types of Phase Inversion Processes

As far as it is concerned, there are four main types of phase inversion

processes that exist, and they are stated as follows:

1. Wet cast / wet phase inversion

2. Dry cast / wet phase inversion
3. Dry cast / dry phase inversion
4. Dry cast / dry-wet phase inversion

The big difference lies between the type 1(wet cast) and types 2, 3 and 4 (dry
cast), where the casting process used are not similar. The distinction refers to
whether the outlet of the casting knife that drags the casting solution from a closed
reservoir is exposed to the air or directly submerged to a non-solvent coagulation
medium. This is considered important because during the time between extrusion of
the nascent membrane and its immersion, evaporation of the solvent could occur.
Subsequently producing a more concentrated polymer region near the air-solution
interface to promote the formation of a skin layer. Nevertheless, dry cast / dry-wet
phase inversion process will be given the focus, as it is the process produces most of
the membranes today.

2.5.1 Dry-wet Phase Inversion

Most of the membranes in use today are phase inversion membranes obtained
by dry/ wet phase inversion technique. Phase inversion membranes can be prepared
from variety of polymers. The only requirement is that the polymer must be soluble
in a solvent or a solvent mixture. In the formation process of a membrane, two types
 29

of phase inversion can be distinguished. The dry phase inversion takes place in the
atmosphere by evaporation of the volatile solvent. The wet phase inversion is carried
out by immersing the polymer solution membrane into a coagulation bath of a non-
solvent takes place and the membrane formed. The dry/wet phase inversion
technique is a relatively new process which arose out of the quest to fabricate ultra-
thin and defect-free on asymmetric gas separation membranes. The dry/wet phase
inversion technique requires multi-component casting solutions consisting of
polymer, at least one volatile solvent and one less volatile non-solvent then bringing
the solution to phase separation by means of solvent outflow and/or non-solvent
inflow (Wijmans et al., 1983). However, it has been found that the use of two
solvents, a primary volatile solvent and a secondary less volatile solvent, allows finer
control of solvent evaporation and polymer coagulation rates. All solvents and non-
solvents should be miscible with the coagulation bath medium and the non-solvent is
added to the casting solution until the solution nears its phase boundary (Sourirajan
et al., 1993). The evaporation process for a typical ternary casting system used for
the preparation of membranes made by dry/wet phase inversion is illustrated
schematically in Figure 2.4.

Dope Casting Convective Dry Phase

Formulation Evaporation Separation

Solvent
Exchange and Vitrification Wet Phase Free Standing
Drying Separation Evaporation

Figure 2.4 Steps involved in the formation of asymmetric flat sheet membranes
using dry/wet phase separation process (Clausi and Koros, 2000).
 30

The process, from the most basic standpoint, consists of the formation of a
nascent membrane, followed by interfacial phase separation induced through the
evaporation of a volatile solvent. After a short ‘healing’ period not less than 3s and
more than 10s, the nascent membrane is then immersed in a non-solvent bath where
phase separation occurs throughout the rest of the membrane (Clausi and Koros,
2000).

2.6 Membrane Formation Processes

Recently, new challenges are directed towards development of high

performance asymmetric membranes for gas separation, in which further insight and
dramatic progress are being made. According to earlier studies, formation of
ultrathin and defect-free skin structure has been performed through manipulation of
phase inversion and rheological factors. The former controls general morphology of
membrane whereas the latter further affects molecular orientation in membrane.
Polymer concentration, solvent ratio (ratio of less volatile solvent to more volatile
solvent), forced-convective evaporation time and casting shear rate have been
identified as dominant fabrication factors in controlling skin thickness and skin
integrity, and thus have substantial effects on separation properties of resultant
membranes.

Many previous investigations have been made so far to elucidate relationship

between the aforementioned parameters with membrane morphology and properties.
However, most of their studies have neglected interaction effects between these
fabrication parameters due to the complex nature of membrane formation process.
Therefore, a systematic study was currently carried out to investigate effects and
interactions of polymer concentration, solvent ratio, evaporation time and shear rate
in developing defect-free and ultrathin-skinned asymmetric membranes with superior
gas separation performance.
 31

2.6.1 Phase Inversion Factors

The properties of skin layer are intimately related to polymer concentration of

casting solution. Nowadays, polymeric materials are widely used as membrane
materials because of their unique properties. Optimum polymer concentration of
casting solution has to be determined in order to achieve defect-free and ultrathin-
skinned asymmetric membranes for gas separation. Solution viscosity increases with
increasing polymer concentration. According to Chung et al. in 1997, dopes that
exhibit a sign of significant chain entanglement were essential to yield a useful gas
separation membrane with minimum defects (Chung and Kafchinskin, 1997; Chung
et al., 1997). Therefore, casting asymmetric membranes from a concentrated
polymer solution results in an increase in skin thickness and a decrease in mean pore
size and surface porosity of asymmetric membrane. Consequently, a relatively high
degree of selectivity is accompanied by a low permeability for gas separation or vice
versa (Pesek and Koros, 1993; Hwang et al., 1996; Chung et al., 1997).

Membrane formation process involves solution-processing method that

includes certain solvents as well as nonsolvent additives (if necessary), which
attribute to a considerable effect on membrane structures and properties. Solvating
power, diffusivity and volatility characteristics of solvents and nonsolvents are
critical for membrane formation. Solution contains a primary more volatile solvent
and a secondary less volatile solvent allows finer adjustment of solvent evaporation
and polymer coagulation. Since skin layer is generated during solvent evaporation,
ratio of less volatile solvent to more volatile solvent or “solvent ratio” (mass ratio) in
solution becomes a paramount parameter for development of defect-free and
ultrathin-skinned asymmetric membrane for gas separation. Decreasing solvent ratio
of casting solution results in a higher evaporation rate and a lower coagulation rate.
A relatively thick skin layer with a decrease in mean pore size and surface porosity
of asymmetric membrane is produced, thus increasing selectivity but decreasing
permeability for gas separation; or vice versa (Pesek and Koros, 1993; Hwang et.al.,
1996; Shieh and Chung, 1998).
 32

2.6.2 Rheological Factors

Manipulation of rheological factors in membrane formation process is a novel

approach in membrane technology, which provides a potential platform to develop
defect-free and ultrathin-skinned asymmetric membranes for gas separation.
Rheological factors would affect morphology, physical properties and separation
performance of asymmetric membrane. Recently, rheological factors in membrane
formation process have been investigated by a number of researchers (Shilton et al.,
1994; Shilton et al., 1996; Ismail, 1997; Ismail et al., 1997; Shilton et al., 1997;
Ismail et al., 1999; Chung et al., 2000a; Chung et al., 2000b).

Membrane formation process involves casting of a homogeneous multi-

component solution. Behavior of amorphous polymeric materials under shear is
described by response to tangential stress, which is related to molecular orientation
or preferential alignment of randomly coiled chain molecules (Ismail, 1997).
Polymer solution is often shear-thinning suggesting a progressive alignment of
polymer molecules under shear in flow direction (Ismail, 1997; Shilton et al., 1997).
Stretching of polymer chains between entanglement junctions leads to a decrease in
solution viscosity (Ismail, 1997). An empirical relationship has been proposed by de
Waele and Ostward, which is known as power law;

τ s = ωγ& θ (2.1)

where τs is shear stress and γ& is shear rate. ω and θ are constants for a particular
fluid. ω is a measure of fluid consistency; a high value of ω indicates a more
viscous fluid. θ is a measure of non-Newtonian behavior; θ < 1 indicates a shear-
thinning behavior (Ismail, 1997).

Polymer solution also exhibits viscoelastic behavior, which relates to

relaxation process (Ismail, 1997; Shilton et al., 1997). After the stress imposed on
polymer solution is released, relaxation occurs. Relaxation is reflected in negative
strain or recoil that eventually reaches equilibrium state. Elastic and viscous
influences are working together, which can be analogous to a spring and dashpot
 33

system (Ismail, 1997). In stretching portion of castline, polymer molecules are

maintained in an oriented (partially) conformation by castline deformation. After
casting, polymer molecules would relax to some preferred state. However, they
recover only a portion of their total deformation (Hagler, 1981).

The as-cast membrane is then going through forced-convective evaporation.

Dry phase separation progresses instantaneously and limits conformational and
configurational rearrangement especially in nascent skin region. Polymeric material
has no chance of relaxing and therefore shear-induced molecular orientation will be
frozen into nascent skin layer of membrane (Pinnau and Koros, 1993; Wang et al.,
1995b; Ismail, 1997; Shilton et al., 1997). Besides that, dope formulation is tailored
to be close to thermodynamic instability limit and approaching phase transition
boundary. Nonsolvent is added into polymer solution in order to speed up
preprecipitation of phase-separated structures and reduce relaxation effects on
molecular orientation (Chung et.al, 2000b). In addition, shear fields (over a certain
value) can distort phase diagram and hence alter phase stability, demixing and
precipitation kinetics of membrane formation process (Sharpe et al., 1999). The
nascent membrane is then immersed in a coagulation bath for wet phase separation.
The nascent skin layer with sufficiently rigid structures is solidified immediately to
form a well-defined skin layer with enhanced molecular orientation (Shilton et al.,
1994).

According to results determined by using polarized reflection infrared

spectroscopy and gas permeation tests, molecular orientation is enhanced in high-
sheared membranes, which has a favorable effect on membrane properties (Shilton et
al., 1994; Ismail et al., 1997; Shilton et al., 1997; Ismail et al., 1999). Permeability
and selectivity of membrane are found to increase with increasing shear; some even
surpass the generally recognized intrinsic selectivity (Ismail et al., 1997; Shilton et
al., 1997).
 34

2.7 Previous Methods in Overcoming Water Losses In Lead Acid Batteries

As mentioned earlier in the introductory chapter, it has been revealed that

relevant water losses of lead acid batteries are mainly due to the gases evolving
during electrolysis. If the losses of water are to be reduced, the gases forming during
electrolysis must be recombined to water and led back to the battery as they use in
the recombinator battery systems. Recombinators are already employed presently for
some applications. Figure 2.5 shows a cross section of such a “recombinator”.
Essential part of this recombinator reaction is a catalytic converter plated with a
noble metal where the recombining reaction itself takes place. In front of this sieve is
a protective mat to keep aggressive spray from the converter (Linden, 1989).

Recombination is above all a thermal problem. 70% of the heat encountered

is pure reactional heat, whereas 30% results from the condensation process. The
efficiency of such recombinators is 90% catalytic efficiency and 80% evaporative
efficiency, as not

30% QR 30% QR

Figure 2.5 Cross section of a recombinator (Dietz and Dittmar, 1992)

 35

all the water that is recombined is also condensed and flows back into the battery, but
20% escapes as water vapor through openings that the converter has to have because
oxygen and hydrogen are not always produced at the same rate.

2.7.1 Valve-regulated Lead Acid Batteries with Immobilized Electrolyte

The other alternative to reduce comprehensively the electrolysis is employed

in “enclosed” lead-acid accumulators. Their operating principle is comparable to that
of the gastight sealed Ni/Cd batteries with one difference: a fully sealed gastight lead
acid battery cannot be realized.

An essential characteristic of this principle is a non-proportional evolution of

the gases hydrogen and oxygen to the charge current during overcharge. The
overcharge current forces an oxygen cycle as demonstrated in Figure 2.6. The
oxygen developed on the positive electrode is reduced on the negative electrode, and
this is by direct electrochemical reduction corresponding to the equation on the
bottom left of the Figure 2.6. In case the negative electrode reaches the rest potential.
Then the oxygen can oxidize the lead of the negative electrode to lead-oxide
(chemical discharge), the lead-oxide will react with the sulfuric acid to form lead-
sulfate and finally be recharged to
 36

Figure 2.6 Valve regulated lead acid battery with immobilized electrolyte (Dietz and
Dittmar, 1992)

lead. This sequence of reactions is demonstrated in the first three equations on the
left side of figure 2.6. The addition of the three equations gives the equation below.
The kind of reaction delivering lead oxide has the same result as the direct reaction.
Functional preconditions for the oxygen cycle are:

i. Oxygen may not escape from the cell

ii. Quick transport of oxygen to the negative electrode

The second means the cell has to have no liquid electrolyte, because a low
diffusion speed of oxygen in the sulfuric acid reduces the oxygen cycle on very little
current. Thus, the main characteristics of enclosed batteries is the immobilization of
the electrolyte while the sulfuric acid is soaked in a glass mat or fixed as a gel. In
both cases open pores allow easy oxygen transport to the negative electrode as
mentioned in Figure 2.6.
 37

On the negative electrode the overcharge reaction consists mainly of a

reduction of oxygen, but a minimum of hydrogen development always remains
because the rest potential of the negative electrode is far below the equilibrium
potential for hydrogen development. Minimum hydrogen development is the gassing
rate of the negative electrode combined with the self-discharge, in optimum
3mA/100Ah, (3% self-discharge per minute) (Linden, 1989). Therefore “enclosed”
lead-acid accumulators always have to be equipped with a valve, except very little
cells where the hydrogen can escape by diffusion through the plastic made cell walls
to avoid extended pressure in the cell.

The so-called valve-regulated lead-acid batteries in small sizes have been on

the market for about 35 years. The availability of suitable glass felts with fiber
diameters in the range of µm has accelerated the development of such kind of
batteries and the employment of the principle likewise to larger batteries such as
automotive batteries, stationary batteries and traction batteries.

However, there is a major problem of sealed lead acid batteries and that is the
control of the gas pressure. Whereas the efficiency of the oxygen cycle in sealed lead
acid batteries is close to 100%, an analogous hydrogen cycle cannot be achieved, as
the hydrogen oxidation is kinetically hindered at the working potential of the positive
electrode. Therefore, in sealed lead acid batteries: (i) the hydrogen evolution is
usually suppressed (by charging at low constant voltage, using cell components of
high purity, especially antimony-free lead alloys); (ii) evolved hydrogen can be
oxidized, e.g., electrochemically at (catalyzed) auxiliary electrodes or by currentless
catalytic hydrogen/oxygen recombination, and (iii) excess hydrogen is removed by
means of a safety-valve together with oxygen (Dietz and Dittmar, 1992)

Meanwhile the catalytic recombination principle has been frequently

proposed for lead acid batteries with flooded electrolyte:

i) as catalytic plug for the hydrogen/oxygen recombination in order to achieve

maintenance-free operation
 38

ii) in combination with auxiliary electrodes held at special potentials (by means
of diodes connected to the battery electrodes) to ensure oxygen reduction or
hydrogen oxidation

However, there are some obstacles that have not allowed industrial
application on a large scale yet. These are the complicated voltage control measures
and the disadvantages involved in the application of noble metal catalysis (high
costs, expensive precautions against poisoning of the catalyst and explosion hazards
at high reaction yields, risk of increasing self-discharge by the decrease of the
hydrogen over potential caused by noble metal traces in the electrolyte).

2.7.2 Suppression of Hydrogen Evolution and Oxygen Reduction Effect

Many workers have been studying on how to suppress the hydrogen evolution
and oxygen reduction in lead acid batteries. This is because the main factor that
causes gassing reaction to be occurring in lead acid batteries. During the production
of lead acid battery, additives were introduced into lead paste to make it more
durable and strong, as lead is a very soft substance. Normally, substances like
antimony and calcium were used added in lead paste to the earlier mentioned
objective, however these substances cause marked influence on gassing reaction to
occur.

As studied by Maja and Penazzi, in terms of the H2 evolution, experiments

have confirmed that marked deleterious influence exerted by antimony (Sb),
tellurium (Te), and cobalt (Co). Arsenic (As) and nickel (Ni) were also shown to
promote H2 evolution whereas bismuth (Bi), stanum (Sn) and chromium (Cr)
markedly inhibited. Conversely, O2 reduction on sponge lead is enhanced, in
diminishing order, by antimony (Sb), tellurium (Te), stanum (Sn), arsenic (Ar),
nickel (Ni) ans selenium (Se) and inhibited by cobalt (Co) and chromium (Cr).
Examination of these results suggested, that gas recombination in lead acid batteries,
 39

using the oxygen cycle, could improve their performance in the presence of bismuth
(Bi), stanum (Sn) and selenium (Se) (Maja and Penazzi, 1988).

In a related publication (Dietz, 1990), there is a study that suggests these

solutions would decrease the rate of hydrogen evolution in lead acid battery:

i) Directly decreasing H2 evolution current, I (H2 ev), i.e., by increasing the

hydrogen over voltage using hydrogen-evolution inhibitors and decreasing the
antimony content of the grid alloy, or by decreasing the charging voltage;

ii) Indirectly increasing O2 reduction current, I (O2 red), i.e., by increasing

partial pressure of oxygen, p(O2), or improving the conditions of the oxygen
recombination, e.g., by decreasing the amount of electrolyte in the electrode-
separator package;

iii) Indirectly increasing PbSO4 reduction current, I (PbSO4 red), i.e., by lowering
the state-of-charge of the negative electrode.

However, method (i) has practical relevance since neither I (O2 red) nor the
Ampere-hour capacity are decreased. Efficient removal of H2 is also possible by
catalyzing the hydrogen/ oxygen recombination (Dietz, 1990).

2.7.3 The Use of Additional Electrolyte Volume In Lead Acid Battery

The performance of lead acid batteries can be improved considerably by

modifying the design according to certain criteria. One of the problems that has been
detected is the low ratio of the volume of electrolyte to the amount of active matter
content in the plates: with this goal, the influence that a greater quantity of
electrolyte, in relationship of the active matter to be used. In lead acid cells the
shortage of electrolyte quantity inside the cell accelerates the acid depletion at the
electrode surface when the system operates at low rate discharges, making the battery
to collapse earlier.
 40

The problem can be solved by the addition of electrolyte to the cell. The new
design allows the more concentrated electrolyte from the reservoir to fall down by
gravity and mix with the depleted electrolyte in the cell as discharge is proceeding,
thus maintaining the electrolyte concentration. The system works properly during
discharge, but needs an extra overcharging process to homogenize the electrolyte
reservoir. This reduces the cycle efficiency and accelerates the electrode corrosion
and plate ageing (Armenta-Deu, 1998).

In lead acid batteries, the cell performance has noticeably been improved
with the use of a circulation system that homogenizes the electrolyte concentration,
achieves longer discharge time, and increases the output voltage. Further
improvements have been obtained when the battery has been attached to an
electrolyte reservoir supplying sulfuric acid to the main cell. In this case the acid
depletion at the electrode interface is compensated by the forced flow created by the
electrolyte circulation, and hence the higher concentration gradient between the bulk
solution and the interface. The result is the enhancement of the discharge process
(Armenta-Deu, 1998).
 CHAPTER 3

RESEARCH METHODOLOGY

3.1 Research Design

This research consists of various kinds of experiments that must be done in

stages to obtain results that may represent the whole research parameters. Therefore a
research design must be constructed before executing any experimental work. The
research design for this research is shown graphically in Figure 3.1. After deciding
on what materials will be used in the experiment, the first step is preparing the
casting solution in the continuous stirred flange flask. Afterwards, the formation of
asymmetric gas separation flat sheet membrane is done by using pneumatically
controlled casting machine via dry/wet phase inversion. There are two casting
parameters that are being investigated in this study, which are the polymer
concentration and the casting shear rate. Various membranes were prepared from
different formulations and casting shear rates to determine the best fabricating
conditions that suit the characteristic of a good electrolyte-retaining device.

Next, the membrane is cut accordingly to the permeation cell shape to

determine the permeability and selectivity of the membrane. Subsequently, the
membrane is applied on top of the lead acid battery cap to determine its effectiveness
in maintaining electrolyte level. The most suitable membrane is the one that
minimizes electrolyte
 42

Material Selection

Casting Solution Preparation

Dry/Wet Casting Process

Formation of Flat sheet Membranes

Using Pneumatically Controlled
Casting Machine
Polymer Casting
Concentration Shear Rate

Gas Permeation Cell Test

Membrane-assisted Lead Acid Battery

Charging Test

Optimum Polymer Critical Casting

Concentration Shear Rate

Optimized Membrane-assisted Lead Acid

Battery Charging with Heat Supply Test

Flat Sheet Membrane

Characterization
Scanning Electron Raman Spectroscopy
Micrograph Intensity Analysis

Figure 3.1 Research Design

 43

losses from the lead acid battery as well as minimizing the pressure build up inside
the battery casing. The optimized membrane will be tested in the membrane-assisted
lead acid battery charging test to observe the effect of high temperature condition on
the electrolyte losses in lead acid battery during charging process. Membrane
characterization using Scanning Electron Microscopy (SEM) and Raman Spectroscopy
were also carried out to investigate the structure of the resultant membrane and to
differentiate the components of the permeated electrolytes from both membrane-assisted
and conventional batteries.

3.2 Experimental Methods

3.2.1 Membrane Preparation

3.2.1.1 Materials

Before casting of a flat sheet membrane can be made, a casting solution has
to be prepared first. Generally, a casting solution will consist of a polymer, a solvent
and a nonsolvent. For this research, polysulfone has been selected as the base
polymer for all the casting solution made. As for the solvent, N,N-dimethylacetamide
(DMAc), dimethylformamide (DMF) and tetrahydrofuran (THF) have been selected
due to the strong interaction with polymer and miscibility with water. Meanwhile the
nonsolvent used in this experiment is an aliphatic alcohol, ethanol. It is used as a
nonsolvent additive for polysulfone.

Polysulfone (Udel bisphenol A polysulfone (Udel P1700)) (purchased from

Amoco Performance Products) was being selected as one of the membrane materials
because of the commercial availability, processing ease and favorable selectivity-
permeability characteristics, mechanical and thermal properties. Polysulfone (PSF)
is an amorphous glassy polymer, containing sulfone group, ether linkage and
aromatic nuclei in polymer backbone, as depicted in Figure 3.2. All the chemicals
such as N,N-
 44

CH 3

SO 2 O C O
CH 3 n

Figure 3.2 Monomer unit of a Polysulfone (PSF)

dimethylacetamide (DMAc), dimethylformamide (DMF) ethanol and tetrahydrofuran

(THF) were laboratory grade and purchased from Aldrich Co.

3.2.1.2 Casting Solution Preparation

Apparatus for forming polymer solution had been set up as shown in Figure
3.3. Polysulfone pellets were dried in a vacuum oven at 70oC overnight before used
in making dope solution. This is to remove any absorbed water or moisture contents
on the polymer surface. The polymer and less volatile solvent, N,N-
dimethylacetamide (DMAc) were weighted according to the percentage on an
electronic scale and kept inside an aluminium foil sealed beaker. Once the dope
solution apparatus is set and the stirrer is controlled at medium speed, the less
volatile solvent is poured into it.

When the temperature of the solvent has reached 50 to 55 oC, polymer pellets
were added gradually into the flask. Afterwards, the polymer pellets were ensured to
be totally dissolved in the solvent before inserting new pellets into the vessel. This is
done to avoid agglomeration of polymer. Right after the addition of the polymer
pellets into the flask, temperature is slowly increased to 70 to 90 oC, while the stirrer
is set at a much higher speed to ensure the polymer pellets were fully dissolved.
After all of the pellets were added into the vessel and fully dissolved, the more
volatile solvent, tetrahydrofuran (THF) is added into the vessel. After almost an hour,
non-solvent, ethanol is poured slowly into the vessel.

The solution is then stirred continuously until the all bubbles inside the
solution disappear. Once the solution is ready, the stirrer, the heater, the blower and
 45

the cooling water is switched off. The dope solution is then kept tightly inside a
bottle. In order to remove residual bubbles trapped inside the dope solution, the
bottle is immersed inside an ultrasonic bath for about 3-4 hours before casting.

Stirrer

Condenser Thermometer

Feed Funnel

Flange Reaction
Flask

Heating Unit

Figure 3.3 Apparatus for polymer solution preparation

3.2.1.3 Preparation of Asymmetric Membrane

Presently, flat-sheet membranes are used herein for laboratory-scale

experiments, which is the most appropriate form. Furthermore, flat-sheet membranes
are also widely utilized in plate-and-frame and spiral wound systems. Casting
process was performed by using a pneumatically controlled casting machine such as
shown in Figure 3.4. Casting solution was cast on a glass plate with a casting knife
for gap setting of 150µm at an appropriate casting shear. Casting was carried out at
 46

ambient atmosphere (30oC and 84% relative humidity). The flat sheet casting shear
rate can be calculated using the Equation 3.1 as follows:
v
γ& =
g
(3.1)

where v is velocity of casting knife and g is gap setting of casting knife (Ismail,
1997).

Figure 3.4 Pneumatically-controlled casting machine

 47

After that, the nascent membrane was quenched immediately into an aqueous
bath at room temperature (28°C) and remained there for 2 days. Finally, the washed
membrane was solvent-exchanged with methanol for 1 day and then air-dried for 1
day.

3.3 Membrane Permeation Cell Test

Gas permeation cell test is done to determine the membrane’s permeability

towards certain gases. This test is based on the principle of air bubble flow meter. A
schematic drawing of a gas permeation testing rigs being given in Figure 3.5. The
pure gas cylinder was connected to the rig via a flexible high-pressure Teflon hose. A
multi-stage pressure regulator on the gas cylinder controlled the feed gas pressure to
the permeation cell. The feed pressure was indicated by a pressure gauge and on/off
valve positioned at the upstream chamber of the permeation cell.

As said earlier, the objective of this test is to determine the permeability or

the gas flux. Gas flux is obtained from the time needed for a certain volume of gas to
permeate through the membrane. The shape of membrane for this test is round and
it’s surface area is 11.945cm2. Pure gas coming out of the cylinder tank is pressure
regulated at 0.5 and 1.0 bar, permeates through the membrane. The time taken to
permeate 10cm3 of pure hydrogen is clocked down and the permeability can be
calculated through the equation:

Qi = ( V / t ) (3.2)

where Qi is the flow rate of the permeating gas (cm/s), V is the volume of the gas
collected ( 10 cm3 ) and t is the time needed for gas to permeate (seconds).
Therefore, permeability can be determined by using the following equation:
 48

Pi = Qi / ( A.∆p ) (3.3)

where Pi is the gas permeability ( cm3/ s.cm2.cmHg or GPU), A is the membrane

surface area ( 11.945 cm2 ) while ∆p is the pressure difference (cmHg)

Figure 3.5 Gas Permeability Testing Rig

 49

3.4 Lead Acid Battery Charging Simulation Test

After various types of membranes were fabricated, they were then tested on
lead acid battery to find out whether they are capable of maintaining electrolyte level
inside the battery. In order to put the membrane up to the real test, the membrane is
applied on the battery cap and then the battery is charged by an alternator. This
analysis is done in three stages whereas to optimize the fabricating conditions so that
electrolyte losses can be minimized. The tests were done accordingly as below:

i) First Stage
- Preliminary membrane-assisted lead acid battery charging test
ii) Intermediate Stage
- Membrane-assisted lead acid battery charging test
iii) Final Stage
- Membrane-assisted lead acid battery charging test with heat supply

3.4.1 Preliminary Membrane-assisted Lead Acid Battery Charging Test

Before putting the membrane up to the real test, a preliminary test is done to
see which membrane formulation that suits to be applied on the lead acid battery.
This is done to screen down the suitable membrane formulation to be used in the
membrane assisted lead acid battery-charging test. Through this preliminary test, all
the membranes fabricated in the earlier stage were cut accordingly to the battery vent
hole size and then applied on each of the six lead acid battery vent holes with epoxy
adhesive to prevent any leakages. Then the battery is continuously charged using an
alternator and charged on average 12 to 15 Amps per hour. The objective of this test
is to select a membrane formulation with the most suitable polymer concentration.
This is done by observing the electrolyte level inside the battery. The membrane that
has the most retained electrolyte level throughout the experiment will be the chosen
one. A control test, run without any application of membrane on the battery holder,
was done to differentiate how much electrolyte losses can be minimized. Prior to this
screening process, the selected membrane formulation will proceed to the second
stage experiment, which is the membrane applied lead acid battery-charging test.
 50

3.4.2 Membrane-assisted Lead Acid Battery Charging Test

After the first stage of experiment has been established, the most suitable
membrane formulation will be chosen and reproduced with different casting shear
rates. The objective of this experiment is to determine the best shear rate so that the
electrolyte losses can be further minimized. Therefore during the membrane-assisted
lead acid battery-charging test with heat supply, the performance is already
optimized.

As the membranes were produced with different shear rates, they were cut
into circular sheets with the diameter of 3.5 cm. The membrane will be applied into a
battery cap as shown in Figure 3.7. Subsequently, this spiral end stainless steel
battery cap is applied on battery vent hole, and then sealed with epoxy sealant to
prevent any leakages. Charged using an alternator at the average rate of 15 Amps per
hour, the battery is charged for approximately three straight hours. Gas permeation
from the battery cap is measured as such shown in Figure 3. 8, where it uses the
principle of soap bubble flow meter. During this experiment, three parameters were
subsequently observed, which are the flow rate of the permeating vaporized
electrolyte; the electrolyte losses and the pressure build up measured inside battery.
At the end of the experiment, the membrane with the best casting shear rate will be
selected and will proceed to the final stage of the experiment. The best casting shear
will be expected to exhibit the best performance in minimizing electrolyte losses as
well as minimizing pressure build up.
 51

Figure 3.6 Schematic drawing and cross section of battery cap

Figure 3.7 Membrane-assisted lead acid battery charging test

 52

3.4.3 Membrane-assisted Lead Acid Battery Charging Test with Heat Supply

This experiment will be the third and the final stage experiment in evaluating
the effectiveness of membrane application on lead acid battery. It is quite similar to
the membrane-assisted lead acid battery charging test, where all of the equipment
configurations are all the same except that there is a water bath inclusion for this
experiment. The objective of this test is to investigate the effect of heat supply to the
battery on the electrolyte losses. Membrane with the most suitable polymer
concentration and casting shear rate which is selected from two previous
experiments, will be tested in this experiment to observe the effectiveness of the
membrane in retaining electrolyte within the existence of high temperature condition.

Similar to the membrane applied lead acid battery charging test, membranes
are cut into circular sheets with the diameter of 3.5 cm and applied into battery caps
as shown in Figure 3.7. Subsequently, this spiral end stainless steel battery cap is
applied on battery vent hole, and then sealed with epoxy sealant to prevent any
leakages. Charged using an alternator at the average rate of 15 Amps per hour, the
battery is charged for approximately three straight hours. This time, instead of
placing the lead acid battery on a weight scale, it is put inside a temperature
controlled water bath, as shown in Figure 3.9. To measure the water losses from the
lead acid battery, the initial mass of the battery is measured before starting the
experiment. After the test is done the mass of the battery is measured again to see the
electrolyte losses.
 53

Figure 3.8 Membrane-assisted lead acid battery charging test with heat supply

3.5 Vaporized Electrolyte Composition Measurement Using Raman

Spectroscopy

3.5.1 Selection of Analytical Instrument

Vaporized electrolyte composition detection test is done to recognize the

chemical composition of vaporized electrolyte that is coming out of the lead acid
battery during charging simulation test. This test is aimed to differentiate
quantitatively the elements contained in the vapor with and without the application of
membrane on the lead acid battery cap. Gas composition measurements can rather be
a difficult task to do since the nature of the sample of this experiment is known to be
high in moisture and can be very acidic to some sensitive types of analyzers, such as
gas chromatography. In addition to that, preparation of gas samples is not easy to
perform under very low pressure (few kPa) or very high pressures, where air
contamination or losses of gas could happen. Therefore, Raman Spectroscopy has
been selected to analyze the
 54

vaporized electrolyte composition, based on the advantages posed against the

analysis using gas chromatography relatively to the nature of this experiment, as
tabulated in Table 3.1.

3.5.2 Raman Spectrometer

Raman spectrometer is a useful technique for the identification of a wide

range of substances – solids, liquids and gases. It is a straightforward, non-
destructive technique that requires no sample preparation. This spectroscopy
involves illuminating a sample with a monochromatic light and uses a spectrometer
to examine the light scattered by the sample.

Raman spectrometer comprises the family of spectral measurements made on

molecular media based on inelastic scattering of monochromatic radiation. During
this process energy is exchanged between the photon and the molecule such that the
scattered photon is of higher or lower energy than the incident photon. The
difference in energy is made up by a change in the rotational and vibrational energy
of the molecule and gives information on its energy levels, and this has helped for
understanding molecular structure of a substance.

Table 3.1: Comparison on Raman Spectrometer and Gas Chromatography

Raman spectrometer Gas chromatography

1. Easy sample preparation. 1. Quite tedious sampling preparation.

2. No high purity gas carrier needed
3. Sample has no detrimental factor on
the detector of this equipment.
4. Could be executed even on low
pressure.
2. High purity carrier gas required.
3. Sample could damage capillary sensor
due to its acidity and moist content.
4. Low pressure operation could cause air
contamination and gas losses.
 55

At the molecular level, photons can interact with matter by absorption or

scattering processes. Scattering may occur either elastically, or inelastically. The
elastic process is termed Rayleigh scattering, whilst the inelastic process is termed
Raman scattering. The electric field component of the scattering photon perturbs the
electron cloud of the molecule and may be regarded as exciting the system to a
‘virtual’ state. Raman scattering occurs when the system exchanges energy with the
photon, and the system subsequently decays to vibrational energy levels above or
below that of the initial state. The frequency shift corresponding to the energy
difference between the incident and scattered photon is termed the Raman shift.
Depending on whether the system has lost or gained vibrational energy, the Raman
shift occurs either as an up- or down-shift of the scattered photon frequency relative
to that of the incident photon. The down-shifted and up-shifted components are
called respectively the Stokes and anti-Stokes lines. A plot of detected number of
photons versus Raman shift from the incident laser energy gives a Raman spectrum.
Different materials have different vibrational modes, and therefore characteristic
Raman spectra. This makes Raman spectroscopy a useful technique for material
identification. There is one important distinction to make between the Raman
spectra of gases and liquids, and those taken from solids - in particular, crystals. For
gases and liquids it is meaningful to speak of the vibrational energy levels of the
individual molecules which make up the material. Crystals do not behave as if
composed of molecules with specific vibrational energy levels, instead the crystal
lattice undergoes vibration. These macroscopic vibrational modes are called phonon.

3.5.3 Experimental Set-up

The test includes a Raman Spectrometer that is linked to a desktop computer, to

analyze the intensity of the vapor. In this case, all of the six lead acid battery caps
were fitted with tubing to channel the vapor inside the battery before collected inside
a glass holder. This glass holder will be placed manually in the Raman Spectrometer
chamber, where the source X-ray light will be directed on the sample. Both
conventional and membrane applied lead acid batteries were charged and the
vaporized electrolyte samples will collected every 20 minutes for three hours period.
The Raman Spectrometer is linked to a computer for the data collection and
 56

processing using customized software. The test is schematically shown as in Figure

3.6. The Raman spectrum will feature a Raman Shift versus intensity form of data.
From the spectrum, the peaks will be analyzed accordingly to the wave number and
the intensity of the samples.

Raman
Spectroscopy

Computer
Battery

Alternator

Figure 3.9 Vaporized electrolyte composition measurement using Raman

Spectroscopy

3.6 Scanning Electron Microscopy (SEM) Analysis

Scanning electron microscopy is an apparatus that is capable of magnifying a

very discrete surface into a larger and clearer image. This analysis is done on the
membrane surface to examine the morphology, or specifically the membrane
structure, pore distribution, defects and presence of impurities. After that, the
samples were imaged and photographed by employing a scanning electron
microscope (Philips SEMEDAX; XL40; PW6822/10) with potentials of 10 kV under
magnifications ranging from 500x to 5000x.
 CHAPTER 4

RESULTS AND DISCUSSION

4.1 Performance Analysis on The Resultant Membrane

4.1.1 Gas Permeation Test Results

In the gas permeation test, the two main gases, oxygen and hydrogen, that
were formed in the battery during charging were tested using gas permeation test rig.
Every membrane sample from different types of formulations was tested to observe
the effect of different casting formulation on the performance of lead acid battery.
There are eight different types of membrane with different formulations that were
successfully cast. The solution formulations are tabulated in Table 4.1.

Each and every type of the cast membranes was tested for its permeation of
pure hydrogen and oxygen gases. Data for low polymer concentration membranes
such as GS 6, GS 7 and GS 8 cannot be obtained due to the rapidness of gas
permeating from these membranes. Therefore, permeation rates of these membranes
cannot be calculated.
 58

Table 4.1: Casting solution formulations

Polymer Solution GS 1 GS 2 GS 3 GS 4 GS 5 GS 6 GS 7 GS 8
Composition

Polysulfone (PSF) 22% 18.7% 15.2% 20 % 15 % 13 % 12.5% 11%

N,N-dimethylacetamide 31.8% 33.2% 34.6% - - - - -

(DMAc)

Dimethylformamide - - - 80 % 85 % 87% 87.5% 89%

(DMF)

Tetrahydrofuran (THF) 31.8% 33.2% 34.6% - - - - -

Ethanol 14.4% 14.9% 15.6% - - - - -

Figure 4.1 depicted the membrane produced from ternary system such as in
GS 1, GS 2 and GS 3. It was observed that the permeation rate for GS 3 is higher
than that of GS 1. This phenomenon occurs because of higher polymer concentration
in the casting solution produces thicker skin layer, thus resulted in lower permeation
rate. The scenario also happens in binary system casting solutions. It seems that the
polymer concentration for GS 5 is lower than of GS 4, therefore permeation rate for
GS 5 is higher than GS 4. The only difference between binary and ternary system is
the structure of the resultant membrane. Binary system tends to form membranes
having more uniform structure rather than that of ternary system as proven in the
SEM images.
 59

H2 Test O2 Test
18
16
14
Gas Permeation Rate,
cm3/ cm2.s. cmHg

12
10
8
6
4
2
0
GS 1 GS 2 GS 3 GS 4 GS 5

Figure 4.1 Permeation rate for five different membranes

4.1.2 Preliminary Screening of Membrane for Membrane-Assisted Lead Acid

Battery Charging Test Analysis

Optimum polymer concentration of casting solution has to be determined in

order to achieve minimum electrolyte losses during lead acid battery charging
process. In this study, casting solutions consisted of polysulfone as the polymer, N,N-
dimethylacetamide (DMAc), dimethylformamide (DMF) and tetrahydrofuran (THF)
as the solvent and ethanol as the non-solvent. As shown in Table 4.1, different
casting formulations have been prepared from binary and ternary systems in search
of the optimum composition which can retain the most electrolyte in lead acid battery
during charging process. Therefore, effects of polymer concentration on membrane
properties and structures could be investigated.
 60

The solutions were cast at the shear rate of 210 s-1 prior to coagulation bath.
Shear rate was calculated from equation (3.3) with the gap of casting knife of 150 µm
and casting velocity at 3.15 cm/s.

4.1.2.1 Effect of Membrane Formulation on The Performance of Membrane in

Retaining Electrolyte Level

In this study, the performance of membranes cast from ternary and binary
systems were tested in retaining electrolyte from being disposed to the atmosphere.
Since no previous work has been done on this area, the experiment had to be done
based on direct observation on the lead acid battery during charging process.

The observation done was based on electrolyte level during recharging of a

lead acid battery. This is a way to simulate the charging condition inside a car,
whereas the alternator charges the battery. This condition is said to be the main factor
that causes water decomposition. Hydrogen, oxygen and water vapor forms
whenever overcharging of a lead acid battery. From the observations made, after a
few hours of charging, the membrane that was applied on top of the battery cap had
swollen. Other observation was the battery casing also became swollen and the level
of electrolyte fluctuates. This is due to the pressure build-up inside the battery casing
because of the membrane skin layer was too thick for the vaporized electrolyte to
diffuse through. The next step taken after observing the battery casing became
swollen was to stop the charging process.

As tabulated in Table 4.2, the results of the membrane-assisted battery test

showed that ternary system solution (one polymer, one solvent, one non-solvent)
membranes, GS1, GS2 and GS3 are still too tight as the pressure builds up inside the
battery casing and causes the casing to swollen. The application of binary system
(one polymer, one solvent) solution cast membranes GS4 and GS5, have better
results than those shown in ternary system membranes. The pressure build-up
featured in GS 4 and GS5 took longer charging period to swell the battery casing and
the losses are quite
 61

Table 4.2: Preliminary screening of membrane for membrane-assisted lead acid

battery test result
Rate of electrolyte
Membrane loss after Remarks
charging, %
Battery casing severely swollen
GS 1 10
after 2 hours of charging
Battery casing swollen severely
GS 2 10
after 2.5 hours of charging
Battery casing severely swollen
GS 3 13
after 3 hours of charging
Battery casing severely swollen
GS 4 13
after 3.25 hours of charging
Battery casing swollen after 3.5
GS 5 15
hours of charging
Battery casing moderately
GS 6 15
swollen after 4 hours of charging
Battery casing mildly swollen
after 2 hours of charging, but
GS 7 20
droplets of water emerge on the
membrane surface
Battery casing mildly swollen
GS 8 25 after 1.5 hours of charging, but
the membrane sheet ruptured

minimal compared to GS1, GS2 and GS3. This is due to the thickness of the skin
layer possessed by the ternary system (one polymer, one solvent and one non-
solvent) solution cast membranes. This result agreed with the conclusion made by
previous works (Chung et al., 1997; Hachisuka et al., 1996).

Meanwhile, the lower polymer concentration membranes such as in GS 6, GS

7 and GS 8 showed better permeability compared to the latter membranes. This is
proved through the observation of battery electrolyte level and the compactness of
the swollen battery casing. However, GS 7 displayed poor electrolyte retaining
characteristics as water droplets emerge on its surface. Meanwhile GS 8 membrane
had ruptured after the battery was charged for 1.5 hour. This indicates that the
polymer matrixes found in GS7 and GS 8 are not that strong and compact as those
membranes permeate gases easily. As for GS 6, with polymer concentration of 13.0
wt/wt % polysulfone and 87 wt/wt % of DMF solvent, shows the best permeation of
 62

vaporized electrolyte and at the same time shows minimum pressure build-up inside
the battery casing. It can be justified that GS 6 membrane, has passed the preliminary
test and practically can be used as an electrolyte-retaining device.

4.1.3 Membrane-assisted Lead Acid Battery Charging Test Analysis

Rheological factors in membrane formation process can be manipulated and

is considered one of the latest approaches in membrane formation process today. It
can provide a prospect for a potential platform to the development of defect-free and
ultrathin-skinned asymmetric membranes for gas separation and even on application
on lead acid battery as an electrolyte-retaining device. Prior to the preliminary
membrane-assisted lead acid battery charging test, GS6 casting solution with the
formulation of 13 wt/wt % of Polysulfone (PSF) and 87 wt/wt % of N-N-
dimethylformamide (DMF) was selected as the most suitable membrane that is going
to be tested on the real battery simulation test.

Polysulfone contained casting solutions, which is proven as shear-thinning

and moderately viscoelastic under rheological characterization (Ismail, 1997; Sharpe
et al., 1999; Ismail et al., 1997; Ismail et al., 1999). Flat sheet membranes were cast
on a glass plate with a casting knife which the gap between the two was set at
150µm. In this analysis, GS6 membranes prepared with varied shear rates ranging
from 175 s-1 to 300 s-1 were tested to investigate the effect of casting shear rate on
the performance and structure of the membrane. The membranes were cast into six
different shear rates and substituted with the names as shown in Table 4.3.
 63

Table 4.3: GS6 membranes prepared with different shear rates

Membrane Casting Shear Rate (s-1) Substitute Name

300 7s

262.5 8s

233.33 9s

210 10s

190.91 11s

175 12s

The test consists of battery charged by an alternator with the average

charging rate of 12 to 15 Ampere per hour. Three parameters were observed here,
which are the flow rate of the permeating gas coming out of the battery vent hole, the
electrolyte losses during the battery charging and the pressure build-up measure
inside the battery casing. At the end of this test analysis, one particular shear rate will
be selected as the optimum shear that is going to be tested on membrane applied lead
acid battery charging test with heat supply. In order to select the most optimimum
casting shear rate, the analysis must acquire these characteristics prior to the
membrane applied lead acid battery-charging test:

i) Minimized electrolyte losses

ii) Minimized pressure build-up inside battery casing with good flow rate
profile of vaporized electrolyte.
 64

4.1.3.1 Effect of Shear Rate on The Performance of Membrane in Minimizing

Electrolyte Losses

During membrane-assisted lead acid battery charging test, the most

important parameter observed here is the electrolyte losses. This is because the main
objective of this research is to minimize the electrolyte losses from the lead acid
battery during charging process. One of the criteria in selecting the best shear rate for
the membrane is its capability in retaining the electrolyte volume from being
disposed into the atmosphere.

As shown in Figure 4.2, the chart shows the profile of electrolyte losses of
three selected membrane shear rates and one control test. The other three profiles can
be seen in Appendix A2. The electrolyte loss for the control test was continuously
increasing until the end of the test. At the end of the three-hour experiment, the
control test battery lost about 80 grams of electrolyte, and has an average electrolyte
losses rate of 26.67 grams per hour. Meanwhile the overall electrolyte losses were
tabulated in Table 4.4. As it can be seen here, for batteries that were applied with
membranes, the electrolyte losses were found to be the coherent in shear rates of 7s,
11s and 12s, with the rate of losses of 20 grams per hour. Whereas for the shear rates
of 8s, 9s and 10s, the average rate of electrolyte losses was minimally around 6.67
grams per hour.

As depicted in Figure 4.3, the calculated percentage of electrolyte losses

minimization using GS 6 membranes cast at different shear rates compared to the
conventional lead acid battery. The percentage of electrolyte losses minimization was
calculated as follows:

(Electroly te loss for control test - Electrolyt e loss with membrane )

= x 100% (4.1)
(Electroly te loss for control test)
 65

Figure 4.3 shows that 7s, 11s and 12s membranes were able to decrease the
electrolyte losses by 25%. However, 8s, 9s and 10s membranes showed 75%
reduction in electrolyte losses. This indicates that the critical shear lies within the
range of 210s-1 to 262.5s-1.

In order obtain out the critical shear rate, a comparison analysis must be made
on other parameters, which are the pressure build-up inside the battery casing and the
flow rate of the vaporized electrolyte profile. The critical shear rate will feature a
minimal pressure build-up inside the battery casing and smoothest flow rate profile
of vaporized electrolyte.

Table 4.4: Total and average rate of electrolyte losses during membrane-assisted
lead acid battery charging test

Membrane Used Total Electrolyte Losses Rate of Electrolyte

(grams of electrolyte) Losses
(grams per hour)
Control Test 80 26.67
7s 60 20
8s 20 6.67
9s 20 6.67
10s 20 6.67
11s 60 20
12s 60 20
 66

13.85

13.84

13.83

13.82

13.81
Electrolyte Losses (kg)

13.8

Control Test
13.79
7s
9s
13.78
12s

13.77

13.76

13.75

13.74

13.73
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180
13.72

Charging Time (minute)

Figure 4.2 Effect of membrane casting shear rate on the performance of membrane in minimizing electrolyte losses
 67

Figure 4.3 Minimization of electrolyte losses with comparison to the conventional lead
acid battery

4.1.3.2 Effect of Membrane Casting Shear Rate on The Performance of Membrane

in Minimizing Pressure Build-Up

Figure 4.4 shows typical pressure profiles of pressure build-up during

membrane-assisted lead acid battery charging test. There is no pressure profile for the
control test as there was no pressure build-up since all of the vaporized electrolytes were
disposed through the vent hole.

Membranes cast at six different shear rates show different values of maximum
pressure build-up with similar trend of profile. Each of the membranes had a sudden
increase of pressure build-up during the first twenty minutes of charging. The next
phenomenon seen after the sudden increase is the pressure build-up starts to show
tendency in becoming constant as the flow rate of vaporized electrolyte becomes faster.
 68

During the first twenty minutes of charging, the vaporized electrolyte could not
be permeated smoothly since the pressure build-up is still low. Since membrane flux is
pressure driven, the vaporized electrolyte could not permeate through the selective skin
and therefore is trapped inside the battery casing. The pressure build-up has increased
until it reaches the point where the pressure becomes constant and the vaporized
electrolyte permeation rate becomes constant too. This is the point when the condition
reaches its “working pressure”, where the pressure build-up is stabilized with the smooth
and constant permeation of vaporized electrolyte.

In selecting the critical shear rate within the six different shear rates applied, the
pressure profile must feature a minimum value of “working pressure” as well as
minimizing electrolyte losses during the charging process. In this case, the 9s membrane
(cast at 233 s-1) had the lowest pressure build-up profile with the final build-up pressure
of only 0.73 bar after three hours of charging. Compared to the other shear rates, 7s
membrane recorded 0.93 bar; 8s membrane - 1.02 bar; 10s membrane - 0.88 bar; 11s
membrane – 0.96 bar and 12s membrane – 0.93 bar, 9s membrane relatively has the
lowest final pressure.
 69

1.1

0.9

0.8

0.7
Build-up Pressure (bar)

0.6 7s
8s
0.5 9s
10s
0.4 11s
12s
0.3

0.2

0.1

0
0 10 20 30 40 60 80 100 120 140 160 180
Charging Time (minute)

Figure 4.4 Effect of shear ate on the pressure build-up inside battery casing
 70

As shown in Figure 4.5, the flow rate of gas permeation from the battery during
charging in the control test is continuously increasing. This shows that, electrolyte is
continuously decomposed without any application of membrane. Most of the membranes
have shown a slow increase of vaporized electrolyte flow rate except for 9s membrane.
The rate of increment for vaporized electrolyte flow rate in 7s, 8s, 10s 11s and 12s
membranes were not that distinct from what had been shown in the 9s membrane flow
rate profile. The flow rate of gas permeation from the battery during charging with the
application of 9s membrane is quite slow at the early stages of charging and the rate is
increasing as time elapse. During the first sixty minutes of charging, 9s membrane have
shown slower flow rate of vaporized electrolyte due to its electrolyte retaining
characteristics. However after the first sixty minutes, 9s membrane’s profile almost
emulates the flow rate of the control test, and this proves that the vaporized electrolyte is
being well circulated inside the battery without tolerating the minimization of electrolyte
losses during charging. This indicated that as charging proceed, the permeation of gas
will continuously increase and pressure build-up inside the battery casing could be
minimized.

Effects of shear experienced in casting process on membrane properties were

intimately correlated to the structural knowledge at molecular level. As shown in Figure
4.3 and 4.4, the critical shear would be selected from analyzing the performance of each
of the shear rates in minimizing electrolyte losses as well in minimizing pressure build-
up during charging process. According to the results achieved, the critical shear rate was
determined to be about 233.33 s-1 as in 9s membrane, due to its minimal electrolyte
losses and lowest pressure build-up among the other casting shear rates.

In the region prior to the critical shear rate (233.33 s-1), formation of dense skin
occur due to demixing and precipitation mechanism, which was considered to be
independent of shear rate. Increasing shear rate enhance molecular orientation in skin
layer and in turn, improving selectivity in asymmetric membrane (Ismail et al., 1997;
Shilton, 1997).
 71

2.25

1.75

1.5
Ctrl Test
Vaporized Electrolyte
Flowrate (cm3/s)

7s
1.25 8s
9s
1 10s
11s
12s
0.75

0.5

0.25

0
10 20 30 40 60 80 100 120 140 160 180

Charging Time(minutes)

Figure 4.5 Effect of shear rates on the flow rate profile of vaporized electrolyte
 72

This has been proven where electrolyte losses were seemed to be further
minimized. Meanwhile the permeation rate of asymmetric membrane was also found to
increase when the shear rate is approaching to the critical shear, which was consistent
with the reduction in skin thickness, where this is evindenced by pressure build-up
which seemed to be reduced (Shilton et al., 1994).

Since the solution used in this study is a shear thinning, when shear rate reached
beyond the critical point (233.33 s-1), a severe decrease in solution viscosity occurred
presumably due to chain entanglement losses in solution. In this case, membrane might
undergo an instant demixing and precipitation to result in a highly oriented skin layer.
(Sharpe et al., 1999; Chung et al., 2000). Furthermore, casting over the critical shear rate
(233.33 s-1) which is considered high shear rate, could pull molecular chains or phase
separated domains apart and began to create slight defects or imperfections in skin layer
(Sharpe et al., 1999). As shown in the Figure 4.4, casting polysulfone membrane at shear
rates of 262.15 s-1 to 300 s-1 causes a decrease in selectivity where electrolyte losses
seemed to be higher than those feature near the critical shear rate region.
 73

4.1.4 Membrane-assisted Lead Acid Battery Charging Test with Heat Supply
Analysis

4.1.4.1 Effect of Water Bath Temperature on Electrolyte Losses of a Lead Acid

Battery During Charging

As depicted in Figure 4.6, the chart shows the total electrolyte losses for both
batteries, membrane applied and conventional ones, during the membrane-assisted lead
acid battery charging test with the temperature set at 60 oC and 80oC respectively. This
test, eventually simulates the condition within the engine compartment, where the
battery is charge at the average rate of 15 Amps per hour and with the effect of high
temperature of 60 oC and 80oC. The objective is to observe how the membrane performs
in minimizing electrolyte losses, even with the existence of extreme temperature effect.

For the control test results, the electrolyte losses for the battery that was charged
for three straight hours in a water bath set at 60 oC was 60 grams . As calculated, the
average electrolyte losses rate for this conventional battery is 20 grams per hour.
Meanwhile the electrolyte losses for the GS6-9s membrane applied battery in the same
condition was only 40 grams , where the average electrolyte losses rate is 13.33 grams
per hour. As resulted in the control test, the electrolyte losses for the battery charged for
three straight hours in a water bath set at 80 oC was 100 grams, while the losses for the
GS6-9s membrane applied lead acid battery in the same condition was only 60 grams.
On average, the rate of electrolyte losses for a conventional battery when the
temperature is 80 oC is 33.33 grams per hour while for the membrane applied battery is
only 20 grams per hour.

As shown in Figure 4.7 and by calculating using equation (4.1) during lead acid
battery charging process in the engine compartment, when the temperature reaches 60
o
C, the membrane-assisted lead acid battery can save up to 33.33% of electrolyte
compared to the conventional battery. Meanwhile, when the temperature reaches 80 oC,
 74

0.12

0.1
Electrolyte Losses (kg)

0.08

0.06

0.04

0.02

0
Ctrl Test; With GS6-9s; Ctrl Test; With GS6-9s;
T=60 oC T=60 oC T=80 oC T=80 oC

Figure 4.6 Total electrolyte losses during membrane-assisted lead acid battery charging
test with heat supply

the membrane-assisted lead acid battery can save up to 40% of electrolyte during the
charging process.

Comparing to the results from the previous charging test, the average electrolyte
losses rate for the membrane applied lead acid battery at room temperature is 6.67 grams
per hour, which is about 50% less than when the temperature is set at 60 oC, and 66.67%
less than when the temperature is set at 80 oC. This means that high temperature
conditions has an enormous effect on the electrolyte losses for a membrane-assisted lead
acid battery during charging. Although with the membrane application on lead acid
battery can minimize up to 40% of electrolyte losses in conventional battery during the
temperature is 80oC, the losses can still be further minimized with preventive measures.
This can be done with better heat insulation of the battery casing or altering the battery
placement in engine compartment; which prevents heat being transferred into the
battery.
 75

0.45

0.4

0.35

0.3
Percentage (%)

0.25

0.2

0.15

0.1

0.05

0
Water bath Water bath
set at 60oC set at 80oC

Figure 4.7 Minimization of electrolyte losses with compared to the conventional lead
acid battery

4.1.4.2 Effect of Water Bath Temperature on Pressure Build-Up in a Lead Acid

Battery During Charging

The objective is to observe how the membrane performs in minimizing pressure

build up, even with the existence of extreme temperature effect. Figures 4.8 and 4.9
show the pressure build-up and vaporized electrolyte flow rate profiles during membrane
applied lead acid battery charging test with heat supply.

The pressure profile of the membrane applied lead acid battery charged in a
water bath set at 60 oC and 80 oC showed almost similar increment of pressure for a
battery that is charged without any heat supply. The only difference existing is the final
pressure is slightly higher than the previous test. When the temperature is set at 60 oC the
final pressure is about 0.77 bar, while the final pressure when the temperature set at 80
o
C is about 0.78 bar. Compared to the battery charged without any heat supply, the final
pressure was about 0.73 bar. This means that within the effect of the high
 76

0.8

0.6
Build-up Pressure (bar)

With GS6-
0.4
9s; T=60oC

With GS6-
9s; T=80oC

0.2

0
0 10 20 30 40 60 80 100 120 140 160 180
Charging Time (minute)

Figure 4.8 Effect of water bath temperature on pressure build-up in a lead acid battery during charging
 77

2.5

2.3

2.1
Vaporized Electrolyte Flowrate (m3/s)

1.9

1.7
Control Test;
1.5
T=60oC
With GS6-9s;
1.3 T=60oC
Control Test;
1.1 T=80oC
With GS6-9s;
0.9 T=80oC

0.7

0.5
10 20 30 40 60 80 100 120 140 160 180
Charging Time (minute)

Figure 4.9 Effect of water bath temperature on the flow rate profile of vaporized electrolyte
 78

temperature during charging, the pressure build-up is increased by only minimal margin.
Therefore, in high temperature conditions, the pressure build-up will not differ largely
from the battery that is being charged at room temperature. This is due to the fact that
the flow rate of vaporized electrolyte have been consistently fast even on the early stages
of charging process. With the smoothly permeating vaporized electrolyte, this condition
has assisted the system to reduce the pressure build-up inside the battery.

For the vaporized electrolyte flow rate profile, the vaporized electrolyte flow rate
for both control tests run at 60 oC and 80 oC were permeating very fast. The fact that the
effect of high temperature on the formation of more vaporized electrolyte had increased
the flow rate of the permeating vaporized electrolyte. But compared to the membrane
applied lead acid battery, the flow rate of vaporized electrolyte during the early stages of
charging was quite low due to electrolyte retaining characteristics possessed in the
membrane. As the charging elapses, the pressure had increased and the vaporized
electrolyte flow rate became faster as to minimize the pressure build-up inside the
battery.

4.2 Vaporized Electrolyte Composition Measurement With Raman

Spectroscopy

This analysis involved collecting gas samples consisting of vaporized electrolyte

evolving from both conventional and membrane applied lead acid batteries were
collected every 20 minutes during charging process and analyzed in the Raman
Spectrometer instrument. Once all the Raman spectrums were collected from the
analysis, the intensity peaks of the diagnosed elements were assessed. In this analysis,
two main elements were investigated which are the hydrogen and oxygen. For most of
the Raman analysis, the average relative normalized differential Raman scattering cross
sections for hydrogen and oxygen gases are 4156 cm-1 and 1555 cm-1 respectively
(Weber, 1979). It is customary for Raman Spectrometer instrument to feature their data
in intensity form. Previous efforts have been made to determine partial pressures for gas
samples based on linear relationship that exists between the Raman intensity and the
 79

concentration of molecules (Henn, 1996). Therefore, in this analysis, the results can
describe the concentration of each hydrogen and oxygen gases through the Raman
integrated intensity data. This indeed to show the effectiveness of membrane application
in retaining hydrogen and oxygen gases from being disposed into the atmosphere.

As shown in the Figure 4.10(a), the chart shows the example Raman spectrum
for a vaporized electrolyte gas sample collected from a conventional battery, while
Figure 4.10(b) features the Raman spectrum for the membrane-assisted lead acid battery
vaporized electrolyte gas sample. It can be seen that a strong and potent peak discovered
at the range of 3800-3900 cm-1 , where this indicated the existence of hydrogen element
in the sample with quite high concentration. The chart also depicts the indication of
oxygen element in the range of 1500-1650 cm-1 but compared to hydrogen, the quantity
is smaller.
 80

0.011

0.01

0.009

0.008

0.007

Intensity
0.006

0.005

0.004

0.003

0.002
4100 3900 3700 3500 3300 3100 2900 2700 2500 2300 2100 1900 1700 1500 1300 1100 900 700 500
Raman Shift (cm-1)

Figure 4.10(a) Raman Spectrum for vaporized electrolyte (conventional battery) sample
taken at 100 minutes of charging process

0.0065

0.006

0.0055

0.005

0.0045
Intensity

0.004

0.0035

0.003

0.0025

0.002
4100 3900 3700 3500 3300 3100 2900 2700 2500 2300 2100 1900 1700 1500 1300 1100 900 700 500
Raman Shift (cm-1)

Figure 4.10(b) Raman Spectrum for vaporized electrolyte (membrane-assisted battery)

sample taken at 120 minutes of charging process
 81

The rest of the data of this analysis have been compiled in Appendix B and were
plotted in Figure 4.11 and Figure 4.12 to show the overall intensities for hydrogen and
oxygen gases during the three hour charging process. As depicted in the Raman
spectrums, the Raman shift (wave number) for the detected hydrogen and oxygen
intensity peaks would not only be fixed at 4155 cm-1 and 1555 cm-1 respectively, but
also can be found at the regions near to these two plots. This phenomenon occurred due
to the fact that gas samples were having high kinetic energy. Therefore, the mobility of
the molecules forces of the scattering process happened at different Raman shifts.
However, it was still in the near regions of the normallized differential Raman scattering
cross section.

As depicted in Figure 4.11, the intensities for hydrogen in conventional battery

gas samples were seemed to be marginally higher when compared to the intensities
found in the membrane-assisted lead acid battery. It can be determined that, the
intensities for conventional battery gas samples were mostly 50-60% higher than those
found in the membrane-assisted battery gas samples. These intensities indicated the
concentration of hydrogen gas contained in the gas samples and simultaneously
described that most of the hydrogen gas evolved during charging process were still
retained in the membrane applied battery.

Meanwhile in Figure 4.12, similar phenomenon of hydrogen intensities were

displayed, where the oxygen intensities for conventional battery gas samples were
higher compared to the intensities found in the membrane applied battery. As calculated,
the intensities for oxygen gas samples in conventional battery were 10-30% higher
compared to the membrane-assisted battery gas samples. The vaporized electrolyte in
membrane assisted lead acid battery had lower oxygen concentration due to the fact that
most of the oxygen gas evolved during charging process were being retained in the
battery casing.
 82

0.014

0.012

0.01

Conventional
0.008
Battery
Intensity

Membrane
0.006 Applied Battery

0.004

0.002

0
20 40 60 80 100 120 140 160 180
Charging Time (minute)

Figure 4.11 Overall hydrogen intensities for vaporized electrolyte gas samples for conventional and membrane-assisted lead acid
batteries.
 83

0.012

0.01

0.008
Intensity

Conventional
0.006
Battery

Membrane
0.004
Applied Battery

0.002

0
20 40 60 80 100 120 140 160 180
Charging Time (minutes)

Figure 4.12 Overall oxygen intensities for vaporized electrolyte gas samples for conventional and membrane-assisted lead acid
batteries.
 84

These scenarios indicated that the concentration of hydrogen and oxygen in

conventional battery are higher than that in membrane applied battery. The
explanation to this phenomenon is that most of the hydrogen and oxygen gases
evolved during charging process are being retained inside the membrane applied
battery instead of being disposed freely as in the conventional battery. The
application of membrane on lead acid battery during charging seemed able to reduce
the rate of vaporized electrolyte disposal into the atmosphere and to a certain extent,
has successfully functioned as an electrolyte retaining device for lead acid battery.
Therefore, this has shown that the membrane has given a tremendous effect in
minimizing electrolyte losses in lead acid batteries during charging process.

However, further increment of membranes efficiency in minimizing

electrolyte losses can be reached by introducing a recombination mechanism into the
membrane application so that the hydrogen and oxygen gases can create the bond to
form water droplets again. Through this way, instead of just lowering the rate of
hydrogen and oxygen disposal into the atmosphere, the electrolyte can be saved by
the formation of water droplets and only minimal traces of unrecombined gases will
be disposed through the membrane. With the existence of catalysts such as nickel
and platinum, it is believed that rate of water formation reaction can be increased,
without being involved in the reaction itself.

4.3 Membrane Characterization Using Scanning electron Microscopy (SEM)

4.3.1 Effect of Polymer Concentration on Membrane Morphology

Membrane structure and morphology were further characterized by using

Scanning Electron Micrscope (SEM). As shown in the micrographs of Figure 4.13,
the prepared membranes showed a typical asymmetric structure. As can be observed,
there is two layer structure; which consists of a thin and dense selective skin; and a
porous sublayer that supports the selective skin. A trend of average pore size can be
detected in the images (Figure 4.13(a-c)) where the higher the polymer concentration
in the casting solution, the smaller is the average pore size and vise versa (Koros,
1993)
 85

Another observation made on the micrograph images here is that the

membranes prepared from casting solution with higher polymer concentration
exhibited a thicker skin layer (Figure 4.13(a)). Furthermore, a transition layer was
significantly found in the higher polymer concentration membrane. After casting,
dry phase-separated structure beneath the nascent skin would tend to redissolve from
the underlying homogenous solution (Pesek and Koros, 1993) However, in high
polymer concentration solutions the redissolution step was delayed by their highly
viscous characteristics. Therefore, the remaining dry phase separated region would
be presumably transformed into a transition layer. In contrast, the redissolution step
was promoted by solutions with low polymer concentration, therefore there is no
formation of transition layer for the lower polymer concentration solutions (Figure
4.13(b-c)). This is in agreement with the suggestion of skin thickness of polysulfone
membranes increases with increasing polymer concentration (Mulder, 1985)
 86

Skin Layer
Transition layer

Substructure

(a)

Skin Layer

Substructure

(b)

Skin Layer

Substructure

Macrovoids

(c)
Figure 4.13 Scanning electron micrographs of membrane cross section with different
polymer concentration ( a: 15.0 wt/wt%; b: 13.0 wt/wt%; c: 12.5 wt/wt%)
 87

This has been proven that casting asymmetric membranes from a dilute
polymer solution produced a thin and porous skin layer, leading to a high
permeability of vaporized electrolyte and low pressure build up. While increasing
polymer concentration of casting solution forms a denser and thicker skin layer,
resulting in a more pressure build up but less vaporized electrolyte permeation in
asymmetric membranes for the application on lead acid battery during charging.

Also observed in the Figure 4.13(c) the existence of macrovoid-filled open-

cell substructure (where pores penetrated each other and became interconnected by
round holes) were formed. The existence of these macrovoids is said to be due to the
fact that high solvent ratio casting solutions (Kimmerle and Strathman, 1990). Some
researchers have concluded that the existence of these macrovoids have the effect on
the mechanical strength of the membrane, where possible failures such as
compaction or collapse of membranes would occur when being applied to high
pressure operation for gas separation process (Lai et al., 1999; Zeman, 1994). This
was proved to be in agreement with the suggested theory where in the preliminary
membrane-assisted lead acid battery charging test, GS 8 membrane ruptured even
after one and a half hours of charging.

4.3.2 Effect of Casting Shear Rate on the Membrane Morphology

The electron micrographs of cross sections of the membranes are shown in

Figure 4.14. As expected, the developed asymmetric polysulfone membrane was
composed of an ultrathin, dense skin layer with a sponge-like porous substructure, as
observed in the Figure 4.14(a-c). Uniform voids are thoroughly isolated throughout
the membrane sublayer.

However, as it can be seen here, the skin thickness of membrane was found
to be decreasing with the increase of shear rate during casting process. In addition to
this, as seen in Figure 4.14(c), a relatively thicker transition layer was found existing
in the polysulfone membrane with the casting shear rate of 300 s-1 . There was not
much of a difference in the outloook of substructures for the membranes cast at
different shear rates. However, casting over the critical shear rate (233.33 s-1) which
 88

is considered high shear rate, could pull molecular chains or phase separated domains
apart and began to create slight defects or imperfections in skin layer and the
substructure itself. It can be seen in Figure 4.14 (c), that the voids in the substructure
of the membrane cast over the critical shear rate were arranged uniformly compared
to that shown in Figure 4.14(b) where most of the voids were arranged distributively.
 89

Skin layer

Substructure

(a)
Skin layer

Substructure

(b)

Skin layer
Transition layer

Substructure

(c)
Figure 4.14 Scanning electron micrographs of membrane cross section at different
shear rates ( a: 210-1; b: 233.33 s-1 ; c: 300 s-1)
 CHAPTER 5

GENERAL CONCLUSIONS AND RECOMMENDATIONS

FOR FUTURE WORK

5.1 Conclusions

In this chapter, a brief overview of the obtained results will be elucidated to

sum up all the experimental work and to consolidate the detailed discussions
elaborated in the previous chapter.

The application of gas separation membrane on lead acid battery during

charging process for the purpose of minimizing electrolyte losses can be optimized
with proper manipulation of fabricating conditions during the flat sheet membrane
formation process. Phase inversion and rheological factors such as polymer
concentration and casting shear rate were investigated during this study to produce
the most suitable gas separation membrane that can minimize electrolyte losses as
well as minimizing the pressure build up within the battery casing. Another factor
that contributes to electrolyte losses in lead acid battery, which is the temperature,
was also studied during the research. Based on results of this study, conclusions were
drawn and stated as following:

i) Increasing polymer concentration of casting solution increased

solution viscosity and skin thickness of asymmetric membrane. As a
result, membrane with high polymer concentration minimizes
 91

electrolyte losses but increases pressure build-up in battery casing

during charging process; or vice versa.
ii) An increase of shear rate enhanced molecular orientation in the skin
layer of asymmetric membrane. Increasing shear rate seemed to
reduce the membrane skin layer thickness, and as the result the
electrolyte losses were minimized and pressure build up were
reduced. Membrane cast at critical shear rate had shown minimized
electrolyte as well as reduced pressure build up during battery
charging process. However, casting over the critical shear rate pulled
molecular chains or phase separated domains apart and began to
create slight defects or imperfections in skin layer.
iii) Temperature condition during lead acid battery charging plays an
important effect on the electrolyte losses during charging process. At
the temperature of 60oC, the electrolyte losses were two folds of the
battery that is charged at room temperature. Meanwhile at 80oC, the
electrolyte losses were three folds of the battery charged at room
temperature.
iv) The concentration of hydrogen and oxygen gas molecules have been
estimated to be reduced about 50-60% and 10-30% respectively, when
membrane is applied on the battery during charging process. This has
been proven by the intensity data obtained from the Raman
Spectroscopy of the vaporized electrolyte composition detection
analysis.
v) Based on the obtained results, the most suitable gas separation
membrane to be applied on lead acid battery for the purpose of
minimizing electrolyte losses is prepared from the casting solution of
13 wt/wt% and 87 wt/wt% and cast at the shear rate of 233 s-1.
Compared to the conventional battery, the application of this
membrane into lead acid battery during charging process can
minimize up to 75% of electrolyte losses at room temperature and 40
% at temperature of 80oC.
 92

As a conclusion, the application of gas separation membrane on lead acid

battery during charging process had successfully functioning as an electrolyte
retaining device. The combined effects of phase inversion and rheological factors
played an important role in the development of asymmetric gas separation
membranes for the application on lead acid battery during charging process.

5.2 Recommendations for Future Work

Based from all the experimental work experienced and results obtained in this
study, some recommendations for a better and more comprehensive execution of the
future work in this particular area have been drawn:

1. A study on other fabrication parameters of flat sheet membrane such

casting formulation, forced convection evaporation; coagulation medium
and temperature should be carried out to optimize the membrane
formation process and its performance.

2. Lead acid battery charging test parameters such as rate of charging and
charging period should also be carried out to analyze the performance of
the membrane under extreme conditions.

3. Lead acid battery charging tests should be done in a well designed battery
casing for the placement of the membrane in order to prevent leakages
and stabilize the pressure build up inside.

4. Composition measurement of vaporized electrolyte should be further

characterized using chromatographic methods that are tolerable to
moisture and acidic samples.
 93

5. Structure and properties of flat sheet membrane should be investigated by

using other microscopic methods such as Atomic Force Microscopy
(AFM) and Differential Scanning Chromatography (DSC). Through the
AFM method, important membrane properties such as pore size, pore
distribution of membranes, surface roughness and also the size of
macromolar nodules can measured.
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 PUBLICATIONS

Ismail, A. F., Hafiz, W. A. (2002), “Effect of Polysulfone Concentration on the

Performance of Membrane-assisted Lead Acid Battery.”, Songklanakarin
Journal of Science and Technology, 24, 815-821

Ismail, A. F., Hafiz, W. A. (2002), “Effect of Polysulfone Concentration on the

Performance of Membrane-assisted Lead Acid Battery.”, 1st Regional
Symposium on Membrane Science and Technology, Songkhla, January 2002

Ismail, A. F., Hafiz, W. A. and T. C. Khoo., (2004), “Effect of Shear Rate on the
Performance of Membrane-assisted Lead Acid Battery.”, 2nd Regional
Symposium on Membrane Science and Technology, Johor Bahru, 21-25
April 2004

Ismail, A. F., T. C. Khoo and Hafiz, W. A. (2004), “Development of a Maintenance

Free Tropicalized Lead Acid Battery Enhanced by Membrane Technology”,
2nd Regional Symposium on Membrane Science and Technology, Johor
Bahru, 21-25 April 2004

Ismail, A. F., Hafiz, W. A. (2004) “Introduction of Asymmetric Polysulfone Gas

Separation Membrane into Lead Acid Battery as a Water Retaining Device in
Tropical Countries”, accepted in Journal of Power Sources
 103

Appendix A1(a) Membrane-assisted Lead Acid Battery Charging Test Results

Control Test (Conventional Battery)

Battery Electrolyte
Time Mass Losses
(sec) (kg) (kg)
10 12.72 0.02
20 12.72 0.02
30 12.72 0.02
40 12.72 0.02
60 12.7 0.04
80 12.7 0.04
100 12.7 0.04
120 12.7 0.04
140 12.68 0.06
160 12.68 0.06
180 12.66 0.08

Time Time to Permeate (sec) Flowrate (m3/sec) Min St. Dev

(sec) T1 T2 T3 T4 T5 T6 F1 F2 F3 F4 F5 F6 (m3/sec) (m3/sec)
10 1.77 1.93 1.96 1.94 1.93 1.56 1.13 1.04 1.02 1.03 1.04 1.28 1.09 0.1026
20 1.44 1.53 1.59 1.69 1.69 1.47 1.39 1.31 1.26 1.18 1.18 1.36 1.28 0.0874
30 1.33 1.19 1.33 1.29 1.60 1.16 1.50 1.68 1.50 1.55 1.25 1.72 1.54 0.1676
40 1.19 1.11 1.21 1.14 1.31 1.17 1.68 1.80 1.65 1.75 1.53 1.71 1.69 0.0950
60 1.13 1.08 1.16 1.16 1.19 1.16 1.77 1.85 1.72 1.72 1.68 1.72 1.75 0.0591
80 1.15 1.13 1.18 1.04 1.10 1.06 1.74 1.77 1.69 1.92 1.82 1.89 1.81 0.0877
100 1.16 1.15 1.10 1.10 1.06 1.06 1.72 1.74 1.82 1.82 1.89 1.89 1.81 0.0697
120 0.98 1.01 1.07 1.03 1.09 1.07 2.04 1.98 1.87 1.94 1.83 1.87 1.92 0.0788
140 0.97 1.07 0.94 1.05 0.99 1.11 2.06 1.87 2.13 1.90 2.02 1.80 1.96 0.1252
160 0.99 0.98 1.03 1.03 0.99 1.06 2.02 2.04 1.94 1.94 2.02 1.89 1.98 0.0607
180 0.98 0.98 0.99 0.97 0.99 1.05 2.04 2.04 2.02 2.06 2.02 1.90 2.01 0.0561

Time Pressure (bar) Min St. Dev

(sec) C1 C2 C3 C4 C5 C6 (bar) (bar)
10 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
20 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
30 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
40 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
60 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
80 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
100 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
120 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
140 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
160 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
180 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
 104

Appendix A1(b) Membrane-assisted Lead Acid Battery Charging Test Results

Membrane Used = 7s Membrane (300 s-1)

Battery Elecrolyte
Time Mass Losses
(sec) (kg) (kg)
10 13.48 0
20 13.46 0.02
30 13.46 0.02
40 13.46 0.02
60 13.46 0.02
80 13.44 0.04
100 13.44 0.04
120 13.44 0.04
140 13.42 0.06
160 13.42 0.06
180 13.42 0.06

Time Time to Permeate (sec) Flowrate (m3/sec) Min St. Dev

(sec) T1 T2 T3 T4 T5 T6 F1 F2 F3 F4 F5 F6 (m3/sec) (m3/sec)
10 24.53 12.67 15.34 20.19 14.85 25.64 0.08 0.16 0.13 0.10 0.13 0.08 0.11 0.0322
20 17.12 10.73 15.28 16.41 14.61 16.55 0.12 0.19 0.13 0.12 0.14 0.12 0.14 0.0259
30 16.69 9.41 15.03 11.41 14.33 17.83 0.12 0.21 0.13 0.18 0.14 0.11 0.15 0.0382
40 16.46 9.27 14.61 10.43 13.99 16.55 0.12 0.22 0.14 0.19 0.14 0.12 0.15 0.0395
60 16.21 8.36 13.20 9.92 13.65 15.34 0.12 0.24 0.15 0.20 0.15 0.13 0.17 0.0454
80 15.99 8.34 13.34 8.73 13.08 15.22 0.13 0.24 0.15 0.23 0.15 0.13 0.17 0.0501
100 15.68 8.29 13.81 7.92 12.34 15.01 0.13 0.24 0.14 0.25 0.16 0.13 0.18 0.0556
120 15.54 8.03 12.53 7.23 11.92 14.76 0.13 0.25 0.16 0.28 0.17 0.14 0.19 0.0617
140 15.26 7.60 11.64 6.91 10.81 14.35 0.13 0.26 0.17 0.29 0.19 0.14 0.20 0.0654
160 14.78 7.21 10.97 6.58 9.22 13.96 0.14 0.28 0.18 0.30 0.22 0.14 0.21 0.0696
180 14.67 6.89 10.23 6.03 8.49 13.38 0.14 0.29 0.2 0.33 0.24 0.15 0.22 0.0777

Time Pressure (bar) Min St. Dev

(sec) C1 C2 C3 C4 C5 C6 (bar) (bar)
10 0.75 0.50 0.85 0.75 0.75 0.50 0.68 0.1472
20 0.75 0.55 0.85 0.80 0.80 0.60 0.73 0.1214
30 0.75 0.55 0.85 0.80 0.80 0.65 0.73 0.1125
40 0.80 0.60 0.90 0.85 0.80 0.70 0.78 0.1084
60 0.80 0.65 0.90 0.85 0.85 0.70 0.79 0.0970
80 0.85 0.70 0.95 0.90 0.85 0.75 0.83 0.0931
100 0.85 0.70 0.95 0.90 0.85 0.75 0.83 0.0931
120 0.85 0.70 0.95 0.95 0.90 0.80 0.86 0.0970
140 0.85 0.75 1.00 0.95 0.90 0.80 0.88 0.0935
160 0.90 0.75 1.00 0.95 0.90 0.85 0.89 0.0861
180 0.90 0.80 1.05 1.00 0.95 0.90 0.93 0.0876
 105

Appendix A1(c) Membrane-assisted Lead Acid Battery Charging Test Results

Membrane Used = 8s Membrane (262.5 s-1)

Battery Electrolyte
Time Mass Losses
(sec) (kg) (kg)
10 13.94 0
20 13.94 0
30 13.94 0
40 13.94 0
60 13.94 0
80 13.94 0
100 13.94 0
120 13.94 0
140 13.92 0.02
160 13.92 0.02
180 13.92 0.02

Time Time to Permeate (sec) Flowrate (m3/sec) Min St. Dev

(sec) T1 T2 T3 T4 T5 T6 F1 F2 F3 F4 F5 F6 (m3/sec) (m3/sec)
10 7.36 3.8 4.62 6.05 4.45 7.69 0.27 0.53 0.43 0.33 0.45 0.26 0.38 0.1073
20 5.13 3.52 3.82 4.92 4.38 4.95 0.39 0.57 0.52 0.41 0.46 0.40 0.46 0.0730
30 3.53 3.35 3.51 3.42 4.29 4.62 0.57 0.60 0.57 0.58 0.47 0.43 0.54 0.0688
40 3.32 3.26 3.49 3.39 4.19 4.21 0.60 0.61 0.57 0.59 0.48 0.48 0.56 0.0627
60 3.16 3.20 3.34 3.26 4.09 3.91 0.63 0.63 0.60 0.61 0.49 0.51 0.58 0.0621
80 3.12 3.15 3.26 3.12 3.92 3.51 0.64 0.63 0.61 0.64 0.51 0.57 0.60 0.0524
100 3.09 3.12 3.21 3.09 3.7 3.36 0.65 0.64 0.62 0.65 0.54 0.60 0.62 0.0418
120 3.02 3.09 3.17 3.05 3.57 3.12 0.66 0.65 0.63 0.66 0.56 0.64 0.63 0.0373
140 3.02 3.03 3.12 3.02 3.24 3.02 0.66 0.66 0.64 0.66 0.62 0.66 0.65 0.0184
160 2.98 3.01 3.09 3.01 3.12 3.01 0.67 0.66 0.65 0.66 0.64 0.66 0.66 0.0118
180 2.83 2.89 2.87 2.97 3.07 2.89 0.71 0.69 0.70 0.67 0.65 0.69 0.69 0.0198

Time Pressure (bar) Min St. Dev

(sec) C1 C2 C3 C4 C5 C6 (bar) (bar)
10 0.30 0.30 0.30 0.35 0.35 0.30 0.32 0.0258
20 0.50 0.60 0.55 0.60 0.50 0.50 0.54 0.0492
30 0.65 0.75 0.75 0.80 0.65 0.65 0.71 0.0665
40 0.70 0.80 0.80 0.80 0.70 0.75 0.76 0.0492
60 0.70 0.95 1.00 0.95 0.70 0.80 0.85 0.1342
80 0.75 1.00 1.10 1.00 0.75 0.85 0.91 0.1463
100 0.75 1.00 1.05 1.00 0.75 0.90 0.91 0.1320
120 0.75 1.05 1.10 1.05 0.80 0.95 0.95 0.1449
140 0.80 1.05 1.10 1.05 0.85 0.95 0.97 0.1211
160 0.85 1.10 1.10 1.10 0.90 0.95 1.00 0.1140
180 0.90 1.10 1.10 1.10 0.90 1.00 1.02 0.0983
 106

Appendix A1(d) Membrane-assisted Lead Acid Battery Charging Test Results

Membrane Used = 9s Membrane (233.33 s-1)

Battery Electrolyte
Time Mass Losses
(sec) (kg) (kg)
10 13.92 0
20 13.92 0
30 13.92 0
40 13.92 0
60 13.92 0
80 13.92 0
100 13.92 0
120 13.92 0
140 13.9 0.02
160 13.9 0.02
180 13.9 0.02

Time Time to Permeate (sec) Flowrate (m3/sec) Min St. Dev

(sec) T1 T2 T3 T4 T5 T6 F1 F2 F3 F4 F5 F6 (m3/sec) (m3/sec)
10 2.37 2.60 2.43 2.36 4.07 4.89 0.84 0.77 0.82 0.85 0.49 0.41 0.70 0.1952
20 2.34 2.55 2.11 2.21 3.51 2.92 0.85 0.78 0.95 0.90 0.57 0.68 0.79 0.1427
30 2.24 2.43 2.09 2.13 2.12 2.15 0.89 0.82 0.96 0.94 0.94 0.93 0.91 0.0496
40 2.15 2.54 2.01 2.01 1.73 1.96 0.93 0.79 1.00 1.00 1.16 1.02 0.98 0.1205
60 2.08 2.32 1.86 1.94 1.40 1.50 0.96 0.86 1.08 1.03 1.43 1.33 1.12 0.2201
80 2.01 2.12 1.62 1.86 1.21 1.41 1.00 0.94 1.23 1.08 1.65 1.42 1.22 0.2739
100 1.67 1.45 1.51 1.54 1.06 1.17 1.20 1.38 1.32 1.30 1.89 1.71 1.47 0.2698
120 1.54 1.18 1.20 1.37 1.02 1.21 1.30 1.69 1.67 1.46 1.96 1.65 1.62 0.2253
140 1.32 1.17 1.19 1.24 1.12 1.19 1.52 1.71 1.68 1.61 1.79 1.68 1.66 0.0919
160 1.24 1.15 1.16 1.14 1.15 1.15 1.61 1.74 1.72 1.75 1.74 1.74 1.72 0.0524
180 1.13 1.20 1.15 1.09 1.06 1.12 1.77 1.67 1.74 1.83 1.89 1.79 1.78 0.0762

Time Pressure (bar) Min St. Dev

(sec) C1 C2 C3 C4 C5 C6 (bar) (bar)
10 0.65 0.75 0.70 0.60 0.60 0.55 0.64 0.0736
20 0.65 0.75 0.70 0.65 0.65 0.60 0.67 0.0516
30 0.65 0.80 0.75 0.65 0.70 0.65 0.70 0.0632
40 0.65 0.80 0.75 0.65 0.70 0.70 0.71 0.0585
60 0.70 0.80 0.75 0.65 0.70 0.75 0.73 0.0524
80 0.70 0.75 0.75 0.65 0.70 0.75 0.72 0.0408
100 0.70 0.75 0.75 0.65 0.70 0.75 0.72 0.0408
120 0.70 0.75 0.75 0.65 0.70 0.75 0.72 0.0408
140 0.70 0.75 0.75 0.65 0.70 0.75 0.72 0.0408
160 0.70 0.75 0.75 0.70 0.70 0.75 0.73 0.0274
180 0.70 0.75 0.75 0.70 0.75 0.75 0.73 0.0258
 107

Appendix A1(e) Membrane-assisted Lead Acid Battery Charging Test Results

Membrane Used = 10s Membrane (210 s-1)

Battery Electrolyte
Time Mass Losses
(sec) (kg) (kg)
10 13.66 0
20 13.66 0
30 13.66 0
40 13.66 0
60 13.66 0
80 13.66 0
100 13.64 0.02
120 13.64 0.02
140 13.64 0.02
160 13.64 0.02
180 13.64 0.02

Time Time to Permeate (sec) Flowrate (m3/sec) Min St. Dev

(sec) T1 T2 T3 T4 T5 T6 F1 F2 F3 F4 F5 F6 (m3/sec) (m3/sec)
10 1.50 1.49 1.49 1.42 1.28 1.50 1.33 1.34 1.34 1.41 1.56 1.33 1.39 0.0906
20 1.49 1.48 1.46 1.22 1.24 1.46 1.34 1.35 1.37 1.64 1.61 1.37 1.45 0.1389
30 1.45 1.46 1.44 1.17 1.20 1.45 1.38 1.37 1.39 1.71 1.67 1.38 1.48 0.1601
40 1.44 1.45 1.42 1.32 1.13 1.44 1.39 1.38 1.41 1.52 1.77 1.39 1.48 0.1530
60 1.43 1.41 1.41 1.33 1.16 1.43 1.40 1.42 1.42 1.50 1.72 1.40 1.48 0.1272
80 1.42 1.39 1.39 1.25 1.09 1.38 1.41 1.44 1.44 1.60 1.83 1.45 1.53 0.1648
100 1.41 1.38 1.35 1.17 1.13 1.37 1.42 1.45 1.48 1.71 1.77 1.46 1.55 0.1510
120 1.38 1.35 1.31 1.11 1.09 1.34 1.45 1.48 1.53 1.80 1.83 1.49 1.60 0.1729
140 1.32 1.28 1.28 1.11 1.04 1.29 1.52 1.56 1.56 1.80 1.92 1.55 1.65 0.1679
160 1.29 1.26 1.21 1.09 1.03 1.23 1.55 1.59 1.65 1.83 1.94 1.63 1.70 0.1545
180 1.21 1.22 1.19 1.08 1.03 1.22 1.65 1.64 1.68 1.85 1.94 1.64 1.73 0.1299

Time Pressure (bar) Min St. Dev

(sec) C1 C2 C3 C4 C5 C6 (bar) (bar)
10 0.70 0.65 0.65 0.70 0.70 0.70 0.68 0.0258
20 0.70 0.65 0.65 0.75 0.75 0.70 0.70 0.0447
30 0.70 0.65 0.70 0.80 0.80 0.70 0.73 0.0612
40 0.70 0.65 0.70 0.80 0.80 0.75 0.73 0.0606
60 0.75 0.70 0.75 0.85 0.85 0.75 0.78 0.0612
80 0.75 0.70 0.75 0.85 0.85 0.80 0.78 0.0606
100 0.75 0.70 0.75 0.85 0.85 0.80 0.78 0.0606
120 0.75 0.75 0.75 0.90 0.90 0.80 0.81 0.0736
140 0.85 0.75 0.80 0.90 0.90 0.85 0.84 0.0585
160 0.85 0.80 0.80 0.95 0.95 0.85 0.87 0.0683
180 0.85 0.80 0.80 0.95 0.95 0.90 0.88 0.0689
 108

Appendix A1(f) Membrane-assisted Lead Acid Battery Charging Test Results

Membrane Used = 11s Membrane (190.91 s-1)

Battery Electrolyte
Time Mass Losses
(sec) (kg) (kg)
10 13.78 0
20 13.78 0
30 13.78 0
40 13.78 0
60 13.76 0.02
80 13.76 0.02
100 13.74 0.04
120 13.74 0.04
140 13.74 0.04
160 13.72 0.06
180 13.72 0.06

Time Time to Permeate (sec) Flowrate (m3/sec) Min St. Dev

(sec) T1 T2 T3 T4 T5 T6 F1 F2 F3 F4 F5 F6 (m3/sec) (m3/sec)
10 1.80 1.79 1.79 1.70 1.54 1.80 1.11 1.12 1.12 1.18 1.30 1.11 1.16 0.0746
20 1.79 1.78 1.75 1.46 1.49 1.75 1.12 1.12 1.14 1.37 1.34 1.14 1.21 0.1167
30 1.74 1.75 1.73 1.40 1.44 1.74 1.15 1.14 1.16 1.43 1.39 1.15 1.24 0.1345
40 1.73 1.74 1.70 1.58 1.36 1.73 1.16 1.15 1.18 1.27 1.47 1.16 1.23 0.1261
60 1.72 1.69 1.69 1.60 1.39 1.72 1.16 1.18 1.18 1.25 1.44 1.16 1.23 0.1071
80 1.70 1.67 1.67 1.50 1.31 1.66 1.18 1.20 1.20 1.33 1.53 1.20 1.27 0.1366
100 1.69 1.66 1.62 1.40 1.36 1.64 1.18 1.20 1.23 1.43 1.47 1.22 1.29 0.1253
120 1.66 1.62 1.57 1.33 1.31 1.61 1.20 1.23 1.27 1.50 1.53 1.24 1.33 0.1446
140 1.58 1.54 1.54 1.33 1.25 1.55 1.27 1.30 1.30 1.50 1.60 1.29 1.38 0.1399
160 1.55 1.51 1.45 1.31 1.24 1.48 1.29 1.32 1.38 1.53 1.61 1.35 1.41 0.1270
180 1.45 1.46 1.43 1.30 1.24 1.46 1.38 1.37 1.40 1.54 1.61 1.37 1.44 0.1046

Time Pressure (bar) Min St. Dev

(sec) C1 C2 C3 C4 C5 C6 (bar) (bar)
10 0.85 0.80 0.90 0.80 0.70 0.80 0.81 0.0665
20 0.90 0.80 0.95 0.85 0.75 0.85 0.85 0.0707
30 0.95 0.85 0.95 0.85 0.75 0.85 0.87 0.0753
40 0.95 0.85 0.95 0.85 0.75 0.90 0.88 0.0758
60 0.95 0.85 0.95 0.85 0.75 0.90 0.88 0.0758
80 0.95 0.85 0.95 0.85 0.75 0.90 0.88 0.0758
100 0.95 0.85 0.95 0.85 0.75 0.90 0.88 0.0758
120 0.95 0.85 1.00 0.85 0.80 0.90 0.89 0.0736
140 1.00 0.90 1.00 0.90 0.80 0.95 0.93 0.0758
160 1.00 0.90 1.00 0.90 0.80 0.95 0.93 0.0758
180 1.05 0.95 1.05 0.90 0.85 0.95 0.96 0.0801
 109

Appendix A1(g) Membrane-assisted Lead Acid Battery Charging Test Results

Membrane Used = 12s Membrane (175 s-1)

Battery Electrolyte
Time Mass Losses
(sec) (kg) (kg)
10 13.78 0
20 13.78 0
30 13.78 0
40 13.76 0.02
60 13.76 0.02
80 13.76 0.02
100 13.76 0.02
120 13.74 0.04
140 13.74 0.04
160 13.72 0.06
180 13.72 0.06

Time Time to Permeate (sec) Flowrate (m3/sec) Min St. Dev

(sec) T1 T2 T3 T4 T5 T6 F1 F2 F3 F4 F5 F6 (m3/sec) (m3/sec)
10 2.02 2.00 2.00 1.90 1.72 2.02 0.99 1.00 1.00 1.05 1.16 0.99 1.03 0.0680
20 2.00 1.99 1.96 1.64 1.67 1.96 1.00 1.01 1.02 1.22 1.20 1.02 1.08 0.1023
30 1.95 1.96 1.94 1.57 1.61 1.95 1.03 1.02 1.03 1.27 1.24 1.03 1.10 0.1205
40 1.94 1.95 1.90 1.77 1.52 1.94 1.03 1.03 1.05 1.13 1.32 1.03 1.10 0.1138
60 1.93 1.89 1.89 1.79 1.56 1.93 1.04 1.06 1.06 1.12 1.28 1.04 1.10 0.0949
80 1.90 1.87 1.87 1.68 1.47 1.86 1.05 1.07 1.07 1.19 1.36 1.08 1.14 0.1207
100 1.89 1.86 1.81 1.57 1.52 1.84 1.06 1.08 1.10 1.27 1.32 1.09 1.15 0.1121
120 1.86 1.81 1.76 1.49 1.47 1.80 1.08 1.10 1.14 1.34 1.36 1.11 1.19 0.1279
140 1.77 1.72 1.72 1.49 1.40 1.74 1.13 1.16 1.16 1.34 1.43 1.15 1.23 0.1246
160 1.74 1.69 1.62 1.47 1.39 1.66 1.15 1.18 1.23 1.36 1.44 1.20 1.26 0.1130
180 1.62 1.64 1.60 1.46 1.39 1.64 1.23 1.22 1.25 1.37 1.44 1.22 1.29 0.0929

Time Pressure (bar) Min St. Dev

(sec) C1 C2 C3 C4 C5 C6 (bar) (bar)
10 0.70 0.65 0.50 0.90 0.70 0.40 0.64 0.1744
20 0.75 0.70 0.60 0.90 0.70 0.50 0.69 0.1357
30 0.75 0.70 0.60 0.90 0.75 0.70 0.73 0.0983
40 0.75 0.70 0.65 0.90 0.75 0.70 0.74 0.0861
60 0.80 0.70 0.65 0.90 0.75 0.70 0.75 0.0894
80 0.80 0.70 0.70 0.90 0.75 0.75 0.77 0.0753
100 0.85 0.70 0.70 0.95 0.80 0.75 0.79 0.0970
120 0.85 0.70 0.80 0.95 0.80 0.80 0.82 0.0816
140 0.90 0.75 0.80 0.95 0.85 0.80 0.84 0.0736
160 0.90 0.75 0.85 1.00 0.85 0.85 0.87 0.0816
180 0.95 0.85 0.90 1.05 0.90 0.90 0.93 0.0689
 110

Appendix A2
Electrolyte Losses Profile During Membrane-assisted Lead Acid Battery Charging
Test

13.805

13.8

13.795
Electrolyte Losses (kg)

13.79

13.785

13.78

13.775

13.77
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180
Charging Time (minute)

Electrolyte Losses Profile During Membrane-assisted Lead Acid Battery Charging

Test for 8s Membrane

13.825

13.82

13.815
Electrolyte Losses (kg)

13.81

13.805

13.8

13.795

13.79
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180
Charging Time(minute)

Electrolyte Losses Profile During Membrane-assisted Lead Acid Battery Charging

Test for 10s Membrane
 111

13.81

13.8

13.79

13.78
Electrolyte Losses (kg)

13.77

13.76

13.75

13.74

13.73

13.72

13.71
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180
Charging Time (minute)

Electrolyte Losses Profile During Membrane-assisted Lead Acid Battery Charging

Test for 11s Membrane
 112

Appendix A3 (a)
Membrane-assisted Lead Acid Battery Charging Test Results with Heat Supply
Control Test (Conventional Battery)
Water Bath Temperature = 60oC

Time Time to Permeate (sec) Flowrate (m3/sec) Min St. Dev

(sec) T1 T2 T3 T4 T5 T6 F1 F2 F3 F4 F5 F6 (m3/sec) (m3/sec)
10 1.27 1.25 1.41 1.36 1.43 1.21 1.57 1.60 1.42 1.47 1.40 1.65 1.52 0.1045
20 1.18 1.17 1.24 1.27 1.13 1.12 1.69 1.71 1.61 1.57 1.77 1.79 1.69 0.0838
30 1.03 1.03 1.15 1.21 1.21 1.07 1.94 1.94 1.74 1.65 1.65 1.87 1.80 0.1356
40 0.99 1.01 1.09 1.13 1.15 1.07 2.02 1.98 1.83 1.77 1.74 1.87 1.87 0.1123
60 0.98 0.99 1.08 1.11 1.13 1.07 2.04 2.02 1.85 1.80 1.77 1.87 1.89 0.1129
80 0.97 0.95 1.07 1.09 1.11 1.06 2.06 2.11 1.87 1.83 1.80 1.89 1.93 0.1258
100 0.96 0.90 1.06 1.05 1.07 1.06 2.08 2.22 1.89 1.90 1.87 1.89 1.98 0.1446
120 0.95 0.87 1.05 1.03 1.05 1.04 2.11 2.30 1.90 1.94 1.90 1.92 2.01 0.1593
140 0.92 0.87 1.02 0.98 1.01 0.99 2.17 2.30 1.96 2.04 1.98 2.02 2.08 0.1311
160 0.86 0.85 0.97 0.92 0.98 0.94 2.33 2.35 2.06 2.17 2.04 2.13 2.18 0.1321
180 0.81 0.79 0.87 0.81 0.95 0.88 2.47 2.53 2.30 2.47 2.11 2.27 2.36 0.1609

Time Pressure (bar) Min St. Dev

(sec) C1 C2 C3 C4 C5 C6 (bar) (bar)
0 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
10 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
20 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
30 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
40 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
60 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
80 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
100 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
120 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
140 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
160 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
180 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
 113

Appendix A3 (b)
Membrane-assisted Lead Acid Battery Charging Test Results With Heat Supply
Membrane Used = 9s Membrane (233.33 s-1)
Water Bath Temperature = 60oC

Time Time to Permeate (sec) Flowrate (m3/sec) Min St. Dev

(sec) T1 T2 T3 T4 T5 T6 F1 F2 F3 F4 F5 F6 (m3/sec) (m3/sec)
10 2.87 3.13 2.68 2.74 3.24 2.91 0.70 0.64 0.75 0.73 0.62 0.69 0.69 0.0502
20 2.29 2.38 2.21 2.24 2.42 2.31 0.87 0.84 0.90 0.89 0.83 0.87 0.87 0.0300
30 2.07 2.14 1.99 2.03 2.15 2.09 0.97 0.93 1.01 0.99 0.93 0.96 0.96 0.0289
40 1.82 1.97 1.75 1.81 1.94 1.84 1.10 1.02 1.14 1.10 1.03 1.09 1.08 0.0481
60 1.69 1.77 1.68 1.65 1.78 1.75 1.18 1.13 1.19 1.21 1.12 1.14 1.16 0.0364
80 1.46 1.51 1.47 1.42 1.54 1.52 1.37 1.32 1.36 1.41 1.30 1.32 1.35 0.0407
100 1.21 1.27 1.19 1.20 1.29 1.29 1.65 1.57 1.68 1.67 1.55 1.55 1.61 0.0606
120 1.09 1.13 1.04 1.07 1.13 1.14 1.83 1.77 1.92 1.87 1.77 1.75 1.82 0.0672
140 1.03 1.07 0.95 1.01 1.06 1.08 1.94 1.87 2.11 1.98 1.89 1.85 1.94 0.0944
160 0.97 1.05 0.90 0.95 1.03 1.03 2.06 1.90 2.22 2.11 1.94 1.94 2.03 0.1224
180 0.95 1.03 0.87 0.92 1.01 0.99 2.11 1.94 2.30 2.17 1.98 2.02 2.09 0.1340

Time Pressure (bar) Min St. Dev

(sec) C1 C2 C3 C4 C5 C6 (bar) (bar)
0 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.0000
10 0.30 0.35 0.25 0.20 0.25 0.25 0.27 0.0516
20 0.40 0.45 0.35 0.30 0.35 0.45 0.38 0.0606
30 0.50 0.55 0.45 0.45 0.50 0.55 0.50 0.0447
40 0.55 0.65 0.50 0.55 0.60 0.60 0.58 0.0524
60 0.60 0.65 0.55 0.60 0.60 0.60 0.60 0.0316
80 0.60 0.65 0.60 0.60 0.65 0.65 0.63 0.0274
100 0.65 0.70 0.65 0.70 0.65 0.65 0.67 0.0258
120 0.65 0.70 0.70 0.70 0.70 0.70 0.69 0.0204
140 0.70 0.70 0.70 0.75 0.70 0.70 0.71 0.0204
160 0.70 0.70 0.75 0.75 0.75 0.75 0.73 0.0258
180 0.75 0.75 0.75 0.80 0.75 0.80 0.77 0.0258
 114

Appendix A3 (c)
Membrane-assisted Lead Acid Battery Charging Test Results with Heat Supply
Control Test (Conventional Battery)
Water Bath Temperature = 80oC

Time Time to Permeate (sec) Flowrate (m3/sec) Min St. Dev

(sec) T1 T2 T3 T4 T5 T6 F1 F2 F3 F4 F5 F6 (m3/sec) (m3/sec)
10 1.15 1.13 1.27 1.21 1.25 1.32 1.74 1.77 1.57 1.65 1.60 1.52 1.64 0.0983
20 1.12 1.10 1.16 1.14 1.13 1.19 1.79 1.82 1.72 1.75 1.77 1.68 1.76 0.0482
30 1.04 1.02 1.08 1.05 1.04 1.11 1.92 1.96 1.85 1.90 1.92 1.80 1.89 0.0575
40 1.03 1.01 1.08 1.03 1.03 1.09 1.94 1.98 1.85 1.94 1.94 1.83 1.92 0.0580
60 1.02 0.99 1.07 1.02 1.03 1.07 1.96 2.02 1.87 1.96 1.94 1.87 1.94 0.0588
80 1.01 0.97 1.06 1.01 1.02 1.05 1.98 2.06 1.89 1.98 1.96 1.90 1.96 0.0626
100 0.98 0.95 1.05 0.99 1.01 1.04 2.04 2.11 1.90 2.02 1.98 1.92 2.00 0.0754
120 0.95 0.90 1.04 0.97 0.99 1.02 2.11 2.22 1.92 2.06 2.02 1.96 2.05 0.1075
140 0.92 0.85 1.01 0.94 0.98 0.99 2.17 2.35 1.98 2.13 2.04 2.02 2.12 0.1363
160 0.89 0.78 0.99 0.88 0.92 0.94 2.25 2.56 2.02 2.27 2.17 2.13 2.23 0.1851
180 0.81 0.71 0.87 0.87 0.93 0.90 2.47 2.82 2.30 2.30 2.15 2.22 2.38 0.2406

Time Pressure (bar) Min St. Dev

(sec) C1 C2 C3 C4 C5 C6 (bar) (bar)
0 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
10 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
20 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
30 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
40 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
60 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
80 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
100 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
120 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
140 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
160 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
180 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
 115

Appendix A3 (d)
Membrane-assisted Lead Acid Battery Charging Test Results With Heat Supply
Membrane Used = 9s Membrane (233.33 s-1)
Water Bath Temperature = 80oC

Time Time to Permeate (sec) Flowrate (m3/sec) Min St. Dev

(sec) T1 T2 T3 T4 T5 T6 F1 F2 F3 F4 F5 F6 (m3/sec) (m3/sec)
10 2.15 2.31 2.19 2.24 2.28 2.29 0.93 0.87 0.91 0.89 0.88 0.87 0.89 0.0252
20 1.89 2.09 2.01 1.99 2.02 2.04 1.06 0.96 1.00 1.01 0.99 0.98 1.00 0.0339
30 1.51 1.67 1.52 1.51 1.54 1.50 1.32 1.20 1.32 1.32 1.30 1.33 1.30 0.0511
40 1.33 1.41 1.29 1.34 1.29 1.31 1.50 1.42 1.55 1.49 1.55 1.53 1.51 0.0494
60 1.15 1.24 1.17 1.26 1.21 1.26 1.74 1.61 1.71 1.59 1.65 1.59 1.65 0.0643
80 1.09 1.17 1.12 1.14 1.18 1.22 1.83 1.71 1.79 1.75 1.69 1.64 1.74 0.0697
100 1.05 1.09 1.04 1.06 1.13 1.15 1.90 1.83 1.92 1.89 1.77 1.74 1.84 0.0753
120 0.99 0.98 0.94 0.97 1.03 1.06 2.02 2.04 2.13 2.06 1.94 1.89 2.01 0.0864
140 0.95 0.93 0.87 0.92 0.97 0.98 2.11 2.15 2.30 2.17 2.06 2.04 2.14 0.0934
160 0.91 0.89 0.85 0.89 0.94 0.96 2.20 2.25 2.35 2.25 2.13 2.08 2.21 0.0961
180 0.87 0.85 0.81 0.86 0.89 0.92 2.30 2.35 2.47 2.33 2.25 2.17 2.31 0.1000

Time Pressure (bar) Min St. Dev

(sec) C1 C2 C3 C4 C5 C6 (bar) (bar)
0 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.0000
10 0.30 0.25 0.35 0.35 0.35 0.35 0.33 0.0418
20 0.50 0.45 0.55 0.60 0.50 0.55 0.53 0.0524
30 0.60 0.50 0.60 0.65 0.60 0.60 0.59 0.0492
40 0.65 0.55 0.60 0.70 0.65 0.65 0.63 0.0516
60 0.70 0.60 0.65 0.70 0.70 0.65 0.67 0.0408
80 0.70 0.65 0.70 0.70 0.70 0.65 0.68 0.0258
100 0.75 0.65 0.70 0.75 0.70 0.70 0.71 0.0376
120 0.75 0.70 0.70 0.75 0.75 0.70 0.73 0.0274
140 0.75 0.70 0.75 0.75 0.75 0.70 0.73 0.0258
160 0.80 0.75 0.75 0.80 0.75 0.70 0.76 0.0376
180 0.80 0.75 0.80 0.80 0.80 0.75 0.78 0.0258
 116

Appendix B1: Raman Spectrum for Vaporized Electrolyte From Conventional

Battery During Charging Process
0.008

0.007

0.006

Intensity
0.005

0.004

0.003

0.002
4200 4000 3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600 400 200 0
Raman Shift (cm-1)

Raman Spectrum for Vaporized Electrolyte (Conventional Battery) Sample Taken

After 20 minutes of Charging Process

0.012

0.01

0.008

0.006 Intensity

0.004

0.002

0
4200 4000 3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600 400 200 0
Raman Shift (cm-1)

Raman Spectrum for Vaporized Electrolyte (Conventional Battery) Sample Taken

After 40 minutes of Charging Process
 117

0.0163

0.0143

0.0123

0.0103

Intensity
0.0083

0.0063

0.0043

0.0023
4200 4000 3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600 400 200 0
Raman Shift (cm-1)

Raman Spectrum for Vaporized Electrolyte (Conventional Battery) Sample Taken

After 60 minutes of Charging Process

0.011

0.01

0.009

0.008

0.007

Intensity
0.006

0.005

0.004

0.003

0.002
4100 3900 3700 3500 3300 3100 2900 2700 2500 2300 2100 1900 1700 1500 1300 1100 900 700 500
Raman Shift (cm-1)

Raman Spectrum for Vaporized Electrolyte (Conventional Battery) Sample Taken

After 100 minutes of Charging Process
 118

0.014

0.012

0.01

0.008

Intensity
0.006

0.004

0.002

0
4000 3500 3000 2500 2000 1500 1000 500 0
Raman Shift (cm-1)

Raman Spectrum for Vaporized Electrolyte (Conventional Battery) Sample Taken

After 140 minutes of Charging Process

0.015

0.014

0.013

0.012

0.011

Intensity
0.01

0.009

0.008

0.007

0.006
4200 4000 3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600
Raman Shift (cm-1)

Raman Spectrum for Vaporized Electrolyte (Conventional Battery) Sample Taken

After 180 minutes of Charging Process
 119

Appendix B2: Raman Spectrum for Vaporized Electrolyte From Membrane-assisted

Battery During Charging Process
0.0065

0.006

0.0055

0.005

0.0045

Intensity
0.004

0.0035

0.003

0.0025

0.002
4000 3500 3000 2500 2000 1500 1000 500 0
Raman Shift (cm-1)

Raman Spectrum for Vaporized Electrolyte (Membrane Assisted Battery) Sample Taken
After 40 minutes of Charging Process

0.0045

0.004

0.0035

0.003

Intensity
0.0025

0.002

0.0015

0.001
5000 4000 3000 2000 1000 0
Raman Shift (cm-1)

Raman Spectrum for Vaporized Electrolyte (Membrane Assisted Battery) Sample Taken
After 60 minutes of Charging Process
 120

0.0063

0.0058

0.0053

0.0048

0.0043

Intensity
0.0038

0.0033

0.0028

0.0023

0.0018

0.0013
4000 3500 3000 2500 2000 1500 1000 500 0
Raman Shift (cm-1)

Raman Spectrum for Vaporized Electrolyte (Membrane Assisted Battery) Sample

Taken After 80 minutes of Charging Process

0.0065

0.006

0.0055

0.005

0.0045

Intensity
0.004

0.0035

0.003

0.0025

0.002
4100 3900 3700 3500 3300 3100 2900 2700 2500 2300 2100 1900 1700 1500 1300 1100 900 700 500
Raman Shift (cm-1)

Raman Spectrum for Vaporized Electrolyte (Membrane Assisted Battery) Sample Taken
After 120 minutes of Charging Process
 121

0.0065

0.006

0.0055

0.005

0.0045

Iintensity
0.004

0.0035

0.003

0.0025

0.002
4000 3500 3000 2500 2000 1500 1000 500 0
Raman Shift (cm-1)

Raman Spectrum for Vaporized Electrolyte (Membrane Assisted Battery) Sample

Taken After 140 minutes of Charging Process

0.0065

0.006

0.0055

0.005

0.0045

Intensity
0.004

0.0035

0.003

0.0025

0.002
4000 3500 3000 2500 2000 1500 1000 500 0
Raman Shift (cm-1)

Raman Spectrum for Vaporized Electrolyte (Membrane Assisted Battery) Sample Taken
After 160 minutes of Charging Process