SECTION 3: LITERATURE REVIEW AND CONCEPTUAL FRAMEWORK

3.1 Study of recent practices

Batteries are mainly divided into primary and secondary types.Further categorisation is
based upon types of electrode material used, type of electrolyte,ion exchange
membrane, type of electrochemical reaction occuring,dual chambered,single
chambered and battery size(from micro watt to mega watts)[1], consequently hundreds
of configurations have been tried out upto this time.Mostly batteries use inorganic
electrolyte so they are outside scope of this literature review.So major part of review
includes organic acids or alkalis or thier synthetic counterpart as electrolyte .Also
overview of simple flow batteries is given with aim to deeply understand its
nature.Additionally, Bio batteries or even their counterpart, bio fuel cells, as fastly
emerging technology, is also been reviewed with owing to subtle similarities among the
two types such as biological electrolyte, finds its link in my research work.
Here review of batteries and fuel cells based on the recent literature is compiled. The
different modes of the fuel cells and battery are critically reviewed and a variety of
possible applications are considered. The technical challenges of such energy storage
systems are highlighted and future research directions are discussed.

3.2 Technology Options

Apart from simple batteries ,Energy storage technology options range from fuel cell,
pumped hydroelectric storage, solar fuel, super conducting magnetic storage, flywheel,
compressed air energy storage, Super capacitor/ capacitor/ and thermal
energy.Particularly dozens of battery types exist,differing rom each other based on
dierent electrode coniguration or electrolyte.[1] Unconventional approaches for incorporating
flexible batteries in smart textiles have also developed. The first one uses galvanic cell made of aluminum-
sodium hypochlorite with innovative packaging to make batteries in form of flexible fiber that could weave
directly into textile. The second method illustrates Lithium ion chemistry within electrolytes of solid polymer
that are utilized to make completely rechargeable soft solid for the foresaid battery that can be stitched
into textile at next stage, or can be incorporated as strips during machine weaving process.[3]

An extensive argument of solution phenomenon in liquid ammonia (base)

is elaborated. The solvent properties of alkaline ammonia for different categories of mixtures for battery is
presented in terms of its relatively high basicity,hydrogen bonding, dielectric constant or high dipole
moment. In nutshell, liquid ammonia is a best solvent for covalent molecules, but poor solvent for ionic
species. Conductivity and spectral data is presented to support the contention that species in liquid
ammonia undergo ion association, the aggregates being predominantly ion-separated ion-pairs in dilute
solution. A brief discussion of the chemical properties of metal with ammonia solutions is presented.
Electrochemical behavior as exemplified by static potential measurements and polarographic techniques is
discussed. A detailed discussion of acid-base phenomena including proton transfer reactions is presented
with a summary and discussion of the quantitative data available for these systems.[8]Liquid ammonia is a
good solvent for organic molecules for e.g esters, amines and benzene. It is better solvent for organic
compounds than water, but worse solvent for inorganic compounds. The change in solubility of inorganic
salts in fluid ammonia as compared to water, as well as the lower temperature of liquid ammonia, studied
in this paper isolation of unstable compounds. For instance, making of ammonium nitrate by reaction of
NaNO3 and NH4Cl in water results in formation of nitrogen and water due to decomposition of nitrate.[10]

Liquid electrodes are another innovtive work on part of batteries.Sodium hypochlorite [NaOCl] cathode for
use in an aluminum-based seawater battery is presented. NaOCl is basically alkaline in nature with pH 13-
14 range. This catholyte attains a high power density, positive redox potential, and a high Faradaic current
capacity. Sodium hypochlorite is cost effective, stable and environmentally safe. aluminum alloys and99%
pure aluminum, serving as anodes, were tested in 3, 5, and 8.0 Molar NaOH solution at varied
temperature such as 45-65C and 80 °C. The catholyte concentration and temperature effects were
optimized, and the best electro catalyst was chosen to carry out the NaOCl reduction. Optimization
experiments were carried out on a half-cell basis using a potentiostat in a three-electrode configuration with
Ag/AgCl as the reference electrode and a carbon rod as the counter electrode. Full cell testing
incorporating the optimum conditions was performed with a flowing electrolyte apparatus. A catholyte
concentration of 0.70 M NaOCl proved optimum in combination with 3.0 M NaOH at the temperature 55 °C
and 5.0 M NaOH at the temperature65 °C. The temperature 45 °C was not high enough for aluminum
activation, the 80 °C data did not show an improvement over the 65 °C data, and polarization was not
dramatically enhanced in 8.0 M NaOH. Nickel foil and porous nickel separately electroplated with palladium
were found to be the most effective electro catalysts. Full-cell data demonstrates a successful
electrochemical system with current densities approaching 1200 mA/cm2 and voltages above 1.0 V.[6]

Innovation on part of electrolyte is that elctrolyte is made from biological organisms.The need for future
devices that employ inspiration from live bio organisms consequently need for either biomimetic or bio
inspired approach arises and are used in electro motive transport These are environment friendly, low cost
electrochemical devices .[7]Electrolyte in bio battery needs regular replacement like
continuous fuel supply in fuel cell.Electrodes are consumed during reaction.External
oxygen or fuel is not needed. It has features of both battery and fuel cell like
electrochemical conversion takes place in both. It operates at STP unlike conventional
fuel cells and more like battery.Power outputs of both have been reported in same
range.It is single or dual chambered.It has direct electron transfer to electrodes.It does
not employ proton exchange membrane Nayyar discuss bio electricity generation from varying
concentrations industrial waste (100%, 80% and 20%) water via Bio fuel cell. He elaborates basic
components of bio fuel cells, their types and factors affecting their performance .Wastewater from sugar
industry used as electrolyte .It contain glucose and bacteria. The micro nutrients in bio film of electrode
oxidize these organic compounds and ship electrons to anode and cathode that have been made of
graphite having a surface area of 6.67cm2. The effects achieved with the aid of treating a hundred% sugar
industry wastewater giving a most of 1.6mA current and open circuit voltage of 7.031mV with a basic
chemical oxygen demand of sixty five%.[15]

Another sort of Bio battery made of 9 cells is made on paper as substrate. Paper pulp contains bacteria
which completes respiration and give electrons to bio electro chemical cell. Paper is cheap and absorbs
liquid agents which facilitate rapid electron transfer to electrodes. Such cells are stacked in series and
parallel combination to make for practical use.SEM characterization is used.[22]

Presence and concentration of organic acids from fruit juices determine conductivity of electrolyte and other
attributes. Because organic acid profiles are distinct to each type of fruit juice, one evidence of amperage can
be evaluated by comparing the known juice to that of its associated acid. Organic acid profiles can also
determine juice ionic strength ,mostly organic acids are weak acids. Masson et al used ion chromatography to
verify organic acids in fresh juice via The Thermo Scientific Dione .[9] Fruit and salt batteries are explored in this
study. Other examples like air batteries where metals react with oxygen in air to produce free electrons, flowing
through external circuit and does work. we know that salt is made by combination of acid and base and fruit
water containing such electrolyte facilitates electrons from the anode towards cathode. but it leaves the battery
as a black box, Chemistry behind such black box or batteries is written with regard to electrochemistry to
demonstrate this, air battery is made using copper as cathode, aluminum as anode, and saltwater. This activity
could be used in consideration of alternative energy and provides framework for illustrating fuel cell.[11].
Geovany Ramírez et al utilized different ratio of soil mixed with organic matter such as fruits and vegetables
(50:50, 25:75, 75: 25) in single chambered microbial fuel cell for producing bioelectricity over a period of 60 day.
More electricity was generated in fruit wastes as compared to vegetables waste due to high monosaccharide and
glucose content in fruits which aids in better oxide-reduction reactions in bio-electric current generation.
Maximum peak voltage observed was 300mV. Such biodegradable cultures contain micro organisms,. Inverse
relation was observed between them and voltage.[13]. Max open circuit voltage is 0.76 volts and efficiency is far
more than economical (only 9 USD/KWh) than typical 1.5 volt AA battery. To demonstrate electrical energy
needs LED were lightened with vegetative battery for minimum 3 hours hence proves low cost bio electrolytic
source.[20]Madiha investigated different fruits and vegetables such as spinach paste, potato, apple, lemon,
onion, garlic, plants and other biological species in solid and semi liquid mode were used to find peak voltage and
current. Findings of bio electrochemical cell were analyzed via DMM and Kethley 2410 source meter. Peak
voltage observed was 1.01 volts and current in micro amperes range. Future work demands to bridge gap of
electrical power from micro watt range to milli watt and beyond.[27] Ami Elazari invented a device which can
extract electrical power from living plants using gold electrodes. Mechanism of photosynthesis used. When
sunlight falls on plants, electrons emit in chlorophyll and move via series of light and dark reactions. These
electrons can be captured without hampering plant growth and connected in series parallel to light a bulb. One
cell yields 1.5 Volts. Spinach is used as demonstration plant. It confirms the fact that appreciable amount of
electrical energy can be yielded from plants. (US patent)[28]
The feasibility of living micro organism to convert their chemical energy into electrical energy is investigated
in Electrochemical cell made of biological and photosynthetic bacteria. One electrode immersed in
(Rhodospirillum rubrum) specie and second in blue green algae. Potential difference under dark and light
conditions gave 0.96 Volts and 75 micro ampere current for several days provided fresh supply of nutrients
was given to cell. It serves as valuable bio fuel cell prototype despite its limited viability.There are subtle
similarities between single chambered DET bio fuel cell and battery in literature as both
go side by side. So we can consider such bio fuel cell as bio battery R. S. Berk
demonstrated, feasibility of assembling such biological fuel cell, [12] Soheil Ghaffari Bio fuel cell made of
blood glucose is fabricated and simulated .Gold acts as catalyst inside anodic chamber. It is implantable
and used for pace makers, insulin pumps, drug delivery. Krezenmacher Model is used for simulation. Peak
power is 1.2 micro watt/cm2.[21] K. Rabaey discuss critical role of Bio films, developing onto the anode of a
MFC, form as a multilayer matrix, wherein soluble mediators are embedded. via these embedded
mediators, electrical contact can be present among the pinnacle layer of the bio film and the substrate. This
enables the pinnacle layer micro organism to apply the substrate as electron acceptor and as a result, get
entry to the bio film electron donors. He found that phenazines play a critical breathing position in
conditions of excessive bacterial densities, poor blending, and oxygen dilemma. In short it acts as catalyst
to facilitate electron transfer to electrode. Measurements of the power output corresponded to 39 µw m-2.
These findings have significant impact on power output of bio fuel cell.[14]Xuee Wua, single chambered bio
fuel cell based on direct electron transfer (DET) method is made utilizing glucose/fructose.and cyclic
voltammetric, potentiostatic discharge and chronoamperometric techniques were used to evaluate
performance of bio electrode .Power density of 126 micro watt/cm2 and OCV of 663 mV is observed. Its
performance is comparatively high and stable over long terms.[23]

Chlorophyll is naturally occurring compound present in all green plants such as spinach, mint or green peel
of un ripened fruits. It is responsible for electron emission in similar fashion as semi conducting elements
via light and dark reactions during process of photosynthesis (procedure utilized by plants catch daylight
and change it into chemical energy). So it is used as electrolyte between metallic conductors inside battery.
A simple study was made to investigate its different properties such as energy band, electrical conductivity,
current voltage characterization .The band gap is 5.5eV while conductivity is 1.92*10^-9 ohm per meter.
Maximum peak voltage observed was 0.996 Volts. All this depicts natural electrical power generation
capacity of plants.[16] Houman Yaghoubi studied Bio-photo electrochemical cell in detail. Bio hybrid device
was made by Coating surface of one of electrodes with RC protein of plants .When sunlight fall on them,
electrons are emitted from RC and transferred to electrodes via reversible Redox reactions. And opposite
charges move to second electrode. The more layers ,higher would be current.24 layers of RC give about 80
micro Amp current per cm^2. History of successful devices is also quoted in this text dating back to 1994
onwards to current ongoing practices.[17] Kien B. Lam. A micro fabricated bio mimetic sun oriented cell
was illustrated anode/PEM/cathode setup that resembles the natural sub-cell thylakoid photo systems
(found in plants) detached from spinach cells to convert light into power. Subject to light power of 2000
µmol photons/m2/s, it produced an open circuit voltage of 470 mV furthermore; a present thickness of 1.0
µA/cm2 at 5.2 µV, yield that is practically identical to other micro fabricated natural power modules. In the
present, the bio-sun based cell can yield 1% efficiency. [18]Frank Davis, In 2006, the journal “Biosensors
and Bioelectronics” distributed an exceptional issue committed only to bio fuel cells, including research
papers and a broad audit of the field. It is also a review article and concisely devoted to history and
historical advances of bio fuel cells. The survey is planned to a great extent focus on and gives complete
picture of the recent advances made and useful utilization of bio fuel cells.[24] G.Silveira et al illustrated
very cost effective and simple bio fuel cell made from yeast ,its fabrication and analysis.[34]

In fact photo electrochemical cell started not very far in the past, photovoltaics , the change of sunlight to
electrical power has been overpowered by solid state semiconductors, basically made of
silicon. However, the uncommon late progress in making and depicting nano crystalline
materials has opened up whole new vistas of possibility. [19] Photo bio electro chemical cell is
made using simple household items like spinach and titanium dioxide taken from common tooth paste.
Electrons in chlorophyll of spinach get excited by light and pass through conduction band of titanium
dioxide (semiconductor), hence negatively charged. It passes electrons to first electrode, electrolyte and
ultimately to second electrode due to potential difference. The second electrode is covered with graphite of
lead pencil which acts as catalyst. Halogen diascope is used as light source. Outputs are 200 mV and 60
uAmp and power is 0.1 watt.[25] Samantha Dietrich Different types of potatoes such as raw, fried and
baked is used in potato battery (bio electro chemical cell).Zinc and copper electrodes and digital multimeter
.Blues potato yield .946 V, Idaho potato 0.819 V, sweet potato 0.88,baked potato -.888, and French fried
potato 0.81 volts.[26] A. M. Kannan reviewed Bio batteries, bio fuel cells and emphasized need of proper
packaging material for them.[29] ] S. Venkata Mohan used two tubes/pipes as anode cathode and joined
them in U shape and filled with substrate made of mixed vegetable waste/sludge (cabbage/ spinach
leaves/potato peels/ cucumber/ carrot). 88990mW/m.sq2 is maximum power density reported which is quite
appreciable.[31]Different configurations of bio batteries are Patented with example. Voltage output is not
very impressive despite a lot of effort made on expensive materials, electrodes and additive catalysts.
.[32]Robert discussed many different techniques for biological cell lysis including but not limited to optical,
acoustic, electrical, mechanical and chemical techniques.[33]

3.3 Current Status

Acid base flow battery is an environmental friendly way of storing energy consisting of
NaCl salt as electrolyte .A large proportion of energy is generated by unlimited sources
such as wind and sun, to keep electricity grid reliable, he offered connection of large
scale electricity storage to this grid as promising solution. Current battery storage
technologies, while providing promising energy and power densities, suffer from safety
issues as well as technological challenges[2].
Another The new Acid-Base Electrochemical Flow Battery [AB-EFB] is highlighted where such system is
made of highly concentrated acid and base solutions. The solutions are kept apart by proton exchange
membrane, with hydrogen acting as both product and reactant. Such proof of concept model was verified
for over twenty charge capacities, getting maximum power density as much as 20 mW per cm square at
49 mA/sq. cm. So coulombic efficiency near 95 % and energy efficiency of 55 % are also produced. Last
but not least, the recycling of hydrogen gas is a beneficial aspect to be considered.[4]

S. Abdalla explored that Food may be used as power source. Maximum open circuit voltage 1.39 and short
circuit current of 1.7 micro ampere have been observed using food (potato) as electrolyte in bio battery. It is
26 times cost effective than AA alkaline battery available market. Output power is 400 micro watt/cm.sq[30]

3.4 Method Used

Bases and alkalis such as , calcium hypochlorite, sodium hypochlorite, potassium ferricyanide, and
hydrogen peroxide are investigated experimentally as electrolytes for batteries.Varied factors such as
concentration of NaOH or electrolyte, current density J, Or temperature effect are explored using
statistical method called Taguchi l method. Moreover ANOVA was utilized to find significance of each
parameter on battery performance . For each one of these four chemistries, array of L9 orthogonal shape
with four factors of control each at three levels was employed for alkali based batteries.[5]

For acid batteries,for achieving high specific energy, the method of charging and discharging cycles over
complete pH range 0–14, at different current densities is used. The demonstrated stable performance at
high energy density is 2.9 Wh per litre. Main reason for energy loss or dissipation is due to unnecessary
hydroxyl ion and proton transport which causes low faradic efficiency.[2]
For combined acid base electrochemical cells, proton exchange membranes are used between two
external electrolytes with two metallic electrodes.Some mebraneless conigurations are also seen.. In such
configuration, neutralization energy acts as voltage source. Thus, in charging cycle, hydrogen is oxidized to
hydronium ions at positive electrode, consequently it acidifies posilyte, on the other hand, H2 gas resulting
from water at negative electrode basifies the negalyte. During the discharge, both electrolytes were
neutralized via hydrogen evolution and hydrogen oxidation reactions. The titanium electrode with platinum
coating is chosen for HER and the platinum catalyzed gas diffused electrode is employed for HOR[4]
Alex Golberg electrical characterization of zinc-copper vegetative batteries along with cost analysis was
made. Three different modes were used first being fresh potato (electrolyte), second boiled potato and third
ones irreversibly electroplated potatoes placed between electrodes. performance was evaluated by
computer controlled electrochemical analyzer. Bio Cell membranes were distorted upon boiling or electro
poration.

3.5 Challenges
Another goal of this review is to identify weakness in organic acid batteries and to
overcome that part thus assess the feasibility of acid base battery as an alternative to
generating power . Acid base battery has emerged in the recent years as the next
potential power source [4].

Such a cell would not be superior to conventional fuel cells due to certain inherent problems with systems
of this kind For instance, substrate exhaustion, harmful item collection, constrained feasibility of biological
cells, and electrolyte confinements. Consequently, it is doubtful that biological fuel cells could yield energy
efficiencies equivalent to conventional solar cells. However, the use of bio electrochemical techniques for
the study of organic-metal interactions could ultimately become an invaluable research tool.[12]

3.6 Output
Energy density range from microwatt to milli watt and beyond; such as 20 mW [saez] to 2.9 Wh per litre is
obtaned from NaCl acid base battery.[egmond],but their cost is comparitively high.
20 hour power was able to light 2 LEDS from five potato series cell, wherby phosphoric acid from potato is
electrolyte.[alex]
Very scarce data is present in true sense of acid base battery from organic sources at low cost. High power
application is the missing gap to be filled.

3.7 Opportunities
Current batteries have eletrolyte as only acidic or only basic aqueous solutions in which
electrodes plates are dipped.What seperates such electrochemical battery system from
the rest is combining both acid and base from natural sources in single cell for optimum
output.The base will absorb protons of acid as sponge,thus dissociation and movement
of ions generates current in appreciable amounts,which is not possible if only weak
organic acids are used.