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1
CHAPTER – 1
INTRODUCTION TO PAPER BATTERY
1.1 INTRODUCTION TO ORDINARY BATTERY
Ordinary paper could one day be used as a lightweight battery to power the devices that are now
enabling the printed word to be eclipsed by e-mail, e-books an online news. Scientist at Stanford
University in California reported on Monday they have succefully tuned paper coated with the
ink made of silver and carbon nano materials into a “paper battery” that holds promise for new
types of lightweight, high-performance energy storage.
The same feature that helps ink to paper allows it to hold onto the single-walled carbon
nanotubes and silver Nano wire films. Earlier research found that silicon nano wires could be
used to make batteries 10 times as powerful as lithium-ion batteries now used to power devices
such as laptop computers.
Fig 1.1.1 Ordinary battery
2
"Taking advantage of the mature paper technology, low cost, light and high performance energy-
storage are realized by using conductive paper as current collectors and electrodes," the scientists
said in research published in the Proceedings of the National Academy of Sciences. This type of
battery could be useful in powering electric or hybrid vehicles, would make electronics lighter
weight and longer lasting, and might even lead someday to paper electronics, the scientists said.
Battery weight and life has been an obstacle to commercial viability of electric-powered cars and
trucks."Society really needs a low-cost, high-performance energy storage device, such as
batteries and simple super capacitors," Stanford assistant professor of materials science and
engineering and paper co-author Yi Cui said.
Cui said in an e-mail that in addition to being useful for portable electronics and wearable
electronics, "Our paper super capacitors can be used for all kinds of applications that require
instant high power.”
Fig 1.1.2 Conventional battery
3
"Since our paper batteries and super capacitors can be very low cost, they are also good for grid-
connected energy storage," he said. Peidong Yang, professor of chemistry at the University of
California Berkeley, said the technology could be commercialized within a short time.
1.2 INTRODUCTION TO PAPER BATTERY
A paper battery is a flexible, ultra-thin energy storage and production device formed by
combining carbon nanotube with a conventional sheet of cellulose-based paper. A paper battery
acts as both a high-energy battery and super capacitor, combining two components that are
separate in traditional electronics. This combination allows the battery to provide both long-term,
steady power production and bursts of energy. Non-toxic, flexible paper batteries have the
potential to power the next generation of electronics, medical devices and hybrid vehicles,
allowing for radical new designs and medical technologies.
Fig 1.2.1 Carbon nanotubes
4
Paper batteries may be folded, cut or otherwise shaped for different applications without any loss
of integrity or efficiency. Cutting one in half halves its energy production. Stacking them
multiplies power output. Early prototypes of the device are able to produce 2.5 volt s of
electricity from a sample the size of a postage stamp.
Fig 1.2.2 Paper battery
The devices are formed by combining cellulose with an infusion of aligned carbon nanotubes
that are each approximately one millionth of a centimeter thick. The carbon is what gives the
batteries their black color. These tiny filaments act like the electrode s found in a traditional
battery, conducting electricity when the paper comes into contact with an ionic liquid solution.
Ionic liquids contain no water, which means that there is nothing to freeze or evaporate in
extreme environmental conditions. As a result, paper batteries can function between -75 and 150
degrees Celsius.
One method of manufacture, developed by scientists at Rensselaer Polytechnic Institute and
MIT, begins with growing the nanotubes on a
5
Silicon substrate and then impregnating the gaps in the matrix with cellulose. Once the matrix
has dried, the material can be peeled off of the substrate, exposing one end of the carbon
nanotubes to act as an electrode.
Fig 1.2.3 Paper battery
When two sheets are combined, with the cellulose sides facing inwards, a super capacitor is
formed that can be activated by the addition of the ionic liquid. This liquid acts as an electrolyte
and may include salt-laden solutions like human blood, sweat or urine. The high cellulose
content (over 90%) and lack of toxic chemicals in paper batteries makes the device both
biocompatible and environmentally friendly, especially when compared to the traditional lithium
ion battery used in many present-day electronic devices and laptops.
Widespread commercial deployment of paper batteries will rely on the development of more
inexpensive manufacturing techniques for carbon nanotubes. As a result of the potentially
transformative applications in electronics, aerospace, hybrid vehicles and medical science,
however, numerous companies and organizations are pursuing the development of Paper
batteries.
6
In addition to the developments announced in 2007 at RPI and MIT, researchers in Singapore
announced that they had developed a paper battery powered by ionic solutions in 2005. NEC has
also invested in R & D into paper batteries for potential applications in its electronic devices.
Specialized paper batteries could act as power sources for any number of devices implanted in
humans and animals, including RFID tags, cosmetics, drug-delivery systems and pacemakers.
A capacitor introduced into an organism could be implanted fully dry and then be gradually
exposed to bodily fluids over time to generate voltage. Paper batteries are also biodegradable, a
need only partially addressed by current e-cycling and other electronics disposal methods
increasingly advocated for by the green computing movement.
1.2 BATTERY LIFETIME
1.3.1 PRIMARY BATTERIES LIFETIME
Even if never taken out of the original package, disposable or primary batteries can lose 8 to 20
percent of their original charge every year at a temperature of about 20°–30°C.This is known as
the "self discharge" rate and is due to non-current-producing "side" chemical reactions, which
occur within the cell even if no load is applied to it. The rate of the side reactions is reduced if
the batteries are stored at low temperature, although some batteries can be damaged by freezing.
High or low temperatures may reduce battery performance. This will affect the initial voltage of
the battery. For an AA alkaline battery this initial voltage is approximately normally distributed
around 1.6 volts.
1.3.2 LIFE OF RECHARGEABLE BATTERIES
Rechargeable batteries traditionally self-discharge more rapidly than disposable alkaline
batteries, especially nickel-based batteries; a freshly charged NiCd loses 10% of its charge in the
first 24 hours, and thereafter discharges at a rate of about 10% a month.
7
However, modern lithium designs have reduced the self-discharge rate to a relatively low level
(but still poorer than for primary batteries). Most nickel-based batteries are partially discharged
when purchased, and must be charged before first use.
1.3.3 EXTENDING LIFE BATTERIES
Battery life can be extended by storing the batteries at a low temperature, as in a refrigerator or
freezer, because the chemical reactions in the batteries are slower. Such storage can extend the
life of alkaline batteries by ~5%; while the charge of rechargeable batteries can be extended from
a few days up to several months.
In order to reach their maximum voltage, batteries must be returned to room temperature;
discharging an alkaline battery at 250 mAh at 0°C is only half as efficient as it is at 20°C. As a
result, alkaline battery manufacturers like Duracell do not recommend refrigerating or freezing
batteries.
8
CHAPTER – 2
LITERATURE SURVEY
2. MANUFACTURING OF PAPER BATTERY
2.1 MANUFACTURING OF CARBON NANOTUBES
One method of manufacturing, developed by scientists at Rensselaer Polytechnic Institute,
begins with growing the nano tubes on a silicon substrate and then impregnating the gaps in the
matrix with cellulose. Once the matrix has dried, the material can be peeled off of the substrate,
exposing one end of the carbon nano tubes to act as electrode.
Fig 2.1.1 Paper battery
When two sheets are combined, with the cellulose sides facing inwards, a super capacitor is
formed that can be activated by the addition of the ionic liquid. This liquid acts as an electrolyte
and may include salt-laden solutions like human blood, sweat or urine. The high cellulose
content (over 90%) and lack of toxic chemicals in paper batteries makes the device both
biocompatible and environmentally friendly, especially when compared to the traditional lithium
ion battery used in many present-day electronic devices and laptops.
9
Specialized paper batteries could act as power sources for any number of devices implanted in
humans and animals, including RFID tags, cosmetics, drugs delivery systems and pacemakers.
A capacitor introduced into an organism could be implanted fully dry and then gradually exposed
to bodily fluids over time to generate voltage. Paper batteries are also biodegradable, a need only
partially addressed by current e-cycling and other electronics disposal methods increasingly
advocated for by the green computing movement.
Carbon nanotubes are the main concept behind paper battery. Carbon nanotubes (CNTs; also
known as buckytubes) are allotropes of carbon with a cylindrical nanostructure. CNTs exhibit
extraordinary strength and unique electrical properties, and are efficient thermal conductors.
Fig 2.1.2 Carbon nanotubes
Carbon nanotube is an allotrope of carbon. Allotropy is nothing but different structural
modifications of an element. Carbon nano ink which is black in colour is a solution of nano rods,
surface adhesive agent and ionic salt solutions. Carbon nano ink is spread on one side of the
paper. The paper is kept in the oven at 150 degree Celsius. This evaporates the water content on
the paper. The battery is ready and would provide a terminal voltage enough to power an LED.
Cellulose is a complex organic substance found in paper and pulp; not digestible by humans.
A Carbon Nano Tubes (CNT) is a very tiny cylinder formed from a single sheet of carbon atoms
rolled into a tiny cylinder. These are stronger than steel and more conducting than the best
semiconductors.
CarbonNanotubeRolled at angleGraphene Structure
10
They can be Single-walled or Multi-walled. Presently, the devices are only a few inches across
and they have to be scaled up to sheets of newspaper size to make it commercially viable.
2.2 DEVELOPMENT
The creation of this unique nano composite paper drew from a diverse pool of disciplines,
requiring expertise in materials science, energy storage, and chemistry. The researchers used
ionic liquid, essentially a liquid salt, as the battery’s electrolyte. The use of ionic liquid, which
contains no water, means there’s nothing in the batteries to freeze or evaporate. “This lack of
water allows the paper energy storage devices to withstand extreme temperatures,” Kumar said.
It gives the battery the ability to function in temperatures up to 300 degrees Fahrenheit and down
to 100 below zero. The use of ionic liquid also makes the battery extremely biocompatible; the
team printed paper batteries without adding any electrolytes, and demonstrated that naturally
occurring electrolytes in human sweat, blood, and urine can be used to activate the battery
device. Cellulose-based paper is a natural abundant material, biodegradable, light, and recyclable
with a well-known consolidated manufacturing process. These attribute turn paper a quite
interesting material to produce very cheap disposable electronic devices with the great advantage
of being environmental friendly. The recent (r) evolution of thin-film electronic devices such as
paper transistors, transparent thin-film transistors based on semiconductor oxides, and paper
memory, open the possibility to produce low cost disposable electronics in large scale. Common
to all these advances is the use of cellulose fiber-based paper as an active material in Opposition
to other ink-jet printed active-matrix display and thin-film transistors reports where paper acts
only as a passive element (substrate). Batteries in which a paper matrix is incorporated with
carbon nanotubes, or bio fluid - and water-activated batteries with a filter paper have been
reported, but it is not known a work where the paper itself is the core of the device perfor
11
Fig 2.2.1 development of paper battery
With the present work, we expect to contribute to the first step of an incoming disruptive concept
related to the production of self-sustained paper electronic systems where the power supply is
integrated in the electronic circuits to fabricate fully self sustained disposable, flexible, low cost
and low electrical consumption systems such as tags, games or displays.
In achieving such goal we have fabricated batteries using commercial paper as electrolyte and
physical support of thin film electrodes. A thin film layer of a metal or metal oxide is deposited
in one side of a commercial paper sheet while in the opposite face a metal or metal oxide with
opposite electrochemical potential is also deposited. The simplest structure produced
is Cu/paper/Al but other structures such as Al paper WO TCO were also tested, leading to
batteries with open circuit voltages varying between 0.50 and 1.10 V.
12
On the other hand, the short current density is highly dependent on the relative humidity (RH),
whose presence is important to recharge the battery. The set of batteries characterized show
stable performance after being tested by more than 115 hours, under standard atmospheric
conditions [room temperature, RT (22 C) and 60% air humidity, RH]. In this work we also
present as a proof of concept a paper transistor in which the gate ON/OFF state is controlled by a
non-encapsulated 3 V integrated paper battery.
13
CHAPTER – 3
EXPERIMENTAL DETAILS
3.1 EXPERIMENTAL DETAILS
The paper batteries produced have the Al/paper/Cu structure, where the metal layers were
produced by thermal evaporation at RT. The thickness of the metal elect rode varied between
100 and 500 nm. The electrical characteristics of the batteries were obtained through I-V curves
and also by sweep voltammeter using scanning speed o 25 mVs and the electrodes area of 1cm.
A Keithley 617 Programmable Electrometer with a National Instruments GPIB acquisition board
was used to determine the I-V characteristics.
Fig 3.1 Dependence of temperature on discharge capacity
The cyclic voltammeter was performed with a potenciostat Gamry Instruments Ref. 600 in a
two-electrode configuration. The electrical performances of the batteries were determined by
monitoring the current of the battery under variable RH conditions. The surface analysis of the
paper and paper batteries was performed by S-4100 Hitachi scanning electron microscopy
(SEM), with a 40 tilt angle.
14
The electrical properties of the paper transistor controlled by the paper battery were monitored
with an Agilent 4155C semiconductor parameter analyzer and a Cascade M150 microprobe
station.
Fig 3.2 Typical series connections method
15
CHAPTER – 4
RESULT AND DISCUSSION
4.1 RESULT AND DISCUSSION
The Al/paper/Cu thin batteries studied involved the use of three different classes of paper:
commercial copy white paper (WP: 0.68 g/cm, 0.118 mm thick); recycled paper (RP: 0.70 g/cm,
0.115 mm thick); tracing paper (TP: 0.58 g/cm, 0.065 mm thick). The TP is made of long pine
fibers and according to FRX (X-ray fluorescence) mainly Al2 O3 (24%), SiO2 (37%), SO2
(15%), CaO (9%), and Na2 O (4%).
The role of the type of paper and electrodes thickness on the electrical parameters of the battery,
such as the Voc and Jsc are indicated in Table I, for RH of 50%–60%, using metal electrodes
with different thicknesses (t1=100 nm; tot2=250 nm;t3=500 nm). Jsc for WP is ~ 40%–50%
lower than of TP, and RP is one order of magnitude lower than WP. Consequently, the Voc is
reduced by merely a ~ 0.1 V when moving from WP to RP only for thickness (t1=100 nm) while
it increases for t2 and t3.
Fig 4.1 Photograph of the paper batteries with a sketch of the cross section
16
The thickness of the metal layer does not play a remarkable role on electrical characteristics of
the batteries. The results show that it is enough to guarantee the step coverage of the randomly
dispersed fibers by metal or metal–oxide thin films to allow the carriers to find a continuous
pathway without the inhibition of water vapor absorption by the paper fibers. Considering that
the tracing paper is less dense and thinner than white and recycled paper, the difference on the
current density observed can be related to ions recombination either due to impurities inside the
foam/mesh-like paper structure or charge annihilation by vacant sites associated to the surface of
the paper fibers, existing in thicker papers.
Other possible explanation is that the adsorption of water vapor is favored in less dense paper.
Fig. 4.1 shows a photograph and a sketch of a paper battery analysis it contains with an Al anode
while the cathode is Cu, whose difference in work functions influences the set of chemical
reactions that take place within the paper mesh structure.
The paper SEM image of Fig. 4.2 is the surface morphology of tracing paper used. There, large
(50 m). This mesh-like structure favors OHx absorption on the surface of the fibers, in line with
data depicted in Table 4.1, where the batteries produced in WP show currents one order of
magnitude lower than the ones produced in TP.
Fig 4.2 SEM image of the paper surface
17
Fig 4.3 SEM image of the anode (AL) surface
For RP, two orders of magnitude difference in is observed. Voc is reduced by 0.1–0.2 V when
moving from WP to RP as electrolyte. The paper battery prototype used is non-encapsulated and
so, its electrical performance is influenced by the atmospheric constituents. This behavior was
confirmed by measuring the current of one cell in vacuum and under atmospheric pressure. The
results demonstrated a reduction of one order of magnitude in Jsc value after vacuum reaching
10 Pa. These results were reproducible after performing several tests. We attributed this behavior
to the incorporation of OH radicals from adsorbed water and its contribution to the enhancement
of current through the typical reactions of 2H2 O→ O2+ 4H+ +4e- and/or4 OH- →O2+2 H2
O+4e- and subsequent reactions with the paper fibers constituents (cellulose and ions). This was
confirmed by measuring the current variation as RH changes.
The graph of Fig. 4.4 shows the short circuit-current density variation as RH increases for TP. A
variation of about three orders of magnitude is observed when RH changes from 60% to 85%,
and it is reversible, meaning that no battery damage is verified. We conclude that this type of
battery is a mixture of a secondary battery and a fuel cell where the fuel is the water vapor and so
its application requires environment with RH>40 % or proper encapsulation with controlled
humidity via holes through which we can allow the battery to breathe.
18
Fig 4.4 continues measurement ofthe short
Circuit current density ofthe paper
Battery as it is under gradual relative humidity.
This is the case in applications with typically high RH, as in the food industry, where these
batteries could be used to turn electronic tags auto sustained. From the data taken, each battery
element is able to supply a power from 75 nW/cm to 350 W/cm, depending on RH. The desired
voltage and power output can be achieved by integrating in series and in parallel the battery
elements produced.
In the present case, a prototype battery able to supply a 3 V was produced to actuate the gate of a
paper transistor working in the depletion mode. Fig. 4.4 shows a photograph of the prototype
made of 10 cells (with only 8 cells connected in series) and the graph of the drain current of the
paper transistor when the paper battery is connected to the gate ( 3 V) or disconnected (0 V). The
connection/disconnection was repeated during 400 s in intervals of 25 s and the current was
monitored continuously.
The results clearly show the sustainability of the paper battery in powering the gate of the
transistor and how the results are reproducible. The drain current of the paper transistor at 0 V is
2 10 A and at 3V is 10 A, similar to the values obtained when measuring the transfer
characteristics of the same devices with a semiconductor analyzer.
19
CHAPTER – 5
APPLICATION AND USE OF PAPER BATTERY
5.1 IN COSMETICS
Anti-aging and wrinkles
Dark spots / Discoloration
Skin lightening / Whitening
Firming and lifting
Moisturizing
Fig 5.1.1 Anti-aging and wrinkles
20
Fig 5.1.2 LG Ion Patch (For whitening)
Fig 5.1.3 Iontophoresis mechanism
21
Fig 5.1.4 estee lauder (for wrinkles)
5.2 USE OF PAPER BATTERY
It can be used to power smart tags. It can be used to power signal use medical devices. It can be
used to make items like gaming cards interactive at very low cost making them attractive for
portable electronics, aircraft, automobiles, and toys (such as model aircraft), while their ability to
use electrolytes in blood make them potentially useful for medical devices such as pacemakers.
The medical uses are particularly attractive because they do not contain any toxic materials and
can be biodegradable; a major drawback of chemical cells However, Professor Sperling cautions
that commercial applications may be a long way away, because nanotubes are still relatively
expensive to fabricate.
22
Currently they are making devices a few inches in size. In order to be commercially viable, they
would like to be able to make them newspaper size; a size which, taken all together would be
powerful enough to power a car.
While a conventional battery contains a number of separate components, the paper battery
integrates all of the battery components in a single structure, making it more energy efficient. A
paper battery is a battery engineered to use a paper-thin sheet of cellulose infused with aligned
carbon nanotubes. Nanotubes act as electrodes; allowing the storage devices to conduct
electricity. Functions as both a lithium-ion battery and a super capacitor, can provide a long,
steady power output comparable to a conventional battery, as well as a super capacitor's quick
burst of high energy.
Paper battery extreme flexibility; the sheets can be rolled, twisted, folded, or cut into numerous
shapes with no loss of integrity or efficiency, or stacked, like printer paper (or a Voltaic pile), to
boost total output. The paper-like quality of the battery combined with the structure of the
nanotubes embedded within gives them their light weight and low cost, making them attractive
for portable electronics, aircraft, automobiles, and toys.
5.3 DURABILITY
The use of carbon nanotubes gives the paper battery extreme flexibility; the sheets can be rolled,
twisted, folded, or cut into numerous shapes with no loss of integrity or efficiency, or stacked,
like printer paper (or a Voltaic pile), to boost total output. As well, they can be made in a variety
of sizes, from postage stamp to broadsheet.
23
CHAPTER- 6
CONCLUSION & FUTURE SCOPE
In this paper we show the functionality of a non-encapsulated thin-film battery using paper as
electrolyte and also as physical support. The battery is self rechargeable when exposed to relative
humidity above 40%, being Jsc highly influenced by RH>60%. In this case, Jsc varies from 150
nA /cm2 to 0.8 Ma /cm2, as RH varies from 60% to 85%. This constitutes the first step towards
future fully integrated self sustained flexible, cheap and disposable electronic devices, with great
emphasis on the so-called paper electronics.
The range of possible applications for paper batteries derives from their important advantages as
compared to conventional battery technologies. They can be made in virtually any shape and
size to meet the requirements of each application. The batteries are rechargeable, and have
reduced cost and weight which in itself may give birth to new applications. Paper battery could
solve all the problems associated with electrical energy storage. However the reality is still very
far away, though the researches are promising. Being Biodegradable, Light-weight and Nontoxic,
flexible paper batteries have potential adaptability to power the next generation of electronics,
medical devices and hybrid vehicles, allowing for radical new designs and medical technologies.
But India still has got a long way to go if it has to be self-dependant for its energy solution.
Literature reflects that Indian researchers have got the scientific astuteness needed for such
revolutionary work. But what hinders their path is the lack of facilities and funding. Of course,
the horizon of inquisitiveness is indefinitely vast and this paper is just a single step towards this
direction.
The black piece of paper can power a small light. Flexible paper batteries could not meet the
energy demands of the next generation of gadgets. The ambition is to produce reams of paper
that could one day power a car. The paper battery was a glimpse into the future of power storage.
24
They have produced a sample slightly larger than a postage stamp that can store enough energy
to illuminate a small light bulb. But the ambition is to produce reams of paper that could one day
power a car.
Professor Robert Linhardt, of the Rensselaer Polytechnic Institute, said the paper battery was a
glimpse into the future of power storage. The team behind the versatile paper, which stores
energy like a conventional battery, says it can also double as a capacitor capable of releasing
sudden energy bursts for high-power applications.
25
REFERENCE
[1] Anderson, P.; Nilsson, D.; Swenson, P. O.; Chen, M. X.; Maelstrom, A.; Ramones, T.;
Kugler, T.; Berggren, M.Active Matrix Displays Based on All-Organic Electrochemical Smart
Pixels Printed on Paper. Adv. Mater.2002, 14, 1460–1464.
[2] Eder, F.; Klauk, H.; Halik, M.; Zschieschang, U.; Schmidt, G.; Dehm, C. Organic Electronics
on Paper. Appl. Phys. Lett. 2004, 84, 2673–2675.
[3] Kim, D. H.; Kim, Y. S.; Wu, J.; Liu, Z. J.; Song, J. Z.; Kim, H. S.; Huang, Y. G. Y.; Hwang,
K.C.; Rogers, J. A. Ultrathin Silicon Circuits with Strain-Isolation Layers and Mesh Layouts for
High-Performance Electronics on Fabric, Vinyl, Leather, and Paper. Adv. Mater. 2009, 21,
3703–3707.
[4] Tarascon, J. M.; Armand, M. Issues and Challenges Facing Rechargeable Lithium Batteries.
Nature 2001, 414, 359–367.
[5] Hu, L.; Hecht, D. S.; Gruner, G. Percolation in Transparent and Conducting Carbon
Nanotube Networks. Nano Lett. 2004, 4, 2513–2517.
[6] Kaempgen, M.; Chan, C. K.; Ma, J.; Cui, Y.; Gruner, G. Printable Thin Film Super capacitors
Using Single-Walled Carbon Nanotubes. Nano Lett. 2009, 9, 1872–1876.
[7] Hu, L. C., J.; Yang, Y.; La Mantia, F.; Jeong, S.; Cui, Y. Highly Conductive Paper for
Energy Storage. Proc. Natl. Acad. Sci. U.S.A. 2009, 106, 21490–21494.
[8] Islam, M. F.; Rojas, E.; Bergey, D. M.; Johnson, A. T.; Yodh, A. G. High Weight Fraction
Surfactant Solubilization of Single-Wall Carbon Nanotubes in Water. Nano Lett. 2003, 3, 269–
273.
26
[9] Tracton, A. A. Coating Handbook; Marcel Dekker, Inc: New York, 2001.
[10] Cao, Q.; Zhu, Z. T.; Lemaitre, M. G.; Xia, M. G.; Shim, M.; Rogers, J. A. Transparent
Flexible Organic Thin-Film Transistors That Use Printed Single-Walled Carbon Nanotube
Electrodes. Appl. Phys. Lett. 2006, 88, 113511–113513.
[11] Hu, L.; Hecht, D.; Gru¨ ner, G. Carbon Nanotube Thin Films: Fabrications, Properties, and
Applications. Chem. Rev. 2010, doi: 10.1021/cr9002962.
[12] Muriset, G. Influence of the Impurities in the Foil, Electrolyte and Paper in the Electrolytic
Capacitor. J. Power Sources 1952, 99, 285–288.
[13] Geng, H. Z.; Kim, K. K.; So, K. P.; Lee, Y. S.; Chang, Y.; Lee, Y. H. Effect of Acid
Treatment on Carbon Nanotube-Based Flexible Transparent Conducting Films. J. Am. Chem.
Soc. 2007, 129, 7758–7759.
[14] Ng, S. H. W., J.; Guo, Z. P.; Chen, J.; Wang, G. X.; Liu, H. K. Single Wall Carbon
Nanotube Paper as Anode for Lithium- Ion Battery. Electroc him. Acta 2005, 51, 23–28.
[15] Kufian, M. Z.; Majid, S. R. Performance of Lithium-Ion Cells Using 1 M LiPF6 in EC/DEC
(v/v _ 1/2) Electrolyte with Ethyl Propionate Additive. Ionics 2009, 16, 409–416.

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Page 3

  • 1. 1 CHAPTER – 1 INTRODUCTION TO PAPER BATTERY 1.1 INTRODUCTION TO ORDINARY BATTERY Ordinary paper could one day be used as a lightweight battery to power the devices that are now enabling the printed word to be eclipsed by e-mail, e-books an online news. Scientist at Stanford University in California reported on Monday they have succefully tuned paper coated with the ink made of silver and carbon nano materials into a “paper battery” that holds promise for new types of lightweight, high-performance energy storage. The same feature that helps ink to paper allows it to hold onto the single-walled carbon nanotubes and silver Nano wire films. Earlier research found that silicon nano wires could be used to make batteries 10 times as powerful as lithium-ion batteries now used to power devices such as laptop computers. Fig 1.1.1 Ordinary battery
  • 2. 2 "Taking advantage of the mature paper technology, low cost, light and high performance energy- storage are realized by using conductive paper as current collectors and electrodes," the scientists said in research published in the Proceedings of the National Academy of Sciences. This type of battery could be useful in powering electric or hybrid vehicles, would make electronics lighter weight and longer lasting, and might even lead someday to paper electronics, the scientists said. Battery weight and life has been an obstacle to commercial viability of electric-powered cars and trucks."Society really needs a low-cost, high-performance energy storage device, such as batteries and simple super capacitors," Stanford assistant professor of materials science and engineering and paper co-author Yi Cui said. Cui said in an e-mail that in addition to being useful for portable electronics and wearable electronics, "Our paper super capacitors can be used for all kinds of applications that require instant high power.” Fig 1.1.2 Conventional battery
  • 3. 3 "Since our paper batteries and super capacitors can be very low cost, they are also good for grid- connected energy storage," he said. Peidong Yang, professor of chemistry at the University of California Berkeley, said the technology could be commercialized within a short time. 1.2 INTRODUCTION TO PAPER BATTERY A paper battery is a flexible, ultra-thin energy storage and production device formed by combining carbon nanotube with a conventional sheet of cellulose-based paper. A paper battery acts as both a high-energy battery and super capacitor, combining two components that are separate in traditional electronics. This combination allows the battery to provide both long-term, steady power production and bursts of energy. Non-toxic, flexible paper batteries have the potential to power the next generation of electronics, medical devices and hybrid vehicles, allowing for radical new designs and medical technologies. Fig 1.2.1 Carbon nanotubes
  • 4. 4 Paper batteries may be folded, cut or otherwise shaped for different applications without any loss of integrity or efficiency. Cutting one in half halves its energy production. Stacking them multiplies power output. Early prototypes of the device are able to produce 2.5 volt s of electricity from a sample the size of a postage stamp. Fig 1.2.2 Paper battery The devices are formed by combining cellulose with an infusion of aligned carbon nanotubes that are each approximately one millionth of a centimeter thick. The carbon is what gives the batteries their black color. These tiny filaments act like the electrode s found in a traditional battery, conducting electricity when the paper comes into contact with an ionic liquid solution. Ionic liquids contain no water, which means that there is nothing to freeze or evaporate in extreme environmental conditions. As a result, paper batteries can function between -75 and 150 degrees Celsius. One method of manufacture, developed by scientists at Rensselaer Polytechnic Institute and MIT, begins with growing the nanotubes on a
  • 5. 5 Silicon substrate and then impregnating the gaps in the matrix with cellulose. Once the matrix has dried, the material can be peeled off of the substrate, exposing one end of the carbon nanotubes to act as an electrode. Fig 1.2.3 Paper battery When two sheets are combined, with the cellulose sides facing inwards, a super capacitor is formed that can be activated by the addition of the ionic liquid. This liquid acts as an electrolyte and may include salt-laden solutions like human blood, sweat or urine. The high cellulose content (over 90%) and lack of toxic chemicals in paper batteries makes the device both biocompatible and environmentally friendly, especially when compared to the traditional lithium ion battery used in many present-day electronic devices and laptops. Widespread commercial deployment of paper batteries will rely on the development of more inexpensive manufacturing techniques for carbon nanotubes. As a result of the potentially transformative applications in electronics, aerospace, hybrid vehicles and medical science, however, numerous companies and organizations are pursuing the development of Paper batteries.
  • 6. 6 In addition to the developments announced in 2007 at RPI and MIT, researchers in Singapore announced that they had developed a paper battery powered by ionic solutions in 2005. NEC has also invested in R & D into paper batteries for potential applications in its electronic devices. Specialized paper batteries could act as power sources for any number of devices implanted in humans and animals, including RFID tags, cosmetics, drug-delivery systems and pacemakers. A capacitor introduced into an organism could be implanted fully dry and then be gradually exposed to bodily fluids over time to generate voltage. Paper batteries are also biodegradable, a need only partially addressed by current e-cycling and other electronics disposal methods increasingly advocated for by the green computing movement. 1.2 BATTERY LIFETIME 1.3.1 PRIMARY BATTERIES LIFETIME Even if never taken out of the original package, disposable or primary batteries can lose 8 to 20 percent of their original charge every year at a temperature of about 20°–30°C.This is known as the "self discharge" rate and is due to non-current-producing "side" chemical reactions, which occur within the cell even if no load is applied to it. The rate of the side reactions is reduced if the batteries are stored at low temperature, although some batteries can be damaged by freezing. High or low temperatures may reduce battery performance. This will affect the initial voltage of the battery. For an AA alkaline battery this initial voltage is approximately normally distributed around 1.6 volts. 1.3.2 LIFE OF RECHARGEABLE BATTERIES Rechargeable batteries traditionally self-discharge more rapidly than disposable alkaline batteries, especially nickel-based batteries; a freshly charged NiCd loses 10% of its charge in the first 24 hours, and thereafter discharges at a rate of about 10% a month.
  • 7. 7 However, modern lithium designs have reduced the self-discharge rate to a relatively low level (but still poorer than for primary batteries). Most nickel-based batteries are partially discharged when purchased, and must be charged before first use. 1.3.3 EXTENDING LIFE BATTERIES Battery life can be extended by storing the batteries at a low temperature, as in a refrigerator or freezer, because the chemical reactions in the batteries are slower. Such storage can extend the life of alkaline batteries by ~5%; while the charge of rechargeable batteries can be extended from a few days up to several months. In order to reach their maximum voltage, batteries must be returned to room temperature; discharging an alkaline battery at 250 mAh at 0°C is only half as efficient as it is at 20°C. As a result, alkaline battery manufacturers like Duracell do not recommend refrigerating or freezing batteries.
  • 8. 8 CHAPTER – 2 LITERATURE SURVEY 2. MANUFACTURING OF PAPER BATTERY 2.1 MANUFACTURING OF CARBON NANOTUBES One method of manufacturing, developed by scientists at Rensselaer Polytechnic Institute, begins with growing the nano tubes on a silicon substrate and then impregnating the gaps in the matrix with cellulose. Once the matrix has dried, the material can be peeled off of the substrate, exposing one end of the carbon nano tubes to act as electrode. Fig 2.1.1 Paper battery When two sheets are combined, with the cellulose sides facing inwards, a super capacitor is formed that can be activated by the addition of the ionic liquid. This liquid acts as an electrolyte and may include salt-laden solutions like human blood, sweat or urine. The high cellulose content (over 90%) and lack of toxic chemicals in paper batteries makes the device both biocompatible and environmentally friendly, especially when compared to the traditional lithium ion battery used in many present-day electronic devices and laptops.
  • 9. 9 Specialized paper batteries could act as power sources for any number of devices implanted in humans and animals, including RFID tags, cosmetics, drugs delivery systems and pacemakers. A capacitor introduced into an organism could be implanted fully dry and then gradually exposed to bodily fluids over time to generate voltage. Paper batteries are also biodegradable, a need only partially addressed by current e-cycling and other electronics disposal methods increasingly advocated for by the green computing movement. Carbon nanotubes are the main concept behind paper battery. Carbon nanotubes (CNTs; also known as buckytubes) are allotropes of carbon with a cylindrical nanostructure. CNTs exhibit extraordinary strength and unique electrical properties, and are efficient thermal conductors. Fig 2.1.2 Carbon nanotubes Carbon nanotube is an allotrope of carbon. Allotropy is nothing but different structural modifications of an element. Carbon nano ink which is black in colour is a solution of nano rods, surface adhesive agent and ionic salt solutions. Carbon nano ink is spread on one side of the paper. The paper is kept in the oven at 150 degree Celsius. This evaporates the water content on the paper. The battery is ready and would provide a terminal voltage enough to power an LED. Cellulose is a complex organic substance found in paper and pulp; not digestible by humans. A Carbon Nano Tubes (CNT) is a very tiny cylinder formed from a single sheet of carbon atoms rolled into a tiny cylinder. These are stronger than steel and more conducting than the best semiconductors. CarbonNanotubeRolled at angleGraphene Structure
  • 10. 10 They can be Single-walled or Multi-walled. Presently, the devices are only a few inches across and they have to be scaled up to sheets of newspaper size to make it commercially viable. 2.2 DEVELOPMENT The creation of this unique nano composite paper drew from a diverse pool of disciplines, requiring expertise in materials science, energy storage, and chemistry. The researchers used ionic liquid, essentially a liquid salt, as the battery’s electrolyte. The use of ionic liquid, which contains no water, means there’s nothing in the batteries to freeze or evaporate. “This lack of water allows the paper energy storage devices to withstand extreme temperatures,” Kumar said. It gives the battery the ability to function in temperatures up to 300 degrees Fahrenheit and down to 100 below zero. The use of ionic liquid also makes the battery extremely biocompatible; the team printed paper batteries without adding any electrolytes, and demonstrated that naturally occurring electrolytes in human sweat, blood, and urine can be used to activate the battery device. Cellulose-based paper is a natural abundant material, biodegradable, light, and recyclable with a well-known consolidated manufacturing process. These attribute turn paper a quite interesting material to produce very cheap disposable electronic devices with the great advantage of being environmental friendly. The recent (r) evolution of thin-film electronic devices such as paper transistors, transparent thin-film transistors based on semiconductor oxides, and paper memory, open the possibility to produce low cost disposable electronics in large scale. Common to all these advances is the use of cellulose fiber-based paper as an active material in Opposition to other ink-jet printed active-matrix display and thin-film transistors reports where paper acts only as a passive element (substrate). Batteries in which a paper matrix is incorporated with carbon nanotubes, or bio fluid - and water-activated batteries with a filter paper have been reported, but it is not known a work where the paper itself is the core of the device perfor
  • 11. 11 Fig 2.2.1 development of paper battery With the present work, we expect to contribute to the first step of an incoming disruptive concept related to the production of self-sustained paper electronic systems where the power supply is integrated in the electronic circuits to fabricate fully self sustained disposable, flexible, low cost and low electrical consumption systems such as tags, games or displays. In achieving such goal we have fabricated batteries using commercial paper as electrolyte and physical support of thin film electrodes. A thin film layer of a metal or metal oxide is deposited in one side of a commercial paper sheet while in the opposite face a metal or metal oxide with opposite electrochemical potential is also deposited. The simplest structure produced is Cu/paper/Al but other structures such as Al paper WO TCO were also tested, leading to batteries with open circuit voltages varying between 0.50 and 1.10 V.
  • 12. 12 On the other hand, the short current density is highly dependent on the relative humidity (RH), whose presence is important to recharge the battery. The set of batteries characterized show stable performance after being tested by more than 115 hours, under standard atmospheric conditions [room temperature, RT (22 C) and 60% air humidity, RH]. In this work we also present as a proof of concept a paper transistor in which the gate ON/OFF state is controlled by a non-encapsulated 3 V integrated paper battery.
  • 13. 13 CHAPTER – 3 EXPERIMENTAL DETAILS 3.1 EXPERIMENTAL DETAILS The paper batteries produced have the Al/paper/Cu structure, where the metal layers were produced by thermal evaporation at RT. The thickness of the metal elect rode varied between 100 and 500 nm. The electrical characteristics of the batteries were obtained through I-V curves and also by sweep voltammeter using scanning speed o 25 mVs and the electrodes area of 1cm. A Keithley 617 Programmable Electrometer with a National Instruments GPIB acquisition board was used to determine the I-V characteristics. Fig 3.1 Dependence of temperature on discharge capacity The cyclic voltammeter was performed with a potenciostat Gamry Instruments Ref. 600 in a two-electrode configuration. The electrical performances of the batteries were determined by monitoring the current of the battery under variable RH conditions. The surface analysis of the paper and paper batteries was performed by S-4100 Hitachi scanning electron microscopy (SEM), with a 40 tilt angle.
  • 14. 14 The electrical properties of the paper transistor controlled by the paper battery were monitored with an Agilent 4155C semiconductor parameter analyzer and a Cascade M150 microprobe station. Fig 3.2 Typical series connections method
  • 15. 15 CHAPTER – 4 RESULT AND DISCUSSION 4.1 RESULT AND DISCUSSION The Al/paper/Cu thin batteries studied involved the use of three different classes of paper: commercial copy white paper (WP: 0.68 g/cm, 0.118 mm thick); recycled paper (RP: 0.70 g/cm, 0.115 mm thick); tracing paper (TP: 0.58 g/cm, 0.065 mm thick). The TP is made of long pine fibers and according to FRX (X-ray fluorescence) mainly Al2 O3 (24%), SiO2 (37%), SO2 (15%), CaO (9%), and Na2 O (4%). The role of the type of paper and electrodes thickness on the electrical parameters of the battery, such as the Voc and Jsc are indicated in Table I, for RH of 50%–60%, using metal electrodes with different thicknesses (t1=100 nm; tot2=250 nm;t3=500 nm). Jsc for WP is ~ 40%–50% lower than of TP, and RP is one order of magnitude lower than WP. Consequently, the Voc is reduced by merely a ~ 0.1 V when moving from WP to RP only for thickness (t1=100 nm) while it increases for t2 and t3. Fig 4.1 Photograph of the paper batteries with a sketch of the cross section
  • 16. 16 The thickness of the metal layer does not play a remarkable role on electrical characteristics of the batteries. The results show that it is enough to guarantee the step coverage of the randomly dispersed fibers by metal or metal–oxide thin films to allow the carriers to find a continuous pathway without the inhibition of water vapor absorption by the paper fibers. Considering that the tracing paper is less dense and thinner than white and recycled paper, the difference on the current density observed can be related to ions recombination either due to impurities inside the foam/mesh-like paper structure or charge annihilation by vacant sites associated to the surface of the paper fibers, existing in thicker papers. Other possible explanation is that the adsorption of water vapor is favored in less dense paper. Fig. 4.1 shows a photograph and a sketch of a paper battery analysis it contains with an Al anode while the cathode is Cu, whose difference in work functions influences the set of chemical reactions that take place within the paper mesh structure. The paper SEM image of Fig. 4.2 is the surface morphology of tracing paper used. There, large (50 m). This mesh-like structure favors OHx absorption on the surface of the fibers, in line with data depicted in Table 4.1, where the batteries produced in WP show currents one order of magnitude lower than the ones produced in TP. Fig 4.2 SEM image of the paper surface
  • 17. 17 Fig 4.3 SEM image of the anode (AL) surface For RP, two orders of magnitude difference in is observed. Voc is reduced by 0.1–0.2 V when moving from WP to RP as electrolyte. The paper battery prototype used is non-encapsulated and so, its electrical performance is influenced by the atmospheric constituents. This behavior was confirmed by measuring the current of one cell in vacuum and under atmospheric pressure. The results demonstrated a reduction of one order of magnitude in Jsc value after vacuum reaching 10 Pa. These results were reproducible after performing several tests. We attributed this behavior to the incorporation of OH radicals from adsorbed water and its contribution to the enhancement of current through the typical reactions of 2H2 O→ O2+ 4H+ +4e- and/or4 OH- →O2+2 H2 O+4e- and subsequent reactions with the paper fibers constituents (cellulose and ions). This was confirmed by measuring the current variation as RH changes. The graph of Fig. 4.4 shows the short circuit-current density variation as RH increases for TP. A variation of about three orders of magnitude is observed when RH changes from 60% to 85%, and it is reversible, meaning that no battery damage is verified. We conclude that this type of battery is a mixture of a secondary battery and a fuel cell where the fuel is the water vapor and so its application requires environment with RH>40 % or proper encapsulation with controlled humidity via holes through which we can allow the battery to breathe.
  • 18. 18 Fig 4.4 continues measurement ofthe short Circuit current density ofthe paper Battery as it is under gradual relative humidity. This is the case in applications with typically high RH, as in the food industry, where these batteries could be used to turn electronic tags auto sustained. From the data taken, each battery element is able to supply a power from 75 nW/cm to 350 W/cm, depending on RH. The desired voltage and power output can be achieved by integrating in series and in parallel the battery elements produced. In the present case, a prototype battery able to supply a 3 V was produced to actuate the gate of a paper transistor working in the depletion mode. Fig. 4.4 shows a photograph of the prototype made of 10 cells (with only 8 cells connected in series) and the graph of the drain current of the paper transistor when the paper battery is connected to the gate ( 3 V) or disconnected (0 V). The connection/disconnection was repeated during 400 s in intervals of 25 s and the current was monitored continuously. The results clearly show the sustainability of the paper battery in powering the gate of the transistor and how the results are reproducible. The drain current of the paper transistor at 0 V is 2 10 A and at 3V is 10 A, similar to the values obtained when measuring the transfer characteristics of the same devices with a semiconductor analyzer.
  • 19. 19 CHAPTER – 5 APPLICATION AND USE OF PAPER BATTERY 5.1 IN COSMETICS Anti-aging and wrinkles Dark spots / Discoloration Skin lightening / Whitening Firming and lifting Moisturizing Fig 5.1.1 Anti-aging and wrinkles
  • 20. 20 Fig 5.1.2 LG Ion Patch (For whitening) Fig 5.1.3 Iontophoresis mechanism
  • 21. 21 Fig 5.1.4 estee lauder (for wrinkles) 5.2 USE OF PAPER BATTERY It can be used to power smart tags. It can be used to power signal use medical devices. It can be used to make items like gaming cards interactive at very low cost making them attractive for portable electronics, aircraft, automobiles, and toys (such as model aircraft), while their ability to use electrolytes in blood make them potentially useful for medical devices such as pacemakers. The medical uses are particularly attractive because they do not contain any toxic materials and can be biodegradable; a major drawback of chemical cells However, Professor Sperling cautions that commercial applications may be a long way away, because nanotubes are still relatively expensive to fabricate.
  • 22. 22 Currently they are making devices a few inches in size. In order to be commercially viable, they would like to be able to make them newspaper size; a size which, taken all together would be powerful enough to power a car. While a conventional battery contains a number of separate components, the paper battery integrates all of the battery components in a single structure, making it more energy efficient. A paper battery is a battery engineered to use a paper-thin sheet of cellulose infused with aligned carbon nanotubes. Nanotubes act as electrodes; allowing the storage devices to conduct electricity. Functions as both a lithium-ion battery and a super capacitor, can provide a long, steady power output comparable to a conventional battery, as well as a super capacitor's quick burst of high energy. Paper battery extreme flexibility; the sheets can be rolled, twisted, folded, or cut into numerous shapes with no loss of integrity or efficiency, or stacked, like printer paper (or a Voltaic pile), to boost total output. The paper-like quality of the battery combined with the structure of the nanotubes embedded within gives them their light weight and low cost, making them attractive for portable electronics, aircraft, automobiles, and toys. 5.3 DURABILITY The use of carbon nanotubes gives the paper battery extreme flexibility; the sheets can be rolled, twisted, folded, or cut into numerous shapes with no loss of integrity or efficiency, or stacked, like printer paper (or a Voltaic pile), to boost total output. As well, they can be made in a variety of sizes, from postage stamp to broadsheet.
  • 23. 23 CHAPTER- 6 CONCLUSION & FUTURE SCOPE In this paper we show the functionality of a non-encapsulated thin-film battery using paper as electrolyte and also as physical support. The battery is self rechargeable when exposed to relative humidity above 40%, being Jsc highly influenced by RH>60%. In this case, Jsc varies from 150 nA /cm2 to 0.8 Ma /cm2, as RH varies from 60% to 85%. This constitutes the first step towards future fully integrated self sustained flexible, cheap and disposable electronic devices, with great emphasis on the so-called paper electronics. The range of possible applications for paper batteries derives from their important advantages as compared to conventional battery technologies. They can be made in virtually any shape and size to meet the requirements of each application. The batteries are rechargeable, and have reduced cost and weight which in itself may give birth to new applications. Paper battery could solve all the problems associated with electrical energy storage. However the reality is still very far away, though the researches are promising. Being Biodegradable, Light-weight and Nontoxic, flexible paper batteries have potential adaptability to power the next generation of electronics, medical devices and hybrid vehicles, allowing for radical new designs and medical technologies. But India still has got a long way to go if it has to be self-dependant for its energy solution. Literature reflects that Indian researchers have got the scientific astuteness needed for such revolutionary work. But what hinders their path is the lack of facilities and funding. Of course, the horizon of inquisitiveness is indefinitely vast and this paper is just a single step towards this direction. The black piece of paper can power a small light. Flexible paper batteries could not meet the energy demands of the next generation of gadgets. The ambition is to produce reams of paper that could one day power a car. The paper battery was a glimpse into the future of power storage.
  • 24. 24 They have produced a sample slightly larger than a postage stamp that can store enough energy to illuminate a small light bulb. But the ambition is to produce reams of paper that could one day power a car. Professor Robert Linhardt, of the Rensselaer Polytechnic Institute, said the paper battery was a glimpse into the future of power storage. The team behind the versatile paper, which stores energy like a conventional battery, says it can also double as a capacitor capable of releasing sudden energy bursts for high-power applications.
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