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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 successfully turned paper coated with ink made of

silver and carbon nano materials into a "paper battery" that holds promise for

new types of light weight, high-performance energy storage.

The same feature that helps ink adhere 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.

Figure 1.1.1 Ordinary battery

"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 scientist’s said in research published in the

Proceedings of the National Academy of Sciences.

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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

have 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.”

Figure 1.1.2 Conventional battery

"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.

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1.2 INTRODUCTION OF PAPER BATTERY

A paper battery is a flexible, ultra-thin energy storage and production device

formed by- combining carbon nanotubes 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

batterie’s have the potential to power the next generation of electronics,

medical device’s and hybrid vehicles, allowing for radical new designs and

medical technologies.

Figure 1.2.1 carbon nanotubes

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Paper batteries may be folded, cut or otherwise shaped for different

applications without any loss of integrity or efficiency . Cutting one in half

halve s its energy production. Stacking them multiplies power output. Early

prototypes of the device are able to produce 2.5 volts of electricity from a

sample the size of a postage stamp.

Figure 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 the traditional battery,

conducting electricity when the paper comes into contact with an ionic

liquid solution.
Ionic liquids contain no water, which means tha there is nothing to freez e or

evaporate in extreme environmenta 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

silicon substrate and then impregnating the gaps in the matrix with cellulose.
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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 .

Figure 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 o r urine. The high cellulose content (over 90%) and

lack of toxic chemicals in paper batterie’s 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 echniques 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. 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.

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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 human s 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.

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2. MANUFACTURING OF PAPER BATTERY

2.1 MANUFACTURING OF CARBON NANOTUBES

One method of manufacture, developed by scientists at Rensselaer

Polytechnic Institute and MIT, 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 an electrode .

Figure 2.1 paper battery

When two sheets are combined, with the cellulose sides facing inwards, a

super capacitor is formed that can be activated by the a ddition 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.

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Specialized paper batteries could act as power sources for 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.

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

attributes turn paper a quite interesting material to produce very cheap

disposable electronic devices, with the great advantage of

being environmental friendly.

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The recent (r) evolution of thin -film electronic devices

such as paper transistors transparent thin-film transistors basedon semiconductor

oxides and paper memory open the possibility toproduce low cost disposable

electronics in large scale. Common to all these advances is the use of

cellulose fiber -based paper as an active material inopposition to other ink -jet

transistors reports where paper act s only as a passive element (substrate).

Batteries in which, a paper matrix is incorporated with carbon nanotubes

or biofluid - and water- activated batteries with a filter paper have been

reported, bu t it is not known a work where the pape r itself is the core of the

devic e performance.

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Figure 2.2 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 o r meta l oxide is deposited in one side of a commercial paper sheet

while in the opposite, face a metal or metal oxide with opposite

electrochemical potentia l 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.

On the other hand, the short current density is highly dependent on the

relative humidity (RH), whose presence is important to recharge the battery.

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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 thicknesses of the

metal electric rodes varied between 100 and 500 nm. The electrical
characteristics of the batteries were obtained through I–V curves and also by

sweep voltammetry using scanning speed of 25 mV/s and the electrodes area

of 1 cm . A Keithley 617 Programmable Electrometer with a National

Instruments GPIB acquisition board were used to determine the I–V

characteristics.

Figure 3.1 Dependence of temperature on discharge capacity

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The cyclic voltammetry 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. The electrical properties of the paper

transistor controlled by, the paper battery were monitored with an Agilent

4155C semiconductor parameter, analyzer and a Cascade M 150 microprobe

station.

Figure 3.2 Typical series connection method

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4. RESULTS AND DISCUSSION

4.1 RESULTS 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.

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Figure 4.1 Photograph of the paper batteries with a sketch of the cross section

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 tha t the

tracing paper is less dense and thinne than white and recycled paper, the

difference on the current density observed can b e 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 favore d 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.

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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.

figure 4.2 SEM image of the paper surface.

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Figure 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 /or 4 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.

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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 vapo 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.

Figure 4.4 Continuous measurement of the short circuit current density of the paper
battery as it is under gradual relative humidity

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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 were 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 .

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5. APPLICATION AND USES OF PAPER BATTERY

5.1 IN COSMETICS

Anti-aging and wrinkles

Dark spots / Discoloration

Skin lightening / Whitening

Firming and lifting

Moisturizing

Figure 5.1.1 Anti-aging and wrinkles

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Figure 5.1.2 LG Ion Patch (For whitening)

Figure 5.1.3 Iontophoresis mechanism

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Figure 5.1.4 estee lauder (for wrinkles)

5.2 USES OF PAPER BATTERY

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 (such as model aircraft), while their ability to use electrolytes in blood

make them potentially useful for medical devices such as pacemakers.

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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.

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.

5.3 DURABILITY

The use of carbon nanotubes gives the pape r 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. “It’s essentially a regular piece of paper but

it’s made in a very intelligent way,” said Linhardt, “We’re not putting pieces

together — it’s a single, integrated device,” he said.

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6.CONCLUSION

In this paper we show the functionality of a non- encapsulated thin-film

battery using paper as electrolyte and also as physical support. Batteries able
to supply a Voc≈.70V and Jsc>100nA/cm2 at RH>60% were fabricated using

respectively as anode and cathode thin metal films of Al and Cu as thin as

100 nm. 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.

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7.REFERENCES

➢ S. Balu , M. Mahalakshmi (August 2014)- “: Paper Thin Power”

➢ Thu H Nguyen, Arwa Fraiwan, Seokheun Choi (2014)- “Paper-based batteries: A
review”
➢ Preeti Yadav, Swati (July-Dec., 2014)- “Paper Battery”
➢ Zhonghui Wanga, Hongfa Xianga, Lijuan Wanga, Ru Xiab, Shuping Nieb, Chunhua
Chenc, Haihui Wangd,( 2016)- “A paper-supported inorganic composite separator for
high-safety lithium-ion Batteries”
➢ Xinhang Chena,b, Hongli Tanga,b, Zongyu Huanga,b, Jie Zhoua,b, Xiaohui Rena,b,
Kai Huanga,b (17 October 2016)- “Flexible Bismuth Selenide /Graphene composite
paper for lithium-ion Batteries”

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