1

PROJECT REPORT
MAY-JULY 2013




AQUEOUS RECHARGABLE AND FLEXIBLE
LITHIUM ION BATTERY






Prepared by
Rahul Kumar
B.Tech Nanotechnology (3
rd
Year)
Amity Institute of Nanotechnology
Amity University, Noida
Uttar Pradesh
2


ACKNOWLEDGEMENT

I express my sincere gratitude towards Dr. Prem Kalra, Director, IIT Jodhpur,
Rajasthan for allowing me to undertake my project at IIT Jodhpur, Rajasthan.

I am thankful to Mr. Ritesh Patel and Mr Belal Usmani, for their invaluable
support and encouragement. I am grateful to him for providing me all the facilities
that I have utilized to accomplish my project.

I take immense pleasure, in expressing my gratitude to my guide Dr. Harinipriya
Sheshadri, for her expert guidance and constant encouragement throughout the
period of my project. I am grateful for her motivation, patience and precious time
that she devoted for my project work. It has truly been a wonderful experience to
have worked under her able guidance.




Rahul Kumar


3

CERTIFICATE
This is to certify that Mr. Aditya Sharma, 3
rd
year,B.Tech. Nanotechnology, Amity
University, Noida has undergone a summer training in Energy system of Indian
Institute of technology Jodhpur, Rajasthan for a period of 8 weeks from 12
th
may
to 14
th
July 2012 on, Aqueous rechargeable and flexible lithium ion battery.
His report contains no confidential or restricted information.
During this period his conduct was good. He was sincere, hardworking and always
willing to learn things.




Dr. Harinipriya Sheshadari

Assistant Professor
IIt Jodhpur, Rajasthan


4

TABLE OF CONTENTS

Acknowledgements 2
Certificate 3
1. Abstract 6
2. Literature Review 7
2.1 Cathode Material(LiMn
2
O
4
) 9
2.2 Anode Material(CNT) 10
3. Cell Construction 12
3.1 LiMn
2
O
4
Cathode Synthesis 12
3.2 CNT Ink Anode Synthesis 12
3.3 Cell Construction 12
4. Data Analysis, results and Interpretation 14
4.1 XRD analysis 14
4.2 SEM analysis 15
5. References 18








5

LIST OF FIGURES

Figure 1: Lithium Ion battery mechanism 7
Figure 2: XRD graphs of different samples of LiMn
2
O
4
Powder 14
Figure 3: SEM images of different sample of LiMn
2
O
4
Powder 17

6

1. Abstract
New and improved materials for energy storage are urgently required to make
more efficient use of our finite supply of fossil fuels, and to enable the effective
use of renewable energy sources. Lithium ion batteries are a key resource for
mobile energy, and one of the most promising solutions for environment-friendly
transportation. We report the synthesis of Nanostructured LiMn
2
O
4
Powder as the
cathode material for rechargeable lithium ion batteries. Synthesis was done by
starch assisted sol-gel method. Multi walled Carbon Nanotubes (MWCNTs) of
average diameter from 10 nm to 20 nm in the form of thin films were used as
anode material. Lithium Sulphate and Agar-Agar solution was used as the
electrolyte for charge transfer between two electrodes. Characterization was done
by powder XRD, SEM, UV and FTIR.













7

2. Literature Review
A lithium-ion battery is a member of a family of rechargeable battery types in
which lithium ions move from the anode to the cathode during discharge and back
when charging. Li-ion batteries use an intercalated lithium compound as the
electrode material, compared to the metallic lithium used in non-rechargeable
lithium battery. Lithium-ion batteries are common in consumer electronics. They
are one of the most popular types of rechargeable battery for portable electronics,
with one of the best energy densities, no memory effect and only a slow loss of
charge when not in use. You can find them in laptops, PDAs, cell phones and
iPods. They're so common because, pound for pound, they're some of the most
energetic rechargeable batteries available.


Figure-1: Li-ion Battery

Since Sony introduced its model No.-18650 cell in 1990, Li-ion batteries with
excellent electrochemical performance have been manufactured and occupied a
prime position in the market place to power portable and non-portable devices.

8


There are three main parts of the Li-ion Battery: -
1) Cathode Material
2) Anode Material
3) Electrolyte
Batteries are broadly grouped as primary and secondary batteries. Primary batteries
are single-use devices and cannot be recharged; secondary batteries are also called
rechargeable batteries and can be recharged for many times.
The reason for this relevance is that compared to traditional rechargeable batteries
such as, lead acid and Ni-Cd, the lithium-ion battery shows several advantages,
such as lighter in weight, smaller in dimension and higher energy density.
Moreover, although capacity values may be similar to other rechargeable systems,
voltages are approximately three times higher, affording higher energy.
In general, the commercial lithium-ion batteries use graphite-lithium composite,
Li
x
C
6
, as anode, lithium cobalt oxide, LiCoO
2
, as cathode and a lithium-ion
conducting electrolyte. When the cell is charged, lithium is extracted from the
cathode and inserted at the anode. On discharge, the lithium ions are released by
the anode and taken up again by the cathode. Owing to the importance of lithium
ion batteries, these cells are still object of intense research to enhance their
properties and characteristics. The searches focus on all aspects of these batteries,
including improved anodes, cathodes and electrolytes. However, most of these
efforts are concentrated in new cathode materials, since the most used cathode
material (LiCoO
2
) is expensive and is somewhat toxic. The active cathode material
of a secondary lithium ion battery is a host compound, where lithium ions can be
inserted and extracted reversibly during the cycling process.
But with the advent of nanotechnology, the efficiency of Li-ion batteries has been
increasing. Researchers are more focused on increasing the efficiency by using
nanostructured material for cathode and anode.

9


2.1 Cathode Material (LiMn
2
O
4
)
The cathode materials for Li-ion batteries are usually oxides of transition metals
due to their high electrochemical. Currently there are three intercalation materials
that are used commercially as cathode materials for rechargeable lithium batteries:
LiCoO
2
, LiNiO
2
, and LiMn
2
O
4
.
We used the LiMn
2
O
4
powder, which is a very promising material for cathode. It
forms a spinel structure, in which manganese occupies the octahedral sites and
lithium predominantly occupies the tetrahedral sites. In this case, the paths for
lithiation and delithiation are a 3-dimensional network of channels rather than
planes. LiMn
2
O
4
is lower cost and safer than LiCoO2, but has a lower capacity as
compared to the cathode materials that form the NaFeO
2
structure. However, the
high cost, toxicity, and limited abundance of cobalt have been recognized to be
disadvantageous. As a result, alternative cathode materials have attracted much
interest. LiMn
2
O
4
is one of promising candidate for cathode. Which has a charge
storage capacity of 148 mAh/g. Spinel LiMn2O4 has the advantages of low-cost,
environmental friendliness, and high abundance. One of the challenges in the use
of LiMn2O4 as a cathode material is that phase changes can occur during cycling.
For example, LiMn2O4 cathodes have been field tested in the DC power supply of
an operating telecommunications transceiver. During this test, a relatively rapid
loss of capacity occurred in the first few days, but the rate of capacity loss
subsequently decreased. The initial loss has been attributed to loss of oxygen
during charging. Capacity loss has also been observed during storage due to
dissolution of manganese in the electrolyte, or due to changes in particle
morphology or crystallinity.
The performance of cathode materials can be improved by doping, but the
interpretation of doping effects can be complicated by the interrelations between
doping and microstructure and morphology, since the microstructure formed can
be affected by the dopant additions. Some examples in which the effects of doping
on the electrochemical properties of the electrode are attributed to the effects of the
dopant on the cathode microstructure or morphology rather than the effects on the
10

material properties include cesium doping of LiMn2O4, copper-doping of
phosphates and aluminum-doping of LiCoO2.
Another transition metal that has been used as a dopant for cathode materials is
ruthenium, which has been added as a dopant to spinel electrode material.
2.2 Anode Material (CNT)
An anode is an electrode through which electric current flows into a polarized
electrical device. The direction of electric current is, by convention, opposite to the
direction of electron flow.
MWCNTs, with concentric graphene layers spaced 0.34 nm apart, display
diameters from 10 to 20 nm and lengths of hundreds of microns were taken as
anode material for li-ion battery. Carbon nanotubes (CNTs) have displayed great
potential as anode materials for lithium ion batteries due to their unique structural,
mechanical, and electrical properties. Carbon nanotubes (CNTs), an allotrope of
graphite, have been reported to show much improved lithium capacity compared to
graphite, due to their unique structures and properties. However, due to the
multiple rolled layers, MWCNTs are able to insert Li ions in a way similar to
graphite, making them a promising candidate as an anode material for LIBs.
Except for the inter-planar spacing of graphitic sheets that allows for the
intercalation/deintercalation of lithium ions, the hollow cores of MWCNTs are also
available for lithium ion intercalation. Therefore, the unique structures of
MWCNTs should result in a higher capacity than that of graphite. Much work has
been done to verify the excellent electrochemical performance of MWCNT-based
anode materials in LIBs applications.
CNTs have been reported to display conductivities as high as 106 S/m and 105 S/m
for single-walled carbon nanotubes (SWCNTs) and multi-walled carbon nanotubes
(MWCNTs), respectively, and high tensile strength up to 60 GPa. The vertically
aligned MWCNTs also displayed substantially greater rate capability than the non-
aligned ones, which emphasizes the important role that structure order plays in
electrode performance. Recently, many investigations have focused on CNT-based
anodes for LIBs with varying success, depending on the treatments employed. This
paper provides an overview of the recent research of CNTs in LIB anode
applications with respect to structural and morphological factors.
11

It has been suggested that lithium atoms are stored via two mechanisms:
intercalation and alloying. We briefly describe the intercalation and diffusion of Li
at different sites on CNTs. Many studies have been performed in order to
investigate the mechanism by which lithium ions are stored in CNTs, including
theoretical works proposed a surface mechanism by which the naked surface of
CNTs and carbon nanoparticles are able to store lithium species, through
investigation of the electrochemical intercalation of lithium into raw end-closed
CNTs.
It is well known that the morphology of CNTs is of great importance for the
electrochemical performance of LIBs when CNTs are used as anode materials.
This means that the defects, lengths, and diameters of CNTs can influence the
performance of CNT-based anode materials. Generally, there are two widely
applied methods to modify the morphologies of CNTs: chemical etching and ball-
milling. These treatments are reported to result in structural changes and the
formation of surface functional groups on CNTs. The structural changes, including
the lateral defects on the surface of CNTs and the shortening of the length of
CNTs, can increase the Li insertion capacity.










12

3 Experiment Work
3.1 LiMn
2
O
4
Cathode Synthesis
All the chemicals were analytically pure. All the chemicals were purchased
by Alfa Aesar and Fisher Scientific. LiMn
2
O
4
powder was synthesizes by starch
assisted sol-gel method. A solution of 6.4g starch in 400ml distilled water was
taken and heated at 150c with stirring till it becomes transparent. Then a mixture of
5mM of Manganese nitrate tetrahydrate Mn (NO
3
)
2
in 800ml water and solution of
2.5mM Lithium Nitrate LiNO
3
in 400ml water was added in solution of starch and
initially heated and stirred at 250C for 1h till it becomes homogeneous. Then
temperature was raised till 450C till the solution gets vaporized and precursor was
obtained in the form of foam. Then foam was further dried for 3hours at 400C.
Black powder is obtained after the foam was completely dried. Then powder was
further grinded in granite mortar to fine powder. Then powder was calcinated at
700C for 3hours in box furnace. X-Ray diffraction, UV, FTIR and SEM analysis
was done. This powder was further used for making thin sheet of 1g of LiMn
2
O
4

was added in a Solution of 6g Ethyl Cellulose in 50 ml Amyl Acetate under
vigorous stirring for 2h. Then obtained solution was spray coated on PET sheets
and uniform thin films of Cathode were obtained.
3.2 CNT Ink Anode Synthesis
MWCNTs, with concentric graphene layers spaced 0.34 nm apart, display
diameters from 10 to 20 nm and lengths of hundreds of microns were taken as
anode material for li-ion battery. Solution of 6g Ethyl Cellulose in 50 ml Amyl
Acetate was prepared under vigorous stirring for 2h. Then 1g of MWCNT was
added in the solution and continued the stirring for 1h. Then solution was spray
coated on PET sheets of dimension 14.5cm x 9.5cm with the help of spray gun and
a uniform thin layer was obtained.
3.3 Cell Construction
A solution of lithium Sulphate of 1 molar concentration in 100 ml distilled water
and 20 g of Agar-Agar was prepared as electrolyte for Li-ion battery. This solution
was heated for 20 minutes till the solution become viscous gel. Silver paste was
used to make the contacts on both the electrodes to increase the conductivity. The
13

electrolytic gel was placed between the two electrodes and copper wire was used
for charging the battery. Then the gel become hard, cell was sealed with m-seal.


















14

4 Data Analysis, results and Interpretation
4.1 XRD Analysis
The powder XRD of LiMn
2
O
4
powder was done by Brukers D8 Advance. The
XRD graphs of different samples have shown below. The material was crystalline
in nature. The hkl values and 2 theta values were matched with standard data.
20 30 40 50 60 70 80
0
100
200
300
400
500


I
n
t
e
n
s
i
t
y

(
a
.
u
)
2 Theta
Sample no-1
LiMn
2
O
4
Powder
20 30 40 50 60 70 80
0
50
100
150
200
250


I
n
t
e
n
s
i
t
y
2 Theta
Sample No- 2
LiMn
2
O
4
Powder
20 30 40 50 60 70 80
0
100
200
300
400
500


I
n
t
e
n
s
i
t
y
2 Theta
Sample No-3
LiMn
2
O
4
Powder
20 30 40 50 60 70 80
0
50
100
150
200
250
300
350


I
n
t
e
n
s
i
t
y
2 Theta
Sample No-4
LiMn
2
O
4
Powder
20 30 40 50 60 70 80
0
100
200
300
400
500

I
n
t
e
n
s
i
t
y
2 Theta
Sample No-5
LiMn
2
O
4
Powder


Figure 2: XRD graphs of different samples of LiMn
2
O
4
Powder

15

4.2 SEM Analysis
SEM images were taken from Carl ZEISS SEM EVO 18 edition instrument.
Nanostructures were formed in all the samples synthesized by this method.
LiMn
2
O
4
Powder was crystalline and chain was formed due to the starch reaction.
SEM images are shown below.








16








17



Figure 3: SEM images of different sample of LiMn
2
O
4
Powder used as cathode for
the Lithium Ion battery. A scale appears in all the pictures.













18

5 References
1. J. Braz. Chem. Soc., Vol. 17, No. 4, 627-642, 2006.
2. Chem. Mater. 2003, 15, 4211-4216.
3. Materials 2013, 6, 1138-1158.
4. Int. J. Electrochem. Sci., 8 (2013) 6775 6783.
5. Materials Science and Engineering R 73 (2012) 5165.
6. Nano Lett., 2008, 8 (11), 3948-3952.
7. J. Mater. Chem. A, 2013, 1, 3518.