Professional Documents
Culture Documents
Master of Science
In
Chemistry
by
NIKITA YADAV
(Roll No. 1420807015)
Under the supervision of
Dr. D. ARUMUGAM
Assistant Professor
to the
May- 2016
1
CERTIFICATE
Date:
Place: Bareilly
( Dr.D.Arumugam)
Assistant Professor in Chemistry,
Department of Applied Science and Humanities,
INVERTIS UNIVERSITY,
Bareilly - Lucknow Highway-24,
Bareilly - 243123, Uttar Pradesh,
INDIA
ABSTRACT
Li battery is a energy storage device it applicable for laptop smart phone,
cell phone etc. it play a very significant role in today's life A carbon-coated plate
like LiFePO4 particle space group was prepared by employing a hydrothermal
method at 190C. The obtained particle had a preferred crystal orientation with
(020) texture, which was revealed by transmission electron microscopy and
electron diffraction. After the hydrothermal treatment, further heat-treatments at
high temperatures (400) (800C) were carried out to increase the electrical
conductivity of the carbon layer, and the conductivity was considerably improved
by heat-treatment at temperatures higher than 700C. The obtained LiFePO 4/C
particle exhibited a high-rate chargedischarge capability in a liquid electrolyte of
1.0 mol dm3 LiPF6/ethylene carbonate + diethyl carbonate (1:1) volume ratio_.
The discharge capacity of the particle was more than 100 mAh g1 at a discharge
rate of 10 C. Furthermore, an all-solid-state cell comprising Li/polymer
electrolyte/LiFePO4 was fabricated using a block copolymer electrolyte consisting
of polyethylene oxide and polystyrene, and the chargedischarge performance of
the cell was examined at 30C. In this paper, the specific capacities as a
function of discharge rate of over 40 different LiFePO4 materials
ACKNOWLEDGEMENT
This research project is made possible through the help and support from everyone,
including: parents, teachers, family, friends, and in essence, all sentient beings.
specially, please allow me to dedicate my acknowledgment of gratitude toward the
following significant advisors and contributors:
First and foremost, I would like to thank to our Honourable Chancellor, Vice
Chancellor, Pro. vice chancellor for provide the well facility for complete of my
M.Sc. in Chemistry and my research project.
I also thanks to Dean and Engineering Prof. R. K. Shukla Ph.D and our HOD Prof.
Shalabh Saxena P.hD; for constant support of my completion of thesis.
I would like to specially thanks to our Dr. D. ARUNMUGAM for his most support
and encouragement. He kindly read my project and offered invaluable detailed
advices on grammar, organization, hand the theme of the project
Second, I would like to show my gratitude towards all people who help and show
their guidance for completion of this project.
And also, I sincerely thank to my parents, family, and friends, who provide the
advice and financial support. The product of this research project would not be
possible without all of them.
INDEX
CHAPTER
CONTENT
PAGE No.
1.
Introduction
01-16
2.
Literature Survey
17-18
3.
19-21
4.
Experimental
22-25
5.
26-34
6.
Conclusions
35
7.
References
37
1. INTRODUCTION
1.1 Electrochemistry
The branch of Science which deals with the relationship between electrical
and chemical energy and their inter conversion is called Electrochemistry. The
device in which conversion of electrical energy into chemical energy is done is
called Electrolyte Cell while Galvanic or Voltaic Cell is a device in which redox
reaction is used to convert chemical energy into electrical energy. Electrochemistry
is the study of chemical processes that causes electrons to move . This movements
of electrons is called Electricity, which can be generated by movements of
electrons from one elements to another in a reaction known as an oxidation
reduction (redox) The main difference between these two cells are in electrolytic
cell, anode is positive electrode while cathode is negative electrode. On the other
hand , in galvanic cell, anode is negative electrode and cathode is positive
electrode.
1) Primary Batteries -The batteries are those in which the cell reaction occurs
only once and the battery becomes dead after use over a period of time and cannot
be reused again. e.g.:- Dry Cell ( like: Laclanche Cell , Mercury Cell ). a)
Leclanche Cell : A commercial dry cell containing of a graphite (carbon) cathode
in a zinc container ; the later acts as a anode. b) Mercury Cell : Here the reducing
cell is zinc and the oxidizing agent is mercury (II) oxide.
a) Lead Storage Battery - The most important secondary cell is lead storage
battery , commonly used in automobiles and invertors. b) Nickel Cadmium Battery
:- Another important secondary battery is Ni-Cd battery with longer life but more
expensive.
different shapes and sizes, ranging from button cells to megawatt systems
connected to stabilizean electrical distribution network. Several different
combinations of electrode materials and electrolytes are used, including lead-acid
nickel cadmium (NiCd), nickel metal hydride(NiMH),lithium ion (Li-ion), and
lithium ion polymer (Li-ion polymer).
Rechargeable batteries initially cost more than disposable batteries, but have
a much low total cost of ownership and environmental impact, as they can be
recharged inexpensively many times before they need replacing.
NMC batteries can have either a high specific energy or high specific power. They
cannot , however, have both properties. The cathode combination ratio is usually
one-third nickel, one-third manganese and one-third cobalt , meaning that the raw
materials cost is lower than for other option, as cobalt on its own can be quiet
expensive. This battery is commonly preferred for electric vehicles due to its very
low self-heating rate.
e) Lithium Nickel Cobalt Aluminium Oxide- It is also called NCA batteries and
are increasingly important in electric powertrains and in grid storage .NCA
batteries are not common in the consumer industry , but are promising for the
automotive industry. NCA batteries provide a high energy option with a good
lifespan ,even though it is not a safe battery as it quietly costly.NCA batteries used
in vehicles , could skyrocket.
f) Lithium Titanate- Finally, Lithium Titanate is also known as Li-titanate, is a
class of battery that allows for ever more applications. The main advantage of the
Li-titanate battery is its remarkably fast recharge time. Currently manufacture of
electric automobiles and bikes use Li-titanate batteries and there is a potential for
this type of battery to be used in electric buses for public transportation. However,
these batteries have lower inherent voltage ,or lower energy densities than other
Lithium-ion batteries. Still, the density of lithium titanate batteries is still higher
than other non-lithium ion batteries.
11
Application for these batteries can include military and aerospace uses and they
may also be used for storing wind and solar energy and creating smart grids.
12
13
family of batteries includes a variety of products that cater to different user needs
for high energy density and/or high load capacity.
2. LITERATURE SURVEY
Research on cathode materials has been continuously studied since early
1960's. The cathode materials prepared were focused mainly on the preparation
method,as well as the structural analysis. Those LiMVO4 cathode where, M= Cu ,
Ni, Co, Zn, Cd, Mg and Be are the most cathode materials that have been
synthesized using various types of technique. Cathode also used in rechargeable
lithium air batteries especially the non-aqueous type are considered the most
promising energy storage and conversion device candidates for use in future
electric vehicle applications due to their ultrahigh energy density. The air cathode
has been identified as a key factor affecting the overall performances of Li -ion
batteries . The low level performances of air cathode is the major challenges
hindering commercial applications of Li- air batteries .
In the past decade, a great many cathode materials , structures and
fabrication processes have been developed and investigated with the goal of
enhancing cathode performance. The role of the cathode in non-aqueous Li-air
batteries including the cathode reactions mechanism, and the properties and
morphologies of cathode materials , followed by approaches to optimize cathode
performance. Technical challenges are analyzed and insight into future research
directions for overcoming these development challenges of rechargeable nonaqueous Li-air battery cathode are also identical. The oil crisis in mid - 1970's has
16
driven the demand of high power energy sources for light electronics , alternative
materials to avoid the poisonous Pb and Cd for environmental protection . Thus, the
commercialization of Lithium battery was finally achieved in late 1980's. Today's
largest manufacture for both lithium rechargeable and nickel metal hydride
batteries.
The demand for the lithium ion batteries has created everyone attentions since their
commencement in the market in 1991. To date, the necessity for portable power
sources with high energy density has tremendously increase due to the
advancement of the portable power sources such as cell phones , notebook,
computers , camcordors and so on. The famous cathode materials such as LiCO 2,
LiNiO2 AND LiMnO2 are among various transition metal oxides used in most
reported work. We also discussing about NCA Cathode material (Nickel-based
Cathode Materials) : LiNiCoAlO2 The features of " High capacity and High specific
energy" in comparison to Lithium cobalt oxide(LCO). In recent years, even higher
capacity Lithium-ion Rechargeable Battery (LIB) is required , so NCA Cathode
Material is attracting attentions. Application of NCA Cathode Materials: Laptop,
tablets smartphones, digital camera , game device, power tool, electric vehicles,
electric power storage system and so on. So, Cathode plays a significant role in
batteries life.
4. EXPERIMENTAL
1) Optimized LiFePO4-Polyacene Cathode Materials for Lithium-Ion Battery
The LiFePO 4-PAS composite was prepared by using a spherical
FePO4.2H2O precursor. A stoichiometric mixture of Li2CO3, FePO4.2H2O and the
desired amount of phenol-formaldehyde resin was added. The mixture was milled
for 10 hrs, followed by heat treatment to obtain a final LiFePO 4-PAS composite.
The spherical iron phosphate (FePO4.2H2O) powder were prepared via a suitable
controlled crystallization method using Fe(NO3), H3PO4. The aqueous solutions of
Fe(NO3), H3PO4 and NH3 with conc. of 2.0, 2.0 and 6.0M respectively were
pumped into the reactor separately with a metering pump. The reactor was filled
20
deionized water. In this reaction, the flux of the solution of Fe(NO 3) and H3PO3 was
controlled at a rate of 120cm3 h, while the flux of the aq. ammonia solution was
adjusted to retain the pH of the mixture in the range of 4.0-4.2. The temperature in
the reactor was controlled at 50 degree. Then, the mixed materials were transferred
into a receiving jar.
After the reactor was fed continuously 20 h , it was stopped. The materials in
the jar was centrifuged to separate the solid from solution. The solid was washed
with deionised water repeatedly until the pH of the water reached 6 or higher. The
product was dried for 3h in a drying box at 90 degree. Finally, the spherical iron
was obtained.
2.Carbon-Nanotube-Decorated Nano-LiFePO4 @C Cathode Material with
Superior High-Rate and Low-Temperature Performance for Lithium-Ion
Batteries
The double nano-carbon decorated LFP@C/CNT was prepared by using the
modified polyol route followed by a carbon coating procedure, multiwalled CNTs
were added to tetraethylene glycol and ultrasonically dispersed for several hours to
form a uniform suspension. Secondly, ferrous acetate, lithium acetate and
phosphoric acid were dissolved into the suspension at a molar ratio in the sequence.
Then, the obtained suspension was refluxed at the boiling point of tetraethylene
glycol for 6 hrs. The LiFePO4 nanoparticles were collected by the centrifuging and
washing the suspension several times with ethanol and distilled water, and finally
dried in vaccum.
21
22
% H2 for 1 hrs. The carbon content of the prepared powder was determined by
elemental analysis.
23
24
Figure 1. XRD patterns of the prepared LiFePO4PAS powders. Sample Ais spherical powder
prepared by using a spherical FePO42H2O precursor; sample B is a disordered LiFePO4PAS
composite.
Figure 2. Discharge curves of LiFePO4PAS (sample A) cathode material at different rates. The
material is used in a conventional lithium-ion battery electrode design (84 wt% active materials, 8
25
wt% carbon black, and 8 wt% polyvinylidene fluoride, 35 mgcm2 loading) against a lithium
metal counter electrode. The discharge rates are the same as the charge rates separately in cycle
Figure 3 shows the cycle performance of the experiment cells operate dat 20, 10,
0, 20, 40, and 60 C. The cycle performance was excellent at various temperatures.
The discharge capacity of the cell increased as the operating temperature was
raised. At60C the initial discharge capacity reached 145 m Ah g1 (1 C),
approximately 12% higher than what was observed at 20 C. At 0 C, the initial
discharge capacity was 112 m Ah g1,15%lower than what was observed at 20 C.
26
transmission
electron
microscopy
27
(HRTEM),
and
Figure 4 . a) XRD pattern, b) SEM, d) schematic illustration of the prepared LFP@C/CNT nanocomposite.
28
Figure 5. XRD patterns of the LiFePO4/C samples annealed at various temperatures after hydrothermal
treatment: (a) unannealed, (b) 400, (c) 500, (d) 600, (e) 700, and (f) 800C.
Figure 6. Chargedischarge curves of LiFePO4/C samples between 0.1 C_48 _A cm2_ and 10 C _4.86
m A cm2_: (a) unannealed sample and (b) sample annealed at 700C.
of
the
LiFePO4C
particle,
30
although
the
electrical
Figure
7. Plots of the discharge
capacities
of
the LiFePO4C samples as
a function of the C rate. The samples were annealed at various temperatures after
hydrothermal treatment: (a) unannealed, (b) 400, (c) 500, (d) 600, (e) 700, and (f)
800C.
31
Figure 8. _Color online_ The specific capacity as a function of the discharge rate of various LiFePO 4
cathode materials reported in the literature.-The sample no. in Table for samples A, B, C, and D is , and
,respectively.
Fig.9 Dela court etal. studied the rate performance of LiFePO4 with a uniform
particle size of 140 nm prepared by direct precipitation (DP). They found that
when the cathode was prepared using a slurry mixture (SL) containing 17 wt %
conductive carbon, the sample(SL-17C)showed excellent rate performance, which
is comparable to the best sample A. However, when the conductive carbon loading
was reduced to 5 wt %, the sample (SL-5C)prepared using the same LiFePO 4
material had its capacities of 10 15 m A hg lower than the sample
containing 17% C see Fig.9 Changing the powder mixing
32
Figure 9. The influence of conductive carbon loading and powder mixing procedure
in cell preparation on the rate capacity of LiFePO 4 materials. The SL-17C and SL-5C
samples are sample no. 11 in Table I prepared using a slurry mixture with 17 and 5
wt % conductive carbon, respectively. The dry-17C and dry-5C samples are sample
no. 11 in Table I prepared using a dry mixing procedure containing 17 and 5 wt %
conductive carbon, respectively.
34
6.Conclusions
Electrochemical measurements of Li-ion batteries have demonstrated that
LiFePO4-PAS has high discharge capacity and superior cycling performance in the
range of -20 to 60 degree C. This idea is a promising aspect in the design of novel
battery materials.
We have developed a new design by decorating LiFePO4 nanoparticles with
two types of carbonaceous materials to improve the electrochemical properties of
LiFePO4 cathode materials. A carbon-coated plate like LiFePO 4 particles was
prepared by using the hydrothermal method at a temperature of 140 degree C.
However, the electrical conductivity of the carbon layer was very low without
postannealing. Review of the specific capacities of various LiFePO4 materials in the
literature indicates that the electronic conductivity between the LiFePO 4 powders
and the current collector plays a determining role in the high rate performance of
the battery cell.
7. References
[1] a) A.K. Padhi, K.S. Nanjundaswamy, J.B. Goodenough, J. Electrochem. Soc.
1997, 144, 1188; b) A.K. Padhi, K.S. Nanjundaswamy, C. Masquelier, S. Okada, J.
Electrochem. Soc.1997, 144,1609.
35
[2] R. Amin, P . Balaya, J. Maier, Electrochem. Solid-State Lett. 2007, 10, A13.
[3] A. L. Bard, L.R. Faulker, Electrochemical Methods, 2nd ed, Wiley, 2001.
[4] B. Kang, G. Ceder, Nature 2009, 458, 190.
[5] J. Wang, X. Sun, Energy Environ. Sci. 2012, 5, 5163.
[6] X. Z. Liao, Z. F. Feng, Y. S. He, J. Electrochem. Soc. 2005, 152, A 1969.
[7] S. Shi, C. Ouyang, Z. Xiong, Phys. Rev. B: Condens. Matter Mater. Phys. 2005,
71, 144414.
[8] K. Striebel, J. Shim,V. Srinivasan, J. Electrochem. Soc.2005, 152, A664.
[9] H. S. Skim, B. W. Cho, J. Power Sources 2004, 132 235.
[10] G. X. Wang, L. Yang, Y. Chen, Electrochem, Acta 2005, 50, 4649.
[11] A. K. Padhi, K. S. Nanjundaswamy, and J. B. Goodenough, J ,Electrochem,
Soc.,144, 1188 (1997).
[12] A. Yamada, S. C. Chung, and K. Hinokuma, J. Electrochem, Soc., 148, A224
(2001).
[13] S. Y. Chung, J. T. Bloking, and Y. M. Chiang, Nature Mater., 1, 123 (2002).
[14] B. Wang, Y. Qiu, and S. Ni, Solid State Ionics, 178, 843 (2007).
[15] J. Barker, M. Y. Saidi, and J.L. Swoyer, Electrochem. Solid-State Lett., 6, A53
(2003).
[16] W. F. Howard and R. M. Spontnitz, J. Power Sources, 165, 887 (2007).
[17] M. S. Whittingham, MRS Bull., 33, 411 (2008)
[18] C. S. Sun, Z. Zhou, Z. G. Xu, D.G. Wang, J. P. Wei, X. K. Bian, and J. Yan, J.
Power Sources, 193, 841 (2009).
[19] Z. Xu, L. Xu, Q. Lai, and X. Ji, Mater. Res. Bull., 42, 883 (2007).
[20] G. Ceder and B. Kang, J. Power Sources, 194, 1024 (2009).
36
LIST OF FIGURE
Figure 1. XRD patterns of the prepared LiFePO4PAS powders. Sample A is
spherical powder prepared by using a spherical FePO42H2O precursor; sample B is
a disordered LiFePO4PAS composite.
Figure 2. Discharge curves of LiFePO4PAS (sample A) cathode material at
different rates. The material is used in a conventional lithium-ion battery electrode
design (84 wt% active materials, 8 wt% carbon black, and 8 wt% polyvinylidene
fluoride, 35 mgcm2 loading) against a lithium metal counter electrode. The
discharge rates are the same as the charge rates separately in cycle.
Figure 3. Specific capacities and cyclic performances of LiFePO 4PAS (sample A)
at different temperatures. The experiment cells were charged and discharged at the
same rate of 1 C.
Figure 4 . a) XRD pattern, b) SEM, d) schematic illustration of the prepared
LFP@C/CNT nanocomposite
.
Figure 5. XRD patterns of the LiFePO4/C samples annealed at various
temperatures after hydrothermal treatment: (a) unannealed, (b) 400, (c) 500, (d)
600, (e) 700, and (f) 800C.
Figure 6. Chargedischarge curves of LiFePO4/C samples between 0.1 C_48 _A
cm2_ and 10 C _4.86 mA cm(2): (a) unannealed sample and (b) sample annealed
at 700C.
Figure 7. Plots of the discharge capacities of the LiFePO 4C
samples as a function of the C rate. The samples were annealed
at various temperatures after hydrothermal treatment: (a)
unannealed, (b) 400, (c) 500, (d) 600, (e) 700, and (f) 800C.
37
Figure 8. _Color online_ The specific capacity as a function of the discharge rate
of various LiFePO4 cathode materials reported in the literature.-The sample no. in
Table for samples A, B, C, and D is , and ,respectively.
Figure 9. The influence of conductive carbon loading and powder
mixing procedure in cell preparation on the rate capacity of
LiFePO4 materials. The SL-17C and SL-5C samples are sample no.
11 in prepared using a slurry mixture with 17 and 5 wt %
conductive carbon, respectively. The dry-17C and dry-5C samples
are sample no. 11 in prepared using a dry mixing procedure
containing 17 and 5 wt % conductive carbon, respectively.
Figure 10 . The rate capacities of doped LiFePO 4 materials
without carbon-coating.
38