“Fabrication of Cathode-Anode and Carbon Nanotube

composites’ in Lithium Batteries”

Literature Review
By Louis Murray

Abstract

In today’s society, nearly all aspects of a person’s everyday life incorporate some

form of electronics. Mainly, convenience, safety, and comfort-ability are driving forces of

electronics popularity. In order to power electronic devises, much research has been

incorporated to improve battery performance. Recently, the cathodes contained within

electrodes have been given attention. There exist few improvements to the cathodes. Its

chemical composition of a lithium oxide and a metal was improved by replacing the

oxides with phosphates. This improvement does make the cathode more stable under

harsh conditions but it introduces new problems. The incorporation of carbon nanotubes

promises to improve storage capacity and other characteristics. This review will analyze

recent research in lithium battery and carbon nanotube integration and explore current

integration and synthesis methods such as the Two-Step, Atomic Layer Deposition, and

Chemical Vapor Deposition methods.

Introduction

Technology exists in many forms of our society. We are constantly bombarded with

many tasks that are only increasing. Many of them attempt to increase productivity but

are dictated by means of electronic devices. Since our work load is increasing, so is the

technological demand. In order to supply this demand, electric devices must keep up as

well in terms of performance.

Batteries that power many devices are rechargeable with a limited life span. It is

often a complaint that the storage capacity degrades over a short period of time. Much

research has been conducted to improve the electrodes of batteries and particularly

anodes. However, little attention and research has been devoted to cathodes. Even though

anodes and cathodes are generally improving, the imbalance between the anode and

cathode make-up is counterproductive which marginally results in any beneficial

performance enhancements.

Researchers are improving electrodes with the latest advances in nanotechnology.

The anodes have experienced improvements by methods in this field such as the use of

graphene and silicons. Cathodes on the other hand, have been infused with carbon

nanotubes only after its chemical rendition of substituting oxides with phosphates. For

example, the chemical makeups of common cathodes are LiCo O2 and Li Mn2 O 4

.With the proposed substitution of oxygen with phosphates, the chemical makeup is

similar to LiFe PO 4 .The oxides in the former chemical arrangement have displayed a
tendency to potentially release hazardous oxygen and become unstable upon operation,

phosphates sought to address this issue. They were a more stable substitute but

intrinsically presented their own problems.

Integration of carbon nanotubes allows for increased performance by reducing

electrode polarization and charge transfer resistance, increasing electronic conductivity,

and stability with higher power output. Fabrication of them along with the phosphates

merges naturally during production. Various growth methods of carbon nanotubes are

employed, such as chemical vapor deposition and atomic layer deposition. This review

will compare synthesized carbon nanotube methods outlined within original research

articles.

Literature Review

Two-Step Method

Creating high rate lithium batteries is a main focus to supply an ever increasing

demand. To help improve current phosphate cathodes, carbon nanotubes and phosphates

are synthesized by a solution-based two-step method that is detailed in the article,

“Carbon nanotube-embedding as a cathode material for high rate lithium

LiFePO 4

batteries.”
 The first step consisted of a coaxial nanocomposite of , which
FePO 4∗H 2 O/CNT

is synthesized by a precipitation method [1]. Four tenths of a gram of the carbon

nanotube powder is immersed in a urea solution and sonicated for thirty minutes. Next,

citric acid, , and is stirred into the mixture, the mixture is

FeSO 4∗7 H 2 O NH 4 H 2 PO 4

then heated for three hours to 60 ͦ and washed with distilled water. The mix is held at
C

that temperature during drying for a time of twenty four hours (Fig. 1a).

Before the second step, the compound is heated to 300 for six hours. This results
C

in a decrease in hydrated water. In the second step, the is then

FePO 4∗H 2 O/CNT

lithiated in acetonitrile for twenty-four hours while being held in an argon filled box.

After which, the compound is rinsed with acetone and dried for twelve hours at a

temperature of 60 ͦ . Finally, in an argon and hydrogen atmosphere, the dried powder

C

is heat treated to 700 ͦ for three hours. This method results in carbon nanotubes that
C

are embedded with (Fig. 1b).

LiFePO 4
 Fig. 1a. a) SEM image and b) TEM image of , product after (Step 1) [1].
FePO 4∗H 2 O/CNT

Fig. 1b. a) SEM image CNT- embedding and b) SEM image of embedded
LiFePO 4 LiFePO 4

nanoparticles after CNT’s burnt away (Step 2) [1].

After embedding lithium phosphates onto carbon nanotubes and using the material

for cathodes, performance rates increased. Using such a method, the expected discharge

capacity is 165 mA at .1 , 120 mA at 30 , and 78 mA at 120

hg
−1 C hg
−1 C hg
−1

.
C
 In Summary, this method shows a performance increase but at the cost of much time.

It is a fairly simple method to employ that mainly uses heat treatments and rinsing in

various solutions. To improve the disadvantage of time for the wanted result, proposing

heat treating at higher temperatures and at extremely low pressures may result in quicker

results.

Atomic Layer Deposition Method

As much research continues and interest continues to influence the field of

rechargeable batteries, advancements of synthesis techniques of carbon nanotubes and

cathodes are increasing. In the article, “Atomic layer deposition of amorphous iron

phosphates on carbon nanotubes as cathode materials for lithium-ion batteries,” carbon

nanotubes performance was increased by the infusion of iron phosphate thin films.

Iron phosphate is used as an electrode material for cathodes. Since the material has

low electric conductivity, a reduction of its particle size by using it as a surface coating

and synthesizing it with carbon nanotubes has shown to overcome this flaw. Iron

phosphate, , allows for enhanced electrochemical activity and can reversibly

FePO 4

release and store lithium ions. Developing by atomic layer deposition allows for
FePO 4

more freedom in the control and development of thin film thicknesses along with a
greater capability for uniform deposits [2].

Synthesizing carbon nanotubes and iron phosphates for improved performance,

begins with the use of carbon nanotubes doped with nitrogen that were developed by

chemical vapor deposition. They will in turn be used as substrates for

FePO 4

deposition. Nitrogen is utilized as a carrying and purging gas during the atomic layer

deposition process. By introducing , , , and TMPO in to the reaction

FeCp 2 O3 H2O

chamber, the deposition of was achieved. The carbon nanotubes were with
FePO 4

thin films homogeneously at various temperatures while undergoing 500 ALD

FePO 4

cycles. The temperature ranges and corresponding deposition change is shown in Fig. 2.
 Fig. 2 Images of coated on CNTs with 500 ALD cycles at a) 200, b) 250, c) 300, and d) 350
FePO 4 C
[2].

The results of creating thin films on the carbon nanotubes resulted in a cathode

material that was electrochemically active with a discharge rate of 177 mA after
−1
hg

the first cycle and could achieve a discharge rate of 141 mA after 100 cycles [2].
−1
hg

In Summary, integrating thin films and carbon nanotubes and embedding cathodes
with this material aids in the formation of interconnected networks. Having such

connections is an advantage for cathode in regards to stability during high use under

harsh conditions such as higher temperatures. Particle movement and transfer is increased

due to the network. Although there are critical limits to how much matter that can be

added to the cathode before negative effects take place, increasing the proportions of the

cathode composite would possibly increase the life of the cathode and furthermore the

stability.

Chemical Vapor Deposition, Ball-Milling, and Spray Pyrolysis-Combination method

In the article, “Fabrication and characterization of carbon-coated

Li 2 FeSiO 4

nanoparticles reinforced by carbon nanotubes as high performance cathode materials for

lithium-ion batteries,” researches possible solutions to increase electronic conductivity

and facilitate lithium-ion transfer of phosphate cathodes. Among many previous

techniques, such as decreasing the size of the cathode material, electronic conductive

material coatings, and isovalent ion host framework doping have all attempted to address

the phosphates inherent problems [3].

A plausible solution was that of introducing a carbon layer. Not only would the layer

increase electronic conductivity, but it leads to the formation of interconnected networks

of the nanoparticles and carbon nanotubes. In order to achieve a synthesis

Li 2 FeSiO 4
with the carbon nanotubes, researchers used a novel technique that is a combination of

chemical vapor deposition, a spray pyrolysis method, and sintering.

The technique of combing the carbon nanotubes with , used CNTs,

Li 2 FeSiO 4

having a diameter of ten nanometers, that were refluxed or in nitric acid for five hours

then rinsed with distilled water. A homogeneous solution was then formed with the

nanotubes and fifty milliliters of ethanol with a mass ratio of 1:20. The solution was then

mixed with stoichiometric amounts of , and tetraethyl

Li 2 FeSiO 4 FeC 2 O4∗2 H 2 O

orthosilicate. This mixture was ball-milled for ten hours that resulted in a slurry. This

slurry was pray dried at 180 ͦ while being coated with a carbon layer using a
C

chemical vapor deposition process.

In the deposition process, the dried precursor was heated from room temperature to

400 ͦ and held at that temperature for five hours in a flowing argon and ethanol vapor
C

gas mixture. The ethanol vapor was absorbed on the surface of the precursor and

carbonized to form a coating of a carbon layer. The mixture result was sintered after

mixed with a mortar for ten hours at 600 ͦ to improve the carbon layer quality and to
C

synthesis crystallized . This process ensured a well carbon nanotube and

Li 2 FeSiO 4
 mix that was further interconnected by the development of a carbon layer.
Li 2 FeSiO 4

Fig. 3. Illustration of /CNTs/C synthesis. [3]

Li 2 FeSiO 4

The reported results of the technique show improved performance such as high

specific capacity and rates. It showed a discharge capacity of 189.2 mA at .1

−1
hg C

and 71.6 mA at 5 . It was also shown that nanoparticles allowed

hg
−1 C Li 2 FeSiO 4

for better lithium diffusion due to short transfer pathways.

In Summary, combining multiple techniques to create the cathode composites, as this

particular article suggests, does produce useful products. The results show high discharge

rates for lower temperatures and a great decrease in performance with rising

temperatures. These multi-method produced cathodes are practical in two situations. The

first would be to implement this technology in low demand environments, but such uses

defeats the driving motivations for creating cathodes. Secondly, implementing this
technology in cold environments would beneficially justify the technique. The authors of

the article neglected to comment on the composites estimated life cycles. Not knowing an

estimated life higher performance at low temperatures may possibly be short lived.

Conclusion

Various techniques have been developed in order to increase the properties of

materials that comprise cathodes. The few techniques presented in this paper presented

three methods for the cathode material improvement. The first two step solution based

method intended to embed lithium phosphate into carbon nanotubes. According Jegal’s

and Kim’s results, the method achieved it’s intended results of increased rate but only an

increase of about 165 mA at .1 , 120 mA at 30 , and 78 mA

hg
−1 C hg
−1 C hg
−1

at 120 . These results are somewhat low when compared to a few other methods.
C

Combing lithium phosphates and carbon nanotubes with a thin film of iron phosphate

by using Atomic Layer Deposition, allows for a better interconnected network. These

networks help traveling particles maneuver with greater freedom. This method of thin

layers in addition to carbon nanotubes would intrinsically be a better method with

capacity rates of 177 mA after the first cycle and 141 mA after 100 cycles.
−1 −1
hg hg
 Further substituting phosphates for silicon’s such as in anodes [4], resulted in even

higher experimental rates but only for low temperature use. The third method of

combining fabrication techniques such as ball-milling, chemical vapor deposition,

sintering, and spray drying produced a carbon nanotube lithium silicate mixture with a

carbon layer. The experimental rates of the mixture was 189.2 mA at .1 and
hg
−1 C

71.6 mA at 5 . It can be seen that although the third method produced higher
hg
−1 C

rates, the performance dropped considerably at slightly higher temperatures.

It would appear that phosphates in combination with carbon nanotubes produce

optimum rates for prolonged cycles. Fabrication of nanotubes is fairly simple with low

production time. But when operating temperatures are taken into account, using cathodes

made of carbon nanotubes and lithium phosphates that are produced by the solution based

two-step process, experimentally proves to be an optimum cathode composite fabrication

method.

References

[1] Jong-Pil Jegal, Kwang-Bum Kim, 2013,“Carbon nanotube-embedding LiFePO4 as

a cathode material for high rate lithium ion batteries.” Journal of Power Sources. 243,

pp. 859-864.

[2] Jian Liu, Biwei Xiao, Mohammad N. Banis, Ruying Li, Tsun-Kong Sham, Xueliang
 Sun, 2014, “Atomic layer deposition of amorphous iron phosphates on carbon

nanotubes as cathode materials for lithium-ion batteries.”Electrochimica Acta. 162,

pp. 275-281.

[3] Zhang, Zheng, Xingquan Liu, Liping Wang, Yue Wu, Hongyuan Zhao, Bing Chen,

and Weiqiang Xiong., 2015, "Fabrication and Characterization of Carbon-coated

Li2FeSiO4 Nanoparticles Reinforced by Carbon Nanotubes as High Performance

Cathode Materials for Lithium-ion Batteries." Electrochimica Acta.168, pp. 8-15.

[4] Jiangfeng Ni, Ling Zhang, Shidong Fu, S.V. Savilov, S.M. Aldoshin, Li Lu, 2015, “A

review on integrating nano-carbons into polyanion phosphates and silicates for

rechargeable lithium batteries.” Carbon. 92, pp. 15-25.

[5] Huang, X., Li, X., Wang, H., Pan, Z., Qu, M., & Yu, Z. , 2010,“Synthesis and

electrochemical performance of Li 2FeSiO 4/carbon/carbon nano-tubes for lithium

ion battery.”Electrochimica Acta. 168, pp. 8-15