FABRICATION AND

ELECTROCHEMICAL
CHARECTARIZATION OF THE
CR2032 COIN CELLS USING THE
DEVELOPED PURE AND CARBON
COATED LiMPO4 (M= Mn, Co & Ni)
NANOPARTICLES

CHAPTER – VI
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 CHAPTER - VI
FABRICATION AND ELECTROCHEMICAL
CHARACTERIZATION OF THE CR2032 COIN CELLS USING THE
DEVELOPED PURE AND CARBON COATED LiMPO4 (M= Mn, Co
& Ni) NANOPARTICLES

6.1 General introduction

6.2 Fabrication of CR2032 coin cells

6.3 Electrochemical characterization

6.3.1 LiMnPO4/Li and carbon coated LiMnPO4/ Li cells

6.3.2 LiCoPO4/Li and carbon coated LiCoPO4/ Li cells

6.3.3 LiNiPO4/Li and carbon coated LiNiPO4/ Li cells

6.4 Conclusions

References

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6.1 General Introduction

The international electrotechemical commission (IEC) is developing standards for the

designation, marking, electrical testing, and safety testing of Li-ion cells and batteries. A

proposed designation and marking system for Li-ion cells utilize five figures in the case

of cylindrical cells and six figures in the case of prismatic cells. For example, the

common round cell that uses the C/LiCoO2 cell chemistry is designated ICR2032. The

first letter “I” designates an intercalation negative electrode. The second letter designates

the type of positive electrode employed, such as C for a cobalt type, N for Nickel type, M

for Manganese type or V for a Vanadium type, etc... The third letter will designate the

shape of the cell, R for round. The next two figures will designate the diameter in

millimeters and then the next three figures the height of the cell, in tenths of millimeters,

as they are 20 mm in diameter and 3.2 mm in height. Battery researchers will use to call

ICR2032 cell as CR2032.

In this chapter, The CR2032 coin cells were assembled with a metallic Li anode to

evaluate the pure and carbon coated LiMPO4 (M=Mn, Co & Ni) and evaluate their

electrochemical properties. There are two types of processes to evaluate the

electrochemical properties of material. The first is rate capability test, here the cell is

charged at slow rate with a constant voltage and then the fully charged cell is discharged

at various current rates to measure the capacity obtained from each discharge rate.

Another one is capacity retention test, in this method; the cell is charged at specific rate

and is discharged at the same rate and measure how long the cell sustains the initial

capacity without significant degradation of the capacity. The effect of carbon coating

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over LiMPO4 (M= Mn, Co & Ni) on the electrochemical properties of carbon coated

LiMPO4/ Li batteries have been investigated and presented in this chapter.

6.2 Fabrication of CR2032 coin cells

The cathode materials are coated on aluminum foil and metallic lithium is used as anode.

The aluminum foil acts as a current collector for conducting the current in and out of the

cell. Both of cathode and anode materials are delivered to the factory in the form of black

powder and to the untrained eye and these are almost indistinguishable from each other.

Since contamination between the anode and cathode materials will ruin the battery, great

care must be taken to prevent these materials from coming into contact with each other.

For this reason, the anodes and cathodes are usually processed in different rooms. The

flowchart for the general electrode processing is shown in figure 6.1.

The electrochemical performance of CR2032 coin-type cells made up of pure and carbon

coated LiMPO4 (M= Mn, Co & Ni) nanoparticles were evaluated. The cathodes were

prepared by the following process. First, the synthesized samples of pure and carbon

coated LiMPO4 (M= Mn, Co & Ni) were ground to slurry with carbon black (C65,

Timcal cooperation, USA) and PVDF (Polyvinylidene fluoride; Sigma Aldrich) binder in

N-Methyl-2-pyrrolidone (NMP) solvent. The formulation of electrode was 80 (active

material): 15(carbon black): 5(binder) in weight percentage. Cathodes were prepared by

coating of cathode materials slurries on aluminum foil and then dried at 80 oC for 5 h

under vacuum. Lithium metal (Sigma Aldrich) was used as an anode, and a micro porous

plastic film (Cellgard 2400, Cellgard Co., USA) was used as separator and the electrolyte

solution used comprised of 1.5 M LiPF6 in a 1:1:1 mixture of ethylene carbonate (EC),

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eythyl methyl carbonate (EMC), and dimethyl carbonate (DMC) in weight percent

procured from Sigma Aldrich. We have used DMC: DEC: EMC ratio as 1:1:1 for

electrolytes of LiCoPO4 and LiNiPO4 cathode materials cells to avoid the oxidation

polymerization of EC in to PEC. CR2032 coin cells were assembled for all

electrochemical testing, purchased from Hohsen Crop., USA. Figure 6.2 shows the

schematic diagram of CR2032 coin cell construction. Figure 6.3 shows the photographs

of fabricated CR 2032 coin cells using the prepared LiMnPO4 nanorods.

Figure 6.1: Flowchart for the general electrode processing for the lithium ion batteries

185
 Coin cell

Figure 6.2: Schematic diagram of CR2032 coin cell construction

Figure 6.3: Photographs of fabricated CR 2032 coin cells using the prepared LiMnPO4

nanorods

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6.3 Electrochemical performance

6.3.1 LiMnPO4/Li and carbon coated LiMnPO4/ Li cells

The voltage profiles obtained using the measured voltage between 2.9 to 4.5 V at 1C rate

for the 1st and 30th cycles of cells made up of the pure and carbon coated LiMnPO4

nanorods are shown in Figure 6.4. The discharge curves of LiMnPO4/Li cells showed

continuous sloping because of the electronic structure and nanosized properties of the

material. Kim et. al, suggested that nano-size particles resulted in continuous sloping in

discharge curves of the Li/LiMnPO4 cell, because electronic structure and property of

nano-size particle lies in between bulk crystalline material and individual molecular state

and Jahn–Teller distortions leading to capacity fading [1]. However, the carbon coated

LiMnPO4 nanorods showed better discharge capacity at 1C than the pure ones. The

discharge capacity for the 1st cycle of pure LiMnPO4 nanorods was almost same as the

30th cycle of the carbon coated LiMnPO4 nanorods, indicating an improvement in the rate

capability by coating of carbon over LiMnPO4. From figure 6.4, the LiMnPO4/Li cells are

delivered discharge capacity of 98 mAh g-1 during the 1st cycle and 64 mAh g-1 during

30th cycle at 1 C rate. Carbon coated LiMnPO4/Li cells are delivered 122 mAh g-1 during

the 1st cycle and 30th cycle it was 97 mAh g-1 at 1C rate. Figure 6.5 shows the capacity

retention of the pure and carbon coated LiMnPO4 nanorods at 1C rate. From figure 6.5,

the cells made up of pure and carbon coated materials showed good capacity retention

with cycling. The carbon coated LiMnPO4 achieved 122 mAh g-1 at 1C, which is higher

than the capacity of the pure LiMnPO4 (about 98 mAh g-1). The improved capacity was

attributed to a one dimensional electron transport pathway in LiMnPO4 nanorods [2,3].

The significance of our pure LiMnPO4 nanorods is its increased capacity at 1C compared

187
to recently reported nanocomposite LiMnPO4/C, [4] off-stoichiometric LiMnPO4,[5]

carbon coated LiMnPO4 particles,[6] and also, multiwalled carbon nanotube coated

LiMnPO4 thumb shaped nanorods [7].

Figure 6.4: Discharge profile of the lithium batteries fabricated using pure and carbon

coated LiMnPO4 nanorods

188
Figure 6.5: Capacity retain plot of the lithium batteries fabricated using pure and carbon

coated LiMnPO4 nanorods

189
6.3.2 LiCoPO4/Li and carbon coated LiCoPO4/ Li cells

Figure 6.6 shows the charge-discharge curves of the cells made up of pure and carbon

coated LiCoPO4 samples at 0.1C rate. These cells were characterized between the

voltages of 4.1- 5 V up to 20 cycles. Both pure and carbon coated LiCoPO4 samples

exhibited flat voltage plateau at 4.8 V, which is the characteristics of the lithium

intercalation at 4.8 V (Vs. Li) of LiCoPO4/Li cell. Similarly, cells made up of carbon

coated LiCoPO4 sample delivered high capacity than pure LiCoPO4/Li cell. From figure

6.6a, the pure LiCoPO4/Li cells show the continuous discharge curve, which may be due

to the capacity fading. The discharge capacity of LiCoPO4/Li cells at 0.1C rate during the

1st cycle was observed as 144 mAh g-1, while at the 20th cycle it was 133 mAh g-1. From

figure 6.6b, The LiCoPO4/Li cell shows the flat lithium intercalation voltage curve at 4.8

V (Vs. Li). The discharge capacity of lithium-ion coin cells at 0.1C rate during the 1st

cycle was observed as 180 mAh g-1, while at the 20th cycle it was 162 mAh g-1. The

discharge capacity loss in the Li/carbon coated LiCoPO4 cell was around 18% between

the 1st and the 20th cycles.

Figure 6.7 shows the cycling performance of cells made up of pure and carbon coated

LiCoPO4 samples at 0.1C. The capacities of LiCoPO4/Li, carbon coated LiCoPO4/Li cells

were found to be 144 mAh g-1 and 180 mAh g-1 respectively. The enhancement in

electrochemical performance of carbon coated LiCoPO4/Li cells compared to pure

LiCoPO4/Li may be due to the increased electrical conductivity through carbon coating.

The capacity retentions of both pure and carbon coated LiCoPO4 were almost 80% even

after 20 cycles, which indicate that the pure and carbon coated LiCoPO4 nanoparticle

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cathode materials prepared by PVP assisted polyol process had the better cycling

performance [8].

Figure 6.6: Discharge profile of the lithium batteries fabricated using a) pure and b)

carbon coated LiCoPO4 nanoparticles

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Figure 6.7: Capacity retain plot of the lithium batteries fabricated using pure and carbon

coated LiCoPO4 nanoparticles

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6.3.3 LiNiPO4, carbon coated LiNiPO4/ Li cells

The discharge curves of the cells made up of pure and carbon coated LiNiPO4 samples,

characterized between 5.3- 4.3 V at 0.1 C shown in figure 6.8. All the cells exhibited

voltage plateau at 5.1 V as a characteristic of the oxidation/reduction reaction of LiNiPO4

with respect to lithium anode. From figure 6.8a, the discharge capacity of pure

LiNiPO4/Li cell is 74 mAh g-1 for 1st cycle and 56 mAh g-1 for 20th cycles at 0.1C rate.

From figure 6.8b, the carbon coated LiNiPO4/Li cell is showing enhanced discharge

capacities like 98 mAh g-1 for 1st cycle and 66 mAh g-1 for 20th cycles at 0.1C rate. Figure

6.9 shows the cycling performance of the cells made up of pure and carbon coated

LiNiPO4 samples at 0.1C. The capacities of pure and carbon coated LiNiPO4 samples

were found to be 74 mAh g-1 and 98 mAh g-1 respectively. The improvement in

discharge capacity for carbon coated sample might be due to the enhancement in

electrical conductivity of material. The capacity retentions of both pure and carbon

coated LiNiPO4 were almost 80% even after 20 cycles, which indicated that LiNiPO4

prepared by PVP assisted polyol process also has the good cycling performance and it

can be used as a high voltage cathode in lithium batteries [9].

It is reported that the electrochemical performance of cathodes could be significantly

improved by adding amount of conductive materials [10-15]. In this work, we have

successfully synthesized pure and carbon coated Lithium transition metal phosphate

nanoparticles with high electrochemical properties compared to earlier reported results.

The discharge capacities of all prepared compounds along with previous work are listed

in table 6.1.

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 a

Figure 6 8: Discharge profile of lithium batteries fabricated using a) pure and b) carbon

coated LiNiPO4 nanoparticles

194
 Figure 6.9: Capacity retain plot of lithium batteries fabricated using pure and carbon

coated LiNiPO4 nanoparticles

Table 6.1: Discharge capacities of all pure and carbon coated LiMPO4 (M= Mn, Co &
Ni) nanoparticles along with reported work
Compound Present obtained Reported capacity References
capacity (mAh g-1) (mAh g-1)
LiMnPO4 98 99 6, 7
LiMnPO4/C 122 108 6,
LiCoPO4 144 58 7
LiCoPO4/C 178 89 7
LiNiPO4 72 54 9
LiNiPO4/C 97 - -

195
6.4 Conclusion

In this chapter, CR2032 coin cells fabricated by using synthesized pure and carbon coated

LiMPO4 (M= Mn, Co & Ni) cathode materials and their electrochemical properties were

discussed. The discharge capacity of the carbon coated LiMPO4 (M= Mn, Co & Ni)

nanomaterial increased 20% compared to the pure ones. Furthermore, the pure and

carbon coated LiMPO4 (M= Mn, Co & Ni) material shows the good electrochemical

performance, especially rate capability. This improvement is partly ascribed to small

particle size, which acts as an inhibitor for grain growth because small particles improve

bulk lithium transport. Carbon coating upon the LiMPO4 (M= Mn, Co & Ni) materials

will increase the electronic conductivity of the cathodes. Therefore, these electrode

materials show the extremely high discharge capacity and good cycleability. Hence,

newly developed carbon coated LiMnPO4 nanorods, using modified polyol and resin

coating processes will improve the lithium battery performance.

196
Reference

[1] T. R. Kim, D. H. Kim, H. W. Ryu, J. H. Moon, J. H. Lee, S. Boo, and J. Kim, J. Phys.

Chem. Solids, 68 (2007)1203-1206.

[2] D. K. Kim, P. Muralidharan, H. W. Lee, R. Ruffo, Y. Yang, C. K. Chan, H. Peng,R.

A. Huggins, and Y. Cui, Nano Lett., 8 (2008) 3948-3952.

[3] C. K. Chan, X. F. Zhang, and Y. Cui, Nano Lett., 8 (2008) 307-309.

[4] Z. Bakenov and I. Taniguchi, Electrochem. Commun., 12 (2010) 75-78.

[5] B. Kang and G. Ceder, J. Electrochem. Soc., 157 (2010) A808-A811.

[6] S. K. Martha, B. Markovsky, J. Grinblat, Y. Gofer, O. Haik, E. Zinigrad, D. Aurbach,

T. Drezen, D. Wang and G. Deghenghi, J. Electrochem. Soc., 156 (2009) A541-

A552.

[7] A. V. Murugan, T. Muraliganth, and A. Manthiram, J. Inorg. Chem., 48(2009) 946-

952.

[8] P. Ramesh Kumar, M. Venkateswarlu, Manjusri Misra, Amar K. Mohanty, N.

Satyanayana, J. Nanosci. Nanotech., 11(2011) 3314–3322.

[9] M. Minakshia, P.Singha, D. Appadoob and D. E. Martin, Electrochimica Acta 56

(2011) 4356–4360

[10] C. Li, H. P. Zhang, L. J. Fu, H. Liu, Y. P. Wu, E. Rahmb, R. Holze, H. Q. Wu,

Electrochimica Acta, 51 (2006) 3872–3883.

[11] G. X. Wang, L. Yang, S. L. Bewlay, Y. Chen, H. K. Liu, J. H. Ahn, J. Power

Sources, 146 (2005) 521–524.

[12] J. Cho, J. Power Sources, 126 (2004) 186–189.

197
[13] V. Aravindan, K. Karthikeyan, K. S. Kang, W. S. Yoon, W. S. Kim, Y. S. Lee, J.

Mater. Chem., 21 (2011) 2470-2475.

[14] F. Pan, X. Chen, H. Li, X. Xin, Q. Chang, K. Jiang, W. L. Wang, Electrochem.

Comm., 13 (2011) 726–729.

[15] B. L. Cushing, John B. Goodenough, Solid State Sci., 4 (2002) 1487–1493.

198