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Solar Powered New Lithium – Ion Battery Incorporating High Performing

Electrode Materials Solar Powered New Lithium – Ion Battery Incorporating
High Performing Electrode Materials

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 RSC Advances

Solar Powered New Lithium – Ion Battery Incorporating

High Performing Electrode Materials

Journal: RSC Advances

Manuscript ID: RA-ART-08-2012-021999.R1

Article Type: Paper

Date Submitted by the Author: 18-Sep-2012

Complete List of Authors: jcs, Nithya; Central Electrochemical Research Institute, Electrochemical
Power Systems division
Sukumaran, Gopukumar; CECRI,
Page 1 of 7 RSC Advances
Journal Name Dynamic Article Links ►

Cite this: DOI: 10.1039/c0xx00000x

[Link]/xxxxxx ARTICLE TYPE
Solar Powered New Lithium – Ion Battery Incorporating High
Performing Electrode Materials
S. Gopukumara*, C. Nithyaa, P. H. Maheshwarib, R. Ravikumara, R. Thirunakarana,
A. Sivashanmugama, S. K. Dhawanb, R. B. Mathurb
5 Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX
DOI: 10.1039/b000000x

The development of portable electronic communities requires above mentioned materials; however, it delivers half of the
the high performing and high power lithium rechargeable 50 theoretical capacity, and also expensive. Various methods to
batteries. Herein, we explore the new lithium ion battery overcome these shortcomings such as coating with inactive metal
10 incorporated with new carbon based anode and cobalt based oxides15 and doping with metal cations16, 17 improve the capacity
cathode which delivers the energy output of 280 Wh/kg and in the limited voltage regions (~4.3V), but this strategy fails at the
the cycling efficiency is 97% over the investigated 500 cycles deep discharge states as reported by many researchers. Deepa et
(1C rate) of lithium ion cell. 55 al18 and M. Zou et al19 reported that the conductivity of LiCoO2
was enhanced by Cu and operates well at 4.5V and delivers
The commercialization of lithium ion cell was successful in the highest capacity retention. Since increasing the potential >4.5V,
15 early 1990’s by Sony Corporation. Almost 90% of the requires the necessity of suitable dopant to increase the structural
commercial lithium ion batteries consist of lithium cobalt oxide stability as well as cycling stability at high voltages. Mg is the
cathode1 and graphite anode, which is being separated by a 60 most promising dopant to stabilize the layered structure of
lithium ion–conducting electrolyte for example 1M LiPF6 in 1:1 LiCoO2 as reported by many authors20–23. Further the presently
(Ethylene carbonate: Diethylene carbonate). Only 5–10% of the used lithium ion cells deliver the energy output of 100–250
20 lithium ion cells made by using LiFePO4 or LiNi1/3Co1/3Mn1/3O2 Wh/kg and the cycling efficiency only 80–90%24. To overcome
based cathodes and carbon based anodes. The commercial the above problems in electrode materials and lithium ion cells,
success of lithium ion batteries still limits in performance at high 65 we have developed a new lithium ion cell comprises graphite
voltages and high rates because the non–availability of suitable paper anode and Cu, Mg doped LiCoO2 cathode.
electrode materials for this intention. Tin based amorphous oxide Fig. 1 shows the XRD patterns of Carbon paper and
25 anode material exhibits the high capacity for storing of Li+ ions as LiMg0.025Cu0.175Co0.8O2 materials. XRD patterns of the carbon
reported by Y. Yu et al2. Recently TiO23 and carbon nano tube paper indicate that the presence of graphitic nature and the
based anode4 materials exhibit high capacities are reported by 70 cathode material clearly shows the layered structure with R3–m
various research groups. However, large volume change during space group. The clear splitting of the (006) (102) (Fig. 1c) and
cycling smash up the anode structure results poor capacity (108) (110) (Fig. 1d) peak doublets indicates that an ordered
30 retention over prolonged cycling. In this view, researchers still distribution of lithium and transition metal ions are exist in the
focus the graphite based anode materials like graphene5, 6 which structure25. Unit cell parameters of the synthesized materials are
exhibits excellent capacity and cycleability. 75 calculated by using X’Pert’ high score plus software. Lattice
Beside this, the cathode material also limited the storage parameters ‘a’ (2.816), ‘c’ (14.057) and unit cell volume (96.087)
capacity of rechargeable lithium batteries. K. Kang et al7 reported increases after doping with Cu and Mg in LiCoO2. The c/a
35 the safe, inexpensive LiNi0.5Mn0.5O2 cathode material delivers the (4.991) ratio > 4.9, I003/I104>1 and ‘R’ value (0.34) suggests that
discharge capacity of 125 mAhg–1 at 1C rate. Recently Recham et the formation of well developed layered structure. Fig. 2 depicts
al8 reported the LiFeSO4F cathode materials exhibit good 80 the SEM images of carbon paper and LiMg0.025Cu0.175Co0.8O2
capacity retention however, voltage (3.6 Vs Li) is lower than materials. The anode materials exhibits the morphology of
LiCoO2. Iron and manganese based phosphate materials such as micro–fibres textured of graphitic nature and the cathode
40 LiFePO4 9–12 and LiCoxMn1-xPO413 have much attraction towards materials appears as the bunch of flakes. This kind of
lithium ion batteries; however these materials encountered the morphology of anode and cathode would easily extract and insert
problem like conductivity and lower voltage which is overcome 85 the lithium ions during charge and discharge. The size of the
by carbon coating and nano–sized particles. LiNi0.8Mn0.1Co0.1O2 flakes is around 0.5µm.
surrounded by concentration gradient outer layer exhibits high Figure 3a shows the first charge/discharge curves and cycling
45 capacity but after 50 cycles capacity fades very rapidly as performance of carbon paper (Vs Li/Li+) at 0.2 and 1C rates
reported by Y.K. Sun et al14. Due to the above shortcomings, cycled between 0.01–1.5V. The carbon paper delivers the
researchers still focus the LiCoO2 cathode materials because it 90 discharge capacity of 225 and 100 mAhg–1 at 0.2 and 1C rate
has high theoretical capacity and high voltages compared to the respectively. A very low irreversible capacity (< 5 mAh/g) is

This journal is © The Royal Society of Chemistry [year] [journal], [year], [vol], 00–00 | 1
 RSC Advances Page 2 of 7

obtained in both the cases, which are due to the formation of very also supports for repeated lithium insertion and deinsertion. It
thin SEI layer, which consumes small amount of Li+ ions. This 60 delivers the energy output of 280 Wh/kg (average specific
charge/discharge process is coupled with intercalation and capacity per kilo gram x average cell voltage = 75.5 Ah/kg x 3.7
deintercalation of lithium in to the layers of carbon. Figure 3b V= 280 Wh/kg), the charge/discharge efficiency is 97% at both
5 presents the cycling performance of carbon paper; at the end of C–rates. Fig. 4c shows glowing of LED lights (16 LEDs) using
100th cycle it retains 95 and 96% of the initial capacity at 0.2 and this assembled lithium ion cell powered by solar power. The
1C rates respectively. This excellent cycling stability is due to the 65 assembled lithium ion cell can be charged either by means of
formation of thin SEI layer on the initial cycle, which assists the solar or normal charging. This excellent performance is superior
movement of Li+ ions in the subsequent cycles. This is the than the presently used lithium ion cells[24] in which the energy
10 excellent cycling stability at high rates as compared to the output of 100–250 Wh/kg and the charge/discharge efficiency is
previous works 3–6. 80–90%. The capacity fade of this lithium ion cell after 500
The charge/discharge curves and cycling performance of the 70 cycles is only 4% at 1C rate which is superior as compared to the
LiMg0.025Cu0.175Co0.8O2 material (Vs Li/Li+) at different C–rates previously reported work31 incorporating Sn–C anode and
cycled between the potential limits 2.9–4.6V as shown in Fig. 3c. Li[Ni0.45Co0.1Mn1.45]O4 as cathode exhibits the capacity fade of
15 This material delivers the initial discharge capacities are 230, 14%.
180, 147 and 128 mAhg–1 at 0.2C, 0.5C, 1C and 2C rates To further confirm the highest discharge capacity of the
respectively. In this material, 0.826 Li+ and 0.798 Li+ ions are 75 LiMg0.025Cu0.175Co0.8O2 cathode materials in the lithium ion
extracted and reinserted in the first cycle, after prolonged cycling battery we carried out the conductivity measurements and cyclic
the extraction and insertion amount of Li+ ions are decreases very voltammetry studies. The electronic conductivity of the cathode
20 slightly. The highest capacity of this material is ascribed to the material is very important for a better charge transfer process
increase of structural stability and conductivity of Mg2+ ions (Fig. during lithium intercalation–deintercalation process in lithium ion
5), further the dopant Cu2+ ions also completely participates in the 80 cell. The electrical conductivity of the synthesized materials was
redox reactions (Fig. 6). The larger ionic radii of Cu2+ and Mg2+ determined by using four–probe DC method from a set of
ions than Co3+ enlarges the lattice volume, which is favorable for voltage–current values using a power source controlled by a PC.
25 intercalation and deintercalation of Li+ ions. In general, when the The values were obtained by taking σ = 1/ρ, ρ = RA/L where L is
cell cycled at high voltages, it could extract and insert the large distance between voltage contacts and A is the sample cross
amount of Li+ ions and also the redox event takes place 85 section. Fig. 5 shows the electronic conductivities of the LiCoO2,
completely. Figure 3d depicts the cycling performance of this LiCu0.2Co0.8O2 and LiMg0.025Cu0.175O2 materials at different
material at different C–rates; the capacity retention obtained at temperatures. While the temperature increases from 25 to 150°C,
30 0.2C, 0.5C, 1C and 2C rates are 95.2, 92.3, 90.1, and 89.32 the conductivity of material increases and hence the conductivity
respectively over the investigated 100 cycles. It is interesting to of both Cu and Mg doped material have two orders of magnitude
note that the discharge capacities are higher and the capacity fade 90 higher than the pristine LiCoO2 material. Fig. 6 shows the cyclic
is very minimal at high voltage and high discharge rates as voltammogram of LiMg0.025Cu0.175O2 material carried out
compared to the previous reports8, 9, 12–14, 18–23, 26─31. This excellent between the potential limits 2.9 and 4.6V. Two pairs of redox
35 capacity retention of Cu and Mg doped material is due to the peaks observed for LiMg0.025Cu0.175O2 material which is the
structural stability of the layered LiMg0.025Cu0.175Co0.8O2 characteristic behaviour of Li+ ion intercalation and
materials enhanced by Mg2+ addition. Since the Mg2+ ions are 95 deintercalation. Redox peaks observed for Cu2+/Cu+ ions at 3.6
electrochemically inactive, however, Mg2+ ions act as pillars to and 3.59V which is in well agreement with previous works32. The
prevent the collapse of the CoO2 interslab and also not hinder the above obtained results confirm that the highest capacity of
40 lithium ion diffusion because it has the similar ionic radii of Li+ LiMg0.025Cu0.175O2 material is due to the highest conductivity of
ions. Further the Mg2+ suppresses the Co4+ ion dissolution into Mg2+ ions (also enhance the structural stability by pillaring effect)
the electrolyte due to the stronger Mg–O bond than Co–O bond. 100 and Cu2+ ions which completely participate in the redox
This kind of pillar effect affords more space for Li+ions during reactions.
cycling and offers excellent cycling stability.
45 To investigate the performance of the above–mentioned two
electrode materials in lithium ion cell we assembled the coin cell
using carbon paper as the anode, LiMg0.025Cu0.175Co0.8O2 as the 105

cathode and 1M LiPF6 in 1:1 EC/DEC as the electrolyte. Figure

4a presents the charge/discharge behaviour of the lithium ion cell
50 at 1C and 2C rates. The discharge capacities are 38 (specific
discharge capacity 77 mAhg–1) and 27 mAh (specific discharge
capacity 55 mAhg–1) at 1C and 2C rates when cycled between 110

2.9–4.2V. Fig. 4b shows the cycling performance of the lithium

ion cell over the 500 cycles and the inset presents the cycling
55 behaviour at 1C rate. The capacity retention over the investigated
500 cycles is 96 and 97.5% at 1C and 2C rates [Link]
highest capacity retention is due to the pillaring effect of dopant 115

ions in the cathode materials and the structure of the carbon paper

2 | Journal Name, [year], [vol], 00–00 This journal is © The Royal Society of Chemistry [year]
Page 3 of 7 RSC Advances

40

45

50

55

5
60
Fig. 1 a) XRD patterns of carbon paper and b) LiMg0.025Cu0.175Co0.8O2
materials. Magnified patterns of c) (006) (102) and d) (108) (110) peak
doublets.

10
a

15
65

20
b

70
25

30
Fig. 3 a) Initial charge/discharge of curves carbon paper at 1C and 0.2C
Fig. 2 SEM images of a) carbon paper and b) LiMg0.025Cu0.175Co0.8O2 75 rate cycled between 0.01–1.5V b) Cycling performance of carbon paper c)
materials. Initial charge/discharge curves of LiMg0.025Cu0.175Co0.8O2 at different rates
cycled between 2.9–4.6V d) Cycling performances of
LiMg0.025Cu0.175Co0.8O2 materials at different C–rates.

35

80

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 RSC Advances Page 4 of 7

10
35 Fig. 5 Conductivity measurements of LiMgxCuyCo1-x-yO2 materials.

15

C
Lithium Ion cell

20

Fig. 6 Cyclic voltammogram of LiMg0.025Cu0.175Co0.8O2 material.

40

25 Fig. 4 a) Charge/discharge curves of lithium ion cell at 1C and 2C rates.

b) Cycling performance of the Lithium Ion Cell at 1C and 2C rates over
500 cycles. Inset shows the cycling behaviour of the lithium ion cell at 1C
rate. c) Assembled lithium ion pouch cell charged by solar power used to
glow LED lights.

30

45

4 | Journal Name, [year], [vol], 00–00 This journal is © The Royal Society of Chemistry [year]
Page 5 of 7 RSC Advances

Conclusions 65 20 I. Saadoune, C. Delmas, J. Solid State Chem. 1998, 136, 8.

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70 23 R. Vasanthi, I. Ruthmangani, S. Selladurai, Inorg. Chem.
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a
20 CSIR-Network Institutes of Solar Energy (CSIR-NISE), CSIR-Central
Electrochemical Research Institute, Karaikudi, India – 630 006.
Fax:914565 227779 E-mail:deepika_41@[Link]
b
CSIR-National Physical Laboratory, New Delhi, India-110 007. 90
† Electronic Supplementary Information (ESI) available: Experiemtal
25 details. See DOI: 10.1039/b000000x/

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Lithium ion battery incorporated with new high performing electrode materials charged by solar
power.

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