Materials Letters 78 (2012) 116119

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Materials Letters
journal homepage: www.elsevier.com/locate/matlet

Enhanced electrochemical properties of LiMn2O4 cathode material coated by 5 wt.% of nano-La2O3

Lijun Feng, Shuping Wang, Lu Han, Xuyang Qin, Huiying Wei, Yanzhao Yang
Key Laboratory for Special Functional Aggregated Materials of Education Ministry, School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, PR China

a r t i c l e

i n f o

a b s t r a c t
Spinel LiMn2O4 was synthesized by solid state reaction. 5.0 wt.% of La2O3 was coated on the surface of LiMn2O4 via ball-milling method, followed by calcination at 650 C for 5 h in the air. The uncoated and La2O3-coated LiMn2O4 materials were physically characterized using X-ray diffraction, scanning electron microscopy, transmission electron microscopy, BrunauerEmmettTeller surface area measurements. It was observed that Li/LiMn2O4 electrode obtained the capacity retention of 76.7% after 205 cycles at 1 C rate at 25 C while that of the coated sample was 90.1%. At 55 C, the bare and coated LiMn2O4 showed a capacity retention of 69.4% and 82.6% after 95 cycles, respectively. Rate capability was also improved. The capacity retention of uncoated and La2O3-coated materials reduced to 46.9% and 80.3% at 10 C-rate, respectively. 2012 Elsevier B.V. All rights reserved.

Article history: Received 23 February 2012 Accepted 8 March 2012 Available online 17 March 2012 Keywords: LiMn2O4 Coated Composite materials Electronic materials Lithium ion batteries

1. Introduction In recent years, spinel LiMn2O4 as a cathode material for lithium-ion battery has been studied intensively because of its low cost, richness in natural sources and low toxicity [14]. However, its disadvantage is poor cycling behavior caused by JahnTeller distortion, dissolution of manganese into organic electrolyte, and decomposition of electrolyte solution on the electrode [5,6]. Many researchers have considered partial substitution of the manganese-ions with several divalent or trivalent metal ions, such as Ce2 +, Zn2 +, Ga 3 +, Co3 +, Al 3 + and Cr3 + [710] which can enhance the structural stability and improve the cycle performance. However, the manganese cannot be prohibited to dissolve in the electrolyte. Therefore, surface modication with electrochemically inactive metal oxides is proved to be an important method. For example, SiO2 [11], TiO2 [12], Al2O3 [13], ZrO2 [14], CeO2 [15] and Cr2O3 [16] were applied to cover the surface of LiMn2O4, leading to the improved electrochemical performance. Different from the metal oxides mentioned above, La2O3 is a highly efcient lithium ion conductor. Muralidharan et al. [17] reported that La2O3-coated LiCoO2 particles possess high discharge capacities and excellent cycle stability. Arumugam et al. [18] reported that the electrochemical performances of the spinel LiMn2O4 cathode has been improved by coating with 2.0 wt.% of La2O3 with a capacity retention of 86.3% after 100 cycles at 30 C. In this study, we synthesized the 5.0 wt.% of La2O3 coated LiMn2O4 composite material via ball-milling method and examined the electrochemical performance for lithium-ion battery.
Corresponding author. Tel.: + 86 531 88365431; fax: + 86 531 88364464. E-mail address: yzhyang@sdu.edu.cn (Y. Yang). 0167-577X/$ see front matter 2012 Elsevier B.V. All rights reserved. doi:10.1016/j.matlet.2012.03.019

2. Experimental 2.1. Synthesis of the spinels LiMn2O4 spinels was synthesized by the solid-state method from reagent grade Li(I) and Mn(II) acetates. The precursor was sintered at 450 C for 3 h and then calcined at 750 C for 10 h in the air to produce LiMn2O4 powder. The calculated 5%(wt) La2O3 formed from La(NO3)3nH2O and LiMn2O4 powders were milled together at 500 rpm for 5 h, followed by calcination at 650 C for 5 h to obtain La2O3-coated LiMn2O4 powders. La(NO3)3nH2O was calcinated under the same condition to conrm the composition of the product. The schematic diagram of the La2O3 coating process is shown in Fig. 1. 2.2. Characterization of the spinels The crystal structures of the uncoated and La2O3-coated LiMn2O4 powders were identied by powder XRD (Rigaku D/Max 2200PC, Japan) with a graphite monochromator and Cu K radiation ( = 0.15418 nm). The morphology and microstructure of the products

Fig. 1. Schematic diagram of the La2O3 coating process.

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2.3. Electrochemical evaluations The study of the electrochemical properties of uncoated and La2O3-coated LiMn2O4 powders was performed in a two-electrode lithium cell. The electrodes were fabricated by mixing LiMn2O4 or La2O3-coated LiMn2O4 powders with conductive carbon (super P) and binder (PVDF) at a weight ratio of 80:15:5 in N-methyl-2-pyrrolidinone (NMP), respectively. The cathode sheet was prepared by casting the slurry in Al foil and drying at 80 C for 12 h. A 2032 type cell was fabricated by combining the cathode and Li metal anode with electrolyte which is a mixture of 1 M LiPF6 in an ethylene carbonate (EC)-diethyl carbonate (DEC)-ethyl methyl carbonate (EMC) mixture (1:1:1 in volume ratio). The cells were assembled in an argon-protected glove box and then measured using a Land CT2001 battery tester within the potential range of 3.3 to 4.35 V at different C rates at 25 C and 55 C.

Fig. 2. XRD patterns of LiMn2O4 (a) and La2O3-coated LiMn2O4 powders (b) and the calcination products of La(NO3)3nH2O calcined at 650 C for 5 h (c).

3. Results and discussion 3.1. X-ray photon spectroscopy analysis

were characterized using a transmission electron microscope (TEM, JEM 100-CX II) with an accelerating voltage of 80 kV, and a eldemission scanning electron microscope (QUANTA-FEG-250) with the energy dispersive spectrometer (EDS) analysis capability.

Fig. 2(a) and (b) show the XRD patterns of both the uncoated and La2O3-coated LiMn2O4 powders. All the well-dened diffraction peaks agree well with those from the JCPDS 35-0782 card and correspond to Fd3m space group. There is no signicant change in the XRD patterns

Fig. 3. SEM images of (a) LiMn2O4 and (b) La2O3-coated LiMn2O4 particles; EDS graph of (c) LiMn2O4 and (d) La2O3-coated LiMn2O4 particles; TEM images of (e) LiMn2O4 and (f) La2O3-coated LiMn2O4 particles.

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for the La2O3-coated powder compared with the bare one. No LiMnO or LaO impurity was detected. The XRD pattern in Fig. 2(c) shows that the material can be readily indexed to the hexagonal La2O3 phase in P-3m space group (JCPDS No. 05-0602) [19]. In a word, XRD results indicate that La2O3 is only coated on the surface of the LiMn2O4 powders. This conclusion is supported by SEM, TEM and EDS data presented in the following section. 3.2. Surface morphology analysis Fig. 3(a) and (b) show that the surface of the powders changed noticeably upon coating. The bare LiMn2O4 is found smooth and angular without other phases on the surface. On the contrary, the surface morphology of the coated particles is coarse. EDS were used to identify the elements on the surface of uncoated and coated LiMn2O4 powders [20]. Fig. 2(c) and (d) revealed the presence of La elemental peaks after coating. It indicates that the La2O3 layer is formed on the surface of the LiMn2O4 powder. TEM study demonstrates that translucent and uniform La2O3 layer was formed over the bare LiMn2O4 powder with the coating thickness of around 12 nm. The BET surface areas of the uncoated and La2O3-coated powders are 4.067 and 5.882 m 2g 1, respectively. The increased surface area of the cathode material may be due to the greater surface area of the La2O3 coating material [17]. 3.3. Electrochemical evaluations

voltage plateaus at 4.0 and 4.1 V which is the characteristic of Li/ LiMn2O4 cell. This shows that the La2O3 modication does not change the intrinsic property of LiMn2O4. Fig. 4(b) and (c) show that the initial discharge capacity of the bare LiMn2O4 is 117.5 mAh/g at 25 C, while the La2O3-coated LiMn2O4 provides a slightly lower capacity of 116.4 mAh/g. The capacity retention of the bare LiMn2O4 is only 76.7% over 205 cycles, while 90.1% is obtained for La2O3-coated LiMn2O4. At 55 C, the discharge capacity of the bare LiMn2O4 declined from 118.5 mAh/g to 82.3 mAh/g with a capacity retention of 69.4% after 95 cycles. However, La2O3-coated LiMn2O4 provides initial discharge capacity of 118.1 mAh/g and remains at 97.6 mAh/g with a capacity retention of 82.6%. It is indicated that the electrochemical performances of LiMn2O4 electrodes are improved signicantly by La2O3 layer at 25 C and 55 C, which is attributed to the reduced contact area between the electrolyte and the electrode. According to Fig. 4(d), the samples exhibit similar initial discharge capacity at the lower C-rate (0.5 C). With the increasing of the current density, the discharge capacity decreases in both powders, while the modied powder decreases less and shows a higher discharge capacity than the bare material. At 10 C-rate, the capacity retention of uncoated and La2O3-coated materials is 46.9% and 80.3%, respectively. It is speculated that the La2O3 layer acts as a highly efcient lithium ion conductor and the channel for Li ion diffusion is not hindered [17,21]. In addition, the La2O3 coating layer stabilizes the structure of the cathode material when cycled at higher current density. 4. Conclusions

Fig. 4(a) shows the initial discharge curves of bare and La2O3-coated LiMn2O4 samples at a discharge rate of 0.5 C between 3.3 and 4.35 V at 25 C. The two samples have similar discharge curves with two clear

Compared with the bare LiMn2O4 material, no signicant change is found in the La2O3-coated powder in XRD patterns. It is indicated

Fig. 4. Initial discharge curves (a) and cycling performance at 1 C discharge rate at 25 C (b) and 55 C (c) of Li/LiMn2O4 and Li/La2O3-coated LiMn2O4 cells; rate capability of Li/LiMn2O4 and Li/La2O3-coated LiMn2O4 cells at 55 C (d).

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in the TEM images that translucent and uniform La2O3 layer was formed over the bare LiMn2O4 powder with a coating thickness of around 12 nm. This study conrms that 5.0 wt.% of La2O3 coating layer could improve the electrochemical properties of LiMn2O4 sample at ambient and elevated temperature as cathode material for lithium ion battery. Acknowledgement This work was supported by the Natural Science Foundation of China (Grant 21076115) and the 973 Project of China (No. 2011CB935901). References
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