Ionics DOI 10.

1007/s11581-010-0438-x

REVIEW

Synthesis, structure, and electrochemistry of Ag-modified LiMn2O4 cathode materials for lithium-ion batteries
Shiau Fong Tay & Mohd Rafie Johan

Received: 20 January 2010 / Revised: 6 March 2010 / Accepted: 6 April 2010 # Springer-Verlag 2010

Abstract The composite of silver-modified lithium manganese oxide were prepared using thermal decomposition method of different mole ratio. Structural characterization was carried out by X-ray diffraction (XRD). XRD analysis revealed different patterns as the content of the dopant in the spinel increases. Phase analysis shows that Ag particles were dispersed on the LiMn2O4 surface instead of entering the spinel structure. On the other hand, the electrochemical behavior of cathode powder was examined by using twoelectrode test cells consisting of a cathode, metallic lithium as anode, and a solid polymer electrolyte of 0.87PEO0.13LiCF3SO3-0.10DBP. According to the electrochemical tests results, the influence of the Ag additive content on the electrochemical properties of Ag/LiMn2O4 composites is clearly shown. Keywords Ag/LiMn2O4 . Chemical synthesis . Conductivity . Electrochemical analysis PACS 82 . 80 . F

Introduction Among various power systems, lithium batteries offer the greatest promise for high specific energy and power. LiMn2O4 is more attractive than other materials (such as LiCoO2 and LiNiO2) because of its low material cost, rich
S. F. Tay (*) : M. R. Johan Advanced Materials Research Laboratory, Department of Mechanical Engineering, University of Malaya, 50603 Kuala Lumpur, Malaysia e-mail: nicotay@perdana.um.edu.my

abundance of Mn resources, low toxicity of Mn ion, and environment compatibility. A major problem prohibiting them from being widely used as a cathode for lithium-ion batteries is the fading capacity. Fading capacity of the spinel LiMn2O4 in commercial lithium-ion batteries is due to distortion of Mn2+ ion, the dissolution of manganese into electrolyte, loss of crystalline during cycling, and electrolyte decomposition at high potential regions. Several investigations have been made to overcome the fading capacity either by doping the spinel with several cations such as Al3+, Co2+, Cr2+, Ni2+, and Fe3+ or by surface modification of LiMn2O4 with different materials such as TiO2, MgO, LiAlO2, and Al2O3 as demonstrated [14]. High electronic conductivity is very important for the good performance of LiMn2O4 electrodes in the lithium-ion secondary batteries. Usually, carbon is used as the conductive agent adding to the cathode material for composing the electrode with relatively good electronic conductivity. However, the carbon will reduce the energy efficiency because of its inactive of Li-battery property as demonstrated [5]. There are researches dealing with the silver (Ag) deposition on the electrode materials such as LiFePO4, LiCoO2, and Li4Ti5O12, as demonstrated [68], and achieved an improved electrochemical performance. It is mainly because that the Ag additives efficiently increases the electrical conductivity between the electrode material particles and decreases the polarization of cathode. Wu et al. [9] had prepared the Ag-doped LiMn2O4 thin films using solution deposition method and obtain higher capacity retention than the un-doped LiMn2O4 during cycling. Some silver agglomeration on the thin films surface appears as Ag doping content increases. The resistivity of the film decreases with the increase of Ag

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content, while the specific capacity increases then followed by a decrease. The film with higher Ag content has a smaller capacity reduction as the discharge current density increases. Meanwhile, Son et al. [5] had reported that cycling performance and capacity of LiMn2O4 powder by Ag coating based on a chemical reduction process using NH4OH and HCHO as the reducing agent improved. Huang et al. [10] developed a chemical deposition process that would result in uniform distribution of nanosized Ag particles in the LiMn2O4 powders with good cycling properties. However, the electrochemical tests focused on the Ag-LiMn2O4 composites powders are still limited, and the influence of the Ag content on the electrochemical performance of the Ag-LiMn2O4 powders has not been investigated yet. Therefore, more studies on the electrochemical properties of Ag-LiMn2O4 composites powders are needed. Zhou et al. [11] employed a simple thermal decomposition method to prepare the Ag-LiMn2O4 composites with different silver contents in order to improve the cycling performance of the pristine LiMn2O4. The structural property and electrochemical performance of the material are examined in detail. Various electrochemical analysis indicate that the Ag-LiMn2O4 composites show much better reversibility, cycling stability, and lower resistance compared with the unmodified LiMn2O4. This is true, especially when the mole ratio of Ag:LiMn2O4 is 0.1, the composite has the highest initial discharge capacity and superior cycleability. The improved cycling performance is mainly due to the enhanced electronic conductivity of LiMn2O4 particles by the high ion conduction effect of Ag and the modified surface of LiMn2O4 helping to prevent the dissolution of the Mn3+ ions from the material, which is one of the main reasons for the capacity fading of LiMn2O4 as demonstrated [1]. The results of structure and electrochemical tests indicate the fact that the incorporation of Ag particles to the surface of LiMn2O4 can be applied to effectively improve the fading capacity of pristine LiMn2O4 upon repeated cycling, which is a significant requirement for the practical application of LiMn2O4-based lithium-ion battery. Zhou et al. have found that the content of Ag additive can observably affect the cycling capability of the composite. Among all the samples, Ag (0.1)/LMO composite shows the best battery performance with higher initial discharge capacity, better cycle stability, and excellent rate capability. Therefore, Ag-modified LiMn2O4 could be employed as a very promising candidate of cathode materials for lithiumion battery. In this work, we employ thermal decomposition method to prepare the Ag/LiMn2O4 composite with different silver contents in order to improve the conductivity of the asreceived LiMn2O4.

Experimental Sample preparation Fifty milliliters deionized water and 10 ml ethanol were mixed in a 500-ml beaker. The mole ratio of AgNO3 and LiMn2O4 was both 0.05. The powder was suspended in the solution and stirred vigorously using a magnetic stirrer for 1 h to make the suspension dispersed homogeneously and then dried for 4 h in the oven at 100 C to evaporate the solvent. Then, the obtained powder was heated in a furnace at 450 C for 2 h in air environment and then cooled to room temperature naturally. The steps were repeated with different mole ratio of 0.1, 0.2, and 0.3, respectively. Small amount of powder obtained then was sent for X-ray diffraction (XRD) and scanning electron microscopy (SEM) to determine the purity and the distribution of silver. Impedance spectroscopy (IS) testing is used to determine the bulk resistance of the samples. Electrolyte preparation The electrolyte was prepared by using solution-casting techniques. Appropriate weights of the PEO and LiCF3SO3 in the ratio of 0.87:0.13 were dissolved in 50-ml acetonitrile. In this work, 0.87 g of PEO and 0.13 g of LiCF3SO3 were used. The solution was then stirred continuously for 48 h at room temperature until it took a homogenous viscous liquid appearance. Ten weight percent of DBP of the total PEO + LiCF3SO3 weight was then added to the solution. In this work, 0.11 g of DBP was used. The solution was then stirred continuously again to obtain a homogenous viscous appearance. The mixture was then immediately casted in Petri dish. The acetonitrile allowed evaporating completely. This procedure provides a thin polymer electrolyte film. The thin film was then palletized into a round shape for battery fabrication. Battery fabrication The composition with the highest electrical conductivity of Ag-modified LiMn2O4 powder was used as cathode for battery fabrication. Lithium metal and combination of PEO + LiCF 3SO 3 + DBP was used as anode and electrolyte, respectively. The open circuit voltage of the battery was measured using Fluke 175 True FMS Multimeter. The internal resistance of battery was measure by connecting the battery to the rheostat and multimeter. Total of five resistant values were set by using rheostat, that is, 5, 10, 15, 20, and 25 . Graph of voltage (V) versus current (I) was plotted, and the internal resistance was determined from the graph gradient.

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Results and discussion XRD studies Figure 1 shows the XRD patterns of as-received LiMn2O4 and different weight ratio of Ag/LiMn2O4. It is shown that all the peaks are in good agreement with the patterns of LiMn2O4. The main peaks of LiMn2O4 are labeled with h, k, and l indexes and assigned to the spinel compound without any impurity phases. With the increases of Ag content, the peak density of Ag gradually goes up, as shown in Fig. 1(d, e). From the XRD patterns, it is hard to clearly identify each of the peak characteristics of Ag in the XRD patterns of Ag/LiMn2O4 composites. This phenomenon is mainly due to the small amount of the Ag additives, and mostly the peaks of Ag almost overlap with the peaks of LiMn2O4. The lattice parameter values were calculated from the diffraction data by a least square method and are in the range of 8.167 to 8.175 , which is in accordance with that of the as-received LiMn2O4 (8.171 ). It is evident that an Ag additive does not enter spinel structure, and it is dispersed on the surface of the LiMn2O4. SEM studies The surface morphology of the Ag/LiMn2O4 composite is presented in Figs. 2 and 3. From Fig. 3, it can be observed that Ag particles (the white spot) are highly dispersed on the surface of LiMn2O4 particles. The SEM photographs of other Ag/LiMn2O4 composite with different Ag contents are almost the same as that of the Ag(0.1)/LMO composite.

Fig. 2 Scanning electron microscopy image of the as-received LiMn2O4

With the increase of Ag content in the composite, the appearance of Ag particles is much more obvious and uniformly distributed on the surface of the LiMn2O4. IS studies Figure 4 shows the ColeCole plots for the impedance spectra of Li+ ions with prepared cathode materials at room temperature. Both the spectra contain only a single arc, although the arc has non-zero intersection with real axis in the high frequency region. The diameter within the semicircle of the plot decreases with addition of Ag. This may be associated with the substantial decreases in grain boundary resistance of the materials when the Ag is added. Figure 5 shows the temperature dependence conductivity of Ag/LiMn2O4. The electronic conductivity increases with an increase in temperature. The ionic conductivity changes from low to high at a critical temperature. To be noticed, the high value of the ionic conductivity decreases, i.e., from

Fig. 1 X-ray diffraction patterns obtained from the as-received LiMn2O4 and Ag/LiMn2O4 composites with different Ag content: (a) LiMn2O4, (b) Ag (0.05)/LiMn2O4, (c) Ag (0.10)/LiMn2O4, (d) Ag (0.20)/LiMn2O4, and (e) Ag (0.30)/LiMn2O4. f Vertical bars stand for the characteristics X-ray patterns of Ag metal

Fig. 3 Scanning electron microscopy image of the prepared Ag (0.10)/LMO composite

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Fig. 4 The ColeCole plot of as-received LiMn2O4 and Ag (0.10)/ LMO composite

Fig. 6 Graph of voltage versus current

2.0630105 to 1.2449105 S cm1, passing from 70 C to 30 C. From the graph, the activation energy is calculated as 4.71 eV. Figure 6 shows the linear dependence of voltage with current. The value of open circuit voltage and internal resistance obtained are 2.57 V and 2.17 , respectively. Compare to other types of batteries such as nickel-cadmium batteries, its open circuit voltage is 1.4 V, which is lower than lithium-ion batteries. The lower the internal resistance, the lesser restriction the battery encounters in delivering the needed power spikes. A high mW reading can trigger an early low battery indication on a seemingly good battery because the available energy cannot be delivered in the required manner and remains in the battery. The internal

resistance of lithium-ion batteries is high compared to other rechargeable chemistries such as nickel-metal hydride and nickel-cadmium. Rising internal resistance causes the voltage at the terminals to drop under load, reducing the maximum current that can be drawn from them. Eventually, they reach a point at which the battery can no longer operate the equipment it is installed in for an adequate period.

Conclusion Silver metal was successfully modifying lithium manganese oxide by thermal decomposition method. Among the series of Ag/LiMn2O4 composites, it is shown that a composite with a mole ratio of 0.10 is the most outstanding property in this work. The Ag additives have enhanced the electronic conductivity and electrochemical performance mainly due to its low resistance. Therefore, Ag-modified LiMn2O4 could be employed as a very promising candidate of cathode materials for lithium-ion battery. The temperature dependence conductivity performed at sample Ag(0.10)/ LiMn2O4 shows that conductivity increases from room temperature to 70 C. The low activation energy of 4.71 eV can be use to support the mobility of Li+ ion. The Ag particles are advantageous to form a more conductive film on the surface of the active material because of its high electronic conductivity, which is more efficiently to reduce the resistance for Li+ migration through the surface films and finally results in a low bulk resistance. As a conclusion, Ag additive has a good ionic conductivity; it will greatly increase the ionic conduction between spinel particles after

Fig. 5 Plot of log conductivity versus 1,000/T for Ag (0.10)/LMO composite

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it has widely dispersed on the surface of the pristine LiMn2O4 and, therefore, remarkably reduce the whole resistance of the composite electrode.
Acknowledgements The authors thank the technical staffs of the University Malaya, Faculty of Engineering and especially En. Mohd Said bin Sakat.

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