1506 Bull. Korean Chem. Soc. 2010, Vol. 31, No. 6 DOI 10.5012/bkcs.2010.31.6.

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V. Aravindan et al.

LiMnBO3/C: A Potential Cathode Material for Lithium Batteries

V. Aravindan, K. Karthikeyan, S. Amaresh, and Y. S. Lee,* The Research Institute for Catalysis and Faculty of Applied Chemical Engineering, Chonnam National University, Gwangju 500-757, Korea. *E-mail: [email protected] Received December 12, 2009, Accepted March 25, 2010
LiMnBO3 was successfully synthesized by a solid-state reaction method both with and without a carbon coating. Adipic acid was used as source material for the carbon coating. LiMnBO3 was composed of many small polycrystalline particles with a size of about 50 - 70 nm, which showed a very even particle morphology and highly ordered crystalline particulates. Whereas the carbon coated LiMnBO3 was well covered by mat-like, fine material consisting of amorphous carbon derived from the carbonization of adipic acid during the synthetic process. Carbon coated cell exhibited improved and stable discharge capacity profile over the untreated. Two cells delivered an initial discharge capacity of 111 and 58 mAh/g for LiMnBO3/C and LiMnBO3, respectively. Carbon coating on the surface of the LiMnBO3 drastically improved discharge capacity due to the improved electric conductivity in the LiMnBO3 material.

Key Words: LiMnBO3, Carbon coating, Nano materials, Adipic acid, Impedance spectroscopy

Introduction As of late, an increasing interest is being devoted towards the development of cathode materials for lithium secondary batteries that bear a high capacity, are affordable, and are environmentally friendlier than existing, commercial, toxic LiCoO2. Recently, growing interest has focused on polyanion framework struc1 tured compounds. Generally, a polyanion containing a counteraction with a relatively high electronegativity functions as an electron withdrawing functional group where the electronwithdrawing density is obtained from the covalent bonds of the nearest-neighbor redox cations. This inductive effect lowers the redox potential of the metal used in the cathodes and substantially increases cell voltage effect and has been successfully explored for olivine framework structures, in particular, 2-4 LiFePO4. Further, LiFePO4 possesses several benefits, including a flat discharge profile, the ability to sustain high current rates, low expense, natural abundance, thermal and chemical stability, and is eco-friendlier than Co.5,6 Legagneur et al.7 first explored the possibility of using the boron-based compounds (LiMBO3, M = Fe, Mn, & Co) as positive electrodes in lithium batteries. Since then, very few works 7-10 have reported boron-based cathodes. The advantages of boron include being lightweight, high relative abundance in the earths crust, environmental friendliness, and slightly less electronegativity than phosphorous. However, these compounds also suffer in terms of their inherent electronic conductivity similar to those of the olivine framework. The controlled particle size, carbon coating, and appropriate synthesis conditions for LiFePO4 dra6 matically improve cathodic performance; a similar procedure is expected here to improve the boron-based cathodes. Very 8,9 recently, Dong et al. reported upon the LiFeBO3-based material with high discharge capacity values in different scenarios. Nevertheless, LiMnBO3-based materials have yet to succeed lithium 10 batteries. Given this current state, an attempt was made herein to synthesize LiMnBO3 via a solid-state reaction method both with and without carbon coating. The results emphasize the

drastic improvement of capacity using adipic acid as a carbon source. Experimental High purity, analytical grade LiOHH2O (Junsei, Japan), MnCO3 (Sigma-Aldrich, USA), and H3BO3 (Junsei, Japan) were used as the starting materials for the synthesis. C6H10O4 (adipic acid, Dae-Jung, Korea) was used as a carbon source material (0.1 mol. against the total metal ion present in the compound). Stoichiometric amounts of the starting materials were fineo ground using a mortar and precalcined at 250 C for 3 h for decomposition of carbonates and hydroxides. Then, the resultant material was again fine-ground using a mortar and heat-treato ed in the presence of Ar at 750 C for 15 h to obtain the resulting material. Powder X-ray diffraction (XRD, Rint 1000, Rigaku, Japan) was employed for structural analysis using Cu K radiation. The carbon content of the synthesized LiMnBO3 particles was determined using an elemental analyzer (CHN Flash EA series, CE Instruments, Italy). The surface morphological features were observed using a field emission scanning electron microscope (FE-SEM, S-4700, Hitachi, Japan). Electrochemical impedance spectroscopy (EIS) was performed using a BioLogic (SP-150, Bio-Logic SAS, France) electrochemical workstation. The LiMnBO3 electrodes served as working electrode and metallic lithium as counter and reference electrodes respectively between 3 MHz to 32 Hz at room temperature. The cycling performance was studied using a CR2032 coin-type cell and the cathode fabricated with 20 mg of precisely weighed active material, 3.0 mg of Ketjen black, and 3.0 mg of conductive binder (2.0 mg of Teflonized acetylene black (TAB) and 1.0 mg 2 of graphite). This was pressed on a 200 mm stainless steel mesh 2 used as the current collector under a pressure of 300 kg/cm o and dried at 130 C for 5 h in a vacuum oven. The coin cell was composed of a cathode with metallic lithium as the anode, separated by a porous polypropylene film (Celgard 3401). The 1.0 M LiPF6, in a mixture of ethylene carbonate (EC)/dimethyl

A Potential Cathode Material for Lithium Batteries carbonate (DMC) (1:1 v/v, Techno Semichem Co., Ltd, Korea), was used as an electrolyte. The cycling studies were carried out between 1.25 - 4.8 V at a C/20 rate under room temperature.
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Powder X-ray diffraction patterns of the LiMnBO3 both with and without carbon-coated materials were presented in Fig. 1. The structure of the LiMnBO3 was isotopic with the hexagonal form of LiCdBO3, which was built up from MnO5 square pyramids, planar BO3 groups, and LiO4 in the tetrahedral sites. The MnO5 pyramidal shared two opposite edges of its square base with two adjacent pyramids, thus forming chains along the c-axis. In the BO3 planes, the B atoms were not located in the 10 centre portion of the triangle. Planar polar groups were linked by edge-sharing and lithium ions occupied the tetrahedral sites n of the LiO4 in the three-dimensional polyanionic [MnBO3]n framework. Further, the LiO4 tetrahedral sites shared two O and planer BO3 groups and link to form a chain via corner sharing. Within this framework, Li atoms were occupying statisti7,9 cally tetrahedral sites sharing a face. Thus, the electronic conduction must occur via Mn-O-Mn bonding, unlike many polyanion structures, for example, NASICON, where the polyanions were completely isolated from each transition metal polyhed10 rons. The obtained XRD patterns of the LiMnBO3 were in good agreement with the earlier report of Legagneur et al.7 The morphological features of the LiMnBO3 and LiMnBO3/C were analyzed by field emission scanning electron microscopy (SEM). LiMnBO3 (Fig. 2a) was composed of many small polycrystalline particles with a size of about 50-70 nm, which showed a very even particle morphology and highly ordered crystalline particulates. Each particle was completely separated and located alone without any linkage. Whereas the LiMnBO3/C was concerned (Fig. 2b), the surface of the LiMnBO3 particles was well covered by mat-like, fine material consisting of carbon derived from the carbonization of adipic acid during the synthetic process. Moreover, this coating are also greatly interconnected with other particulates, yielding an increase in electronic conductivity of the LiMnBO3. The carbon content of LiMnBO3/C material was 0.9 wt %. Cycling performance of the Li/LiMnBO3 or LiMnBO3/C was presented in Fig. 3. Figure 3(a) represented the initial chargedischarge curves of the cells cycled between 1.25 - 4.8 V under ambient temperature at a C/20 rate. To improve the small discharge capacity in LiMnBO3 in ref [10], it was conducted cycling test in wide voltage region in this study. These cells delivered an initial discharge capacity of 111 and 58 mAh/g against the charge capacity of 181 and 100 mAh/g for LiMnBO3/C and LiMnBO3, respectively. The loss in capacity might be due to the formation of a solid electrolyte interface (SEI) on the electrodes. After 30 cycles, discharge capacities 89 and 69 mAh/g were maintained for carbon-coated and uncoated LiMnBO3. The LiMnBO3 contained one lithium ion per formula unit, thus, if one could completely extract the lithium and com2+ 3+ pletely oxidize Mn to Mn , the theoretical capacity would be 222 mAh/g. However, full capacity was rarely achieved owing to their limitations in structure and need for high electronic and ionic conductivity and composition of the materials.

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V. Aravindan et al. frequency semicircle was ascribed to the SEI film and/or contact resistance, the semicircle in the medium frequency region was assigned to the charge-transfer (CT) impedance on the electrode/ electrolyte interface, and the inclined line at an approximate o 45 angle to the real axis corresponds to the lithium diffusion 13 kinetics towards the electrodes. It could be seen that the diameter of the semicircle in the medium-frequency region for the LiMnBO3/C electrode was much smaller than the LiMnBO3 electrode, revealing lower CT impedance and indicating that the electronic conductivity of the LiMnBO3/C was dramatically improved after carbon coating, which significantly improved cycling performance of the cell. Conclusion To conclude, LiMnBO3 cathodes, both with and without carbon coating, were successfully synthesized by a solid-state reaction method under an Ar flow. The LiMnBO3/C exhibited stable and improved discharge capacities over the uncoated. This improved performance may be attributable to the coating of carbon on the surface of the particles by the carbonization of adipic acid. Acknowledgments. This work was supported by Korea Research Foundation Grant funded by the Korean Government (MOEHRD) (KRF-2007-412-J02003). References
1. Thackeray, M. Nat Mater. 2002, 1, 81. 2. Manthiram, A.; Goodenough, J. B. J. Solid State Chem. 1991, 71, 349. 3. Manthiram, A.; Murugan, A. V.; Sarkar, A.; Muraliganth, T. Energy Environ. Sci. 2008, 1, 621. 4. Li, Z.; Zhang, D.; Yang, F. J. Mater. Sci. 2008, 44, 2435. 5. Padhi, A. K.; Nanjundswamy, K. S.; Goodenough, J. B. J. Electrochem. Soc. 1997, 144, 1188. 6. Jugovi, D.; Uskokovi, D. J. Power Sources 2009, 190, 538. 7. Legagneur, V.; An, Y.; Mosbah, A.; Portal, R.; Le Gal La Salle, A.; Verbaere, A.; Guyomard, D.; Piffard, Y. Solid State Ionics 2001, 139, 37. 8. Dong, Y. Z.; Zhao, Y. M.; Fu, P.; Zhou, H.; Hou, X. M. J. Alloys Comp. 2008, 461, 585. 9. Dong, Y. Z.; Zhao, Y. M.; Shi, Z. D.; An, X. N.; Fu, P.; Chen, L. Electrochim. Acta 2008, 53, 2339. 10. Allen, J. L.; Xu, K.; Zhang, S. S.; Jow, T. R. Mater. Res. Soc. Symp. Proc. 2002, 730, V1.8. 11. Reddy Ch, V. S.; Walker, E. H. Jr.; Wicker Sr, S. A.; Williams, Q. L.; Kalluru, R. R. Curr. Appl. Phys. 2009, 9, 1195. 12. Lim, H. H.; Chang, I. C.; Lee, S. B.; Karthikeyan, K.; Aravindan, V.; Lee, Y. S. J. Alloys and Compounds 2010, 495, 181. 13. Yang, S.; Song, H.; Chen, X. Electrochem Commun. 2006, 8, 137.

LiMnBO /C LiMnBO 3/C 3 LiMnBO LiMnBO 33

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Z' () Figure 4. Electrochemical Impedance Spectroscopy (EIS) plots of LiMnBO3 recorded at room temperature.

Carbon coating on the surface of the LiMnBO3 drastically improved discharge capacity due to the improved conductivity derived from good contact between the nearest neighbor particles through such coating. It is well known that the capacity improvement in LiFePO4 cell due to small particle size, forming a carbon coating layer using various carbon materials 11 and surfactants. In this study, we firstly have chosen adipic acid as carbon source material for the LiMnBO3 system, which due to the appealing properties like, cost effective, environmental friendly, easily prepared at any laboratories. Furthermore, this was convincingly proven herein for the LiFePO4 12 system. Allen et al. has also tested several carbon sources for LiMnBO3, but only a maximum discharge capacity of 20 mAh/g 10 was achieved. Figure 3(b) displayed the discharge capacity profile with the number of cycles. The carbon-coated LiMnBO3 material exhibited very stable discharge behavior, whereas uncoated material showed irregular capacity behavior. This may be ascribed to the uniform carbon coating derived from carbonization of a chelating agent such as adipic acid, leading to enhanced performance. The effects of the carbon coating on the electrical conductivity of the LiMnBO3/C, a.c. impedance measurements, were conducted. From the ac impedance spectrum, a typical equivalent circuit is depicted in Fig. 4 (inset), where R1 is the ohmic resistance of the electrolyte, membrane and electrode, corresponding to the high frequency intercept of the semicircle with the horizontal axis, Q and Rct represent constant phase element (CPE) and the charge-transfer resistance, respectively, corresponding to the semicircle, and Zw is the Warburg impedance + arising from the diffusion of Li ions in electrode, corresponding to the inclined straight line in low frequency. The high-