Metal-Organic Frameworks (MOFs) Derived Porous Co3O4/Carbon Composites for Lithium-Air Batteries

Abstract

Commercial Li-ion batteries (LIBs) cannot meet the requirements in high performance energy storage systems because of its low specific capacity (372 mAh g-1) and limited rate capability [1]. For this reason, lithium-air batteries (LABs) have been researched due to their highest theoretical energy density (11,140 Wh kg-1) [2]. Metal oxides such as MnO2, Co3O4, RuO2 and LaFeO3 have attracted as a cathode catalyst for LABs since they have efficient ORR/OER catalytic effect in LAB batteries. Among them, Cobalt oxides (Co3O4) is considered as a promising candidate of cathode catalyst due to its excellent catalytic performance properties, including their initial capacity, capacity retention, and low charging voltages (4 V) [3]. However, low electrical conductivity and agglomeration of its particles will bring about negative effect such as electrode pulverization, capacity loss and poor cycling performance. To alleviate these problems, there are many strategies have been studied. One of the major methods is fabrication of Co3O4 with nanostuctures, such as nanoparticles, nanosheets, nanowires, nanoflowers which permitting the high surface area, small dimension of these nanostructured Co3O4 [4-7]. But, the aggregation of these nanostructured Co3O4 particles and the collapse of their structure during charge-discharge test or fabrication steps still hinder LAB performances. Another competitive strategy is to synthesis hybrid materials consist of nanostructured Co3O4and carbon-based materials, such as graphene, carbon nanotubes, carbon nanofibers [8-10]. This strategy helps to release the volumetric change and improve the electrical conductivity. Recently, metal-organic frameworks (MOFs) have been investigated as a nanoporous materials because of their diverse structural topologies and tunable functionalities [11]. They have used a wide range of application in catalyst, gas separation, and energy storage with no further process. More recently, MOFs can be employed for the synthesis of porous carbon materials as the self-sacrificial templates. Herein, we synthesize mesoporous Co3O4/carbon hybrid composites for LABs using aliphatic ligand-based MOFs as the precursor. Lower thermal stability of aliphatic ligand results in interconnected porous structures and uniform distribution of Co3O4 in carbonaceous matrix. When we apply this Co3O4/carbon hybrid composite to cathode catalyst for LABs, it exhibit high capacity, good rate capability, and improved cycle performance. Reference [1] L.Z. Bai, D.L. Zhao, T.M. Zhang, W.G. Xie, J.M. Zhang, Z.M. Shen, Electrochimica Acta 107 (2013) 555–561. [2] N. Imanishi, O. Yamamoto, Materials Today. 17 (2014) 24–30 [3] C. Sun, R. Li, C. Ma, Y. Wang, Y. Ren, W. Yang, Z. Ma, J. Li, Y. Chen, Y. Kim, L. Chen, J. Mater. Chem. A 2 (2014) 7188–7196. [4] Y.N. Huang, C.C. Chen, C.H. An, C.C. Xu, Y.N. Xu, Y.J. Wang, L.F. Jiao, H.T. Yuan, Electrochimica Acta 145 (2014) 34–39. [5] L. Tian, H.L. Zou, J.X. Fu, X.F. Yang, Y. Wang, H.L. Guo, X.H. Fu, C.L. Liang, M.M. Wu, P.K. Shen, Q.M. Gao, Advanced Functional Materials 20 (2010) 617–623. [6] K. Feng, H.W. Park, X.L. Wang, D.U. Lee, Z.W. Chen, Electrochimica Acta 139 (2014) 145–151. [7] X.X. Qing, S.Q. Liu, K.L. Huang, K.Z. Lv, Y.P. Yang, Z.G. Lu, D. Fang, X.X. Liang, Electrochimica Acta 56 (2011) 4985–4991. [8] Y.B. Lou, J. Liang, Y.L. Peng, J.X. Chen, Physical Chemistry Chemical Physics 17 (2015) 8885–8893. [9] G. Huang, F.F. Zhang, X.C. Du, Y.L. Qin, D.M. Yin, L.M. Wang, ACS Nano 9 (2015) 1592–1599. [10] B.W. Huang, L. Li, Y.J. Hea, X.Z. Liao, Y.S. H, W. Zhang, Z.F. Ma, Electrochimica Acta 137 (2014) 183–189. [11] D. Zhu, F. Zheng, S. Xu, Y. Zhang and Q. Chen, Dalton Trans 44 (2015) 16946-16952 Acknowledgements “This research was supported by the MSIP(Ministry of Science, ICT and Future Planning), Korea, under the “IT Consilience Creative Program” (IITP-2015-R0346-15-1008) supervised by the IITP(Institute for Information & Communications Technology Promotion)