Comparative Study about Differently Structured Transitional Metal Molybdates as Negative Electrodes for LIBs

The nanostructured materials represent the center of fundamental advances to design new era electrodes for high energy density batteries. Especially, one-dimensional nanomaterials are recognized as a solution due to their large surface area, short diffusion distance and high volume accommodation ability. In this sense, first in literature a comparative study has been done to examine the electrochemical performances of differently fabricated transition metal oxide molybdate powders: lithium storage capabilities of nickelcobalt-molybdate composite is compared to that of the cobalt oxide decorated nickel molybdate powders. To measure the effect of cobalt atom, bare nickel molybdate powders have been also fabricated and tested. The lithiation mechanism of these electrodes are discussed based on the cyclic voltammetry curvatures. SEI layer formation on the electrodes and the electrode/electrolyte stability upon cycling are analyzed following the electrochemical impedance spectroscopy test results (after 1st, 2nd and 4th cycles). The results reveal that the addition of cobalt changes the powder morphology and improves the electrochemical performance of the electrode. Among three samples, the cobalt oxide decorated nickel molybdate performs higher retention and rate performance since the top layer promotes more stable electrode/electrolyte interface providing a capacity of 290 mAh/g after 100 cycles. The rate performance of the sample is also found promising, the electrode delivers 200 mAh/g even under a current load of 400mA/g.Keywords: Metal molybdates, lithium ion batteries, hydrothermal method, anode

PDF

___

[1] C. T. Cherian, M. V. Reddy, S. C. Haur, B. V. R. Chowdari “Interconnected Network of CoMoO4 Submicrometer Particles As High Capacity Anode Material for Lithium Ion Batteries,” ACS Appl. Mater. Interfaces, vol. 5, pp. 918−923, 2013.
[2] Q.Yang, S.-Y. Lin, “Rationally designed nanosheet-based CoMoO4–NiMoO4 nanotubes for high-performance electrochemical electrodes,” RSC. Adv., vol.6, pp. 10520-10526, 2016.
[3] N.N. Leyzerovich, K.G. Bramnik, T. Buhrmester, H. Ehrenberg, H. Fuess, “Electrochemical intercalation of lithium in ternary metal molybdates MMoO4 (M: Cu, Zn, Ni and Fe),” J. Power Sources, vol. 127, pp. 76–84, 2004.
[4] P. R. Jothi, K. Shanthi, R. R. Salunkhe, M. Pramanik, V. Malgras, S. M. Alshehri, Y. Yamauchi “Synthesis and Characterization of α-NiMoO4 Nanorods for Supercapacitor Application,” Eur. J. Inorg. Chem., pp. 3694– 3699, 2015.
[5] S.-S. Kim, S. Ogura, H. Ikuta, Y. Uchimoto, M. Wakihara “Reaction mechanisms of MnMoO4 for high capacity anode material of Li secondary battery,” Solid State Ionics, vol. 146, pp. 249–256, 2002.
[6] 6. D. Zhang, R. Zhang, C. Xu, Y. Fan, B. Yuan, “Microwave-assisted solvothermal synthesis of nickel molybdate nanosheets as a potential catalytic platform for NADH and ethanol sensing” Sens. Actuators B, vol. 206, pp. 1–7, 2015.
[7] H. Wan, J. Jiang, X. Ji, L. Miao, L. Zhang, K. Xu, H. Chen, Y. Ruan, “Rapid microwaveassisted synthesis NiMoO4·H2O nanoclusters for supercapacitors,” Mater. Lett. Vol. 108, pp. 164–167, 2013.
[8] 8. M. C. Liu, L. B. Kong, C. Lu, X. J. Ma, X. M. Li, Y. C. Luo, L. Kang, “Design and synthesis of CoMoO4–NiMoO4·xH2O bundles with improved electrochemical properties for supercapacitors,” J. Mater. Chem. A, vol.1, pp. 1380–1387, 2013.
[9] S. Vidya, S. Solomon, J. K. Thomas, “Single step combustion synthesis of nanocrystalline scheelite Ba0.5Sr0.5MoO4 for optical and LTCC applications: Its structural, optical and dielectric properties,” J. Electroceramics vol.36, pp.142-149, 2016.
[10] M. P.-Kalamuei, M. M.-Kamazani, M. S.- Niasari,S. M. H.-Mashkani, “A simple sonochemical approach for synthesis of selenium nanostructures and investigation of its light harvesting application,” Ultrason. Sonochem., vol 23, pp.246-256, 2015.
[11] M. Devi, U. V. Varadaraju, “Lithium insertion in lithium iron molybdate,” Electrochem. commun., vol.18,pp.112-115, 2012
[12] M. Zhou, X. Jiang, C. Li, Z. Lin, J. Yao, Y. Wu, “The Double Molybdate Rb2Ba(MoO4)2: Synthesis, Crystal Structure, Optical, Thermal, Vibrational Properties, and Electronic Structure,” Z. Anorg. Allg. Chem., vol.641, 2321-2525, 2015
[13] W. Xiao, J. S. Chen, C. M. Li, R. Xu, X. W. Lou “Synthesis, Characterization, and Lithium Storage Capability of AMoO4 (A = Ni, Co) Nanorods, ” Chem. Mater., vol. 22, pp.746–754, 2010.
[14] X. Li, J. Bai, H. Wang, “Synthesis of hierarchical free-standing NiMoO4/reduced graphene oxide membrane for highperformance lithium storage,” J Solid State Electrochem., vol. 22, pp. 2659–2669, 2018.
[15] B. Wang, S. Li, X. Wu, W. Tian, J. Liu, M. Yu “Integration of network-like porous NiMoO4 nanoarchitectures assembled with ultrathin mesoporous nanosheets on threedimensional graphene foam for highlyreversible lithium storage,” J. Mater. Chem. A, vol.3, pp. 13691-13698, 2015.
[16] D. Lyu, L. Zhang, H. Wei, H. Geng, H. Gu “Synthesis of graphene wrapped porous CoMoO4 nanospheres as high-performance anodes for rechargeable lithium-ion batteries” RSC Adv., vol. 7, pp. 51506– 51511, 2017.
[17] J. Xu, S. Z. Gu, L. Fan, P. Xu and B. G. Lu, “Electrospun Lotus Root-like CoMoO4@Graphene Nanofibers as HighPerformance Anode for Lithium Ion Batteries,” Electrochim. Acta, vol. 196,pp. 125–130, 2016.
[18] K. Schuh, “Hydrothermal synthesis of molybdenum based oxides for the application in catalysis,” Dissertation, Karlsruher Institut für Technologie, 2014.
[19] Y. Ding, Y. Wan, Y.-L. Min, W. Zhang, S.- H. Yu “General Synthesis and Phase Control of Metal Molybdate Hydrates MMoO4·nH2O (M:Co, Ni, Mn and n:0, 3/4, 1) Nano/Microcrystals by a Hydrothermal Approach: Magnetic, Photocatalytic, and Electrochemical Properties,” Inorganic Chem., vol.47, pp.7813-7823, 2008.
[20] X. Tian, X. Li, T. Yang, K. Wang, H. Wang, Y. Song, Z. Liu, Q. Guo, “Porous worm-like NiMoO4 coaxially decorated electrospun carbon nanofiber as binder-free electrodes for high performance supercapacitors and lithium-ion batteries,” Appl. Surface Science, vol. 434 pp.49–56, 2018.
[21] S.-S.Kim, S. Ogura, H. Ikuta, Y. Uchimoto, M. Wakihara, “Reaction mechanisms of MnMoO4 for high capacity anode material of Li secondary battery,” Solid State Ionics, vol. 146, pp.249–256, 2002.
[22] S. Denis, E. Baudrin, M. Touboul, J.-M. Tarascon, “Synthesis and Electrochemical Properties of Amorphous Vanadates of General Formula RVO4 (R = In, Cr, Fe, Al, Y) vs. Li,” J. Electrochem. Soc., vol.144, pp.4099-4109, 1997.
[23] C. Tan, J. Cao, A. M. Khattak, F. Cai, B. Jiang, G. Yang, S. Hu “High-performance tin oxide-nitrogen doped graphene aerogel hybrids as anode materials for lithium-ion batteries,” J. Power Sources, vol. 270, pp. 28-33, 2014.