Electrochemical evaluation of LiZnxMn2−xO4 (x≤0.10) cathode material synthesized by solution combustion method
Introduction
Recently, many researchers are interested in spinel LiMn2O4 for its low cost, superior safety and environmental friendliness etc. [1], [2], [3]. Nevertheless, the capacity fading of LiMn2O4 is a deadly obstacle which limits its commercial use. The reasons of the spinel LiMn2O4 capacity fade were mainly included the following several factors: (1) the dissolution of Mn3+, (2) the Jahn–Teller distortion effect, (3) the decomposition of electrolyte [4], [5], [6]. To restrict the Jahn–Teller distortion effect, the partial substitutions of Mn by other cations, such as Ni2+ [7], [8], Si4+ [9], [10], Mg2+ [11], [12], Cu2+ [13], [14], Al3+ [15], [16] and Zn2+ [17], [18] have been studied and single doped or multiple doped has been proposed as an effective way to inhibit capacity fading upon cycling. Among these materials, the single Zn2+ ion doped LiMn2O4 were studied only by a few researchers [18], [19], [20]. Zn2+ doped spinel LiMn2O4 with improved cycling stability was reported that Gummow et al. [18]. Ein-Eli et al. [19] synthesized the LiZnxMn2−xO4 (x=0, 0.25 and 0.5) by sol–gel method and Zn doped spinel LiZn0.25Mn1.75O4 delivered discharge capacity of 70 mA h g−1 during the first cycle. Arumugam et al. [20] prepared spinel LiZnxMn2−xO4 (x=0.00–0.15) by sol–gel technique using succinic acid as the chelating agent, and among them Zn doped spinel LiZn0.10Mn1.90O4 has improved the structural stability, high reversible capacity and excellent electrochemical performance of rechargeable lithium batteries. The initial discharge capacities for LiZn0.10Mn1.90O4 is 117 mA h g−1 at 1 C, and the capacity retention reached 58% after 100 cycles. To the best of our knowledge, no reports are available in the literature about the Zn-doped LiMn2O4 prepared via solution combustion route.
In this work, LiZnxMn2−xO4 (x≤0.10) cathode materials were produced by solution combustion method, and the structural, morphology and performance of the spinel LiZnxMn2−xO4 materials were studied in detail.
Section snippets
Experimental
The spinel LiZnxMn2−xO4 (x=0, 0.02, 0.05, and 0.10) samples were prepared by H3NO3-assisted solution combustion method, and stoichiometric raw materials of LiNO3, Mn(CH3COO)2·4H2O and Zn(CH3COO)2·2H2O were weighted and placed into a 300 mL crucible. Then, the 9 mol L−1 nitric acid were added to the mixture. Finally, the mixture was heated in a muffle furnace at 600 °C for 3 h. LiZnxMn2−xO4 powders were obtained after cooling to room temperature. The electrode for electrochemical test was prepared by
Structure analysis
The XRD patterns of the LiZnxMn2−xO4 (x=0, 0.02, 0.05, and 0.10) samples presented in Fig. 1 exhibit the characteristic diffraction peaks of cubic spinel LiMn2O4 with the Fd3m space group (JCPDS, PDF 35-0782) corresponding to the eight crystal planes of (111), (311), (222), (400), (331), (511), (440) and (531). There is no significant difference in the crystal structure after Zn substitution. This indicates the addition of Zn does not change the spinel structure of LiMn2O4. However, a small
Conclusions
Zn-doped LiZnxMn2−xO4 powders were successfully synthesized via solution combustion method. The agglomeration of the samples decreased with increasing Zn content. LiZn0.05Mn1.95O4 produced by this method exhibited a capacity retention of 82.9% at a discharge rate of 1 C after 500 cycles, showing excellent cycling stability. LiZn0.05Mn1.95O4 showed good reversibility and a high peak current in electrochemical studies, which are favorable for electrodes in LIBs. Electrochemical impedance
Acknowledgments
This work was financially supported by the National Natural Science Foundation of China (51262031, 51462036), Program for Innovative Research Team (in Science and Technology) in University of Yunnan Province (2011UY09), Yunnan Provincial Innovation Team (2011HC008), and Innovation Program of Yunnan Minzu University (2015TX09, 2015YJCXZ24, 2015YJCXZ21).
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2019, Ceramics InternationalCitation Excerpt :It can be found that the zinc-doping leads to the reduction of lattice parameter and shrinking of unit cell volume. This is principally because that the chemical bond of Zn-O possesses shorter bond length compared to the chemical bond of Mn-O [26]. As a result, the LiMn1.95Zn0.05O4 nanorods and LiMn1.95Zn0.05O4 particles can show more stable structural stability, which is beneficial for the performance optimization of LiMn2O4 [12,13,36].