All-manganese-based Li-ion batteries with high rate capability and ultralong cycle life
Graphical abstract
An all-manganese-based Li-ion battery based on core–shell MnO@C nanowires and LiMn2O4 nanoparticles is constructed, and shows high energy density, high-rate capability and ultralong cycle life.
Introduction
Li-ion batteries (LIBs) have become one of the most important electrochemical energy storage technologies that show great promise as power sources in a broad application from portable electronics to electric vehicles [1], [2]. The current electrode materials used in commercial LIBs typically involve graphite anode and LiCoO2 cathode. However, both the conventional materials cannot meet the ever-growing demands of higher energy/power densities, lower cost, and safer operation for the next generation LIBs, because (i) the graphite anode suffers from a low theoretical capacity (372 mAh g−1), slow reaction kinetics, and safety issues due to its low discharge voltage (<0.2 V) that renders the possible formation of lithium dendrites; and (ii) the cobalt in the LiCoO2 cathode is expensive, of natural scarcity, and highly toxic [3], [4], [5]. Therefore, it is imperative to advance new LIBs with enhanced energy/power densities, low cost, natural abundance, non-toxicity, and improved safety and reliability [6].
Manganese belongs to a transition metal element that can constitute a myriad of promising chemical compounds for advanced LIB electrode materials. In particular, manganese-containing materials offer additional attractive characteristics of low cost, environmental benignity, rich abundance on earth, and high intrinsic mass density [7]. For example, LiMn2O4 is a promising cathode material that has a Li-ion storage capacity of 148 mAh g−1, high operating voltage, and high rate capability due to its three-dimensional (3D) spinel structure offering fast Li+ intercalation and deintercalation paths. It has been demonstrated that the electrochemical performance of LiMn2O4 strongly depends on the phase crystallinity, purity, particle size, and distribution [8], [9], [10], [11], [12]. Nanosized LiMn2O4 with high-quality crystallinity is believed to offer high power density and good cyclability due to its fast reaction kinetics and structural stability. With regard to the anode materials, manganese oxides (MnOx) possess a 2–4 times higher theoretical capacity than graphite and a lower discharge voltage (0.4–0.5 V vs. Li/Li+) compared with other transition metal oxides (e.g., CoOx, NiO, FeOx, etc.), enabling a higher energy density in full cells [13], [14]. However, MnOx faces two critical issues of poor electrical conductivity and large volumetric changes during Li+ insertion/extraction processes, thereby limiting its high power delivery capability and long-term cycling stability [15]. To mitigate these problems, incorporation of nanostructured MnOx into a conductive and elastic carbon matrix has been proven to be an effective and promising approach [16]. There are a considerable number of studies reporting MnOx/C nanostructures with improved performance in half cells [17], [18], [19], [20], [21], [22], [23], [24], [25], [26], but very few work paid their attention to the electrochemical properties when coupled with cathodes in full cell configurations [27], [28]. Surprisingly, these limited reports on full cells demonstrated a poor rate capability and short cycling endurance (250 cycles) which were attributed to the MnOx side in the full cells [27]. Therefore, it is of great interest yet challenge to develop all manganese-based LIBs that feature high capacity, high rate capability, long cycle life, as well as low cost, environmental friendliness, and safety.
In this work, we report a high-rate and long-cycle-life all-manganese-based Li-ion full cell using MnO@C core–shell nanowires as the anode and LiMn2O4 nanoparticles as the cathode. A rational and green approach has been developed to synthesize MnO@C core–shell nanowires with uniform carbon nanoshells and internal void spaces along the one-dimensional configuration, which permit the hybrid nanostructures to show a high specific capacity (~900 mAh g−1), excellent rate capability, and great cycle stability. The MnO@C anode is coupled to the high crystalline LiMn2O4 nanoparticle cathode to constitute a full LIB cell. Impressively, the MnO@C∥LiMn2O4 full cells can deliver a high energy density of 397 Wh kg−1, a high-rate performance at 13.5 C, and an exceptional low capacity decay rate of 0.087% per cycle over an extended cycling operation (1000 cycles).
Section snippets
Material synthesis
MnO2 nanowire: In a typical procedure, 2 mmol of KMnO4 and 2 mmol of NH4F were dissolved in 75 ml of deionized water to form a dark pink solution under magnetic stirring. Then the solution was transferred into a Teflon-lined stainless steel autoclave with 100 ml capacity. The autoclave was sealed and heated at 160 °C for 24 h. Black powders were collected after naturally cooling down to room temperature.
MnO@C nanowire: 100 mg of the as-prepared MnO2 powders were dispersed in 30 ml of deionized water.
MnO@C anode materials
As discussed earlier, the electrochemical performance of a full cell is closely associated with the MnOx anode materials. Although carbon coating strategy has been proven to be effective to address the critical issues of MnOx (i.e., a low electric conductivity and large volumetric variation), it is still a significant challenge to create a uniform carbon coating layer onto a MnOx matrix. Fig. 1(a) shows the schematic illustration of our unique synthesis protocol of MnO@C nanocomposites. Herein,
Conclusions
In summary, we have demonstrated the excellent electrochemical performance of the all-manganese-based LIB full cells constructed with the unique MnO/C core–shell nanowire anodes and the nanostructured LiMn2O4 cathodes. A facile interfacial polymerization strategy is applied to synthesize 1D MnO@C anode nanocomposites with uniform carbon shells and internal void spaces, which manifest a high and stable reversible capacity of 978 mAh g−1 after 100 cycles and a high-rate capacity of 356 mAh g−1 at 5000
Acknowledgments
The authors acknowledge the financial supports of this work by the National Natural Science Foundation of China (51402236, 51472204, 53102219, 51221001), the Natural Science Foundation of Shannxi Province (2015JM5180), the Fundamental Research Funds for the Central Universities (3102014JCQ01020 and 3102015BJ(II)MYZ02), the Research Fund of the State Key Laboratory of Solidification Processing (NWPU), China (Grant no.: 123-QZ-2015) and the Program of Introducing Talents of Discipline to
Dr. Jian-Gan Wang is currently an associate professor in the School of Materials Science and Engineering at Northwestern Polytechnical University. He received his Ph.D. degree in Materials Science from Tsinghua University in 2013. Then he joined in the Center for Nano Energy Materials. His research interests involve nanomaterial science and technology, especially for energy storage systems and photovoltaics.
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Dr. Jian-Gan Wang is currently an associate professor in the School of Materials Science and Engineering at Northwestern Polytechnical University. He received his Ph.D. degree in Materials Science from Tsinghua University in 2013. Then he joined in the Center for Nano Energy Materials. His research interests involve nanomaterial science and technology, especially for energy storage systems and photovoltaics.
Dandan Jin received her B.S. degree from Northwestern Polytechnical University in 2014, and she is now an M.S. candidate at Northwestern Polytechnical University. Her current research includes the development of nanostructured materials for energy storage.
Huanyan Liu received his B.S. degree from Qilu University in 2014, and he is now an M.S. candidate at Northwestern Polytechnical University. His research focuses on the synthesis of nanomaterials and composites for energy storage.
Cunbao Zhang received his B.S. degree from Zhengzhou University in 2013, and he is an M.S. candidate at Northwestern Polytechnical University. His primary research involves synthesizing nanomaterials for Li-ion batteries.
Rui Zhou received her B.S. degree from Northwestern Polytechnical University in 2015, and she is an M.S. candidate at Northwestern Polytechnical University. Her research interests are the development of nanomaterials for supercapacitors and Li-ion batteries.
Dr. Chao Shen received his Ph.D. degree in Metallurgical physical chemistry in 2015 from Central South University, China. He is currently an assistant professor at the State Key Laboratory of Solidification Processing and the School of Materials Science and Engineering at Northwestern Polytechnical University. His research focuses on Li-ion batteries and Na-ion batteries.
Dr. Keyu Xie received his Ph.D. degree in 2012 from Central South University, China. From 2010 to 2013, he stayed at Hong Kong Polytechnic University as a Research Assistant and Postdoctoral Research Associate successively. He is currently an associate professor at the State Key Laboratory of Solidification Processing and the School of Materials Science and Engineering at Northwestern Polytechnical University. His research interests include nano-materials and their application in energy storage and conversion devices, such as lithium batteries, supercapacitors, and solar cells.
Bingqing Wei is currently a Professor in the Department of Mechanical Engineering at the University of Delaware (UD). Before joining UD, he was an Assistant Professor in the Department of Electrical & Computer Engineering and Center for Computation & Technology at Louisiana State University. He had worked as a Post-doctorate Research Associate at Rensselaer Polytechnic Institute, Department of Materials Science and Engineering and Rensselaer Nanotechnology Center from 2000 to 2003. He was a visiting scientist for Max-Planck InstitutfurMetallforschung, Stuttgart, Germany in 1998 and 1999. From 1992 to 2001, he was a faculty member serving as an Associate Professor from 1994 to 2001 and Lecturer from 1992 to 1994 in the Department of Mechanical Engineering at Tsinghua University, Beijing, China. He has published more than 200 papers in refereed international journals, including Nature and Science, in his field of interest “Carbon Nanotubes and Nanotechnology”.