We developed two-step solution-phase reactions to form hybrid materials of Mn3O4 nanoparticles on reduced graphene oxide (RGO) sheets for lithium ion battery applications. Mn3O4 nanoparticles grown selectively on RGO sheets over free particle growth in solution allowed for the electrically insulating Mn3O4 nanoparticles wired up to a current collector through the underlying conducting graphene network. The Mn3O4 nanoparticles formed on RGO show a high specific capacity up to ~900mAh/g near its theoretical capacity with good rate capability and cycling stability, owing to the intimate interactions between the graphene substrates and the Mn3O4 nanoparticles grown atop. The Mn3O4/RGO hybrid could be a promising candidate material for high-capacity, low-cost, and environmentally friendly anode for lithium ion batteries. Our growth-on-graphene approach should offer a new technique for design and synthesis of battery electrodes based on highly insulating materials.

Mn3O4-Graphene Hybrid as a High Capacity Anode Material for Lithium Ion Batteries

Energy storage devices that can deliver high powers have many applications, including hybrid vehicles and renewable energy. Much research has focused on increasing the power output of lithium batteries by reducing lithium-ion diffusion distances, but outputs remain far below those of electrochemical capacitors and below the levels required for many applications. Here, we report an alternative approach based on the redox reactions of functional groups on the surfaces of carbon nanotubes. Layer-by-layer techniques are used to assemble an electrode that consists of additive-free, densely packed and functionalized multiwalled carbon nanotubes. The electrode, which is several micrometres thick, can store lithium up to a reversible gravimetric capacity of approximately 200 mA h g(-1)(electrode) while also delivering 100 kW kg(electrode)(-1) of power and providing lifetimes in excess of thousands of cycles, both of which are comparable to electrochemical capacitor electrodes. A device using the nanotube electrode as the positive electrode and lithium titanium oxide as a negative electrode had a gravimetric energy approximately 5 times higher than conventional electrochemical capacitors and power delivery approximately 10 times higher than conventional lithium-ion batteries.

High-Power Lithium Batteries from Functionalized Carbon Nanotube Electrodes

Lithium-ion batteries have witnessed meteoric advancement the last two decades. The anode area has seen unprecedented research activity on Si and Sn, the two anode alternatives to currently used carbon following the initial seminal work by Fuji on tin oxide nanocomposites. Recent reports on silicon nanowires, porous Si, and amorphous Si coatings on graphite nanofibers (GNF) have been very encouraging. High capacity and long cycle life anodes are still, however, elusive and much needed to meet the ever increasing energy storage demands of modern society. Herein, we report for the first time the synthesis of novel 1D heterostructures comprising vertically aligned multiwall CNTs (VACNTs) containing nanoscale amorphous/nanocrystalline Si droplets deposited directly on VACNTs with clearly defined spacing using a simple two-step liquid injection CVD process. A hallmark of these single reactor derived heterostructures is an interfacial amorphous carbon layer anchoring the nanoscale Si clusters directly to the VACNTs. The defined spacing of nanoscale Si combined with their tethered CNT architecture allow for the silicon to undergo reversible electrochemical alloying and dealloying with Li with minimal loss of contact with the underlying CNTs. The novel heterostructures thus exhibit impressive reversible stable capacities approximately 2050 mAh/g with very good rate capability and an acceptable first cycle irreversible loss approximately 20% comparable to graphitic anodes indicating their promise as high capacity Li-ion anodes. Although warranting further research, particularly with regard to long-term cycling, it can be envisaged that optimization of this simple approach could lead to reversible high capacity next generation Li-ion anodes.

http://ma.ecsdl.org/content/MA2010-01/5/352.full.pdf

Nanostructured Hybrid Silicon/Carbon Nanotube Heterostructures: Novel Reversible High-Capacity Lithium-Ion Anodes

Lithium-ion batteries (LIBs), with relatively high energy density and power density, have been considered as a vital energy source in our daily life, especially in electric vehicles. However, energy density and safety related to thermal runaways are the main concerns for their further applications. In order to deeply understand the development of high energy density and safe LIBs, we comprehensively review the safety features of LIBs and the failure mechanisms of cathodes, anodes, separators and electrolyte. The corresponding solutions for designing safer components are systematically proposed. Additionally, the in situ or operando techniques, such as microscopy and spectrum analysis, the fiber Bragg grating sensor and the gas sensor, are summarized to monitor the internal conditions of LIBs in real time. The main purpose of this review is to provide some general guidelines for the design of safe and high energy density batteries from the views of both material and cell levels. Safety of lithium-ion batteries (LIBs) with high energy density becomes more and more important in the future for EVs development. The safety issues of the LIBs are complicated, related to both materials and the cell level. To ensure the safety of LIBs, in-depth understanding of the safety features, precise design of the battery materials and real-time monitoring/detection of the cells should be systematically considered. Here, we specifically summarize the safety features of the LIBs from the aspects of their voltage and temperature tolerance, the failure mechanism of the LIB materials and corresponding improved methods. We further review the in situ or operando techniques to real-time monitor the internal conditions of LIBs.

/pdf/building-safe-lithium-ion-batteries-for-electric-vehicles-a-35800kw1rs.pdf

Building Safe Lithium-Ion Batteries for Electric Vehicles: A Review

Rechargeable Na-based battery systems, including Na-ion batteries, room temperature Na–S, Na–O2, Na–CO2, and all-solid-state Na metal batteries, have attracted significant attention due to the high energy density, abundance, low cost, and suitable redox potential of Na metal However, the Na metal anode faces several challenges, including: (1) the formation of Na dendrites and short circuiting; (2) low Coulombic efficiency (CE) and poor cycling performance; and (3) an infinite volume change due to its hostless nature Furthermore, the issues associated with Na metal anodes have also been noticed in practical Na metal batteries (NMBs) In recent years, the importance of the Na metal anode has been highlighted and many studies have provided potential solutions to address the issues of its use This review article focuses on the recent developments of Na metal anodes, including insight into the fundamental understanding of its electrochemical processes, novel characterization methods, approaches for protecting the anode and future perspectives Our review will accelerate further improvement in the characterization and application of Na metal anodes for next-generation NMB systems

Recent developments and insights into the understanding of Na metal anodes for Na-metal batteries

Transformational changes in battery technologies are critically needed to enable the effective use of renewable energy sources, such as solar and wind, and to allow for the expansion of the electrification of vehicles. Developing high-performance batteries is critical to meet these requirements, which certainly relies on material breakthroughs. This review article presents the recent progresses and challenges in discovery of high-performance anode materials for Li-ion batteries related to their applications in future electrical vehicles and grid energy storage. The advantages and disadvantages of a series of anode materials are highlighted.

Yi Cui

Papers

High-Performance Anode Materials for Rechargeable Lithium-Ion Batteries