Srinivasan Madhavi

Constructing Hierarchical Spheres from Large Ultrathin Anatase TiO2 Nanosheets with Nearly 100% Exposed (001) Facets for Fast Reversible Lithium Storage

Synthesis of nanocrystals with exposed high-energy facets is a well-known challenge in many fields of science and technology. The higher reactivity of these facets simultaneously makes them desirable catalysts for sluggish chemical reactions and leads to their small populations in an equilibrated crystal. Using anatase TiO(2) as an example, we demonstrate a facile approach for creating high-surface-area stable nanosheets comprising nearly 100% exposed (001) facets. Our approach relies on spontaneous assembly of the nanosheets into three-dimensional hierarchical spheres, which stabilizes them from collapse. We show that the high surface density of exposed TiO(2) (001) facets leads to fast lithium insertion/deinsertion processes in batteries that mimic features seen in high-power electrochemical capacitors.

Formation of Fe2O3 microboxes with hierarchical shell structures from metal-organic frameworks and their lithium storage properties.

Fe(2)O(3) microboxes with hierarchically structured shells have been synthesized simply by annealing Prussian blue (PB) microcubes. By utilizing simultaneous oxidative decomposition of PB microcubes and crystal growth of iron oxide shells, we have demonstrated a scalable synthesis of anisotropic hollow structures with various shell architectures. When evaluated as an anode material for lithium ion batteries, the Fe(2)O(3) microboxes with a well-defined hollow structure and hierarchical shell manifested high specific capacity (~950 mA h g(-1) at 200 mA g(-1)) and excellent cycling performance.

Assembling carbon-coated α-Fe2O3 hollow nanohorns on the CNT backbone for superior lithium storage capability

Novel hierarchical nanostructures composed of carbon coated α-Fe2O3 hollow nanohorns on carbon nanotube (CNT) backbones have been constructed by direct growth and thermal transformation of β-FeOOH nanospindles on CNTs, followed by carbon nanocoating. When evaluated as a potential anode material for lithium-ion batteries, such hierarchical structures exhibit superior lithium storage capabilities by virtue of their advantageous structural features.

Insertion-Type Electrodes for Nonaqueous Li-Ion Capacitors

Vanchiappan Aravindan,*,† Joe Gnanaraj,*,‡ Yun-Sung Lee,* and Srinivasan Madhavi*,†,∥ †Energy Research Institute @ NTU (ERI@N), Nanyang Technological University, Research Techno Plaza, 50 Nanyang Drive, Singapore 637553, Singapore ‡Yardney Technical Products, Inc., 2000 South County Trail, East Greenwich, Rhode Island 02818, United States Faculty of Applied Chemical Engineering, Chonnam National University, Gwang-ju 500-757, Korea School of Materials Science and Engineering, Nanyang Technological University, Singapore 639798, Singapore

LiMnPO4 – A next generation cathode material for lithium-ion batteries

Development of an eco-friendly, low cost and high energy density (∼700 W h kg−1) LiMnPO4 cathode material became attractive due to its high operating voltage ∼4.1 V vs. Li falling within the electrochemical stability window of conventional electrolyte solutions and offers more safety features due to the presence of a strong P–O covalent bond. The vacancy formation energy for LiMnPO4 was 0.19 eV higher than that for LiFePO4, resulting in a 10−3 times-diluted complex concentration, which represents the main difference between the kinetics in the initial stage of charging of two olivine materials. This review highlights the overview of current research activities on LiMnPO4 cathodes in both native and substituted forms along with carbon coating synthesized by various synthetic techniques. Further, carbon coated LiMnPO4 was also prepared by a solid-state approach and the obtained results are compared with previous literature values. The challenges and the need for further research to realize the full performance of LiMnPO4 cathodes are described in detail.

Engineering nonspherical hollow structures with complex interiors by template-engaged redox etching

Despite the significant advancement in making hollow structures, one unsolved challenge in the field is how to engineer hollow structures with specific shapes, tunable compositions, and desirable interior structures. In particular, top-down engineering the interiors inside preformed hollow structures is still a daunting task. In this work, we demonstrate a facile approach for the preparation of a variety of uniform hollow structures, including Cu(2)O@Fe(OH)(x) nanorattles and Fe(OH)(x) cages with various shapes and dimensions by template-engaged redox etching of shape-controlled Cu(2)O crystals. The composition can be readily modulated at different structural levels to generate other interesting structures such as Cu(2)O@Fe(2)O(3) and Cu@Fe(3)O(4) rattles, as well as Fe(2)O(3) and Fe(3)O(4) cages. More remarkably, this strategy enables top-down engineering the interiors of hollow structures as demonstrated by the fabrication of double-walled nanorattles and nanoboxes, and even box-in-box structures. In addition, this approach is also applied to form Au and MnO(x) based hollow structures.

Lithium-ion conducting electrolyte salts for lithium batteries

This paper presents an overview of the various types of lithium salts used to conduct Li(+) ions in electrolyte solutions for lithium rechargeable batteries. More emphasis is paid towards lithium salts and their ionic conductivity in conventional solutions, solid-electrolyte interface (SEI) formation towards carbonaceous anodes and the effect of anions on the aluminium current collector. The physicochemical and functional parameters relevant to electrochemical properties, that is, electrochemical stabilities, are also presented. The new types of lithium salts, such as the bis(oxalato)borate (LiBOB), oxalyldifluoroborate (LiODFB) and fluoroalkylphosphate (LiFAP), are described in detail with their appropriate synthesis procedures, possible decomposition mechanism for SEI formation and prospect of using them in future generation lithium-ion batteries. Finally, the state-of-the-art of the system is given and some interesting strategies for the future developments are illustrated.

3D micro-porous conducting carbon beehive by single step polymer carbonization for high performance supercapacitors: the magic of in situ porogen formation

We report non-templated synthesis of interconnected microporous carbon (IMPC) sheets having beehive morphology by direct pyrolysis of poly(acrylamide-co-acrylic acid) potassium salt in inert atmosphere without any activation. The presence of the alkali metal in the selected polymer precursor results in a high specific surface area of 1327 m2 g−1. Importantly, 80% of the pore volume is contributed by micropores with pore size ranging from 1–2 nm which is ideal for use as an electrode for supercapacitors. Whereas the rest of the surface area was contributed by a small fraction of mesopores and macropores due to the interconnected structure. The presence of three different types of pores make the material ideal for supercapacitor electrodes. IMPC was tested as an electrode in both aqueous and non-aqueous supercapacitors. All the aqueous measurements were done in 1 M H2SO4 solution with a potential window 1 V. A specific capacitance of 258 F g−1 was realized at a constant charge–discharge current of 0.5 A g−1 and it maintained at a value of 150 F g−1 at 30 A g−1. A long cycle stability of 90% capacitance retention was observed after 5000 charge–discharge cycles at a current density of 2 A g−1. At the highest power density 13 600 W kg−1 the energy density was found to be 3.1 W h kg−1. Non aqueous performance was tested in the presence of 1 M LiPF6 in ethylene carbonate–di-methyl carbonate with 5 mg active material loading. A specific capacitance of 138 F g−1 was obtained at a current density of 0.25 A g−1 and it retained at a value of 100 F g−1 at 10 A g−1. The material can deliver an energy density of 31 W h kg−1 at its highest power density of 11 000 W kg−1 in a two electrode system based on active material loading.

CuO nanostructures supported on Cu substrate as integrated electrodes for highly reversible lithium storage

Arrays of CuO nanostructures, including nanorods and nanosheets, supported on a Cu substrate have been rationally fabricated from their morphology-controlled Cu(2)(OH)(3)NO(3) precursors by thermal annealing. The as-prepared CuO samples can be directly used as integrated electrodes for lithium-ion batteries without the addition of other ancillary materials such as carbon black or a binder to enhance electrode conductivity and cycling stability. The unique nanostructural features endower them excellent electrochemical performance as demonstrated by high capacities of 450-650 mAh g(-1) at 0.5-2 C and almost 100% capacity retention over 100 cycles after the second cycle.

Activated carbons derived from coconut shells as high energy density cathode material for Li-ion capacitors

In this manuscript, a dramatic increase in the energy density of ~ 69 Wh kg−1 and an extraordinary cycleability ~ 2000 cycles of the Li-ion hybrid electrochemical capacitors (Li-HEC) is achieved by employing tailored activated carbon (AC) of ~ 60% mesoporosity derived from coconut shells (CS). The AC is obtained by both physical and chemical hydrothermal carbonization activation process, and compared to the commercial AC powders (CAC) in terms of the supercapacitance performance in single electrode configuration vs. Li. The Li-HEC is fabricated with commercially available Li4Ti5O12 anode and the coconut shell derived AC as cathode in non-aqueous medium. The present research provides a new routine for the development of high energy density Li-HEC that employs a mesoporous carbonaceous electrode derived from bio-mass precursors.