LiCoPO4 cathode from a CoHPO4·xH2O nanoplate precursor for high voltage Li-ion batteries.

A highly crystalline LiCoPO4/C cathode material has been synthesized without noticeable impurities via a single step solid-state reaction using CoHPO4·xH2O nanoplate as a precursor obtained by a simple precipitation route. The LiCoPO4/C cathode delivered a specific capacity of 125 mAhg(-1) at a charge/discharge rate of C/10. The nanoplate precursor and final LiCoPO4/C cathode have been characterized using X-ray diffraction, thermogravimetric analysis - differential scanning calorimetry (TGA-DSC), transmission electron microscopy (TEM), and scanning electron microscopy (SEM) and the electrochemical cycling stability has been investigated using different electrolytes, additives and separators.

Toward the design of high voltage magnesium-lithium hybrid batteries using dual-salt electrolytes.

We report a design of high voltage magnesium-lithium (Mg-Li) hybrid batteries through rational control of the electrolyte chemistry, electrode materials and cell architecture. Prototype devices with a structure of Mg-Li/LiFePO4 (LFP) and Mg-Li/LiMn2O4 (LMO) have been investigated. A Mg-Li/LFP cell using a dual-salt electrolyte 0.2 M [Mg2Cl2(DME)4][AlCl4]2 and 1.0 M LiTFSI exhibits voltages higher than 2.5 V (vs. Mg) and a high specific energy density of 246 W h kg(-1) under conditions that are amenable for practical applications. The successful demonstrations reported here could be a significant step forward for practical hybrid batteries.

Controlling porosity in lignin-derived nanoporous carbon for supercapacitor applications.

Low-cost renewable lignin has been used as a precursor to produce porous carbons. However, to date, it has not been easy to obtain high surface area porous carbon without activation processes or templating agents. Here, we demonstrate that low molecular weight lignin yields highly porous carbon with more graphitization through direct carbonization without additional activation processes or templating agents. We found that molecular weight and oxygen consumption during carbonization are critical factors to obtain high surface area, graphitized porous carbons. This highly porous carbon from low-cost renewable lignin sources is a good candidate for supercapacitor electrode materials.

Chemically bonded phosphorus/graphene hybrid as a high performance anode for sodium-ion batteries.

Room temperature sodium-ion batteries are of great interest for high-energy-density energy storage systems because of low-cost and natural abundance of sodium. Here, we report a novel phosphorus/graphene nanosheet hybrid as a high performance anode for sodium-ion batteries through facile ball milling of red phosphorus and graphene stacks. The graphene stacks are mechanically exfoliated to nanosheets that chemically bond with the surfaces of phosphorus particles. This chemical bonding can facilitate robust and intimate contact between phosphorus and graphene nanosheets, and the graphene at the particle surfaces can help maintain electrical contact and stabilize the solid electrolyte interphase upon the large volume change of phosphorus during cycling. As a result, the phosphorus/graphene nanosheet hybrid nanostructured anode delivers a high reversible capacity of 2077 mAh/g with excellent cycling stability (1700 mAh/g after 60 cycles) and high Coulombic efficiency (>98%). This simple synthesis approach and unique nanostructure can potentially be applied to other phosphorus-based alloy anode materials for sodium-ion batteries.

Multi-electron redox reaction of an organic radical cathode induced by a mesopore carbon network with nitroxide polymers.

An organic radical based composite cathode comprised of poly(2,2,6,6-tetramethylpiperidinyloxy-4-yl methacrylate) (PTMA)-Ketjenblack was developed by a simple solvent-less electrode fabrication method. The composite cathode demonstrated a two-electron redox reaction of PTMA that is from an aminoxy anion (n-type) via a radical to an oxoammonium cation (p-type) with the corresponding redox potential at 2.8-3.1 V and 3.5-3.7 V vs. Li/Li(+) when evaluated in lithium half cells. Moreover, the PTMA-Ketjenblack composite electrode exhibits fast electrode reaction kinetics and an enhanced solid electrolyte interface by cyclic voltammetry and electrochemical impedance spectroscopy measurements. These improved electrochemical properties contribute to increased capacity (300 mA h g(-1)), a high rate (50% capacity retention after 100 C rate excursions) and a long cycle life in the cell performance evaluations. Morphological and compositional characterization indicates a unique mesopore network of Ketjenblack with the PTMA matrix, which highly facilitates the interaction between the conductive media and the radical species, resulting in the performance enhancement of the PTMA-Ketjenblack composite cathode.

Catalytic templating approaches for three-dimensional hollow carbon/graphene oxide nano-architectures.

We report a catalytic templating method to synthesize well-controlled three-dimensional carbon nano-architectures. Depending on graphene oxide content, the morphology can be systematically tuned from layered composites to 3D hollow structures to microporous materials. The composites with high surface area and high porosity induce a significant enhancement to its capacitance at high current density.

Anthraquinone with tailored structure for a nonaqueous metal-organic redox flow battery.

A nonaqueous, hybrid metal-organic redox flow battery based on tailored anthraquinone structure is demonstrated to have an energy efficiency of ~82% and a specific discharge energy density similar to those of aqueous redox flow batteries, which is due to the significantly improved solubility of anthraquinone in supporting electrolytes.

High-performance LiNi0.5Mn1.5O4 spinel controlled by Mn3+ concentration and site disorder.

The complex correlation between Mn(3+) ions and the disordered phase in the lattice structure of high voltage spinel, and its effect on the charge transport properties, are revealed through a combination of experimental study and computer simulations. Superior cycling stability is achieved in LiNi(0.45)Cr(0.05)Mn(1.5)O(4) with carefully controlled Mn(3+) concentration. At 250th cycle, capacity retention is 99.6% along with excellent rate capabilities.

Electrochemical performances of LiMnPO4 synthesized from non-stoichiometric Li/Mn ratio.

In this paper, the influences of the lithium content in the starting materials on the final performances of as-prepared Li(x)MnPO(4) (x hereafter represents the starting Li content in the synthesis step which does not necessarily mean that Li(x)MnPO(4) is a single phase solid solution in this work.) are systematically investigated. It has been revealed that Mn(2)P(2)O(7) is the main impurity when Li < 1.0 while Li(3)PO(4) begins to form once x > 1.0. The interactions between Mn(2)P(2)O(7) or Li(3)PO(4) impurities and LiMnPO(4) are studied in terms of the structural, electrochemical, and magnetic properties. At a slow rate of C/50, the reversible capacity of both Li(0.5)MnPO(4) and Li(0.8)MnPO(4) increases with cycling. This indicates a gradual activation of more sites to accommodate a reversible diffusion of Li(+) ions that may be related to the interaction between Mn(2)P(2)O(7) and LiMnPO(4) nanoparticles. Among all of the different compositions, Li(1.1)MnPO(4) exhibits the most stable cycling ability probably because of the existence of a trace amount of Li(3)PO(4) impurity that functions as a solid-state electrolyte on the surface. The magnetic properties and X-ray absorption spectroscopy (XAS) of the MnPO(4)·H(2)O precursor, pure and carbon-coated Li(x)MnPO(4) are also investigated to identify the key steps involved in preparing a high-performance LiMnPO(4).

In situ transmission electron microscopy observation of microstructure and phase evolution in a SnO2 nanowire during lithium intercalation.

Recently we have reported structural transformation features of SnO(2) upon initial charging using a configuration that leads to the sequential lithiation of SnO(2) nanowire from one end to the other (Huang et al. Science2010, 330, 1515). A key question to be addressed is the lithiation behavior of the nanowire when it is fully soaked into the electrolyte (Chiang Science2010, 330, 1485). This Letter documents the structural characteristics of SnO(2) upon initial charging based on a battery assembled with a single nanowire anode, which is fully soaked (immersed) into an ionic liquid based electrolyte using in situ transmission electron microscopy. It has been observed that following the initial charging the nanowire retained a wire shape, although highly distorted. The originally straight wire is characterized by a zigzag structure following the phase transformation, indicating that during the phase transformation of SnO(2) + Li ↔ Li(x)Sn + Li(y)O, the nanowire was subjected to severe deformation, as similarly observed for the case when the SnO(2) was charged sequentially from one end to the other. Transmission electron microscopy imaging revealed that the Li(x)Sn phase possesses a spherical morphology and is embedded into the amorphous Li(y)O matrix, indicating a simultaneous partitioning and coarsening of Li(x)Sn through Sn and Li diffusion in the amorphous matrix accompanied the phase transformation. The presently observed composite configuration gives detailed information on the structural change and how this change takes place on nanometer scale.

LiMnPO4 nanoplate grown via solid-state reaction in molten hydrocarbon for Li-ion battery cathode.

Electrochemically active LiMnPO(4) nanoplates have been synthesized via a novel, single-step, solid-state reaction in molten hydrocarbon. The olivine-structured LiMnPO(4) nanoplates with a thickness of approximately 50 nm appear porous and were formed as nanocrystals were assembled and grew into nanorods along the [010] direction in the (100) plane. After carbon coating, the prepared LiMnPO(4) cathode demonstrated a flat potential at 4.1 V versus Li with a specific capacity reaching as high as 168 mAh/g under a galvanostatic charging/discharging mode, along with an excellent cyclability.

Ternary self-assembly of ordered metal oxide-graphene nanocomposites for electrochemical energy storage.

Surfactant or polymer directed self-assembly has been widely investigated to prepare nanostructured metal oxides, semiconductors, and polymers, but this approach is mostly limited to two-phase materials, organic/inorganic hybrids, and nanoparticle or polymer-based nanocomposites. Self-assembled nanostructures from more complex, multiscale, and multiphase building blocks have been investigated with limited success. Here, we demonstrate a ternary self-assembly approach using graphene as fundamental building blocks to construct ordered metal oxide-graphene nanocomposites. A new class of layered nanocomposites is formed containing stable, ordered alternating layers of nanocrystalline metal oxides with graphene or graphene stacks. Alternatively, the graphene or graphene stacks can be incorporated into liquid-crystal-templated nanoporous structures to form high surface area, conductive networks. The self-assembly method can also be used to fabricate free-standing, flexible metal oxide-graphene nanocomposite films and electrodes. We have investigated the Li-ion insertion properties of the self-assembled electrodes for energy storage and show that the SnO2-graphene nanocomposite films can achieve near theoretical specific energy density without significant charge/discharge degradation.

Self-assembled TiO2-graphene hybrid nanostructures for enhanced Li-ion insertion.

We used anionic sulfate surfactants to assist the stabilization of graphene in aqueous solutions and facilitate the self-assembly of in situ grown nanocrystalline TiO2, rutile and anatase, with graphene. These nanostructured TiO2-graphene hybrid materials were used for investigation of Li-ion insertion properties. The hybrid materials showed significantly enhanced Li-ion insertion/extraction in TiO2. The specific capacity was more than doubled at high charge rates, as compared with the pure TiO2 phase. The improved capacity at high charge-discharge rate may be attributed to increased electrode conductivity in the presence of a percolated graphene network embedded into the metal oxide electrodes.

EQCM immunoassay for phosphorylated acetylcholinesterase as a biomarker for organophosphate exposures based on selective zirconia adsorption and enzyme-catalytic precipitation.

A zirconia (ZrO(2)) adsorption-based immunoassay by electrochemical quartz crystal microbalance (EQCM) has been initially developed, aiming at the detection of phosphorylated acetylcholinesterase (Phospho-AChE) as a potential biomarker for bio-monitoring exposures to organophosphate (OP) pesticides and chemical warfare agents. Hydroxyl-derivatized monolayer was preferably chosen to modify the crystal serving as the template for directing the electro-deposition of ZrO(2) film with uniform nanostructures. The resulting ZrO(2) film was utilized to selectively capture Phospho-AChE from the sample media. Horseradish peroxidase (HRP)-labeled anti-AChE antibodies were further employed to recognize the captured phosphorylated proteins. Enzyme-catalytic oxidation of the benzidine substrate resulted in the accumulation of insoluble product on the functionalized crystal. Ultrasensitive EQCM quantification by mass-amplified frequency responses as well as rapid qualification by visual color changes of product could be thus, achieved. Moreover, 4-chloro-1-naphthol (CN) was studied as an ideal chromogenic substrate for the enzyme-catalytic precipitation. Experimental results show that the developed EQCM technique can allow for the detection of Phospho-AChE in human plasma with a detection limit of 0.020 nM. Such an EQCM immunosensing format opens a new door towards the development of simple, sensitive, and field-applicable biosensor for biologically monitoring low-level OP exposures.

Direct detection of Pb in urine and Cd, Pb, Cu, and Ag in natural waters using electrochemical sensors immobilized with DMSA functionalized magnetic nanoparticles.

Urine is universally recognized as one of the best non-invasive matrices for biomonitoring exposure to a broad range of xenobiotics, including toxic metals. Detection of metal ions in urine has been problematic due to the protein competition and electrode fouling. For direct, simple, and field-deployable monitoring of urinary Pb, electrochemical sensors employing superparamagnetic iron oxide (Fe3O4) nanoparticles with a surface functionalization of dimercaptosuccinic acid (DMSA) has been developed. The metal detection involves rapid collection of dispersed metal-bound nanoparticles from a sample solution at a magnetic or electromagnetic electrode, followed by the stripping voltammetry of the metal in acidic medium. The sensors were evaluated as a function of solution pH, the binding affinity of Pb to DMSA-Fe3O4, the ratio of nanoparticles per sample volume, preconcentration time, and Pb concentrations. The effect of binding competitions between the DMSA-Fe3O4 and urine constituents for Pb on the sensor responses was studied. After 90 s of preconcentration in samples containing 25 vol.% of rat urine and 0.1 g L(-1) of DMSA-Fe3O4, the sensor could detect background level of Pb (0.5 ppb) and yielded linear responses from 0 to 50 ppb of Pb, excellent reproducibility (%RSD of 5.3 for seven measurements of 30 ppb Pb), and Pb concentrations comparable to those measured by ICP-MS. The sensor could also simultaneously detect background levels (<1 ppb) of Cd, Pb, Cu, and Ag in river and seawater.

Nanostructured calcium phosphates for biomedical applications: novel synthesis and characterization.

Materials play a key role in several biomedical applications, and it is imperative that both the materials and biological aspects are clearly understood for attaining a successful biological outcome. This paper illustrates our approach to implement calcium phosphates as gene delivery agents. Calcium phosphates (CaP) belong to the family of biocompatible apatites and there are several CaP phases, the most ubiquitous being hydroxyapatite (HAp, Ca(10)(PO(4))(6)(OH)(2). Other CaP structures include brushite (B, CaHPO(4).2H(2)O) and tricalcium phosphate (TCP, Ca(3)(PO(4))(2)). Several low and high temperature approaches have been reported for synthesizing HAp and brushite, while TCP is primarily synthesized using high temperature methods. Novel low temperature chemical methods have been developed by us to synthesize nanostructured HAp, brushite and TCP phases. The new low temperature approach results in the formation of stoichiometric and nanosized HAp under physiological conditions. Moreover, the synthesis methods were designed to be biocompatible with biological systems such as cells, DNA and proteins so that the CaP structures can be studied for gene delivery. The use of HAp type CaP phases for gene delivery is well known but to our knowledge, other forms of CaP have not been studied for gene delivery due to the lack of a biocompatible synthesis method. In addition to the biocompatible synthesis of CaP structures, we have also performed ion substitution that would provide us the appropriate tools to study the DNA-to-particle interactions and assess how these ionic substitutions would affect the level of DNA uptake by the cell and then its release to the cell nucleus. Substitution of calcium by 14% magnesium results in the formation of crystalline ( approximately 20 mum) brushite platelets that remains stable at pH 7.5. Further substitution results in unique nanostructured spherical morphologies of brushite from which rosette shaped high specific surface area ( approximately 200 m(2)/g) nanocrystals ( approximately 80 nm) of beta-TCMP phase can be grown. The novelty lies in the formation of stable phases of HAp, brushite and beta-TCMP under physiological conditions making them potential candidates for use as carriers for non-viral gene delivery or more generally in biological systems. The resultant nanocrystalline phosphates have been characterized for their structure, morphology, thermal stability, and composition. Results of the in vitro transfection are also described.