Xiqing Wang

Highly Active, Nonprecious Metal Perovskite Electrocatalysts for Bifunctional Metal-Air Battery Electrodes.

Perovskites are of great interest as replacements for precious metals and oxides used in bifunctional air electrodes involving the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). Herein, we report the synthesis and activity of a phase-pure nanocrystal perovskite catalyst that is highly active for the OER and ORR. The OER mass activity of LaNiO3, synthesized by the calcination of a rapidly dried nanoparticle dispersion and supported on nitrogen-doped carbon, is demonstrated to be nearly 3-fold that of 6 nm IrO2 and exhibits no hysteresis during oxygen evolution. Moreover, strong OER/ORR bifunctionality is shown by the low total overpotential (1.02 V) between the reactions, on par or better than that of noble metal catalysts such as Pt (1.16 V) and Ir (0.92 V). These results are examined in the context of surface hydroxylation, and a new OER cycle is proposed that unifies theory and the unique surface properties of LaNiO3.

Reviving rechargeable lithium metal batteries: enabling next-generation high-energy and high-power cells

Herein reported is a fundamentally new strategy for reviving rechargeable lithium (Li) metal batteries and enabling the emergence of next-generation safe batteries featuring a graphene-supported Li metal anode, including the highly promising Li–sulfur, Li–air, and Li–graphene cells with exceptionally high energy or power densities. All the Li metal anode-based batteries suffer from a high propensity to form Li dendrites (tree-like structures) at the anode upon repeated discharges/charges. A dendrite could eventually penetrate through the separator to reach the cathode, causing internal short-circuiting and even explosion, the main reason for the battery industry to abandon rechargeable lithium metal batteries in the early 1990s. By implementing graphene sheets to increase the anode surface areas, one can significantly reduce the anode current density, thereby dramatically prolonging the dendrite initiation time and decreasing the growth rate of a dendrite, if ever initiated, possibly by a factor of up to 1010 and 105, respectively.

Preparation of activated mesoporous carbons for electrosorption of ions from aqueous solutions

Mesoporous carbon with a narrow pore size distribution centered at about 9 nm, which was prepared by self assembly of block copolymer and phloroglucinol-formaldehyde resin via the soft-template method, was activated by CO2 and potassium hydroxide (KOH). The effects of activation conditions, such as the temperature, activation time, and mass ratio of KOH/C, on the textural properties of the resulting activated mesoporous carbons were investigated. Activated mesoporous carbons exhibit high BET specific surface areas (up to ∼ 2000 m2 g−1) and large pore volumes (up to ∼ 1.6 cm3 g−1), but still maintain a highly mesoporous structure. Heat treatment of mesoporous carbons by CO2 generally requires a moderate to high extent of activation in order to increase its BET surface area by 2–3 times, while KOH activation needs a much smaller degree of activation than the former to reach an identical surface area, ensuring high yields of activated mesoporous carbons. In addition, KOH activation allows a controllable degree of activation by adjusting the mass ratio of KOH/C (2–8), as evidenced by the fact that surface area and pore volume increase with the mass ratio of KOH/C. The electrosorption properties of activated mesoporous carbons were investigated by cyclic voltammetry in 0.1 M NaCl aqueous solutions. Upon activation, the electrosorption capacitance of activated mesoporous carbons was greatly enhanced.

Hybrid MnO2–disordered mesoporous carbon nanocomposites: synthesis and characterization as electrochemical pseudocapacitor electrodes

MnO2–mesoporous carbon hybrid nanocomposites were synthesized to achieve high values of redox pseudocapacitance at scan rates of 100 mV s−1. High-resolution transmission electron microscopy (HRTEM) along with energy dispersive X-ray spectroscopy (EDX) demonstrated that ∼1 nm thick MnO2 nanodomains, resembling a conformal coating, were uniformly distributed throughout the mesoporous carbon structure. HRTEM and X-ray diffraction (XRD) showed formation of MnO2 nanocrystals with lattice planes corresponding to birnessite. The electrochemical redox pseudocapacitance of these composite materials in aqueous 1 M Na2SO4 electrolyte containing as little as 2 wt% MnO2 exhibited a high gravimetric MnO2 pseudocapacitance (CMnO2) of 560 F gMnO2−1. Even for 30 wt% MnO2, a high CMnO2 of 137 F gMnO2−1 was observed at 100 mV s−1. Sodium ion diffusion coefficients on the order of 10−9 to 10−10 cm2 s−1 were measured using chronoamperometry. The controlled growth and conformal coating of redox-active MnO2–mesoporous carbon composites offer the potential for achieving high power energy storage with low cost materials.

Nitrogen-enriched ordered mesoporous carbons through direct pyrolysis in ammonia with enhanced capacitive performance

Self-assembly of phenolic resins and a Pluronic block copolymer via the soft-template method enables the formation of well-organized polymeric mesostructures, providing an easy way for preparation of ordered mesoporous carbons (OMCs). However, direct synthesis of OMCs with high nitrogen content remains a significant challenge due to the limited availability of nitrogen precursors capable of co-polymerizing with phenolic resins without deterioration of the order of mesostructural arrangement and significant diminishment of nitrogen content during carbonization. In this work, we demonstrate pyrolysis of the soft-templated polymeric composites in ammonia as a direct, facile way towards nitrogen-enriched OMCs (N-OMCs). This approach does not require any nitrogen-containing carbon precursors or post-treatment, but takes advantage of the preferential reaction and/or replacement of oxygen with nitrogen species, generated by decomposition of ammonia at elevated temperatures, in oxygen-rich polymers during pyrolysis. It combines carbonization, nitrogen functionalization, and activation into one simple process, generating N-OMCs with a uniform pore size, large surface area (up to 1400 m2 g−1), and high nitrogen content (up to 9.3 at%). More importantly, the ordering of the meso-structure is well-maintained as long as the heating temperature does not exceed 800 °C, above which (e.g., 850 °C) a slight structural degradation is observed. When being used as electrode materials for symmetric electric double layer capacitors, N-OMCs demonstrate enhanced capacitance (6.8 μF cm−2vs. 3.2 μF cm−2) and reduced ion diffusion resistance compared to the non-NH3-treated sample.

High pseudocapacitance of MnO2 nanoparticles in graphitic disordered mesoporous carbon at high scan rates

Nanocomposites composed of MnO2 and graphitic disordered mesoporous carbon (MnO2/C) were synthesized for high total specific capacitance and redox pseudocapacitance (CMnO2) at high scan rates up to 200 mV s−1. High resolution transmission electron microscopy (HRTEM) with energy dispersive X-ray spectroscopy (EDX) demonstrated that MnO2 nanodomains were highly dispersed throughout the mesoporous carbon structure. According to HRTEM and X-ray diffraction (XRD), the MnO2 domains are shown to be primarily amorphous and less than 5 nm in size. For these composites in aqueous 1 M Na2SO4 electrolyte, CMnO2 reached 500 F/gMnO2 at 2 mV s−1 for 8.8 wt% MnO2. A capacitance fade of only 20% over a 100-fold change in scan rate was observed for a high loading of 35 wt% MnO2 with a CMnO2 of 310 F/gMnO2 at the highest scan rate of 200 mV s−1. The high electronic conductivity of the graphitic 3D disordered mesoporous carbon support in conjunction with the thin MnO2 nanodomains facilitate rapid electron and ion transport offering the potential of improved high power density energy storage pseudocapacitors.

Molecular-Sieving Capabilities of Mesoporous Carbon Membranes

The size-sieving properties of a mesoporous carbon membrane were studied via molecular permeation and cyclic voltammetry experiments. Two phenomena, simple diffusion and electrochemically aided diffusion, were investigated. Molecular diffusion through the membrane was caused by a concentration gradient across the membrane and was facilitated by electrosorption of ions under an externally applied electric field. The diffusion of molecules transported through the membrane was characterized by the values of permeability and apparent diffusion coefficient in the membrane. Because larger molecules are more restricted in terms of penetrating the pores, the size-based selectivity of the mesoporous carbon membrane could be readily observed. For example, in the two-component permeation experiment, a high selectivity (alpha=56.9) of anilinium over Rhodamine B was found. It is inferred that the diffusive transport of the larger Rhodamine B molecules with a more extensive retardation comes from the competitive mechanism between the two kinds of molecules in accessing the pore. A series of voltammetric experiments involving a mesoporous carbon membrane immersed in various electrolytes with ions of different sizes allowed the observation of ion-exclusion phenomena. It was found that the size effect is significant for electrochemically aided diffusion and electrosorption processes. The number of cations inside the pores of the membrane decreases with increasing cation size. This phenomenon is due to the size-exclusion effect, which could be demonstrated by the values of electrical double-layer capacitance for sodium, magnesium, and tetrahexylammonium cations, at potentials ranging from negative values to the point of zero charge, corresponding to 86.7, 73.1, and 50.0 F/g, respectively. The findings of this work manifest that the relationship between the pore size and the dimensions of the molecules determines the transport and sorption behavior of nanoporous carbon materials.