Zn Microbatteries Explore Ways for Integrations in Intelligent Systems.

As intelligent microsystems develop, many revolutionary applications, such as the swallowing surgeon proposed by Richard Feynman, are about to evolve. Nonetheless, integrable energy storage satisfying the demand for autonomous operations has emerged as a major obstacle to the deployment of intelligent microsystems. A reason for the lagging development of integrable batteries is the challenge of miniaturization through microfabrication procedures. Lithium batteries, generated by the most successful battery chemistry, are not stable in the air, thus creating major manufacturing challenges. Other cations (Na+ , Mg2+ , Al3+ , K+ ) are still in the early stages of development. In contrast, the superior stability of zinc batteries in the air brings high compatibility to microfabrication protocols and has already demonstrated excellent practicability in full-sized devices. To obtain energy-dense and high-power zinc microbatteries within square-millimeter or smaller footprints, sandwich, pillar, and Swiss-roll configurations are developed. Thin interdigital and fiber microbatteries find their applications being integrated into wearable devices and electronic skin. It is foreseeable that zinc microbatteries will find their way into highly integrated microsystems unlocking their full potential for autonomous operation. This review summarizes the material development, configuration innovation, and application-oriented integration of zinc microbatteries.

Highly Accessible Co-Nx Active Sites-Doped Carbon Framework with Uniformly Dispersed Cobalt Nanoparticles for the Oxygen Reduction Reaction in Alkaline and Neutral Electrolytes.

Porous carbon materials with nitrogen-coordinated transition metal active sites have been widely regarded as appealing alternatives to replace noble metal catalysts in oxygen-based electrochemical reaction activities. However, improving the electrocatalytic activity of transition-metal-based catalysts remains a challenge for widespread application in renewable devices. Herein, we use a simple one-step pyrolysis method to construct a Co nanoparticles/Co-Nx-decorated carbon framework catalyst with a near-total external surface structure and uniform dispersion nanoparticles, which displays promising catalytic activity and superior stability for oxygen reduction reactions in both alkaline and neutral electrolytes, as evidenced by the positive shift of half-wave potential by 44 and 11 mV compared to 20% Pt/C. Excellent electrochemical performance originates from highly accessible Co nanoparticles/Co-Nx active sites at the external surface structure (this is, exposing active sites). The thus-assembled liquid zinc-air battery using the synthesized electrocatalyst as the cathode material delivers a maximum power density of 178 mW cm-2 with an open circuit potential of 1.48 V and long-term discharge stability over 150 h.

Tungsten phosphide on nitrogen and phosphorus-doped carbon as a functional membrane coating enabling robust lithium-sulfur batteries.

Lithium-sulfur batteries (LSBs) hold great potential as future energy storage technology, but their widespread application is hampered by the slow polysulfide conversion kinetics and the sulfur loss during cycling. In this study, we detail a one-step approach to growing tungsten phosphide (WP) nanoparticles on the surface of nitrogen and phosphorus co-doped carbon nanosheets (WP@NPC). We further demonstrate that this material provides outstanding performance as a multifunctional separator in LSBs, enabling higher sulfur utilization and exceptional rate performance. These excellent properties are associated with the abundance of lithium polysulfide (LiPS) adsorption and catalytic conversion sites and rapid ion transport capabilities. Experimental data and density functional theory calculations demonstrate tungsten to have a sulfophilic character while nitrogen and phosphorus provide lithiophilic sites that prevent the loss of LiPSs. Furthermore, WP regulates the LiPS catalytic conversion, accelerating the Li-S redox kinetics. As a result, LSBs containing a polypropylene separator coated with a WP@NPC layer show capacities close to 1500 mAh/g at 0.1C and coulombic efficiencies above 99.5 % at 3C. Batteries with high sulfur loading, 4.9 mg cm-2, are further produced to validate their superior cycling stability. Overall, this work demonstrates the use of multifunctional separators as an effective strategy to promote LSB performance.

Microbiologically induced calcite precipitation for in situ stabilization of heavy metals contributes to land application of sewage sludge.

Microbiologically induced calcite precipitation (MICP) has shed new light on solving the problem of in situ stabilization of heavy metals (HMs) in sewage sludge before land disposal. In this study, we examined whether MICP treatment can be integrated into a sewage sludge anaerobic digestion-land application process. Our results showed that MICP treatment not only prevented the transfer of ionic-state Cd from the sludge to the supernatant (98.46 % immobilization efficiency) but also reduced the soluble exchangeable Pb and Cd fractions by up to 100 % and 48.54 % and increased the residual fractions by 22.54 % and 81.77 %, respectively. In addition, the analysis of the stability of HMs in MICP-treated sludge revealed maximum reductions of 100 % and 89.56 % for TCLP-extractable Pb and Cd, respectively. Three-dimensional fluorescence, scanning electron microscopy-energy-dispersive X-ray spectroscopy, X-ray diffraction, and Fourier-transform infrared spectroscopy analyses confirmed the excellent performance of the ureolytic bacteria Sporosarcina ureilytica ML-2 in the sludge system. High-throughput sequencing showed that the relative abundance of Sporosarcina sp. reached 53.18 % in MICP-treated sludge, and the urease metabolism functional genes unit increased by a maximum of 239.3 %. The MICP technology may be a feasible method for permanently stabilizing HMs in sewage sludge before land disposal.

Performance evaluation of H2S and NH3 removal by biological trickling filter reactors with various fillers under heterotrophic conditions.

A pilot-scale biological trickling filter (BTF) reactor (13.5 L) packed with different fillers (Pine bark, Cinder, Straw, and MBBR (mobile bed biofilm reactor) filler was employed to evaluate their removal performance of H2S and NH3 after heterotrophic bacterium addition, and some parameters, including different packing heights, empty bed residence time (EBRT), inlet titers, loading ratios, and restart trial, were investigated in this study. According to the experimental results, BTF filled with pine bark exhibited better removal efficiency than other reactors under a variety of conditions. The removal efficiency of H2S and NH3 reached to as high as 81.31 % and 91.72 %, respectively, with the loading range of 3.29-67.70 g/m3·h. Moreover, due to the addition of heterotrophic bacterium, the removal efficiency was enhanced and capable to eliminate majority of H2S and NH3 even though the packing height was reduced to 400 mm. After 15 days of idle, the BTF reactor was able to resume rapidly and execute deodorization with high efficiency. The degradation mechanism was further explored by a thorough examination of microbial species which degraded contaminants, as well as by functional prediction and correlation analyses. In a word, these results laid a foundation for the application of heterotrophic microorganisms in BTF, which could improve the removal efficiency of biological deodorization.

Nitrogen removal characteristics of efficient heterotrophic nitrification-aerobic denitrification bacterium and application in biological deodorization.

A heterotrophic nitrifying aerobic denitrifying (HN-AD) strain HY-1 with excellent capacity, identified as Paracoccus denitrificans, was isolated from activated sludge. HY-1 was capable of removing NH4+, NO2-, and NO3- with the corresponding rate of 17.33 mg-N L-1 h-1, 21.83 mg-N L-1 h-1, and 32.37 mg-N L-1 h-1, as well as the mixture of multiple nitrogen sources. Meanwhile, HY-1 could execute denitrification function under anaerobic conditions with a rate of 14.56 mg-N L-1 h-1. HY-1 required less energy investment, which exhibited average denitrification rate of 5.19 mg-N L-1 h-1 at carbon-nitrogen ratio was 1. After nitrification-denitrification metabolic pathway analysis, HY-1 was applied in a biological trickling filter reactor for compost deodorization. The results showed that adding of HY-1 greatly reduced the ionic concentration of NH4+ and NO3- in the circulating liquid without impairing the deodorization effect (NH3 removal rate＞98.07%). These findings extend the field of application of HN-AD and provide new insights for biological deodorization.

Platinum nanoparticles on defect-rich nitrogen-doped hollow carbon as an efficient electrocatalyst for hydrogen evolution reactions.

Design and synthesis of efficient electrocatalysts with low usage of precious metal and of high stability are essential for their practical applications in hydrogen evolution reactions. In this work, we synthesize an electrocatalyst through the deposition of platinum nanoparticles on defect-rich nitrogen-doped hollow carbon derived from surface-attached poly(4-vinylpyridine) monolayers. The platinum nanoparticles with an average diameter of about 1.8 nm are well dispersed on the outer surface of the pre-synthesized carbon material and the platinum loading is about 8.6 wt%. The mass activity of the as-synthesized catalyst under an overpotential of 55 mV is about 5.0 A mgPt -1, about 4.93 times higher than that of commercial Pt/C catalysts. Moreover, the synthesized catalyst is also more electrochemically stable than commercial Pt/C catalysts as evidenced by continuous cyclic voltammetry and chronoamperometric response measurements.

Self-Templating Synthesis of Hollow Co3O4 Nanoparticles Embedded in N,S-Dual-Doped Reduced Graphene Oxide for Lithium Ion Batteries.

The design and synthesis of hollow-nanostructured transition metal oxide-based anodes is of great importance for long-term operation of lithium ion batteries. Herein, we report a two-step calcination strategy to fabricate hollow Co3O4 nanoparticles embedded in a N,S-co-doped reduced graphene oxide framework. In the first step, core-shell-like Co@Co3O4 embedded in N,S-co-doped reduced graphene oxide is synthesized by pyrolysis of a Co-based metal organic framework/graphene oxide precursor in an inert atmosphere at 800 °C. The designed hollow Co3O4 nanoparticles with an average particle size of 25 nm and wall thickness of about 4-5 nm are formed by a further calcination process in air at 250 °C via the nanoscale Kirkendall effect. Both micropores and mesopores are generated in the HoCo3O4/NS-RGO framework. Benefiting from the hierarchical porous structure of the hollow Co3O4 and the co-doping of nitrogen and sulfur atoms in reduced graphene oxide, the thus-assembled battery exhibits a high specific capacity of 1590 mAh g-1 after 600 charge-discharge cycles at 1 A g-1 and a promising rate performance from 0.2 to 10 A g-1.

A general method to fabricate MoO3/C composites and porous C for asymmetric solid-state supercapacitors.

MoO3 is one of the most promising electrodes for high energy density supercapacitors due to its layered structure, which facilitates the insertion/removal of small ions. However, the commercial recognition of MoO3-based electrodes has been hampered by their low electronic conductivity, poor structural stability and narrow working potential window. A MoO3/C composite (MCs) has been synthesized by a polymerization method followed by calcination of the obtained hydrogel. The obtained MCs electrode exhibits remarkable electrochemical performance in both aqueous (432.5 F g-1 at a current density of 0.5 A g-1, 100% capacity retention after 10 000 cycles) and all-solid (220.5 F g-1 at 0.5 A g-1) systems with porous C as the positive electrode, demonstrating its potential in commercial utilization.