Greatly Enhanced Thermoelectric Performance of Flexible Cu2-xS Composite Film on Nylon by Se Doping.

In this work, flexible Cu2-xS films on nylon membranes are prepared by combining a simple hydrothermal synthesis and vacuum filtration followed by hot pressing. The films consist of Cu2S and Cu1.96S two phases with grain sizes from nano to submicron. Doping Se on the S site not only increases the Cu1.96S content in the Cu2-xS to increase carrier concentration but also modifies electronic structure, thereby greatly improves the electrical properties of the Cu2-xS. Specifically, an optimal composite film with a nominal composition of Cu2-xS0.98Se0.02 exhibits a high power factor of ~150.1 µW m-1 K-2 at 300 K, which increases by ~138% compared to that of the pristine Cu2-xS film. Meanwhile, the composite film shows outstanding flexibility (~97.2% of the original electrical conductivity is maintained after 1500 bending cycles with a bending radius of 4 mm). A four-leg flexible thermoelectric (TE) generator assembled with the optimal film generates a maximum power of 329.6 nW (corresponding power density of 1.70 W m-2) at a temperature difference of 31.1 K. This work provides a simple route to the preparation of high TE performance Cu2-xS-based films.

Largely Enhanced Thermoelectric Performance of Flexible Ag2Se Film by Cationic Doping and Dual-Phase Engineering.

Recent studies have shown that silver selenide is a promising thermoelectric material at room temperature. Herein, flexible films with a nominal composition of (Ag1-xCux)2Se are prepared by a simple and efficient one-pot method combined with vacuum-assisted filtration and hot pressing. The thermoelectric properties of the films are regulated by both cationic doping and a dual-phase strategy via a wet chemical method. As the x increases, not only Cu is doped into the Ag2Se, but different new phases (CuAgSe and/or CuSe2) also appear. The (Ag1-xCux)2Se film with x = 0.02 composed of Cu-doped Ag2Se and CuAgSe shows a high PF of ∼2540 µW m-1 K-2 (ZT ∼ 0.90) and outstanding flexibility at room temperature. The high thermoelectric properties of the film are due to the effect of Cu doping and the CuAgSe phase, including the increase in electrical conductivity caused by doping, the enhanced phonon scattering at the Ag2Se/CuAgSe interface, and the interaction between the energy filtering effect and the doping effect. In addition to the high output performance (PDmax = 28.08 W m-2, ΔT = 32.2 K), the flexible device assembled with the (Ag0.98Cu0.02)2Se film also has potential applications as a temperature sensor.

Largely Enhanced Thermoelectric Power Factor of Flexible Cu2-xS Film by Doping Mn.

Copper-sulfide-based materials have attracted noteworthy attention as thermoelectric materials due to rich elemental reserves, non-toxicity, low thermal conductivity, and adjustable electrical properties. However, research on the flexible thermoelectrics of copper sulfide has not yet been reported. In this work, we developed a facile method to prepare flexible Mn-doped Cu2-xS films on nylon membranes. First, nano to submicron powders with nominal compositions of Cu2-xMnyS (y = 0, 0.01, 0.03, 0.05, 0.07) were synthesized by a hydrothermal method. Then, the powders were vacuum-filtrated on nylon membranes and finally hot-pressed. Phase composition and microstructure analysis revealed that the films contained both Cu2S and Cu1.96S, and the size of the grains was ~20-300 nm. By Mn doping, there was an increase in carrier concentration and mobility, and ultimately, the electrical properties of Cu2-xS were improved. Eventually, the Cu2-xMn0.05S film showed a maximum power factor of 113.3 µW m-1 K-2 and good flexibility at room temperature. Moreover, an assembled four-leg flexible thermoelectric generator produced a maximum power of 249.48 nW (corresponding power density ~1.23 W m-2) at a temperature difference of 30.1 K, and had good potential for powering low-power-consumption wearable electronics.

Field investigation of temporal variation and diffusion of hydrogen sulfide on waste working face and intermediate landfill cover.

This paper presents the study on the variation, influencing factors and diffusion regularity of hydrogen sulfide (H2S) concentration and surface flux on the working face and intermediate geomembrane cover of a landfill. Field investigations were conducted using static chambers at a large-scale municipal solid waste landfill in Hangzhou, China, from January 2019 to June 2021. The analytical models of H2S transport in the working face and intermediate cover were developed to investigate the surface flux under various conditions. The CALPUFF model was used to demonstrate the diffusion path. The H2S surface flux on the working face ranged from 7.1 × 10-3 to 1.7 mg/m2/h, whereas the range was found to be 1.5 × 10-4 to 0.9 mg/m2/h on the intermediate geomembrane cover. This observation indicated that the geomembrane can reduce H2S emissions. In addition, the H2S surface fluxes at the HDPE GMB seams and near the gas collecting wells were generally 1-2 orders of magnitude larger than that in the intact GMB. The analytical model estimates that the intact GMB exhibits a diffusion coefficient of H2S ranging from 2.7 × 10-11 to 2.2 × 10-10 m2/s. However, the diffusion coefficient increases significantly to a range of 3.3 × 10-11-9.8 × 10-7 m2/s on the GMB seams. According to CALPUFF results, only the H2S diffusion from the working face had areas exceeding the standard concentration.

Gas transport in landfill cover system: A critical appraisal.

Landfill gas (LFG) emission is gaining more attention from the scientific fraternity and policymakers recently due to its threat to the atmosphere and human health of the populace living in surrounding premises. Though landfill cover (LFC) (viz., daily, intermittent and final cover) is widely used by landfill operators to mitigate or reduce these emissions, their overall performance is still under question. A critical analysis of available literature, primarily pertaining to (i) the composition of the landfill gases and their migration in the LFC system, (ii) experimental and mathematical investigations of the transport mechanism of gas and (iii) the impact of additives to cover soils on transport and fate of gas, has been conducted and presented in this manuscript. Investigation of the efficiency of modified soil was mainly focused on laboratory test. More field tests and application of amended cover soils should be conducted and promoted further. Studies on nitrous oxide and emerging pollutants, including poly-fluoroalkyl substances transport in landfill cover system are limited and need further research. The transport mechanisms of these unconventional contaminants should be considered regarding the selection of LFC materials including geomembrane and geosynthetic clay liners. The existing analytical and numerical models can provide a basic understanding of LFG transport mechanisms and are able to predict the migration behaviour of LFG; however, there are still knowledge gaps concerning the interaction between different species of the gas molecule when modeling multi-component gas transport. Gas transport through fractured cover should also be considered when evaluating LFG emission in the future. Simplified design method for landfill cover system regarding LFG emission based on analytical models should be proposed. Overall, mathematical models combined with experiments can facilitate more visualized and intensive insights, which would be instrumental in devising climate adaptive landfill covers.

Numerical model for static chamber measurement of multi-component landfill gas emissions and its application.

The quantitative assessment of landfill gas emissions is essential to assess the performance of the landfill cover and gas collection system. The relative error of the measured surface emission of landfill gas may be induced by the static flux chamber technique. This study aims to quantify effects of the size of the chamber, the insertion depth, pressure differential on the relative errors by using an integrated approach of in situ tests, and numerical modeling. A field experiment study of landfill gas emission is conducted by using a static chamber at one landfill site in Xi'an, Northwest China. Additionally, a two-dimensional axisymmetric numerical model for multi-component gas transport in the soil and the static chamber is developed based on the dusty-gas model (DGM). The proposed model is validated by the field data obtained in this study and a set of experimental data in the literature. The results show that DGM model has a better capacity to predict gas transport under a wider range of permeability compared to Blanc's method. This is due to the fact that DGM model can explain the interaction among gases (e.g., CH4, CO2, O2, and N2) and the Knudsen diffusion process while these mechanisms are not included in Blanc's model. Increasing the size and the insertion depth of static chambers can reduce the relative error for the flux of CH4 and CO2. For example, increasing the height of chambers from 0.55 to 1.1 m can decrease relative errors of CH4 and CO2 flux by 17% and 18%, respectively. Moreover, we find that gas emission fluxes for the case with positive pressure differential (∆Pin-out) are greater than that of the case without considering pressure fluctuations. The Monte Carlo method was adopted to carry out the statistical analysis for quantifying the range of relative errors. The agreement of the measured field data and predicted results demonstrated that the proposed model has the capacity to quantify the emission of landfill gas from the landfill cover systems.

Thermoelectric performance of nanostructured In/Pb codoped SnTe with band convergence and resonant level prepared via a green and facile hydrothermal method.

SnTe is considered as a promising alternative to the conventional high-performance thermoelectric material PbTe, which inspired the thermoelectric community for a while. Here, we design a green, facile and low-energy-intensity hydrothermal route without involving any toxic or unstable chemicals to fabricate SnTe-based thermoelectric materials. Ultralow lattice thermal conductivity and enhanced thermoelectric performance are achieved via the combination of band engineering and nanostructuring. Enhanced Seebeck coefficient and power factor are induced by converging the band structure and creating resonant levels due to Pb and In doping. More importantly, due to the reduced grain sizes, nanoparticles, and dual-atom point defect scattering, ultralow lattice thermal conductivity was obtained in the bulk samples fabricated by the hydrothermal route. Benefiting from the enhanced power factor and significantly reduced thermal conductivity, the peak ZT is enhanced to ∼0.7 in In/Pb codoped SnTe, a 60% improvement over pure SnTe.

Field investigation of temporal variation of volatile organic compounds at a landfill in Hangzhou, China.

Variation of volatile organic compound (VOC) concentration and composition in an active landfill were monitored by a developed static chamber for 2 years. The landfill gas from 82 sampling points including 70 points on working face, 8 points on geomembrane (GMB), and 4 points on final cover were analyzed for VOCs by GC-MS. Twenty-eight types of VOCs were detected, including terpenes, sulfur compounds, aromatics, hydrocarbon, oxygenated compounds, aldehyde compounds, and halogenated compounds. Terpenes were the dominant VOCs recorded in the spring, autumn, and winter seasons, whereas sulfur compounds dominated in the summer season. Limonene, ethyl alcohol, and acetone were identified as the main VOCs emitted from the waste working face of the landfill. Limonene dominated the terpenes with a maximum concentration of 43.29 µg m-3 in the autumn season. Limonene was also the dominant VOC escaping from the defects of geomembrane temporary cover reaching an average concentration 38 µg m-3. The defects of geomembranes can be a great emission source of VOCs. Emission rate of limonene was 2.24 times higher than that on the working face. VOC concentrations on the final cover can be 166 times less than those obtained on the working face. VOC emitted from the landfill did not represent a health threat for human health. However, concentrations of methyl mercaptan and ethanethiol on the working face were 3.4-22.8 times greater than their odor threshold, which were the main compounds responsible for odor nuisance. Results obtained from CALPUFF model indicated that methyl mercaptan and ethanethiol would not be a nuisance for the residents around the landfill. However, these compounds are harmful to the workers on the landfill.

Methane hotspot localization and visualization at a large-scale Xi'an landfill in China: Effective tool for landfill gas management.

The variation characteristics and influence factors of methane emission at Jiangchungou landfill, one of the largest landfill in China, has been investigated by a one-year field monitoring campaign during 2015-2016. The methane concentration above the landfill surface varied widely from negligible to 33,975 ppm. At least 75% of the methane concentration values of the sampling points are lower than the allowed limit (500 ppm). More than 95% of the high concentration zones (>500 ppm) were located in the temporary cover area (TA). Several environmental factors were found to be related to the variation of the concentration values. A clear correlation was observed between barometric pressure and exceeding-standard areas with a correlation coefficient of -0.743 (p < 0.1). The concentration values in the final cover area (FA) were about one order of magnitude lower than those observed in the TA due to the fact that rapid methane production rate happened in the first 180 days after the high kitchen content wastes were landfilled. The percentages of the measured concentration values exceeding 500 ppm near the gas collection wells in TA zone were 71.5% in November, 2015 and 55.7% in January, 2016 due to the leakage from the sides of gas collection wells. The average methane concentration values on the HDPE geomembrane was higher than those observed on the loess cover due to the fact that the geomembrane was relatively thin (0.5 mm) and can be easily damaged by the operation vehicles. Thicker geomembranes (>1.5 mm) with a good construction quality control are expected to provide better performance at this site.