Utilization of Polycyclic Aromatic Solid Additives for Morphology and Thermal Stability Enhancement in Photoactive Layers of Organic Solar Cells.

Volatile solid additives have emerged as a promising strategy for enhancing film morphology and promoting the power conversion efficiency (PCE) of organic solar cells (OSCs). Herein, a series of novel polycyclic aromatic additives with analogous chemical structures, including fluorene (FL), dibenzothiophene (DBT), and dibenzofuran (DBF) derived from crude oils, are presented and incorporated into OSCs. All these additives exhibit strong interactions with the electron-deficient terminal groups of L8-BO within the bulk-heterojunction OSCs. Moreover, they demonstrate significant sublimation during thermal annealing, leading to increase free volumes for the rearrangement and recrystallization of L8-BO. This phenomenon leads to an improved film morphology and an elevated glass-transition temperature of the photoactive layers. Consequently, the PCE of the PM6:L8-BO blend has been boosted from 16.60% to 18.60% with 40 wt% DBF additives, with a champion PCE of 19.11% achieved for ternary PM6:L8-BO:BTP-eC9 OSCs. Furthermore, the prolonged shelf and thermal stability have been observed in OSCs with these additives. This study emphasizes the synergic effect of volatile solid additives on the performance and thermal stability of OSCs, highlighting their potential for advancing the field of photovoltaics.

Multi-Functional Solid Additive Induced Favorable Vertical Phase Separation and Ordered Molecular Packing for Highly Efficient Layer-by-Layer Organic Solar Cells.

Layer-by-layer (LBL) deposition strategy enabling favorable vertical phase distributions has been regarded as promising candidates for constructing high-efficient organic photovoltaic (OPV) cells. However, solid additives with the merits of good stability and reproducibility have been rarely used to fine-tune the morphology of the LBL films for improved efficiency and stability. Herein, hierarchical morphology control in LBL OPV is achieved via a dual functional solid additive. Series of LBL devices are fabricated by introducing the solid additive individually or simultaneously to the donor or acceptor layer to clarify the functions of additives. Additive in the donor layer can facilitate the formation of preferable vertical component distribution, and that in the acceptor layer will enhance the molecular crystallinity for better charge transport properties. The optimized morphology ultimately contributed to high PCEs of 16.4% and 17.4% in the binary and quaternary LBL devices. This reported method provides an alternative way to controllably manipulate the morphology of LBL OPV cells.

Predicting manure volatile solid output of lactating dairy cows.

Organic matter (OM) in livestock manure consisting of biodegradable and nonbiodegradable fractions is known as volatile solids (VS). According to the Intergovernmental Panel on Climate Change (IPCC) Tier 2 guidelines, methane produced by stored manure is determined based on VS. However, only biodegradable OM generates methane production. Therefore, estimates of biodegradable VS (dVS; dVS = VS - lignin) would yield better estimates of methane emissions from manure. The objective of the study was to develop mathematical models for estimating VS and dVS outputs of lactating dairy cows. Dry matter intake, dietary nutrient contents, milk yield and composition, body weight, and days in milk were used as potential predictor variables. Multicollinearity, model simplicity, and random study effects were taken into account during model development that used 857 VS and dVS measurements made on individual cows (kg/cow per day) from 43 metabolic trials conducted at the USDA Energy and Metabolism laboratory in Beltsville, Maryland. The new models and the IPCC Tier 2 model were evaluated with an independent data set including 209 VS and dVS measurements (kg/cow per day) from 2 metabolic trials conducted at the University of California, Davis. Organic matter intake (kg/d) and dietary crude protein and neutral detergent fiber contents (% of dry matter) were significantly associated with VS. A new model including these variables fitted best to data. When evaluated with independent data, the new model had a root mean squared prediction error as a percentage of average observed value (RMSPE) of 12.5%. Mean and slope biases were negligible at <1% of total prediction bias. When energy digestibility of the diet was assumed to be 67%, the IPCC Tier 2 model had a RMSPE of 13.7% and a notable mean bias for VS to be overpredicted by 0.4 kg/cow per day. A separate model including OM intake as well as dietary crude protein and neutral detergent fiber contents as predictor variables fitted best to dVS data and performed well on independent data (RMSPE = 12.7%). The Cornell Net Carbohydrate and Protein System model relying on fat-corrected milk yield and body weight more successfully predicted dry matter intake (DMI; RMSPE = 14.1%) than the simplified (RMSPE = 16.9%) and comprehensive (RMSPE = 23.4%) models to predict DMI in IPCC Tier 2 methodology. New models and the IPCC Tier 2 model using DMI from the Cornell Net Carbohydrate and Protein System model predicted VS (RMSPE = 17.7-19.4%) and dVS (RMSPE = 20%) well with small systematic bias (<10% of total bias). The present study offers empirical models that can accurately predict VS and dVS of dairy cows using routinely available data in dairy farms and thereby assist in efficiently determining methane emissions from stored manure.

Crossbreeding Effect of Chalcogenation and Iodination on Benzene Additives Enables Optimized Morphology and 19.68% Efficiency of Organic Solar Cells.

Volatile solid additives have attracted increasing attention in optimizing the morphology and improving the performance of currently dominated non-fullerene acceptor-based organic solar cells (OSCs). However, the underlying principles governing the rational design of volatile solid additives remain elusive. Herein, a series of efficient volatile solid additives are successfully developed by the crossbreeding effect of chalcogenation and iodination for optimizing the morphology and improving the photovoltaic performances of OSCs. Five benzene derivatives of 1,4-dimethoxybenzene (DOB), 1-iodo-4-methoxybenzene (OIB), 1-iodo-4-methylthiobenzene (SIB), 1,4-dimethylthiobenzene (DSB) and 1,4-diiodobenzene (DIB) are systematically studied, where the widely used DIB is used as the reference. The effect of chalcogenation and iodination on the overall property is comprehensively investigated, which indicates that the versatile functional groups provided various types of noncovalent interactions with the host materials for modulating the morphology. Among them, SIB with the combination of sulphuration and iodination enabled more appropriate interactions with the host blend, giving rise to a highly ordered molecular packing and more favorable morphology. As a result, the binary OSCs based on PM6:L8-BO and PBTz-F:L8-BO as well as the ternary OSCs based on PBTz-F:PM6:L8-BO achieved impressive high PCEs of 18.87%, 18.81% and 19.68%, respectively, which are among the highest values for OSCs.

Tackling Energy Loss in Organic Solar Cells via Volatile Solid Additive Strategy.

The energy loss induced open-circuit voltage (VOC) deficit hampers the rapid development of state-of-the-art organic solar cells (OSCs), therefore, it is extremely urgent to explore effective strategies to address this issue. Herein, a new volatile solid additive 1,4-bis(iodomethyl)cyclohexane (DIMCH) featured with concentrated electrostatic potential distribution is utilized to act as a morphology-directing guest to reduce energy loss in multiple state-of-art blend system, leading to one of highest efficiency (18.8%) at the forefront of reported binary OSCs. Volatile DIMCH decreases radiative/non-radiative recombination induced energy loss (ΔE2/ΔE3) by rationally balancing the crystallinity of donors and acceptors and realizing homogeneous network structure of crystal domain with reduced D-A phase separation during the film formation process and weakens energy disorder and trap density in OSCs. It is believed that this study brings not only a profound understanding of emerging volatile solid additives but also a new hope to further reduce energy loss and improve the performance of OSCs.

Intrinsic Role of Volatile Solid Additive in High-Efficiency PM6:Y6 Series Nonfullerene Solar Cells.

Organic nonfullerene solar cells (ONSCs) have made unprecedented progress; however, morphology optimization of ONSCs is proven to be particularly challenging relative to classical fullerene-based devices. Here, a novel volatile solid additive (VSA), 2-hydroxy-4-methoxybenzophenone (2-HM), is reported for achieving high-efficiency ONSCs. 2-HM functions as a universal morphology-directing agent for several well-known PM6:Y6 series nonfullerene blends, viz. PM6:Y6, PM6:BTP-eC9, PM6:L8-BO, leading to a best efficiency of 18.85% at the forefront of reported binary ONSCs. VSAs have recently emerged, while the intrinsic kinetics is still unclear. Herein, a set of in situ and ex situ characterizations is employed to first illustrate the molecule-aggregate-domain transition dynamic process assisted by the VSA. More specifically, the role of 2-HM in individual donor PM6 and acceptor Y6 systems is unlocked, and the function of 2-HM in altering the PM6:Y6 bulk heterojunction blends is further revealed for enhanced photovoltaic performance. It is believed that the achievement brings not only a deep insight into emerging volatile solid additive, but also a new hope to further improve the molecular ordering, film microstructure, and relevant performance of ONSCs.

Vertical Phase Regulation with 1,3,5-Tribromobenzene Leads to 18.5% Efficiency Binary Organic Solar Cells.

The sequential deposition method assists the vertical phase distribution in the photoactive layer of organic solar cells, enhancing power conversion efficiencies. With this film coating approach, the morphology of both layers can be fine-tuned with high boiling solvent additives, as frequently applied in one-step casting films. However, introducing liquid additives can compromise the morphological stability of the devices due to the solvent residuals. Herein, 1,3,5-tribromobenzene (TBB) with high volatility and low cost, is used as a solid additive in the acceptor solution and combined thermal annealing to regulate the vertical phase in organic solar cells composed of D18-Cl/L8-BO. Compared to the control cells, the devices treated with TBB and those that underwent additional thermal processing exhibit increased exciton generation rate, charge carrier mobility, charge carrier lifetime, and reduced bimolecular charge recombination. As a result, the TBB-treated organic solar cells achieve a champion power conversion efficiency of 18.5% (18.1% averaged), one of the highest efficiencies in binary organic solar cells with open circuit voltage exceeding 900 mV. This study ascribes the advanced device performance to the gradient-distributed donor-acceptor concentrations in the vertical direction. The findings provide guidelines for optimizing the morphology of the sequentially deposited top layer to achieve high-performance organic solar cells.

Process-Aid Solid Engineering Triggers Delicately Modulation of Y-Series Non-Fullerene Acceptor for Efficient Organic Solar Cells.

Volatile solids with symmetric π-backbone are intensively implemented on manipulating the nanomorphology for improving the operability and stability of organic solar cells. However, due to the isotropic stacking, the announced solids with symmetric geometry cannot modify the microscopic phase separation and component distribution collaboratively, which will constrain the promotion of exciton splitting and charge collection efficiency. Inspired by the superiorities of asymmetric configuration, a novel process-aid solid (PAS) engineering is proposed. By coupling with BTP core unit in Y-series molecule, an asymmetric, volatile 1,3-dibromo-5-chlorobenzene solid can induce the anisotropic dipole direction, elevated dipole moment, and interlaminar interaction spontaneously. Due to the synergetic effects on the favorable phase separation and desired component distribution, the PAS-treated devices feature the evident improvement of exciton splitting, charge transport, and collection, accompanied by the suppressed trap-assisted recombination. Consequently, an impressive fill factor of 80.2% with maximum power conversion efficiency (PCE) of 18.5% in the PAS-treated device is achieved. More strikingly, the PAS-treated devices demonstrate a promising thickness-tolerance character, where a record PCE of 17.0% is yielded in PAS devices with a 300 nm thickness photoactive layer, which represents the highest PCE for thick-film organic solar cells.

Optimization of operating parameters for biogas production using two-phase bench-scale anaerobic digestion of slaughterhouse wastewater: Focus on methanogenic step.

The objective of the present study was an optimization of operating parameters and the performance of the methanogenesis reactor in phased anaerobic digestion (AD) of slaughterhouse wastewater at 37.5°C. Accordingly, the feedstock of the methanogenic reactor was effluent from the hydrolytic-acidogenic reactor operating at HRT of 3-days and OLR of 1789 mg/L. The methanogenesis phase was also investigated at different hydraulic retention time (HRT) values ranging from 12 to 3 days at 3-day intervals, and organic loading rates (OLR) of 149, 199, 298, and 596 mg of COD/L. The methanogenesis reactor effluent concentrations of TN, TP, PO4- 3, SO4- 2, and S2- 2 were ranging between 424-464, 83-117, 63-86, 130-197, and 0.98-1.02 mg/L, respectively. The removal efficiencies of TN and TP were vary from 10-17% to 17-21%, respectively. The average biogas production was 125 ± 16, 150 ± 10, 185 ± 4, and 154 ± 17 mL at HRT of 12, 9, 6, and 3 days, respectively. Methane quality (%) and yield (mg/L of COD) were 55-67% and 0.02-0.03, respectively. Furthermore, the average stability indicator parameter values of (total volatile fatty acid (TVFA) = 520 ± 19 mg/L, total alkalinity (TotA) = 1424 ± 10 mg/L, TVFA:TotA. Ratio = 0.36, salinity = 1172 mg/L, pH = 6.92) and performance indicator parameters removal efficiency (RE) for (chemical oxygen demand (COD) = 81%, volatile solid (VS) RE = 95%, biogas production = 185 ± 4 mL, methane yield = 0.03 per mg COD consumed) were achieved at HRT of 6 days and OLR of 298 mg of COD/L. Low removal efficiencies of TP and TN at all HRT/OLR were observed for the methanogenic reactor signifying further treatment system.

Nutrient removal from digested swine wastewater by combining ammonia stripping with struvite precipitation.

Typical biological processing is often challenging for removing ammonia nitrogen and phosphate from swine wastewater due to inhibition of high ammonia on activity of microorganisms, exhaustion of time, and low efficiency. In this study, a physicochemical process by combining ammonia stripping with struvite precipitation has been tested to simultaneously remove ammonia nitrogen, phosphate, and chemical oxygen demand (COD) from digested swine wastewater (DSW) with high efficiency, low cost, and environmental friendliness. The pH, temperature, and magnesium content of DSW are the key factors for ammonia removal and phosphate recovery through combining stripping with struvite precipitation. MgO was used as the struvite precipitant for NH4+ and PO43- and as the pH adjusted for air stripping of residual ammonia under the condition of 40 °C and 0.48 m3 h-1 L-1 aeration rate for 3 h. The results showed that the removal efficiency of ammonia, total phosphate, and COD from DSW significantly increased with increase of MgO dosage due to synergistic action of ammonia stripping and struvite precipitation. Considering the processing cost and national discharge standard for DSW, 0.75 g L-1 MgO dosage was recommended using the combining technology for nutrient removal from DSW. In addition, 88.03% NH4+-N and 96.07% TP could be recovered from DSW by adsorption of phosphoric acid and precipitation of magnesium ammonium phosphate (MAP). The combined technology could effectively remove and recover the nutrients from DSW to achieve environmental protection and sustainable and renewable resource of DSW. An economic analysis showed that the combining technology for nutrient removal from DSW was feasible.

Influence of feedstock-to-inoculum ratio on performance and microbial community succession during solid-state thermophilic anaerobic co-digestion of pig urine and rice straw.

This study investigated the effect of the feedstock-to-inoculum (F/I) ratio on performance of the solid-state anaerobic co-digestion of pig urine and rice straw inoculated with a solid digestate, and clarified the microbial community succession. A 44-day biochemical methane potential test at F/I ratios of 0.5, 1, 2 and 3 at 55 °C and a 35-day large-scale batch test at F/I ratios of 0.5 and 3 at 55 °C were conducted to investigate the effects of F/I ratio on anaerobic digestibility and analyze microbial community succession, respectively. The highest cumulative methane yield was 353.7 m3/t VS in the large-scale batch test. Volatile fatty acids did not accumulate at any F/I ratios. The volatile solids reduction rate was highest at a F/I ratio of 0.5. Microbial community structures were similar between F/I ratios of 3 and 0.5, despite differences in digestion performance, suggesting that stable operation can be achieved at these ratios.

Artificial neural network based modeling to evaluate methane yield from biogas in a laboratory-scale anaerobic bioreactor.

The performance of a laboratory-scale anaerobic bioreactor was investigated in the present study to determine methane (CH4) content in biogas yield from digestion of organic fraction of municipal solid waste (OFMSW). OFMSW consists of food waste, vegetable waste and yard trimming. An organic loading between 40 and 120kgVS/m(3) was applied in different runs of the bioreactor. The study was aimed to focus on the effects of various factors, such as pH, moisture content (MC), total volatile solids (TVS), volatile fatty acids (VFAs), and CH4 fraction on biogas production. OFMSW witnessed high CH4 yield as 346.65LCH4/kgVS added. A target of 60-70% of CH4 fraction in biogas was set as an optimized condition. The experimental results were statistically optimized by application of ANN model using free forward back propagation in MATLAB environment.

The cumulative methane production from dairy cattle slurry can be explained by its volatile solid, temperature and length of storage.

In order to refine the national estimate of methane emission from stored cattle slurry, it is important to comprehend the basic characteristics of methane production. Two dairy cattle slurries were obtained from livestock farms located in Hokkaido (a northern island) and Kyushu (a southern island). The slurries were diluted with water into three levels: undiluted, three times diluted, and 10 times diluted. Three hundred mL of the slurries were put into a bottle with a headspace volume of 2.0 L, which was filled with nitrogen gas and then sealed by butyl rubber. Four levels of temperature were used for incubation: 35, 25, 15 and 5 °C. The time course of the cumulative methane production per volatile solid (VS) was satisfactorily expressed by an asymptotic regression model. The effect of dilution on the methane production per VS was not distinctive, but that of temperature was of primary importance. In particular, higher temperature yields a higher potential production and a shorter time when the cumulative production reaches half of the potential production. The inclusive and simple models obtained in this study indicate that the cumulative methane production from stored cattle slurry can be explained by VS, temperature and length of storage.

Biogas production from co-digestion of corn stover and chicken manure under anaerobic wet, hemi-solid, and solid state conditions.

Corn stover (CS) and chicken manure (CM) are ubiquitous agricultural wastes at low cost and have the potential to achieve a nutrient-balance when mixed together to produce biomethane via anaerobic digestion (AD). The main objective of this work was to investigate methane production at different CS to CM ratios and to evaluate the process stability under wet (W-AD), hemi-solid state (HSS-AD) and solid state (SS-AD) conditions. Results showed that synergistic effects were found when mixing two substrates at CS:CM ratios of 3:1 and 1:1 (on volatile solid basis). The highest methane yield of 218.8 mL/g VS added was achieved in W-AD at CS:CM ratio of 3:1. In SS-AD, the highest volumetric methane productivity of 14.2L methane/L reactor volume was found at CS:CM of 1:1. The results of this work provide useful information to improve the efficiency and stability of co-digestion of CS and CM under different AD conditions.