Chemical Degradation Mechanisms Research Articles

An example of a wastewater treatment project for high concentrations of benzene, xylene, acetophenone, and DOPO generated in the production of phosphorus flame retardant

ABSTRACT Wastewater generated in the production of phosphorus flame retardants contains benzene, xylene, acetophenone, and 9, 10-dihydro-9-oxa-10-phosphoxanthine-10-oxide (DOPO) with larger benzene rings, which are more difficult to biodegrade directly. In this study, the wastewater generated in the production of phosphorus flame retardants applied for high-temperature nylon and reactive phosphorus flame retardant was first treated by the combined process of lime emulsion–flocculation reaction and precipitation–ozone oxidation reaction for degradation of benzene, xylene, acetophenone, and DOPO, and then processed by the secondary combined process of upflow anaerobic sludge bed anaerobic digestion–air flotation–membrane bioreactor bio-contact oxidation; thus, the final concentration of pollutants in the wastewater can reach the relevant limit either for external discharge or as the supplemental water for other production devices. In addition, the detailed chemical degradation mechanisms and removal effects of benzene, xylene, acetophenone, and DOPO in an ozone reactor were explored. After the project had been normally operated for half a year, the test results of the effluent were as follows: chemical oxygen demand, 50 mg/L; BOD5, 20 mg/L; NH3-N, 5.0 mg/L; total phosphorus, 0.5 mg/L; benzene ≤ 0.1 mg/L; xylene ≤ 0.4 mg/L; acetophenone ≤ 0.4 mg/L; and DOPO ≤ 0.02 mg/L. Ultimately, the cost was 2.1 $/m3. It provides a useful process for wastewater treatment related to phosphorus flame retardants.

Degradation of Polymer Materials in the Environment and Its Impact on the Health of Experimental Animals: A Review

The extensive use of polymeric materials has resulted in significant environmental pollution, prompting the need for a deeper understanding of their degradation processes and impacts. This review provides a comprehensive analysis of the degradation of polymeric materials in the environment and their impact on the health of experimental animals. It identifies common polymers, delineates their degradation pathways, and describes the resulting products under different environmental conditions. The review covers physical, chemical, and biological degradation mechanisms, highlighting the complex interplay of factors influencing these processes. Furthermore, it examines the health implications of degradation products, using experimental animals as proxies for assessing potential risks to human health. By synthesizing current research, the review focuses on studies related to small organisms (primarily rodents and invertebrates, supplemented by fish and mollusks) to explore the effects of polymer materials on living organisms and underscores the urgency of developing and implementing effective polymer waste management strategies. These strategies are crucial for mitigating the adverse environmental and health impacts of polymer degradation, thus promoting a more sustainable interaction between human activities and the natural environment.

Thermal Weathering of 3D-Printed Lunar Regolith Simulant Composites.

The production of lunar regolith composites is a promising venture, especially when enabled by extrusion-based additive manufacturing techniques such as direct ink write. However, both three-dimensional (3D) printing production and usage of polymer composites containing regolish on the lunar surface are challenges due to harsh environmental conditions such as severe thermal cycling. While thermal degradation in polymer composites under thermal cycling has been studied, there is limited understanding of how polymer properties impact the mechanical performance of lunar regolith composites when both printing and usage are carried out under extreme thermal conditions. Here, we aim to bridge that gap through the creation of composites containing a lunar Highlands regolith simulant suspended in an ultraviolet (UV) curable binder, which were printed at -30 °C and thermally cycled between weekly lunar day (127 °C) and weekly night (-190 °C) temperatures. We validate that thermal stresses cause both physical and chemical degradation since the regolith simulant composites become stiffer, more porous, and show yellowing after exposure to thermal cycling. Moreover, we indicate that chemical degradation mechanisms seem to compete with residual polymerization in certain formulations. We attribute this phenomenon to partial crystallization of monomer species during printing at -30 °C, resulting in low vinyl bond conversion during initial curing. The results presented here shed light on the intricate interplay between thermal stresses, uncured polymer properties, and degradation mechanisms, which can help guide future use cases of regolith composites for lunar infrastructure needs.

STEM Investigation of Structural and Chemical Degradation Mechanisms in Na-Based Batteries

STEM Investigation of Structural and Chemical Degradation Mechanisms in Na-Based Batteries

Comprehensive aging model coupling chemical and mechanical degradation mechanisms for NCM/C6-Si lithium-ion batteries

The aging of lithium-ion batteries (LIBs) is synergistically influenced by multiple chemical/mechanical degradation mechanisms. Therefore, conventional models that incorporate only partial mechanisms exhibit limited predictive accuracy and applicability, failing to fully reflect the effects of chemical/mechanical degradation under complex operating conditions. Here, we propose an aging model for NCM/C6-Si LIBs coupled with comprehensive chemical/mechanical degradation mechanisms. The model includes chemical mechanisms at the C6-Si anode solid electrolyte interface (SEI), Li plating, and NCM cathode electrolyte interface (CEI), as well as mechanical mechanisms of loss of active material (LAM) for C6, Si, and NCM. Based on this model, we comprehensively investigate the effect of capacity loss by (dis)charge rates and ambient temperatures, obtaining the aging characteristics and the contribution of each mechanism to loss under different variables. Furthermore, we quantitatively analyze the sensitivity and response characteristics of the degradation sub-mechanism to (dis)charge rate and temperature. This study introduces an advanced aging analysis model for NCM/C6-Si LIBs, which can effectively decouple the operational characteristics of the degradation mechanism and provide guidance for developing next-generation high-energy LIBs.

Theoretical Studies on the Chemical Degradation and Proton Dissociation Property of PBI used in High-Temperature Polymer Electrolyte Membrane Fuel Cells.

High-temperature polymer electrolyte membrane fuel cells (HT-PEMFCs) are gaining more and more attention due to their higher efficiency than low-temperature ones. Polybenzimidazole (PBI) membranes are the most popular membranes used in HT-PEMFCs. However, their chemical stability and chemical degradation mechanisms, which directly affect the lifetime of fuel cells, have been hardly reported. We applied the density functional theory and used ABPBI as an example membrane to investigate the chemical degradation mechanisms of PBI membranes. The possible degradation mechanisms that occurred on eight sites have been proposed, where sites 2 and 3 located on the phenyl ring are determined as two weak sites toward OH radical and oxygen molecule attack. When the terminal is the H atom at site 7, it is also weak under OH radical attack. Regarding these, the substituent effect on the chemical stability of polymers has been studied. By introducing four -C2F5 or -CN groups, the barrier heights of the corresponding degradation reactions are increased; thus, the chemical stabilities of related membranes are improved. The selection of terminal atoms was also explored for alleviating the chemical degradation of the membrane. The investigated proton transfer properties of nine model compounds revealed that introducing four -C2F5 or -CN groups improves the proton dissociation properties occurring at the cathode. The increase of phosphoric acid concentration is helpful for the proton transfer at both the membrane and the cathode. This work may hopefully help the design and synthesis of HT-PEMFCs with good stability and high efficiency.

The effects of crystal structure on the chemical durability of yttrium disilicate.

Amorphous, α, β, and γ-phase yttrium disilicate Y2Si2O7 pellets were synthesized by spark plasma sintering, and their chemical durability and degradation mechanisms were investigated via semi-dynamic leaching test in pH = 3 nitric acid at 90 °C. All crystalline phases displayed relatively congruent dissolution with a slight preferential release of Y. The amorphous sample showed clear incongruent dissolution with preferential release of Y, leading to a surface reorganization reaction and the formation of a SiO2 passivation layer 20-25 μm thick on the surface of the sample. This passivation layer led to a continuous decrease in the elemental release rates of the amorphous sample. The γ-phase sample displayed the lowest short-term and long-term leaching rates of Y and Si, followed by the β, α, and then amorphous sample. The crystalline samples showed increasing release rates over time indicating a dissolution-controlled reaction mechanism. Post-leaching microstructural characterization of the β and γ samples revealed variations in the corrosion levels of the surface grains, indicating a dependence on grain orientation.

(Invited) Challenges for Accelerating Life Testing of Commercial Lithium-Ion Batteries

Life testing of commercial lithium-ion batteries is critical for predicting lifetime, anticipating failure, and guaranteeing safe operation of real-world battery energy storage systems. The traditional method for conducting life testing is to use accelerated aging experiments, where stress factors such as temperature, charge/discharge rate, or daily charge-throughput are pushed to extremes to drive cell failure, while taking care not to induce degradation mechanisms that do not reflect real-world use. But even ‘accelerated’ aging tests generally require 6 months to several years of testing to reach end-of-life for the current generation of mass-produced lithium-ion batteries. So, many efforts have been made to accelerate ‘accelerated aging’ of commercial cells throughout the battery community. But it is critical to ensure that the results of invasive or novel accelerated life testing experiments match well with not only changes to the electrochemical performance of traditionally aged cells, but also that the impacts of physical or chemical degradation mechanisms are also well characterized.This work compares the results of a 2-year accelerated aging test conducted on 23 commercial large-format NMC-Gr cells with a variety of other accelerated life testing experiments. Coin-cell experiments using both full-cell and symmetric-cell configurations were used to study the microstructural changes and electrochemical behavior of both NMC and graphite electrodes, with the small format allowing for destructive characterization of many test replicates throughout cell lifetime; these experiments can be conducted more quickly than their large-format counterparts, and enable more detailed understanding of the degradation trajectory than the large-format test. However, difficulties in transferring electrochemical trends from the coin-cell format to the large-format cell will be discussed. In addition, cascading failure mechanisms observed in the large-format cells may not occur in coin-cells due to differences in the mechanical and thermal environment of each system. Implications for the design of small-format accelerated life testing using electrodes harvested from commercial batteries will be discussed. Calendar aging was accelerated by monitoring daily self-discharge and quantifying both reversible and irreversible capacity losses; challenges for making quantitative predictions from short-term calendar aging tests will be presented.

Stabilized Positive Electrode Material to Enable High Energy/Power Density Lithium-Ion Batteries

Recently, the large-scale deployment of electric vehicles (EVs) and stationary battery systems has putforward urgent requests for rechargeable batteries with higher energy/power density and longerlifespans. As such, next-generation Li-ion batteries (LiBs) are expected to meet these requirements. Thepossibility of using Ni-rich high-capacity cathode materials (NMC) can help to achieve that goal, however,they still suffer from significant capacity fade via several chemical and mechanical degradation modes.One is crack formation within secondary particles which leads to parasitic reactions that evolve oxygenand potentially initiate the formation of inactive crystal structures. LiBs mechanical and chemicaldegradation mechanisms can be extended by applying protective coatings to the cathode’s surface. Manystudies explore atomic layer deposition (ALD) for this purpose. However, the complementary molecularlayer deposition (MLD) technique might offer the benefit of depositing flexible hybrid coatings that canaccommodate potential volume changes of the electrode during the battery cycling. This study reportsthe deposition of novel organic-inorganic films via the ALD-MLD method. Characterization analysis suchas FTIR, XPS, SEM-EDS, and TEM confirmed the film deposition on the surface of the NMC electrode.Besides, the electrochemical results showed the enhancement of the coated electrode, as evidenced byproviding a longer life with a 93% capacity retention after 150 cycles (3.0-4.4 V vs. Li/Li+), while theuncoated one retained only 83% of its initial capacity. Moreover, in situ dilatometry showed irreversiblevolume change for uncoated NMC while it was mostly reversible for coated ones during the cycling. Itrevealed the dilation behavior of the electrode, resulting in crack formation, which is significantlysuppressed for the coated samples. Stable cycling of Ni-rich cathode materials in crucial conditions suchas high voltage windows and elevated temperatures is still extremely challenging. To evaluate this, in situdilatometry was performed at elevated temperatures (40 °C and 55 °C) and higher voltage ranges (3.0-4.6V). The results confirmed that in both conditions, the dilation behavior of the coated sample is still undercontrol while the capacity is comparable to the uncoated sample. This revealed that the coatings presentgood lithium-ion kinetics and reduce electrolyte decomposition. Overall, this work showed the liability ofthe ALD-MLD films deposited on NMC electrodes to mitigate the degradation mechanisms and providesinsight into a method that seems promising as a protective and elastic coating for future high-energylithium-ion battery cathodes. Figure 1

Nanoscale in-Situ Characterization of Polymer Electrolyte Membrane Fuel Cell Catalyst Layers for Improved Water Management

Polymer electrolyte membrane fuel cells (PEMFCs) facilitate a sustainable energy infrastructure by offering emission-free electricity generation using renewably sourced hydrogen gas. The electrochemical reactions in a fuel cell occur at platinum-loaded catalyst layers (CLs), which are susceptible to degradation. Obstructing catalyst sites (triple phase boundaries1) with reaction by-products, such as water2,3, is the primary degradation mechanism in PEMFCs. Although various CL designs have been tested for improved electrochemical performance, in situ nanoscale visualization of platinum degradation and water accumulation in the CL at controlled temperature and relative humidity (RH) values are required to understand fundamental water mechanics through platinum and carbon nanostructures.In this work, we employed scanning transmission X-ray microscopy (STXM) and X-ray absorption fine structure spectroscopy (XANES) to evaluate the effect of temperature on pristine and broken-in fuel cell CLs. We developed a novel CL in-situ sample cell to enable nanostructured characterization of catalyst layers using STXM in a controlled temperature environment. Carbon 1s, Fluorine 1s, and Oxygen 1s spectral edges were probed utilizing near-edge X-ray absorption fine structure spectroscopy (NEXAFS) to reveal chemical degradation mechanisms and differentiate material structure. Through our custom in-situ cell, we demonstrate that the chemical composition and water accumulation throughout the PEMFC CLs at low, intermediate, and high operating temperatures (25°C, 40°C, and 60°C, respectively) can be quantified, along with thermal expansion analyses of the CL and ionomer membrane. Moreover, we reveal realistic structural and chemical characteristics of nanoscale catalysts by distinguishing regions of Nafion® Ionomer, catalyst carbon support, and platinum throughout the PEMFC’s membrane electrode assembly at industrially relevant fuel cell temperatures. The insights from this work will inform strategies to mitigate water flooding from a nanoscale perspective in addition to the novel in-situ spectromicroscopy characterization of current CL features.1. Fouzaï, I., Gentil, S., Bassetto, V. C., Silva, W. O., Maher, R., & Girault, H. H. (2021). 9(18), 11096-11123.2. Li, H., Tang, Y., Wang, Z., Shi, Z., Wu, S., Song, D., ... & Mazza, A. (2008). 178(1), 103-117.3. Kumsa, D. W., Bhadra, N., Hudak, E. M., Kelley, S. C., Untereker, D. F., & Mortimer, J. T. (2016). 13(5), 052001.

Poor Cycling Performance of Rechargeable Lithium-Oxygen Batteries under Lean-Electrolyte and High-Areal-Capacity Conditions: Role of Carbon Electrode Decomposition.

There is growing demand for practical implementation of lithium-oxygen batteries (LOBs) due to their superior potential for achieving higher energy density than that of conventional lithium-ion batteries. Although recent studies demonstrate the stable operation of 500Whkg-1 -class LOBs, their cycle life remains fancy. For further improving the cycle performance of LOBs, the complicated chemical degradation mechanism in LOBs must be elucidated. In particular, the quantitative contribution of each cell component to degradation phenomenon in LOBs under lean-electrolyte and high-areal-capacity conditions should be clarified. In the present study, the mass balance of the positive-electrode reaction in a LOB under lean-electrolyte and high-areal-capacity conditions is quantitatively evaluated. The results reveal carbon electrode decomposition to be the critical factor that prevents the prolonged cycling of the LOB. Notably, the carbon electrode decomposition occur during charging at voltages higher than 3.8V through the electrochemical decomposition of solid-state side products. The findings of this study highlight the significance of improving the stability of the carbon electrode and/or forming Li2 O2 , which can decompose at voltages lower than 3.8V, to realize high-energy-density LOBs with long cycle life.

Biodegradable Microrobots and Their Biomedical Applications: A Review.

During recent years, microrobots have drawn extensive attention owing to their good controllability and great potential in biomedicine. Powered by external physical fields or chemical reactions, these untethered microdevices are promising candidates for in vivo complex tasks, such as targeted delivery, imaging and sensing, tissue engineering, hyperthermia, and assisted fertilization, among others. However, in clinical use, the biodegradability of microrobots is significant for avoiding toxic residue in the human body. The selection of biodegradable materials and the corresponding in vivo environment needed for degradation are increasingly receiving attention in this regard. This review aims at analyzing different types of biodegradable microrobots by critically discussing their advantages and limitations. The chemical degradation mechanisms behind biodegradable microrobots and their typical applications are also thoroughly investigated. Furthermore, we examine their feasibility and deal with the in vivo suitability of different biodegradable microrobots in terms of their degradation mechanisms; pathological environments; and corresponding biomedical applications, especially targeted delivery. Ultimately, we highlight the prevailing obstacles and perspective solutions, ranging from their manufacturing methods, control of movement, and degradation rate to insufficient and limited in vivo tests, that could be of benefit to forthcoming clinical applications.

A Comprehensive Review on Adsorption, Photocatalytic and Chemical Degradation of Dyes and Nitro-Compounds over Different Kinds of Porous and Composite Materials.

Dye and nitro-compound pollution has become a significant issue worldwide. The adsorption and degradation of dyes and nitro-compounds have recently become important areas of study. Different methods, such as precipitation, flocculation, ultra-filtration, ion exchange, coagulation, and electro-catalytic degradation have been adopted for the adsorption and degradation of these organic pollutants. Apart from these methods, adsorption, photocatalytic degradation, and chemical degradation are considered the most economical and efficient to control water pollution from dyes and nitro-compounds. In this review, different kinds of dyes and nitro-compounds, and their adverse effects on aquatic organisms and human beings, were summarized in depth. This review article covers the comprehensive analysis of the adsorption of dyes over different materials (porous polymer, carbon-based materials, clay-based materials, layer double hydroxides, metal-organic frameworks, and biosorbents). The mechanism and kinetics of dye adsorption were the central parts of this study. The structures of all the materials mentioned above were discussed, along with their main functional groups responsible for dye adsorption. Removal and degradation methods, such as adsorption, photocatalytic degradation, and chemical degradation of dyes and nitro-compounds were also the main aim of this review article, as well as the materials used for such degradation. The mechanisms of photocatalytic and chemical degradation were also explained comprehensively. Different factors responsible for adsorption, photocatalytic degradation, and chemical degradation were also highlighted. Advantages and disadvantages, as well as economic cost, were also discussed briefly. This review will be beneficial for the reader as it covers all aspects of dye adsorption and the degradation of dyes and nitro-compounds. Future aspects and shortcomings were also part of this review article. There are several review articles on all these topics, but such a comprehensive study has not been performed so far in the literature.

Impact of the Chlorination of Lithium Argyrodites on the Electrolyte/Cathode Interface in Solid‐State Batteries

AbstractLithium argyrodite‐type electrolytes are regarded as promising electrolytes due to their high ionic conductivity and good processability. Chemical modifications to increase ionic conductivity have already been demonstrated, but the influence of these modifications on interfacial stability remains so far unknown. In this work, we study Li6PS5Cl and Li5.5PS4.5Cl1.5 to investigate the influence of halogenation on the electrochemical decomposition of the solid electrolyte and the chemical degradation mechanism at the cathode interface in depth. Electrochemical measurements, gas analysis and time‐of‐flight secondary ion mass spectrometry indicate that the Li5.5PS4.5Cl1.5 shows pronounced electrochemical decomposition at lower potentials. The chemical reaction at higher voltages leads to more gaseous degradation products, but a lower fraction of solid oxygenated phosphorous and sulfur species. This in turn leads to a decreased interfacial resistance and thus a higher cell performance.

Impact of the Chlorination of Lithium Argyrodites on the Electrolyte/Cathode Interface in Solid-State Batteries.

Lithium argyrodite-type electrolytes are regarded as promising electrolytes due to their high ionic conductivity and good processability. Chemical modifications to increase ionic conductivity have already been demonstrated, but the influence of these modifications on interfacial stability remains so far unknown. In this work, we study Li6 PS5 Cl and Li5.5 PS4.5 Cl1.5 to investigate the influence of halogenation on the electrochemical decomposition of the solid electrolyte and the chemical degradation mechanism at the cathode interface in depth. Electrochemical measurements, gas analysis and time-of-flight secondary ion mass spectrometry indicate that the Li5.5 PS4.5 Cl1.5 shows pronounced electrochemical decomposition at lower potentials. The chemical reaction at higher voltages leads to more gaseous degradation products, but a lower fraction of solid oxygenated phosphorous and sulfur species. This in turn leads to a decreased interfacial resistance and thus a higher cell performance.

Theoretical speculation on the chemical reaction activity site and degradation mechanism of chloramphenicol

Chemical reaction active sites of chloramphenicol are investigated by density functional theory. Three atomic sites are considered the most possible nucleophilic sites. Results indicate that the chemical reaction active sites are formed around four bond sites associated with three nucleophilic atom sites. CAP is a case of joint electrostatic and electron transfer control, and N5 is the most favourable site with electrostatic control, while the reaction between CAP and free radical is transfer control. Moreover, a detailed explanation on why bond (C1C2) is considered the reactivity center of CAP and why no N-related products are generated in experiments is provided.

Chemical mechanism and atmospheric degradation of C4F9N initiated by OH radical: Ab initio kinetic exploration

AbstractThis work presents a thoroughgoing theoretical study on the OH‐initiated combustion chemical kinetics and atmospheric degradation mechanism of C4F9N by employing high‐level quantum chemical methods and RRKM/master‐equation theory. Stationary points on potential energy surface were cautiously investigated at B3LYP/6‐311++G(d,p) level for geometry optimizations, and thereby their single‐point energies were refined by applying CCSD(T)/6‐311++G(d,p) method. Based on quantum calculations, kinetics and branching ratios for the major channels were predicted within 300–3000 K and 0.01–100 atm by solving the RRKM/master‐equations. The OH addition to C4F9N generating M1 dominates the overall kinetics at low temperatures. Subsequently, its two β‐scission channels of CC bonds to CF3CF2NCF(OH) + CF3 and CF2NCF(OH)CF3 + CF3 become competitive and play a lead role in whole C4F9N + OH system at the corresponding high temperatures and elevated pressures. The CF3 radical generated prompts these two routes to potentially have the significant contribution to flame inhibition in actual applications. Additionally, the complex degradation pathways of C4F9N were also looked into by successively reacting with various oxides, including OH, O2, NO, and HO2, to finally generate the removal products CF3CF2N(OOH)CF(OH)CF3, CF3CFO, and CF3CF2NO. The atmospheric lifetime of C4F9N was evaluated as 49 years regarding to the kinetic for one step addition of OH radical.

(Invited) Operando EPR Study on Radicals in Anion-Exchange Membrane Fuel Cells

In the rapidly developing modern society, there is an urgent need for the wide-ranging availability of advanced and eco-friendly energy sources. One of the possible alternatives is the application of anion exchange membrane fuel cells (AEMFCs) with a catalyst reducing dioxygen efficiently. These promising devices can revolutionize the energy sector since they practically produce no pollution. However, to make them more widely used, several obstacles must be overcome. As a result, vast-ranging investigations focus on improving the properties of conductive polymer membranes [1] and catalysts for the oxygen reduction reaction (ORR) [2]. The durability of the membrane electrode assembly (MEA) is one of the critical requirements for the successful commercialization of anion exchange membrane fuel cells (AEMFCs). Despite significant impacts of nucleophilic degradation on ion-exchange capability and the anionic conductivity of investigated membranes, it is believed to affect only cationic sites of membrane polymers and thus cannot explain the reported loss in the mechanical strength of degraded AEMs. Such a phenomenon might be related to polymer backbone degradation caused by free radicals. This was widely described in the literature in the case of fuel cells using proton-conducting membranes [3] but barely mentioned for AEMFCs [4]. Since the oxidative degradation of hydrocarbon polymers is very well known, we aimed to comprehensively investigate the formation of the short-lived species generated during the operation of AEMFCs as well as stable radicals present in the polymer membranes.We investigated the LDPE-base membranes with Pt black, Pd black, PdAg, and Ag as the ORR catalysts, whereas for HOR the Pt black, Pd black, and NiFe catalysts were used. The in-situ measurements are performed with a micro-AEMFC inserted into a resonator of an electron paramagnetic resonance (EPR) spectrometer, which enables separate monitoring of radicals formed on the anode and cathode sides. The creation of radicals was monitored by the EPR spin trapping technique. In Figure 1 the EPR spectra of DMPO spin adducts trapped during operation of micro-fuel cell placed in EPR spectrometer cavity are presented. In this experiment, the LDPE-base membrane with platinum catalysts on both sides was used. The main detected adducts during the operation of the micro-AEMFC were DMPO-OOH and DMPO-OH on the cathode side and DMPO-H on the anode side. Additionally, we clearly show the formation and presence of stable radicals in AEMs during and after long-term AEMFC operation [5]. Preliminary results suggest that the creation of the short-living radicals during AEMFCs operation is independent of the used membrane. However, the applied catalysts determine the number of detected radicals. The EPR investigations indicate that, in addition to the known chemical degradation mechanisms of the cationic ammonium groups of the membrane, oxidative degradation, including radical reactions, has to be taken into account when the stability of an anion conductive polymer for AEMFCs is investigated. The formation of stable radicals in AEMs was proven for the first time in this study. All short-living radicals formed during the AEMFC operation were fully identified. The presence of radicals in the AEM after AEMFC testing indicates that reactive oxygen species may play a very important role in the degradation mechanism of the anion conducting polymers. Results from this study shed light on the understanding of radical formation and presence in the membranes during AEMFC tests, which in turn may help to solve the challenge of anion exchange membrane stability. Acknowledgments. This work was supported by the Polish National Science Centre (NCN) project OPUS-14, No. 2017/27/B/ST5/01004.

Water Uptake in an Anion Exchange Membrane Based on Polyamine: A First-Principles Study.

An atomistic level study of a single monomer of polyamine interacting with water molecules and hydroxide anions (OH–) was carried out to investigate the role of the polyamine structure in the hydrated morphology of anion exchange membranes (AEMs) for alkaline fuel cells and its influence on ionic conductivity and chemical stability. DFT calculations were performed to find the ground state of the system, studying the interactions of the solvent species with three different regions of the polymer—the amine functional group, the backbone, and the carbonyl group. The hydrophilic/hydrophobic behavior of each segment was determined, with calculated binding energies and Bader charge analysis providing a more quantitative analysis of the interactions and activation and reaction energies computed to investigate the chemical degradation mechanism. The results show the tendency of both OH– and water molecules to form water clusters in the proximity of the ionized amine group. As such, these regions constitute the preferential pathway for ionic conductivity. Besides, the essential role of the water content is pointed out, not only to enhance conductivity but also to reduce degradation in an alkaline environment. The present work provides a baseline to assess the impact of polymer chemistry on the ionic conductivity of the membrane and acts as the first step for the development of high-performance AEMs and for an improvement of the overall performance of the fuel cell.

Chemical stability and degradation mechanism of Mg3Sb2-xBix thermoelectrics towards room-temperature applications

Mg3Sb2-xBix compounds have recently attracted surging research attention owing to their low cost and high thermoelectric performance that is comparable with the commercialized Bi2Te3-xSex alloys. For practical applications, chemical stability is another key factor that determines the lifetime of the materials, which is rarely investigated for Mg3Sb2-xBix. Here we show that Mg3Sb2-xBix is more sensitive to moisture, but not to the conventionally considered oxygen. A spontaneous decomposition to crystalline Bi/Sb and amorphous Mg(OH)2 is thermodynamically favorable in the moist ambient air, leading to catastrophically degraded thermoelectric performance. Moreover, such an irreversible degradation was also found to occur in other Bi-contained Zintl phase compounds. Thankfully, if moisture is eliminated, the thermoelectric properties of Mg3Sb2-xBix keep nearly unchanged after two months’ exposure to the dry air. This work provides insight into the degradation mechanism of Mg3Sb2-xBix and other Bi-contained thermoelectric materials, paving the way for their protection in future applications.