The properties of highly concentrated aqueous CH3COOK/Na binary electrolyte and its use in sodium-ion batteries

Highly concentrated aqueous binary solutions of acetate salts are emerging as promising systems for advanced energy storage applications. Together with superior solubility of CH3COOK helpful in achieving water-in-salt electrolyte concentrations, the presence of CH3COOLi or CH3COONa permits intercalation of desired cations in electrode crystalline phases. Although these systems have captured profound scientific attention in recent years, a fundamental understanding of their physicochemical properties is still lacking. In this work, the thermal, rheological, transport, and electrochemical properties for a series of solutions comprising of 20 mol kg-1 of CH3COOK with different concentrations of CH3COONa are reported and discussed. The most concentrated solution, i.e., 20 mol kg-1 of CH3COOK with 7 mol kg-1 of CH3COONa came out to be the best in terms of a compromise between transport properties and electrochemical stability window. Such a solution has a conductivity of 21.2 mS cm-1 at 25°C and shows a stability window up to 3 V in “ideal” conditions, i.e., using small surface area and highly electrocatalytic electrode in a flooded cell. As a proof of concept of using this solution in sodium-ion batteries, carbon-coated LiTi2(PO4)3 (NASICON) demonstrated the ability to reversibly insert and de-insert Na+ ions at about -0.7 V vs. SHE with a first cycle anodic capacity of 85 mAh g-1, average charge efficiency of 96% at low current and a 90% capacity retention after 60 cycles. The very good kinetic properties of the interface are also demonstrated by the low value of activation energy for the charge transfer process (0.12 eV).

Visualizing the three-step freezing process and three-phase reaction not predicted by the (NH4) 2SO4/H2O phase diagram

According to the conventional phase diagrams, aqueous solutions freeze at the liquidus and are frozen/solid below the eutectic solidus. Herein, using differential scanning calorimetry (DSC) and optical cryo-microscopy (OC-M), we demonstrate that hy-poeutectic, eutectic 40 wt% (NH4)2SO4 and hypereutectic (NH4)2SO4/H2O remain liquid well below the eutectic solidus before freezing in three steps: fast-slow-fast. The first fast freezing produces a ramified ice microstructure (IM) and freeze-concentrated solution (FCS) containing up to ~70 wt% (NH4)2SO4. As temperature decreases further, the slow freezing of FCS precedes its fast freezing, which produces a striped IM and (NH4)2SO4 microcrystals. Videos recorded upon warming of frozen (NH4)2SO4/H2O reveal a new three-phase reaction, which is the recrystallization of ice and (NH4)2SO4 microcrystals into the lamellar eutectic ice-(NH4)2SO4 superlattice. This work demonstrates limitations of the (NH4)2SO4/H2O phase diagram and pro-poses an effective strategy for studying other deeply supercooled solutions whose behavior is not predicted by the phase dia-gram.

Simple superphosphate by two-stage acid treatment of phosphate raw materials

The distinguishing feature of the proposed flow method before the classical (chamber) method is that the entire production cycle of natural phosphate processing is carried out in two stages. At the first stage, the phosphorite is treated with a stoichiometric flow rate of concentrated sulphuric acid (at least 93%), under conditions of complete decomposition of phosphorite to form phosphoric acid and crystals of anhydrite (calcium sulfate). The reaction temperature is 122 °C. In the second stage, the resulting concentrated solution of phosphoric acid in a mixture with sulphur is involved in a reaction with an additional input of phosphorite, which is the basis for the mechanism of chemical formation of monocalciumphosphate and granulation of superphosphate mass. The processes for neutralizing phosphoric acid on monocalciumphosphate and for granulating the product by coagulation are combined in one apparatus. The drying stage of the product is excluded from the scheme.

Simple Approach to Enhance Green Tea Epigallocatechin Gallate Stability in Aqueous Solutions and Bioavailability: Experimental and Theoretical Characterizations

Because of its antioxidant, antimutagenic, and anti-infectious properties, epigallocatechin gallate (EGCG) is the most interesting compound among the green tea catechins polyphenols. However, its health effects are inconclusive due to its very low bioavailability, largely due to a particular instability that does not allow EGCG to reach the potency required for clinical developments. Over the last decade, many efforts have been made to improve the stability and bioavailability of EGCG using complex delivery systems such as nanotechnology, but these efforts have not been successful and easy to translate to industrial use. To meet the needs of a large-scale clinical trial requiring EGCG in a concentrated solution to anticipate swallowing impairments, we developed an EGCG-based aqueous solution in the simplest way while trying to circumvent EGCG instability. The solution was thoroughly characterized to sort out the unexpected stability outcome by combining experimental (HPLC-UV-mass spectrometry and infrared spectroscopy) and computational (density functional theory) studies. Against all odds, the EGCG–sucrose complex under certain conditions may have prevented EGCG from degradation in aqueous media. Indeed, in agreement with the ICH guidelines, the formulated solution was shown to be stable up to at least 24 months under 2–8 °C and at ambient temperature. Furthermore, considerable improvement in bioavailability in rats, against EGCG powder formulated in hard-gel capsules, was shown after gavage. Thus, the proposed formulation may provide an easily implementable platform to administer EGCG in the context of clinical development.

Ce-exchange capacity of zeolite L in different cationic forms: a structural investigation

Cerium exchange by microporous materials, such as zeolites, has important applications in different fields, for example, rare earth element recovery from waste or catalytic processes. This work investigated the Ce-exchange capacity of zeolite L in three different cationic forms (the as-synthesized K form and Na- and NH4-exchanged ones) from a highly concentrated solution. Chemical analyses and structural investigations allowed determination of the mechanisms involved in the exchanges and give new insights into the interactions occurring between the cations and the zeolite framework. Different cation sites are involved: (i) K present in the original LTL in the cancrinite cage (site KB) cannot be exchanged; (ii) the cations in KD (in the 12-membered ring channel) are always exchanged; while (iii) site KC (in the eight-membered ring channel) is involved only when K+ is substituted by NH4 +, thus promoting a higher exchange rate for NH4 + → K+ than for Na+ → K+. In the Ce-exchanged samples, a new site occupied by Ce appears in the centre of the main channel, accompanied by an increase in the number of and a rearrangement of H2O molecules. In terms of Ce exchange, the three cationic forms behave similarly, from both the chemical and structural point of view (exchanged Ce ranges from 38 to 42% of the pristine cation amount). Beyond the intrinsic structural properties of the zeolite L framework, the Ce exchange seems thus also governed by the water coordination sphere of the cation. Complete Ce recovery from zeolite pores was achieved.

Pilot Plant for the Capture of Ammonia from the Atmosphere of Pig and Poultry Farms Using Gas-Permeable Membrane Technology

Gas-permeable membrane (GPM) technology is a possible solution to reduce ammonia (NH3) emissions from livestock housing. This paper presents the results obtained with an NH3-capture prototype based on the use of expanded polytetrafluoroethylene (ePTFE) membranes in real conditions in a gestating sow house and a free-range laying hen house, comparing them with the results obtained in controlled laboratory conditions for the same type of waste. The NH3 present in the air of the livestock housing was captured by reaction with an acidic solution flowing inside the membranes. The periods of continuous operation of the pilot plant were 232 days at the pig farm and 256 days at the poultry farm. The NH3 recovery rate at the end of those periods was 2.3 and 0.4 g TAN·m−2·d−1 in the pig and the poultry farms, respectively. The limiting factor for the capture process was the NH3 concentration in the air, with the highest recovery occurring in the most concentrated atmosphere. Differences in NH3 capture were observed between seasons and farms, with capture efficiencies of 1.62 and 0.33 g·m−2·d−1 in summer and 3.85 and 1.20 g·m−2·d−1 in winter for pig and poultry farms, respectively. The observed differences were mainly due to the higher ventilation frequency in the summer months, which resulted in a lower NH3 concentration inside the houses compared to the winter months. This is especially important when considering the real applicability of this technology. The results obtained suggest that GPM technology holds promise for limiting NH3 emissions from livestock housing with NH3 ambient concentrations close to 20 ppm or as part of manure storage facilities, given that it allows for recovery of nitrogen in a stable and concentrated solution, which can be used as a fertilizer.

Ammonium and Phosphate Recovery in a Three Chambered Microbial Electrolysis Cell: Towards Obtaining Struvite from Livestock Manure

Ammonia and phosphate, which are present in large quantities in waste streams such as livestock manure, are key compounds in fertilization activities. Their recovery will help close natural cycles and take a step forward in the framework of a circular economy. In this work, a lab-scale three-chambered microbial electrolysis cell (MEC) has been operated in continuous mode for the recovery of ammonia and phosphate from digested pig slurry in order to obtain a nutrient concentrated solution as a potential source of fertilizer (struvite). The maximum average removal efficiencies for ammonium and phosphate were 20% ± 4% and 36% ± 10%, respectively. The pH of the recovered solution was below 7, avoiding salt precipitation in the reactor. According to Visual MINTEQ software modelling, an increase of pH value to 8 outside the reactor would be enough to recover most of the potential struvite (0.21 mmol L−1 d−1), while the addition of up to 0.2 mM of magnesium to the nutrient recovered solution would enhance struvite production from 5.6 to 17.7 mM. The application of three-chambered MECs to the recovery of nutrients from high strength wastewater is a promising technology to avoid ammonia production through industrial processes or phosphate mineral extraction and close nutrient natural cycles.