A Binary Ionogel Electrolyte for the Realization of an All Solid-State Electrical Double-Layer Capacitor Performing at Low Temperature.

Over the last years, solid-state electrolytes made of an ionic liquid (IL) confined in a solid (inorganic or polymer) matrix, also known as ionogels, have been proposed to solve the leakage problems occurring at high temperatures in classical electrical double-layer capacitors (EDLCs) with an organic electrolyte, and thereof improve the safety. However, making ionogel-based EDLCs perform with reasonable power at low temperature is still a major challenge due to the high melting point of the confined IL. To overcome these limitations, the present contribution discloses ionogel films prepared in a totally oxygen/moisture-free atmosphere by encapsulating 70 wt % of an equimolar mixture of 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide and 1-ethyl-3-methylimidazolium tetrafluoroborate - [EMIm][BF4]0.5[FSI]0.5 - into a poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP) network. The further called "binary ionogel" films demonstrated a high flexibility and a good ionic conductivity of 5.8 mS cm-1 at 20 °C. Contrary to the ionogels prepared from either [EMIm][FSI] or [EMIm][BF4], displaying melting at Tm=-16 °C and -7 °C, respectively, the crystallization of confined [EMIm][BF4]0.5[FSI]0.5 is quenched in the binary ionogel, which shows only a glass transition at -101 °C. This quenching enables an increased ionicity and ionic diffusion at the interface with the PVdF host network, leading the binary ionogel membrane to display higher ionic conductivity below -20 °C than the parent binary [EMIm][BF4]0.5[FSI]0.5 liquid. Laminate EDLCs were built with a 100 µm thick binary ionogel separator and electrodes made from a hierarchical micro-/mesoporous MgO-templated carbon containing a reasonable proportion of mesopores to enhance the mass transport of ions, especially at low temperature where the ionic diffusion noticeably decreases. The EDLCs operated up to 3.0 V with ideal EDL characteristics from -40 °C to room temperature. Their output specific energy under a discharge power of 1 kW kg-1 is ca. 4 times larger than with a cell implementing the same carbon electrodes together with the binary [EMIm][BF4]0.5[FSI]0.5 liquid. Hence, this binary ionogel electrolyte concept paves the road for developing safe and flexible solid-state energy storage devices operating at subambient temperatures in extreme environments.

Towards Low Temperature Operation of Catalytic Gas Sensors: Mesoporous Co3O4-Supported Au-Pd Nanoparticles as Functional Material.

It is shown that the operating temperature of pellistors for the detection of methane can be reduced to 300 °C by using Au-Pd nanoparticles on mesoporous cobalt oxide (Au-Pd@meso-Co3O4). The aim is to reduce possible catalyst poisoning that occurs during the high-temperature operation of conventional Pd-based pellistors, which are usually operated at 450 °C or higher. The individual role of Au-Pd as well as Co3O4 in terms of their catalytic activity has been investigated. Above 300 °C, Au-Pd bimetallic particles are mainly responsible for the catalytic combustion of methane. However, below 300 °C, only the Co3O4 has a catalytic effect. In contrast to methane, the sensor response and the temperature increase of the sensor under propane exposure is much larger than for methane due to the larger heat of combustion of propane. Due to its lower activation energy requirement, propane exhibits a higher propensity for oxidation compared to methane. As a result, the detection of propane can be achieved at even lower temperatures due to its enhanced reactivity.

Rechargeable Solid-State Na-Metal Battery Operating at -20 °C.

Achieving satisfactory performance for a solid-state Na-metal battery (SSNMB) with an inorganic solid electrolyte (SE), especially under freezing temperatures, poses a challenge for stabilizing a Na-metal anode. Herein, this challenge is addressed by utilizing a Natrium super ionic conductor (NASICON) NASICON-type solid electrolyte, enabling the operation of a rechargeable SSNMB over a wide temperature range from -20 to 45 °C. The interfacial resistance at the Na metal/SE interface is only 0.4 Ω cm2 at 45 °C and remains below 110 Ω cm2 even at -20 °C. Remarkably, long-term Na-metal plating/stripping cycles lasting over 2000 h at -20 °C are achieved with minimal polarization voltages at 0.1 mA cm-2 . Further analysis reveals the formation of a uniform Na3- x Cax PO4 interphase layer at the interface, which significantly contributes to the exceptional interfacial performance observed. By employing a Na3 V1.5 Al0.5 (PO4 )3 cathode, the full battery system demonstrates excellent adaptability to low temperatures, exhibiting a capacity of 80 mA h g-1 at -20 °C over 50 cycles and retaining a capacity of 108 mAh g-1 (88.5% of the capacity at 45 °C) at 0 °C over 275 cycles. This research significantly reduces the temperature threshold for SSNMB operation and paves the way toward solid-state batteries suitable for all-season applications.

Selecting the Optimal Fluorinated Ether Co-Solvent for Lithium Metal Batteries.

To guide the selection of a suitable fluorinated ether (FE) co-solvent for lithium metal batteries, it is crucial to understand the relationship between the organic structures of the FEs and the electrochemical performance of an FE-containing electrolyte. In this work, 1,1,2,2-tetrafluoro-1-(2,2,2-trifluoroethoxy)ethane (FEE), 1,1,2,2-tetrafluoro-3-(1,1,2,2-tetrafluoroethoxy)propane (TTE), and 1,2-bis(1,1,2,2-tetrafluoroethoxy)ethane (OFDEE) were chosen as representative FE co-solvents because of their distinct structural properties. The structure-activity relationship between the FEs and the electrochemical performance of Li||LiNi0.6Mn0.2Co0.2O2 (Li||NMC622) cells was correlated and quantified by Fourier-transform infrared and multi-dimensional nuclear magnetic resonance techniques. Sand's model was also employed to assess the extent of lithium dendrite formation in the cells using various FE electrolytes. The cycling performance of Li||NMC622 cells using different FE co-solvents follows the order FEE > TTE > OFDEE. Since the direct measurement of Sand's time is difficult, we introduced relative Sand's time to probe the diffusion behavior of each electrolyte, and the results showed that the best performance was obtained in the electrolyte with the longest relative Sand's time. Moreover, the lithium metal cell using the electrolyte with FEE co-solvent showed similar capacity retention compared with the baseline electrolyte at room temperature, but it demonstrated significantly improved low-temperature performance. The results indicate that FEE is a promising co-solvent candidate for improving the low-temperature performance of lithium metal batteries because it possesses not only non-solvating behavior but also very low viscosity and non-flammability. The advanced electrolyte LiPF6-FEC-DMC-FEE enables very stable cycling of lithium metal batteries at various temperatures.

Simultaneous nitrification, denitrification, and phosphorus removal from municipal wastewater at low temperature.

A lab-scale sequencing batch reactor was employed to study simultaneous nitrification, denitrification, and phosphorus removal (SNDPR) when treating municipal wastewater at 10 °C for 158 days. An anaerobic/aerobic configuration that had previously been effective when treating synthetic wastewater was explored, however, these conditions were relatively ineffective for real municipal wastewater. Incorporation of a post-anoxic phase (i.e., anaerobic/aerobic/anoxic) improved nitrogen and phosphorus removals to 91.1 % and 92.4 %, respectively while achieving a simultaneous nitrification and denitrification efficiency of 28.5 %. Activity tests indicated that 15.8 % and 56.0 % of nitrogen were removed by denitrifying phosphorus accumulating organisms in the aerobic phase and heterotrophs using hydrolyzed carbon in the post-anoxic phase, respectively. 16S rRNA gene analysis and stoichiometric ratios indicated the system was rich in phosphorus accumulating organisms (Dechloromonas and Ca. Accumulibacter). Overall, implementation of the post-anoxic phase eliminated carbon uptake for denitrification in the anaerobic phase and was essential to maintaining SNDPR at low temperatures.

Solvation and Interfacial Engineering Enable -40 °C Operation of Graphite/NCM Batteries at Energy Density over 270 Wh kg-1.

Li-ion batteries (LIBs) that can operate under low temperature (LT) conditions are essential for applications in orbital missions, subsea areas, and electric vehicles. Unfortunately, severe capacity loss is witnessed due to tremendous kinetic barriers that emerge at LT. Herein, to surmount such kinetic limitations, a low dielectric environment is tamed throughout the bulk electrolyte, which efficaciously brought the Li+ desolvation energy down to 30.76 kJ mol-1 . At the meantime, the adoption of sodium cations (Na+ ) is proposed as a hetero-cation additive, and a Li-Na hybrid and fluoride-rich interphase is further identified via preferential reduction of Na+ -(solvent/anion) clusters, which is found to efficiently facilitate Li+ migration through the LiF/NaF grain boundaries. Based on a N/P ratio of 1.1, the graphite/LiNi0.5 Co0.2 Mn0.3 O2 (NCM) full cell (cathode loading of ≈18.5 mg cm-2 ) delivers a capacity as high as 125.1 mAh g-1 under -20 °C with prolonged cycling to 100 cycles. Finally, a 270 Wh kg-1 graphite/NCM pouch cell is assembled, which affords a discharge capacity of 108.7 mAh g-1 under -40 °C during the initial cycles. With an eye to both fundamental and practical aspects, this work will propel additional advancements and allow LIBs to fill more roles under extreme operation temperatures than ever before.

Quantitative and qualitative variations of biopolymers in a pilot-scale membrane bioreactor treating municipal wastewater throughout 3 years of operation.

In this study, the fouling potential of mixed liquor suspension samples collected from a pilot-scale membrane bioreactor (MBR) that treated municipal wastewater was monitored for more than 3 years. The fouling potential was assessed by batch filtration experiments using the same type of membrane as equipped in the MBR. The fouling potential increased when the temperature of the mixed liquor suspension in the MBR decreased. However, the polysaccharide and protein concentrations in the mixed liquor suspension, which have been focused on many previous studies, did not correlate with the fouling potential (R2 = 0.15 and 0.39, respectively). In contrast, the concentration of biopolymers, quantified by liquid chromatography-organic carbon detection (LC-OCD), exhibited a marked correlation with the fouling potential (R2 = 0.89). A high concentration of biopolymers with large molecular weight (>1 million Da) was likely responsible for the high fouling potential. Fourier transform infrared (FTIR) analysis of the dissolved organic matter in the mixed liquor suspension indicated that the chemical properties of the biopolymers considerably varied with the seasonal temperature variation, which has rarely been reported and gives insights into fouling in MBRs. The effect of temperature on the biopolymer concentration and molecular weight of biopolymers was also investigated in a separate bench-scale experiment in which temperature was controlled. It was clearly shown that a low temperature induced an increase in the biopolymer concentration and an associated increase in the fouling potential of the mixed liquor suspension.

Partially Reduced Titanium Niobium Oxide: A High-Performance Lithium-Storage Material in a Broad Temperature Range.

The existing electrode materials for lithium-ion batteries (LIBs) generally suffer from poor rate capability at low temperatures, severely limiting their applications in winter and cold climate area. Here, partially reduced TiNb24 O62 (PR-TNO) are reported that demonstrates excellent electrochemical performance in a broad temperature range, notably at low temperatures. Its crystal structure is similar to that of Ti2 Nb10 O29 upon partial reduction in H2 . The titanium and niobium ions in PR-TNO enable multielectron transfer, safe operation, and high Coulombic efficiencies. Benefiting from the increased electronic conductivity of the partially reduced phase and its robust crystal structure with a large interlayer spacing, PR-TNO shows fast electron and Li+ transport, small volume change associated with Li+ storage, and notable capacitive behavior, resulting in good electrochemical performance even at very low temperatures. At -20 °C, a large reversible capacity of 313 mAh g-1 is obtained at 0.1C, reaching 83.3% of that at 25 °C. At 5C, high rate capability (58.3% of that at 0.5C) is achieved, only slightly lower than that at 25 °C (60.7%). Furthermore, PR-TNO demonstrates excellent cyclic stability with 99.2% of the initial capacity after 1680 cycles, confirming its excellent suitability for low-temperature LIBs.

Characterization and modelling of soluble microbial products in activated sludge systems treating municipal wastewater with special emphasis on temperature effect.

Soluble microbial products (SMP) classified as utilization-associated products (UAP) and biomass-associated products (BAP) are the predominant foulants determining fouling in tertiary filtration. However, the exact mechanisms of BAP and UAP generation when treating real wastewaters under cold temperatures remain unrevealed. This paper presents the first study linking biological processes and SMP formation when treating real wastewaters through a combination of bioprocess modelling and advanced SMP characterization. Further, the impact of low operating temperatures on SMP production which has received relatively little attention was studied in detail. The use of liquid chromatography-organic carbon detection (LC-OCD) revealed a significant increase in protein and polysaccharide concentrations in the treated effluents as temperature decreased with a more sensitive impact on polysaccharides. The generation of SMP from biomass decay (BAP) and substrate utilization (UAP) was derived from the LC-OCD data on the basis of protein and polysaccharide mass balances. UAP and BAP yields were estimated as the ratios of the observed generation rates to the rates of substrate utilization and endogenous decay respectively, which both declined as temperature increased. A strong correlation was observed between temperature and BAP/UAP yields whereas the generation of BAP was more temperature sensitive than UAP. Such process modelling can be employed to assist with the optimization of the design and operation of membrane processes when treating wastewaters under challenging conditions like low temperature.

Electrical Double-Layer Capacitors Based on a Ternary Ionic Liquid Electrolyte Operating at Low Temperature with Realistic Gravimetric and Volumetric Energy Outputs.

We report on electrical double-layer capacitors (EDLCs) performing effectively at low temperature (down to -40 °C), owing to the tuned characteristics of both the ionic liquid (IL) electrolyte and carbonaceous electrodes. The transport properties of the electrolyte have been enhanced by adding a low-viscosity IL with the tetracyanoborate anion, [EMIm][TCB], to a mixture of [EMIm][FSI] with [EMIm][BF4 ], which was already successfully applied for this application. The formulated ternary electrolyte, [EMIm][FSI]0.6 [BF4 ]0.1 [TCB]0.3 , remained in the liquid state until it reached the glass transition at -99 °C and displayed a relatively low viscosity and high conductivity (η=23.6 mP s and σ=14.2 mS cm-1 at 20 °C, respectively). The electrodes were made of a hierarchical SiO2 -templated carbon with well-defined and uniform mesopores of ∼9 nm facilitating ion transport to the interconnected micropores accounted for the charge storage, whereas the high density of the electrodes promoted high volumetric energy outputs of the cells.

Designing Advanced Lithium-based Batteries for Low-temperature Conditions.

Energy-dense rechargeable batteries have enabled a multitude of applications in recent years. Moving forward, they are expected to see increasing deployment in performance-critical areas such as electric vehicles, grid storage, space, defense, and subsea operations. While this at first glance spells great promise for conventional lithium-ion batteries, all of these use-cases, unfortunately, share periodic and recurring exposures to extremely low-temperature conditions, a performance constraint where the lithium-ion chemistry can fail to perform optimally. Next-generation chemistries employing alternative anodes with increased solvent compatibility or altogether different operating mechanisms could present an avenue for overcoming many of the low-temperature hurdles intrinsic to the lithium-ion battery. In this article, we provide a brief overview of the challenges in developing lithium-ion batteries for low-temperature use, and then introduce an array of nascent battery chemistries that may be intrinsically better suited for low-temperature conditions moving forward. Specifically, we evaluate the prospects of using lithium-metal, lithium-sulfur, and dual-ion batteries for performance-critical low-temperature applications. These three chemistries are presented as prototypical examples of how the conventional low-temperature charge-transfer resistances can be overcome. However, these three chemistries also present their own unique challenges at low temperatures, highlighting the balance between traditional low-temperature electrolyte design and next-generation approaches.

POSS-Based Electrolyte for Efficient Solid-State Dye-Sensitized Solar Cells at Sub-Zero Temperatures.

To expand the application of solid-state dye-sensitized solar cells (ssDSSCs) to low temperatures, it is necessary to develop new solid electrolytes with low glass transition temperature (Tg). The Tg is regulated by varying the length of alkyl chain that is connected with the nitrogen atom in the imidazolium ring linked to the polyhedral oligomeric silsesquioxane (POSS). The Tg as low as -8.8 °C is achieved with the POSS grafted with methyl-substituted imidazolium. The effect of alkyl group on the conductivity, Tg, and photovoltaic performance has also been investigated. The conductivity and power conversion efficiency increase with the alkyl length, while the Tg first increases and then decreases with the alkyl length. Among the synthesized POSS-based ionic conductors, the POSS grafted with the methyl-substituted imidazolium yields the highest power conversion efficiency of 6.98% at RT due to its highest conductivity, and the efficiency (6.52%) is still good at -4 °C, as its Tg (-8.8 °C) is lower than the working temperature (-4 °C). This finding suggests that the POSS-based solid electrolyte is promising for subzero-temperature applications of ssDSSCs.