Concentrated Alkaline Research Articles

High-entropy oxide synthesis in concentrated alkaline solutions for plasma-catalytic formaldehyde oxidation

High-concentration NaOH co-precipitation makes high-entropy oxides with high surface area of 173 m2 g−1. Tests show that HEO-10%-400 boosts formaldehyde removal by 59.7%, reduces O3 by 93.1%, and NOx by 91.8% over plasma alone.

Формирование условий надежной эксплуатации анкеров фрикционного закрепления

Safe performance of work in mine workings is ensured by securing exposed surfaces. Along with traditional anchor supports, «Change No. 1» to GOST 31559-2012 defines the possibility and technical requirements for anchors with friction fastening. An analysis of their designs showed that the main indicator that determines reliable operation – load-bearing capacity, is defined as the minimum value of three load capacity values: the anchor rod, the stop on the anchor, the base plate. It has been established that the load-bearing capacity of the friction fastening anchor must coincide with the load capacity of the stop on the anchor. Maintaining the original load capacity for the entire service life is ensured by applying protective coatings to all surfaces of the anchor. As a result of the research carried out, the feasibility of using a coating obtained on the basis of high-density polyethylene compositions with a thickness of 600-800 microns was substantiated. A comparative analysis of resistance to concentrated alkaline and salt environments showed retention of tensile strength.

Unraveling the local stress corrosion cracking behavior of Alloy 690 plug in a high-temperature concentrated alkaline solution

Unraveling the local stress corrosion cracking behavior of Alloy 690 plug in a high-temperature concentrated alkaline solution

Highly Efficient and Durable Water Electrolysis at High KOH Concentration Enabled by Cationic Group-Free Ion Solvating Membranes in Free-standing Gel Form.

The degradation of fixed cationic groups in most anion exchange membranes (AEMs) under alkaline environments limits their durability for alkaline water electrolysis (AWE). Ion-solvating membranes (ISMs) have emerged as a promising alternative to address this issue. Herein, a cationic group-free ion solvating membrane in a free-standing gel form (ISM-PBI-FG) is presented, created through a sol-to-gel transformation process followed by KOH imbibing. This approach yields a 3D porous microstructure composed of entangled polybenzimidazole (PBI) nanofibrils, achieving 89% porosity, which enables ultrahigh alkali uptake (346% in 6 M KOH) and exceptional ionic conductivity (763 mS cm-1 at 80 °C). The absence of cationic groups avoids the attack by OH-, thus ensures good alkaline stability with a conductivity retention rate of 91.6% over a 3120 h ex situ test in 6 M KOH. The resulting membrane delivered outstanding AWE performance with current densities of 5.5 A cm-2 using platinum-group-metal (PGM) catalysts and 2.2 A cm-2 using PGM-free catalysts at 2.0 V. Notably, the in situ electrolyzer device based on ISM-PBI-FG offers extensive operational flexibility ranging from 40-100 °C and demonstrates record durability in concentrated alkaline conditions, with a voltage decay rate of only 23.5µVh-1, outperforming most reported AEMs and ISMs.

Quantitative Analysis and Manipulation of Alkali Metal Cations at the Cathode Surface in Membrane Electrode Assembly Electrolyzers for CO2 Reduction Reactions

The electrochemical CO2 reduction reaction (CO2RR) has garnered significant attention due to its potential for achieving high CO2 conversion rates under ambient temperature and pressure conditions.[1-3] For practical applications of CO2RR, improving energy efficiency, enhancing selectivity toward high-value products, and increasing production rates are critical. In particular, the production of multi-carbon compounds (C2+, such as ethylene, ethanol, acetic acid, and n-propanol), with high current density and low energy consumption, is of paramount importance.Recently, we successfully increased the partial current density for CO2 electroreduction to C2+ products to a record value of 1.7 A cm−2 using gas diffusion electrodes (GDEs) carrying Cu nanoparticles.[4,5]. However, this study employed liquid electrolytes as the catholyte, which led to an ohmic drop in the electrolyte, resulting in decreased energy efficiency, particularly under high-current electrolysis conditions. To address this issue, researchers have begun utilizing membrane electrode assembly (MEA) cells with solid polymer electrolytes for CO2RR.[6] In previous studies, anion-exchange membranes (AEMs), Cu-based catalysts loaded on GDEs, and concentrated alkaline solutions, such as 1 M KOH or 0.1 M KHCO3, were used as electrolytes, cathodes, and anolytes, respectively; these configurations have become standard for MEA-based CO2RR systems. However, alkali metal cations are transported from the anode to the cathode through the AEM, leading to the formation of bicarbonate salts at the cathode, which disrupts stable CO2RR operation. Therefore, to achieve stable CO2 electrolysis in an MEA-based cell, the amount of alkali metal cations must be reduced or eliminated. However, the quantity of alkali metal cations transported from the anode to the cathode has yet to be quantitatively analyzed.In this study, we quantify the transfer of alkali metal cations from the anode to the cathode and investigate their role in C2+ compound formation, determining the optimal concentration of alkali metal cations required for stable operation.[7] While the presence of alkali metal cations at the cathode surface significantly contributes to C2+ production, the transport rate of K+ ions did not correlate with C2+ selectivity, suggesting that a continuous, high supply of K+ to the cathode surface is not essential for C2+ formation (Figure). Based on these findings, we achieved a faradaic efficiency (FE) and partial current density for C2+ products of 77% and 230 mA cm−2, respectively, even after switching the anode solution from 0.1 M KHCO3 to a diluted K+ solution (<7 mM). These results were nearly identical to those obtained with continuous 0.1 M KHCO3 supply. Furthermore, by intermittently supplying concentrated KHCO3, we significantly improved system durability against salt precipitation compared to continuous supply.[1] K. Kamiya et al. Chem. Lett. 2021, 50,166.[2] S. Kato, K. Kamiya et al. Chem. Sci., 2023 , 14, 613[3] P. Su, K. Kamiya et al., Chem. Sci., 2018, 9, 3941[4] A. Inoue, K. Kamiya et al. EES Catal. 2023 , 1, 9.[5] T. Liu, K. Kamiya et al. Small 2022 , 18, 2205323.[6]C. M. Gabardo, et al. , Joule 2019, 3, 2777.[7] S. Kato, K. Kamiya et al. ChemSusChem doi:10.1002/cssc.202401013. Figure 1

Effect of synthesis temperature on the properties and photocatalytic performance of peroxo-titanate nanotubes prepared by bottom-up synthesis method

The alkaline treatment synthesis of titania/titanate nanotubes (TNTs) requires highly concentrated alkaline solutions (≥ 10 mol/L), which pose environmental and productivity limitations. In contrast, a bottom-up synthesis method for peroxo-titanate nanotubes (PTNTs) has been developed. This method offers two advantages: it can synthesize materials using low-concentration alkaline solutions (1.5 mol/L) and produce photocatalytic materials that are responsive to visible light. In general, the higher the crystallinity of a catalyst, the better its properties. However, PTNTs synthesized at temperatures close to their boiling point (around 100 °C) exhibit low crystallinity. This study hypothesizes a hydrothermal synthesis method at higher temperatures will enhance the crystallinity and photocatalytic performance of PTNTs, synthesizing them at temperatures ranging from 120 to 200 °C using a method capable of exceeding the boiling point. Higher synthesis temperatures resulted in improved morphological and crystallographic properties of the PTNTs. However, the formation of peroxo-bonding, crucial for visible light responsiveness, decreased. Nevertheless, peroxo-bonding formation was still achievable at the highest temperature of 200 °C, and the sample exhibited the best Rhodamine B (Rh B) photodegradation performance under visible light due to its enhanced specific surface area and crystallinity. This study highlights the novelty and environmental significance of hydrothermally synthesized PTNTs as superior photocatalysts by optimizing the synthesis temperature while using lower concentration alkaline solutions.

Ni-Derived NiO Nanosphere Electrocatalyst for Hydrogen Evolution Reaction: The Effect of Synthesis Variables on Activity and Durability

Transition to a decarbonized society will rely on clean energy resources, in particular on "green” hydrogen—a renewable energy carrier that can be generated via water electrolysis [1]. Unlike proton exchange membrane water electrolyzers (PEMWE), anion exchange membrane water electrolyzers (AEMWEs) enable the use of earth-abundant transition metals in both the cathode and anode [2]. In addition, unlike liquid alkaline water electrolyzers, which use a highly concentrated alkaline media (6 M KOH), AEMWEs can operate with low-concentrated electrolyte, and even pure water [3]. Developing active and durable platinum group metal-free (PGM-free) electrocatalysts is crucial for the large-scale implementation of the AEMWE technology. Ni-based electrocatalysts have shown good activity towards the hydrogen evolution reaction (HER) in alkaline media [4]. Herein, carbon supported Ni-derived NiO nanosphere electrocatalysts are synthetized via a sol-gel method followed by thermal treatment under reducing atmosphere. We explored several synthesis parameters, i.e., Ni-to-carbon ratio, annealing temperature, and annealing time. We also investigated the impact of these synthesis variables on the HER activity in alkaline electrolyte. The catalysts were characterized by XRD, SEM, and EDS. The formation of Ni metal particles with a thin oxygen-rich layer on the surface was demonstrated by microscopy and crystallographic characterization. Following optimization, the HER overpotential of the best performing electrocatalyst at a current density of 10 mA cm−2 was reduced to ca. 130 mV. The catalyst durability was tested over 100 h in KOH solutions at different electrolyte concentrations using various testing protocols such as constant current hold and potential cycling. The catalyst showed higher HER activity (100 mV lower HER overpotential) and better durability behavior (0.15 mV/h lower degradation rate) compared to a commercial Ni supported Vulcan XC-72 electrocatalyst.

Boosting the Performance of Aluminum-Air Batteries by Interface Modification.

The large-scale application of aqueous Al-air batteries is highly restricted by the performance of Al anodes. The severe self-corrosion and hydrogen evolution of the Al anode in a concentrated alkaline electrolyte are the main reason. Here, aimed at relieving side reactions and enhancing the utilization of metal Al, we propose a hybrid electrolyte additive of 2-mercaptobenzothiazole (MBT) and ZnO to form a protective film at the anode/electrolyte interface and to decrease the hydrogen evolution active site. The strong absorption capability of MBT on the metal surface, along with the reduced Zn-containing layer, enables a compact protective film with high hydrogen evolution potential on the Al surface. With this benefit, the hydrogen evolution reaction (HER) inhibition efficiency is up to 83.58%, endowing a superior Al-air battery with an energy density of 2376.71 Wh kgAl-1 under a current density of 25 mA cm-2. The conception of constructing a hybrid protective film on the metal surface not only favors the development of metal-air batteries but also facilitates metal corrosion protection.

A Dual-Cation Exchange Membrane Electrolyzer for Continuous H2 Production from Seawater.

Direct seawater splitting (DSS) offers an aspirational route toward green hydrogen (H2) production but remains challenging when operating in a practically continuous manner, mainly due to the difficulty in establishing the water supply-consumption balance under the interference from impurity ions. A DSS system is reported for continuous ampere-level H2 production by coupling a dual-cation exchange membrane (CEM) three-compartment architecture with a circulatory electrolyte design. Monovalent-selective CEMs decouple the transmembrane water migration from interferences of Mg2+, Ca2+, and Cl- ions while maintaining ionic neutrality during electrolysis; the self-loop concentrated alkaline electrolyte ensures the constant gradient of water chemical potential, allowing a specific water supply-consumption balance relationship in a seawater-electrolyte-H2 sequence to be built among an expanded current range. Even paired with commercialized Ni foams, this electrolyzer (model size: 2 × 2 cm2) continuously produces H2 from flowing seawater with a rate of 7.5 mL min-1 at an industrially relevant current of 1.0 A over 100 h. More importantly, the energy consumption can be further reduced by coupling more efficient NiMo/NiFe foams (≈6.2 kWh Nm-3 H2 at 1.0 A), demonstrating the potential to further optimize the continuous DSS electrolyzer for practical applications.

B-site disorder driven Griffiths-like phase and electrochemical behavior in Y2NiCrO6 double perovskite

In this investigation, nanoparticles of B-site disordered Y2NiCrO6 (YNCO) double perovskite were synthesized by the facile sol–gel method to evaluate their magnetic and electrochemical properties. Their crystallographic structure is monoclinic and the average size of the particles is 79±16 nm. XPS analysis indicated a mixed oxidation states of B-site transition metals Ni2+/Ni3+ and Cr2+/Cr3+. The mixed valence states of Ni and Cr, along with the mixed magnetic phases of YNCO, constitute a signature of the B-site disorder. This antisite disorder contributed to the observation of a Griffiths-like phase arising from ferromagnetic short-range interactions above the magnetic transition up to the Griffiths temperature, T G = 137 K. The synthesized YNCO double perovskite demonstrated a promising behavior as an electrode material for electrochemical supercapacitors. In a three-electrode system, it displayed a specific capacitance of 270 F g−1 at a current density of 0.5 A g−1. In a symmetric two-electrode system, YNCO exhibited a specific capacitance of 180 F g−1 at 0.5 A g−1, alongside an energy density of 6.25 Wh kg−1 at 250 W kg−1 power density. In both cases, we employed a mild 0.5 M neutral aqueous Na2SO4 solution as the electrolyte, in contrast to the typically employed corrosive and concentrated alkaline aqueous solution. The fascinating magnetic and charge storage properties of the B-site disordered YNCO double perovskite indicate its potential for use in spintronic devices and as efficient electrodes in symmetric hybrid supercapacitors.

Creation of Cationic Polymeric Nanotrap Featuring High Anion Density and Exceptional Alkaline Stability for Highly Efficient Pertechnetate Removal from Nuclear Waste Streams.

There is an urgent need for highly efficient sorbents capable of selectively removing 99TcO4- from concentrated alkaline nuclear wastes, which has long been a significant challenge. In this study, we present the design and synthesis of a high-performance adsorbent, CPN-3 (CPN denotes cationic polymeric nanotrap), which achieves excellent 99TcO4- capture under strong alkaline conditions by incorporating branched alkyl chains on the N3 position of imidazolium units and optimizing the framework anion density within the pores of a cationic polymeric nanotrap. CPN-3 features exceptional stability in harsh alkaline and radioactive environments as well as exhibits fast kinetics, high adsorption capacity, and outstanding selectivity with full reusability and great potential for the cost-effective removal of 99TcO4-/ReO4- from contaminated water. Notably, CPN-3 marks a record-high adsorption capacity of 1052 mg/g for ReO4- after treatment with 1 M NaOH aqueous solutions for 24 h and demonstrates a rapid removal rate for 99TcO4- from simulated Hanford and Savannah River Site waste streams. The mechanisms for the superior alkaline stability and 99TcO4- capture performances of CPN-3 are investigated through combined experimental and computational studies. This work suggests an alternative perspective for designing functional materials to address nuclear waste management.

A Mild Method for the Activation of Cation Exchange Membranes Used in Tubular PEM Electrolyzers.

Co-extrusion of both half-cells in tubular PEM water electrolyzers can lower the costs for hydrogen production, since the number of components is reduced and the production process is simplified. However, after co-extrusion of the inner half-cell and the ion exchange membrane, the membrane is in its fluoride sulfonyl form and must be hydrolyzed to achieve the proton conductive sulfonic acid to be ready for use. Common practice is the hydrolysis using concentrated alkaline solutions, which causes a corrosion of the laminated anode electrode. We developed a less corrosive method using triethylsilanol as reactant. Tubular membranes hydrolyzed with this new procedure were characterized and tested in an electrolyzer laboratory test setup.

Ultramicroporous crosslinked polyxanthene-poly(biphenyl piperidinium)-based anion exchange membranes for water electrolyzers operating under highly alkaline conditions.

Anion exchange membrane water electrolyzers (AEMWEs) suffer from low efficiencies and durability, due to the unavailability of appropriate anion exchange membranes (AEM). Herein, a rigid ladder-like polyxanthene crosslinker was developed for the preparation of ultramicroporous crosslinked polyxanthene-poly(biphenyl piperidinium)-based AEMs. Due to the synergetic effects of their ultramicroporous structure and microphase-separation morphology, the crosslinked membranes showed high OH- conductivity (up to 163 mS cm-1 at 80 °C). Furthermore, these AEMs also exhibited moderate water uptake, excellent dimensional stability, and remarkable alkaline stability. The single-cell AEMWE based on QPBP-PX-15% and equipped with non-noble catalysts achieved a current density of 3000 mA cm-2 at 2.03 V (compared to PiperION's 2.26 V) in 6 M KOH solution at 80 °C, which outperformed many AEMWEs that used platinum-group-metal catalysts. Thus, the crosslinked AEMs developed in this study showed significant potential for application in AEMWEs fed with concentrated alkaline solutions.

Controlling surface wetting in high-alkaline electrolytes for single facet Pt oxygen evolution electrocatalytic activity mapping by scanning electrochemical cell microscopy.

Scanning electrochemical cell microscopy (SECCM) has been used to explore structure-electrocatalytic activity relationships through high-resolution mapping of local activities of electrocatalysts. However, utilizing SECCM in strongly alkaline conditions presents a significant challenge due to the high wettability of the alkaline electrolyte leading to a substantial instability of the droplet in contact with the sample surface, and hence to unpredictable wetting and spreading of the electrolyte. The spreading phenomena in SECCM is confirmed by the electrochemical response of a free-diffusing redox probe and finite element method (FEM) simulations. Considering the significance of alkaline electrolytes in electrocatalysis, these wetting issues restrict the application of SECCM for electrocatalyst elucidation in highly alkaline electrolytes. We resolve this issue by incorporating a small percentage of polyvinylpyrrolidone (PVP) in the electrolyte inside the SECCM capillary to increase the surface tension of the electrolyte. To demonstrate successful wetting mitigation and stable SECCM mapping, we performed oxygen evolution reaction (OER) mapping on polycrystalline Pt by using 1 M KOH with an optimized PVP concentration. The OER activity maps correlated with the orientation of the exposed facets determined by electron backscatter diffraction and reveal different activities between Pt facets, hence confirming our methodology for exploring electrocatalytic activities in single facet scale in concentrated alkaline media. Interestingly, the maximum OER current density was highest for (110) and (111) which contradicts the activity trends in acidic electrolyte for which (100) is most active for the OER.

Enhancing corrosion resistance in Mg[sbnd]Li alloy through plasma electrolytic oxidation coatings — Exploring the impact of ionic liquids (BmimBF4)

The wide application of MgLi alloys is limited by the poor corrosion resistance, which needs to be improved by surface treatment. Plasma electrolytic oxidation (PEO) method is one of the most promising methods for the formation of oxide coatings on MgLi alloys. However, the conventional PEO technique with high energy consumption causes poor coating compactness and hampers efforts to enhance corrosion resistance. In this study, various concentrations of ionic liquids (1-butyl-3-methylimidazolium tetrafluoroborate, BmimBF4) are introduced into the concentrated alkaline electrolyte to facilitate the formation of a PEO coating on the surface of LA91 magnesium‑lithium (MgLi) alloy. The influence of BmimBF4 on PEO coatings has been investigated. The results indicate that a concentrated electrolyte significantly lowers the working voltage of PEO, thereby enhancing energy efficiency. Uneven adsorption on the substrate surface, resulting from the low concentration of BmimBF4 (≤20 mL/L) in the electrolyte, induces partial discharge, leading to high surface roughness and the formation of large pores. However, when an excessive amount of BmimBF4 (>20 mL/L) is present, it uniformly adsorbed onto the substrate surface during the initial stage of PEO process, forming a corrosion inhibitor layer. This leads to a consistent discharge on the surface of substrate throughout the entire PEO process, resulting in a reduction in both surface roughness and micropore size. Among these coatings, the one prepared in an electrolyte containing 20 mL/L BmimBF4 exhibits the highest contact angle (66.8° ± 3.8°) and the best long-term corrosion resistance (hydrogen evolution rates <0.02 mL·cm−2·h−1). These properties can be attributed to the physical and chemical adsorption of BmimBF4, which contains hydrophobic long alkyl chains, as well as the maximum thickness with extended discharging channels. This study offers a guiding strategy for further reducing energy consumption and enhancing the corrosion resistance of PEO coatings.

Synergistic effect of surfactant and 1,10-decanedithiol as corrosion inhibitor for zinc anode in alkaline electrolyte of zinc-air batteries

The self-discharge by corrosion of zinc-air batteries (ZABs) will result in the reduced coulombic efficiency and lower energy efficiency. The additives in electrolyte should not only inhibit the occurrence of self-corrosion during battery dormancy, but also achieve a stable cycle of adsorption–desorption during battery operation, improving the durability of discharge cycles. But the former requires strong binding between additives and zinc to form a dense protective film, while the latter requires easy desorption of additives and zinc without affecting discharge power, which is contradictory to balance. In this study, a dynamic combination of additives and zinc, as well as a design of multi-channel strategy for the corresponding protective layer, have been proposed to solve the issues of self-corrosion and discharge cycle stability. Specifically, the surfactant (octylphenol polyoxyethylene ether phosphate (OP-10P)) and 1,10-decanedithiol (DD) have been selected as the combined anti-corrosion additives in ZABs with concentrated alkaline solution. The synergistic inhibition mechanism and the stabilization mechanism in zinc-air full cells have been studied systematically. The results indicated that the combined inhibitors inhibited the self-corrosion of Zn efficiently in the dormancy, and the inhibition efficiency reached 99.9 % at the optimized proportion. OP-10P achieve the preferential adsorption on the zinc surface, and then the chelates of DD with Zn2+ deposit on the outer layer to form the protective film with fine hydrophobic performance. The stability of ZABs in discharge and charging cycles has been improved owing to the multilayer adsorption film on zinc surface, which retains ion transport channels with the homogeneously pores to weaken the dendrites and side reactions during galvanostatic cycles. A probable model on zinc surface was established to discuss the actual working mechanism.

Nickel Oxide-Aerogel Electrocatalysts for Oxygen Evolution Reaction in Alkaline Media: Experimental Approaches and Modeling-Assisted Strategies for Improving Performance and Durability

Anion exchange membrane water electrolyzers (AEMWEs) represent an attractive technology for producing “green” hydrogen that enables operation on pure water using platinum group metal (PGM)-free electrocatalysts at both anode and cathode. Also, AEMWEs do not require the use of highly concentrated and corrosive alkaline electrolytes and PGM-based catalysts, which are the major drawbacks of the incumbent low-temperature liquid-alkaline and proton exchange membrane electrolyzers, respectively.1,2 In this context, the development of PGM-free electrocatalysts for oxygen evolution reaction (OER) in alkaline media has attracted considerable research interest. Among different types of transition metal-based oxides, Ni oxides doped with Fe have shown the highest OER activity in alkaline media.3,4 Recently, we have developed at Los Alamos National Laboratory (LANL) a series of Ni oxide-based aerogel materials that, primarily in combination with Fe in different proportions, have shown respectable OER performance in the electrochemical cell and at the AEMWE anode operating on either neat deionized water or with a supporting electrolyte, 0.1 M KOH or K2CO3.5 For application at the AEMWE anode, the catalyst integration into the electrode catalyst layer, i.e., combining the catalyst with anion exchange ionomer (AEI) and binding agents, is crucial to prevent catalyst layer delamination and to create a good catalyst/electrolyte interface, which in turn enables high OH- conductivity within the catalyst layer.6 This latter aspect is especially important for achieving high AEMWE performance in pure water operation. In this work, we investigate the impact of combining our Ni-Fe oxide aerogel catalysts with different AEIs (various backbone chemistries, OH- functional groups) and different binding agents (e.g., Nafion ionomer) on the AEMWE performance. We will show that full activation of the catalyst by phase transformation from the original Ni oxide-like structure to the active layered (oxy)hydroxide is essential for achieving high OER activity, and it can be influenced by the catalyst layer composition. By advanced characterization techniques such as high-resolution scanning transmission electron microscopy, X-ray absorption spectroscopy, and Mössbauer spectroscopy, we will shed light onto the phase transformation process that results in superior OER activity of these materials in alkaline media.Following our prior machine learning studies aimed at optimizing for the synthesis of oxygen reduction electrocatalysts,7,8 we will also show how to improve the synthesis of Ni oxide aerogel-based OER catalysts to maximize activity and stability. This work is further supported by density functional theory (DFT) modeling studies to better understand reaction mechanisms, active sites, and ultimately what role transition metal dopants (Fe and Co) play in modifying OER activity. Studies of in situ dissolution of these dopants using DFT-generated, phase-constrained Pourbaix diagrams9 will guide synthesis through understanding this likely materials degradation pathway. References H. A. Miller et al., Sustain. Energy Fuels, 4, 2114–2133 (2020).C. Santoro et al., ChemSusChem, 202200027 (2022).S. Fu et al., Nano Energy, 44, 319–326 (2018)D. Xu et al., ACS Catal., 9, 7–15 (2019).P. Zelenay and D. Myers, "ElectroCat (Electrocatalysis Consortium);” U.S. Department of Energy, Energy Efficiency and Renewable Energy, Hydrogen and Fuel Cell Technologies Program, 2022 Annual Merit Review and Peer Evaluation Meeting, June 6-8, 2022. https://www.hydrogen.energy.gov/pdfs/review22/fc160_myers_zelenay_2022_o.pdfL. Osmieri et al., J. Power Sources, 556, 232484 (2023).M. R. Karim et al., ACS Appl. Energy Mater., 3, 9083–9088 (2020).W. J. M. Kort-Kamp et al., J. Power Sources, 559 (2023).E. F. Holby, G. Wang, and P. Zelenay, ACS Catal., 10, 14527–14539 (2020).

Preparation of dual cross-linked hydrogel electrolytes containing modified lignin for supercapacitors and sensors

Hydrogel electrolytes have the dual functions of electrolyte and separator and combine the advantages of liquid and solid electrolytes, making them one of the most ideal candidates for supercapacitors and sensors. However, hydrogel electrolytes are prone to deactivate when the operating temperature is too low. Therefore, dual cross-linked hydrogels with chemical bonds and multiple noncovalent interactions were prepared at room temperature using activated modified lignin. Dual cross-linked hydrogel had excellent mechanical performance and fatigue resistance, whose tensile elongation could reach 700 %. Because the hydrogel contained a concentrated alkaline solution, the electrolyte achieved excellent freezing resistance and a high ionic conductivity of 0.345 S cm−1 (−40 ℃, 0.044 S cm−1). Supercapacitors assembled with the hydrogel electrolyte demonstrated a high specific capacitance of 210 F g−1 (−40 ℃, 176 F g−1) at 1.0 A g−1. Furthermore, the hydrogel electrolyte exhibited good electrochemical properties not only in alkaline environments but also in neutral and acidic conditions. The hydrogel could also act as a flexible sensor with a sensitivity of 1.34 within a 100 % strain, making it a promising material for wearable sensors to monitor joint activities in the human body.

N-Methylquinuclidinium-Based Anion Exchange Membrane with Ultrahigh Alkaline Stability.

Anion-exchange-membrane (AEM) water electrolysis is a promising technology for hydrogen production from renewable energy sources. However, the bottleneck of its development is the poor comprehensive performance of AEM, especially the stability at highly concentrated alkaline condition and temperature. Herein, a new cationic group N-methylquinuclidinium with enhanced alkaline stability is proposed and hereby a full-carbon chain poly(aryl quinuclidinium) AEM is prepared. Compared with reported AEMs, it shows ultrahigh comprehensive alkaline stability (no chemical decomposition, no decay of conductivity) in 10m NaOH aqueous solution at 80°C for more than 1800h, excellent dimensional stability (swelling ratio: <10% in pure water, <2% in 10m NaOH) in OH- form at 80°C, high OH- conductivity (≈139.1mScm-1 at 80°C), and high mechanical properties (tensile strength: 41.5MPa, elongation at break: 50%). The water electrolyzer using the AEM exhibits a high current density (1.94Acm-2 at 2.0V) when assembled with nickel-alloy foam electrodes, and high durability when assembled with nickel foam electrodes.

Assessment of the performance of alkali-activated slag/fly ash using liquid and solid activators: early-age properties and efflorescence

The use of solid activators to prepare alkali-activated materials (AAM) holds great potential for on-site applications, as it eliminates the need to transport and store large quantities of concentrated alkaline solutions. This study compared the early-age properties and efflorescence between alkali-activated slag/fly ash (AASF) using solid and liquid sodium silicates as activators. The results revealed that AASF with solid sodium silicates exhibited comparable mechanical strength while possessing reduced initial setting time and flowability. All AASF mixtures were susceptible to efflorescence and carbonation, resulting in varying mineralogical compositions of carbonation products: Vaterite was detected in AASF with solid activators, while aragonite and pirssonite were identified in AASF with liquid activators containing 4 and 6 wt.% Na2O, respectively. The efflorescence of AASF exposed to bottom water was more severe than those exposed to natural conditions, as evidenced by the decalcification of reaction products, migration of alkalis, and formation of crystalline carbonates.