Technological Advances and Market Developments of Solid-State Batteries: A Review.

Batteries are essential in modern society as they can power a wide range of devices, from small household appliances to large-scale energy storage systems. Safety concerns with traditional lithium-ion batteries prompted the emergence of new battery technologies, among them solid-state batteries (SSBs), offering enhanced safety, energy density, and lifespan. This paper reviews current state-of-the-art SSB electrolyte and electrode materials, as well as global SSB market trends and key industry players. Solid-state electrolytes used in SSBs include inorganic solid electrolytes, organic solid polymer electrolytes, and solid composite electrolytes. Inorganic options like lithium aluminum titanium phosphate excel in ionic conductivity and thermal stability but exhibit mechanical fragility. Organic alternatives such as polyethylene oxide and polyvinylidene fluoride offer flexibility but possess lower ionic conductivity. Solid composite electrolytes combine the advantages of inorganic and organic materials, enhancing mechanical strength and ionic conductivity. While significant advances have been made for composite electrolytes, challenges remain for synthesis intricacies and material stability. Nuanced selection of these electrolytes is crucial for advancing resilient and high-performance SSBs. Furthermore, while global SSB production capacity is currently below 2 GWh, it is projected to grow with a >118% compound annual growth rate by 2035, when the potential SSB market size will likely exceed 42 billion euros.

A mixed-ligand Co metal-organic framework and its carbon composites as excellent electrocatalysts for the oxygen evolution reaction in green-energy devices.

Oxygen evolution reaction (OER) electrocatalysts are frequently made from noble metal-based oxides like ruthenium/iridium oxides. However, because of their scarcity and high price, researchers are now focusing on creating innovative OER catalysts based on affordable transition metals that have improved electrical conductivity and accessibility to active sites. Metal-organic frameworks (MOFs), a unique class of inorganic materials with excellent physical and chemical properties, have witnessed significant progress in promising green energy systems. In this work, a novel mixed-ligand metal-organic framework [Co(µ-1κN,2κN'-BDP)(µ3-1κoo',2κo''2κo'''-BTC)]n·nH2O (BDP = boron-dipyrromethene or BODIPY; BTC = benzene tricarboxylate) denoted as CoBDPMOF has been synthesized, and its composites with different carbon materials have been designed. Compared to the pristine MOF, the composites showed enhanced electrocatalytic activity toward the oxygen evolution reaction (OER) in alkaline media. In addition, the CoBDPMOF with activated carbon showed the highest OER performance with a low Tafel slope (82 mV dec-1) and the highest j600 (59.8 mA cm-2), outperforming noble metal IrO2, the OER benchmark electrocatalyst. This study presents new insights into the design and application of CoBDPMOF-based materials for energy conversion and suggests promising avenues for further research and development in electrocatalysis.

Applications of Polymer Electrolytes in Lithium-Ion Batteries: A Review.

Polymer electrolytes, a type of electrolyte used in lithium-ion batteries, combine polymers and ionic salts. Their integration into lithium-ion batteries has resulted in significant advancements in battery technology, including improved safety, increased capacity, and longer cycle life. This review summarizes the mechanisms governing ion transport mechanism, fundamental characteristics, and preparation methods of different types of polymer electrolytes, including solid polymer electrolytes and gel polymer electrolytes. Furthermore, this work explores recent advancements in non-aqueous Li-based battery systems, where polymer electrolytes lead to inherent performance improvements. These battery systems encompass Li-ion polymer batteries, Li-ion solid-state batteries, Li-air batteries, Li-metal batteries, and Li-sulfur batteries. Notably, the advantages of polymer electrolytes extend beyond enhancing safety. This review also highlights the remaining challenges and provides future perspectives, aiming to propose strategies for developing novel polymer electrolytes for high-performance Li-based batteries.

Bipolar Membranes for Direct Borohydride Fuel Cells-A Review.

Direct liquid fuel cells (DLFCs) operate directly on liquid fuel instead of hydrogen, as in proton-exchange membrane fuel cells. DLFCs have the advantages of higher energy densities and fewer issues with the transportation and storage of their fuels compared with compressed hydrogen and are adapted to mobile applications. Among DLFCs, the direct borohydride-hydrogen peroxide fuel cell (DBPFC) is one of the most promising liquid fuel cell technologies. DBPFCs are fed sodium borohydride (NaBH4) as the fuel and hydrogen peroxide (H2O2) as the oxidant. Introducing H2O2 as the oxidant brings further advantages to DBPFC regarding higher theoretical cell voltage (3.01 V) than typical direct borohydride fuel cells operating on oxygen (1.64 V). The present review examines different membrane types for use in borohydride fuel cells, particularly emphasizing the importance of using bipolar membranes (BPMs). The combination of a cation-exchange membrane (CEM) and anion-exchange membrane (AEM) in the structure of BPMs makes them ideal for DBPFCs. BPMs maintain the required pH gradient between the alkaline NaBH4 anolyte and the acidic H2O2 catholyte, efficiently preventing the crossover of the involved species. This review highlights the vast potential application of BPMs and the need for ongoing research and development in DBPFCs. This will allow for fully realizing the significance of BPMs and their potential application, as there is still not enough published research in the field.

State of the Art Membrane Science and Technology in the Iberian Peninsula 2021-2022.

This Special Issue of the journal Membranes arises from the need to highlight the developments in the field of membrane research and membrane processes that have been emerging in recent years by researchers and research groups based in the Iberian Peninsula [...].

Effect of carbon support on the activity of monodisperse Co45Pt55 nanoparticles for oxygen evolution in alkaline media.

Oxygen evolution reaction (OER) represents the efficiency-limiting reaction in water electrolyzers, metal-air batteries, and unitized regenerative fuel cells. To achieve high-efficiency OER in alkaline media, we fabricated three novel electrocatalysts by the assembly of as-prepared Co45Pt55 alloy nanoparticles (NPs) on three different carbon-based support materials: reduced graphene oxide (CoPt/rGO), mesoporous graphitic carbon nitride (CoPt/mpg-CN), and commercial Ketjenblack carbon (CoPt/KB). Voltammetry studies revealed that CoPt/rGO electrocatalyst provided lower OER overpotentials accompanied by higher currents and specific current density values than the other two studied materials. Moreover, CoPt/rGO outperformed commercial CoPt/C electrocatalysts in terms of notably higher specific current densities. Additionally, it was found that CoPt/rGO electrocatalyst activity increases with increasing temperature up to 85°C, as suggested by the increase in the exchange current density. Electrochemical impedance spectroscopy studies of three electrocatalysts in OER revealed similar charge transfer resistance, although CoPt/rGO provided a higher current density. The main issue observed during long-term chronoamperometry and chronopotentiometry studies is the materials' instability under OER polarization conditions, which is still to be tackled in future work.

Highly Efficient Oxygen Electrode Obtained by Sequential Deposition of Transition Metal-Platinum Alloys on Graphene Nanoplatelets.

A set of platinum (Pt) and earth-abundant transition metals (M = Ni, Fe, Cu) on graphene nanoplatelets (sqPtM/GNPs) was synthesised via sequential deposition to establish parallels between the synthesis method and the materials' electrochemical properties. sqPtM/GNPs were assessed as bifunctional electrocatalysts for oxygen evolution (OER) and reduction (ORR) reactions for application in unitised regenerative fuel cells and metal-air batteries. sqPtFe/GNPs showed the highest catalytic performance with a low potential difference of ORR half-wave potential and overpotential at 10 mA cm-2 during OER, a crucial parameter for bifunctional electrocatalysts benchmarking. A novel two-stage synthesis strategy led to higher electrocatalytic performance by facilitating the reactants' access to the active sites and reducing the charge-transfer resistance.

Transformation of waste seed biomass of Cordia myxa into valuable bioenergy through membrane bioreactor using green nanoparticles of indium oxide.

Depletion of non-renewable fuel has obliged researchers to seek out sustainable and environmentally friendly alternatives. Membranes have proven to be an effective technique in biofuel production for reaction, purification, and separation, with the ability to use both porous and non-porous membranes. It is demonstrated that a membrane-based sustainable and green production can result in a high degree of process intensification, whereas the recovery and repurposing of catalysts and alcohol are anticipated to increase the process economics. Therefore, in this study sustainable biodiesel was synthesized from inedible seed oil (37 wt%) of Cordia myxa using a membrane reactor. Transesterification was catalyzed by heterogenous nano-catalyst of indium oxide prepared with leaf extract of Boerhavia diffusa. Highest biodiesel yield of 95 wt% was achieved at methanol to oil molar ratio of 7:1, catalyst load 0.8 wt%, temperature 82.5 °C and time 180 min In2O3 nanoparticles exhibited reusability up to five successive transesterification rounds. The production of methyl esters was confirmed using Fourier-transform infrared spectroscopy and Nuclear Magnetic Resonance. The predominant fatty acid methyl ester detected in the biodiesel was 5, 8-octadecenoic acid. Biodiesel fuel qualities were determined to be comparable to worldwide ASTM D-6571 and EN-14214 standards. Finally, it was concluded that membrane technology can result in a highly intensified reaction process while efficient recovery of both nano catalysts and methanol increases the economics of transesterification and lead to sustainable production.

Facile Synthesis of Low-Cost Copper-Silver and Cobalt-Silver Alloy Nanoparticles on Reduced Graphene Oxide as Efficient Electrocatalysts for Oxygen Reduction Reaction in Alkaline Media.

Copper-silver and cobalt-silver alloy nanoparticles deposited on reduced graphene oxide (CuAg/rGO and CoAg/rGO) were synthesized and examined as electrocatalysts for oxygen reduction reaction (ORR) and hydrogen peroxide reduction reaction (HPRR) in alkaline media. Characterization of the prepared samples was done by transmission electron microscopy (TEM), Fourier-transform infrared spectroscopy (FTIR), Raman spectroscopy, X-ray diffraction analysis (XRD), and scanning electron microscopy with integrated energy-dispersive X-ray spectroscopy (SEM-EDS). CuAg/rGO and CoAg/rGO nanoparticles diameter ranged from 0.4 to 9.2 nm. The Ag loading was ca. 40 wt.% for both electrocatalysts, with that for Cu and Co being 35 and 17 wt.%, respectively. CoAg/rGO electrocatalyst showed a Tafel slope of 109 mV dec-1, significantly lower than that for CuAg/rGO (184 mV dec-1), suggesting faster ORR kinetics. Additionally, a higher diffusion current density was obtained for CoAg/rGO (-2.63 mA cm-2) than for CuAg/rGO (-1.74 mA cm-2). The average value of the number of electrons transferred during ORR was 2.8 for CuAg/rGO and 3.3 for CoAg/rGO electrocatalyst, further confirming the higher ORR activity of the latter. On the other hand, CuAg/rGO showed higher peak current densities (-3.96 mA cm-2) for HPRR compared to those recorded for CoAg/rGO electrocatalyst (-1.96 mA cm-2).

Platinum-Dysprosium Alloys as Oxygen Electrodes in Alkaline Media: An Experimental and Theoretical Study.

Platinum-dysprosium (Pt-Dy) alloys prepared by the arc melting technique are assessed as potential electrodes for the oxygen reduction reaction (ORR) using voltammetry and chronoamperometry in alkaline media. A relatively small change (10 at.%) in the alloy composition brought a notable difference in the alloys' performance for the ORR. Pt40Dy60 electrode, i.e., the electrode with a lower amount of Pt, was identified to have a higher activity towards ORR as evidenced by lower overpotential and higher current densities under identical experimental conditions. Furthermore, DFT calculations point out the unique single-atom-like coordination and electronic structure of Pt atoms in the Pt40Dy60 surface as responsible for enhanced ORR activity compared to the alloy with a higher Pt content. Additionally, Pt-Dy alloys showed activity in the oxygen evolution reaction (OER), with the OER current density lower than that of pure Pt.

Rational design of mixed ionic-electronic conducting membranes for oxygen transport.

The mixed ionic-electronic conducting (MIEC) oxides have generated significant research efforts in the scientific community during the last 40 years. Since then, many MIEC compounds, most of which are based on perovskite oxides, have been synthesized and characterized. These compounds, when heated to high temperatures, form solid ceramic membranes with high oxygen ionic and electrical conductivity. The driving force for oxygen ion transport is the ionic transfer of oxygen from the air as a result of the differential partial pressure of oxygen across the membrane. Electronic and ionic transport in a range of MIEC materials has been studied using the defect theory, particularly when dopants are introduced to the compound of interest. As a result, many types of ionic oxygen transport limits exist, each with a distinct phase shift depending on the temperature and partial pressure of oxygen in use. In combination with theoretical principles, this work attempts to evaluate the research community's major and meaningful achievements in this subject throughout the preceding four decades.

Polyvinyl Alcohol/Polyaniline/Carboxylated Graphene Oxide Nanocomposites for Coating Protection of Cast Iron in Simulated Seawater.

In our daily lives and product manufacturing, metal corrosion causes significant economic losses. Numerous polymeric composite coatings have been shown to be resistant to harsh environments, such as those found in marine environments. In this study, a composite of polyvinyl alcohol/polyaniline blend loaded with carboxylated graphene was explored in the search for long-lasting coatings to resist electrochemical deterioration of cast iron in desalination systems of saltwater. Polyvinyl alcohol/polyaniline/carboxylated graphene oxide nanocomposite was spin-coated onto cast iron samples. Electrochemical impedance spectroscopy (EIS) and electrochemical DC corrosion testing with a three-electrode system were used to study corrosion resistance in uncoated and coated cast iron samples. The results exhibit effective corrosion protection properties. The EIS data indicated better capacitance and higher impedance values for coated samples than bare metal, depicting enhanced corrosion resistance against the saline environment. Tafel analysis confirmed a significant decrease in the corrosion rate of the PVA/PANI/GO-COOH coated sample.

Steps towards highly-efficient water splitting and oxygen reduction using nanostructured ß-Ni(OH)2.

ß-Ni(OH)2 nanoplatelets are prepared by a hydrothermal procedure and characterized by scanning and transmission electron microscopy, X-ray diffraction analysis, Raman spectroscopy, and X-ray photoelectron spectroscopy. The material is demonstrated to be an efficient electrocatalyst for oxygen reduction, oxygen evolution, and hydrogen evolution reactions in alkaline media. ß-Ni(OH)2 shows an overpotential of 498 mV to reach 10 mA cm-2 towards oxygen evolution, with a Tafel slope of 149 mV dec-1 (decreasing to 99 mV dec-1 at 75 °C), along with superior stability as evidenced by chronoamperometric measurements. Similarly, a low overpotential of -333 mV to reach 10 mA cm-2 (decreasing to only -65 mV at 75 °C) toward hydrogen evolution with a Tafel slope of -230 mV dec-1 is observed. Finally, ß-Ni(OH)2 exhibits a noteworthy performance for the ORR, as evidenced by a low Tafel slope of -78 mV dec-1 and a number of exchanged electrons of 4.01 (indicating direct 4e--oxygen reduction), whereas there are only a few previous reports on modest ORR activity of pure Ni(OH)2.

Overview of Membrane Science and Technology in Portugal.

Membrane research in Portugal is aligned with global concerns and expectations for sustainable social development, thus progressively focusing on the use of natural resources and renewable energy. This review begins by addressing the pioneer work on membrane science and technology in Portugal by the research groups of Instituto Superior Técnico-Universidade de Lisboa (IST), NOVA School of Science and Technology-Universidade Nova de Lisboa (FCT NOVA) and Faculdade de Engenharia-Universidade do Porto (FEUP) aiming to provide an historical perspective on the topic. Then, an overview of the trends and challenges in membrane processes and materials, mostly in the last five years, involving Portuguese researchers, is presented as a contribution to a more sustainable water-energy-material-food nexus.

Advanced Materials for Electrochemical Energy Conversion and Storage Devices.

Electrochemical energy conversion and storage is attracting particular attention due to the drawbacks and limitations of existing fossil fuel-based technologies [...].

Carbon-Supported Trimetallic Catalysts (PdAuNi/C) for Borohydride Oxidation Reaction.

The synthesis of palladium-based trimetallic catalysts via a facile and scalable synthesis procedure was shown to yield highly promising materials for borohydride-based fuel cells, which are attractive for use in compact environments. This, thereby, provides a route to more environmentally friendly energy storage and generation systems. Carbon-supported trimetallic catalysts were herein prepared by three different routes: using a NaBH4-ethylene glycol complex (PdAuNi/CSBEG), a NaBH4-2-propanol complex (PdAuNi/CSBIPA), and a three-step route (PdAuNi/C3-step). Notably, PdAuNi/CSBIPA yielded highly dispersed trimetallic alloy particles, as determined by XRD, EDX, ICP-OES, XPS, and TEM. The activity of the catalysts for borohydride oxidation reaction was assessed by cyclic voltammetry and RDE-based procedures, with results referenced to a Pd/C catalyst. A number of exchanged electrons close to eight was obtained for PdAuNi/C3-step and PdAuNi/CSBIPA (7.4 and 7.1, respectively), while the others, PdAuNi/CSBEG and Pd/CSBIPA, presented lower values, 2.8 and 1.2, respectively. A direct borohydride-peroxide fuel cell employing PdAuNi/CSBIPA catalyst in the anode attained a power density of 47.5 mW cm-2 at room temperature, while the elevation of temperature to 75 °C led to an approximately four-fold increase in power density to 175 mW cm-2. Trimetallic catalysts prepared via this synthesis route have significant potential for future development.

Bimetallic Co-Based (CoM, M = Mo, Fe, Mn) Coatings for High-Efficiency Water Splitting.

Bimetallic cobalt (Co)-based coatings were prepared by a facile, fast, and low-cost electroless deposition on a copper substrate (CoFe, CoMn, CoMo) and characterized by scanning electron microscopy with energy dispersive X-ray spectroscopy and X-ray diffraction analysis. Prepared coatings were thoroughly examined for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in alkaline solution (1 M potassium hydroxide, KOH) and their activity compared to that of Co and Ni coatings. All five coatings showed activity for both reactions, where CoMo and Co showed the highest activity for HER and OER, respectively. Namely, the highest HER current density was recorded at CoMo coating with low overpotential (61 mV) to reach a current density of 10 mA·cm-2. The highest OER current density was recorded at Co coating with a low Tafel slope of 60 mV·dec-1. Furthermore, these coatings proved to be stable under HER and OER polarization conditions.

Carbon-Supported Mo2C for Oxygen Reduction Reaction Electrocatalysis.

Molybdenum carbide (Mo2C)-based electrocatalysts were prepared using two different carbon supports, commercial carbon nanotubes (CNTs) and synthesised carbon xerogel (CXG), to be studied from the point of view of both capacitive and electrocatalytic properties. Cation type (K+ or Na+) in the alkaline electrolyte solution did not affect the rate of formation of the electrical double layer at a low scan rate of 10 mV s-1. Conversely, the different mobility of these cations through the electrolyte was found to be crucial for the rate of double-layer formation at higher scan rates. Molybdenum carbide supported on carbon xerogel (Mo2C/CXG) showed ca. 3 times higher double-layer capacity amounting to 75 mF cm-2 compared to molybdenum carbide supported on carbon nanotubes (Mo2C/CNT) with a value of 23 mF cm-2 due to having more than double the surface area size. The electrocatalytic properties of carbon-supported molybdenum carbides for the oxygen reduction reaction in alkaline media were evaluated using linear scan voltammetry with a rotating disk electrode. The studied materials demonstrated good electrocatalytic performance with Mo2C/CXG delivering higher current densities at more positive onset and half-wave potential. The number of electrons exchanged during oxygen reduction reaction (ORR) was calculated to be 3, suggesting a combination of four- and two-electron mechanism.

Molybdenum Carbide Nanoparticles on Carbon Nanotubes and Carbon Xerogel: Low-Cost Cathodes for Hydrogen Production by Alkaline Water Electrolysis.

Low-cost molybdenum carbide (Mo2 C) nanoparticles supported on carbon nanotubes (CNTs) and on carbon xerogel (CXG) were prepared and their activity for the hydrogen evolution reaction (HER) was evaluated in 8 m KOH aqueous electrolyte at 25-85 °C. Measurements of the HER by linear scan voltammetry allowed us to determine Tafel slopes of 71 and 74 mV dec(-1) at 25 °C for Mo2 C/CNT and Mo2 C/CXG, respectively. Stability tests were also performed, which showed the steady performance of the two electrocatalysts. Moreover, the HER kinetics at Mo2 C/CNT was enhanced significantly after the long-term stability tests. The specific activity of both materials was high, and a higher stability was obtained for the activated Mo2 C/CNT (40 A g(-1) at -0.40 V vs. the reversible hydrogen electrode).

Molecular Beam-Thermal Desorption Spectrometry (MB-TDS) Monitoring of Hydrogen Desorbed from Storage Fuel Cell Anodes.

Different types of experimental studies are performed using the hydrogen storage alloy (HSA) MlNi3.6Co0.85Al0.3Mn0.3 (Ml: La-rich mischmetal), chemically surface treated, as the anode active material for application in a proton exchange membrane fuel cell (PEMFC). The recently developed molecular beam-thermal desorption spectrometry (MB-TDS) technique is here reported for detecting the electrochemical hydrogen uptake and release by the treated HSA. The MB-TDS allows an accurate determination of the hydrogen mass absorbed into the hydrogen storage alloy (HSA), and has significant advantages in comparison with the conventional TDS method. Experimental data has revealed that the membrane electrode assembly (MEA) using such chemically treated alloy presents an enhanced surface capability for hydrogen adsorption.