Porous Electrodes Research Articles

Organic-Inorganic Hybrid Solid Composite Electrolytes for High Energy Density Lithium Batteries: Combining Manufacturability, Conductivity, and Stability.

The deployment of solid and quasi-solid electrolytes in lithium metal batteries is envisioned to push their energy densities to even higher levels, in addition to providing enhanced safety. This article discusses a set of hybrid solid composite electrolytes which combine functional properties with electrode compatibility and manufacturability. Their anodic stability >5V versus Li+/Li and compatibility with lithium metal stem from the incorporated ionic liquid electrolyte, whereas the organic-inorganic hybrid host structure boosts their conductivity up to 2.7mScm-1 at room temperature. The absence of strong acids enables compatibility with porous NMC811 electrodes. Liquid precursor solutions can be readily impregnated into porous electrodes, facilitating cell assembly. Electrolytes containing TFSI- as the only anion have a superior compatibility toward high-voltage positive electrode materials, whereas electrolytes containing both FSI- and TFSI- have a better compatibility toward lithium metal. Using the former as catholyte and the latter as anolyte, NMC811/Li coin cells retain up to 100% of their initial capacity after 100 cycles (0.2C, 3.0-4.4V vs Li+/Li). Because of their unprecedented combination of functional properties, electrode compatibility, and manufacturability, these hybrid solid composite electrolytes are potential candidates for the further development of lithium metal battery technology.

Electronic Synergistic Effects on the Stability and Oxygen Evolution Reaction Efficiency of the Mesoporous LiMn2-xMxO4 (M = Mn, Fe, Co, Ni, and Cu) Electrodes.

Stable porous manganese oxide-based electrodes are essential for clean energy generation and storage because of their high natural abundance and health safety. This investigation focuses on mesoporous LiMn2-xMxO4 (where M is Fe, Co, Ni, and Cu and x is 0, 0.1, 0.3, 0.5, and 0.67) electrodes and thin/thick films. The mesoporous electrodes and films are fabricated by coating clear and homogeneous ethanol solutions of the salts (LiNO3, [Mn(OH2)4](NO3)2, and [M(OH2)x](NO3)2) and surfactants (P123 and CTAB) and calcining at elevated temperature (denoted as F-LiMn2-xMxO4, G-LiMn2-xMxO4, and meso-LiMn2-xMxO4, respectively). The electrochemical properties, stability, and oxygen evolution reaction (OER) performance of the F/G-LiMn2-xMxO4 electrodes are investigated in alkaline media using a three electrode setup. The F-LiMn1.33M0.67O4 electrodes (where M is Mn, Fe, Co, and Ni) exhibit low Tafel slopes of 60, 43, 44, and 32 mV/dec, respectively. While all the Mn-rich and F-LiMn2-xFexO4 electrodes degrade via Mn(VI) disproportionation reaction, the 33% Co electrode shows high stability during the OER. The nickel-based electrodes are stable with as little as 15% Ni and display excellent OER performance over 25% Ni, albeit undergoing a transformation that accumulates Ni(OH)2 species on the electrode surface. Copper in the F-LiMn2-xCuxO4 electrodes is homogeneous at low Cu percentages but forms a CuO phase above 15% Cu, undergoes degradation, and displays a weak OER performance. In short, Co and Ni stabilize the F-LiMn1.33Co0.67O4 and F-LiMn1.7Ni0.3O4 electrodes, which display excellent OER performance.

Influence of Electrolyte Saturation on the Performance of Li-O2 Batteries.

Electrolyte saturation can strongly affect the Li-O2 battery performance. However, it is unclear to what extent saturation reduction will impact the battery capacity. In this study, we investigated the influence of electrolyte saturation and distribution within a porous positive electrode on the deep discharge-charge capacities and cycling stability. The study used both models and experiments to investigate the change of electrolyte distribution, double-layer capacitance, ohmic resistance, and O2 concentration in the positive electrode at different electrolyte saturations. Results revealed that electrodes with 60% electrolyte saturation achieved almost the same maximum discharge (6.38 vs 6.76 mAh/cm2) and charge (5.52 vs 5.65 mAh/cm2) capacities with fully saturated electrodes. The partially wet positive electrode (40% saturation) obtained more cycles than the electrode with 100% saturation before the discharge capacity dropped below the cutoff point. However, the electrode with 40% saturation had a low average charging efficiency of 88.76%, whereas the fully saturated electrode obtained 98.96% charging efficiency. Moreover, the fully wet positive electrode had the lowest overpotential during cycling (1.26-1.39 V). The measured electrochemically active surface areas showed that even 40% saturation could sufficiently wet the positive electrode surface and obtain a double-layer capacitance (18.12 mF) similar to that with 100% saturation (20.4 mF). Furthermore, a considerable increase in O2 concentration at wetted surface areas was observed for the electrolyte saturation of less than 60% due to the significantly higher O2 diffusivity in the gas phase.

Front Cover: High‐performance Porous Electrodes for Flow Batteries: Improvements of Specific Surface Areas and Reaction Kinetics (ChemElectroChem 21/2024)

Front Cover: High‐performance Porous Electrodes for Flow Batteries: Improvements of Specific Surface Areas and Reaction Kinetics (ChemElectroChem 21/2024)

3D-printed Bio-inspired porous electrode by bidirectional enhancement strategy with high mass loading and enhanced energy density for supercapacitors

The effective strategy for increasing areal capacity involves the use of 3D printed thick-electrode with high mass loading. However, thick-electrode still encounters challenges such as incomplete electrolyte penetration and slow ion transport. Here, we successfully prepared lignocellulosic nanofibrils (LCNFs) from abundant bamboo biomass and developed functional ink composed of LCNFs/ carbon nanotubes (CNTs) / polyaniline (PANI) / polyvinyl alcohol (PVA) for printing. An innovative 3D printing bidirectional enhancement strategy was proposed to increase the mass loading of active materials in the vertical direction and construct ion transport channels in the transverse direction. The biomimetic porous N-doped electrode obtained after annealing treatment exhibits a more continuous conductive network, larger surface area, higher utilization of active materials, and smoother ion transport pathways compared to thick-electrode. Therefore, the Triangles biomimetic electrode exhibits an enhanced areal/specific capacitance compared to thick-electrode, reaching 5.30F·cm−2 (184.03F·g−1) and 4.40F·cm−2 (122.22F·g−1) at 2 mA·cm−2, respectively. The symmetric device demonstrates an areal capacitance of 1.34F·cm−2 at 1 mA·cm−2 and achieves an energy density of 0.186 mWh·cm−2 at a power density of 0.49 mW·cm−2. The work provides valuable insights into the design of electrode structures for high-performance supercapacitors.

Porous activated carbon electrodes derived from Eleusine coracana biowaste in electric double layer capacitors: Nanoarchitectonics and performance

The development of high-performance supercapacitors from biowaste is crucial for advancing sustainable and renewable energy storage technologies. In this study, we report the fabrication of electrodes for high-performance supercapacitors using porous carbon derived from red millet (Eleusine coracana) straw. Porous carbon was synthesized via a two-step chemical activation process using KOH, resulting in a hierarchical pore structure comprising macro-, meso-, and micropores. The red millet-based porous carbon electrodes, assembled in a two-electrode symmetrical supercapacitor, exhibited a specific capacitance of 68 Fg⁻1 at a current density of 0.5 Ag⁻1 in a 1 M Na₂SO₄ aqueous electrolyte. At a mass loading of 5 mg per electrode, the system demonstrated a specific capacitance of 300 Fg⁻1 at 1 Ag⁻1, with an energy density of 9.1 Whkg⁻1 and a power density of 1.86 kWkg⁻1, as determined from galvanostatic charge-discharge measurements. Additionally, the supercapacitor showed excellent cyclic stability, retaining 98.78% of its initial capacitance after 5000 cycles at 10 Ag⁻1. These findings highlight the potential of porous carbon derived from agricultural biowaste for scalable applications in electric double-layer capacitors.

Breaking the Limitations of Activity and Stability in Powdered Materials for Oxygen Evolution Reaction: The Critical Role of Catalyst-Inducing Seeds

Powdered catalysts are extensively employed in industrial-scale energy conversion devices but struggle with weak powder-substrate adhesion and inherent instability in gas-evolving and highly oxidative oxygen evolution reactions (OER). This work introduces an innovative strategy in which powdered materials serve a critical role as catalyst-inducing seeds to break these limitations. Specifically, powdered Ti2CTx MXene with anchored cobalt single atoms (Co-SAs) shows negligible catalytic activity on its own but serves as catalyst-inducing seeds, significantly enhancing the catalytic activity of the conductive FeNi substrate. Mechanistic studies demonstrate that Co-SAs accelerate the oxidation rate of Ti2CTx, leading to the micro-battery corrosion behavior between oxidized Co/Ti2CTx and FeNi alloy, which generates highly OER-active corrosion products tightly bonded to FeNi alloy, thereby enhancing catalytic activity and ensuring stability. The prepared porous electrode shows a low overpotential of 303mV to deliver an ultra-high current density of 1000mAcm-2 and maintains activity for 1200hours under high current density conditions, rivaling advanced self-supporting electrodes. Moreover, replacing Co in Co/Ti2CTx with metals like Fe, Ni or Mn, yields comparable effects, suggesting the scalability of catalyst-inducing seeds. This approach breaks traditional limitations of powdered materials in OER, offering an effective pathway to engineer advanced catalytic electrodes.

Topology optimization for the full-cell design of porous electrodes in electrochemical energy storage devices

Topology optimization for the full-cell design of porous electrodes in electrochemical energy storage devices

Development of Polymer Composite Membrane Electrolytes in Alkaline Zn/MnO2, Al/MnO2, Zinc/Air, and Al/Air Electrochemical Cells.

This paper reports on the novel composite membrane electrolytes used in Zn/MnO2, Al/MnO2, Al/air, and zinc/air electrochemical devices. The composite membranes were made using poly(vinyl alcohol), poly(acrylic acid), and a sulfonated polypropylene/polyethylene separator to enhance the electrochemical characteristics and dimensional stability of the solid electrolyte membranes. The ionic conductivity was improved significantly by the amount of acrylic acid incorporated into the polymer systems. In general, the ionic conductivity was also enhanced gradually as the testing temperature increased from 20 to 80 °C. Porous zinc gel electrodes and pure aluminum plates were used as the anodes, while porous carbon air electrodes or porous MnO2 electrodes were used as the cathodes. The cyclic voltammetry properties and electrochemical impedance characteristics were investigated to evaluate the cell behavior and electrochemical properties of these prototype cells. The results showed that these prototype cells had a low bulk resistance, a high cell power density, and a unique device stability. The Al/MnO2 cell achieved a density of 110 mW cm-2 at the designated current density for the discharge tests, while the other cells also exhibited good values in the range of 70-100 mW cm-2. Furthermore, the Zn/air cell consisting of the PVA/PAA = 10:5 composite membrane revealed an excellent discharge capacity of 1507 mAh. This represented a very high anode utilization of 95.7% at the C/10 rate.

Understanding the Wettability of C1N1 (Sub)Nanopores: Implications for Porous Carbonaceous Electrodes

AbstractUnderstanding how water interacts with nanopores of carbonaceous electrodes is crucial for energy storage and conversion applications. A high surface area of carbonaceous materials does not necessarily need to translate to a high electrolyte‐solid interface area. Herein, we study the interaction of water with nanoporous C1N1 materials to explain their very low specific capacitance in aqueous electrolytes despite their high surface area. Water was used to probe chemical environments, provided by pores of different sizes, in 1H MAS NMR experiments. We observe that regardless of their high hydrophilicity, only a negligible portion of water can enter the nanopores of C1N1, in contrast to a reference pure carbon material with a similar pore structure. The common paradigm that water easily enters hydrophilic pores does not apply to C1N1 nanopores below a few nanometers. Calorimetric and sorption experiments demonstrated strong water adsorption on the C1N1 surface, which restricts water mobility across the interface and impedes its penetration into the nanopores.

Tailored Design of a Nanoporous Structure Suitable for Thick Si Electrodes on a Stiff Oxide-Based Solid Electrolyte.

Oxide-based all-solid-state batteries are ideal next-generation batteries that combine high energy density and high safety, but their realization requires the development of interface bonding technology between the stiff solid electrolyte and electrode. Even if the interface could be bonded, it is difficult to hold the interface, because only the electrode expands/contracts unilaterally during charge/discharge reactions. In particular, silicon (Si), which has eagerly awaited as a next-generation negative-electrode material for many years, changes in volume by several hundred percent. To solve these problems, in this work, highly porous silicon oxide (SiOx) electrodes with different porous structures were fabricated on a stiff garnet-type Li7La3Zr2O12 solid electrolyte, the three-dimensional nanoporous structure was analyzed quantitatively, and the charge/discharge characteristics were investigated. The microscopic observation and electrochemical analysis revealed how we should control the porous structure, such as sizes of pores and SiOx, size distribution, and porosity, for repeated and stable charge/discharge cycles. In addition, the resultant porous SiOx electrodes demonstrated superior charge/discharge cycle performance even when it thickened to 5 μm, whereas non-porous SiOx easily peeled off from the solid electrolyte when its thickness exceeded 0.1 μm. The thick SiOx films greatly improved the energy density per unit area (mAh cm-2). Nanosized fine pores with an interconnected open-pore architecture effectively mitigated the internal and interfacial stress upon expansion (charge)/contraction (discharge) of Si, and as a result, the thick and porous SiOx electrode maintained the interfacial joint with the stiff solid electrolyte after repeated charge/discharge cycles. These results will provide useful insights for effectively designing more practical porous SiOx powder effectively.

Spray-Coated Ultrathin and Porous Films for Physiological Sensing and Force Detection.

Epidermal electronics employed on human skin for the long term require good breathability and nonforeign wearing. In this work, we combine phase separation and spray coating to fabricate a porous and ultrathin electrode within minutes as well as micrometer-scale porous pressure sensors. The resulting electrodes show a water vapor transmission rate of 18.4 mg·cm-2·h-1, sheet resistance of 5.2 Ω/sq, and thickness below 5 μm. The introduction of the biogel further reduced the electrode-skin impedance, which is lower than that of the commercial gel electrode, indicating that the electrode can have a high degree of conformal contact with the skin. The epidermal electronics prepared by this strategy exhibit an excellent performance in force sensing. Such results strongly prove the efficiency and practicality of the strategy.

Recent Advances in electrode optimization of electrochemical energy devices using Topology Optimization

Abstract Topology optimization (TO) has emerged as a prominent trend in recent years, driven by its ability to explore optimized material distributions from scratch. Recently, there has been a significant shift in the application of TO, in optimizing systems involving complex electrochemical reactions, particularly electrode porous structures. This paper aims to examine the utilization of TO in enhancing electrodes across various electrochemical devices. It encompasses a broad spectrum of applications, including the optimization of porous electrodes through the density-based method and interfaces between electrodes and electrolytes through the level-set method. The paper will delve into the challenges and opportunities associated with employing TO in electrode design for electrochemical devices. These challenges involve addressing computational complexity, the absence of theoretical foundations for optimized structures, and the fabrication of complex structures for practical real-world applications. Additionally, beyond TO, the paper will spotlight other notable techniques in the structural design of porous electrodes using mathematical optimization. By offering insights into state-of-the-art research and developments in TO's application to electrode design, this paper provides researchers with valuable resources to navigate the evolving landscape of electrode design for electrochemical energy devices.

Macroscopic properties of solid oxide fuel cell electrodes via microstructure‐based numerical homogenization

AbstractDue to climate change, sustainable and energy‐efficient power supply is urgently required. To increase the performance of solid oxide fuel cells, the effects of the microstructure of their porous electrodes need to be studied. Therefore, real tomography images are used to (i) characterize specific geometrical features such as the two‐point correlation function or the tortuosity and (ii) determine the effective conductivities (thermal, ionic, electronic) and the effective permeability. The temperature‐dependent and anisotropic physical properties based on the first‐order homogenization method are described by the dissipation potential. The results can be used in macroscopic fuel cell simulations to bridge the gap between the micro and macro scale and to gain a better understanding of which characteristics of electrode microstructures are favorable for higher efficiency.

High-fidelity reconstruction of porous cathode microstructures from FIB-SEM data with deep learning

Accurate modeling of lithium-ion battery (LIB) electrode microstructures provides essential references for understanding degradation mechanisms and optimizing materials. Traditional segmentation methods often struggle to accurately capture the complex microstructures of porous LIB electrodes in focused ion beam scanning electron microscopy (FIB-SEM) data. In this work, we develop a deep learning model based on the Swin Transformer to segment FIB-SEM data of a lithium cobalt oxide electrode, utilizing fused secondary and backscattered electron images. The proposed approach outperforms other deep learning methods, enabling the acquirement of 3D microstructure with reduced particle elongated artifacts. Analyses of the segmented microstructures reveal improved electrode tortuosity and pore connectivity crucial for ion and electron transport, emphasizing the necessity of accurate 3D modeling for reliable battery performance predictions. These results suggest a path toward voxel-level degradation analysis through more sensible battery simulation on high-fidelity microstructure models directly twinned from real porous electrodes.

Accessing Elastic Properties of Porous Solid Oxide Fuel Cell Electrodes Using 2D Image-Based Discrete Element Modeling and Deep Learning

Accessing Elastic Properties of Porous Solid Oxide Fuel Cell Electrodes Using 2D Image-Based Discrete Element Modeling and Deep Learning

Low-Energy Desalination Techniques, Development of Capacitive Deionization Systems, and Utilization of Activated Carbon

Water desalination technology has emerged as a critical area of research, particularly with the advent of more cost-effective alternatives to conventional methods, such as reverse osmosis and thermal evaporation. Given the vital importance of water for life and the scarcity of potable water for agriculture and livestock—especially in the Kingdom of Saudi Arabia—the capacitive deionization (CDI) method for removing salt from water has been highlighted as the most economical choice compared to other techniques. CDI applies a voltage difference across two porous electrodes to extract salt ions from saline water. This study will investigate water desalination using CDI, utilizing a compact DC power source under 5 volts and a standard current of 2 amperes. We will convert waste materials like sunflower seeds, peanut shells, and rice husks into activated carbon through carbonization and chemical activation to improve its pore structure. Critical parameters for desalination, including voltage, flow rate, and total dissolved solids (TDS) concentration, have been established. The initial TDS levels are set at 2000, 1500, 1000, and 500 ppm, with flow rates of 38.2, 16.8, and 9.5 mL/min across the different voltage settings of 2.5, 2, and 1.5 volts, applicable to both direct and inverse desalination methods. The efficiency at TDS concentrations of 2000, 1500, and 1000 ppm remains between 18% and 20% for up to 8 min. Our results indicate that the desalination process operates effectively at a TDS level of 750 ppm, achieving a maximum efficiency of 45% at a flow rate of 9.5 mL/min. At voltages of 2.5 V, 2 V, and 1.5 V, efficiencies at 3 min are attained with a constant flow rate of 9.5 mL/min and a TDS of 500 ppm, with the maximum desalination efficiency reaching 56%.

Anthracite-Derived Porous Carbon@MoS2 Heterostructure for Elevated Lithium Storage Regulated by the Middle TiO2 Layer.

The rational design of MoS2/carbon composites have been widely used to improve the lithium storage capability. However, their deep applications remain a big challenge due to the slow electrochemical reaction kinetics of MoS2 and weak bonding between MoS2 and carbon substrates. In this work, anthracite-derived porous carbon (APC) is sequential coated by TiO2 nanoparticles and MoS2 nanosheets via a chemical activation and two-step hydrothermal method, forming the unique APC@TiO2@MoS2 ternary composite. The dynamic analysis, in-situ electrochemical impedance spectroscopy as well as theoretical calculation together demonstrate that this innovative design effectively improves the ion/electron transport behavior and alleviates the large volume expansion during cycles. Furthermore, the introduction of middle TiO2 layer in the composite significantly strengthens the mechanical stability of the entire electrode. As expected, the as-prepared APC@TiO2@MoS2 anode displays a high lithium storage capacity with a reversible capacity of 655.8 mAh g-1 after 150 cycles at 200 mA g-1, and robust cycle stability. Impressively, even at a high current density of 2 A g-1, the electrode maintains a superior reversible capacity of 597.7 mAh g-1 after 1100 cycles. This design highlights a feasibility for the development of low-cost anthracite-derived porous carbon-based electrodes.

Glassy Carbon Electrodes Modified with Ru Nanoparticles Loaded in B-Doped Imidazolium Porous Organic Polymers for Hydrogen Evolution Reaction.

Porous organic polymers (POPs) are a type of porous material composed of organic structural units connected by covalent bonds and POPs have been used as efficient electrocatalysts for hydrogen evolution reaction (HER). Herein, glassy carbon electrode (GCE) is chemically modified by B-doped imidazolium-based porous organic polymers loaded with Ru nanoparticles on the GCE surface. The incorporation of B in the POPs regulates the electronic structure of electrocatalysts to enhance their inherent electrocatalytic activity for HER. The optimized modified electrode GCE-Ru/PIM-Br2 exhibits a low overpotential of 271 mV at a current density of 10 mA cm-2 with a small Tafel slope (80 mV dec-1) in acidic solutions, and shows long-term stability for up to 22 h. This work presents a strategy to develop B-doped porous electrodes with loaded metal nanoparticles to strengthen the catalytic performance of electrocatalysts.

Finite Element Analysis of Local pH Variations in Electrolysis with Porous Electrodes, Considering Water Self-Ionization.

A finite element model was developed to simulate ion fluxes and local pH changes within and around porous electrodes during the H2 evolution reaction (HER) in acidic electrolytes. This model is particularly characterized by its ability to simulate scenarios in which the local pH inside and near the cathode exceeds 7, even under bulk acidic conditions (e.g., pH = 1), by considering the self-ionization of water. Steady-state calculations using meshes with an appropriate spatial distribution inside and near the cathode revealed that the relationship between the local pH and the double-layer potential at the interface between the porous catalyst layer and the electrolyte domains changed notably when the local pH exceeded the threshold of 7. By comparing the fluxes of H+ and OH- ions at the interface and using the thickness of the catalyst layer as a variable, we determined that the presence of H+ ions within the pores or the supply of OH- ions from the pores to the interface was responsible for the characteristic change in the local pH observed for the porous electrode. The porous electrode model constructed in this study can potentially serve as a basis that can be extended to a wide range of electrolysis systems, including not only the HER, but also the reduction of CO2, H2O2, and O2, and even oxidation reactions such as the O2 evolution reaction.