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At least 253 records · Page 14

Graphene oxide precursor effects on 3D-printed carbon scaffolds

Manganese oxide (MnO 2 ), an earth-abundant material, is a promising component for energy storage devices, with uses in both pseudocapacitors and batteries. However, high MnO 2 loading often leads to reduced performance due to poor ion diffusion. 3D printing, particularly using the direct ink writing (DIW) technique, offers a solution by enabling the fabrication of electrodes with hierarchical porous structures and open channels that enhance mass transport and ion diffusion. Previous work demonstrated that 3D-printed graphene aerogels with MnO 2 coatings exhibited excellent electrochemical performance, even with thick electrodes, due to their optimized structure. Building on this work, the current study investigates the performance differences between aerogels developed using graphene oxide (GO) and reduced graphene oxide (rGO) as carbon precursors. Both materials were incorporated into thixotropic inks, 3D-printed into lattice structures, and carbonized. Despite expected similarities between the final graphene aerogel, rGO-based aerogels exhibited superior areal capacitance, compared to GO-based aerogels. These differences are attributed to the lower oxygen content and defect density of rGO, which influence its interaction with cellulose viscosifiers in the ink formulation. Brunauer–Emmett–Teller (BET) surface area analysis revealed that rGO aerogels exhibit a larger surface area and mesoporous structure, further enhancing their performance. When coated with MnO 2 , rGO-based aerogels maintained their superior capacitive behavior over GO-based aerogels. This study highlights the effect of carbon precursor on the end performance of graphene aerogels.

Materials science↗

Redox flow cell energy storage systems

The redox flow cell energy storage system being developed by NASA for use in remote power systems and distributed storage installations for electric utilities is presented. The system under consideration is an electrochemical storage device which utilizes the oxidation and reduction of two fully soluble redox couples (acidified chloride solutions of chromium and iron) as active electrode materials separated by a highly selective ion exchange membrane. The reactants are contained in large storage tanks and pumped through a stack of redox flow cells where the electrochemical reactions take place at porous carbon felt electrodes. Redox equipment has allowed the incorporation of state of charge readout, stack voltage control and system capacity maintenance (rebalance) devices to regulate cells in a stack jointly. A 200 W, 12 V system with a capacity of about 400 Wh has been constructed, and a 2 kW, 10kWh system is planned.

Thaller, L. H.↗

Redox flow cell energy storage systems

NASA-Redox systems are electrochemical storage devices that use two fully soluble Redox couples, anode and cathode fluids, as active electrode materials separated by a highly selective ion exchange membrane. The reactants are contained in large storage tanks and pumped through a stack of Redox flow cells where the electrochemical reactions (reduction and oxidation) take place at porous carbon felt electrodes. A string or stack of these power producing cells is connected in series in a bipolar manner. Redox energy storage systems promise to be inexpensive and possess many features that provide for flexible design, long life, high reliability and minimal operation and maintenance costs. These features include independent sizing of power and storage capacity requirements and inclusion within the cell stack of a cell that monitors the state of charge of the system as a whole, and a rebalance cell which permits continuous correction to be made for minor side reactions that would tend to result in the anode fluid and cathode fluids becoming electrochemically out of balance. These system features are described and discussed.

Thaller, L. H.↗

Enabling fast-charging of lithium-ion batteries through printed electrodes

It has been well recognized that introducing secondary porous networks (SPNs) into the electrodes can effectively improve the electrochemical performance of lithium-ion batteries (LIBs), especially under fast-charging operations. However, the process complexity and high cost limit the commercial success of advanced electrodes with SPNs. To address this issue, we developed a facile screen-printing process to produce structured graphite electrodes with SPNs. The experimental results demonstrated that, by tuning the diameter and center-to-center (C2C) distance of emulsion dots on the stencil screen, the pore diameters and C2C pore distances of SPNs in screenprinted electrodes can be precisely controlled in the range of 100 mu m to 1 mm and 100 mu m to 3 mm respectively. In addition, the SPNs with hexagonal and square-shape pore alignments have also been imprinted onto the electrode coatings through adjusting the patterns of screen stencils. Used as anodes, the printed graphite electrodes demonstrated significantly reduced overpotential and voltage fluctuation under fast-charging operations from 2C to 6C. Coupled with LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC622) cathodes, the full cells with printed graphite anodes exhibited an unprecedently stable performance with almost no capacity decay up to 170 cycles when charged to 80 % SOC at 2C. Observations from electron microscopy showed plated lithium undetectable at the surface of printed graphite electrodes after numerous cycles. The electrochemical analysis on the voltage evolution during the cell rest period indicated the significantly delayed onset of lithium plating in the presence of printed graphite electrodes. In conclusion, all these results suggest that the significantly improved cell performance is associated with the shortened Li-ion diffusion distance, reduced polarization and suppressed Li plating in the printed electrodes with patterned SPNs.

25 ENERGY STORAGE↗

Effect of Polymer Electrode Morphology on Performance of a Lithium/Polypyrrole Battery

A variety of conducting polymer batteries were described in the recent literature. In this work, a Li/Polypyrrole secondary battery is described. The effect of controlling the morphology of the polymer on enhancement of counterion diffusion in the polymer phase is explored. A method of preparing conducting polymers was developed which yields high surface area per unit volume of electrode material. A porous membrane is used as a template in which to electrochemically polymerize pyrrole, then the membrane is dissolved, leaving the polymer in a fibrillar form. Conventionally, the polymer is electrochemically polymerized as a dense polymer film on a smooth Pt disk electrode. Previous work has shown that when the polymer is electrochemically polymerized in fribrillar form, charge transport rates are faster and charge capacities are greater than for dense, conventionally grown films containing the same amount of polymer. The purpose is to expand previous work by further investigating the possibilities of the optimization of transport rates in polypyrrole films by controlling the morphology of the films. The utility of fibrillar polypyrrole as a cathode material in a lithium/polymer secondary battery is then assessed. The performance of the fibrillar battery is compared to the performance of an analogous battery which employed a conventionally grown polypyrrole film. The study includes a comparison of cyclic voltammetry, shape of charge/discharge curves, discharge time and voltage, cycle life, coulombic efficiencies, charge capacities, energy densities, and energy efficiencies.

Nicholson, Marjorie Anne↗

Electrocatalysts for oxygen electrodes in fuel cells and water electrolyzers for space applications

In most instances separate electrocatalysts are needed to promote the reduction of O2 in the fuel cell mode and to generate O2 in the energy storage-water electrolysis mode in aqueous electrochemical systems operating at low and moderate temperatures (T greater than or equal to 200 C). Interesting exceptions are the lead and bismuth ruthenate pyrochlores in alkaline electrolytes. These catalysts on high area carbon supports have high catalytic activity for both O2 reduction and generation (1,2). Rotating ring-disk electrode measurements provide evidence that the O2 reduction proceeds by a parallel four-electron pathway. The ruthenates can also be used as self-supported catalysts to avoid the problems associated with carbon oxidation, but the electrode performance so far achieved in the research at Case Western Reserve University (CWRU) is considerably less. At the potentials involved in the anodic mode the ruthenate pyrochlores have substantial equilibrium solubility in concentrated alkaline electrolyte. This results in the loss of catalyst into the bulk solution and a decline in catalytic activity. Furthermore, the hydrogen generation counter electrode may become contaminated with reduction products from the pyrochlores (lead, ruthenium). A possible approach to this problem is to immobilize the pyrochlore catalyst within an ionic-conducting solid polymer, which would replace the fluid electrolyte within the porous gas diffusion O2 electrode. For bulk alkaline electrolyte, an anion-exchange polymer is needed with a transference number close to unity for the Oh(-) ion. Preliminary short-term measurements with lead ruthenates using a commercially available partially-fluorinated anion-exchange membrane as an overlayer on the porous gas-fed electrode indicate lower anodic polarization and virtually unchanged cathodic polarization.

Prakash, Jai↗

Improved plaque materials for aerospace nickel-cadmium cells

Improved cadmium electrode substrates with precisely controlled microstructures for possible use in aerospace nickel-cadmium cells were prepared. The preparative technique was a powder metallurgical process in which a fugitive pore-former and a nickel powder were blended, then isostatically compacted, and subsequently sintered. Cadmium electrodes prepared from such substrates were cycle tested using an accelerated tortuous test regime. It was discovered that plaques of 60% or 80% porosity prepared with a 25 micron pore-former were better than state-of-the-art electrodes in terms of efficienty and/or mechanical strength. The 60% structures were particularly outstanding in this respect in that they had efficiencies only 5-10 percentage points lower than state-of-the-art electrodes and vastly superior mechanical properties. This added strength was observed to eliminate cracking and physical degradation of the electrodes during processing and cycling. The cadmium electrodes prepared from the 80% porous substrates proved to be the best electrodes made during the course of the work from the point of view of highest efficiency. Three-point bend tests were used to measure mechanical properties of the plaques produced and also as a general characterization tool. In addition, the BET surface areas of selected specimens was determined. The SEM was used for judging microscopic uniformity and quantitatively determining the induced pore size and various other fine structures in the substrates. The technique of X-ray radiography was used to follow the bulk uniformity of the substrates at various stages of their processing.

Luksha, E.↗

Print-and-Plate Architected Electrodes for Electrochemical Transformations Under Flow

Flow cell electrodes are typically composed of porous carbon materials, such as papers, felts, and cloths. However, their random architecture hinders the fundamental characterization of electrode structure-performance relationships during in situ operation of porous electrochemical flow systems. This work describes a “print-and-plate” method that combines direct ink writing of micro-periodic lattices with a two-step metal plating process that converts them into highly conductive (sheet resistance 40 mΩ sq -1 ) electrodes. Their operando performance is assessed in an anthraquinone disulfonic acid half-cell using widefield electrochemical fluorescence microscopy, where output current and fluorescence intensity are in excellent agreement. The pressure drop associated with flow through three electrode designs is determined via simulations from which the most efficient design is identified and manufactured via print-and-plate. Confocal fluorescence microscopy is then used to create a 3D map of the state of charge (SOC) inside this print-and-plate electrode. The experimental state of the charge map is in good agreement with computational predictions. The rapid design, simulation, and fabrication of print-and-plate electrodes enable fundamental investigations of how architected porosity affects electrochemical performance under flow.

3D-printing↗

Hybrid Mesoporous Carbon/Copper Ferrite Electrode for Asymmetric Supercapacitors

Asymmetric supercapacitors (ASCs) with two dissimilar electrodes are known to exhibit relatively moderate energy and power densities. If electrodes derived from earth-abundant materials or renewable resources such as lignocellulosic biomass (LCB) are used for fabrication, energy storage systems are expected to become less expensive and more sustainable. Hybrid electrode materials have advantages such as higher surface area, better chemical stability, and superior energy density. This study reports on the synthesis of a novel hybrid electrode material containing porous carbon (POC) and copper ferrite, which is designated as POC@Cu-ferrite, and its electrochemical performance in ASC configuration. Corn stover derived hydrochar is utilized for the sol–gel synthesis of POC@Cu-ferrite hybrid material using earth-abundant Cu and Fe-based precursors. This material is characterized using X-ray diffraction (XRD), Raman spectroscopy, Brunauer–Emmett–Teller (BET) surface area analyzer, and scanning and transmission electron microscopy (SEM/TEM). As-synthesized Cu-ferrite is found to contain 89.2% CuFe 2 O 4 and 10.8% Fe 2 O 3 , whereas other phases such as Fe 3 O 4 , CuFeO 2 , and CuO are observed for the POC@Cu-ferrite. BET-specific surface area (SSA) and pore volume of POC@Cu-ferrite are observed as 1068 m 2 /g and 0.72 cm 3 /g, respectively. POC@Cu-ferrite hybrid electrode is used with POC opposite electrode to fabricate ASC, which is tested using Gamry G-300 potentiostat/galvanostat/ZRA to obtain cyclic voltammetry (CV) profiles and galvanostatic charge–discharge (GCD) plots. ASC is also prepared using Cu-ferrite and POC materials and its specific capacitance and stability are compared with ASCs prepared with POC@Cu-ferrite and POC or graphene nanoplatelets (GNPs) electrodes. POC@Cu-ferrite hybrid electrode is found to be superior with a 2-fold higher capacitance and significant electrochemical stability over 100 GCD cycles as compared to the Cu-ferrite electrode.

36 MATERIALS SCIENCE↗

The application of electrochemical impedance spectroscopy for characterizing the degradation of Ni(OH)2/NiOOH electrodes

The use of wide-band electrochemical impedance spectroscopy is described for characterizing the degradation of porous Ni(OH)2/NiOOH electrodes in concentrated KOH electrolyte solutions. The impedance spectra are interpreted in terms of a finite electrical transmission line and the changes in the components of the electrical analog are followed as a function of cycle number. The degradation of the capacity of rolled and bonded Ni(OH)2/NiOOH electrodes is caused by rupture of ohmic contacts within the active mass and by restructuring which results in a decrease in the number of active pores.

Macdonald, Digby D.↗

Defect–Concentration–Mediated T–Nb 2 O 5 Anodes for Durable and Fast–Charging Li–Ion Batteries

Metastable orthorhombic niobium pentoxide (T-Nb 2 O 5 ) is a promising anode to fulfill the requirements for high-rate Li-ion batteries (LIBs). Stoichiometric T-Nb 2 O 5 is plagued by low electric conductivity and particle pulverization after repeated charge/discharge processes. In this work, oxygen vacancies are implanted into T-Nb 2 O 5 particles via acid immersion of Nb 2 O 5 ·nH 2 O with the formation of Lewis acid sites. The multiple characterizations and simulations reveal the lengthening of Nb–O bonds, and the transformation from NbO 7 pentagonal bipyramids and NbO 6 tetragonal bipyramids in T-Nb 2 O 5–x . The enrichment of oxygen vacancies endows T-Nb 2 O 5–x with higher electric conductivity, better electrochemical kinetics, larger pseudocapacitive contribution. O-doped graphitic C 3 N 4 is creatively proposed as a trace oxygen pump to repair excessive oxygen vacancies, and it also serves as a sacrifice template for Nb 2 O 5–x growth to construct a porous and monolithic electrode network. Defect-modulated Nb 2 O 5–x displays extraordinary cycling stability (164 mAh g –1 at 5 C after 1100 cycles), high capacity retention (104 mAh g –1 ) at an ultrahigh rate (25 C), and large areal capacity (0.74 mAh cm –2 ) under high mass loading (4 mg cm –2 ). The practical prospect is proved by Nb 2 O 5–x /LiNi 0.8 Co 0.1 Mn 0.1 O 2 full cells with high average platform (2.12 V) and high specific capacity (229 mAh g –1 ). Finally, the oxygen-defect modulation strategy on oxide anodes provides an alternative solution to fast-charging and durable LIBs.

25 ENERGY STORAGE↗

Modeling the 4D discharge of lithium-ion batteries with a multiscale time-dependent deep learning framework

The lithium-ion battery (LIB) field is moving towards the direction of investigating spatially resolved physical phenomena in the 3D porous microstructure of electrodes. These pore-scale simulations give new insights into the local dynamics of lithiation/de-lithiation and charge transport, Nevertheless, the computational time of these simulations limits the integration of these models in optimization workflows of cycling conditions or electrode manufacturing processes. Machine learning models present a way of assessing in real-time the performance of materials. While several successful techniques for replicating simulations with machine learning have been proposed, this case study presents a more demanding problem, due to the necessity of understanding the behavior of heterogeneous 3D local data, as it evolves in time: this poses both a scientific and a technical challenge. To this end, we propose an autoregressive multiscale convolutional neural network model to predict relevant quantities at the pore-scale in the solid phase: the lithium concentration (in the active material) and potential (in the active material and carbon binder). Here, these are ultimately used to reconstruct the battery discharge curve. 3D images of the electrode microstructures are the input to the network, trained with a dataset of finite element method simulations to predict the discharge behavior of the cathode side in lithium ion batteries. We propose this machine learning model as a proof-of-concept of the applicability of multiscale networks for time-dependent physics problems. The trained model exhibits very high accuracy (with errors lower than 2 %) in forecasting the discharge behavior of new unseen cathodes.

25 ENERGY STORAGE↗

Understanding the Mechanism of High Capacitance in Nickel Hexaaminobenzene-Based Conductive Metal-Organic Frameworks in Aqueous Electrolytes

Recently, intrinsically conductive metal-organic frameworks (MOFs) have demonstrated promising performance in fast-charging energy storage applications and may outperform some current electrode materials (e.g., porous carbons) for supercapacitors in terms of both gravimetric and volumetric capacitance. In this report, we examine the mechanism of high capacitance in a nickel hexaaminobenzene-based MOF (NiHAB). Using a combination of in situ Raman and X-Ray absorption spectroscopies, as well as detailed electrochemical studies in a series of aqueous electrolytes, we demonstrate in this work that the charge storage mechanism is in fact a pH-dependent surface pseudocapacitance, and, unlike typical inorganic systems, where transition metals change oxidation state during charge/discharge cycles, NiHAB redox activity is ligand-centered.

25 ENERGY STORAGE↗

Preparation and evaluation of advanced electrocatalysts for phosphoric acid fuel cells

Results are presented for hydrogen oxidation and hydrogen oxidation poisoned by carbon monoxide at levels between 0 and 30%. Due to the high activities that are now being observed for our platinum based electrocatalysts, the hydrogen concentrations were reduced to 10% levels in the gas supplies. Perturbation techniques were used to determine that a mechanism for the efficient operation of our porous gas diffusion electrodes is diffusion of the carbon monoxide out of the electrode structure through the electrolyte film on the electro-catalyst. A survey of the literature on platinum group materials (PGM) was carried out so that an identification of successful electrocatalysts could be made. Two PGM electrocatalysts were prepared and performance data for hydrogen oxidation in hot phosphoric acid in the presence of high carbon monoxide concentrations showed that they matched the best platinum on carbon electrocatalysts but with an electrocatalyst cost that was half of the platinum catalyst cost.

Stonehart, P.↗

Pumping power considerations in the designs of NASA-Redox flow cells

Pressure drop data for six different cell geometries of various flow port, manifold, and cavity dimensions are presented. The redox/energy/storage system uses two fully soluble redox couples as anode and cathode fluids. Both fluids are pumped through a redox cell, or stack of cells, where the electrochemical reactions take place at porous carbon felt electrodes. Pressure drop losses are therefore associated with this system due to the continuous flow of reactant solutions. The exact pressure drop within a redox flow cell is directly dependent on the flow rate as well as the various cell dimensions. Pumping power requirements for a specific set of cell operating conditions are found for various cell geometries once the flow rate and pressure drop are determined. These pumping power requirements contribute to the overall system parasitic energy losses which must be minimized, the choice of cell geometry becomes critical.

Hoberecht, M. A.↗

A Survey of Alternative Oxygen Production Technologies

Utilization of the Martian atmosphere for the production of fuel and oxygen has been extensively studied. The baseline fuel production process is a Sabatier reactor, which produces methane and water from carbon dioxide and hydrogen. The oxygen produced from the electrolysis of the water is only half of that needed for methane-based rocket propellant, and additional oxygen is needed for breathing air, fuel cells and other energy sources. Zirconia electrolysis cells for the direct reduction of CO2 arc being developed as an alternative means of producing oxygen, but present many challenges for a large-scale oxygen production system. The very high operating temperatures and fragile nature of the cells coupled with fairly high operating voltages leave room for improvement. This paper will survey alternative oxygen production technologies, present data on operating characteristics, materials of construction, and some preliminary laboratory results on attempts to implement each. Our goal is to significantly improve upon the characteristics of proposed zirconia cells for oxygen production. To achieve that goal we are looking at electrolytic systems that operate at significantly lower temperatures, preferably below 31C to allow the incorporation of liquid CO2 in the electrolyte. Our preliminary results indicate that such a system will have much higher current densities and have simpler cathode construction than a porous gas feed electrode system. Such a system could be achieved based on nonaqueous electrolytes or ionic liquids. We are focusing our research on the anode reaction that will produce oxygen from a product generated at the cathode using CO2 as the feed. Operation at low temperatures also will open up the full range of polymer and metal materials, allowing a more robust system design to withstand the rigors of flight, landing, and long term unattended operation on the surface of Mars.

Lueck, Dale E.↗

Modeling Electrolytic O2 Recovery from Metabolic CO2 for Advanced Closed Loop Life Support Systems in Extraterrestrial Human Missions

The International Space Station (ISS) is currently equipped with a complex, heavy, and power consuming system that recovers approximately 50% of O2 from metabolic CO2. Future long duration human missions to the Moon and Mars will necessitate a sustainable and highly efficient metabolic oxygen recovery system capable of yielding a minimum of 75% O2 recovery. A Macrofluidic Electrochemical Reactor (MFECR) technology development effort is currently underway at NASA Marshall Space Flight Center (MSFC) to significantly increase current metabolic O2 recovery efficiency, expand mission sustainability, and reduce complexity of the system. The novel design combines CO2 conversion to O2 along with C2H4 as byproduct and water electrolysis (currently conducted in two separate units) into a single compact unit that runs at standard conditions and is theoretically capable of generating O2 with a theoretical maximum metabolic CO2 conversion of 73% while consuming less than metabolic water. This paper presents a comprehensive multi-physic 3D model developed at MSFC on CO2 conversion to O2 and C2H4 at standard conditions via MFECR. The 3D spatial domain of the model is a replica of the actual MFECR’s 3D drawing generated for the MFECR fabrication and operated to recover O2 from CO2 yielding C2H4 as byproduct. Electrochemical (EC) physics that includes EC multicomponent reaction mechanisms, mass transport, and electrical current density distributions is coupled in the model with all the other physics phenomena involved in the MFECR’s process, such as two-phase flow, free and porous fluid regimes, multicomponent mass transfer, heat transfer, and DC electrical current generation along with Joule heating effect. The EC reaction sections of the MFECR consists of two porous gas diffusion electrodes (GDE) and an electrolyte serpentine channel sandwiched in the middle. The CO2 feeds the cathode serpentine channel and part of the O2 product is fed back to the anode serpentine chamber. An alkaline solution feeds the electrolyte serpentine chamber wetting the GDEs of both, the anode and cathode allowing the OH- ionic transport between them. The EC reactions in the cathode’s GDE yield C2H4 from CO2 and H2 from water while the EC reaction in the anode’s GDE yields O2. The authors will present in this paper the validation of the model using experimental data and the utilization of the validated model in building a reliable simulator that will not only assist the authors on the MFECR design but also the optimization of its operation in the ISS and future spatial human missions.

Jesus A Dominguez↗