Hydrogen storage capacity of alkali and alkaline earth metal ions doped carbon based materials: A DFT study

The hydrogen storage (H-storage) capacity of alkali (Li⁺, Na⁺ and K⁺) and alkaline earth metal ion (Mg²⁺ and Ca²⁺) doped cubane, cyclohexane and adamantane has been investigated using Density Functional Theory (DFT) based M05-2X functional employing 6-31+G∗∗ basis set. The adsorption of number of H₂ molecules on the metal ion doped complexes depends on ionic radii and charge of the metal ions. Among the 15 complexes investigated in this study, Mg²⁺ ion doped cubane, cyclohexane and adamantane complexes have higher H-storage capacity when compared to other complexes. The calculated binding energy (BE) of 5H₂@Cub-Mg²⁺ complex is 46.85 kcal/mol with binding energy per H₂ molecule (BE/nH₂) of 9.37 kcal/mol. The corresponding gravimetric density of the complexes is 7.3 wt%. In the case of 4H₂@Cyc-Mg²⁺ complex, the BE is 32.19 kcal/mol (BE/nH₂ is 8.05 kcal/mol with 6.9 wt% in gravimetric density). The Adm-Mg²⁺ complexes adsorb 4H₂ molecules with BE of 33.33 kcal/mol, the BE of per H₂ molecule is 8.33 kcal/mol. The corresponding gravimetric density of the complex is around 4.8 wt%, respectively. A new linker modified MOP-9 has been constructed based on the results and their H-storage capacity has also estimated.     

Analysis and simulation of a blue energy cycle

The mixing process of fresh water and seawater releases a significant amount of energy and is a potential source of renewable energy. The so called ‘blue energy’ or salinity-gradient energy can be harvested by a device consisting of carbon electrodes immersed in an electrolyte solution, based on the principle of capacitive double layer expansion (CDLE). In this study, we have investigated the feasibility of energy production based on the CDLE principle. Experiments and computer simulations were used to study the process. Mesoporous carbon materials, synthesized at the Oak Ridge National Laboratory, were used as electrode materials in the experiments. Neutron imaging of the blue energy cycle was conducted with cylindrical mesoporous carbon electrodes and 0.5 M lithium chloride as the electrolyte solution. For experiments conducted at 0.6 V and 0.9 V applied potential, a voltage increase of 0.061 V and 0.054 V was observed, respectively. From sequences of neutron images obtained for each step of the blue energy cycle, information on the direction and magnitude of lithium ion transport was obtained. A computer code was developed to simulate the process. Experimental data and computer simulations allowed us to predict energy production.     

Optimizing electrochemical performance of sonochemically and hydrothermally synthesized cobalt phosphate for supercapattery devices

The supercapattery (hybrid energy storage device) has procured miraculous heed for their significant electrochemical performance, constitute combine features of supercapacitor (prodigious power density) and batteries (substantial energy density), still crave for electrode material with better electrochemical conduct. Here, cobalt phosphate ((Co₃(PO₄)₂) nanostructures were synthesized using sonochemical and hydrothermal approach. The SEM, XRD, and EDX were employed to explore surface morphology, crystal structure, and elemental analysis respectively of as synthesized nanomaterials. The electrochemical performance was evaluated in two and three electrode assembly. The maximum specific capacity of 285 C g^-1 at 3 mV/s and 221 C g^-1 at 4.1 A g^-1 has been obtained by sonochemically synthesized nanomaterial (S1). This electrode material with optimum electrochemical performance was further investigated for supercapattery application. Asymmetric device was fabricated, comprising activated carbon as negative and S1 as positive electrode material. The supercapattery device exhibits a specific capacity of 147.2 C g^-1 bearing an outstanding energy density of 34.8 Whkg^?1 with a power density of 425.0 W kg^-1 at 0.5 A g^-1. The device was found to have a remarkable power density of 6800.0 W kg^-1 while retaining an energy density of 10.0 Whkg^?1 with exceptional capacity preservation of 87.2% after 10,000 consecutive GCD cycles even at 8.0 A g^-1. The device performance was further explored in terms of capacitive and diffusion controlled processes and found to have a maximum capacitive contribution of 63.8% at 100 mV s^-1. The sonochemical method was found to be the optimal route to synthesize nanomaterials for energy storage applications.     

Effects of electrolytes and electrochemical pretreatments on the capacitive characteristics of activated carbon fabrics for supercapacitors

The capacitive characteristics of activated carbon fabrics (ACFs) coated on the graphite substrates were systematically investigated by means of cyclic voltammetry and the galvanostatic charge–discharge technique. Effects of the PVDF contents in the electronically conductive binder, electrochemical pretreatments, and the electrolytes on the capacitive performance of ACFs were compared in aqueous media. These ACF-pasted electrodes showed the more ideally capacitive responses in 1 M NaNO₃ with a specific capacitance of 76 F g⁻¹ when the electronically conductive binder contained 40 wt.% PVDF. The specific capacitance of ACF-pasted electrodes reached a maximum in 0.5 M H₂SO₄ (about 153 F g⁻¹ measured at 25 mV s⁻¹), due to the presence of a suitable density of oxygen-containing functional groups, when they were subjected to the potentiostatic polarization at 1.8 V (versus reversible hydrogen electrode (RHE)) or potentio-dynamic polarization between 1.3 and 1.8 V in NaNO₃ for 20 min. The oxygen-containing functional groups within the electrochemically pretreated ACFs were identified by means of X-ray photoelectron spectroscopy (XPS).     

One-pot sonochemical synthesis of hierarchical MnWO4 microflowers as effective electrodes in neutral electrolyte for high performance asymmetric supercapacitors

In this article, manganese tungstate (MnWO₄) microflowers as electrode materials for high performance supercapacitor applications are prepared by a one-pot sonochemical synthesis. The crystalline structure and morphology of MnWO₄ microflowers are characterized through X-ray diffraction, field emission scanning electron microscopy. The electrochemical properties of the MnWO₄ microflowers are investigated using cyclic voltammograms, galvanostatic charge/discharge and electrochemical impedance spectroscopy. The MnWO₄ microflowers as electrode materials possess a maximum specific capacitance of 324 F g⁻¹ at 1 mA cm⁻² in the potential window from 0 to +1 V and an excellent cycling stability of 93% after 8000 cycles at a current density of 3 mA cm⁻². An asymmetric supercapacitor device is fabricated using the MnWO₄ and iron oxide (Fe₃O₄)/multi-wall carbon nanotube as the positive and negative electrode materials, it can be cycled reversibly at a potential window at 1.8 V. The fabricated ASC device can deliver a high energy density of 34 Wh kg⁻¹ at a power density of 500 W kg⁻¹ with cycling stability of 84% capacitance retained after 3000 cycles. The above results demonstrate that MnWO₄ microflowers can be used as promising high capacity electrode materials in neutral electrolyte for high performance supercapacitors.     

Chemically and thermally reduced graphene oxide supported Pt catalysts prepared by supercritical deposition

Reduced graphene oxide (RGO) is used in many energy applications, especially in Polymer Electrolyte Membrane (PEM) fuel cells, as carbon sourced catalyst support materials. In this study, thermally (T-RGO) and chemically (C-RGO) reduced GO support materials were synthesized for utilization in PEM fuel cells. Pt catalysts were synthesized using supercritical carbon dioxide (SCCO₂) deposition technique over synthesized support materials. Physical (BET, SEM-EDX, FTIR, RAMAN, XRD, TEM, ICP-MS and optical tensiometer) and electrochemical (CV, PEM fuel cell test) characterizations of synthesized support materials and corresponding Pt catalysts were performed. The differences between the structures of thermally and chemically reduced graphene oxide supports and their Pt catalysts were investigated. The ECSA values of the Pt/T-RGO and Pt/C-RGO catalysts are 19.86 m² g^?1 and 6.31 m² g^?1, respectively. The current and power density values of the Pt/T-RGO and Pt/C-RGO catalysts at 0.6 V are 84 mA cm^?2, 80 mA cm^?2 and 50 mW cm^?2, 45 mW cm^?2, respectively. Pt/T-RGO and Pt/C-RGO catalysts showed similar trend in PEMFC environment.     

LiMn2O4 cathode materials synthesized by the cellulose–citric acid method for lithium ion batteries

A new technique was employed to synthesize spinel LiMn₂O₄ cathode materials by adding cellulose and citric acid to an aqueous solution of lithium and manganese salts. Various synthesis conditions such as the calcination temperature and the citric acid-to-metal ion molar ratio (R) were investigated to determine the ideal conditions for preparing LiMn₂O₄ with the best electrochemical characteristics. The optimal synthesis conditions were found to be R = 1/3 and a calcination temperature of 800 °C. The initial discharge capacity of the material synthesized using the optimal conditions was 134 mAh g⁻¹, and the discharge capacity after 40 cycles was 125 mAh g⁻¹, at a current density of 0.15 mA cm⁻² between 3.0 and 4.35 V. Details of how the initial synthesis conditions affected the capacity and cycling performance of LiMn₂O₄ are discussed.     

Hydrogen absorption and desorption properties of Mg/MgH2 with nanometric dispersion of small amounts of Nb(V) ethoxide

A study to determine the optimal content of Nb(V) ethoxide required to efficiently catalyze the H₂ sorption kinetics in the Mg/MgH₂ system is reported. The materials were synthesized by hand mixing different amounts of additive (from 0.10 to 1 mol%) to pre-milled MgH₂. Considering kinetics and capacity the best performance corresponds to a 0.25 mol% of Nb ethoxide concentration. With this material, a remarkable kinetic behavior with excellent reversibility is obtained: 5.3 wt% and 5.1 wt% of hydrogen are absorbed and desorbed respectively at 300 °C in 3 min. At 250 °C the material absorbs 5.2 wt% of hydrogen and releases 3.7 wt% in 10 min. Thermal desorption starts at 247 °C and peaks at 268 °C. The H₂ sorption properties of all the materials remain unchanged after 10 cycles of absorption and desorption at 300 °C, and the best material reversibly takes in and releases 5.3 wt% of H₂ during a 10 min combined cycle. The kinetic improvement of the hydrogen desorption and absorption properties is attributed to an enhancement of the kinetic processes that occur on the surface of the material, due to the excellent spreading of the liquid additive at nanometric level, as revealed by SEM/EDS and TEM/EELS.     

On the activation of polybenzimidazole-based membrane electrode assemblies doped with phosphoric acid

Three different activation procedures of phosphoric acid-doped polymer fuel cells have been analyzed: a discontinuous procedure with daily startup and shutdown, a continuous procedure without interruption and a continuous procedure after 1 h of direct exposure of the MEA to the atmosphere. The investigation was carried out analyzing the voltage profiles over time, the high frequency impedance and complete impedance spectra. The results show that the voltage increase during activation is due to the reduction of the kinetic resistance. The continuous activation leads to the best performance (0.678 V in 100 h) while the discontinuous one leads to a lower performance in a shorter time (0.665 V in 50 h). The initial exposure of the MEA to the atmosphere alters the initial acid distribution and leads to a final performance of (0.664 V in 200 h) in spite of the continuous activation.     

Facile sonochemical synthesis of strontium phosphate based materials for potential application in supercapattery devices

Among hybrid energy storage devices, supercapattery gained profound research interest due to its ability to give high energy density while maintaining the power density and cyclic stability. Herein, novel low-cost strontium based materials are synthesized by controlled sonochemical method and subsequently calcined at various temperatures. The multiple phases of the material synergistically contributed in the electrochemical charge storage process and give high specific capacity of 220 C g⁻¹ (as-prepared material) and 213 C g⁻¹ (calcined at 200 °C) at 0.5 A g⁻¹. A thorough electrochemical performance of optimized material is investigated as an electrode in asymmetric device. The supercapattery (SP2//AC) exhibits a specific capacity of 103.4 C g⁻¹ at 0.5 A g⁻¹ in the voltage range of 0–1.7 V. Furthermore, supercapattery offers a considerably high specific energy of 24.4 Wh kg⁻¹ at a specific power of 425 W kg⁻¹ and an excellent specific power of 1870 W kg⁻¹ by maintaining specific energy at 14.5 Wh kg⁻¹. In addition, the device retained its specific capacity to 90% after 3000 charging/discharging cycles at 1 A g⁻¹. Strontium based materials could be proposed as an appropriate electrode material for energy storage systems.     

Electrocatalytic nickel-based coatings from an ammonia-sulfosalicylic bath for water splitting reactions

The synthesis and research of nickel and nickel-copper coatings on carbon felt from ammonium-sulfosalicylic electrolytes as electrocatalysts of water splitting reactions were carried out. The effect of copper concentration on electrochemical behavior was studied in the range of 5–15 g/L. The materials were investigated using SEM, XRD, EDX, and electrochemical methods. The average size of the crystallites is 15.1 and 16.4 nm for Ni-SS and NC-SS samples, respectively. The obtained materials have improved performance in the evolution reactions of hydrogen (HER) and oxygen (OER). Overpotentials equal to −120 mV for HER and 320 mV for OER on Ni-SS and −80 mV for HER and 300 mV for OER on NC–SS–10 were needed for a nominal current density of 10 mAcm⁻². The stability test demonstrates that the overall water splitting occurs at 1.73 V to Ni-SS and 1.63 V to NC-SS. Impedance analysis indicates a decrease in complex resistance and resistance at the electrode-electrolyte interface for synthesized samples.     

Evaluation of electrochemical hydrogen storage capability of graphene oxide multi-layer coating

Due to its unique physical and chemical properties, graphene oxide (GO) has excellent potential in energy-saving applications, especially in hydrogen storage materials such as bulk and layer coatings. A three-layer GO/Ni/GO coating was applied successfully on the Ni-foam through the hybrid coating process. GO was firstly synthesized by modified Hummers' method and then deposited on Ni-Foam using an electrophoretic deposition (EPD) method at 40, 60, and 80 V at various times (1 and 2 h). Furthermore, Ni-layer was applied on the first applied to GO layer using a Ni-electroplating bath at 3 V for 3 min. For evaluation of the electrochemical hydrogen storage performance, cyclic voltammetry (CV), galvanostatic charge-discharge (GCD), and electrochemical impedance spectroscopy (EIS) were carried out in 1 M NaOH solution at room temperature. Obtained results showed a significant improvement in the amount of adsorbed hydrogen. The hydrogen storage capacity was increased from 88 to 741 F. g^?1, and load transfer resistance decreased from 260 to 35 Ω for uncoated and coated porous substrates, respectively, which is due to the achieved high specific area. Based on the hydrogen storage capacity, the optimum EPD method is 60 V and 2 h.     

Influence of synthesis conditions on electrochemical properties of high-voltage Li1.02Ni0.5Mn1.5O4 spinel cathode material

Li_1.02Ni_0.5Mn_1.5O₄ spinel cathode materials were successfully synthesized by a citric acid-assisted sol-gel method. The structure and morphology of the materials have been examined by X-ray diffraction and scanning electron microscopy, respectively. Electrochemical properties of the materials were investigated using cyclic voltammetry and galvanostatic charge/discharge measurements at two different temperatures (25 and 55 °C) using lithium anode. The initial capacity and capacity retention are highly dependent on the particle size, particle size distribution, crystallinity and purity of the materials. The Li_1.02Ni_0.5Mn_1.5O₄ materials synthesized both at 800 and 850 °C have shown best electrochemical performance in terms of capacity and capacity retention between 3.5 and 4.9 V with a LiPF₆ based electrolyte.     

Optimal experimental conditions for hydrogen production using low voltage electrooxidation of organic wastewater feedstock

The dependence of electrooxidation on experimental conditions of organic molecules was investigated to optimize the production of hydrogen from potential wastewater sources using low voltage sources (∼1 V dc). Electrooxidation on platinum, gold, and stainless steel anodes with hydrogen production on the cathode was investigated using several different organic reductants, including: methanol, ethanol, glycerol, isopropanol, propanal, glycerol, glucose, sucrose, citric acid, and propionic acid. The electrolyte pH was varied from 2 to 12 in a 1 M Na₂SO₄ supporting solution. At 1 V, glycerol, citric acid, ethanol and methanol were found to yield the highest currents at low pH values (pH 2 and 7) on platinum electrode, glucose on gold electrode at pH 12 in 1 M Na₂SO₄ solution produced the highest total current density at 1 V with measured Faradaic efficiency for 1 M glucose of 70%. The hydrogen energy production efficiency was 86%. Practical limitations of glucose oxidation at optimum experimental conditions are discussed.     

Boron substitution effect on adsorption of H2 molecules on organometallic complexes

Hydrogen adsorption properties of Be/Sc doped pentalene complexes are investigated using second ordered Møller-Plesset method (MP2). In order to study the boron substitution effect, pentalene is further modified by substituting two and four boron atoms for carbon atoms at different positions and named as TBP1 and TBP2 for two boron atom substituted structures and FBP1 and FBP2 for four boron atom substituted structures. Two H₂ molecules get adsorbed on each Be doped complex and having 3.25, 3.31, 3.31, 3.38 and 3.38 wt% H₂ uptake capacity for C₈H₆Be₂, TBP1Be₂, TBP2Be₂, FBP1Be₂ and FBP2Be₂ complexes respectively. All Sc doped pentalene and boron substituted pentalene complexes can interact with nine H₂ molecules except TBP2Sc₂ complex. The TBP2Sc₂ complex can adsorb eight H₂ molecules. The H₂ uptake capacity is found to be 8.63, 8.73, 7.84, 8.83 and 8.83 wt% for C₈H₆Sc₂, TBP1Sc₂, TBP2Sc₂, FBP1Sc₂ and FBP2Sc₂ complexes respectively. Gibbs free energy corrected adsorption energy plots show that the H₂ adsorption on all Be doped complexes is possible at all temperatures and pressures considered here. The TBP1Sc₂ complex seems to be more promising hydrogen storage material among all Sc doped complexes over a wide range of temperature and pressure. The H₂ desorption temperatures obtained for the Be doped complexes are higher than the Sc doped complexes. Stability of the complexes is predicted with the help of the gap between the highest occupied molecular orbitals and the lowest unoccupied molecular orbitals.     

Effects of heat treatment time on electrochemical properties and electrode structure of polytetrafluoroethylene-bonded membrane electrode assemblies for polybenzimidazole-based high-temperature proton exchange membrane fuel cells

To improve cell performance, the effects of heat treatment time on the electrochemical properties and electrode structure of PTFE-bonded membrane electrode assemblies for PBI-based high-temperature proton exchange membrane fuel cells are investigated. The cell performance is observed to decrease in the high-current-density region rather than in the low-current-density region with increasing heat treatment time at 350 °C from 1 to 30 min. Microscopic studies reveal remarkable differences in the electrode structure by the agglomeration of dispersed PTFE and adjacent catalyst particles, depending on the heat treatment time. As the heat treatment time increases, only the large pore (secondary pore) volume in the electrode decreases, resulting in increase in mass transport resistance and concentration overpotential in the high-current-density region. Cell performance is not measured without heat treatment because the electrodes are not formed. When the electrodes are heat treated for 1 min at 350 °C, the best cell performance is obtained, 0.67 V at 200 mA cm⁻².     

Effects of pore structure and electrolyte on the capacitive characteristics of steam- and KOH-activated carbons for supercapacitors

Four kinds of activated carbons (denoted as ACs) with specific surface area of ca. 1050 m² g⁻¹ were fabricated from fir wood and pistachio shell by means of steam activation or chemical activation with KOH. Pore structures of ACs were characterized by a t-plot method based on N₂ adsorption isotherms. The amount of mesopores within KOH-activated carbons ranged from 9.2 to 15.3% while 33.3–49.5% of mesopores were obtained for the steam-activated carbons. The pore structure, surface functional groups, and raw materials of ACs, as well as pH and the supporting electrolyte were also found to be significant factors determining the capacitive characteristics of ACs. The excellent capacitive characteristics in both acidic and neutral media and the weak dependence of the specific capacitance on the scan rate of cyclic voltammetry (CV) for the ACs derived from the pistachio shell with steam activation (denoted as P-H₂O-AC) revealed their promising potential in the application of supercapacitors. The ACs derived from fir wood with KOH activation (denoted as F-KOH-AC), on the other hand, showed the best capacitive performance in H₂SO₄ due to excellent reversibility and high specific capacitance (180 F g⁻¹ measured at 10 mV s⁻¹), which is obviously larger than 100 F g⁻¹ (a typical value of activated carbons with specific surface areas equal to/above 1000 m² g⁻¹).     

Potassium manganese–vanadium oxide cathodes prepared by hydrothermal synthesis

Hydrothermal reactions between potassium permanganate and vanadyl sulfate have been used to synthesize new forms of vanadium oxides. Depending on the reactant ratios and pH values of the reaction mixtures, two different layered materials have been identified. The first one formed at a pH value of 1.6 has an interlayer distance of 10.90 Å and a composition of K_0.16Mn_0.04V₂O_4.94·0.14H₂O, while the second one formed at pH values higher than 3.0 has an interlayer distance of 9.45 Å and a composition of K_0.44V₂O_4.96. Structural analysis indicates that they have a δ-type structure with potassium ions residing in between double sheets of vanadium oxide. The structure and composition of these materials have a profound effect on their charge and discharge properties when used as cathodes in lithium batteries. The sample prepared at a pH value of 2.3 shows best overall performance considering both reversible capacity and cyclability, which is explained with the coexistence of two layered phases in the material. This material has a capacity of over 200 mA h/g between 3.6 and 2.2 V and retains a capacity of 190 mA h/g after 30 cycles. Increase of manganese to vanadium ratio during synthesis leads to a gradual loss of the layered structure and decreased lithium insertion capacity.     

All-solid-state lithium secondary batteries using a layer-structured LiNi0.5Mn0.5O2 cathode material

All-solid-state cells of In/LiNi_0.5Mn_0.5O₂ using a superionic oxysulfide glass with high conductivity at room temperature of 10⁻³ S cm⁻¹ as a solid electrolyte were fabricated and the cell performance was investigated. Although a large irreversible capacity was observed at the 1st cycle, the solid-state cells worked as lithium secondary batteries and exhibited excellent cycling performance after the 2nd cycle; the cells kept charge–discharge capacities around 70 mAh g⁻¹ and its efficiency was almost 100%. This is the first case to confirm that all-solid-state cells using manganese-based layer-structured cathode materials work as lithium secondary batteries.     

Easily-prepared bimetallic metal phosphides as high-performance electrode materials for asymmetric supercapacitor and hydrogen evolution reaction

Transition metal phosphides are very attractive because of the remarkable performance in energy storage and conversion. Herein, a series of bimetallic phosphides are synthesized through a one-step solid-state reaction. The obtained bimetallic phosphides show outstanding properties as supercapacitor electrode materials. Results show that the incorporation of secondary metal into phosphides tunes composition, electronic structure and then the electrochemical performance. And electrochemical properties are closely associated with the secondary metal content. Notably, the obtained NiCoP shows the best performance with 2011 F g⁻¹ at 1 A g⁻¹. And an asymmetric supercapacitor (ASC) based on NiCoP shows energy density of 47.6 W h kg⁻¹, along with 90.5% of capacitance maintained after 10000 cycles. In addition, the NiCoP also possesses great performance toward hydrogen evolution reaction (HER), which displays the lowest potential of 0.221 V vs. RHE and 0.173 V vs. RHE at 10 mA cm⁻² in 0.5 M H₂SO₄ as well as 1.0 M KOH, respectively. The excellent properties may result from the enhanced electrical conductivity, synergistic effects among metal elements and the increased local electrical dipole. The regulation of electronic structure through introduction of secondary metal atom sheds considerable light on realization and preparation of the bimetallic transition metal compounds as electrode materials.