Modification of single wall carbon nanotubes (SWNT) for hydrogen storage

Due to unique structural, mechanical and electrical properties of single wall carbon nanotubes, SWNTs, they have been proposed as promising hydrogen storage materials especially in automotive industries. This research deals with investing of CNT’s and some activated carbons hydrogen storage capacity. The CNT’s were prepared through natural gas decomposition at a temperature of 900?C over cobalt-molybdenum nanoparticles supported by nanoporous magnesium oxide (Co–Mo/MgO) during a chemical vapor deposition (CVD) process. The effects of purity of CNT (80–95%wt.) on hydrogen storage were investigated here. The results showed an improvement in the hydrogen adsorption capacity with increasing the purity of CNT’s. Maximum adsorption capacity was 0.8%wt. in case of CNT’s with 95% purity and it may be raised up with some purification to 1%wt. which was far less than the target specified by DOE (6.5%wt.). Also some activated carbons were manufactured and the results compared to CNTs. There were no considerable H₂-storage for carbon nanotubes and activated carbons at room-temperature due to insufficient binding between H₂ molecules carbon nanostructures. Therefore, hydrogen must be adsorbed via interaction of atomic hydrogen with the storage environment in order to achieve DOE target, because the H atoms have a very stronger interaction with carbon nanostructures.     

Activated carbon synthesis from tangerine peel and its use in hydrogen storage

Activated carbon samples were synthesized by chemical and physical activations of tangerine peel. The activated carbons were characterized via using Fourier Transform Infrared-Attenuated Total Reflectance spectroscopy (FTIR-ATR), Scanning Electron Microscopy (SEM), Brunauer-Emmett-Teller (BET), Differential Thermal Analysis-Thermogravimetry (DTA/TG) techniques. It was found that the activated carbon samples were porous, and their surface areas were increased by treating with the various concentrations of ZnCl₂ and KOH. After the formation of activated carbons, they turned into a structure that was formed from carbon atoms, and their residual amounts decreased. In addition, the hydrogen storage capacities of the activated carbon samples were measured in different pressures at 77 and 298 K using the Hiden IMI PSI instrument. The results, confirmed that the hydrogen storage capacities of the activated carbons were higher at the cryogenic temperatures, and higher hydrogen storage capacity were observed by the increasing concentrations of activation agents in the synthesized activated carbons. The activated carbons synthesized by ZnCl₂ had higher hydrogen storage capacity than those by KOH.     

Investigation on platinum loaded multi-walled carbon nanotubes for hydrogen storage applications

Molecular hydrogen uptake of modified carbon nanotubes is a prospect for efficient hydrogen storage in fuel cell vehicles. In this study, a simple and efficient method to decorate the surface of multi-walled carbon nanotubes (MWNT) with platinum nanoparticles is presented. To load the Pt nanoparticles, hexachloroplatinic acid (H₂PtCl₆·6H₂O) is used as a precursor. Surface morphology of these Pt loaded MWNT is observed using Scanning and Transmission Electron Microscopy. Both samples are also characterized by X-Ray Diffraction. Thermal Gravimetric Analysis results indicate that both as purchased MWNT and Pt loaded MWNT have decomposition temperature higher than 500 °C in air. N₂ adsorption experiments yields a BET area of the sample close to 500 m²/g. This MWNT/Pt sample was reduced in 10% of H₂ in Ar, flowing at 900 °C in a tubular furnace for 1 h before hydrogen adsorption measurements. Hydrogen uptake of MWNT/Pt was measured at 2.5 MPa and 77 K. This hydrogen uptake isotherm is also compared with measurements at ambient temperature.     

Automotive hydrogen storage system using cryo-adsorption on activated carbon

An integrated model of a sorbent-based cryogenic compressed hydrogen system is used to assess the prospect of meeting the near-term targets of 36 kg-H₂/m³ volumetric and 4.5 wt% gravimetric capacity for hydrogen-fueled vehicles. The model includes the thermodynamics of H₂ sorption, heat transfer during adsorption and desorption, sorption dynamics, energetics of cryogenic tank cooling, and containment of H₂ in geodesically wound carbon fiber tanks. The results from the model show that recoverable hydrogen, rather than excess or absolute adsorption, is a determining measure of whether a sorbent is a good candidate material for on-board storage of H₂. A temperature swing is needed to recover >80% of the sorption capacity of the superactivated carbon sorbent at 100 K and 100 bar as the tank is depressurized to 3–8 bar. The storage pressure at which the system needs to operate in order to approach the system capacity targets has been determined and compared with the breakeven pressure above which the storage tank is more compact if H₂ is stored only as a cryo-compressed gas. The amount of liquid N₂ needed to cool the hydrogen dispensed to the vehicle to 100 K and to remove the heat of adsorption during refueling has been estimated. The electrical energy needed to produce the requisite liquid N₂ by air liquefaction is compared with the electrical energy needed to liquefy the same amount of H₂ at a central plant. The alternate option of adiabatically refueling the sorbent tank with liquid H₂ has been evaluated to determine the relationship between the storage temperature and the sustainable temperature swing. Finally, simulations have been run to estimate the increase in specific surface area and bulk density of medium needed to satisfy the system capacity targets with H₂ storage at 100 bar.     

Improving comparability of hydrogen storage capacities of nanoporous materials

We present results of investigations into improving methods by which gas sorption data are collected and reported. The focus is the accurate comparison of hydrogen storage capacities of different nanoporous materials. The aim is to produce a more rigorous approach to the assessment of the hydrogen storage capacities of different nanoporous materials through formulation of meticulous and systematic data collection routines for production of universally reproducible H₂ isotherms over a wide range of pressure and temperature conditions. Effects of a range of experimental variables are examined and recommendations for the optimisation of data collection routines are given.     

Ambient temperature hydrogen storage in porous materials with exposed metal sites

Cross-linked porous polymeric complexes with exposed metal sites are synthesized for room temperature hydrogen storage via physisorption. At 298 K and 100 atm, PTF-Cr exhibits high excess hydrogen storage capacity up to 1.5 wt% with Qst of 11.5 kJ mol^?1 while PTF-Mg exhibits 0.5 wt% with Qst of 8 kJ mol^?1. The result provides insight for development of future storage materials with exposed transition metals.     

The mechanism of hydrogen storage in carbon materials

Carbon materials were obtained by the thermal decomposition of organic reagents, and different surface states are achieved by treatment in different conditions. SEM, XRD and BET were used to characterize the samples. Hydrogen storage of the samples was measured at liquid nitrogen temperature. Combining these results and others’ work, a mechanism for hydrogen storage in carbon materials is proposed that hydrogen is stored at different sites with different mechanisms. With this hypothesis, the hydrogen storage properties of carbon materials can be forecasted quantitatively.     

Investigation of hydrogen storage capacity of various carbon materials

Hydrogen storage capacity of various carbon materials, including activated carbon (AC), single-walled carbon nanohorn, single-walled carbon nanotubes, and graphitic carbon nanofibers, was investigated at 303 and 77 K, respectively. The results showed that hydrogen storage capacity of carbon materials was less than 1 wt% at 303 K, and a super activated carbon, Maxsorb, had the highest capacity (0.67 wt%). By lowering adsorption temperature to 77 K, hydrogen storage capacity of carbon materials increased significantly and Maxsorb could store a large amount of hydrogen (5.7 wt%) at a relatively low pressure of 3 MPa. Hydrogen storage capacity of carbon materials was proportional to their specific surface area and the volume of micropores, and the narrow micropores was preferred to adsorption of hydrogen, indicating that all carbon materials adsorbed hydrogen gas through physical adsorption on the surface.     

Copper-doped activated carbon from amorphous cellulose for hydrogen,methane and carbon dioxide storage

The transition away from fossil fuel and ultimately to a carbon-neutral energy sector requires new storage materials for hydrogen and methane as well as new solutions for carbon capture and storage. Among the investigated adsorbents, activated carbons are considered especially promising because they have a high specific surface area, are lightweight, thermally and chemically stable, and easy to produce. Moreover, their porosity can be tuned and they can be produced from inexpensive and environmentally friendly raw materials. This study reports on the development and characterization of activated carbons synthesized starting from amorphous cellulose with and without the inclusion of copper nanoparticles. The aim was to investigate how the presence of different concentrations of metal nanoparticles affects porosity and gas storage properties. Therefore, the research work focused on synthesis and characterization of physical and chemical properties of pristine and metal-doped activated carbons materials and on further investigation to analyze their hydrogen, methane and carbon dioxide adsorption capacity. For an optimized Cu content the microporosity is improved, resulting in a specific surface area increase of 25%, which leads to a H₂ uptake (at 77 K) higher than the theoretical value predicted by the Chahine Rule. For CH₄, the storage capacity is improved by the addition of Cu but less importantly because the size of the molecule hampers easy access of the smaller pores. For CO₂ a 26% increase in adsorption capacity compared to pure activated carbon was achieved, which translated with an absolute value of over 48 wt% at 298 K and 15 bar of pressure.     

A solar hydrogen hybrid system with activated carbon storage

A solar hydrogen hybrid system has been developed to convert, store and use energy from renewable energy sources. The theoretical model has been implemented in a dynamic model-based software environment and applied to real data. A photovoltaic sub-system drives a residential load and, if a surplus of energy is available, an electrolyzer to produce hydrogen which is stored in a cluster of nitrogen-cooled tanks filled with activated carbons; when needed, hydrogen is used in a fuel cell to supply power to the load. Hydrogen storage is achieved through physisorption at low temperature and low pressures. Physisorption storage provides safer operations along with good gravimetric and volumetric capacities at costs comparable to or smaller than compression or liquefaction storage.     

Posidonia Oceanica and Wood chips activated carbon as interesting materials for hydrogen storage

The goal is to investigate the feasibility to use a local biomass (Posidonia Oceanica and Wood chips), as a raw precursor, to the production of activated carbons (AC) with a high surface area and remarkable hydrogen (H₂) adsorption properties.Biomasses (particle size of 0.3–0.4 mm) were pyrolyzed at 600 °C with a heating rate of 5 °C/min under an argon atmosphere. The biochar obtained from the carbonization step was chemically activated with KOH. The activation methodology induces a considerable improvement of the properties of the porous carbon in terms of carbon content (from 58 to 69 wt% to 93–96 wt%), surface area (from 41 to 425 m²/g to 2810–2835 m²/g) and H₂ adsorption in cryogenic condition (from 0,1 wt% to over 5 wt%).All porous carbons were characterized in terms of elemental analysis (CHNS–O), textural properties and H₂ adsorption measurements.     

Investigation of hydrothermal carbonization and chemical activation process conditions on hydrogen storage in loblolly pine-derived superactivated hydrochars

While the challenge of storing hydrogen in inexpensive and renewable adsorbents is relentlessly pursued by researchers all over the world, application of hydrochar derived from biomass is also gaining attention as it can be subsequently chemically activated using activating agents like KOH in order to tailor the development of favorable porosity. However, the synergistic effect of hydrothermal carbonization (HTC) process conditions as well as KOH activating conditions on the development of surface morphology is required to be assessed with the application of such porous superactivated hydrochars in hydrogen storage application. In this study, highly porous superactivated hydrochars were fabricated from inexpensive and abundant loblolly pine. Loblolly pine was hydrothermally carbonized at 180 °C, 220 °C and 260 °C and the hydrochars were then activated at different experimental conditions of 700 °C, 800 °C and 900 °C using solid KOH to loblolly pine hydrochar ratio of 2:1, 3:1 and 4:1 to produce superactivated hydrochars. Superactivated hydrochars as well as loblolly pine and its corresponding hydrochars underwent physicochemical analysis as well as surface morphology analysis by SEM and nitrogen adsorption isotherms at 77 K in order to investigate the effect on BET, pore volume, and pore size distribution due to various process conditions. The superactivated hydrochars were then analyzed to quantify total hydrogen storage capacity of these materials at 77 K and up to pressure of 55 bar. Porosity of superactivated hydrochars were as high as 3666 m²/g of BET specific surface area (SSA), total pore volume of 1.56 cm³/g and micropore volume of 1.32 cm³/g with the hydrogen storage capacity of 10.2 wt% at 77 K and 55 bar. It was conclusive from principal component analysis that higher HTC temperature with moderate activation condition demonstrated favorability in developing porous superactivated hydrochars for hydrogen storage applications.     

Nitrogen-incorporated carbon nanotube derived from polystyrene and polypyrrole as hydrogen storage material

“Synthesis of nitrogen-doped carbon nanotubes from polymeric precursors (polystyrene and polypyrrole) by poly-condensation followed by carbonization under an inert atmosphere is reported. Three different carbonization temperatures (500 °C, 700 °C and 900 °C) were employed to synthesize three different carbon nanostructures with different morphologies. These were designated as NCNR-500 (nitrogen-doped carbon nanorods), NCBCT-700 (nitrogen-doped fused bead carbon nanotubes), and NCNT-900 (nitrogen-doped carbon nanotubes) according to morphology and carbonization temperature. Microstructure, morphology, porosity, and nitrogen content were characterized by several different techniques. The effects of carbonization temperature and the role of functional groups were also investigated. Total and excess hydrogen storage capacities of 2.0 wt% and 1.8 wt%, respectively, were measured at 298 K and 100 bar for the NCNT-900 material. This is higher than the capacities of the NCNR-500 and NCBCT-700 materials. NCNT-900 exhibited a porous structure with high specific surface area and total pore volume of 870 m/g and 0.62 cm³/g, respectively.     

Finite element model for charge and discharge cycle of activated carbon hydrogen storage

One of the main challenges to introduce hydrogen on the energy market is to improve on-board hydrogen storage and develop more efficient distribution technologies to increase the amount of stored gas while lowering the storage pressure. The physisorption of hydrogen on activated carbons (AC) is being investigated as a possible route for hydrogen storage. The objective of this work is to study the performance of adsorption-based hydrogen storage units from a "systems" point of view. A realistic two-dimensional axisymmetric geometric model which couples mass, momentum and energy balances is established based on the thermodynamic conservation laws using finite element method as implemented in COMSOL Multiphysics™. We consider the charging and discharging of the storage unit at a rated pressure of 9 MPa, and at an initial temperature of 302 K. The results are compared with experimental data obtained at the Hydrogen Research Institute of the University of Quebec at Trois-Rivieres. The storage tank is cooled by ice water. Research results show that both the simulated variations of pressure and temperatures during charge and discharge processes are in good agreement with the experimental data. The temperatures in the central region of tank are higher than those at the entrance and near the wall at the end of charge time while they are lower than those at the entrance and near the wall at the end of discharge time. The velocities are largest at the entrance, and decrease gradually along the axis of the tank. Owing to thermal effects, the larger flow rates result in less amount of adsorption in the condition of the same charging pressure. Hence measures of increasing heat transfer should be adopted, such as increasing the thermal conductivity of the storage bed. From the point of view of storage capacity, it is therefore possible to realize rapid hydrogenation, which is conducive to the use of such systems for on-board hydrogen storage based on activated carbon adsorption.     

Chemisorption,physisorption and hysteresis during hydrogen storage in carbon nanotubes

The question of chemisorption versus physisorption during hydrogen storage in carbon nanotubes (CNTs) is addressed experimentally. We utilize a powerful measurement technique based on a magnetic suspension balance coupled with a residual gas analyzer, and report new data for hydrogen sorption at pressures of up to 100 bar at 25 °C. The measured sorption capacity is less than 0.2 wt.%, and there is hysteresis in the sorption isotherms when multi-walled CNTs are exposed to hydrogen after pretreatment at elevated temperatures. The cause of the hysteresis is then studied, and is shown to be due to a combination of weak sorption – physisorption – and strong sorption – chemisorption – in the CNTs. Analysis of the experimental data enables us to calculate separately the individual hydrogen physisorption and chemisorption isotherms in CNTs that, to our knowledge, are reported for the first time here. The maximum measured hydrogen physisorption and chemisorption are 0.13 wt.% and 0.058 wt.%, respectively.     

Hydrogen storage in platinum loaded single-walled carbon nanotubes

To study the hydrogen storage capacity, platinum (Pt) nanoparticles were deposited on single-walled carbon nanotubes (SWNT) using hexachloroplatinic acid (H₂PtCl₆·6H₂O) as a precursor. To verify Pt deposition on the surface of the SWNT, a Transmission Electron Microscope (TEM) was used to obtain surface morphology. The TEM images show that Pt nanoparticles were homogeneously distributed on the surface of SWNT. Commercial SWNT were also used to compare the results. Thermal Gravimetric Analysis at heating rate of 5 °C/min is measured for pure SWNT and Pt loaded SWNT. Before hydrogen storage measurements these samples were reduced in 10% of H₂ in Ar, flowing at 900 °C in a tubular furnace for 1 hour. Hydrogen storage capacity of these SWNT was investigated under 25 bar pressure and room temperature as well as liquid nitrogen temperature.     

CFD model for charge and discharge cycle of adsorptive hydrogen storage on activated carbon

High surface area activated carbons and other microporous adsorbents have generated a significant amount of interest over the past decade as storage media for hydrogen and natural gas, due to their high storage capacity at low temperatures and their use in gas purification processes. This paper uses computational fluid dynamics (CFD) to simulate the charging and discharging of a sorption-based hydrogen storage system. The CFD model is based on the mass, momentum and energy conservation equations of a system formed of gaseous and adsorbed hydrogen, an activated carbon bed and steel tank walls. The adsorption process is modeled using the Dubinin–Astakov adsorption isotherms extended to the supercritical regime. The model is implemented using Fluent. In our study, we can obtain accuracy peak temperature of simulation due to a non-constant isosteric heat of adsorption is used, derived from the model isotherms. We adopt piecewise heat capacity to consider the heat capacity of the adsorbed phase of hydrogen. We can make a conclusion that the simulated temperatures without consideration of heat capacity for hydrogen in adsorbed phase (c_pa), rise faster and reach higher peaks than the simulated temperatures with consideration of c_pa, and diverge more from experimental results. Also, we study the changes of temperature, pressure and adsorption during the charging and discharging processes as well as when the system is idle (which we define as dormancy) in the case of room temperature water cooling. The results are compared with experimental data from a storage unit cooled with room temperature water. The simulated pressure is in a good agreement with the experimental values. The simulated temperature profiles are also generally in good agreement with the experimental values, except close to the inlet and the wall. In addition, we have studied the effect of quality of the mesh on the accuracy and stability of the numerical computation and the influence of the mass flow rates on temperature and adsorption capacity.     

Surface functionalization-enhanced spillover effect on hydrogen storage of Ni–B nanoalloy-doped activated carbon

Surface functionalization-enhanced spillover effect on hydrogen storage behaviors of Ni–B nanoalloy-doped activated carbon is investigated in comparison to the 3D graphene-based material. It is discovered that the hydrogen storage capacity of the activated carbon increases from Ni–B nanoalloy-doping but much less than that of graphene. After surface functionalization, although the specific surface area and micropore volume of the doped activated carbon decrease significantly, a hydrogen storage capacity is still almost as same as that of the unfunctionalized larger surface one, while showing a large desorption hysteresis. We argue that the surface functionalization greatly enhances the spillover process on carbon based adsorbents, thus playing an essential role in hydrogen storage capacity improvement.     

Simulation of heat and mass transfer in activated carbon tank for hydrogen storage

The charging process of hydrogen storage tank based on bed of activated carbon in a steel container at room temperature (295 K) and medium storage pressure (10 MPa) is simulated with an axisymmetric geometry model using the finite volume commercial solver Fluent. The mass flux profile at the entrance is established using user-defined functions (UDFs). The heat and mass transfer processes in the cylindrical steel tank packed with activated carbon are discussed considering the influence of viscous resistance and inertial resistance of the porous media. The velocity distribution and its effect on the temperature distribution are analyzed. The effects of the flow rate at the inlet and of the adsorption factor on the charging process are studied. A computational fluid dynamics (CFD) approach based on finite volume simulations is used. Results show that the temperature near the bottom of the tank is higher than that at the entrance, temperature in the center of the tank is higher than that near the wall and rises somewhat faster along the axial compared to the radial direction. The highest hydrogen absolute adsorption occurs at the entrance of the tank. A good agreement is found between the simulation results and the available experimental data. The maximum magnitude of the axial velocity is much higher than that of the radial component, resulting in more heat energy transfer along the axial direction than radial direction. In addition, the pressure reaches equilibrium earlier when the mass flow is higher, and the temperature reaches a maximum value faster.     

Mechanism of heterogeneous adsorption in the storage of hydrogen in carbon fibers activated with supercritical water and steam

In the present work we study the capacity of storage hydrogen on carbon fibers activated with supercritical water and with steam on the basis of a multisite Langmuir model, with three energetically different adsorption sites that may be associated with pores of different sizes: i) very small micropores, accessible only to hydrogen; ii) micropores detected by the adsorption of CO₂, and iii) micropores detected by the adsorption of N₂. The correlation of the experimental data with the model allowed the amount of hydrogen stored in each of the sites to be quantified and confirmed that hydrogen storage mechanism begins with the filling of the smallest pores. Additionally, from the model it was possible to interpret the dependence of the amount of hydrogen stored with textural parameters such as the micropore volumes. The model also allowed the storage capacity of the fibers to be predicted for pressures higher than those obtained experimentally.