Technical feasibility of a proton battery with an activated carbon electrode

The technical feasibility of a small-scale ‘proton battery’ with a carbon-based electrode is demonstrated for the first time. The proton battery is one among many potential contributors towards meeting the gargantuan demand for electrical energy storage that will arise with the global shift to zero greenhouse emission, but inherently variable, renewable energy sources. Essentially a proton battery is a reversible PEM fuel cell with an integrated solid-state electrode for storing hydrogen in atomic form, rather than as molecular gaseous hydrogen in an external cylinder. It is thus a hybrid between a hydrogen-fuel-cell and battery-based system, combining advantages of both system types. In principle a proton battery can have a roundtrip energy efficiency comparable to a lithium ion battery. The experimental results reported here show that a small proton battery (active area 5.5 cm²) with a porous activated carbon electrode made from phenolic resin and 10 wt% PTFE binder was able to store in electrolysis (charge) mode very nearly 1 wt% hydrogen, and release on discharge 0.8 wt% in fuel cell (electricity supply) mode. A significant design innovation is the use of a small volume of liquid acid within the porous electrode to conduct protons (as hydronium) to and from the nafion membrane of the reversible cell. Hydrogen gas evolution during charging of the activated carbon electrode was found to be very low until a voltage of around 1.8 V was reached. Future work is being directed towards increasing current densities during charging and discharging, multiple cycle testing, and gaining an improved understanding of the reactions between hydronium and carbon surfaces.     

Fabrication and evaluation of stable micro tubular solid oxide fuel cells with BZCY-BZY bi-layer proton conducting electrolytes

Anode-supported proton conducting micro tubular solid oxide fuel cells (MT-SOFCs) with the configuration of Ni–BaZr_0.1Ce_0.7Y_0.2O_3-δ (BZCY)/BZCY/BaZr_0.8Y_0.2O_3-δ (BZY)/La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ (LSCF)-BZY have been prepared by a combination of phase inversion method and suspension-coating technique. The obtained Ni-BZCY anode hollow fiber presents a special asymmetrical structure consisting of a sponge-like layer and a finger-like porous layer, which is propitious to anode electrochemical process. Bi-layer electrolytes consisting of 5 μm thick BZCY and 3 μm thick BZY are successfully fabricated by suspension-coating technique. BZY electrolytes are placed at the cathode side, in order to improve the chemical stability against CO₂. The considerable electrochemical performance and good stability in the presence of CO₂ indicate that the construction of BZY-BZCY bi-layer electrolytes is an effective way for the development of stable proton conducting MT-SOFCs.     

Effect of electrode mass ratio on aging of activated carbon based supercapacitors utilizing organic electrolytes

The accelerated degradation of carbon based supercapacitors utilizing 1 M Et₄NBF₄ in acetonitrile and in propylene carbonate as electrolyte is investigated for a constant cell voltage of 3.5 V as a function of the positive over total electrode mass ratio. The degradation rate of the supercapacitor using acetonitrile as a solvent can be decreased by increasing the mass of the positive electrode. With a mass ratio (positive electrode mass/total electrode mass) of 0.65 the degradation rate is minimum. For the capacitor utilizing propylene carbonate as a solvent a similar effect was observed. The degradation rate was smallest for a mass ratio above 0.5.     

Poly(ethylene glycol) modified activated carbon for high performance proton exchange membrane fuel cells

A high water retention membrane is developed by co-assembling poly(ethylene glycol) (PEG) grafted activated carbon (AC-PEG) with Nafion. The AC-PEG is prepared via a sol–gel process. The use of PEG as a transporting medium in AC-PEG shows a largely improved water retention ability, a higher proton conductivity and a reduced swelling ratio, making it well suited for proton exchange membrane fuel cells (PEMFCs). Further, the composite membranes show improved mechanical properties at high temperature, thus ensuring the structural stability of membranes during the fuel cell operation. Compositional optimized AC-PEG/Nafion composite membrane (15 wt% compared to Nafion) demonstrates a better performance than the commercially available counterpart, Nafion 212, in fuel cell measurements. To identify the key factor of the improved performance, current interrupt technique is used to quantitatively verify the changes of resistance under different relative humidity environment.     

Analysis of heat conducting enhancement measures on the composite for hydrogen storage by incorporation of activated carbon with MOFs

Experiments and numerical simulations were conducted for evaluating measures for enhancing adsorption capacity and heat conducting of an on board MOFs hydrogen storage system by cryo-adsorption. Solvothermal method was employed to synthesize MIL-101(Cr) composite by incorporating activated carbon. The composite was undergone structure characterization, structural morphology observation, thermal conductivity measurement and measurement of isotherm of hydrogen adsorption at 77.15 K within 0–6 MPa. Effect of adding expanded natural graphite (ENG) and equipping a honeycomb heat exchanging device (HHED) on mitigating the thermal effect on a 0.5 L hydrogen storage vessel packed with composite was investigated within a flow rate of hydrogen required by a ship's power unit. It shows that the sample incorporated by 1 wt% activated carbon respectively obtained about 14.5%, 26.2% and 5.7% increment in specific surface area, micropore volume and the maximum excess adsorption amount. Results also reveal that, within the flow rate 5 L·min^?1-25 L min^?1, the mean relative error between the experimental data and those from simulations is less than 1.61%, and the reduction in temperature fluctuation of the storage system is about 5 °C and 4 °C on charge and discharge process while equipping the HHED, which accordingly brought about 17%, 24.3%, 18.5% increment in accumulated amount of charge and discharge as well as the useable capacity ratio (UCR) of the system. It suggests that equipping a HHED is a more promising method for weakening the thermal effect on MOFs-hydrogen storage systems.     

Raman spectroscopy of SrZrO3 based proton conducting electrolyte: Effect of Y-doping and Sr-nonstoichiometry

The present research describes the results of Raman spectroscopic study of undoped and Y-doped SrZrO₃ having a great potential for application in proton-conducting fuel cells. Effects of yttrium doping and strontium nonstoichiometry on the local environment of cations and vibrational properties of strontium zirconate were investigated. Ceramic samples Sr_yZr_1-xY_xO_3-δ (x = 0, 0.02, 0.05; y = 0.94, 0.98, 1.00) were synthesized via a chemical solution method and sintered at 1650 °C. Microstructure, phase and chemical composition of the samples were characterized by Scanning Electron Microscopy (SEM), X-ray diffraction (XRD) and Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES). Analysis of Raman spectra peculiarities upon changes in Sr- and Y- concentrations has shown that yttrium ions can be partitioned over both A- and B-sites in the strontium-deficient zirconates with the dopant concentrations more than 2 at%.     

Structure and electrochemical properties of activated polyacrylonitrile based carbon fibers containing carbon nanotubes

Solution spun polyacrylonitrile (PAN), PAN/multi-wall carbon nanotube (MWCNT), and PAN/single-wall carbon nanotube (SWCNT) fibers containing 5 wt.% carbon nanotubes were stabilized in air and activated using CO₂ and KOH. The surface area as determined by nitrogen gas adsorption was an order of magnitude higher for KOH activated fibers as compared to the CO₂ activated fibers. The specific capacitance of KOH activated PAN/SWCNT samples was as high as 250 F g⁻¹ in 6 M KOH electrolyte. Under the comparable KOH activation conditions, PAN and PAN/SWCNT fibers had comparable surface areas (BET surface area about 2200 m² g⁻¹) with pore size predominantly in the range of 1–5 nm, while surface area of PAN/MWCNT samples was significantly lower (BET surface area 970 m² g⁻¹). The highest capacitance and energy density was obtained for PAN/SWCNT samples, suggesting SWCNT advantage in charge storage. The capacitance behavior of these electrodes has also been tested in ionic liquids, and the energy density in ionic liquid is about twice the value obtained using KOH electrolyte.     

Reasonable construction of proton conducting channel via biomimetic caterpillar-like alumina fiber to improve the properties of its composite proton exchange membrane

In this paper, we prepare a novel biomimetic caterpillar-like alumina fiber with the characteristic of continuous alumina backbone and fine needle whiskers spine. Then the high-performance caterpillar-like alumina fiber composite proton exchange membrane (CAPEM) is obtained by introducing the amino modified biomimetic caterpillar-like alumina fiber into sulfonated polysulfone (SPSF) matrix, which successfully reasonable construction of the proton conducting channels in both vertical and horizontal orientation. The properties of CAPEM, including proton conductivity, methanol permeability, etc. Are systematically studied. The results show that the proton conductivity of CAPEM increases with rising the temperature, which reaches the maximum of 0.263 S/cm at 80 °C and 100% RH, respectively. The excellent proton conductivity of CAPEM is attributed to the long-range continuous proton conducting channel formed by the horizontal continuous alumina skeleton in the in-plane direction and the vertical overlapped fine needle whiskers spine in the through-plane direction. In addition, the interfacial compatibility between amino modified caterpillar-like alumina fiber and SPSF matrix is enhanced through the reasonable construction of proton conducting channels, which effectively inhibits the methanol permeation of the composite membrane with 4.18 × 10^?7 cm² s^?1 and improves the comprehensive performance of the CAPEM.     

Analytic parameter identification of proton exchange membrane fuel cell catalyst layer using electrochemical impedance spectroscopy

A finite transmission line is proposed for proton exchange membrane fuel cell reaction layer, when the faradic current is absent due to purging of Inert gas at the back of cathode and anode. Also a finite transmission line is presented when a charge transfer accrued among catalyst and electrolyte interface. The electrochemical impedances of finite transmission lines are computed using MATLAB software. Relative to the orders and types of the evaluated impedances, some relations to determine and identify the parameters of the proposed models are derived. In first model, it is shown that the electrical elements of transmission line can be extracted explicitly from the Nyquist and Bode diagrams whereas for the second one, some of the parameters cannot directly be investigated. However, using a numerical procedure, some valuable results about parameter variations are obtained.     

Electrochemical behavior of negative electrode of lead-acid cells based on reticulated vitreous carbon carrier

Reticulated vitreous carbon (RVC^®) and RVC^® plated with lead were investigated as carriers for the negative electrode of lead-acid cell. The RVC^® and Pb/RVC^® carriers were pasted with active paste (received from JENOX Ltd., Polish producer of lead-acid batteries) and prepared to be used in lead-acid cell. Comparative study of electrodes based on RVC^® and Pb/RVC^® has been done using constant-current charging/discharging, constant-potential discharging and cycling voltammetry measurements. Scanning electron microscopy (SEM) was employed to determine the morphology of the lead layer deposited on the RVC surface. Hybrid flooded single lead-acid cells containing one negative electrode, based on new type of carrier (RVC^® or Pb/RVC^®), sandwiched between two positive electrodes, based on the Pb-Ca grids, were assembled and subjected to electrochemical tests. It has been found that both materials, RVC^® and Pb/RVC^®, can be used as carriers of negative electrode, but the latter seems to have better influence on the discharge performance.     

Effect of water contamination in the organic electrolyte on the performance of activated carbon/graphite capacitors

The effect of water contamination in the electrolyte on the performance of AC/graphite capacitor has been investigated by electrochemical tests and in situ XRD measurements. The deterioration mechanisms for the charge storage ability of the electrodes in the capacitors using polluted electrolytes have also been addressed.     

Effect of treatment of activated carbon fiber cloth electrodes with cold plasma upon performance of electric double-layer capacitors

Charge/discharge behavior of electric double-layer capacitors composed of activated carbon fiber cloth (ACFC) electrodes and an organic electrolyte was investigated. The modification of the ACFC electrodes was performed using cold plasma generated in argon-oxygen atmosphere. The effect of the cold plasma treatment of the ACPC electrodes on the capacitor performance was discussed on the basis of the physical and chemical properties of the ACFC surface such as pore radius distribution and surface atom concentration.     

Performance of Pd on activated carbon as hydrogen electrode with respect to hydrogen yield in a single cell proton exchange membrane (PEM) water electrolyser

Palladium (Pd) on activated carbon is used as electrocatalyst coated on Nafion 115 membrane as Hydrogen electrode and RuO₂ is coated on other side of membrane used as oxygen electrode. 5 wt% and 10 wt% Pd on activated carbon is prepared as membrane electrode assembly (MEA) and investigated the performance of the same using inhouse prepared 10 cm² single cell. The performance of the single cell assembly and the hydrogen yield are reported during electrolysis operation at temperatures 27 °C, 45 °C and 65 °C at 0.1, 0.2, 0.3, 0.4, 0.5 A/cm² current densities with respect to voltages.     

Utilization of (oxalato)borate-based organic electrolytes in activated carbon/graphite capacitors

The electrolyte salts composed of tetramethylammonium (TMA⁺) cation and difluoro(oxalato)borate (DFOB⁻) or bis(oxalato)borate (BOB⁻) anions have been proposed for the application in activated carbon (AC)/graphite capacitors. The electrochemical performance of AC/graphite capacitors has been studied using these electrolyte salts dissolved in propylene carbonate (PC). The intercalation behaviors of anions (BF₄⁻, DFOB⁻, and BOB⁻) at the graphite positive electrodes have been investigated by in situ XRD measurements. The bigger the anion is, the higher the cell voltage is where the intercalation happens. Accordingly, the bigger the anion is, the smaller discharge capacity delivered by an AC/graphite capacitor. The charge mechanism of TMA⁺ at the AC negative side has also been addressed. Compared with other bigger quaternary alkyl ammonium cations, the specific capacitance of the AC negative electrode towards TMA⁺ adsorption is somehow smaller as estimated.     

Optimization of catalyst ink composition for the preparation of a membrane electrode assembly in a proton exchange membrane fuel cell using the decal transfer

For low interfacial resistance and feasibility of forming catalyst layer (CL), decal transfer (DT) is considered as one of the most effective methods for preparing a membrane electrode assembly. However, optimization of the catalyst ink composition is necessary, because of the complexity of the CL. Here, 1-propanol is adsorbed onto the CL coated onto the decal, as a swelling agent, for complete transfer of the CL onto Nafion membrane. Using this methodology, flat and complete DT is achieved at the hot-pressing conditions of 60 °C and 5 MPa. For optimization, the solvent-to-carbon ratio (SCR) and Nafion-to-carbon ratio (NCR) are controlled to achieve improved cell performance. In this study, by considering the morphology of CL and the cell performance when CL is annealed at temperatures sufficiently below the boiling point of the solvent, optimized SCR and NCR values of approximately 12.0 and 0.65, respectively, are obtained. In addition, microstructure, thickness and various electrochemical properties of the CLs are examined in detail.     

Effects of surface chemical states of carbon nanotubes supported Pt nanoparticles on performance of proton exchange membrane fuel cells

This study synthesized platinum (Pt) nanoparticles supported on carbon nanotubes (CNTs) using a microwave-assisted polyol method. The oxidation treatment of CNTs introduced primarily -OH and -COOH groups to the CNTs, thereby enhancing the reduction of Pt ionic species, resulting in smaller Pt particles with improved dispersion and attachment properties. The Pt particles supported on oxidized CNTs displayed superior durability to those on pristine CNTs or commercially available Pt/C. These improvements are most likely associated with the percentage of metallic Pt in the particles. After 400 cycles, the losses of electrochemical surface area in Pt nanoparticle supported on oxidized CNTs and pristine CNTs catalysts were 66 and 84%, respectively, of that associated with commercial Pt/C. A single proton exchange membrane fuel cell using Pt supported on oxidized CNTs at the cathode with a total catalytic loading of 0.6 Pt mg cm⁻² exhibited the highest power density of 890 mW cm⁻² and displayed a lower mass transfer loss, compared to Pt/C.     

Modelling of a hydrogen thermally driven compressor based on cyclic adsorption-desorption on activated carbon

Thermally driven hydrogen compression by cyclic hydrogen adsorption-desorption on activated carbon is presented therein. Hydrogen compression occurs through heat exchange, which allows physisorbed hydrogen to desorb at higher temperature in a given volume. The physical nature of hydrogen adsorption on porous carbon allows reversible desorption, and a flow of compressed hydrogen is then obtained by running adsorption/desorption cycles repeatedly. We investigated the feasibility of such a system through numerical simulations by taking into account both mass and energy balances, and adsorption thermodynamics. We showed that high-pressure hydrogen, up to 70 MPa, can be obtained by simply lowering and/or increasing the system temperature. Such a system opens new perspectives in the frame of the Hydrogen Supply Chain.     

Dual functions of activated carbon in a positive electrode for MnO2-based hybrid supercapacitor

Utilizing the dual functions of activated carbon (AC) both as a conductive agent and an active substance of a positive electrode, a hybrid supercapacitor (AC-MnO₂&AC) with a composite of manganese dioxide (MnO₂) and activated carbon as the positive electrode (MnO₂&AC) and AC as the negative electrode is fabricated, which integrates approximate symmetric and asymmetric behaviors in the distinct parts of 2 V operating windows. MnO₂ in the positive electrode and AC in the negative electrode together form a pure asymmetric structure, which extends the operating voltage to 2 V due to the compensatory effect of opposite over-potentials. In the range of 0-1.1 V, both AC in the positive and negative electrode assemble as a symmetric structure via a parallel connection which offers more capacitance and less internal resistance. The optimal mass proportions of electrodes are calculated though a mathematical process. In a stable operating window of 2 V, the capacitance of AC-MnO₂&AC can reach 33.2 F g⁻¹. After 2500 cycles, maximum energy density is 18.2 Wh kg⁻¹ with a 4% loss compared to the initial cycle. The power density is 10.1 kW kg⁻¹ with an 8% loss.     

Thermocatalytic decomposition of methane using activated carbon: Studying the influence of process parameters using factorial design

The thermocatalytic decomposition of methane over activated carbon (AC) is proposed as a potential alternative for the production of hydrogen. The experiments were divided into two parts; the first part was conducted using thermogravimetric analyzer (TGA) while the second part was conducted in a bench-scale unit. For the first part, the research objective is to study the main and interaction effects of decomposition temperature (800-950 °C) and methane partial pressure (0.03-0.63 atm) on the initial specific rate of carbon formation by using statistical method. The experiments were carried out as a general full factorial design consisting of 20 experiments. Quadratic model was developed for initial specific rate of carbon formation in term of temperature and methane partial pressure using response surface methodology. The model’s results show that not only the effects of the main parameters are important, but also the interaction effects between them are significant. For the second part, the main effects of decomposition temperature (775-850 °C) and AC weight (20-120 g) on the initial rate of methane decomposition by using the analysis of variance (ANOVA) were investigated. The results showed that AC weight has higher mean effects than decomposition temperature on the initial rate of methane decomposition.     

Hydrogen storage properties of activated carbon confined LiBH4 doped with CeF3 as catalyst

CeF₃ as a catalyst is first added to activated carbon (AC) by ball milling under low rotation speed. Then the treated AC was used as the scaffold to confine LiBH₄ by melt infiltration process. The combined effects of confinement and CeF₃ doping on the hydrogen storage properties of LiBH₄ are studied. The experimental results show that LiBH₄ and CeF₃ are well dispersed in the AC scaffold and occupy up to 90% of the pores of AC. Compared with pristine LiBH₄, the onset dehydrogenation temperature for LiBH₄-AC and LiBH₄-AC-CeF₃ decreases by 150 and 190 °C, respectively. And the corresponding dehydrogenation capacity increases from 8.2 wt% to 13.1 wt% for LiBH₄-AC and 12.8 wt% for LiBH₄-AC-CeF₃, respectively. The maximum dehydrogenation speed of LiBH₄-AC and LiBH₄-AC-CeF₃ is 80 and 288 times higher than that of pristine LiBH₄ at 350 °C. And LiBH₄-AC andLiBH₄-AC-CeF₃ show good reversible hydrogen storage properties. On the during 4th dehydrogenation cycle, the hydrogen release capacity of LiBH₄-AC and LiBH₄-AC-5 wt% CeF₃ reaches 8.1 and 9.3 wt%, respectively.