电解液离子与炭电极双电层电容的关系

以酚醛树脂基纳米孔玻态炭(NPGC)为电极, 通过微分电容伏安曲线的测试, 研究了水相体系电解液离子与多孔炭电极双电层电容的关系. 结果表明, 稀溶液中, 多孔炭电极的微分电容曲线在零电荷点(PZC)处呈现凹点, 电容降低, 双电层电容受扩散层的影响显著；若孔径小, 离子内扩散阻力大, 电容下降更为迅速, 扩散层对双电层电容的影响增大. 而增大炭材料的孔径或电解液浓度, 可明显减弱甚至消除扩散层对电容的影响. 炭电极的单位面积微分电容高, 仅表明孔表面利用率高, 如欲获得高的电容量, 还要有大的比表面积. 离子水化对炭电极的电容产生不利影响, 选用大离子和增大炭材料的孔径, 可有效降低离子水化对炭电极电容性能的影响.     

Role of titania incorporated on activated carbon cloth for capacitive deionization of NaCl solution

Adsorption isotherms of NaCl on activated carbon cloth (ACC) and titania-incorporated activated carbon cloth (Ti-ACC) under an electric field were investigated to deduce the role of titania in capacitive deionization (CDI) of NaCl. Electrosorption of NaCl on the ACC was significantly increased by titania incorporation, whereas its physical adsorption was considerably decreased, resulting in an improved performance of the Ti-ACC as a CDI electrode. Langmuir isotherms based on a localized and fixed amount of adsorption were suitable for the simulation of electrosorption and physical adsorption of ions on the ACC electrodes. The variances of q(m) and b of Langmuir isotherms with electric potential indicate increases in the number of ions per adsorption site and in electrosorption strength of ions by titania incorporation. A cyclic voltammetric study for ion adsorption on ACC electrodes confirms the reversibility between electrosorption and desorption of ions, regardless of titania incorporation.     

Carbon Aerogel Films Synthesized at Ambient Conditions

Carbon aerogels derived from organic sol-gel process and supercritical drying are novel porous materials with interconnect structures and higher electrical conductivity, which are considered to be ideal electrode materials for supercapacitors and rechargeable batteries. The objective of the research was to synthesize carbon aerogel films at ambient conditions. Resorcinol formaldehyde (RF) and carbon aerogel films have been produced with extremely high RC ratio (molar ratio of resorcinol to catalyst) followed by subcritical drying. The structure of the porous films was investigated using electron scanning microscope. The specific surface area was measured by using nitrogen adsorption (BET) and electrical conductivity was measured with four-probe method. It was found that with extremely high RC ratio, the porous structure of RF and carbon aerogel films can be controlled from micro to macro porous at ambient conditions. With respect to the application as electrodes for fuel cells, carbon aerogel films with different porous structures on the two surfaces have been also obtained through optimizing the sol-gel process.     

氯化锌活化对炭气凝胶微球的结构与电化学性能的影响

对炭气凝胶微球在高温下进行氯化锌活化改性,并用于制作超级电容器的电极。采用扫描电镜、N2物理吸附-脱附等对炭气凝胶微球的形貌结构进行表征,采用循环伏安、恒流充放电等测定了材料的电化学性能。结果表明,氯化锌活化有效地改善了炭气凝胶微球的孔结构,通过增加炭气凝胶微球的微孔面积和体积,提高了材料的比表面积和孔隙率。经过氯化锌活化,炭气凝胶微球的电化学性能也随之得到提高,电阻明显减小,比电容提高了2倍以上。     

Carbon materials as electrodes for electrosorption of NaCl in aqueous solutions

Different porous carbons (MWCNT, a carbon aerogel, an activated carbon cloth and a chemically activated carbon) were evaluated as electrode material for the electrosorption of NaCl. The results obtained from the chronoamperometric experiments were correlated to the surface area and the size of the pores present in each carbon. These results indicate that all the surfaces are equivalent for the electrosorption process, demonstrating that both, mesopores and micropores, are equally effective. Nevertheless, the kinetics of the process is influenced by the pore size distribution of the carbon, although it is rather fast for all the carbons studied. The chemically activated carbon seems to be the most suitable carbon material for electrosorption of NaCl due to the combination of a high surface area and an appropriate pore size distribution.     

Carbon/carbon supercapacitors

Supercapacitors, or electrochemical capacitors, are a power storage system applied for harvesting energy and delivering pulses during short periods of time. The commercially available technology is based on charging an electrical double-layer (EDL), and using high surface area carbon electrodes in an organic electrolyte. This review first presents the state-of-the-art on EDL capacitors, with the objective to better understand their operating principles and to improve their performance. In particular, it is shown that capacitance might be enhanced for carbons having subnanometric pores where ions of the electrolyte are distorted and partly desolvated. Then, strategies for using environment friendly aqueous electrolytes are presented. In this case, the capacitance can be enhanced through pseudo-faradaic contributions involving i) surface functional groups on carbons, ii) hydrogen electrosorption, and iii) redox reactions at the electrode/electrolyte interface. The most promising system is based on the use of aqueous alkali sulfate as electrolyte allowing voltages as high as 2 V to be reached, due to the high overpotential for di-hydrogen evolution at the negative electrode.     

Double-layer and pseudocapacitance types of electrochemical capacitors and their applications to the development of hybrid devices

The basis of the complementary use of electrochemical capacitors (so-called supercapacitors) in hybrid electric power generation by rechargeable batteries and fuel cells is explored. Electrochemical capacitors are of two types: one where the interfacial double-layer capacitance of high specific area carbon materials is the basis of electric charge storage (as ions and electrons); and the other where pseudocapacitance, associated with electrosorption and surface redox processes at high-area electrode materials, e.g. RuO₂, or at conducting polymers, provides the basis of charge storage. The former, double-layer, type of capacitance stores charge non-faradaically while the latter type, pseudocapacitance, stores charge indirectly through faradaic chemical processes but its electrical behaviour is like that of a capacitor. Two types of hybrid battery/capacitor system are recognized: one based on combination of an electrochemical capacitor cell with a rechargeable battery or a fuel cell in a load-leveling function, e.g. in an electric vehicle power train; and the other based on combination of a faradaic battery-type electrode coupled internally with a capacitative electrode in a two-electrode hybrid module (termed an asymmetric capacitor). Optimization of operation of such systems in terms of balancing of active masses, of power and charge densities, and choice of maximum but limited states-of-discharge, is treated.     

Observation of Ion Electrosorption in Metal–Organic Framework Micropores with In Operando Small-Angle Neutron Scattering

A molecular-level understanding of transport and adsorption mechanisms of electrolyte ions in nanoporous electrodes under applied potentials is essential to control the performance of double-layer capacitors. Here, in operando small-angle neutron scattering (SANS) is used to directly detect ion movements into the nanopores of a conductive metal–organic framework (MOF) electrode under operating conditions. Neutron-scattering data reveals that most of the void space within the MOF is accessible to the solvent. Upon the addition of the electrolyte sodium triflate (NaOTf), the ions are adsorbed on the outer surface of the protrusions to form a 30 Å layer instead of entering the ionophobic pores in the absence of an applied charging potential. The changes in scattering intensity when potentials are applied suggests the ion rearrangement in the micropores following different mechanisms depending on the electrode polarization. These observations shed insights on ion electrosorption in electrode materials.     

The influence of crystallographic inhomogeneity of a polycrystalline electrode surface on the behavior of the electric double-layer

The specific features of the electric double-layer structure at polycrystalline electrodes in the absence of specific ion adsorption have been examined for two different models: Model I and Model II. In the case of Model I each of the faces showing on the surface of a polycrystalline electrode retains its own Helmholtz and diffuse double layers. In the case of Model II the faces retain only their own Helmholtz layer, whereas the diffuse layer is common to the entire electrode surface. The difference of zero charge potentials of the faces is defined both by their dissimilar hydrophilic properties and by different work functions. The experimental data available at present on the electric double-layer structure at polycrystalline electrodes for which the potentials of zero charge of the faces differ significantly are described by Model I.     

Electrical double layer in surface-inactive electrolyte solution and adsorption of halide ions from 0.1 M solutions on liquid Cd–Ga and In–Ga alloys in gamma-butyrolactone

The double-layer characteristics of liquid renewable Cd–Ga (0.3 at % Cd) and In–Ga (14.2 at % In) electrodes in the gamma-butyrolactone (GBL) solutions of various electrolytes are studied by measuring the differential capacitance and using the method of open-circuit jet electrode. For the (Cd–Ga)/GBL and (In–Ga)/GBL interfaces, the zero-charge potentials, which are not distorted by the specific adsorption of ions, and the chemisorption potential drops of solvent are determined. It is shown that, in spite of the fact that the work function decreases as we pass from (In–Ga) to (Cd–Ga), the chemisorption potential drops of solvent on both electrodes are close. This behavior is explained by a closer approach of GBL dipoles to the surface of (Cd-Ga) electrode providing more effective overlapping of donor–acceptor levels of metal and solvent. It is shown that, in GBL, the adsorption parameters of halide ions and their surface activity series depend on the metal nature. On the (Cd–Ga) and (In–Ga) electrodes, the reversed surface activity series of halide ions is observed: on the Hg electrode in various solvents, the surface activity increases in the series Cl^– < Br^– < I^–, whereas on the (Cd–Ga) and (In–Ga) electrodes in GBL, it varies in the reverse series I^– < Br^– < Cl^–.     

Differential capacity curves at adsorption of organic ions: Model approach I

Theoretical analysis of the double-layer model has been carried out in the presence of the specific adsorption of organic cations accompanied by considerable increase of the inner-layer dimensions. The formulae for calculation of the differential capacity curves of an electrode have been derived. A flat minimum at high negative charges, caused by the diffuse structure of the double layer, has been predicted on the capacity curves. The presence of such minima has been verified experimentally on the mercury and bismuth electrodes. By computer calculation it has been shown that, although. relatively good agreement of the theoretically calculated capacity curves with the experimental curves could he obtained, a physically unrealistic interaction parameter of the specifically adsorbed ions had to be used. As demonstrated, this result is a result of the double-layer model assuming linear dependence of the inner-layer integral capacity of the surface coverage and its independence from the electrode charge.     

Molecular-sieving capabilities of mesoporous carbon membranes

The size-sieving properties of a mesoporous carbon membrane were studied via molecular permeation and cyclic voltammetry experiments. Two phenomena, simple diffusion and electrochemically aided diffusion, were investigated. Molecular diffusion through the membrane was caused by a concentration gradient across the membrane and was facilitated by electrosorption of ions under an externally applied electric field. The diffusion of molecules transported through the membrane was characterized by the values of permeability and apparent diffusion coefficient in the membrane. Because larger molecules are more restricted in terms of penetrating the pores, the size-based selectivity of the mesoporous carbon membrane could be readily observed. For example, in the two-component permeation experiment, a high selectivity (alpha=56.9) of anilinium over Rhodamine B was found. It is inferred that the diffusive transport of the larger Rhodamine B molecules with a more extensive retardation comes from the competitive mechanism between the two kinds of molecules in accessing the pore. A series of voltammetric experiments involving a mesoporous carbon membrane immersed in various electrolytes with ions of different sizes allowed the observation of ion-exclusion phenomena. It was found that the size effect is significant for electrochemically aided diffusion and electrosorption processes. The number of cations inside the pores of the membrane decreases with increasing cation size. This phenomenon is due to the size-exclusion effect, which could be demonstrated by the values of electrical double-layer capacitance for sodium, magnesium, and tetrahexylammonium cations, at potentials ranging from negative values to the point of zero charge, corresponding to 86.7, 73.1, and 50.0 F/g, respectively. The findings of this work manifest that the relationship between the pore size and the dimensions of the molecules determines the transport and sorption behavior of nanoporous carbon materials.     

Electrical Double-Layer Structure at the Rutile-Water Interface as Observed in Situ with Small-Period X-Ray Standing Waves

X-Ray standing wave (XSW) measurements were made of Rb and Sr adsorbed from aqueous solutions at the rutile (110)-water interface. These experiments were performed to address the extent to which direct measurements of electrical double-layer structure are possible. The experimental results show that the Bragg XSW technique, using small-period standing waves generated by Bragg diffraction from the substrate, can precisely measure ion locations within the condensed layer and the in situ partitioning of ions between the condensed and diffuse layers. Differences in condensed layer ion positions were observed for Sr ions (measured in situ) as compared with Rb ions (in situ) and also for Sr ions (ex situ). An additional constraint on the ex situ Sr site geometry was provided by polarization-dependent surface EXAFS measurements. Such measurements can provide important constraints for the development and verification of electrical double-layer theory especially as applied to ion adsorption at the solid-water interface. Copyright 2000 Academic Press.     

Aerogels—Recent Progress in Production Techniques and Novel Applications

Aerogels are sol-gel derived nanostructured materials with extraordinary properties according to their high porosity. Though first prepared more than 60 years ago, silica aerogels became widely known only in the late 1980s when they were used in Cerenkov detectors and their potential was recognized as high performance thermal insulants. Nowadays, aerogel research has attracted many scientists from different fields, resulting in some 100 publications per year and the fifth aerogel symposium (ISA 5) in Montpellier/France in September 1997. This review will focus on recent developments in fast supercritical and ambient pressure drying processes. The state of the art with respect to structural characterization and measuring the material properties is reported including nondestructive techniques and alterations induced by invasive methods. A brief survey is given on modeling the aerogel structure and simulating properties. Special attention will be given to carbon aerogels and their organic precursors. Due to the high electrical conductivity of their graphitic backbone and the large specific inner surface areas, carbon aerogels can be considered ideal electrodes in supercapacitors and fuel cells.     

Sorption of Amino Acids from Aqueous Solutions by a Polarized Carbon Adsorbent

The adsorption and electrosorption of tyrosine, tryptophan, and phenylalanine on an A-4 model carbon adsorbent from 0.1 N K₂SO₄solutions were investigated at various acidity values of the medium. It was found that the sorption of tyrosine and tryptophan is significantly affected by both the polarization potential of the adsorbent and pH of the solution. For phenylalanine, electrosorption dependences were not measured because of its electrochemical instability under experimental conditions. The electrosorption effect was demonstrated for the low-molecular-weight protein, pepsin.     

Electrosorption of uranium ions on activated carbon fibers

A study on the electrosorption of uranium (U(VI)) ions onto a porous activated carbon fiber was performed to treat lagoon sludge containing 100 mg/L uranium and high concentration of chemical salts composed 3.8% NaNO₃, 19.8% NH₄NO₃, 1.9% Ca(NO₃)₂. The applied negative potential increased the adsorption kinetics and capacity in comparison to the open-circuit potential adsorption for uranium ions. When applying potential at −0.9 V (vs. Ag/AgCl) and pH 4, above 99% of the uranium is selectively removed from the 100 mg/L influent by electrosorption, and the cumulative amount of uranium for 50 h is about 600 mg_uranium/g_ACF. The high selectivity of elctrosorption process for uranium was probably caused by the difference of charge density of cations. More than 99% of adsorbed uranium ions was desorbed at a potential of +1.2 V and pH 3. The electrosorption of uranium onto the porous activated carbon fiber electrode is due to an ion exchange type reaction between the uranium ions and surface acid groups on carbon surface. Cyclic electrosorption test consisting of adsorption and desorption step shows that the activated carbon fiber electrode is easily regenerated in situ, indicating it is a reversible process.     

Double-layer phenomena in electrochemistry: controversial views on some fundamental notions related to electrified interfaces

The problem of the distinction between the so-called free charge and the thermodynamic (total) charge of electrodes was discussed in the light of the relevant IUPAC definitions calling attention to the strict relationships existing between charge and mass balances during the formation of a double layer at electrodes or/and particles. It is demonstrated that the origins of controversial views concerning partial charge transfer and electrosorption valency, notions widely used nowadays in the electrochemical literature, could be ascribed to confusion of the free and thermodynamic charges. Although there are, even if sporadic, evidences and theoretical considerations in the literature proving that electrosorption valency as usually defined is an extrathermodynamic and self-contradictory concept, it is widely used by many authors for the interpretation of electrosorption phenomena. One of the most important aims of the present work was to demonstrate that independent of the thermodynamic considerations, the concept of electrosorption valency cannot be reconciled with elementary laws of electrochemistry. On the basis of analysis of real processes occurring in the interfacial layer of electrodes it was urged to avoid the treatment of some double-layer phenomena in terms of electrosorption valency in order to eliminate far-reaching misinterpretations leading to serious contradictions.     

Relation between the charge efficiency of activated carbon fiber and its desalination performance

Four types of activated carbon fibers (ACFs) with different specific surface areas (SSA) were used as electrode materials for water desalination using capacitive deionization (CDI). The carbon fibers were characterized by scanning electron microscopy and N(2) adsorption at 77 K, and the CDI process was investigated by studying the salt adsorption, charge transfer, and also the charge efficiency of the electric double layers that are formed within the micropores inside the carbon electrodes. It is found that the physical adsorption capacity of NaCl by the ACFs increases with increasing Brunauer-Emmett-Teller (BET) surface area of the fibers. However, the two ACF materials with the highest BET surface area have the lowest electrosorptive capability. Experiments indicate that the charge efficiency of the double layers is a key property of the ACF-based electrodes because the ACF material which has the maximum charge efficiency also shows the highest salt adsorption capacity for CDI.     

Supercapacitive Swing Adsorption of Carbon Dioxide

An electrical effect, the supercapacitive swing adsorption (SSA) effect is reported, which allows for reversible adsorption and desorption of carbon dioxide by capacitive charge and discharge of electrically conducting porous carbon materials. The SSA effect can be observed when an electrically conducting, nanoporous carbon material is brought into contact with carbon dioxide gas and an aqueous electrolyte. Charging the supercapacitor electrodes initiates the spontaneous organization of electrolyte ions into an electric double layer at the surface of each porous electrode. The presence of this double layer leads to reversible, selective uptake and release of the CO₂ as the supercapacitor is charged and discharged.     

Study of adsorption of tetraethylammonium ions on Bi single crystal planes from solutions in ethanol

The adsorption of tetraethylammonium (TEA⁺) ions on the (001) and planes of the bismuth single crystal from solutions in ethanol has been investigated by impedance measurement method. The experimental data were obtained in 0.02 M mixed-electrolyte solutions and the calculations performed with electrode potential as the independent electrical variable. The Gibbs energy of adsorption of TEA⁺ ions has been calculated using the simple virial adsorption isotherm, and it was found that the adsorption of TEA⁺ cations is weaker than the adsorption of halide anions. The electrosorption valency evaluated has a nearly constant value in the potential region studied. It was concluded that the formed effective surface dipole is significantly screened by the solvent molecules and the metal electron gas. The analysis of the impedance spectra was performed by fitting the experimental data to the various equivalent circuits. It was found that the behaviour of TEA⁺ ions at Bi(hkl)∣ethanol interface can be described with the equivalent circuit, corresponding to the classical Frumkin–Melik-Gaikazyan model. The results obtained indicate that only weak interaction between TEA⁺ ions and bismuth surface takes place, and there is no remarkable partial charge transfer from the adsorbed ions to the Bi surface atoms.