Relevance of porosity and surface chemistry of superactivated carbons in capacitors

We show, through some examples, that chemical activation by alkaline hydroxides permits the preparation of activated carbons with tailored pore volume, pore size distribution, pore structure and surface chemistry, which are useful for their application as electrodes in supercapacitors. Examples are presented discussing the importance of each of these properties on the double layer capacitance, on the kinetics of the electric double-layer charge-discharge process and on the pseudo-capacitative contribution from the surface functional groups or the addition of a conducting polymer.

Asymmetric hybrid capacitors based on activated carbon and activated carbon fibre–PANI electrodes

Composites consisting of polyaniline (PANI) coatings inside the microporosity of an activated carbon fibre (ACF) were prepared by electrochemical and chemical methods. Electrochemical characterization of both composites points out that the electrodes with polyaniline show a higher capacitance than the pristine porous carbon electrode. These materials have been used to develop an asymmetric capacitor based on activated carbon (AC) as negative electrode and an ACF–PANI composite as positive electrode in H2SO4 solution as electrolyte. The presence of a thin layer of polyaniline inside the porosity of the activated carbon fibres avoids the oxidation of the carbon material and the oxygen evolution reaction is produced at more positive potentials. This capacitor was tested in a maximum cell voltage of 1.6 V and exhibited high energy densities, calculated for the unpackaged active materials, with values of 20 W h kg−1 and power densities of 2.1 kW kg−1 with excellent cycle lifetime (90% during the first 1000 cycles) and high coulombic efficiency.

Design of hybrid asymmetric capacitors in aqueous electrolyte using ZTC and ultraporous activated carbons

The use of two different materials as electrodes allows the construction of asymmetric and hybrid capacitors cells with enhanced energy and power density. This approach is especially well-suited for overcoming the limitations of pseudocapacitive materials that provide a huge capacitance boost, but in a limited potential window. In this work, we introduce the concepts and protocols that are required for a successful design of such systems, which is illustrated by the construction of an asymmetric hybrid cell where a zeolite-templated carbon and an ultraporous activated carbon have been combined.

Design of Activated Carbon/Activated Carbon Asymmetric Capacitors

Supercapacitors are energy storage devices that offer a high power density and a low energy density in comparison with batteries. Their limited energy density can be overcome by using asymmetric configuration in mass electrodes, where each electrode works within their maximum available potential window, rendering the maximum voltage output of the system. Such asymmetric capacitors are optimized using the capacitance and the potential stability limits of the electrodes, with the reliability of the design largely depending on the accuracy and the approach taken for the electrochemical characterization. Therefore, the performance could be lower than expected and even the system could break down, if a well thought out procedure is not followed. In this work, a procedure for the development of asymmetric supercapacitors based on activated carbons is detailed. Three activated carbon materials with different textural properties and surface chemistry have been systematically characterized in neutral aqueous electrolyte. The asymmetric configuration of the masses of both electrodes in the supercapacitor has allowed to cover a higher potential window, resulting in an increase of the energy density of the three devices studied when compared with the symmetric systems, and an improved cycle life.

Improvement of carbon materials performance by nitrogen functional groups in electrochemical capacitors in organic electrolyte at severe conditions

N-doped activated carbon fibers have been synthesized by using chemically polymerized aniline as source of nitrogen. Commercial activated carbon fibers (A20) were chemically modified with a thin film of polyaniline (PANI) inside the microporosity of the carbon fibers. The modified activated carbon fibers were carbonized at 600 and 800 °C, respectively. In this way, activated carbon fibers modified with surface nitrogen species were prepared in order to analyze their influence in the performance of electrochemical capacitors in organic electrolyte. Symmetric capacitors were made of activated carbon fibers and N-doped activated carbon fibers and tested in a two-electrode cell configuration, using triethylmethylammonium tetrafluoroborate/propylene carbonate (TEMA-BF4/PC) as electrolyte. The effect of nitrogen species in the degradation or stabilization of the capacitor has been analyzed through floating durability tests using a high voltage charging (3.2 V). The results show higher stabilizing effect in carbonized samples (N-ACF) than in non-carbonized samples and pristine activated carbon fibers, which is attributed to the presence of aromatic nitrogen group, especially positively charged N-functional groups.

Electrooxidation methods to produce pseudocapacitance-containing porous carbons

Surface oxygen groups play a key role on the performance of porous carbon electrodes for electrochemical capacitors in aqueous media. The electrooxidation method in NaCl electrolyte using a filter press cell and dimensionally stable anodes is proposed as a viable process for the generation of oxygen groups on porous carbon materials. The experimental set-up is so flexible that allows the easy modification of carbon materials with different configurations, i.e. cloths and granular, obtaining different degrees of oxidation for both conformations without the requirement of binders and conductivity promoters. After the electrooxidation method, the attained porosity is maintained between 90 and 75% of the initial values. The surface oxygen groups generated can increase the capacitance up to a 30% when compared to the pristine material. However, a severe oxidation is detrimental since it may decrease the conductivity and increase the resistance for ion mobility.

Carbon–carbon asymmetric aqueous capacitor by pseudocapacitive positive and stable negative electrodes

An asymmetric aqueous capacitor was constructed by employing zeolite-templated carbon (ZTC) as a pseudocapacitive positive electrode and KOH-activated carbon as a stable negative electrode. The asymmetric capacitor can be operated with the working voltage of 1.4 V, and exhibits an energy density that is comparable to those of conventional capacitors utilizing organic electrolytes, thanks to the large pseudocapacitance of ZTC. Despite relatively thick electrode (0.2 mm) configuration, the asymmetric capacitor could be well operated under a current density of 500 mA g −1.

Electrochemical Performance of Hierarchical Porous Carbon Materials Obtained from the Infiltration of Lignin into Zeolite Templates

Hierarchical porous carbon materials prepared by the direct carbonization of lignin/zeolite mixtures and the subsequent basic etching of the inorganic template have been electrochemically characterized in acidic media. These lignin-based templated carbons have interesting surface chemistry features, such as a variety of surface oxygen groups and also pyridone and pyridinic groups, which results in a high capacitance enhancement compared to petroleum-pitch-based carbons obtained by the same procedure. Furthermore, they are easily electro-oxidized in a sulfuric acid electrolyte under positive polarization to produce a large amount of surface oxygen groups that boosts the pseudocapacitance. The lignin-based templated carbons showed a specific capacitance as high as 250 F g−1 at 50 mA g−1, with a capacitance retention of 50 % and volumetric capacitance of 75 F cm−3 at current densities higher than 20 A g−1 thanks to their suitable porous texture. These results indicate the potential use of inexpensive biomass byproducts, such as lignin, as carbon precursors in the production of hierarchical carbon materials for electrodes in electrochemical capacitors.

Electrochemical behaviour of activated carbons obtained via hydrothermal carbonization

Activated carbons were prepared by chemical activation of hydrochars, obtained by hydrothermal carbonisation (HTC) using low cost and abundant precursors such as rye straw and cellulose, with KOH. Hydrochars derived from rye straw were chemically activated using different KOH/precursor ratios, in order to assess the effect of this parameter on their electrochemical behaviour. In the case of cellulose, the influence of the hydrothermal carbonisation temperature was studied by fixing the activating agent/cellulose ratio. Furthermore, N-doped activated carbons were synthesised by KOH activation of hydrochars prepared by HTC from a mixture of glucose with melamine or glucosamine. In this way, N-doped activated carbons were prepared in order to evaluate the influence of nitrogen groups on their electrochemical behaviour in acidic medium. The results showed that parameters such as chemical activation or carbonisation temperature clearly affect the capacitance, since these parameters play a key role in the textural properties of activated carbons. Finally, symmetric capacitors based on activated carbon and N-doped activated carbon were tested at 1.3 V in a two-electrode cell configuration and the results revealed that N-groups improved the capacitance at high current density.

Pseudocapacitance of zeolite-templated carbon in organic electrolytes

Carbon and graphene-based materials often show some amount of pseudocapacitance due to their oxygen-functional groups. However, such pseudocapacitance is generally negligible in organic electrolytes and has not attracted much attention. In this work, we report a large pseudocapacitance of zeolite-templated carbon (ZTC) based on the oxygen-functional groups in 1 M tetraethylammonium tetrafluoroborate dissolved in propylene carbonate (Et4NBF4/PC). Due to its significant amount of active edge sites, a large amount of redox-active oxygen functional groups are introduced into ZTC, and ZTC shows a high specific capacitance (330 F g−1). Experimental results suggest that the pseudocapacitance could be based on the formation of anion and cation radicals of quinones and ethers, respectively. Moreover, ZTC shows pseudocapacitance also in 1 M lithium hexafluorophosphate dissolved with a mixture of ethylene carbonate and diethyl carbonate (LiPF6/EC+DEC) which is used for lithium-ion batteries and lithium-ion capacitors.