Grzegorz Lota

Carbon nanotubes and their composites in electrochemical applications

This paper presents various applications of carbon nanotubes as components of electrode materials for such electrochemical use as electrochemical capacitors, fuel cells, hydrogen electrosorption and accumulators. Generally, carbon nanotubes give exceptional improvement of electrode performance due to their mesoporous and well conducting networks. The cell resistance is drastically reduced and the transport of ions is greatly enhanced. In addition to their good conductivity, carbon nanotubes can be flexible and stretchable which is crucial for cyclability of electrodes, especially if volumetric changes of electrode material occur during operation. Consequently, they serve as excellent support for conducting polymers (e.g. polyaniline, polypyrrole) and metal oxides (e.g. MnO2) giving attractive capacitor electrodes. The presence of nanotubes in carbon precursor rich in heteroatoms, e.g. nitrogen from melamine or oxygen, also supplies an interesting carbonized composite with a good charge propagation for supercapacitor use. Furthermore, carbon nanotubes have been tested for hydrogen electrosorption giving a very moderate hydrogen capacity (0.27 wt.%). However, modification of nanotubes can enhance hydrogen storage. On the other hand, carbon nanotubes can serve as an excellent additive to many electrode materials for improvement of conductivity and cell performance. They could be a good support of the catalytic particles for fuel cell application as well.

Novel insight into neutral medium as electrolyte for high-voltage supercapacitors

This paper is focused on neutral aqueous medium, i.e.lithium, sodium and potassium sulfate solutions in a wide range of concentrations (0.1–2.5 mol L−1) as promising electrolytes for electrochemical capacitors because they are cheap, non-corrosive and allow applying diverse current collectors. These properties make the capacitor assembling process much easier and cheaper. Additionally, such electrolytes are electrochemically stable and environmentally friendly. Electrochemical investigations carried out especially for 1 mol L−1Li2SO4 aqueous solution confirmed the possibility of efficient capacitor work in a wider voltage range, i.e. even at 2.2 V without any significant capacitance fade during 15 000 cycles. The physicochemical properties of ions (i.e. solvation, diffusion or mobility) and their influence on the capacitor electrochemical behaviour are considered.

Room-temperature phosphonium ionic liquids for supercapacitor application

Ionic liquids (ILs) have been used as electrolytes for supercapacitors. Two phosphonium salts such as trihexyl(tetradecyl)phosphonium bis(trifluoromethylsulfonyl)imide (IL1) and trihexyl(tetradecyl) phosphonium dicyanamide (IL2) have been selected for this target. To decrease the viscosity of ILs, a small amount of acetonitrile (from 5 to 25 wt %) was added. Supercapacitor based on activated carbon (AC) as electrodes and IL1 with 25 wt % of acetonitrile supplied capacitance values of 100F∕g at a high operating voltage of 3.4 V. Such a supercapacitor reached a high energy of ∼40Wh∕kg and a good cyclability.

Electrochemistry Serving People and Nature: High‐Energy Ecocapacitors based on Redox‐Active Electrolytes

Positive Poles: A new type of electrochemical capacitor with two different aqueous solutions, separated by a Nafion membrane is described. High capacitance values as well as excellent energy/power characteristics are reported and discussed. The neutral character of the applied electrolytes makes this capacitor an environmentally friendly, easy to assemble, and cost-effective device for energy storage.

Supercapacitors Based on Nickel Oxide/Carbon Materials Composites

In the thesis, the properties of nickel oxide/active carbon composites as the electrode materials for supercapacitors are discussed. Composites with a different proportion of nickel oxide/carbon materials were prepared. A nickel oxide/carbon composite was prepared by chemically precipitating nickel hydroxide on an active carbon and heating the hydroxide at 300 ∘C in the air. Phase compositions of the products were characterized using X-ray diffractometry (XRD). The morphology of the composites was observed by SEM. The electrochemical performances of composite electrodes used in electrochemical capacitors were studied in addition to the properties of electrode consisting of separate active carbon and nickel oxide only. The electrochemical measurements were carried out using cyclic voltammetry, galvanostatic charge/discharge, and impedance spectroscopy. The composites were tested in 6 M KOH aqueous electrolyte using two- and three-electrode Swagelok systems. The results showed that adding only a few percent of nickel oxide to active carbon provided the highest value of capacity. It is the confirmation of the fact that such an amount of nickel oxide is optimal to take advantage of both components of the composite, which additionally can be a good solution as a negative electrode in asymmetric configuration of electrode materials in an electrochemical capacitor.

Synthesis of nanostructured chitin–hematite composites under extreme biomimetic conditions

Chitin of poriferan origin is a unique and thermostable biological material. It also represents an example of a renewable materials source due to the high regeneration ability of Aplysina sponges under marine ranching conditions. Chitinous scaffolds isolated from the skeleton of the marine sponge Aplysina aerophoba were used as a template for the in vitro formation of Fe2O3 under conditions (pH ∼ 1.5, 90 °C) which are extreme for biological materials. Novel chitin–Fe2O3 three dimensional composites, which have been prepared for the first time using hydrothermal synthesis, were thoroughly characterized using numerous analytical methods including Raman spectroscopy, XPS, XRD, electron diffraction and HR-TEM. We demonstrate the growth of uniform Fe2O3 nanocrystals into the nanostructured chitin substrate and propose a possible mechanism of chitin–hematite interactions. Moreover, we show that composites made of sponge chitin–Fe2O3 hybrid materials with active carbon can be successfully used as electrode materials for electrochemical capacitors.

Novel nanostructured hematite–spongin composite developed using an extreme biomimetic approach

The marine sponge Hippospongia communis (Demospongiae: Porifera) is a representative of bath sponges, which possess characteristic mineral-free fibrous skeletons made of a structural protein – spongin. This fibrous skeleton is mechanically robust, resistant to acidic treatment, and thermally stable up to 160 °C. Due to these properties, we decided to use this biological material for the first time for the hydrothermal synthesis of hematite (α-Fe2O3) via catalyzed hydrolysis of FeCl3 to obtain a hematite–spongin composite. The material obtained was studied with Scanning Electron Microscopy (SEM), High-Resolution Transmission Electron Microscopy (HR-TEM), X-ray Photoemission Spectroscopy (XPS) and Raman spectroscopy. The α-Fe2O3–spongin-based composite was tested for its potential application as an anode material in a capacitor. The results indicate that components constructed using this novel composite material have a positive effect on the capacitance of energy storing devices.

Correlation of hydrogen capacity in carbon material with the parameters of electrosorption

AbstractElectrochemical storage of hydrogen in activated carbon material has been investigated using different parameters of cathodic polarization. It has been proven that application of short galvanostatic pulses could be efficient for hydrogen storage in microporous carbon material. Charging current loads from 50 mA g−1 to 32 A g−1 have been used showing correlation between hydrogen capacity, time of charging and electrical efficiency. The anodic charge equivalent to electrooxidation of 1.0 wt% of hydrogen can be already reached after 90 s of cathodic polarization. Temperature effect has been also evaluated and a gradual increase of hydrogen capacity with a better pronounced oxidation plateau was obtained at higher temperatures. Reversible electrosorption of hydrogen is a useful reaction in supercapacitor performance and it might have a potential application for a negative electrode of supercapacitor as well as reversibly operating electrode in the secondary cell.

Removal of herbicidal ionic liquids by electrochemical advanced oxidation processes combined with biological treatment

ABSTRACT Recently a new group of ionic liquids (ILs) with herbicidal properties has been proposed for use in agriculture. Owing to the design of specific physicochemical properties, this group, referred to as herbicidal ionic liquids (HILs), allows for reducing herbicide field doses. Several ILs comprising phenoxy herbicides as anions and quaternary ammonium cations have been synthesized and tested under greenhouse and field conditions. However, since they are to be introduced into the environment, appropriate treatment technologies should be developed in order to ensure their proper removal and avoid possible contamination. In this study, didecyldimethylammonium (4-chloro-2-methylphenoxy) acetate was selected as a model HIL to evaluate the efficiency of a hybrid treatment method. Electrochemical oxidation or electro-Fenton was considered as a pretreatment step, whereas biodegradation was selected as the secondary treatment method. Both processes were carried out in current mode, at 10 mA with carbon felt as working electrode. The efficiency of degradation, oxidation and mineralization was evaluated after 6 h. Both processes decreased the total organic carbon and chemical oxygen demand (COD) values and increased the biochemical oxygen demand (BOD5) on the COD ratio to a value close to 0.4, showing that the electrolyzed solutions can be considered as ‘readily biodegradable.’

Extreme biomimetics: A carbonized 3D spongin scaffold as a novel support for nanostructured manganese oxide(IV) and its electrochemical applications

Composites containing biological materials with nanostructured architecture have become of great interest in modern materials science, yielding both interesting chemical properties and inspiration for biomimetic research. Herein, we describe the preparation of a novel 3D nanostructured MnO2-based composite developed using a carbonized proteinaceous spongin template by an extreme biomimetics approach. The thermal stability of the spongin-based scaffold facilitated the formation of both carbonized material (at 650 °C with exclusion of oxygen) and manganese oxide with a defined nanoscale structure under 150 °C. Remarkably, the unique network of spongin fibers was maintained after pyrolysis and hydrothermal processing, yielding a novel porous support. The MnO2-spongin composite shows a bimodal pore distribution, with macropores originating from the spongin network and mesopores from the nanostructured oxidic coating. Interestingly, the composites also showed improved electrochemical properties compared to those of MnO2. Voltammetry cycling demonstrated the good stability of the material over more than 3,000 charging/discharging cycles. Additionally, electrochemical impedance spectroscopy revealed lower charge transfer resistance in the prepared materials. We demonstrate the potential of extreme biomimetics for developing a new generation of nanostructured materials with 3D centimeter-scale architecture for the storage and conversion of energy generated from renewable natural sources.