This study focusses on the assessment of the electrical conductivity (EC) of biobased electrode materials for the application in energy storage devices and presents a simple and reproducible method to measure the EC of carbonaceous powders under moderate pressure (10–50 N). Based on the pyrolysis of corncob at three different temperatures (600, 800, and 900°C) and further treatments of the biochar obtained at 600°C, 11 different carbonaceous powder materials were produced including biochars, activated carbons, and composites. Composite materials were obtained by adding either metal oxide (RuO2 or Fe3O4) in different proportions or additives which are commonly used in electrode production (5 wt% binder and 15 wt% conductive additive). Furthermore, one physically activated commercial AC based on peat with a known EC of 33 S/m was treated with additives and used as a reference. For all materials, an increase of applied pressure resulted in higher EC values due to closer particle contact. The comparison of two methods (with and without preload) showed that a prepelletization of the samples is not necessary to obtain reliable results. By analyzing the obtained EC values while taking mechanical and physicochemical properties into account, it could be shown that a high carbonization temperature and high specific surface area favor the increase of EC. Furthermore, certain proportions of metal oxides lead to an improvement of EC (40 wt% RuO2, 10 wt% Fe3O4), while the treatment with additives leads to a decrease of EC. The EC values among all samples varied between 0.8 S/m (biochar) and 408 S/m (AC/RuO2 composite) at the highest pressure level (637 kPa). Thus, promising biobased electrode materials for environmentally friendly energy storage technologies are presented with the aim of contributing to the establishment of a biobased resource and product platform for bioeconomy.
This study investigates the production of bio-based carbon materials for energy storage and conversion devices based on two different vineyard residues (pruning, pomace) and cellulose as a model biomass. Three different char categories were produced via pyrolysis at 900 °C for 2 h (biochars, BC), hydrothermal carbonization (HTC) (at 220, 240 or 260 °C) with different reaction times (60, 120 or 300 min) (hydrochars, HC), or HTC plus pyrolysis (pyrolyzed hydrochars, PHC). Physicochemical, structural, and electrical properties of the chars were assessed by elemental and proximate analysis, gas adsorption surface analysis with N2 and CO2, compression ratio, bulk density, and electrical conductivity (EC) measurements. Thermogravimetric analysis allowed conclusions to be made about the thermochemical conversion processes. Taking into consideration the required material properties for the application in electrochemical double-layer capacitors (EDLC) or in a direct carbon fuel cell (DCFC), the suitability of the obtained materials for each application is discussed. Promising materials with surface areas up to 711 m2 g−1 and presence of microporosity have been produced. It is shown that HTC plus pyrolysis from cellulose and pruning leads to better properties regarding aromatic carbon structures, carbon content (>90 wt.%), EC (up to 179 S m−1), and porosity compared to one-step treatments, resulting in suitable materials for an EDLC application. The one-step pyrolysis process and the resulting chars with lower carbon contents and low EC values between 51 and 56 S m−1 are preferred for DCFC applications. To conclude, biomass potentials can be exploited by producing tailored biomass-derived carbon materials via different carbonization processes for a wide range of applications in the field of energy storage and conversion.
The thermal treatment of an activated carbon/chars with a nitrogen precursor is not a sustainable nor an efficient method for the incorporation of N into the carbon structure. This study proposes the use of hydrothermal carbonization (HTC) as an environmentally friendly method for the incorporation of N into the bulk of carbon materials. The authors propose the following sequence for the synthesis of Nenriched carbon materials (NCM) for energy storage applications: HTC of the N precursor and biomass ! activation of N-hydrochar (N-HC). To investigate the proposed method, HTCs of spent coffee grounds (SCG) with N precursors (urea and alanine) were conducted at 220 C for 5 hours. The resulted N-HCs were subjected to a mild thermal activation via pyrolysis at 600 C for 2 hours. The results showed that HTC enhances the incorporation of N into the carbon matrix via many reactions, for example, the Maillard reaction (MR) or the Mannich reaction, which may accompany the formation of HC via the solved-intermediate pathway or the solid-to-solid pathway, respectively. However, adjusting some parameters before HTC, for example, the concentration of the N precursor and the pH value of the slurry is important to avoid a significant reduction in the N-HC yield. The proposed method led to the synthesis of NCM with a N content of 10.3wt% The X-ray photoelectron spectroscopy (XPS) confirmed the incorporation of N into the bulk of NCM and showed a significant increase in the content of heterocyclic N compounds (pyridinic N, pyrrolic N, and graphitic N) in the NCM. The incorporation of N via the proposed method significantly improved the electrochemical properties of NCM as the values of the specific capacitance and the electrical conductivity in the NCM increased by five times and four times, respectively.
This study investigates the production of biobased carbon materials from potato waste and its application in energy storage systems such as supercapacitors. Three different categories of carbons were produced: hydrochar (HC) from hydrothermal carbonization (HTC) at three different temperatures (200 °C, 220 °C, 240 °C) and two different duration times (two hours and five hours), pyrolyzed hydrochar (PHC) obtained via pyrolysis of the HTC chars at 600 °C and 900 °C for two hours and pyrochar from the pyrolysis of biomass at 600 °C and 900 °C for two hours. The carbon samples were analysed regarding their physico-chemical properties such as elemental composition, specific surface area, bulk density and surface functionalities as well as their electrochemical characteristics such as electric conductivity and specific capacity via cyclic voltammetry. N- and O-enriched carbon materials with promising specific surface areas of up to 330 m2 g−1 containing high shares of microporosity were produced. Electric conductivities of up to 203 S m−1 and specific capacities of up to 134 F g−1 were obtained. The presence of high contents of oxygen (4.9–13.5 wt.%) and nitrogen (3.4–4.0 wt.%) of PHCs is assumed to lead to considerable pseudocapacitive effects and favor the high specific capacities measured. These results lead to the conclusion that the potential of agricultural biomass can be exploited by using hydrothermal and thermochemical conversion technologies to create N- and O-rich carbon materials with tailored properties for the application in supercapacitors.
Bio-based activated carbons with very high specific surface area of >3.000 m² g−1 (based on CO2 adsorption isotherms) and a high proportion of micropores (87% of total SSA) are produced by corncobs via pyrolysis and chemical activation with KOH. The activated carbon is further doped with different proportions of the highly pseudocapacitive transition metal oxide RuO2 to obtain enhanced electrochemical properties and tune the materials for the application in electrochemical double-layer capacitors (EDLC) (supercapacitors). The activated carbon and composites are extensively studied regarding their physico-chemical and electrochemical properties. The results show that the composite containing 40 wt.% RuO2 has an electric conductivity of 408 S m−1 and a specific capacitance of 360 Fg−1. SEM-EDX, XPS, and XRD analysis confirm the homogenous distribution of partly crystalline RuO2 particles on the carbon surface, which leads to a biobased composite material with enhanced electrochemical properties.
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