Designing new renewable nano-structured electrode and membrane materials for direct alkaline ethanol fuel cell

Success Story: The NanoElMem project reached its final success. The project presents an innovative approach towards the design and fabrication of materials for the creation of direct alkaline ethanol fuel cells (DAEFC). Emphasis was put on the development of platinum (Pt)-free anode catalysts and nano-composite membranes, where environmentally friendly and sustainable polysaccharides and inorganic materials were employed. The vast potential of graphene, from a scientific and applied point of view, was harnessed as an active component in polysaccharide-based nanocomposite membranes.

Schematic view of mixed ionic-electronic conductivity of bio-based polysaccharide-graphene oxide ion-exchange membrane of alkaline ethanol fuel cell.

In order to arrive at an innovative and efficient product by the end of the project’s run, the work-plan has been constructed around the current technical obstacles, that limit full implementation of fuel cells in a commercial scale; by directly addressing these limitations, i.e. cost, performance and durability. Reducing the costs of existing fuel cells was achieved by development of highly active ethanol oxidation reaction (EOR) catalysts and noble metal free oxygen reduction reaction (ORR) catalysts. Catalysts synthesis routes were published in three high-impact journals (in 2021 Journal of Energy Chemistry, in 2019 Advanced Material Interfaces, in 2019 Applied Catalysis B: Environmental)

In terms of performance, DAEFCs struggle mainly with relatively low power density. This major technical problem was tackled by the design of ion-exchange membranes with enhanced efficiency and durability while maintaining low costs. Here, bio-based polysaccharide polymers were used, which served as the matrix for newly synthesized (N)-doped and quaternized graphene oxide (GO) nano-fillers, which improved membrane ion conductivity, thermal and mechanical stability, and prevented ethanol crossover through cross-linked membranes. Membrane preparation and characteristic were presented in ACS sustainable chemistry & engineering.

In course of the project, Abalonyx has developed a new nitrogen doped graphene oxide, of which preparation has been standardized and a protocol for larger scale preparation is being prepared. The product was launched for sale in October 2020 through Abalonyx online offerings and through distributors in UK, Japan and USA. The product was not patented, the preparation method is being kept as trade secret.

Project presented significant scientific impact with 4 published scientific articles in high-impact journals, 21 conference contributions, of which 5 were invited lectures. At the moment of writing, 2 articles are under revision, among them one is review article on the topic of anion exchange membranes and 2 articles in preparation phase.

Announcement of Success story

The project was financed in the frame of M-era.NET program (NanoElMem – Designing new renewable nano-structured electrode and membrane materials for direct alkaline ethanol fuel cell), grant number C3330-17-500098.

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A pyrrolopyridazinedione-based copolymer for fullerene-free organic solar cells

Our group was involved in the charge transport study of non-fullerene acceptors in organic photovoltaics. Recent success in this field also entails a change in the requirements to the polymer donor in terms of optical and morphological properties leading to a demand for novel conjugated polymers. In the published paper it is reported on the synthesis of a 1,4-bis-(thiophene-2-yl)-pyrrolopyridazinedione based copolymer with 2-ethylhexyl substituents on the pyrrolopyridazinedione moiety. A 2D conjugated benzodithiophene (BDT) was chosen as comonomer. The resulting copolymer T-EHPPD-T-EHBDT showed a molecular weight of 10.2 kDa, an optical band gap of 1.79 eV, a hole mobility of 1.8 × 10−4 cm2 V−1 s−1 and a preferred face-on orientation with regard to the substrate. The comparably wide band gap as well as the determined energy levels (HOMO: −5.47 eV, LUMO: −3.68 eV) match well with the narrow band gap non-fullerene acceptor ITIC-F, which was used as the acceptor phase in the bulk heterojunction absorber layers in the investigated solar cells. The solar cells, prepared in inverted architecture, revealed power conversion efficiencies up to 7.4% using a donor:acceptor ratio of 1 : 1 in the absorber layer. The work is published in

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Molecular alignment on graphene surface determines transport properties of graphene/organic semiconductor transistors

Graphene field-effect transistor structures were used to investigate the role of molecular alignment on charge transport properties of heterostructures comprising a single-layer graphene and variable thickness of N,N′-bis(n- octyl)-(1,7&1,6)-dicyanoperylene-3,4:9,10-bisdicarboximide (PDI8-CN2) – an n-type organic semiconductor. Our atomic force microscopy data show that under selected growth conditions PDI8-CN2 grows in a layer-by-layer fashion up to a second monolayer. The first layer comprises flat-lying molecules, whereas the molecules in the second layer orient themselves in an upright orientation. Transconductance measurements show that the flat-lying molecules have little effect on the position of the Fermi level in graphene. Upright oriented molecules in the second layer instead, have a strong effect as to neutralize native p-type doping of graphene and cause a shift of charge-neutrality level towards the Dirac point. We interpret such behavior in terms of different orientation of the surface dipole on layers with different molecular orientations. At the same time the overall mobility of the charge carriers reaches values exceeding 3000 cm2/Vs. Read more.

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Impedimetric, PEDOT:PSS-Based Organic Electrochemical Sensor for Detection of Histamine for Precision Animal Agriculture

Our research on mixed ion-electron conductivity involved us into a collaboration to develop a histamine biosensor. High concentrations of histamine are associated with subacute ruminal acidosis, a common disease in high-producing lactating dairy cows. Therefore, the accurate detection of low histamine levels is a strategy to monitor and diagnose ruminal acidosis in early stages. For that purpose we have developed an impedimetric histamine biosensor based on an organic semiconductor: poly (3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS). The sensor can be utilized to detect low concentrations of histamine in a phosphate-buffered saline (PBS) buffer and McDougall’s buffer solution (MDBS) with an impedimetric readout technique. With PEDOT:PSS film as the sensing medium, the device displayed a limit of detection of 0.1 μM and an impedance of ∼82 􏰓 at low frequencies in MDBS. More details are available in IEEE Sensors Letters.

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Elucidation of Donor:Acceptor Phase Separation in Nonfullerene Organic Solar Cells and Its Implications on Device Perfor- mance and Charge Carrier Mobility

A joint study revealed that in bulk-heterojunction solar cells, the device performance strongly depends on the donor and acceptor properties, the phase separation in the absorber layer, and the formation of a bicontinuous network. While this phase separation is well explored for polymer:fullerene solar cells, only little is known for polymer:nonfullerene acceptor solar cells. The main hurdle in this regard is often the chemical similarity of the conjugated polymer donor and the organic nonfullerene acceptor (NFA), which makes the analysis of the phase separation via atomic force microscopic (AFM) phase images or conventional transmission electron microscopy difficult. In this work, we use the donor polymer PTB7-Th and the small molecule acceptor O-IDTBR as the model system and visualized the phase separation in PTB7-Th:O-IDTBR bulk-heterojunctions with different donor:acceptor ratios via scanning transmission electron microscopy (STEM) high-angle annular dark-field (HAADF) images and electron energy loss spectroscopy (EELS) based elemental mapping, which resulted in a good contrast between the donor and the acceptor despite very low differences in the chemical composition. AFM as well as grazing-incidence wide-angle X-ray scattering (GIWAXS) investigations support the electron microscopic data. Furthermore, we elucidate the implications of the phase separation on the device performance as well as charge carrier mobilities in the bulk-heterojunction layers, and a high performance of the solar cells was found over a relatively broad range of polymer domain sizes. This can be related to the larger domain sizes of the acceptor phase with higher amounts of O-IDTBR in the blend, while the polymer donor phase still forms continuous pathways to the electrode, which keeps the hole mobility at a relatively constant level. More here.

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Novel Chitosan–Mg(OH)2 -Based Nanocomposite Membranes for Direct Alkaline Ethanol Fuel Cells

We have been involved in a project NanoElMem of novel polymer-based nanocomposite anion-exchange membranes (AEMs) with improved features for direct alkaline fuel cell applications. AEMs based on chitosan (CS), magnesium hydroxide (Mg(OH)2), and graphene oxide (GO) with benzyltrimethylammonium chloride (BTMAC) as the hydroxide conductor were fabricated by a solvent casting method. To impart better mechanical properties and suppressed swelling, the enzymatic cross-linking with dodecyl 3,4,5-trihydroxybenzoate having C-10 alkyl chain was employed. The structure and surface morphology, KOH uptake and swelling ratio, ethanol permeability, mechanical property, ionic conductivity, cell performance, and stability of AEMs were investigated. The as-obtained AEMs showed improved hydroxide conductivity compared with previously reported CS AEMs. The highest value for hydroxide conductivity, 142.5 ± 4.0 mS cm–1 at 40 °C, was achieved for the CS + Mg(OH)2+ GO + BTMAC AEMs with an ethanol permeability value of 6.17 × 10–7 ± 1.17 × 10–7 cm2 s–1 in spite of its relative high KOH uptake (1.43 g KOH/g membrane). The highest peak power density value of 72.7 mW cm–2 was obtained at 209 mA cm–2 when the pristine CS + Mg(OH)2 AEM was used as the polymer electrolyte membrane in the direct alkaline ethanol fuel cell at 80 °C. This is the highest reported power density value for CS-based membranes. More here.M

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Enhancement of Charge Transport in Polythiophene Semi- conducting Polymer by Blending with Graphene Nanoparticles

We presented a study on the charge transport in a composite of liquid‐exfoliated graphene nanoparticles (GNPs) and a polythiophene semiconducting polymer. While the former component is highly conducting, although it consists of isolated nanostructures, the latter offers an efficient charge transport path between the individual GNPs within the film, overall yielding enhanced charge transport properties of the resulting bi‐component system. The electrical characteristics of the composite layers were investigated by means of measurements of time‐of‐flight photoconductivity and transconductance in field‐effect transistors. In order to analyze both phenomena separately, charge density and charge mobility contributions to the conductivity were singled out. With the increasing GNP concentration, the charge mobility was found to increase, thereby reducing the time spent by the carriers on the polymer chains. In addition, for GNP loading above 0.2 % (wt.), an increase of free charge density was observed that highlights an additional key role played by doping. Variable‐range hopping model of a mixed two‐ and three‐dimensional transport is explained using temperature dependence of mobility and free charge density. The temperature variation of free charge density was related to the electron transfer from polythiophene to GNP, with an energy barrier of 24 meV. More here.

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Enhanced photoconductivity of semiconductor polymers using graphene nanoflakes

We have examined the effect of the addition of graphene nanoflakes (GNs) to improve the field-effect mobility of poly(3-hexylthiophene) (P3HT)-based field-effect transistors (FETs). We observe that the FET mobility increases up to 0.02 cm2/Vs at GNs concentration of 0.06 mg/mL. The remarkable increase in FET mobility can be ascribed to the incorporation of highly conducting and highly ordered graphene flakes, which acts like conducting bridges between the P3HT molecules. With further increasing the concentration of GNs, the mobility and Ion/Ioff ratio starts to decrease, due to mismatching of the energy levels of graphene and P3HT. The effect is further evidenced from the time-of-flight photocurrent (TOFP) measurements, in which the transit time (ttr) of the charge carriers are shifted to shorter times in blended layers compared to pristine P3HT. Further, we have analyzed time-resolved photocurrent variation on these samples in terms of hopping transport model using Monte-Carlo (MC) simulations within the framework of Gaussian disorder. These studies reveal that the addition of GNs causes improvement in mobility and reduces the extremely slow carriers and uniform arrival of the charge carriers. More here.

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The role of charge transfer at reduced graphene oxide/organic semiconductor interface on the charge transport properties

We have published the results of a study of the effect of 1-pyrenesulfonicacid sodium salt (1-PSA), tetracyanoethylene (TCNE) and tetrafluoro- tetracyanoquinodimethane (F4-TCNQ) on charge transport properties of reduced graphene oxide (RGO) is examined by measuring the transfer characteristics of field-effect transistors and co-planar time-of-flight photocurrent technique. Evidence of p-type doping and a reduction of mobility of electrons in RGO upon deposition of these materials is observed. Time-resolved photocurrent measurements show a reduction in elec- tron mobility even at submonolayer coverage of these materials. The variation of transit time with different coverages reveals that electron mobility decreases with increasing the surface coverage of 1-PSA, TCNE and F4- TCNQ to a certain extent, while at higher coverage the electron mobility is slightly recovered. All three molecules show the same trend in charge carrier mobility variation with coverage, but with different magnitude. Among all three molecules, 1-PSA acts as weak electron acceptor compared to TCNE and F4-TCNQ. The additional fluorine moieties in F4-TCNQ provides excellent electron withdrawing capability compared to TCNE. The experimental results are consistent with the density functional theory calculations. Click here for the full publication.

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Characterisation of charge carrier transport in thin organic semiconductor layers by time-of-flight photocurrent measure- ments

We have prepared a review of recent advances in characterisation of charge carrier transport in organic semiconductor layers by time-of-flight photocurrent measurements, with the emphasis on the measurements of the samples with co-planar electrodes. These samples comprised an organic semiconductor layer whose thickness is on the order of a μm or less, and thus mimic the structures of organic thin film transistors. In the review we emphasise the importance of considering spatial variation of electric field in these, essentially two-dimensional structures, in interpretation of photocurrent transients. We review the experimental details of this type of measurements and give examples that demonstrate exceptional sensitivity of the method to minute concentration of electrically active defects in the organic semiconductors as well as the capability of probing charge transport along the channels of different mobility that reside in the same sample. Click here to see the review.

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