RESUMEN
The general strategy for n-type organic thermoelectric is to blend n-type conjugated polymer hosts with small molecule dopants. In this work, all-polymer n-type thermoelectric is reported by dissolving a novel n-type conjugated polymer and a polymer dopant, poly(ethyleneimine) (PEI), in alcohol solution, followed by spin-coating to give polymer host/polymer dopant blend film. To this end, an alcohol-soluble n-type conjugated polymer is developed by attaching polar and branched oligo (ethylene glycol) (OEG) side chains to a cyano-substituted poly(thiophene-alt-co-thiazole) main chain. The main chain results in the n-type property and the OEG side chain leads to the solubility in hexafluorineisopropanol (HFIP). In the polymer host/polymer dopant blend film, the Coulombic interaction between the dopant counterions and the negatively charged polymer chains is reduced and the ordered stacking of the polymer host is preserved. As a result, the polymer host/polymer dopant blend exhibits the power factor of 36.9 µW m-1 K-1, which is one time higher than that of the control polymer host/small molecule dopant blend. Moreover, the polymer host/polymer dopant blend shows much better thermal stability than the control polymer host/small molecule dopant blend. This research demonstrates the high performance and excellent stability of all-polymer n-type thermoelectric.
RESUMEN
Ruddlesden-Popper-type oxides exhibit remarkable chemical stability in comparison to perovskite oxides. However, they display lower oxygen permeability. We present an approach to overcome this trade-off by leveraging the anisotropic properties of Nd2 NiO4+δ . Its (a,b)-plane, having oxygen diffusion coefficient and surface exchange coefficient several orders of magnitude higher than its c-axis, can be aligned perpendicular to the gradient of oxygen partial pressure by a magnetic field (0.81 T). A stable and high oxygen flux of 1.40â mL min-1 cm-2 was achieved for at least 120â h at 1223â K by a textured asymmetric disk membrane with 1.0â mm thickness under the pure CO2 sweeping. Its excellent operational stability was also verified even at 1023â K in pure CO2 . These findings highlight the significant enhancement in oxygen permeation membrane performance achievable by adjusting the grain orientation. Consequently, Nd2 NiO4+δ emerges as a promising candidate for industrial applications in air separation, syngas production, and CO2 capture under harsh conditions.
RESUMEN
The ability of n-type polymer thermoelectric materials to tolerate high doping loading limits further development of n-type polymer conductivity. Herein, two alcohol-soluble n-type polythiophene derivatives that are n-PT3 and n-PT4 are reported. Due to the ability of two polymers to tolerate doping loading more significantly than 100 mol%, both achieve electrical conductivity >100 S cm-1 . Moreover, the conductivity of both polythiophenes remains almost constant at high doping concentrations with excellent doping tunability, which may be related to their ability to overcome charging-induced backbone torsion and morphology change caused by saturated doping. The characterizations reveal that n-PT4 has a high doping level and carrier concentration (>3.10 × 1020 cm-3 ), and the carrier concentration continues to increase as the doping concentration increases. In addition, doping leads to improved crystal structure of n-PT4, and the crystallinity does not decrease significantly with increasing doping concentration; even the carrier mobility increases with it. The synergistic effect of these two leads to both n-PT3 and n-PT4 achieving a breakthrough of 100 in conductivity and power factor. The DMlmC-doped n-PT4 achieves a power factor of over 150 µW m-1 K-2 . These values are among the highest for n-type organic thermoelectric materials.
RESUMEN
The development of composites combining multiple components each one imparting a specific function to the ensemble is highly sought after for disruptive applications in chemistry and materials science, with a particular importance for the realization of smart structures. Here, we report on the development of an unprecedented multifunctional cementitious composite incorporating reduced graphene oxide (rGO). By design, this material features significantly enhanced electrical properties while retaining the excellent cement's hydration and microstructure. The multiscale investigation on the chemical and physical properties of the dispersion made it possible to establish an efficient preparation protocol for rGO aqueous dispersion as well as rGO-based cementitious composites using a commercial poly(carboxylate ether)-based superplasticizer. The conduction mechanisms within the matrix of rGO containing mortars were unraveled by electrochemical impedance spectroscopy revealing conductive paths originating from bulk cement matrix and rGO nanosheets in composites with rGO loadings as low as 0.075â wt. %. For this rGO loading, we observed the reduction of the resistivity of bulk cement mortar layers from 18.3â MΩ cm to 2.8â MΩ cm. Moreover, the addition of 0.2â wt. % of rGO resulted in the formation of rGO conductive paths with the resistivity of 51.1â kΩ cm. These findings represent a major step forward towards the practical application of graphene-based materials in structural health monitoring of concrete structures.
RESUMEN
The development of n-type organic semiconductors has evolved significantly slower in comparison to that of p-type organic semiconductors mainly due to the lack of electron-deficient building blocks with stability and processability. However, to realize a variety of organic optoelectronic devices, high-performance n-type polymer semiconductors are essential. Herein, conjugated microporous polymers (CMPs) comprising isoindigo acceptor units linked to benzene or pyrene donor units (BI and PI) showing n-type semiconducting behavior are reported. In addition, considering the challenges of deposition of a continuous and homogeneous thin film of CMPs for accurate Hall measurements, a plasma-assisted fabrication technique is developed to yield uniform thin films. The fully conjugated 2D networks in PI- and BI-CMP films display high electron mobility of 6.6 and 3.5 cm2 V-1 s-1 , respectively. The higher carrier concentration in PI results in high conductivity (5.3 mS cm-1 ). Both experimental and computational studies are adequately combined to investigate structure-property relations for this intriguing class of materials in the context of organic electronics.
RESUMEN
The crystalline lithium oxonitridophosphate Li8+x P3 O10-x N1+x , was obtained in an ampoule synthesis from P3 N5 and Li2 O. The compound crystallizes in the triclinic space group P 1 - ${\mathrel{\mathop{{\rm { 1}}}\limits^{{\rm -}}}}$ with a=5.125(2), b=9.888(5), c=10.217(5) Å, α=70.30(2), ß=76.65(2), γ=77.89(2)°. Li8+x P3 O10-x N1+x is a double salt, the structure of which contains distinctive complex anion species, namely non-condensed P(O,N)4 tetrahedra, and P(O,N)7 double tetrahedra connected by one N atom. Additionally, there is mixed occupation of O/N positions, which enables further anionic species by variation of O/N occupancies. To characterize these motifs in detail, complementary analytical methods were applied. The double tetrahedron exhibits significant disorder in single-crystal X-ray diffraction. Furthermore, the title compound is a Li+ ion conductor with a total ionic conductivity of 1.2×10-7 â S cm-1 at 25 °C, and a corresponding total activation energy of 0.47(2) eV.
RESUMEN
Complex geometries for electrodes are a great challenge in electrochemical applications. Slurry electrodes have been one example, which use complex flow distributors to improve the charge transfer between the current collector and the slurry particles. Here we use titanium-based flow distributors produced by indirect 3D-printing to improve further the electron transfer from highly conductive flow distributors to the slurry particles for a vanadium redox flow application. The titanium static mixers are directly coated with graphite to increase the activity for vanadium redox reactions. Increasing layers of graphite have shown an optimum for the positive and negative electrolytes. The application of heat treatment on the electrodes improves the anodic and cathodic current peaks drastically. Testing the highly conductive static mixers in a self-made redox flow cell results in 110â mA cm-2 discharge polarization.
RESUMEN
Typical n-type conjugated polymers are based on fused-ring electron-accepting building blocks. Herein, we report a non-fused-ring strategy to design n-type conjugated polymers, i.e. introducing electron-withdrawing imide or cyano groups to each thiophene unit of a non-fused-ring polythiophene backbone. The resulting polymer, n-PT1, shows low LUMO/HOMO energy levels of -3.91â eV/-6.22â eV, high electron mobility of 0.39â cm2 â V-1 s-1 and high crystallinity in thin film. After n-doping, n-PT1 exhibits excellent thermoelectric performance with an electrical conductivity of 61.2â S cm-1 and a power factor (PF) of 141.7â µW m-1 K-2 . This PF is the highest value reported so far for n-type conjugated polymers and this is the first time for polythiophene derivatives to be used in n-type organic thermoelectrics. The excellent thermoelectric performance of n-PT1 is due to its superior tolerance to doping. This work indicates that polythiophene derivatives without fused rings are low-cost and high-performance n-type conjugated polymers.
RESUMEN
The development of solid-state proton conductors with high proton conductivity at low temperatures is crucial for the implementation of hydrogen-based technologies for portable and automotive applications. Here, we report on the discovery of a new crystalline metal acid triphosphate, ZrH5 (PO4 )3 (ZP3), which exhibits record-high proton conductivity of 0.5-3.1×10-2 â S cm-1 in the range 25-110 °C in anhydrous conditions. This is the highest anhydrous proton conductivity ever reported in a crystalline solid proton conductor in the range 25-110 °C. Superprotonic conductivity in ZP3 is enabled by extended defective frustrated hydrogen bond chains, where the protons are dynamically disordered over two oxygen centers. The high proton conductivity and stability in anhydrous conditions make ZP3 an excellent candidate for innovative applications in fuel cells without the need for complex water management systems, and in other energy technologies requiring fast proton transfer.
RESUMEN
A zwitterion is a neutral compound that has both a cation and an anion in the same molecule. Quaternary ammonium cations are frequently used for zwitterions. Zwitterions with quaternary ammonium cations are also common in biological molecules, such as phospholipids, which are the main components of cell membranes. Chemically, they have broad applicability because they are dielectric, non-volatile, and highly polar compounds with a large dipole moment. In addition, after salt addition, ion exchange does not occur in the presence of zwitterions. Owing to these characteristics, zwitterions have been applied as novel electrolyte materials targeting high ionic conductivity. In this review, application of zwitterions and their polymers for Li-ion batteries is addressed.
RESUMEN
The Li+ ion conductor Li27-x [P4 O7+x N9-x ]O3 (x≈1.9) has been synthesized from P3 N5 , Li3 N and Li2 O in a Ta ampoule at 800 °C under Ar atmosphere. The cubic compound crystallizes in space group I 4 â¾ 3 d ${I\overline 4 3d}$ with a=12.0106(14) Å and Z=4. It contains both non-condensed [PO2 N2 ]5- and [PO3 N]4- tetrahedra as well as O2- ions, surrounded by Li+ ions. Charge neutrality is achieved by partial occupancy of Li positions, which was refined with neutron powder diffraction data. Measurements of the partial ionic and electronic conductivity show a total ionic conductivity of 6.6×10-8 â S cm-1 with an activation energy of 0.46±0.02â eV and a bulk ionic conductivity of 4×10-6 â S cm-1 at 25 °C, which is close to the ionic conductivity of amorphous lithium nitridophosphate. This makes Li27-x [P4 O7+x N9-x ]O3 an interesting candidate for investigation of structural factors affecting ionic conductivity in lithium oxonitridophosphates.
RESUMEN
Non-crystalline lithium oxonitridophosphate (LiPON) is used as solid electrolyte in all-solid-state batteries. Crystalline lithium oxonitridophosphates are important model structures to retrieve analytical information that can be used to understand amorphous phases better. The new crystalline lithium oxonitridophosphate Li5+x P2 O6-x N1+x was synthesized as an off-white powder by ampoule synthesis at 750-800 °C under Ar atmosphere. It crystallizes in the monoclinic space group P21 /c with a=15.13087(11)â Å, b=9.70682(9)â Å, c=8.88681(7)â Å, and ß=106.8653(8)°. Two P(O,N)4 tetrahedra connected by an N atom form the structural motif [P2 O6-x N1+x ](5+x)- . The structure was elucidated from X-ray diffraction data and the model corroborated by NMR and infrared spectroscopy, and elemental analyses. Measurements of ionic conductivity show a total ionic conductivity of 6.8×10-7 S cm-1 at 75 °C with an activation energy of 0.52±0.01â eV.
RESUMEN
Novel coordination polymers embedding electroactive moieties present a high interest in the development of porous conducting materials. While tetrathiafulvalene (TTF) based metal-organic frameworks were reported to yield through-space conducting frameworks, the use of S-enriched scaffolds remains elusive in this field. Herein is reported the employment of bis(vinylenedithio)-tetrathiafulvalene (BVDT-TTF) functionalized with pyridine coordinating moieties in coordination polymers. Its combination with various transition metals yielded four isostructural networks, whose conductivity increased upon chemical oxidation with iodine. The oxidation was confirmed in a single-crystal to single-crystal X-ray diffraction experiment for the Cd(II) coordination polymer. Raman spectroscopy measurements and DFT calculations confirmed the oxidation state of the bulk materials, and band structure calculations assessed the ground state as an electronically localized antiferromagnetic state, while the conduction occurs in a 2D manner. These results are shedding light to comprehend how to improve through-space conductivity thanks to sulfur enriched ligands.
RESUMEN
The ability to enhance both the solvent and thermal stability of semiconducting π-conjugated polymers is highly desired for various device-related applications. Herein, a series of poly(3-hexylthiophene)-stat-poly[3-(6-hydroxy)hexylthiophene] (P3HT-stat-P3HHT) statistical copolymers with thermally cross-linkable hydroxyl groups is synthesized and their crystalline structures in three different states, solvent and thermal stability for use in organic field-effect transistors (OFETs) are elucidated. Importantly, these initial P3HT-stat-P3HHT thin films in their as-cast state crystallize well in an edge-on orientation. During annealing at 150 °C, these P3HT-stat-P3HHT occur cross-linked and retain edge-on orientation with increased crystallinity and ordering. In contrast, after high-temperature annealing at 300 °C, their edge-on orientation is significantly destroyed due to the cross-linking of hydroxyl groups at melted state. The correlation between different P3HT-stat-P3HHT and their charge mobilities is scrutinized. These cross-linked P3HT-stat-P3HHT exhibit good solvent resistance property and improved thermal stability in OFETs. Conceptually, such side-chain functionalization approach to improve the stability of P3HT-stat-P3HHT can be conveniently extended to other conjugated polymers for diverse optoelectronic applications.
RESUMEN
Hydrogen is expected to play an important role in the near future in the transition to a net-zero economy. Therefore, the development of new in situ and real-time analytical tools able to quantify hydrogen at high temperatures is required for future applications. Potentiometric sensors based on perovskite-structured solid-state electrolytes can be a good option for H2 monitoring. Nevertheless, the geometry of the sensor should be designed according to the specific necessities of each technological field. Conventional shaping processes need several iterations of green shaping and machining to achieve a good result. In contrast, 3D printing methods stand out from conventional ones since they simplify the creation of prototypes, reducing the cost and the number of iterations needed for the obtainment of the final design. In the present work, BaCe0.6Zr0.3Y0.1O3-α (BCZY) was used as a proton-conducting electrolyte for potentiometric sensors construction. Two different shapes were tested for the sensors' electrolyte: pellets (BCZY-Pellet) and crucibles (BCZY-Crucible). Ceramics were shaped using extrusion-based 3D printing. Finally, parameters, such as sensitivity, response time, recovery time and the limit of detection and accuracy, were evaluated for both types of sensors (BCZY-Pellet and BCZY-Crucible) at 500 °C.
RESUMEN
In this work, a class of ionic conductor (La1-x Mx )2 (Nb0.45 Yb0.55 )2 O7-δ (M=Ca, Sr, and Ba) with a cubic pyrochlore structure was reported. Two strategies were adopted to increase the concentration of oxygen vacancies favoring the hydration reaction to introduce protons. One was increasing the cation ratio between Yb and Nb over unity, the other was doping divalent alkaline earth elements to replace trivalent La. Proton conduction was evidenced by confirming the proton incorporation and H/D isotope effect in electrical conductivity. Doping Ca, Sr, and Ba further promoted the proton conduction. The results of crystal structure refinement indicated that the extrinsically introduced oxygen vacancies by the two strategies were accommodated in the tetrahedra (48 f) containing two La and two Yb/Nb cations, while the tetrahedra containing four La cations (8a) were fully occupied by oxide ions. A discussion was thereby performed, leading to the suggestion that not all the tetrahedra in the cubic pyrochlore structure of (La1-x Mx )2 (Nb0.45 Yb0.55 )2 O7-δ helped in incorporating and conducting protons, and only the oxygen vacancies surrounded by four Y cations (48 f site) or two La and two Y cations (8b site) were hydratable. It is thereby suggested that to enhance the proton conduction in pyrochlore oxides, an effective strategy might be tuning the ability of hydration or protonation of the tetrahedra to increase the proton concentration and expand the route for proton conduction.
RESUMEN
Side-chain engineering has been proved to show profound impact on polymer properties and blend morphology. Herein, the critical role of siloxane-terminated alkoxy side chains was revealed by a tiny decorating method through which the molar content of siloxane-terminated alkoxy side chain was fixed to 5 %, and its alkyl linker was the only tuning factor. The pentylene, heptylene, and nonylene linkers were designed and used to synthesize wide-bandgap polymers PQSi505, PQSi705, and PQSi905, respectively. Interestingly, the siloxane pendant of combinatory side chain exhibited a distinct impact on molecular packing when its branching position shifted slightly. Among the three polymers, PQSi705 had the strongest aggregation and the highest packing order. Finally, toluene-processed organic solar cells (OSCs) based on PQSi705 and Y6-BO achieved the best power conversion efficiency of 15.77 %. This work suggests that siloxane pendant can serve as a powerful modulator to enhance the photovoltaic performance of OSCs.
RESUMEN
Most transparent conducting materials are based on Sn:In2O3 (ITO). When applied onto flexible substrates, ITO can be prepared in an oxide-metal-oxide (OMO) configuration, typically ITO/Ag/ITO, where the ductility of the embedded metal layer is intended to reduce the mechanical brittleness and improve the electrical conductivity of the OMO multilayer. Hitherto, the lower limit of the thickness of the Ag layer has been limited by the percolation threshold, which limits the Ag layer to be thicker than â¼10 nm to avoid agglomeration and to ensure conductivity and structural stability. Metal layers of thicknesses below 10 nm are, however, desirable for obtaining OMO coatings with better optical properties. It is known that agglomeration of the metal layer can, to some extent, be suppressed when substituting Ag by an Ag-Pd-Cu (APC) alloy. APC-based OMO films exhibit excellent optical and electrical properties, but still continuous APC films well below 10 nm thickness cannot be achieved. In this work we demonstrate that controlled oxidation of APC results in smooth, ultrathin APC:O continuous coatings (of thickness â¼5 nm) on ITO-coated PET substrates. Moderate oxidation yields superficial PdOx formation, which suppresses Ag agglomeration, while still maintaining excellent conductivity. On the other hand, extensive oxidation of APC leads to extensive Pd oxide nucleation deteriorating the conductivity of the film. The ITO/APC:O/ITO films exhibit low resistivity, attributed to a high Hall mobility associated with suppressed agglomeration, good stability in high humidity/temperature environments, superior transmittance in the visible and infrared region, and excellent mechanical bending properties, thus providing new opportunities for fabricating superior transparent conducting coatings on polymer substrates.
RESUMEN
A flexible transparent heater is presented, based on an all-sprayed composite architecture of indium-doped zinc oxide (IZO) layers that sandwich a network of silver nanowires, on a polyimide-foil substrate. This architecture could be materialized through the development of a low-temperature (240 °C) spray-pyrolysis process for the IZO layers, which is compatible with the thermal stability of the transparent polyimide substrate and allows for the formation of compact and transparent layers, without precipitates. The IZO layers entirely embed the silver nanowires, offering protection against environmental degradation and decreasing the junction resistance of the nanowire network. The resulting transparent heaters have a high mean transmittance of 0.76 (including the substrate) and sheet resistance of 7.5 Ω/sq. A steady-state temperature of ~130 °C is achieved at an applied bias of 3.5 V, with fast heater response times, with a time constant of ~4 s The heater is mechanically stable, reaching or surpassing 100 °C (at 3.5 V), under tensile, respectively, compressive-bending stress. This work shows that high-performance transparent heaters can be fabricated using all-sprayed oxide/silver-nanowire composite coatings, that are compatible with large-scale and low-cost production.
RESUMEN
There is evidence that Deep Brain Stimulation (DBS) produces health benefits in patients even before initiating stimulation. Furthermore, DBS electrode insertion in rat infralimbic cortex (ILC) provokes antidepressant-like effects before stimulation, due to local inflammation and astrogliosis. Consequently, a significant effect of implanting electrodes is suspected. External fields, similar in magnitude to the brain's endogenous fields, induce electric dipoles in conducting materials, in turn influencing neural cell growth through wireless effects. To elucidate if such dipoles influence depressive-like behavior, without external stimulation, the comparative effect of conducting and insulated electrodes along with the glial response is studied in unstressed rats. Naïve and implanted rats with electrically insulated or uninsulated steel electrodes were evaluated in the modified forced swimming test and expression of ILC-glial markers was assessed. An antidepressant-like effect was observed with conducting but not with insulated electrodes. Gliosis was detected in both groups, but astroglial reactivity was larger near uninsulated electrodes. Thus, induced dipoles and antidepressant-like effects were only observed with conducting implants. Such correlation suggests that dipoles induced in electrodes by endogenous fields in turn induce neuron stimulation in a feedback loop between electrodes and neural system. Further research of the effects of unwired conducting implants could open new approaches to regulating neuronal function, and possibly treat neurological disorders.