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The conversion of carbon dioxide (CO2) into value-added chemicals and fuels, preferably using renewable energy and earth-abundant materials, is considered a key priority for future energy research. In this work, a bias-free reactor device for the solar-driven conversion of CO2 to synthesis gas (syngas) has been developed. The integrated fluidic device consists of a cathode made of copper foam coated with low-cost nanosized zinc flakes as catalyst to perform the CO2 reduction reaction (CO2RR) to syngas, an adapted silicon heterojunction solar cell structure as photoanode with nickel foam as catalyst to facilitate the oxygen evolution reaction (OER), and a bipolar membrane separating the respective catholyte and anolyte compartments. The membrane allows for the operation of the catholyte and anolyte at different pH values. Stable and tunable hydrogen-to-carbon monoxide (H2:CO) ratios between 5 and 0.5 along with high CO Faradaic efficiencies of up to 85% and CO current densities of 39.4 mA cm−2 have been demonstrated. Under photoelectrolysis conditions, the photovoltage of the photoanode was varied between 0.6 V and 2.4 V by connecting up to four heterojunction solar cells in series, and thus reducing the overall cell voltage solely by solar energy utilization. Bias-free operation of the integrated device has been achieved under ambient conditions with active areas for CO2RR and OER, respectively, of 10 cm2. An operation current density of 5.0 mA cm−2 was measured under 100 mW cm−2 illumination of the complete device, which corresponds to a solar-to-syngas conversion efficiency of 4.3%.
Previous research has shown that the effects of alcohol on drivers’ performance can differ depending on whether blood alcohol concentrations are increasing or decreasing. The present research used a more ecologically representative alcohol consumption protocol in order to determine whether the same pattern of driver impairment would occur when drinking occurred in social groups over a longer period of time. Forty-four participants were assigned to one of two alcohol dose conditions or a placebo control group and consumed alcohol in groups of three (typically one participant from each condition) such that they gradually reached their target BAC (.05 or .08) and maintained it for 1h. The participants completed a series of cognitive tests (Cogstate test battery) and a simulated driving task (driver attention inhibition and reaction test) over the course of their intoxication curve (approximately 4h). The results showed strong placebo effects on ratings of subjective intoxication. Driving and cognitive performance both showed dose-dependent alcohol impairment, and some measures displayed acute protracted error. The findings provide strong evidence of expectancy effects in contributing to self-perceptions of intoxication.
A family of lithium-ion-conducting composite polymer-glass electrolytes containing the glass composition 14Li2O–9Al2O3–38TiO2–39P2O5 (abbreviated as (LiAlTiP) x O y ) with high ionic conductivity, an excellent electrochemical stability range, and high compatibility with lithium insertion anodes is described. An optimized composition has a room temperature conductivity of 1.7×10−4 Scm−1, an Li+ transference number of 0.39, and an electrochemical stability window to +5.1V versus Li/Li+. It also has good interfacial stability under both open-circuit and lithium metal plating–stripping conditions and provides good shelf-life.
Porous poly(vinylidene fluoride-co-trifluoroethylene) (P(VDF-TrFE)) based composite membranes filled with clays (montmorillonite, MMT), zeolites (Y zeolite, NaY), ceramics (barium titanate, BaTiO3) and carbonaceous (multiwalled-carbon nanotubes, MWCNT) fillers were prepared by solvent casting at room temperature. It is shown that, the thermal, mechanical and electrochemical properties of the membranes are not significantly affected by the presence of the fillers. On the other hand, the overall electrochemical behavior of the separator membranes improves with the inclusion of fillers, with respect to the pure polymer, as shown by the increase of the room temperature ionic conductivity for the composite membranes. Furthermore, cathodic half-cells based on composite membranes showed higher capacity retention and rate performance after 50 cycles than pristine polymer membranes. It is thus concluded that filler type deeply affects membrane separator performance in lithium-ion batteries, the P(VDF-TrFE) membrane with MMT filler being the one with the best performance among the evaluated fillers.
A novel magnetic force driven noncontact electromagnetic-triboelectric hybrid nanogenerator for scavenging biomechanical energy to sustainably power portable electrics is presented. Based on the effective conjunction of electromagnetic induction and triboelectrification, the hybrid nanogenerator with a small dimension consists of an electromagnetic generator (EMG) with a peak output power of 3.4mW under a load resistance of 200Ω and a triboelectric nanogenerator (TENG) with a peak output power of 0.23mW under a load resistance of 25 MΩ. For TENG, the electrospun Fe3O4 nanoparticles embedded PVDF fibers membrane is employed as triboelectric layer. A magnet is utilized as the trigger to non-contactly drive contact-separation mode TENG due to the magnetic responsiveness of triboelectric materials, and the EMG can be drived by coupling magnet with copper coils simultaneously. The hybrid nanogenerator exhibits a good stability for the output performance and charging performance, so it can be utilized to charge energy storage devices and sustainably power some portable electronics. This work demonstrates a novel prototype of hybrid nanogenerators toward harvesting human biomechanical energy and its potential applications in building up self-powered systems.
Lithium rich layered cathode materials containing additional lithium in metal layer are of current interest as they exhibit capacities exceeding 250 mAh g−1. Here, we report Li4FeMoO6, a new lithium rich cathode material containing mixed valent cations with a stoichiometry of Li4Fe2+ 0.45Fe3+ 0.55Mo5+ 0.55Mo6+ 0.45O6. XRD data shows that Li4FeMoO6 crystallizes in monoclinic structure (C2/m space group) similar to Li2MnO3 and hence in the layered structure notion the formula can be written as Li[Li0.33Fe0.33Mo0.33]O2. XRD analysis reveals that Li and Fe are disordered over 4h and 2d sites, whereas 2a sites are only filled with Mo atoms. HRTEM and electron diffraction studies indicate presence of structural disorder and planar lattice defects such as stacking faults (SFs) or twinning. During electrochemical cycling in the potential range of 1.5 ̶ 4.6 V, Li4FeMoO6 exhibits initial charge capacity of 313 mAh g−1. It shows 90% reversible capacity for the first cycle and after 100 cycles the capacity retention is about 75.5%. Above 4.6 V, Mo dissolution is observed which brings down the capacity retention to 44% in 100 cycles. Interestingly, Li4FeMoO6 show high rate performance which can be attributed to good conductivity arising from the presence of mixed valent Mo5+/Mo6+ and Fe2+/Fe3+.
In this article we suggest a working definition for the concept of “neuropsychotherapy” encompassing three areas: the identification of mediators and targets of psychotherapeutic effects, the determination of new therapeutic routes using neurotechnology, and the design of psychotherapeutic interventions based on neuroscientific knowledge. We review neuroimaging studies of the psychotherapy of depression and discuss some of the methodological limitations inherent in functional Magnetic Resonance Imaging (fMRI) and common fallacies perpetrated in interpreting fMRI studies. Finally, we discuss some neuroethical issues related to this new and active field of research. In sum, we argue that neuroscience harbors great potential and add-on value for improving psychotherapeutic practice and research if applied properly.
The copolymers poly(3-hydroxybutyric acid-co-3-hydroxyvaleric acid) (PHBV) are being intensely studied as a tissue engineering substrate. It is known that poly 3-hydroxybutyric acids (PHBs) and their copolymers are quite hydrophobic polyesters. Plasma-surface modification is an effective and economical surface treatment technique for many materials and of growing interest in biomedical engineering. In this study we investigate the advantages of oxygen and nitrogen plasma treatment to modify the PHBV surface to enable the acceleration of Vero cell adhesion and proliferation. PHBV was dissolved in methylene chloride at room temperature. The PHBV membranes were modified by oxygen or nitrogen-plasma treatments using a plasma generator. The membranes were sterilized by UV irradiation for 30 min and placed in 96-well plates. Vero cells were seeded onto the membranes and their proliferation onto the matrices was also determined by cytotoxicity and cell adhesion assay. After 2, 24, 48 and 120 h of incubation, growth of fibroblasts on matrices was observed by scanning electron microscopy (SEM). The analyses of the membranes indicated that the plasma treatment decreased the contact angle and increased the surface roughness; it also changed surface morphology, and consequently, enhanced the hydrophilic behavior of PHBV polymers. SEM analysis of Vero cells adhered to PHBV treated by plasma showed that the modified surface had allowed better cell attachment, spreading and growth than the untreated membrane. This combination of surface treatment and polymer chemistry is a valuable guide to prepare an appropriate surface for tissue engineering application.
We report a facile, one-pot hydrothermal strategy to prepare self-assembled three-dimensional mesoporous ZnFe2O4 submicron-sized spheres wrapped in graphene sheets as high-performance anode material for lithium ion batteries. The mesoporous submicron-sized spheres are composed of numerous nanoparticles where the void spaces between the neighboring nanoparticles provide a cushion to alleviate volume variation issues during the conversion/alloying process and also provide large contact areas with the electrolyte to facilitate lithium ion diffusion and electron transport during cycling. The synergistic effects between ZnFe2O4 submicron-sized spheres and graphene sheets are another positive effect to enhance the electrochemical performance. The electrochemical characterization of ZnFe2O4-graphene composites exhibits a high specific capacity of 1182 mAh g−1 cycling at a specific current of 100 mA g−1, and significantly enhanced rate capability and cycling stability after long-term testing resulting from their unique structure features.
A new strategy was developed to synthesize tin-composite materials. The Sn:BPO4 and Sn:CaSiO3 composites were obtained by solid state reaction, but the BPO4 and CaSiO3 matrices were synthesized by solid state reaction and sol–gel method, respectively. These materials are characterized by X-ray diffraction, 119Sn Mössbauer spectroscopy and electrochemical tests. The results show that these new materials are efficient during electrochemical cycling (500mAhg−1), because of a good dispersion of Sn particles into the matrix. From the second cycle, charge and discharge reversibility is linked to both reversible Li X Sn alloy forming and the modification of the tin particle surface showed by Conversion Electron Mössbauer spectroscopy (CEMS) which allows us to characterize the sample surface. The irreversible capacity observed for the first charge/discharge cycle is due to tin oxide reduction and passivation of the anode surface by electrolyte solution decomposition (SEI layer).
We report here the first in situ Raman microspectrometry study of the electrochemical lithium insertion and de-insertion reaction into crystalline sputtered Li x V2O5 thin films (0≤ x ≤0.94) in liquid electrolyte. We show that the orthorhombic Pmmn symmetry of the pristine material is kept upon lithium intercalation in the Li x V2O5 film (0≤ x ≤ 0.94). In fact, a subsequent and unexpected solid solution behaviour is evidenced, leading to the typical Raman fingerprint of the ɛ-LiV2O5 phase for the Li0.94V2O5 composition. After the charge, a complete recovery of the local structure is found, in good accord with the excellent electrochemical reversibility exhibited by these thin films. Such limited structural changes differ from that usually observed for the bulk material, which emphasizes the key role of the microstructure and morphology on the nature and magnitude of the structural rearrangements induced by the lithium insertion process.
Aqueous processing of lithium nickel manganese cobalt oxide (LiNi0.5Mn0.3Co0.2O2, NMC 532) cathodes was investigated by incorporating carbon nanotubes (CNTs) as the conductive additive. Morphology observation showed CNTs evenly disperse across the electrode, uniformly covering each primary particle, and form three-dimensional electronic pathways. A resistance measurement indicated the CNTs can improve the electronic conductivity of the composite electrode by an order of magnitude compared to carbon black. CNTs based electrodes showed higher rate performance, lower hysteresis, and better cycling performance with 99.4% capacity retention after 200 cycles in full pouch cells compared to 94.6% for carbon black based electrode. Meanwhile, the content of active materials in the electrode was increased from 90 wt% to 96 wt% and the energy density was increased by 11.7%. This research demonstrates an effective combined approach for achieving aqueous processed cathodes with enhanced durability while simultaneously achieving higher energy density by reducing the content of inactive components.
Here we report the synthesis of Co/Co9S8 core-shell structures anchored onto S, N co-doped porous graphene sheets (Co/Co9S8@SNGS) from thiophene-2,5-dicarboxylate (Tdc) and 4,4ˊ-bipyridine (Bpy) dual organic ligands assembled Co-based metal-organic frameworks (Co-MOFs) in situ grown on graphene oxide sheets (Co-MOFs@GO) by a room-temperature solution reaction. S-containing Tdc and N-containing Bpy not only trigger the growth of Co-MOFs nanocrystals with a fixed S/N atomic ratio of 1:2.4 on GO sheets in the presence of Co2+ in H2O/NaOH system, but also provide S, N doping sources in the pyrolysis process of Co-MOFs to form Co/Co9S8 core-shell structure and S, N co-doping in graphene. The results demonstrate that the obtained Co/Co9S8@SNGS at 1000°C (Co/Co9S8@SNGS-1000) by pyrolysis of Co-MOFs@GO exhibits superiorly bifunctional catalytic activities of the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in 0.1M KOH electrolyte, affording an overpotential of 290mV for OER at a current density of 10mAcm−2 and 350mV for HER at a current density of 20mAcm−2. The OER activity of Co/Co9S8@SNGS-1000 is slightly better than that of commercial RuO2 catalyst, simultaneously, Co/Co9S8@SNGS-1000 also exhibits good HER activity. As electrode material for full water splitting in 0.1M KOH solution, the Co/Co9S8@SNGS-1000 electrodes exhibit O2 and H2 generation efficiencies of 2.48 and 4.87μmolmin−1 respectively, at an applied potential of 1.58V (vs. RHE) under the given time range, affording nearly 100% Faradaic yield during electrocatalytic water splitting to produce O2 and H2.
In this work, nanostructured composites of Cr2O3-graphene oxide (Cr2O3/GO) with conducting polymers; polyaniline (PANI) and polypyrrole (PPy) with the shape of cauliflower were synthesized via s simple and low cost one-step chronoamperometry method. The structures and morphologies of the resulting ternary nanocomposites were characterized by using Fourier transform infrared spectroscopy, X-ray diffraction, field emission scanning electron microscopy, and energy-dispersive X-ray spectroscopy. The electrochemical capacitive properties of the prepared nanocomposites were evaluated by using cycle voltammetry, galvanostatic charge-discharge, and electrochemical impedance spectroscopy. The as-synthesized Cr2O3/GO/PANI and Cr2O3/GO/PPy composites exhibit a highest specific capacitance of 525 and 495 F g−1 at 5 A g−1 in the three-electrode tests, respectively. Interestingly, Cr2O3/GO/PANI and Cr2O3/GO/PPy composites retain 84 and 80% of their initial capacitance values after 4000 charge-discharge cycles, suggesting good electrochemical stability of the nanocomposite electrodes. The assembled symmetric devices based on Cr2O3/GO/PANI and Cr2O3/GO/PPy composites show a high specific capacitance of 263 and 100 F g−1 at the current density of 5 A g−1, respectively.
Novolac-derived nanoporous carbon beads were used as conductive matrix for lithium-sulfur battery cathodes. We employed a facile self-emulsifying synthesis to obtain sub-micrometer novolac-derived carbon beads with nanopores. After pyrolysis, the carbon beads showed already a specific surface area of 640 m2 g−1 which was increased to 2080 m2 g−1 after physical activation. The non-activated and the activated carbon beads represent nanoporous carbon with a medium and a high surface area, respectively. This allows us to assess the influence of the porosity on the electrochemical performance of lithium-sulfur battery cathodes. The carbon/sulfur hybrids were obtained from two different approaches of sulfur infiltration: melt-infusion of sulfur (annealing) and in situ formation of sulfur from sodium thiosulfate. The best performance (∼880 mAh gsulfur −1 at low charge rate; 5th cycle) and high performance stability (>600 mAh gsulfur −1 after 100 cycles) were found for the activated carbon beads when using melt infusion of sulfur.
Conventional lithium-ion liquid-electrolyte batteries are widely used in portable electronic equipment such as laptop computers, cell phones, and electric vehicles; however, they have several drawbacks, including expensive sealing agents and inherent hazards of fire and leakages. All solid state batteries utilize solid state electrolytes to overcome the safety issues of liquid electrolytes. Drawbacks for all-solid state lithium-ion batteries include high resistance at ambient temperatures and design intricacies. This paper is a comprehensive review of all aspects of solid state batteries: their design, the materials used, and a detailed literature review of various important advances made in research. The paper exhaustively studies lithium based solid state batteries, as they are the most prevalent, but also considers non-lithium based systems. Non-lithium based solid state batteries are attaining widespread commercial applications, as are also lithium based polymeric solid state electrolytes. Tabular representations and schematic diagrams are provided to underscore the unique characteristics of solid state batteries and their capacity to occupy a niche in the alternative energy sector.
The 4,5-dicyano-2-trifluoromethyl-imidazolide (TDI−) anion is a potential lithium salt anion for lithium-ion batteries. In this paper the transport properties of LiTDI solutions in EC/DMC (50/50wt%) are compared to competing salts such as LiTFSI (lithium bis(trifluoromethylsulfonyl) imide), LiFAP (lithium tris(pentafluoroethane)-trifluorophosphate) and the most commonly used LiPF6 (lithium hexafluorophosphate). LiTDI in EC/DMC exhibits the lowest viscosity among the investigated electrolytes, but also the lowest conductivity: 6.84mScm−1 at 25°C (1molL−1). The self-diffusion coefficients (D(7 Li) and D(19 F)) determined by observing 7Li and 19F nuclei with the pulsed-gradient spin-echo (PGSE) NMR technique allowed access, through application of the Stokes-Einstein and Nernst-Einstein equations, to the lithium transference number (t+ ), the effective ionic radius and the ionic dissociation coefficient (αD) of LiTDI in EC/DMC. The ion-pair dissociation and t+ were also determined using conductivity and viscosity measurements and by following the Bruce-Vincent method respectively and were in good agreement with those obtained by PGSE-NMR. LiTDI displays in EC/DMC a cationic transference number t+ =0.58, which is higher than that of LiPF6 in the same solvent mixture, meaning that the mobility of the PF6 − anion is higher than the larger TDI− anion. Still, results from both methods indicate that, LiTDI, as many other lithium salts is only partially dissociated in EC/DMC. Only 31% of the ion pairs are dissociated at 25°C whereas for LiPF6, LiTFSI and LiFAP this number reaches at least 64% in 1molL−1 solutions.
Cochlear implants (CIs) can provide a sound sensation for those with severe sensorineural hearing loss (SNHL), benefitting speech understanding and quality of life. Nevertheless, rates of implantation remain low, and limited research investigates journeys from traditional hearing aids to implantable devices.
The development of aqueous rechargeable lithium battery (ARLB) is greatly restricted by the anode material. Herein, Na2V6O16·0.14H2O nanowires with high cycling stability in the aqueous solution are firstly proposed as a novel anode material for ARLB. The effect of pH value of the electrolyte on electrochemical behavior of Na2V6O16·0.14H2O is optimized. The CV results demonstrate that the studied electrode possesses high reversible lithium insertion/extraction ability and it is more stable in neutral solution. The ARLB consisting of LiMn2O4 as cathode, Na2V6O16·0.14H2O as anode and saturated Li2SO4 as electrolyte indicates good cycling stability. An initial specific discharge capacity of 122.7 mAh g−1 (based on the mass of anode material) can be reached at 60 mA g−1. The capacity retention is up to 80.1% and 77% of the initial discharge capacity at 300 mA g−1 after 100 and 200 cycles, respectively. The good cycling performance of the ARLB is partially due to suppression of the charge-transfer resistance.
Amorphous MnO2 was synthesized using the sol–gel method by reduction of NaMnO4 with solid fumaric acid. The synthesized product was characterized using X-ray diffraction, scanning electron microscopy, thermogravimetric analysis, BET and chemical analysis. Electrochemical characterization was performed using cyclic voltammetry by a three electrode method, and aqueous NaCl, KCl, and Na2SO4 solutions were used as electrolytes. Prepared material remained amorphous until 400°C and transformed to crystalline Mn2O3 at 500°C. The composition of prepared material was determined to be Na0.25MnO2·0.5H2O. A maximum capacitance of 110F/g was obtained at a scan rate of 5mV/s in 2M NaCl solution. MnO2 yielded almost the same capacitance in 2M and 1M NaCl electrolytes. The specific capacitance of MnO2 remained constant up to 800cycles in 1M NaCl electrolyte at 5mV/s scan rate.
Hybrid MoS2/C nanostructures have shown great promise as an ideal anode for lithium-ion batteries (LIBs) owing to the improved conductivity and electrochemical performance. Nevertheless, if only one side of MoS2 particles is covered by conductive carbon layer, other exposed side is still low conductivity. Meanwhile, the structure of electrodes is relatively not robust. Herein, an effective structural engineering strategy has been proposed for achieving a new type of polypyrrole-derived carbon nanotubes@MoS2@carbon (PCN@MoS2@C) sandwiched architecture via a facile one-pot hydrothermal process. When utilized as anodes for lithium storage, the resulting MoS2/C hybrid exhibits a large specific capacity of 1079 mA h g−1 at 0.1 A g−1 and high coulombic efficiency of above 99.0% over 200 cycles, showing a superior cycling stability and reversibility. The density functional theory (DFT) calculations further demonstrate that ultrathin MoS2 nanosheets with an expanded interlayer distance of 0.98 nm have more accessible space, lower transfer resistance, and faster diffusion kinetics of Li ions. The great improvement in electrochemical properties is mainly ascribed to the design of peculiar hybrid architecture, and the collaborative effect between active MoS2 nanosheets and two different conductive carbon layers. This work sheds a new light on the rational design of advanced electrode materials with boosted performance and stable structural stability.