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Living organisms generate electrical fields. The conduction of electrochemical excitation is a fundamental property of living organisms. Cells, tissues, and organs transmit electrochemical signals over short and long distances. Excitation waves in higher plants are possible mechanisms for intercellular and intracellular communication in the presence of environmental changes. Ionic channels, as natural nanodevices, control the plasma membrane potential and the movement of ions across membranes; thereby, regulating various biological functions. Some voltage-gated ion channels work as plasma membrane nanopotentiostats. Tetraethylammonium chloride and ZnCl2 block K+ and Ca2+ ionic channels. These blockers inhibit the propagation of action potentials induced by blue light, and inhibit phototropism in soybean plants. The irradiation of soybean plants at 450±50nm induces action potentials with duration times of about 0.3ms and amplitudes around 60mV. The role of the electrified nanointerface of the plasma membrane in signal transduction is discussed.
Magnesium-substituted lithium manganese orthosilicate (Li2MnSiO4) cathode materials with a nominal composition of Li2Mg x Mn1−x SiO4, for x =0.4 and 0.5 are synthesized by a solid-state route, at 700°C in argon. The samples are characterized using powder X-ray and neutron diffraction, scanning electron microscopy, and galvanostatic cell-cycling. Rietveld analyses of the powder X-ray and neutron diffraction data show the formation of a monoclinic P21/n structure related to gamma lithium phosphate with no significant impurity peaks. This structure of the Mg-substituted samples is in contrast to the unsubstituted Li2MnSiO4 compound that has a Pmn21 structure when synthesized under the same conditions. Unit-cell volumes of the Mg-substituted materials are intermediate between those of the P21/n structure of Li2MnSiO4 and the isostructural low-temperature form of Li2MgSiO4, indicating the formation of a solid solution. The Mg-substituted materials feature mixed Mg/Mn cation sites, although no evidence of Li/Mn, Li/Mg or Li/Mg/Mn mixed sites are found. The Li2Mg x Mn1−x SiO4 cathodes show improved electrochemical performance over that reported for the unsubstituted Li2MnSiO4 P21/n phase. The Li2Mg x Mn1−x SiO4 cathode performance remains limited by its poor electronic properties and the large particle size of the solid-state synthesized products. Optimization of the synthesis conditions is likely to lead to enhanced electrochemical performance.
Iron vanadate, FeVO4 nanoparticles are synthesized by simple co-precipitation method and explored as the pseudocapacitor negative electrode for the first time. The structural analysis shows the highly crystalline nature and phase purity of the material. The morphological features of FeVO4 particles are polyhedral in shape and are in the range of 100–200nm. The well defined lattice fringes corroborate the highly crystalline nature of FeVO4. The FeVO4 electrode exhibits a pronounced supercapacitive performance in 1M KOH electrolyte than 1M NaOH and 1M LiOH electrolytes due to its smaller hydration sphere radii, increased mobility and ionic conductivity. The obtained higher specific capacitance of 972Fg−1 at 2mVs−1 and 922Fg−1 at 2mAcm−2, inferred that it could be utilized as a suitable negative electrode. On the other hand, LiCoPO4 is tested as the positive electrode (0 to 0.5V) for the first time and delivers a specific capacitance of 320Fg−1 at 5mVs−1. Finally, an asymmetric supercapacitor is fabricated using FeVO4 as negative and LiCoPO4 as positive electrodes. The device exhibits an excellent energy density of 21Whkg−1 with a power density of 1326Wkg−1 in the potential range between 0 to 1.6V.
The electrochemical behaviour of a superporous activated carbon (named as ANK3) with a tailored porosity (high apparent specific surface area and a high volume of micropores with an average pore size of around 1.4 nm) is analysed in different non-aqueous electrolytes. ANK3 shows very high capacitance (higher than 160 F g−1) values in solvent-free electrolytes at different temperatures (20, 40 and 60 °C) as well as in 1 M Et4N BF4/PC, 1 M PYR14 BF4/PC and 1 M PYR14 TFSI/PC. The tailored porosity of the ANK3, makes possible to obtain very high capacitance values, making this superporous activated carbon a promising candidate to be used as electrode for electrochemical capacitors using both organic and ionic liquid electrolytes. It is also confirmed that several parameters, such as the ion/pore size ratio, the ion shape, the ion solvation and the conductivity and viscosity of the electrolyte have a strong influence on the electrochemical behaviour of the ANK3.
Energy harvesting from the environment by portable and flexible power sources can power a variety of devices sustainably. Chen et al. report a hybrid power textile with solar cells and triboelectric nanogenerators that can simultaneously harvest solar and mechanical energy.
The targeted optimization of Li-ion batteries (LIBs) requires a fundamental understanding of the wide variety of interdependencies between electrode design and electrochemical performance. In the present study, the effects of thickness and porosity on the electrochemical performance and Li-ion insertion kinetics of LiNi0.6Co0.2Mn0.2O2-based (NCM-622) cathodes are investigated. Cathodes of different thickness and porosity are prepared and analyzed regarding their rate capability. The polarization behavior is investigated using electrochemical impedance spectroscopy. A simple mathematical model is employed to estimate the impact of Li-ion diffusion limitations in the electrolyte. The results are considered at both, the materials and the full-cell level. The design parameters are found to have distinct impact on the electrolyte, contact and charge transfer resistance as well as the Li-ion diffusion limitations in the electrolyte, significantly influencing the rate capability. The results attest an inherent tradeoff between energy and power density. The insights of this study can be used straightforward for the optimization of gravimetric and volumetric energy density of LIBs depending on the desired application.
Carbon-coated Li3V2(PO4)3 was firstly prepared at 850 °C via two-step reaction method combined sol–gel and conventional solid-state synthesis by using VPO4/carbon as an intermediate. Two different carbon sources, citric acid and glucose as carbon additives in sequence, ultimately deduced double carbon-coated Li3V2(PO4)3 as a high-rate cathode material. The Li3V2(PO4)3/carbon with 4.39% residual carbon has a splendid electronic conductivity of 4.76×10−2 S cm−1. Even in the voltage window of 2.5–4.8 V, the Li3V2(PO4)3/carbon cathode can retain outstanding rate ability (170.4 mAh g−1 at 1.2 C, 101.9 mAh g−1 at 17 C), and no degradation is found after 120 C current rate. These phenomena show that the two-step carbon-coated Li3V2(PO4)3 can act as a fast charge-discharge cathode material for high-power Li-ion batteries. Furthermore, it's believed that this synthesize method can be easily transplanted to prepare other lithiated vanadium-based phosphates.
Sn-SnO2/C photocatalysts with visible light activity have been successfully synthesized by a simple heat-treating process using SnCl4 as precursor. The Sn-SnO2 heterojunction is built by depositing of metallic Sn on crystal lattice oxygen of as-formed SnO2, which obviously increase the amount of adsorbed oxygen on the surface of catalyst. The as-synthesized catalysts display higher photocatalytic activity than SnO2 and SnO2/C for degradation of reactive brilliant blue KN-R under visible light irradiation. The enhancement of photocatalytic performance of Sn-SnO2/C can be attributed to the formation of metallic Sn on the surface of catalysts. The metallic Sn and adsorbed oxygen as the sinks of photoinduced electron and electronic scavenges, respectively, hinder the recombination of photoexcitated electron-hole pairs, sequentially enhance the photocatalytic activity. Furthermore, a possible growth mechanism of the Sn-SnO2/C photocatalysts was proposed.
The kinetics of Li-ion deintercalation in Li1.12[Ni0.5Co0.2Mn0.3]0.89O2 samples is studied by electrochemical impedance spectroscopy (EIS) and galvanostatic intermittent titration technique (GITT) during the first charge process. The impedance response of Li1.12[Ni0.5Co0.2Mn0.3]0.89O2 largely depends on the open-circuit voltage (OCV) of the cell, showing that the mechanism of electrode kinetics under different potentials is dominated by different electro-chemical reactions. Meanwhile, the equivalent circuit is proposed to simulate the EIS data, deducing the circuit elements (R i and C i) which are normally modeled as a multistep process of electro-chemical reactions. The change trend of R sf (the resistance of SEI film) and R ct (the charge-transfer resistance) in the first charge process are exactly similar. The C dl (double-layer capacitance) as a function of voltage gradually increases, particularly after 4.5V. The maximum of C sf (the film capacitor) observed in the first charge process shows that the most intensive ionic fluxes will appear when the Li1.12[Ni0.5Co0.2Mn0.3]0.89O2 electrode reach to the transient equilibrium at different levels of deintercalation. To study the faster capacity fading of Li1.12[Ni0.5Co0.2Mn0.3]0.89O2 during the first charge process, the Li-ion diffusion coefficient (D Li) is also calculated based on the results of EIS and GITT.
Thin films of LiCoO2 with a preferred c-axis orientation were prepared by pulsed laser deposition. Thin films deposited for 1–2h had a preferred c-axis orientation, but films deposited for 3h and longer lost the preferred orientation. The textures of these films were investigated in detail by transmission electron microscopy and selected area electron diffraction. The electrochemical properties of these films were compared by cyclic voltammetry and alternating current impedance spectroscopy. In the cyclic voltammograms of the c-axis oriented films, the anodic and cathodic peaks corresponding to the first-order phase transition at around 3.9V were sharp and their peak separation was small due to their thin and uniform texture. However, their smooth surface and texture of the aligned (003) planes gave a larger charge-transfer resistance and a smaller apparent diffusion coefficient in the direction normal to the substrate, respectively, which resulted in poor utilizations (∼50%) of the active material. The reactivity in the single-phase region at potentials more positive than 4.0V was lower than that of randomly oriented films.
A novel carbon material for use in lithium–sulfur batteries is fabricated from the seaweed Enteromorpha prolifera, a renewable source that grows rapidly in the sea near Qingdao, China, during the summer. The E. prolifera-derived carbon (EPC) possesses a multilevel micropore–mesopore structure and a certain amount of oxygen- and nitrogen-containing functional groups. In addition, the hierarchical porous carbon also possesses a high specific surface area of 3536.58 m2 g−1 and a large pore volume of 1.754 cm3 g−1. The carbon can thus be loaded with a high sulfur content (EPC/S, 74.8 wt%), making it a promising candidate for use as the cathode material in lithium–sulfur batteries. The EPC was characterized using field-emission scanning electron microscopy, Raman spectroscopy, Fourier transform infrared spectroscopy, the Brunauer–Emmett–Teller method, and other methods. The EPC/S cathode exhibited superior electrochemical performance; the first discharge capacity was as high as 1328 mA h g−1 at 0.1 C. Further, the capacity was 520 mA h g−1 after 100 cycles at 0.5 C and 510 mA h g−1 after 100 cycles at 1 C.
Poly(ethylene oxide)–lithium salt composite electrolytes containing two different derivatives of calix[4]arene were tested as anion complexing agents for I− and CF3SO3 −. Both calix[4]arene derivatives studied have identical anion coordination groups but they have different compatibility with the polymer matrix obtained by chemical linking of the oligo(ethylene oxide) chains to one of the studied calixarenes. The impedance spectroscopy studies showed that the addition of the anion receptor significantly changes the conductivity. The character of this changes strongly depends on the receptor used while the electrochemical stability of these two calixarene receptors measured by cyclic voltammetry is similar. It was also proved that addition of the anion receptor strongly changes the polymer matrix morphology and thermal behavior. By the comparison with the liquid systems which electrical properties were similar to the polymer matrix, we can assume that these changes are a result of anion–receptor interactions.
Novel electrode materials with nominal compositions of (1− x)LiVO2·xLi2TiO3 (0≤ x ≤0.6) were synthesized by carbothermal reduction reaction. All the materials were identified to have a layered structure and can be considered as a solid solution related to LiVO2–Li2TiO3 system, in which Li layers was alternately stacked with the layers made of mixture of Li, V, and Ti in a ccp array of oxygen. The redox reaction associated with vanadium ions was not reversible in LiVO2; however, introduction of the redox couple into Li2TiO3 made it much more reversible. A reversible capacity of about 120mAhg−1 remained after 90 cycles for the samples with x =0.5 and 0.6, when they were cycled in the voltage range of 1.0–4.8V.
A high strength Li-Garnet solid electrolyte composite ceramic is successfully prepared via conventional solid state method with Li6.4La3Zr1.4Ta0.6O12 and nano MgO powders. Well sintered ceramic pellets and bars are obtained with 0–9 wt.% MgO. Fracture strength is approximately 135 MPa for composite ceramics with 5–9 wt.% MgO, which is ∼50% higher than that of pure Li6.4La3Zr1.4Ta0.6O12 (90 MPa). Lithium-ion conductivity of the composite is above 5 × 10−4 S cm−1 at room temperature; comparable to the pure Li6.4La3Zr1.4Ta0.6O12 material. SEM cross-sections of the composite ceramic shows a much more uniform microstructure comparing with pure ones, owing to the grain growth inhibition effect of the MgO second phase. A battery cell consisting of Li/composite ceramics/Sulfur-Carbon at 25 °C exhibits a capacity of 685 mAh g−1 at 0.2 C at the 200th cycle, while maintaining a coulombic efficiency of 100%. These results indicate that the composite ceramic Li6.4La3Zr1.4Ta0.6O12-MgO is promising for the production of electrolyte membrane and fabrication of Li-Sulfur batteries.
In this manuscript, performance of a novel concentrated solar thermal collector with evacuated tube is studied. The focus is the optimization of cost and performance in respect to commercially available medium temperature collectors (100–300 °C) using thermal and economic index of heat generation system also known as Levelized Cost of Heat. In this project, Levelized Cost of Heat is optimized with material cost reduction while maintaining high thermal performance using economical aluminum fin (instead of copper), a glass cover and highly truncated aluminum reflector. The reflector is truncated using the nonimaging optics methods in order to maximize the optical efficiency while minimizing the material consumption. Also, in order to predict the thermal performance of the proposed collector, analytical and numerical simulation are studied. Finally, the collector is experimentally tested in three stages to measure maximum temperature, maximum efficiency and thermal efficiency at various temperature of heat transfer fluid. The mathematical, numerical and experimental results were found to have good agreement. The results indicate that the collector can operate with optical efficiency of 60%, maximum temperature of 350 °C, thermal efficiency of 51% and 42% at 100 °C and 200 °C respectively while the cost of energy is as low as 2.9 cents/kWh.
This paper reports studies on the morphology, thermal stability, NMR and electrical spectroscopy of the first lithium zeolitic inorganic–organic polymer electrolyte (Z-IOPE) with the formula [Fe x Pd y (CN) z Cl v (C2n H4n+2O n+1)Li l ]. Both 1H and 7Li NMR linewidth, spin-lattice relaxation, and pulsed field gradient diffusion measurements were conducted, and the results suggest that the lithium ion transport is correlated with polymer mobility, as in the case of “conventional” polymer electrolytes. A detailed study of the mechanism of ion conduction in bulk material has been carried out also by electrical spectroscopy measurements in the 10 mHz–1 GHz range. The electrical spectra for frequencies higher than 15 kHz evidenced the presence of relaxation events associated to local ion motion dynamics and long range diffusion. These two phenomena were interpreted in terms of (a) ion hopping processes; (b) site relaxations; and (c) host medium reorganization processes. Taken together, these studies demonstrated that at temperatures higher than 35°C, the Z-IOPE conducts ionically by charge transfer mechanisms mainly regulated by ion hopping between equivalent polyether coordination sites followed by correlated host medium reorganizations. Finally, a conductivity of 5.3×10−5 S cm−1 at 35°C classifies this hybrid inorganic–organic network as a good lithium ion conductor.
We have investigated an inorganic lithium battery system in which LiCoO2 is used as the positive electrode and lithium, intercalated into graphite, serves as negative electrode. The conducting salt is lithium tetrachloroaluminate (LiAlCl4). The electrolyte is based on SO2. It has been shown that a layer of lithium hydroxide is present on the surface of the lithium cobalt oxide. This has a negative impact on the stability of the electrode. To improve stability, we have developed a purification process for removing the lithium hydroxide from the surface of the positive electrode. After purification the cells show no significant change in either capacity or internal resistance when cycled. Up to 70% of the theoretical capacity of electrodes which have been purified in this way can be used without any negative effects being observed. To prevent the deposition of metallic lithium leading to a hazardous situation, a new safety concept was developed whereby local short circuits are allowable. Safe functioning of the new concept has been demonstrated with tests on complete cells.
Layered xLi2MnO3·(1 −x)LiMnO2 (x =0.57, 0.48, and 0.44) nanoplates are firstly prepared by pyrolysis reducing the electrochemically inactive monoclinic Li2MnO3 nanoplates, which is synthesized via a solid-state reaction by using home-made MnO2 nanoplates as self-template. The obtained xLi2MnO3·(1− x)LiMnO2 nanoplates have a diameter of ∼200nm and thickness of ∼60nm with high crystallinity and the transition metal layers parallel to the plate’s radial direction. Although these xLi2MnO3·(1 −x)LiMnO2 nanoplates cause a longer Li+ diffusion distance, and then a lower reversible capacity as compared to the nanoparticle-like counterpart, the nanoplate-like morphology of these xLi2MnO3·(1− x)LiMnO2 (especially with x <0.5) are beneficial for retarding the layer-to-spinel phase transformation during the charge/discharge processes, and resulting in significant improvement of the cyclic stability. Moreover, the reduced reversible capacity caused by the longer Li+ diffusion distance of the nanoplate-like morphology can be offset by decreasing the x value, and the xLi2MnO3·(1− x)LiMnO2 nanoplates with x =0.44 performs a maximum reversible capacity as high as 270mAhg−1 with a well cyclic performance. The present findings indicate that the cyclic performance and reversible capacity of xLi2MnO3·(1 −x)LiMnO2 can be improved by tailoring the particle’s morphology and composition, and demonstrate a simple and effective strategy for the development of the Co/Ni-free Mn-based layered Li-rich cathode materials with good cyclic and high reversible capacity.
The development of simple and green synthetic strategies to obtain porous carbon with both high energy density and power density for carbon-based supercapacitors has motivated the utilization of sustainable biomass materials, due to their unique microstructures and high heteroatom contents. Herein, a novel, green and efficient activation agent magnesium carbonate is proposed to prepare nitrogen self-doped hierarchical porous carbon materials derived from pine pollen for superior carbon-based supercapacitors. The obtained carbon has a large surface area of 1311.2 m2 g−1, hierarchical porous structure with interconnected meso-/macropores and high nitrogen, oxygen contents. When applied as supercapacitor electrode in a three-electrode system, the carbon-based electrode exhibits a high specific capacitance of 419.6 F g−1 at a current density of 1 A g−1, good rate retention of 60.3% from 1 to 100 A g−1 and superior long-term cycling stability with 2.6% loss of its initial capacitance after 10,000 cycles in 6 M KOH aqueous electrolyte. Additionally, the assembled symmetric supercapacitor can work at a high voltage of 2.0 V in 1 M Na2SO4 aqueous electrolyte, and deliver an ultrahigh energy density of 34.9 Wh kg−1 at a power density of 181.0 W kg−1.
Lithium–sulfur battery is amongst the most promising next-generation energy storage technology owing to their high theoretical capacity and energy density. Nevertheless, the notorious shuttle effect of lithium polysulfides (LiPSs) seriously impedes its practical applications. Here, we report an all-CVD approach to realize the direct growth of ReS2@N-doped graphene (NG) heterostructure, which serves as an ultralight high-performance interlayer for elevated LiPS regulation via easy transfer onto the commercial separator. In contrast to the traditional interlayers constructed via vacuum filtration of nanostructured materials that inevitably increase the thickness and weight of the separator, our all-CVD-enabled ReS2@NG film possesses an area of 15 mm × 100 mm, a thickness of ~0.5 μm and a negligible areal weight of 80–90 μg cm−2. Benefiting from the two-dimensional (2D) vertically-erected nanostructure, adsorptive ReS2-conductive NG interface, and favorable electrical conductivity, thus-derived ReS2@NG interlayer readily enhances reaction kinetics for LiPS conversion and boosts the reutilization of trapped LiPS whilst guaranteeing smooth transportation of lithium ions. Accordingly, an initial discharge capacity of 854 mAh g−1 with an average capacity decay of 0.064% per cycle after 800 cycles can be harvested at 2.0 C. Even at a high sulfur loading of 6.4 mg cm−2, an initial areal capacity of 6.1 mAh cm−2 can be gained, which still retains 5.8 mAh cm−2 after 40 cycles at 0.1 C. This work is anticipated to shed light upon the construction of CVD-enabled versatile 2D heterostructures for enriching the interlayer design with multifunctionality and cost-effectiveness.
Engineering crystal facets to enhance their functionalities often require complex processing routes to suppress the growth of surfaces with the lowest thermodynamic energies. Herein, we report a unique method to control the morphologies of β-MnO2 crystals with different occupancy of {100}/{111} facets through the effect of K+ cations. Combining aberration-corrected scanning transmission electron microscopy (STEM), ultramicrotomy, and dynamic functional theory (DFT) simulation, we clarified that the β-MnO2 crystals were formed through a direct solid-state phase transition process. Increasing the concentration of K+ cations in the precursor gradually changed the morphology of β-MnO2 from bipyramid prism ({100}+{111} facets) to an octahedron structure ({111} facets). The K+ cations controlled the morphology of β-MnO2 by affecting the formation of α-K0.5Mn4O8 intermediate phase and the subsequent phase transition. Utilizing the β-MnO2 crystals as the cathode for Li-ion batteries showed that highly exposed {111} facets offered β-MnO2 crystal better rate performance, with ~70% capacity retention when the charge-discharge rate increased from 20 mA/g to 200 mA/g. Our work revealed a new mechanism to tune the morphology of this earth-abundant metal oxide crystal, which could be used to adjust its electrochemical performance for different applications, such as supercapacitors and catalysts for metal-air batteries and fuel cells.