Search Results (15)

A supercapacitor’s energy storage capability is greatly dependent on electrode materials. Layered double hydroxides (LDHs) were extensively studied as battery-type electrodes because of their 2D structure and quick intercalation/deintercalation of electrolyte ions. However, the energy storage capability for pristine LDHs is limited by their large aggregation tendency and poor electrical conductivity. Herein, a novel NiCoMn-LDH/SWCNTs (single-walled carbon nanotubes) composite electrode material, with ultrathin NiCoMn-LDH nanosheets dispersedly grown among the highly conductive networks of SWCNTs, was prepared via a facile zeolitic imidazolate framework-67 (ZIF-67)-derived in situ etching and deposition procedure. The NiCoMn-LDH/SWCNTs electrode demonstrates a specific capacitance as large as 1704.3 F g⁻¹ at 1 A g⁻¹, which is ascribed to its exposure of more active sites than NiCoMn-LDH. Moreover, the assembled NiCoMn-LDH/SWCNTs//BGA (boron-doped graphene aerogel) hybrid supercapacitor exhibits a superior capacitance of 167.9 F g⁻¹ at 1.0 A g⁻¹, an excellent energy density of 45.7 Wh kg⁻¹ with a power density of 700 W kg⁻¹, and an outstanding cyclic stability with 82.3% incipient capacitance maintained when subjected to 5000 charge and discharge cycles at the current density of 10 A g⁻¹, suggesting the significant potential of NiCoMn-LDH/SWCNTs as the electrode material applicable in supercapacitors. Full article

Solid electrolytes, including polymer electrolytes, are a promising option for improving the performance of environmentally friendly batteries such as rechargeable lithium-ion batteries or fuel cells. Hydrogen–oxygen fuel cells producing only water under power generation are attracting widespread attention, and they need proton conductors as electrolytes. Fluoropolymer electrolytes such as Nafion^® have been utilized for hydrogen–oxygen fuel cells below 100 °C; however, they are not applicable over the working temperature. Therefore, other types of polymer electrolytes are demanded for hydrogen–oxygen fuel cells. Polyoxometalate (POM) inorganic clusters are known as proton conductors and are utilized to prepare POM–polymer composites for solid electrolyte application. In such POM–polymer composites, distinct compositions and structures are significant for improving the performance of proton conductivity. Recently, POM–polymer composites with distinct compositions and structures have been synthesized to obtain high proton conductivity. The key factor is to use single-crystalline compounds. Here, several examples are overviewed by classifying them into three categories: (i) single-crystalline POM–polymer composites, (ii) organically modified POM (org-POM) polymers, and (iii) POM hybrid polymers using polymerizable cations. The application of proton-conductive solid electrolytes is focused on. Full article

In this work, a comprehensive multi-physics electrochemical hybrid stack model is developed for a vanadium redox flow battery (VRFB) stack considering electrolyte flow, mass transport, electrochemical reactions, shunt currents, and as heat generation and transfer simultaneously. Compared with other VRFB stack models, this model is more comprehensive in considering the influence of multiple factors. Based on the established model, the electrolyte flow rate distribution across cells in the stack is investigated. The distribution and variation in shunt currents, single-cell current and single-cell voltage are analyzed. The distribution and variation in temperature and heat generation and heat transfer are also researched. It can be found that the VRFB stack temperature will exceed 40 °C when operating at 60 A and 100 mA cm⁻² at an ambient temperature of 30 °C, which will lead to electrolyte ion precipitation, affecting the performance and safety of the battery. To control the stack temperature below 40 °C, a new tank cooling control strategy is proposed, and the suitable starting cooling point and the controlled temperature are specified. Compared with the common room cooling strategy, the new tank cooling strategy reduces energy consumption by 27.18% during 20 charge–discharge cycles. Full article

Despite the variety of solid electrolytes available, no single solid electrolyte has been found that meets all the requirements of the successor technology of lithium-ion batteries in an optimum way. However, composite hybrid electrolytes that combine the desired properties such as high ionic conductivity or stability against lithium are promising. The addition of conductive oxide fillers to sulfide solid electrolytes has been reported to increase ionic conductivity and improve stability relative to the individual electrolytes, but the influence of the mixing process to create composite electrolytes has not been investigated. Here, we investigate Li₃PS₄ (LPS) and Li₇La₃Zr₂O₁₂ (LLZO) composite electrolytes using electrochemical impedance spectroscopy and distribution of relaxation times. The distinction between sulfide bulk and grain boundary polarization processes is possible with the methods used at temperatures below 10 °C. We propose lithium transport through the space-charge layer within the sulfide electrolyte, which increases the conductivity. With increasing mixing intensities in a high-energy ball mill, we show an overlay of the enhanced lithium-ion transport with the structural change of the sulfide matrix component, which increases the ionic conductivity of LPS from 4.1 × 10⁻⁵ S cm⁻¹ to 1.7 × 10⁻⁴ S cm⁻¹. Full article

Highly transparent, conductive nanosheets are extremely attractive for advanced opto-electronic applications. Previously, we have demonstrated that transparent, conductive Au nanosheets can be prepared by UV irradiation of Au nanoparticle (AuNP) monolayers spread on water, which serves as the subphase. However, thick Au nanosheets cannot be fabricated because the method is not applicable to large Au NPs. Further, in order to fabricate nanosheets with different thicknesses and compositions, it is necessary to prepare the appropriate NPs. A strategy is needed to produce nanosheets with different thicknesses and compositions from a single type of metal NP monolayer. In this study, we show that this UV irradiation technique can easily be extended as a nanosheet modification method by using subphases containing metal ions. UV irradiation of 4.7 nm AuNP monolayers on 480 µM HAuCl₄ solution increased the thickness of Au nanosheets from 3.5 nm to 36.5 nm, which improved conductivity, but reduced transparency. On the other hand, the use of aqueous AgNO₃ and CH₃COOAg solutions yielded Au-Ag hybrid nanosheets; however, their morphologies depended on the electrolytes used. In Au-Ag nanosheets prepared on aqueous 500 µM AgNO₃, Au and Ag metals are homogeneously distributed throughout the nanosheet. On the other hand, in Au-Ag nanosheets prepared on aqueous 500 µM CH₃COOAg, AuNPs still remained and these AuNPs were covered with a Ag nanosheet. Further, these Au-Ag hybrid nanosheets had high conductivity without reduced transparency. Therefore, this UV irradiation method, modified by adding metal ions, is quite effective at improving and diversifying properties of Au nanosheets. Full article

The rapid growth of renewable energy sources and the expanding market for electric vehicles (EVs) have escalated the demand for safe lithium-ion batteries (LIBs) with excellent performance. But the limitations of safety issues and energy density for LIBs continue to be obstacles to their future use. Recently, single-ion covalent-organic-framework-based (COF-based) solid electrolytes have emerged as a promising avenue to address the limitations of traditional liquid electrolytes and enhance the performance of LIBs. COFs have a porous structure and abundant electron-donating groups, enabling the construction of an available ionic conductive network. So, COFs are the subject of extensive and in-depth investigation, especially in terms of the impacts their adjustable porous structure and tunable chemistry on the research of ionic transport thermodynamics and transport kinetics. In this perspective, we present a comprehensive and significant overview of the recent development progress of single-ion COF-based solid electrolytes, highlighting their rare performance and potential applications in solid lithium batteries. This review illustrates the merits of single-ion conducting solid electrolytes and single-ion COF conductor-based solid electrolytes. Furthermore, the properties of anionic, cationic, and hybrid single-ion COF-based conducting electrolytes are discussed, and their electrochemical performance is also compared when applied in Li-ion batteries. Finally, to solve challenges in COF-based Li-ion batteries, strategies are provided to obtain a high lifespan, rate performance, and stable and safe batteries. This work is promising to offer valuable insights for researchers and the energy storage industry. Full article

Carbon materials are promising for use as electrodes for supercapacitors and lithium–ion batteries due to a number of properties, such as non-toxicity, high specific surface area, good electronic conductivity, chemical inertness, and a wide operating temperature range. Carbon-based electrodes, with their characteristic high specific power and good cyclic stability, can be used for a new generation of consumer electronics, biomedical devices and hybrid electric vehicles. However, most carbon materials, due to their low electrical conductivity and insufficient diffusion of electrolyte ions in complex micropores, have energy density limitations in these devices due to insufficient number of pores for electrolyte diffusion. This work focuses on the optimization of a hybrid material based on porous carbon and carbon nanotubes by mechanical mixing. The purpose of this work is to gain new knowledge about the effect of hybrid material composition on its specific capacitance. The material for the study is taken on the basis of porous carbon and carbon nanotubes. Electrodes made of this hybrid material were taken as an object of research. Porous carbon or nitrogen-containing porous carbon (combined with single-, double-, or multi-layer carbon nanotubes (single-layer carbon nanotubes, bilayer carbon nanotubes or multilayer carbon nanotubes) were used to create the hybrid material. The effect of catalytic chemical vapor deposition synthesis parameters, such as flow rate and methane-to-hydrogen ratio, as well as the type of catalytic system on the multilayer carbon nanotubes structure was investigated. Two types of catalysts based on Mo₁₂O₂₈ (μ₂-OH)₁₂{Co(H₂O)₃}₄ were prepared for the synthesis of multilayer carbon nanotubes by precipitation and combustion. The resulting carbon materials were tested as electrodes for supercapacitors and lithium ion intercalation. Electrodes based on nitrogen-containing porous carbon/carbon nanotubes 95:5% were found to be the most efficient compared to nitrogen-doped porous carbon by 10%. Carbon nanotubes, bilayer carbon nanotubes and multilayer carbon nanotubes synthesized using the catalyst obtained by deposition were selected as additives for the hybrid material. The hybrid materials were obtained by mechanical mixing and dispersion in an aqueous solution followed by lyophilization to remove water. When optimizing the ratio of the hybrid material components, the most effective porous carbon:carbon nanotubes component ratio was determined. Full article

New single-ion hybrid electrolytes have been synthetized via an original and simple synthetic approach combining Michael addition, epoxidation, and sol–gel polycondensation. We designed an organic PEO network as a matrix for the lithium transport, mechanically reinforced thanks to crosslinking inorganic (SiO_1.5) sites, while highly delocalized anions based on lithium vinyl sulfonyl(trifluoromethane sulfonyl)imide (VSTFSILi) were grafted onto the inorganic sites to produce single-ion hybrid electrolytes (HySI). The influence of the electrolyte composition in terms of the inorganic/organic ratio and the grafted VSTFSILi content on the local structural organization, the thermal, mechanical, and ionic transport properties (ionic conductivity, transference number) are studied by a variety of techniques including SAXS, DSC, rheometry, and electrochemical impedance spectroscopy. SAXS measurements at 25 °C and 60 °C reveal that HySI electrolyte films display locally a spatial phase separation with domains composed of PEO rich phase and silica/VSTFSILi clusters. The size of these clusters increases with the silica and VSTFSILi content. A maximum ionic conductivity of 2.1 × 10⁻⁵ S·cm⁻¹ at 80 °C has been obtained with HySI having an EO/Li ratio of 20. The Li⁺ ion transfer number of HySI electrolytes is high, as expected for a single-ion electrolyte, and comprises between 0.80 and 0.92. Full article

In this study, we propose tunable pH sensors based on the electric-double-layer transistor (EDLT) with time-dependent sensitivity characteristics. The EDLT is able to modulate the drain current by using the mobile ions inside the electrolytic gate dielectric. This property allows the implementation of a device with sensitivity characteristics that are simply adjusted according to the measurement time. An extended gate-type, ion-sensitive, field-effect transistor consisting of a chitosan/Ta₂O₅ hybrid dielectric EDLT transducer, and an SnO₂ sensing membrane, were fabricated to evaluate the sensing behavior at different buffer pH levels. As a result, we were able to achieve tunable sensitivity by only adjusting the measurement time by using a single EDLT and without additional gate electrodes. In addition, to demonstrate the unique sensing behavior of the time-dependent tunable pH sensors based on organic–inorganic hybrid EDLT, comparative sensors consisting of a normal FET with a SiO₂ gate dielectric were prepared. It was found that the proposed pH sensors exhibit repeatable and stable sensing operations with drain current deviations <1%. Therefore, pH sensors using a chitosan electrolytic EDLT are suitable for biosensor platforms, possessing tunable sensitivity and high-reliability characteristics. Full article

In addition to their use as an additive to improve physical properties of solvent polymeric membranes, plasticizers have a considerable impact on the specificity and sensitivity of membrane-modified electrochemical sensors. In this work, we aim at the hybridization of two different plasticizers using the electropolymerization technique in the development of a cadmium(II)-selective electrochemical sensor based on screen-printed gold electrode along with cyclic voltammetric measurement. At this point, we first screen for the primary plasticizer yielding the highest signal using cyclic voltammetry followed by pairing it with the secondary plasticizers giving rise to the most sensitive current response. The results show that the hybridization of DOS and TOTM with 3:1 weight ratio (~137.7-μm-thick membrane) renders a signal that is >26% higher than that from the sensor plasticized by DOS per se in water. The solution of 0.1 mM hydrochloric acid (pH 4) is the optimal supporting electrolyte. In addition, hybrid plasticizers have adequate redox capacity to induce cadmium(II) transfer from bulk solution to the membrane/water interfaces. Conversion of voltammetric signals to semi-integral currents results in linearity with cadmium(II) concentration, indicating the irreversible cadmium(II) transfer to the membrane. The DOS:TOTM hybrid sensor also exhibits high sensitivity, with a limit of detection (LOD) and limit of quantitation (LOQ) of 95 ppb and 288 ppb, respectively, as well as greater specificity towards cadmium(II) than that obtained from the single plasticizer sensor. Furthermore, recovery rates of spiked cadmium(II) in water samples were higher than 97% using the hybrid plasticizer sensor. Unprecedentedly, our work reports that the hybridization of plasticizers serves as ion-to-electron transducer that can improve the sensor performance in cadmium(II) detection. Full article

Hybrid solid-state batteries using a bilayer of ceramic and solid polymer electrolytes may offer advantages over using a single type of solid electrolyte alone. However, the impedance to Li⁺ transport across interfaces between different electrolytes can be high. It is important to determine the resistance to Li⁺ transport across these heteroionic interfaces, as well as to understand the underlying causes of these resistances; in particular, whether chemical interphase formation contributes to giving high resistances, as in the case of ceramic/liquid electrolyte interfaces. In this work, two ceramic electrolytes, Li₃PS₄ (LPS) and Li_6.5La₃Zr_1.5Ta_0.5O₁₂ (LLZTO), were interfaced with the solid polymer electrolyte PEO₁₀:LiTFSI and the interfacial resistances were determined by impedance spectroscopy. The LLZTO/polymer interfacial resistance was found to be prohibitively high but, in contrast, a low resistance was observed at the LPS/polymer interface that became negligible at a moderately elevated temperature of 50 °C. Chemical characterization of the two interfaces was carried out, using depth-profiled X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry, to determine whether the interfacial resistance was correlated with the formation of an interphase. Interestingly, no interphase was observed at the higher resistance LLZTO/polymer interface, whereas LPS was observed to react with the polymer electrolyte to form an interphase. Full article

In the present era, different allotropes of carbon have been discovered, and graphene is the one among them that has contributed to many breakthroughs in research. It has been considered a promising candidate in the research and academic fields, as well as in industries, over the last decade. It has many properties to be explored, such as an enhanced specific surface area and beneficial thermal and electrical conductivities. Graphene is arranged as a 2D structure by organizing sp² hybridized C with alternative single and double bonds, providing an extended conjugation combining hexagonal ring structures to form a honeycomb structure. The precious structure and outstanding characteristics are the major reason that modern industry relies heavily on graphene, and it is predominantly applied in electronic devices. Nowadays, lithium-ion batteries (LIBs) foremostly utilize graphene as an anode or a cathode, and are combined with polymers to use them as polymer electrolytes. After three decades of commercialization of the lithium-ion battery, it still leads in consumer electronic society due to its higher energy density, wider operating voltages, low self-discharge, noble high-temperature performance, and fewer maintenance requirements. In this review, we aim to give a brief review of the domination of graphene and its applications in LIBs. Full article

Proton-conductive solid electrolytes are significant for fuel-cell battery technology. Especially for use in motor vehicles, proton conductors which work at intermediate temperatures (373–673 K) under an anhydrous atmosphere are desired to improve the fuel cell stability and efficiency. Inorganic–organic hybrid supramolecular architectures are a promising option for the realization of highly conductive proton conductors. Here, a hybrid layered crystal was synthesized for the first time by using an proton-containing decavanadate (V₁₀) anion and a heterocyclic surfactant cation. A simple ion-exchange reaction led to the formation of an inorganic–organic hybrid of V₁₀ by using dodecylpyridazinium (C₁₂pda) as the heterocyclic surfactant. Single crystal X-ray analyses revealed that four C₁₂pda cations were associated with one V₁₀ anion, which was a diprotonated species forming a one-dimensional infinite chain structure through hydrogen bonds. Anhydrous proton conductivity was investigated by alternating current (AC) impedance spectroscopy in the range of 313–393 K, exhibiting a maximum value of 1.7 × 10⁻⁵ S cm⁻¹ at 373 K. Full article

Solid electrolytes are crucial materials for lithium-ion or fuel-cell battery technology due to their structural stability and easiness for handling. Emergence of high conductivity in solid electrolytes requires precise control of the composition and structure. A promising strategy toward highly-conductive solid electrolytes is employing a thermally-stable inorganic component and a structurally-flexible organic moiety to construct inorganic-organic hybrid materials. Ionic liquids as the organic component will be advantageous for the emergence of high conductivity, and polyoxometalate, such as heteropolyacids, are well-known as inorganic proton conductors. Here, newly-designed ionic liquid imidazolium cations, having a polymerizable methacryl group (denoted as MAImC₁), were successfully hybridized with heteropolyanions of [PW₁₂O₄₀]³⁻ (PW₁₂) to form inorganic-organic hybrid monomers of MAImC₁-PW₁₂. The synthetic procedure of MAImC₁-PW₁₂ was a simple ion-exchange reaction, being generally applicable to several polyoxometalates, in principle. MAImC₁-PW₁₂ was obtained as single crystals, and its molecular and crystal structures were clearly revealed. Additionally, the hybrid monomer of MAImC₁-PW₁₂ was polymerized by a radical polymerization using AIBN as an initiator. Some of the resulting inorganic-organic hybrid polymers exhibited conductivity of 10⁻⁴ S·cm⁻¹ order under humidified conditions at 313 K. Full article

Using Rietveld-refined X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and electrochemical cycling, it was established that among sodium vanadium fluorophosphate compositions Na1+yVPO4F1+y (0 ≤ y ≤ 0.75), the single-phase material Na1.5VPO4F1.5 or Na3V2(PO4)2F3 with a tetragonal structure (the P42/mnm S.G.) is formed only for y = 0.5. The samples with y < 0.5 and y > 0.5 possessed different impurity phases. Na3V2(PO4)2F3 could be considered as a multifunctional cathode material for the fabrication of lithium-ion and sodium-ion high-energy batteries. The reversible discharge capacity of 116 mAh•g−1 was achieved upon cycling Na3V2(PO4)2F3 in a hybrid Na/Li cell. Decrease in discharge capacity for the other samples was in accordance with the amount of the electrochemically active phase Na3V2(PO4)2F3. Na3V2(PO4)2F3 showed good cycleability and a high rate of performance, presumably due to operation in the mixed Na/Li electrolyte. The study of the structure and composition of charged and discharged samples, and the analysis of differential capacity curves showed a negligible Na/Li electrochemical exchange, and a predominant sodium-based cathode reaction. To increase the degree of the Na/Li electrochemical exchange in Na3V2(PO4)2F3, it needs to be desodiated first in a Na cell, and then cycled in a lithium cell. In this case, the electrolyte would be enriched with the Li ions. Full article