基于NiCo2O4纳米片电极的非对称混合电容器

The looming global energy crisis and ever-increasing energy demands have catalyzed the development of renewable energy storage systems. In this regard, supercapacitors (SCs) have attracted widespread attention because of their advantageous attributes such as high power density, excellent cycle stability, and environmental friendliness. However, SCs exhibit low energy density and it is important to optimize electrode materials to improve the overall performance of these devices. Among the various electrode materials available, spinel nickel cobaltate (NiCo₂O₄) is particularly interesting because of its excellent theoretical capacitance. Based on the understanding that the performances of the electrode materials strongly depend on their morphologies and structures, in this study, we successfully synthesized NiCo₂O₄ nanosheets on Ni foam via a simple hydrothermal route followed by calcination. The structures and morphologies of the as-synthesized products were characterized by X-ray diffraction, scanning electron microscopy, and Brunauer-Emmett-Teller (BET) surface area analysis, and the results showed that they were uniformly distributed on the Ni foam support. The surface chemical states of the elements in the samples were identified by X-ray photoelectron spectroscopy. The as-synthesized NiCo₂O₄ products were then tested as cathode materials for supercapacitors in a traditional three-electrode system. The electrochemical performances of the NiCo₂O₄ electrode materials were studied and the area capacitance was found to be 1.26 C·cm^-2 at a current density of 1 mA·cm^-2. Furthermore, outstanding cycling stability with 97.6% retention of the initial discharge capacitance after 10000 cycles and excellent rate performance (67.5% capacitance retention with the current density from 1 to 14 mA·cm^-2) were achieved. It was found that the Ni foam supporting the NiCo₂O₄ nanosheets increased the conductivity of the electrode materials. However, it is worth noting that the contribution of nickel foam to the areal capacitance of the electrode materials was almost zero during the charge and discharge processes. To further investigate the practical application of the as-synthesized NiCo₂O₄ nanosheets-based electrode, a device was assembled with the as-prepared samples as the positive electrode and active carbon (AC) as the negative electrode. The assembled supercapacitor showed energy densities of 0.14 and 0.09 Wh·cm^-3 at 1.56 and 4.5 W·cm^-3, respectively. Furthermore, it was able to maintain 95% of its initial specific capacitance after 10000 cycles. The excellent electrochemical performance of the NiCo₂O₄ nanosheets could be ascribed to their unique spatial structure composed of interconnected ultrathin nanosheets, which facilitated electron transportation and ion penetration, suggesting their potential applications as electrode materials for high performance supercapacitors. The present synthetic route can be extended to other ternary transition metal oxides/sulfides for future energy storage devices and systems.     

Improvement of capacitance activity for Cu‐doped Ni‐based metal–organic frameworks by adding potassium hexacyanoferrate into KOH electrolyte

Cu‐doped Ni‐based metal–organic frameworks (MOFs) nanomaterials fabricated through a one‐pot hydrothermal reaction were characterized, and their performance as supercapacitor electrode materials was further studied for the first time. The results indicated that the doping of foreign metals and the introduction of K₃[Fe(CN)₆] in the KOH electrolyte significantly improve the performance of the supercapacitor. The results indicated that the Ni_2.6Cu_0.4 MOFs material shows the highest specific capacitance (1282 F g^?1 at 1 A g^?1 in mixed 2 M KOH and 0.1 M K₃[Fe(CN)₆]) and optimal capacitance retention (85.7% after 2000 cycles). This work provides a feasible optimization strategy for the construction of MOFs‐based supercapacitor electrode materials with excellent performance, and also provides a reliable experimental and theoretical basis for practical industrial production.     

Freestanding Carbon Nanotube Film for Flexible Straplike Lithium/Sulfur Batteries

Flexible lithium/sulfur (Li/S) batteries are promising to meet the emerging power demand for flexible electronic devices. The key challenge for a flexible Li/S battery is to design a cathode with excellent electrochemical performance and mechanical flexibility. In this work, a flexible strap-like Li/S battery based on a S@carbon nanotube/Pt@carbon nanotube hybrid film cathode was designed. It delivers a specific capacity of 1145 mAh g⁻¹ at the first cycle and retains a specific capacity of 822 mAh g⁻¹ after 100 cycles. Moreover, the flexible Li/S battery retains stabile specific capacity and Coulombic efficiency even under severe bending conditions. As a demonstration of practical applications, an LED array is shown stably powered by the flexible Li/S battery under flattened and bent states. We also use the strap-like flexible Li/S battery as a real strap for a watch, which at the same time provides a reliable power supply to the watch.     

NHC-Pd complex heterogenized on graphene oxide for cross-coupling reactions and supercapacitor applications

N-heterocyclic carbene (NHC)-palladium(II) complex (GO@NHC-Pd) was synthesized on graphene oxide (GO) support via a simple and cost-effective multistep approach. The spectroscopic, microscopic, thermal, and surface analyses of GO@NHC-Pd confirmed the successful formation of the catalyst. The investigation of catalytic activity showed that GO@NHC-Pd was very effective in Suzuki–Miyaura as well as Hiyama cross-coupling. Being heterogeneous in nature, GO@NHC-Pd was recovered after each reaction cycle easily and reused for up to nine and six cycles in Suzuki–Miyaura and Hiyama cross-coupling, respectively, without significant loss of activity. Further exploration of the supercapacitor performance of GO@NHC-Pd catalyst assembled in a two-electrode cell configuration shown a maximum attained capacitance of 105.26 F/g at a current density of 0.1 A/g with good cycling stability of 96.89% over 2,500 cycles.     

Proton conductivity study on three CS/IL@fle-MOF membranes

The low-cost, high specific surface area and porosity, controlled pore size, and chemical properties of metal–organic framework (MOF) materials have attracted much attention in the exploration of proton conduction. The method of chemically modifying MOF structures or introducing conductive medium into the holes can effectively improve the proton conductivities of the materials. Here, the structural tunability of ionic liquid (IL) and flexible MOF (fle-MOF) materials are matched to give full play to the conductivity of IL, the framework support, and the microporous effect of MOFs, which achieves the synergistic effect of performance and expands the temperature range of proton transfer. Three kinds of CS/IL@fle-MOF membranes were prepared by combining three fle-MOFs with 1-carboxymethyl-3-methylimidazole (CMMIM) in different proportions to obtain 15 pieces of membranes. The comparative analyses show that CS/IL@fle-MOF membranes have excellent proton conduction performance at a wider temperature range (263–353 K) and lower relative humidity (75% RH). Among them, the proton conductivities of CS/CMMIM@MIL-88A-25% and CS/CMMIM@MIL-88B-125% are up to 1.33 and 1.42 S cm⁻¹ at 75% RH and 353 K, respectively; whereas those of CS/CMMIM@MIL-53(Fe)-75% and CS/CMMIM@MIL-88B-125% reach up to 2.1 × 10⁻³ and 1.28 × 10⁻³ S cm⁻¹ at 75% RH and 263 K, respectively. The E_a of CS/CMMIM@fle-MOFs is in the range of 0.1–0.5 eV, suggesting that the proton transport follows predominantly the typical Grotthuss transfer mechanism. The results of this study indicate that the CS/CMMIM@fle-MOF membranes combinations offer great potential for the design of composite porous proton-conducting materials.     

Green solvent approach for printable large deformation thermoplastic elastomer based piezoresistive sensors and their suitability for biomedical applications

Composites based on biocompatible thermoplastic elastomer styrene‐ethylene/butylene‐styrene (SEBS) as matrix and multi‐walled carbon nanotubes (MWCNT) as nanofillers show excellent mechanical and piezoresistive properties from low to large deformations. The MWCNT/SEBS composites have been prepared following a green solvent approach, to extend their range of applicability to biomedical applications. The obtained composites with 2, 4, and 5 wt % MWCNT content provide suitable piezoresistive response up to 80% deformation with a piezoresistive sensibility near 2.7, depending on the applied strain and MWCNT content. Composite sensors were also developed by spray and screen printing and integrated with an electronic data acquisition system with RF communication. The possibility to accurately control the composites properties and performance by varying MWCNT content, viscosity, and mechanical properties of the polymer matrix, shows the large potential of the system for the development of large deformation printable piezoresistive sensors. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 2092–2103     

A Comparative Study of the Semiconductor Behavior of Organic Thin Films: TCNQ-Doped Cobalt Phthalocyanine and Cobalt Octaethylporphyrin

The structure formed by cobalt phthalocyanine (CoPc) and cobalt octaethylporphyrin (CoOEP) with electron-acceptor tetracyano-π-quinodimethane (TCNQ), was studied by Density Functional Theory (DFT) methods. According to theoretical calculations, both cobalt systems can establish dispersion forces related to TCNQ and also in both cases the link between them is built by means of hydrogen bonds. Based on the results of these DFT calculations, we developed experimental work: the organic semiconductors were doped, and the thermal evaporation technique was used to prepare semiconductor thin films of such compounds. The structure of the films was studied by FTIR and Raman spectroscopy. The optical properties of the CoPc-TCNQ and CoOEP-TCNQ films were investigated by means of UV-Vis measurements. The results obtained were used to estimate the type of transitions and the optical bandgap. The results were compared to the previously calculated theoretical bandgap. The CoOEP-TCNQ film presented the smallest theoretical and experimental bandgap. Finally, the electrical properties of the organic semiconductors were evaluated from a PET (polyethylene terephthalate)/indium tin oxide (ITO)/cobalt macrocycle-TCNQ/silver (Ag) device we prepared. The CoOEP-TCNQ-based device showed an ohmic behavior. The device manufactured from CoPc-TCNQ also showed an ohmic behavior at low voltages, but significantly changed to SCLC (space-charge limited conductivity) at high voltage values.     

Light/Electricity Energy Conversion and Storage for a Hierarchical Porous In2S3@CNT/SS Cathode towards a Flexible Li-CO2 Battery

A photoinduced flexible Li-CO₂ battery with well-designed, hierarchical porous, and free-standing In₂S₃@CNT/SS (ICS) as a bifunctional photoelectrode to accelerate both the CO₂ reduction and evolution reactions (CDRR and CDER) is presented. The photoinduced Li-CO₂ battery achieved a record-high discharge voltage of 3.14 V, surpassing the thermodynamic limit of 2.80 V, and an ultra-low charge voltage of 3.20 V, achieving a round trip efficiency of 98.1 %, which is the highest value ever reported (<80 %) so far. These excellent properties can be ascribed to the hierarchical porous and free-standing structure of ICS, as well as the key role of photogenerated electrons and holes during discharging and charging processes. A mechanism is proposed for pre-activating CO₂ by reducing In³⁺ to In⁺ under light illumination. The mechanism of the bifunctional light-assisted process provides insight into photoinduced Li-CO₂ batteries and contributes to resolving the major setbacks of the system.     

Hierarchical Mn3O4 Anchored on 3D Graphene Aerogels via C−O−Mn Linkage with Superior Electrochemical Performance for Flexible Asymmetric Supercapacitor

Flexible asymmetric supercapacitors are more appealing in flexible electronics because of high power density, wide cell voltage, and higher energy density than symmetric supercapacitors in aqueous electrolyte. In virtues of excellent conductivity, rich porous structure and interconnected honeycomb structure, three dimensional graphene aerogels show great potential as electrode in asymmetric supercapacitors. However, graphene aerogels are rarely used in flexible asymmetric supercapacitors because of easily re-stacking of graphene sheets, resulting in low electrochemical activity. Herein, flower-like hierarchical Mn₃O₄ and carbon nanohorns are incorporated into three dimensional graphene aerogels to restrain the stack of graphene sheets, and are applied as the positive and negative electrode for asymmetric supercapacitors devices, respectively. Besides, a strong chemical coupling between Mn₃O₄ and graphene via the C-O-Mn linkage is constructed and can provide a good electron-transport pathway during cycles. Consequently, the asymmetric supercapacitor device shows high rate cycle stability (87.8 % after 5000 cycles) and achieves a high energy density of 17.4 μWh cm⁻² with power density of 14.1 mW cm⁻² (156.7 mW cm⁻³) at 1.4 V.     

Flexible and Epitaxial Metal Oxide Thin Film Growth by Photoreaction Processing for Electrical and Optical Applications

This review summarizes the use of photoreactions that replace conventional heating processes for growing oxide thin films from chemical solutions. In particular, this review outlines key variables in photoreactions that affect epitaxial and polycrystalline thin film growth, including precursor materials, laser wavelength, laser fluence, and carbon. In addition, the features of the photoreaction process that can be controlled at a low temperature by oxygen non-stoichiometry are examined. Likewise, functions that are neither achieved by developing a gradient structure nor controlled by a thermal equilibrium reaction are detailed. Two new concepts are presented, known as photoreaction of nanoparticles (PRNP) and photoreaction of a hybrid solutions (PRHS), in which crystal nuclei are pre-dispersed in a metal–organic compound film. This method has successfully produced flexible phosphor films used as resistor or thermistor electronic components. Finally, thin film growth using different light sources such as flash lamps and femtosecond lasers (fs) is explored.