不同Ni含量NiCoAl LDH的制备及CNT/Ni0.3CoAl LDH材料的电化学性能

利用水热法一步合成了不同镍、钴元素比例的镍钴铝层状氢氧化物(NiCoAl LDH),并探究了不同Ni元素含量的NiCoAl LDH的电化学性能,在Ni和Co的物质的量之比为3:7时,Ni_(0.3)CoAl LDH具有最优电化学性能。晶格中部分Ni元素被Co元素代替有利于降低氧化电势,提高材料的化学可逆性。然后通过水热法将CNT与Ni_(0.3)CoAl LDH复合,CNT的复合提高了材料的导电性。CNT/Ni_(0.3)CoAl LDH在1 A·g~(-1)的电流密度下比容量为1 332 F·g~(-1),电流密度为10 A·g~(-1)时比容量保持率为60.4%。在5A·g~(-1)的电流密度下循环3 000圈容量保持率为87.6%。     

The pseudocapacitance mechanism of graphene/CoAl LDH and its derivatives:Are all the modifications beneficial?

Cobalt-Aluminum layered double hydroxide(CoAl LDH) is a hopeful electrode material due to the advantage of easy modifiability for preparing LDH-based derivatives.However,there is short of modification methods to prepare the Co-based derivatives from CoAl LDH and also short of an intuitive perspective to analyze the pseudocapacitance mechanism of CoAl LDH and its derivatives.Herein,Graphene/CoAl LDH and its derivatives including Graphene/CoS,Graphene/CoS-1,Graphene/CoOOH,Graphene/CoP were prepared by reasonably using alkali etching treatment,sulfofication and phosphorization.The specific capacitance of Graphene/CoAl LDH,Graphene/CoS,Graphene/CoS-1,Graphene/CoOOH,Graphene/CoP at1 A g^-1 are 260.7,371.3,440.8,61.4 and 122.2 F g^-1,especially.The pseudocapacitance mechanism of Graphene/CoAl LDH and its derivatives was analyzed.Due to the positive effect of sulfofication on the electrical conductivity of GO and cobalt sulfide,the Graphene/CoS and Graphene/CoS-1 exhibit the optimal electrochemical performance and superior rate capability.In addition,due to the repulsion effect between Graphene and OH-,the Graphene/CoAl LDH exhibits optimal cycling stability of 224.1% capacitance retention after 20000 cycles.Besides,the reason of terrible specific capacitance of Graphene/CoOOH is that the presence of H bond in interlayer of CoOOH inhibits the interaction between Co3+ and OHspecies.Hence,not all modifications will increase the specific capacitance of the electrode materials.Overall,this work provides us with a detailed analysis of the electrochemical mechanism and correlation of CoAl LDH and its derivatives from the perspective of crystal structure and composition.     

Layered Al‐substituted Cobalt Hydroxides/GO Composites for Electrode Materials of Supercapacitors

In this work, Al‐substituted α‐Co(OH)₂/GO composites with supercapacitive properties were prepared by chemical co‐precipitated method in which cobalt nitrate and aluminum nitrate were used as the raw material, and graphite oxide was employed as carrier. The as‐prepared materials were characterized by X‐ray diffraction (XRD), field emission scanning electron microscopy (FESEM) and fourier transform infrared spectroscopy (FT‐IR). Cyclic voltammetry (CV) and galvanostatic charge/discharge measurements showed that the Al‐substituted α‐Co(OH)₂/GO electrode material had excellent electrochemical capacitance. The specific capacitance of 1137 F·g⁻¹ was achieved in 6 mol/L KOH solution at a current density of 1 A·g⁻¹ within a potential range of 0–0.5 V. Moreover, only 12% losses of the initial specific capacitance were found after 500 cycles at a current density of 1 A·g⁻¹.     

Copper sulfide nanoneedles on CNT backbone composite electrodes for high-performance supercapacitors and Li-S batteries

Hierarchical-structured copper sulfide nanoneedles were grown on multi-walled carbon nanotube backbone (denoted as CuS@CNT) as electrodes for supercapacitors via a facile template-based hydrothermal conversion approach and further by simply impregnating sulfur into CuS@CNT (S@CuS@CNT) as electrodes for Li-S batteries. The electrochemical measurements showed that the resultant CuS@CNT composite electrodes deliver outstanding electrochemical performance with a specific capacitance up to 566.4 F g^?1 and cyclic stability of 94.5 % of its initial capacitance after 5000 cycles at a current density of 1 A g^?1. A synergistic effect arising from the unique hierarchical structure was responsible for the electrode performance, including a large surface area of 49.3 m² g^?1 and active CuS ultrafine nanoneedles firmly bonded to the highly conductive carbon nanotube (CNT) backbone. When used as an electrode material for Li-S batteries, the S@CuS@CNT (S content 59 wt%) exhibited satisfying electrochemical performance. The S@CuS@CNT electrode showed that coulombic efficiency was close to 100 % and capacity maintained more than 500 mA h g^?1 with progressive cycling up to more than 100 cycles even at a high current density. This strategy of stabilizing S with a small amount of copper sulfide nanoneedles can be a very promising method to prepare free-standing cathode material for high-performance Li-S batteries. The fabrication strategy presented here is low cost, facile, and scalable, which can be considered as a promising material for large-scale energy storage device. In particular, the use of CNT as backbone for the growth of active materials presents many potential merits owing to its lightweight, biodegradable, and stretchable characteristics.     

Preparation of a NiAl‐Oxide@Polypyrrole Composite for High‐Performance Supercapacitors

A core‐shell NiAlO@polypyrrole composite (NiAlO@PPy) with a 3D “sand rose”‐like morphology was prepared via a facile in situ oxidative polymerization of pyrrole monomer, where the role of PPy coating thickness was investigated for high‐performance supercapacitors. Microstructure analyses indicated that the PPy was successfully coated onto the NiAlO surface to form a core‐shell structure. The NiAlO@PPy exhibited a better electrochemical performance than pure NiAlO, and the moderate thickness of the PPy shell layer was beneficial for expediting the electron transfer in the redox reaction. It was found that the NiAlO@PPy₅ prepared at 5.0 mL L^?1 addition amount of pyrrole monomer demonstrated the best electrochemical performance with a high specific capacitance of 883.2 F g^?1 at a current density of 1 A g^?1 and excellent capacitance retention of 91.82 % of its initial capacitance after 1000 cycles at 3 A g^?1. The outstanding electrochemical performance of NiAlO@PPy₅ were due to the synergistic effect of NiAlO and PPy, where the uniform network‐like PPy shell with the optimal thickness made electrolyte ions more easily accessible for faradic reactions. This work provided a simple approach for designing organic–inorganic core‐shell materials as high‐performance electrode materials for electrochemical supercapacitors.     

Synthesis of micro- and mesoporous carbon spheres for supercapacitor electrode

Micro- and mesoporous carbon spheres (MMCSs) are synthesized by the polymerization of colloidal silica-entrapped resorcinol/formaldehyde in the presence of ammonia as catalyst, followed by carbonization, sodium hydroxide (NaOH) etching to remove silica template, and potassium hydroxide (KOH) activation. The morphology and microstructure are characterized by scanning electron microscopy, transmission electron microscopy, and nitrogen adsorption–desorption. The results show that a typical sample (denoted as MMCS-3) unites the characteristics of regular spherical shape (uniform diameters of 500 nm), high specific surface area (1,620 m² g^?1), large pore volume (1.037 cm³ g^?1), and combined micropores and mesopores (11.0 nm), which endows MMCS-3 good electrochemical performance. MMCS-3 as supercapacitor electrode shows a specific capacitance of 314 F g^?1 under a current density of 0.5 A g^?1 and low internal resistance of 0.2 Ω in 6 M KOH aqueous solution. The electrochemical capacitance still retains 198 F g^?1 at a high current density of 10 A g^?1. After 500 cycle numbers of galvanostatic charge/discharge at 0.5 A g^?1, MMCS-3 electrode still remains the specific capacitance of 301 F g^?1 with the retention of 96 %. This study highlights the potential of well-designed MMCSs as electrodes for widespread supercapacitor applications.     

Formation of Double‐Shelled Zinc–Cobalt Sulfide Dodecahedral Cages from Bimetallic Zeolitic Imidazolate Frameworks for Hybrid Supercapacitors

Complex metal–organic frameworks used as precursors allow design and construction of various nanostructured functional materials which might not be accessible by other methods. Here, we develop a sequential chemical etching and sulfurization strategy to prepare well‐defined double‐shelled zinc–cobalt sulfide (Zn‐Co‐S) rhombic dodecahedral cages (RDCs). Yolk‐shelled zinc/cobalt‐based zeolitic imidazolate framework (Zn/Co‐ZIF) RDCs are first synthesized by a controlled chemical etching process, followed by a hydrothermal sulfurization reaction to prepare double‐shelled Zn‐Co‐S RDCs. Moreover, the strategy reported in this work enables easy control of the Zn/Co molar ratio in the obtained double‐shelled Zn‐Co‐S RDCs. Owing to the structural and compositional benefits, the obtained double‐shelled Zn‐Co‐S RDCs exhibit enhanced performance with high specific capacitance (1266 F g⁻¹ at 1 A g⁻¹), good rate capability and long‐term cycling stability (91 % retention over 10,000 cycles) as a battery‐type electrode material for hybrid supercapacitors.     

线状全固态CNTF@ZnCo-OH//CNTF@RGO超级电容器的制备与电化学性能

采用电化学沉积在碳纳米管纤维上复合锌钴氢氧化物纳米片（CNTF@ZnCo-OH）,并研究其电化学性能。实验结果表明CNTF@ZnCo-OH电极在2 A·g^-1的电流密度下比电容为748 F·g^-1,在10 A·g^-1的电流密度下循环2 000圈以后,比电容保持率高达110.4%。该优异循环性能得益于碳纳米管纤维基底的网络结构和ZnCo-OH的纳米片状结构。以CNTF@RGO（石墨烯）为负极、CNTF@ZnCo-OH为正极,组装线状全固态非对称CNTF@ZnCo-OH//CNTF@RGO超级电容器。该器件在0.5 A·g^-1电流密度下比电容为70 F·g^-1,2 000次循环后电容保持率为79.6%,并且在不同的弯曲状态下保持电化学性能不变,具有优良的机械稳定性。该非对称线状器件可以在0.8~1.4 V之间工作,其能量密度高达19.1 Wh·kg^-1,对应的功率密度为1 400.3 W·kg^-1。2个30 mm长的线状器件可持续点亮LED灯10 s。     

Cobalt ion-doped polyaniline,poly(N-methylaniline), and poly(N-ethylaniline): electrosynthesis and characterisation using electrochemical methods in acidic solutions

Cobalt ion (Co²⁺)-doped polyaniline (PANI-Co), poly(N-methylaniline) (PNMA-Co), and poly(N-ethylaniline) (PNEA-Co) films were synthesised electrochemically on a pencil graphite electrode (PGE) and their electrochemical properties were investigated for supercapacitor applications. The polymer film-coated electrodes (PGE/PANI-Co, PGE/PNMA-Co, and PGE/PNEA-Co) thus obtained were characterised by scanning electron microscopy (SEM) and different electrochemical methods. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) measurements were employed in 0.1 M H₂SO₄ solution to calculate the specific capacitance (C _S) values of the electrodes. The maximum C _S of 192.94 F g^?1, 139.83 F g^?1, and 47.12 F g^?1 were achieved for PGE/PANI-Co, PGE/PNMA-Co, and PGE/PNEA-Co at 1 mV s^?1, respectively. On the other hand, the charge/discharge stability of the electrodes was analysed using the repeating chronopotentiometry (RCP) method. The RCP measurements indicate that the electrodes could be used as an electrode active material for low voltage supercapacitor applications.     

Porous cobalt hydroxide film electrodeposited on nickel foam with excellent electrochemical capacitive behavior

A new porous cobalt hydroxide film has been successfully electrodeposited on nickel foam from 0.1?M cobalt nitrate electrolyte at ?1.0?V vs. SCE without adding any surfactant. The microstructure and surface morphology of prepared cobalt hydroxide films were physically characterized by X-ray diffraction analysis and scanning electron microscopy. The results indicate that an interlaced network structure was obtained. The effects of electrodeposition time, deposition potential, and different substrates on the specific capacitance and microstructure of prepared porous ??-Co(OH)₂ thin film were systematically studied. The results indicate that the film deposited on nickel foam at ?1.0?V has excellent electrochemical properties. A maximum specific capacitance of 1473?F?g^?1 could be achieved at a current density of 2?A?g^?1.     

Electrochemical Properties of Yolk–Shell‐Structured Zn–Fe–S Multicomponent Sulfide Materials with a 1:2 Zn/Fe Molar Ratio

Yolk–shell‐structured Zn–Fe–S multicomponent sulfide materials with a 1:2 Zn/Fe molar ratio were prepared applying a sulfidation process to ZnFe₂O₄ yolk–shell powders. The Zn–Fe–S powders had mixed sphalerite (Zn,Fe)S and hexagonal FeS crystal structures. The discharge capacities of the Zn–Fe–S powders sulfidated at 350 °C at a constant current density of 500 mA g^?1 for the first, second, and fiftieth cycles were 1098, 912, and 913 mA h g^?1, respectively. The powders exhibited a high discharge capacity of 602 mA h g^?1 even at the high current density of 10 A g^?1. The synergistic effect of yolk–shell structure and multicomponent composition improved the electrochemical properties of Zn–Fe–S powders.     

Preparation of NiAl double hydroxide@polypyrrole materials for high‐performance supercapacitors

A novel NiAl double hydroxide@polypyrrole (LDH@PPy) core–shell material was designed and fabricated by a facile in situ oxidative polymerization of pyrrole (Py) monomer. The microstructure and morphology of the LDH@PPy composites were determined by X‐ray diffractometer, Fourier transform infrared (FTIR), scanning electron microscopy/transmission electron microscopy, and thermogravimetric and differential thermal, revealing that the polypyrrole (PPy) was successfully coated onto the surface of the NiAl‐LDH (LDH) core and the loading amount of PPy impacted the thickness and the dispersion of the conductive PPy shell. The electrochemical performances of the LDH@PPy composites were also evaluated by cyclic voltammogram, electrochemical impedance spectroscopy, and galvanostatic charge–discharge measurements. The results indicated that the supercapacitor performances were attributed to the synergy of unique core–shell heterostructure and each individual component, where the LDH core provided the high‐energy storage capacity and the PPy shell with networks had high electronic conductivity. These shorted the ion diffusion pathway and made electrolyte ions more easily accessible for faradic reactions to enhance the electrochemical performance of the LDH@PPy composites. It was found that the LDH@PPy composite (LDH@PPy₇) fabricated at 7 mL?L^?1 of Py monomer feed exhibiting the best electrochemical performances with high specific capacitance of 437.5 F?g^?1 at 2 A?g^?1 and excellent capacitance retention of about 91% after 1000 cycles. The work provides a simple approach for designing organic–inorganic core–shell materials with potential application in supercapacitors. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 1653–1662     

Synthesis of Cobalt Sulfide Multi‐shelled Nanoboxes with Precisely Controlled Two to Five Shells for Sodium‐Ion Batteries

We report the synthesis of cobalt sulfide multi‐shelled nanoboxes through metal–organic framework (MOF)‐based complex anion conversion and exchange processes. The polyvanadate ions react with cobalt‐based zeolitic imidazolate framework‐67 (ZIF‐67) nanocubes to form ZIF‐67/cobalt polyvanadate yolk‐shelled particles. The as‐formed yolk‐shelled particles are gradually converted into cobalt divanadate multi‐shelled nanoboxes by solvothermal treatment. The number of shells can be easily controlled from 2 to 5 by varying the temperature. Finally, cobalt sulfide multi‐shelled nanoboxes are produced through ion‐exchange with S^2? ions and subsequent annealing. The as‐obtained cobalt sulfide multi‐shelled nanoboxes exhibit enhanced sodium‐storage properties when evaluated as anodes for sodium‐ion batteries. For example, a high specific capacity of 438 mAh g^?1 can be retained after 100 cycles at the current density of 500 mA g^?1.     

Hybrid Hydrogels of Porous Graphene and Nickel Hydroxide as Advanced Supercapacitor Materials

Graphene‐based hydrogels can be used as supercapacitor electrodes because of their excellent conductivity, their large surface area and their high compatibility with electrolytes. Nevertheless, the large aspect ratio of graphene sheets limits the kinetics of processes occurring in the electrode of supercapacitors. In this study, we have introduced in‐plane and out‐of‐plane pores into a graphene–nickel hydroxide (Ni(OH)₂) hybrid hydrogel, which facilitates charge and ion transport in the electrode. Due to its optimised chemistry and architecture, the hybrid electrode demonstrates excellent electrochemical properties with a combination of high charge storage capacitance, fast rate capability and stable cycling performance. Remarkably, the Ni(OH)₂ in the hybrid contributes a capacitance as high as 3138.5 F g^?1, which is comparable to its theoretical capacitance, suggesting that such structure facilitates effectively charge‐transfer reactions in electrodes. This work provides a facile pathway for tailoring the porosity of graphene‐based materials for improved performances. Moreover, this work has also furthered our understanding in the effect of pore and hydrogel structures on the electrochemical properties of materials.     

Core–Shell Carbon‐Coated CuO Nanocomposites: A Highly Stable Electrode Material for Supercapacitors and Lithium‐Ion Batteries

Herein we present a simple method for fabricating core–shell mesostructured CuO@C nanocomposites by utilizing humic acid (HA) as a biomass carbon source. The electrochemical performances of CuO@C nanocomposites were evaluated as an electrode material for supercapacitors and lithium‐ion batteries. CuO@C exhibits an excellent capacitance of 207.2 F g^?1 at a current density of 1 A g^?1 within a potential window of 0–0.46 V in 6 M KOH solution. Significantly, CuO electrode materials achieve remarkable capacitance retentions of approximately 205.8 F g^?1 after 1000 cycles of charge/discharge testing. The CuO@C was further applied as an anode material for lithium‐ion batteries, and a high initial capacity of 1143.7 mA h g^?1 was achieved at a current density of 0.1 C. This work provides a facile and general approach to synthesize carbon‐based materials for application in large‐scale energy‐storage systems.     

Electrochemical performance of Co–Al layered double hydroxide nanosheets mixed with multiwall carbon nanotubes

Regular hexagonal Co–Al layered double hydroxides (Co–Al LDH) were synthesized by urea-induced homogeneous precipitation. This material proved to be nanosheets by scanning electron microscopy and X-ray diffraction measurements. The electrochemical capacitive behavior of the nanosheets in 1 M KOH solution were evaluated by constant current charge/discharge and cyclic voltammetric measurements, showing a large specific capacitance of 192 F·g⁻¹ even at the high current density of 2 A·g⁻¹. When multiwall carbon nanotubes (MWNTs) were mixed with the Co–Al LDH, it was found that the specific capacitance and long-life performance of all composite electrodes at high current density are superior to pure LDH electrode. When the added MWNTs content is 10 wt%, the specific capacitance increases to 342.4 F·g⁻¹ and remains at a value of 304 F·g⁻¹ until the 400th cycle at 2 A·g⁻¹, showing that this is a promising electrode material for supercapacitors working at heavy load. According to the electrochemical impedance spectra, MWNTs greatly increase the electronic conductivity between MWNTs and the surface of Co–Al LDH, which consequently facilitates the access of ions in the electrolyte and electrons to the electrode/electrolyte interface.     

A Microwave Synthesis of Mesoporous NiCo2O4 Nanosheets as Electrode Materials for Lithium‐Ion Batteries and Supercapacitors

A facile microwave method was employed to synthesize NiCo₂O₄ nanosheets as electrode materials for lithium‐ion batteries and supercapacitors. The structure and morphology of the materials were characterized by X‐ray diffraction, field‐emission scanning electron microscopy, transmission electron microscopy and Brunauer–Emmett–Teller methods. Owing to the porous nanosheet structure, the NiCo₂O₄ electrodes exhibited a high reversible capacity of 891 mA h g^?1 at a current density of 100 mA g^?1, good rate capability and stable cycling performance. When used as electrode materials for supercapacitors, NiCo₂O₄ nanosheets demonstrated a specific capacitance of 400 F g^?1 at a current density of 20 A g^?1 and superior cycling stability over 5000 cycles. The excellent electrochemical performance could be ascribed to the thin porous structure of the nanosheets, which provides a high specific surface area to increase the electrode–electrolyte contact area and facilitate rapid ion transport.     

Design of high-performance core-shell hollow carbon nanofiber@nickel-cobalt double hydroxide composites for supercapacitive energy storage

The supercapacitive performances of supercapacitor mainly depend on the physical nanostructure and micro-morphology of electrode materials. Here, we demonstrated the design, synthesis and electrochemical performances of core-shell hollow carbon nanofiber@nickel-cobalt-layered double hydroxide (HCNF@ Ni_0.67Co_0.33-LDH) nanocomposites with an optimized Ni/Co molar ratio of 2:1. The HCNF was used as superiorly conductive core to sustain the nanoporous silky Ni_0.67Co_0.33-LDH shell, which can efficiently provide fast transport pathways for electrons and electrolyte ions. The outstanding specific capacitance of 2486 F g^?1 at 1 A g^?1 based on galvanostatic charge-discharge curves were acquired for the highly electroactive HCNF@Ni_0.67Co_0.33-LDH. Furthermore, the HCNF@Ni_0.67Co_0.33-LDH electrode delivered a distinguished rate capability with a specific capacitance of 1890 F g^?1 even at 15 A g^?1. Notably, an asymmetric supercapacitor with HCNF@Ni_0.67Co_0.33-LDH as cathode and HCNF as anode was devised, which presented a prominent specific capacitance of 228 F g^?1, good energy density of 62.1 Wh kg^?1, and impressive cycling stability (90.6% capacitance retention after 10,000 cycles).     

Fabrication of Phosphorus-Doped Cobalt Silicate with Improved Electrochemical Properties

The development of electrode materials for supercapacitors (SCs) is greatly desired, and this still poses an immense challenge for researchers. Cobalt silicate (Co₂SiO₄, denoted as CoSi) with a high theoretical capacity is deemed to be one of the sustainable electrode materials for SCs. However, its achieved electrochemical properties are still not satisfying. Herein, the phosphorus (P)-doped cobalt silicate, denoted as PCoSi, is synthesized by a calcining strategy. The PCoSi exhibits 1D nanobelts with a specific surface area of 46 m²∙g⁻¹, and it can significantly improve the electrochemical properties of CoSi. As a supercapacitor’s (SC’s) electrode, the specific capacitance of PCoSi attains 434 F∙g⁻¹ at 0.5 A∙g⁻¹, which is much higher than the value of CoSi (244 F∙g⁻¹ at 0.5 A∙g⁻¹). The synergy between the composition and structure endows PCoSi with attractive electrochemical properties. This work provides a novel strategy to improve the electrochemical performances of transition metal silicates.     

MnO2 Nanosheets Grown on Nitrogen‐Doped Hollow Carbon Shells as a High‐Performance Electrode for Asymmetric Supercapacitors

A hierarchical hollow hybrid composite, namely, MnO₂ nanosheets grown on nitrogen‐doped hollow carbon shells (NHCSs@MnO₂), was synthesized by a facile in situ growth process followed by calcination. The composite has a high surface area (251 m²g^?1) and mesopores (4.5 nm in diameter), which can efficiently facilitate transport during electrochemical cycling. Owing to the synergistic effect of NHCSs and MnO₂, the composite shows a high specific capacitance of 306 F g^?1, good rate capability, and an excellent cycling stability of 95.2 % after 5000 cycles at a high current density of 8 A g^?1. More importantly, an asymmetric supercapacitor (ASC) assembled by using NHCSs@MnO₂ and activated carbon as the positive and negative electrodes exhibits high specific capacitance (105.5 F g^?1 at 0.5 A g^?1 and 78.5 F g^?1 at 10 A g^?1) with excellent rate capability, achieves a maximum energy density of 43.9 Wh kg^?1 at a power density of 408 W kg^?1, and has high stability, whereby the ASC retains 81.4 % of its initial capacitance at a current density of 5 A g^?1 after 4000 cycles. Therefore, the NHCSs@MnO₂ electrode material is a promising candidate for future energy‐storage systems.