超级电容器电极材料MnO_2纳米棒的制备及其电化学性能(英文)

以洋葱碳为还原剂,KMnO4为氧化剂,稀硫酸溶液为溶剂,采用水热法一步制备MnO2纳米棒.利用X射线衍射仪和透射电子显微镜分析了MnO2纳米棒的物相、结构、形貌;将MnO2纳米棒作为电极材料组装了超级电容器,采用电池测试系统测定了超级电容器的电化学性能.结果表明,所得到的产物为α-MnO2,其直径为5~10nm,长度为50~100nm;以MnO2纳米棒作为电极材料组装的超级电容器具有较高的比容量和稳定性,有望在超级电容器的研究和应用中得到推广.     

Polycationic oxides as potential electrode materials for aqueous-based electrochemical capacitors

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电化学电容器电极材料超细MnO2的制备及表征

高性能的电化学电容器具有极其重要和广阔的应用前景(1)。以RuO2等贵重金属氧化物为电极材料的电化学电容器已应用于多个领域(2),但昂贵的价格限制了它们更加广泛的应用。有些廉价金属氧化物也具有一定的氧化还原准电容,如Co3O4、NiO和MnO2等(1,3 6)。二氧化锰价格低廉,资源丰富,电化学性能好,其作为电化学电容器的活性材料具有更大的应用前景和价值。本文采用K2S2O8氧化MnSO4·H2O制得超细MnO2,并通过XRD、TEM和SEM测试对其进行表征,并研究了其在0 5mol/LNa2SO4水溶液中的循环伏安性能、恒流充放性能以及电容稳定性能。1…     

Advanced carbon electrode for electrochemical capacitors

Journal of Solid State Electrochemistry - Electrochemical capacitors are high-power energy storage devices having long cycle durability in comparison to secondary batteries. The energy storage...     

A hierarchical porous MnO2-based electrode for electrochemical capacitor

A hierarchical porous MnO₂-based electrode was prepared and its electrochemical performance for electrochemical capacitors was investigated. In this work, porous MnO₂ film with pore size of 2?C3?nm in diameter was deposited on a three-dimensional porous current collector by cathodic electrodeposition associated with subsequent controlled heat treatment at 200°C for 2?h. Transmission electron microscopy and X-ray photoelectron spectroscopy showed that the heat treatment has a great effect on the formation of the porous structure of MnO₂ layer, and the disordered porous structure was caused by dehydration during the heat treatment. Cyclic voltammetry and galvanostatic charge?Cdischarge tests showed that both energy and power densities are enhanced due to the unique hierarchical porous structure. The electrode delivers a high specific capacitance of 385?F?g^?1 at a high current density of 5?A?g^?1 within a potential window of ?0.05????0.85?V, and also exhibits excellent rate capability and electrochemical stability.     

Partially reduced graphite oxide as an electrode material for electrochemical double-layer capacitors

Partially reduced graphite oxide was prepared from graphite oxide by using synthetic graphite as precursor. The reduction of graphite oxide with a layer distance of 0.57?nm resulted in a reduction of the layer distance depending on the degree of reduction. Simultaneously the amount of oxygen functionalities in the graphite oxide was reduced, which was corroborated by elemental analysis and EDX. The electrochemical activation of the partially reduced graphite oxide was investigated for tetraethylammonium tetrafluoroborate in acetonitrile and in propylene carbonate. The activation potential depends significantly on the degree of reduction, that is, on the graphene-layer distance and on the solvent used. The activation potential decreased with increasing layer distance for both positive and negative activation. The resulting capacitance after activation was found to be affected by the layer distance, the oxygen functionalities and the used electrolyte. For a layer distance of 0.43?nm and with acetonitrile as the solvent, a differential capacitance of 220?Fg(-1) was achieved for the discharge of the positive electrode near the open-circuit potential and 195?Fg(-1) in a symmetric full-cell assembly.     

New ceramic-carbon composites for electrodes for electrochemical capacitors

A new class of composite materials is introduced. Fine powders of silica, titania, Y-modified zirconia, and three types of alumina were pressed and sintered to form porous monoliths with relatively uniform pore structure. Carbon was then deposited in the pores of such monoliths by thermal decomposition of dichloromethane, cyclohexene, and glucose. The structure of the carbon deposit was studied by low-temperature nitrogen adsorption and by thermal analysis. The composite materials were used as electrodes in electrochemical capacitors with 1-ethyl-3-methylimidazolium trifluoromethylsulfonate (a low-temperature ionic liquid) as the electrolyte. High capacitances were observed for glucose-derived materials, which had high specific surface areas.     

MnO2/TiN heterogeneous nanostructure design for electrochemical energy storage

MnO(2)/TiN nanotubes are fabricated using facile deposition techniques to maximize the surface area of the electroactive material for use in electrochemical capacitors. Atomic layer deposition is used to deposit conformal nanotubes within an anodic aluminium oxide template. After template removal, the inner and outer surfaces of the TiN nanotubes are exposed for electrochemical deposition of manganese oxide. Electron microscopy shows that the MnO(2) is deposited on both the inside and outside of TiN nanotubes, forming the MnO(2)/TiN nanotubes. Cyclic voltammetry and galvanostatic charge-discharge curves are used to characterize the electrochemical properties of the MnO(2)/TiN nanotubes. Due to the close proximity of MnO(2) with the highly conductive TiN as well as the overall high surface area, the nanotubes show very high specific capacitance (662 F g(-1) reported at 45 A g(-1)) as a supercapacitor electrode material. The highly conductive and mechanically stable TiN greatly enhances the flow of electrons to the MnO(2) material, while the high aspect ratio nanostructure of TiN creates a large surface area for short diffusion paths for cations thus improving high power. Combining the favourable structural, electrical and energy properties of MnO(2) and TiN into one system allows for a promising electrode material for supercapacitors.     

Mesoporous MnO2 synthesized by hydrothermal route for electrochemical supercapacitor studies

Poorly crystalline mesoporous MnO₂, which is suitable for supercapacitor studies, is synthesized from neutral KMnO₄ aqueous solution by hydrothermal route. But it requires a high temperature (180 °C) and also a long reaction time (24 h). Addition of a tri-block copolymer, namely, poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) (P123), which is generally used as a soft template for the synthesis of nano-structured porous materials, reduces the hydrothermal temperature to 140 °C and also reaction time to 2 h. When the reaction time is increased, the product morphology changes from nanoparticles to nanorods with a concomitant decrease in BET surface area. Also, the product tends to attain crystallinity. The electrochemical capacitance properties of MnO₂ synthesized under varied hydrothermal conditions are studied in 0.1 M Na₂SO₄ electrolyte. A specific capacitance of 193 F?g^?1 is obtained for the mesoporous MnO₂ sample consisting of nanoparticle and nanorod mixed morphology synthesized in 6 h using P123 at 140 °C.     

Galvanostatically electroplated MnO2 nanoplate-type electrode for potential electrochemical pseudocapacitor application

Journal of Solid State Electrochemistry - A manganese oxide (MnO2) nanoplate-type electrode has been prepared using galvanostatic electrodeposition method with an aqueous manganese sulfate solution...     

Preparation of MnO2 and MnO2/carbon nanotubes nanocomposites with improved electrochemical performance for lithium ion batteries

Journal of Solid State Electrochemistry - Manganese dioxide (MnO2) nanomaterials and manganese dioxide/carbon nanotubes (MnO2/CNTs) nanocomposites were prepared by chemical precipitation and...     

Composite electrodes of electrochemical capacitors based on carbon materials with different structure

For composite electrodes based on active carbon DCL Supra 30, ordered mesoporous carbon, and synthetic carbon material Sibunit, the electrical double layer capacitance is studied. The original carbon samples are characterized by the methods of gas adsorption, X-ray diffraction, and transmission electron microscopy. The mesoporous structure of the material synthesized by the template method provides the maximum rate of ion transport in pores and demonstrates an insignificant decrease in the specific capacitance (9.5% in an aqueous electrolyte and 1.1% in an nonaqueous electrolyte) with an increase in the polarizing current.     

Preparation of monodisperse carbon nanospheres for electrochemical capacitors

The efficiently hydrothermal route using sucrose without any catalysts is employed to prepare the uniform carbon spheres. The monodisperse 100–150 nm carbon spheres are obtained with the activation treatment in molten KOH. The carbon spheres are characterized by transmission electron microscope, X-ray diffraction, N₂ adsorption, Raman spectroscopy and electrochemical techniques. The relationships of specific capacitance and surface properties of carbon spheres are investigated. A single electrode of carbon nanosphere materials performs excellent specific capacitance (328 F g⁻¹), area capacitance (19.2 μF cm⁻²) and volumetric capacitance (383 F cm⁻³).     

Mesoporous carbon capsules as electrode materials in electrochemical double layer capacitors

The performance of mesoporous carbon capsules as electrode materials in electrochemical double layer capacitors (EDLCs) was evaluated in the presence of a variety of electrolytes, including room temperature ionic liquids (ILs).     

Synergistic chemical and electrochemical strategy for high-performance Zn//MnO2 batteries

Aqueous rechargeable Zn//MnO₂ batteries have been considered as the promising candidate for future energy storage system due to their economic and environmental merits. However, the high-performance Zn//MnO₂ batteries are plagued by poor sluggish reaction kinetics and capacity degradation due to the strong electrostatic interactions and complicated reaction process. Herein, the synergistic effect of atom defects engineering and phase transformation mechanism is confirmed as the effective strategy to enhance ion/charge transfer kinetics and structural stability. Defects gradient controlling and electrochemically induced phase transformation from spinel to layered structure render the aqueous Zn//λ-MnO₂ system delivers a high discharge capacity of 285 mAh/g and capacity retention of 81% after 500 cycles.     

Persulfate treatment as a method of modifying carbon electrode material for aqueous electrochemical capacitors

The activated carbon was modified by the wet method with a solution of ammonium persulfate at room temperature with different times. Kinetics studies showed that the modification took place mostly during the first 60 min of the process. The physicochemical properties of the obtained carbon were evaluated by thermogravimetric studies, Raman and FTIR spectroscopy, elementary and BET analyses. Furthermore, the fabricated material was applied in symmetric capacitors operated on the three aqueous electrolytes (1 M H₂SO₄, 6 M KOH and 1 M Na₂SO₄). Mild conditions of the modification process are optimal to obtain electroactive groups on the carbon surface, which make this material useful in a supercapacitor application. In our studies, we noticed that this type of functional groups mainly appears on the surface of the activated carbon, in the first oxidation stage. With prolonged oxidation, they may transform into undesirable groups. The results show that this kind of modification improves the capacity of all the tested supercapacitors. It was connected mainly with an increase of the carbon material’s wettability and in the case of capacitor operated in acid and base electrolytes due to a redox reaction of oxygen functional groups.

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Graphical abstract Persulfate treatment of carbon material.

     

Activated carbon/graphene composites with high-rate performance as electrode materials for electrochemical capacitors

Glucose-derived activated carbon (GAC)/reduced graphene oxide (RGO) composites are prepared by pre-carbonization of the precursors (aqueous mixture of glucose and graphene oxide) and KOH activation of the pyrolysis products. The effect of the mass ratio of graphene oxide (GO) in the precursor on the electrochemical performance of GAC/RGO composites as electrode materials for electrochemical capacitors is investigated. It is found that the thermally reduced graphene oxide sheets serves as a wrinkled carrier to support the activated carbon particles after activation. The pore size distribution and surface area are depended on the mass ratio of GO. Besides, the rate capability of GAC is improved by the introduction of GO in the precursor. The highest specific capacitance of 334 F g^?1 is achieved for the GAC/RGO composite prepared from the precursor with a GO mass ratio of 3 %.     

Bismuth oxide coated amorphous manganese dioxide for electrochemical capacitors

With MnSO₄, NaOH and K₂S₂O₈ as the raw materials, the amorphous and δ-type manganese dioxide (MnO₂) is separately prepared by using different chemical precipitation-oxidation methods. The results of charge–discharge and electrochemical impedance spectroscopy (EIS) tests show that (i) the specific capacitance of the amorphous MnO₂ reaches to 301.2 F g⁻¹ at a current density of 200 mA g⁻¹ and its capacitance retention rate after 2000 cycles is 97%, which is obviously higher than 250.8 F g⁻¹ and 71% of the δ-type one, respectively; (ii) good electrochemical capacitance properties of the amorphous MnO₂ should be contributed to easy insertion/extraction of ions within the material; (iii) when 5 wt% Bi₂O₃ is coated on the amorphous MnO₂, its specific capacitance increases to 352.8 F g⁻¹ and the capacitance retention rate is 90% after 2000 cycles.