High performance fiber-shaped flexible asymmetric supercapacitor based on MnO2 nanostructure composited with CuO nanowires and carbon nanotubes

The demand for wearable electronics has greatly promoted the development of flexible supercapacitors. Herein, we develop a series of approaches to fabricate a fiber-shaped supercapacitor with flexibility. In the device, CuO@MnO₂, carbon nanotube (CNT)@MnO₂ and PVA-KOH are respectively used as inner electrode, outer electrode and gel electrolyte. The approaches including in-situ growth of CNTs, in-situ etching removal of SiO₂ template and in-situ filling of gel electrolyte via hydrothermal process are explored to protect the device from structure damage caused by external forces and to maximize effective contact areas between active electrode materials and gel electrolyte. The optimized supercapacitor of copper wire@CuO@MnO₂//PVA-KOH//CNT@MnO₂ demonstrates a good capacitive performance (5.97 F cm^?3) and exhibits a high energy density (0.38 mWh cm^?3) at a power density of 25.5 mW cm^?3. In addition, it has perfect cycling stability (77% after 2000 cycles) with excellent flexibility. Therefore, this work will provide desirable processes to construct fiber-shaped supercapacitors as flexible and wearable energy storage devices.     

Fabrication of a fibrous MnO2@MXene/CNT electrode for high-performance flexible supercapacitor

As shining stars of 2-dimensional materials, transition metal carbides (MXene) and transition metal oxides have attracted much interest in various energy fields due to their excellent conductive and electrochemical properties. However, big challenge still remains in the accessibility of high-performance fibrous electrodes for flexible supercapacitors. In this paper, MnO₂ nanorods are loaded on MXene sheets to obtain MnO₂@MXene composites by a facile hydrothermal method, which are subsequently coated on carbon nanotube fibers (CNTFs). With a fine control on morphology, the resulting MnO₂@MXene/CNTF electrode exhibits a high specific capacitance of 181.8 F/g at 1 A/g, a capacitance retention of 91% after 5000 charge-discharge cycles, as well as superb flexibility, i.e., neglected capacitance loss at a bending angle of 180°. The as-fabricated flexible composite fiber opens a new door for transition metal carbides and transition metal oxides with great potential in flexible electronics.     

Construction of spherical NiO@MnO2 with core-shell structure obtained by depositing MnO2 nanoparticles on NiO nanosheets for high-performance supercapacitor

The 3D spherical NiO@MnO₂ composites grown on Ni foam with core-shell structure were prepared by a hydrothermal process followed by a chemical bath deposition process, and then the mechanism improving the electrochemical performance of NiO by MnO₂ modification were investigated by the first-principles calculations for the first time. This core-shell structure promotes an efficient contact between electrolyte and active materials, and the distinct architecture can offer fast transfer channels of ion and electrons. The initial capacitances of NiO, NiO@MnO₂ (deposition time of MnO₂ is 20 min), NiO@MnO₂ (deposition time of MnO₂ is 30 min) and NiO@MnO₂ (deposition time of MnO₂ is 60 min) at 10 A g⁻¹ are 931.6, 1064.4, 1227.2 and 766.8 F g⁻¹, respectively. After 10000 cycles, the reversible capacitances attenuate to 352.8, 661.0, 1089.4 and 616.6 F g⁻¹, respectively. NiO@MnO₂ (deposition time of MnO₂ is 30 min) shows the most excellent reversible capacitance at each cycle and the highest retention rates after 10000 cycles among all samples. The first-principles calculation confirms that a strong interfacial interaction between NiO and MnO₂ can be generated, and then the atomic relaxations at the interface are rather small due to the well-matched interface and epitaxial bonding, resulting in a relatively small interfacial polarization of NiO@MnO₂ composites during cycling. The outstanding rate capability and cycle performance of NiO@MnO₂ (deposition time of MnO₂ is 30 min) electrode are attributed to the synergistic effect and particular 3 D architectures.     

Microfluidic fabrication of cationic curcumin nanoparticles as an anti-cancer agent

Curcumin nanoparticles of less than 50 nm in diameter are accessible using a continuous flow microfluidic rotating tube processor (RTP) under scalable conditions, at room temperature. A mixture of DDAB and Pluronic F127 renders higher stability of the curcumin nanoparticles in physiological pH 7.4 for up to eight hours. The nanoparticles have enhanced cytotoxicity in estrogens receptor negative and positive breast cancer cell lines compared with free curcumin.     

Binder-less fabrication,some surface studies,and enhanced electrochemical performance of Co,Cu-embedded MnO2 thin film electrodes for supercapacitor application

We report the fabrication of nanocystalline MnO₂ thin film-based electrode on a predeposited indium tin oxide (ITO) film on the glass substrate, using a binderless and simple two-electrode electrofabrication approach. Effects of Co and Cu incorporation on microstructural and electrochemical performance of the electrode were optimally and extensively investigated. The experimental results for the optimum fabrication conditions for Co@MnO₂ and Cu@MnO₂ and pure MnO₂ thin film-based electrode samples showed uniqueness in microstructural features, degrees of crystallinity and roughness, and high electrochemical energy storage performance. Co@MnO₂ film electrode exhibited remarkable specific capacitance (1068 Fg^-1) and areal capacity (25.78 mAh cm^?2) as against other electrode films (Cu@MnO₂ and pure MnO₂) which exhibited specific capacitances 837 and 438 F g^?1 and areal capacities 10.6 and 4.9 mAh cm^?2, respectively. Exceptional stabilities were also recorded for the composite samples (87.2% and 84.4% for Cu@MnO₂ and Co@MnO₂ thin film electrodes, respectively) against the pure MnO₂ film electrode sample (77.8%), after 2000 cycles. In addition, the short time constants (1.27 s and 1.31 s) were respectively realized for the fabricated Co@MnO₂ and Cu@MnO₂ electrode films as against the pure MnO₂ electrodes (4.35 s). These features observed in the composite electrode samples demonstrated an exhibition of faster ion response and higher rate capability by the samples. Moreover, the incorporation of Co into the MnO₂ electrode material relatively improved the supercapacitive activeness by enhancing the charge transition and transport.     

MnO2 depositing on the surface of hollow porous carbon microspheres for supercapacitor application

A supercapacitor electrode material was synthesized by using hollow carbon spheres prepared via high temperature sintering of dopamine hydrochloride and subsequent coating with MnO₂. SEM, TEM and analysis of energy pattern were used to characterize the structure, morphology and elemental composition of the material, which proved that the material had a good hollow structure and uniform surface morphology, and that MnO₂ was successfully coated on the surface of the carbon material. Electrochemical characterization using charge-discharge cycles at constant current and other methods show that the prepared materials have good specific capacitance and cycle stability, and have a specific capacitance of 198 F.g^?1 at a current of 1 A·g^?1. When the charge and discharge cycle is carried out at 10 A·g^?1 for 5000 cycles, the capacitance remains stable at more than 180 F·g^?1.     

一种生物炭基柔性固态超级电容器的制备及性能研究

利用固体农业废弃物玉米秸秆作为原料,经高温煅烧,KOH刻蚀获得具有较大比表面积的多孔生物炭材料,并采用粉末X射线衍射仪(XRD)、场发射扫描电镜(FE-SEM)、红外光谱(FT-IR)、拉曼光谱(Raman)以及比表面积和孔径分析仪(BET)等表征手段,研究其物理、化学结构和微观形貌。结果表明,所制备的生物炭材料具有发达的“微孔-中孔-大孔”三维贯通多级孔道结构,比表面积高达1228 m2·g^-1。将其作为电极材料,与H₂SO₄/PVA凝胶电解质可组装成为具有柔性的全固态超级电容器。利用循环伏安测试(CV)、恒电流充放电(GCD)以及交流阻抗测试(EIS)对柔性超级电容器电化学性能进行了测试。在电流密度为1.0 A·g^-1的条件下,其比容量可达125 F·g^-1。该器件具有良好的机械柔性和电化学稳定性,将其从0°弯曲至180°的过程中,比电容保持率约为93.5%;以不同弯曲角度将其连续弯折100次后,仍能保持较高的比电容。此外,在弯折角度180°、充放电电流密度为5.0 A·g^-1 的条件下经过500次循环充放电后,比电容值保持率约为95.6%,库仑效率约为94.9%。说明所制备的柔性超级电容器具有优异的充放电性能和长效循环稳定性。作为一种柔性、质轻、便携的储能装置,在可穿戴电子器件领域内具有潜在应用价值。同时该方法也为固体农业废弃物玉米秸秆的高附加值转化利用和新型绿色能源器件创新研制提供了新的技术途径。     

活性炭/二氧化锰纳米复合材料的合成及超级电容性能

以商业活性炭为载体,通过硝酸表面改性活性炭,引入含氧官能团,为棒状二氧化锰(MnO2)和活性炭的结合提供桥梁。采用化学沉淀法在炭表面反应生成纳米结构的棒状二氧化锰,制备二氧化锰/改性活性炭(MnO2/OAC)复合电极材料。采用扫描电镜(SEM)、X射线衍射(XRD)对其结构进行表征;采用循环伏安法、恒流充放电对其电化学性能进行研究。结果表明,生成的MnO2均匀地负载在碳的表面,颗粒的直径在20~50nm;在1mol/L的Na2SO4电解液中,MnO2/OAC6复合电极材料体现了极佳的比电容,达到369.7F/g。材料优异的电化学性能归功于活性炭发达的孔隙结构和MnO2提供的法拉第电容。     

Electrochemical fabrication of polyaniline/MnO2/graphite felt as free‐standing,flexible electrode for supercapacitors

Polyaniline/MnO₂/graphite felt (PMGF) composite, which can be used as a novel free‐standing, flexible electrode for supercapacitors, was fabricated via a facile electrochemical method. Polyaniline/graphite felt (PANI/GF) electrode was prepared by electropolymerization of PANI onto the GF. Subsequently, manganese dioxide (MnO₂) was electrodeposited on the surface of the PANI/GF electrode to prepare PMGF electrode. The microstructure and morphology of the as‐prepared samples were characterized by Fourier transform infrared spectra, X‐ray diffraction, scanning electron microscopy, and transmission electron microscopy. Specific surface area was examined using N₂ adsorption/desorption test. Cyclic voltammogram, chronopotentiometry techniques and electrochemical impedance spectroscopy were introduced to investigate the electrochemical performance of the composites. The PMGF electrode exhibited specific capacitance as high as about 630 F g⁻¹ at the current density of 0.5 A g⁻¹, which is much higher than that of PANI/MnO₂ composites reported previously. The high specific capacitance of PMGF may be attributed to the fact that the porous GF is a good conductive matrix for the dispersion of PANI/MnO₂ and it can facilitate easy access of electrolytes to the electrode, which results in enhancement of the electrochemical performance of the composite. Moreover, the specific capacitance of PMGF is much larger than that of MnO₂/GF (MGF), which may be ascribed to the participant of PANI, which contributes additional pseudocapacitance and electron transport path. POLYM. COMPOS., 34:819–824, 2013. © 2013 Society of Plastics Engineers     

The additive-free electrode based on the layered MnO2 nanoflowers/reduced,graphene oxide film for high performance supercapacitor

The MnO₂ nanoflowers/reduced graphene oxide composite is coated on a nickel foam substrate (denoted as MnO₂ NF/RGO @ Ni foam) via the layer by layer (LBL) self-assembly technology without any polymer additive, following the soft chemical reduction. The layered MnO₂ NF/RGO composite is uniformly anchored on the Ni foam skeleton to form the 3D porous framework, and the interlayers have access to lots of ions channels to improve the electron transfer and diffusion. This special construction of 3D porous structure is beneficial to the enhancement of electrochemical property. The specific capacitance is up to 246 F g⁻¹ under the current density of 0.5 A g⁻¹. After 1000 cycles, it can retain about 93%, exhibiting excellent cycle stability. The electrochemical impedance spectroscopy measurements confirm that MnO₂ NF/RGO @ Ni foam electrode has lower R_ESR and R_CT values when compared to MnO₂ @ Ni foam and RGO @ Ni foam. This study opens a new door to the preparation of composite electrodes for high performance supercapacitor.     

High performance of a solid-state flexible asymmetric supercapacitor based on graphene films

Solid-state flexible energy storage devices hold the key to realizing portable and flexible electronic devices. Achieving fully flexible energy storage devices requires that all of the essential components (i.e., electrodes, separator, and electrolyte) with specific electrochemical and interfacial properties are integrated into a single solid-state and mechanically flexible unit. In this study, we describe the fabrication of solid-state flexible asymmetric supercapacitors based on an ionic liquid functionalized-chemically modified graphene (IL-CMG) film (as the negative electrode) and a hydrous RuO(2)-IL-CMG composite film (as the positive electrode), separated with polyvinyl alcohol-H(2)SO(4) electrolyte. The highly ordered macroscopic layer structures of these films arising through direct flow self-assembly make them simultaneously excellent electrical conductors and mechanical supports, allowing them to serve as flexible electrodes and current collectors in supercapacitor devices. Our asymmetric supercapacitors have been optimized with a maximum cell voltage up to 1.8 V and deliver a high energy density (19.7 W h kg(-1)) and power density (6.8 kW g(-1)), higher than those of symmetric supercapacitors based on IL-CMG films. They can operate even under an extremely high rate of 10 A g(-1) with 79.4% retention of specific capacitance. Their superior flexibility and cycling stability are evident in their good performance stability over 2000 cycles under harsh mechanical conditions including twisted and bent states. These solid-state flexible asymmetric supercapacitors with their simple cell configuration could offer new design and fabrication opportunities for flexible energy storage devices that can combine high energy and power densities, high rate capability, and long-term cycling stability.     

制备单分散复乳的微流体装备技术

复合乳液的单分散性以及内部乳滴数量和粒径大小等性质,对其应用至关重要,因而对其制备技术也提出了更高的要求.综述了能严格控制复乳单分散性及其内部乳滴数量和粒径大小的两类微流体乳化装备技术,即T型交叉流乳化装置和同轴聚焦流乳化装置,并详细介绍了这两种装备技术的特点及研究现状.     

A green and high energy density asymmetric supercapacitor based on ultrathin MnO2 nanostructures and functional mesoporous carbon nanotube electrodes

A green asymmetric supercapacitor with high energy density has been developed using birnessite-type ultrathin porous MnO(2) nanoflowers (UBMNFs) as positive electrode and functional mesoporous carbon nanotubes (FMCNTs) as negative electrode in 1 M Na(2)SO(4) electrolyte. Both of the electrode materials possess excellent electrochemical performances, with high surface areas and narrow pore size distributions. More significantly, the assembled asymmetric supercapacitor with optimal mass ratio can be cycled reversibly in the high-potential range of 0-2.0 V and exhibits an excellent energy density as high as 47.4 W h kg(-1), which is much higher than those of symmetric supercapacitors based on UBMNFs//UBMNFs and FMCNTs//FMCNTs supercapacitors. Furthermore, our asymmetric supercapacitor (ASC) device also exhibits a superior cycling stability with 90% retention of the initial specific capacitance after 1000 cycles and stable Coulombic efficiency of ~98%. These intriguing results exhibit great potential in developing high energy density "green supercapacitors" for practical applications.     

MnO_2纳米颗粒的制备及其对亚甲基蓝的吸附性能

采用一步氧化还原法室温制备了Mn O2纳米颗粒,并考察了其对亚甲基蓝的吸附性能。结果表明,制备的Mn O2纳米颗粒大小均一,为无定型的δ-Mn O2,其对亚甲基蓝具有较好的吸附性能,最大吸附量可达157.7 mg/g,且吸附过程符合Langmuir等温模型和准二级动力学方程。     

Amaryllis-like NiCo2S4 nanoflowers for high-performance flexible carbon-fiber-based solid-state supercapacitor

Low-cost dynamic materials for Faradaic redox reactions are needed for high-energy storage supercapacitors. A simple and cost-effective hydrothermal process was employed to synthesize amaryllis-like NiCo₂S₄ nanoflowers. The sample was characterized by X-ray powder diffraction, Brunauer–Emmett–Teller method, scanning electron microscopy, and transmission electron microscopy. NiCo₂S₄ nanoflowers were coated onto carbon fiber fabric and used as a binder-free electrode to fabricate a solid-state supercapacitor compact device. The solid-state supercapacitor exhibited excellent electrochemical performance, including high specific capacitance of 360 F g⁻¹ at scan rate of 5 mV s⁻¹ and high energy density of 25 W h kg⁻¹ at power density of 168 W kg⁻¹. In addition, the supercapacitor possessed high flexibility and good stability by retaining 90% capacitance after 5000 cycles. The high conductivity and Faradic-redox activity of NiCo₂S₄ nanoflowers resulted in high specific energy and power. Thus, NiCo₂S₄ nanoflowers are promising pseudocapacitive materials for low-cost and lightweight solid-state supercapacitors.     

Delafossite CuCrO2 nanoparticles as possible electrode material for electrochemical supercapacitor

Delafossites are popularly known materials for thermoelectric and electrochemical device applications due to their layered structural features. In this paper, delafossite CuCrO₂ nanoparticles (NPs) have been synthesized using a simple chemical procedure and are investigated as a supercapacitor material. To determine the phases of delafossite CuCrO₂ NPs, the morphological and phase formation experiments were conducted using diffraction patterns and microscopic analysis. The cyclic voltammetry (CV) and galvanostatic charge/discharge (GCD) studies were performed to evaluate the supercapacitative behavior of delafossite CuCrO₂ NPs. As prepared delafossite CuCrO₂ NPs based electrode showed an outstanding electrochemical property as compared to annealed delafossite CuCrO₂ NPs at 300–500 °C. A good specific capacitance of ～464.7 Fg^-1 at 0.01 Vs^-1 was found for the fabricated supercapacitor using non-annealed delafossite CuCrO₂ NPs based electrode, which was further validated by GCD results. The electrochemical supercapacitor fabricated with both non-annealed and annealed delafossite CuCrO₂ NPs displayed considerably the outstanding cycling stability by maintaining up to ～88% after 5000 cycles. This work sets the pace for a new and efficient method of preparing delafossite CuCrO₂ for high-performance electrochemical supercapacitors.     

Ultratough and recoverable ionogels based on multiple interpolymer hydrogen bonding as durable electrolytes for flexible solid-state supercapacitor

The emerging application of ionogels in flexible devices require it enough durable under repeated mechanical deformation while maintaining their superior electrochemical properties. In this work, ultratough and recoverable ionogels, where ionic liquids are confined in chemically and interpolymer hydrogen-bonding hybrid crosslinked network, were fabricated by in situ copolymerization of acrylic acid and 1-vinylimidazole monomer within 1-buty-3-methylimidazolium chloride ionic liquid. The reversible hydrogen bonds between imidazole and carboxylic acid groups of polymer chains in the network work as reversible “sacrificial bonds” to toughen ionogel, which makes the ionogels tough (tensile strength 1.62 MPa, toughness 8.7 MJ m⁻³), stretchable (elongation at break 1090%), and recoverable (91% recovery resting for 30 min, at 534 kPa stress and 500% strain). Moreover, the hydrogen-bonded ionogels exhibit high ionic conductivity of 2.3 S m⁻¹ at 80°C to 3.2 S m⁻¹ at 150°C. Furthermore, the ionogel-based flexible electrical double-layer capacitor can be operated up to 1.5 V with a capacitance of 341.47 F g⁻¹ at 0.5 A·g⁻¹ and exhibits excellent capacitance retention after 1000 cycles as well as superior electrochemical performance over a wide range of temperature. This work provides new insights into the synthesis of tough and recoverable ionogels for high-performance flexible supercapacitors.     

Fabrication of carbon nanofiber-polyaniline composite flexible paper for supercapacitor

In this work we report a low cost technique, via simple rapid-mixture polymerization of aniline using an electrospun carbon nanofiber (CNF) paper as substrate, to fabricate free-standing, flexible CNF-PANI (PANI=polyaniline) composite paper. The morphology and microstructure of the obtained products are characterized by FESEM, FTIR, Raman and XRD. As results, PANI nanoparticles are homogeneously deposited on the surface of each CNF, forming a thin, light-weight and flexible composite paper. The resulting composite paper displays remarkably enhanced electrochemical capacitance compared with the CNF paper, making it attractive for high-performance flexible capacitors.     

Structural evolution of multi-walled carbon nanotube/MnO2 composites as supercapacitor electrodes

Multi-walled carbon nanotube (MWCNT)/MnO₂ supercapacitor electrodes containing MnO₂ nanoflakes in the MWCNT network are fabricated through the oxidation of manganese acetate with poly(4-styrenesulfonic acid) (PSS) dispersed MWCNTs. The structural evolution of the electrodes under charge/discharge (reduction/oxidation) cycles and its impact on the electrodes’ electrochemical properties are evaluated. Structural evolution involves the dissolution of MnO₂ upon reduction, the diffusion of the reduced Mn species from the MWCNT network toward the electrolyte solution, and the deposition of MnO₂ on the electrode surface upon oxidation. Electrode structural changes, including the electrode dissolution and the growth of the MnO₂ crystals, are scan rate dependent and have deteriorating effect on the electrode's electrochemical properties including the specific capacitance and cyclic stability.