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.     

Anode electrodeposition of 3D mesoporous Fe2O3 nanosheets on carbon fabric for flexible solid-state asymmetric supercapacitor

Novel nanostructured Fe₂O₃ with a network of 3D mesoporous nanosheets was synthesized by depositing on carbon fabric (Fe₂O₃@CF) for use as an anode using a potentially low-cost electrodeposition technique. The electrode with freestanding binder-free Fe₂O₃@CF of high surface area displayed an exceptional specific capacitance of 394.2?F?g^?1. Moreover, a flexible solid-state asymmetric supercapacitor (ASC) was fabricated with a negative electrode based on Fe₂O₃@CF and a positive electrode based on MnO₂@CF in the presence of PVA-LiCl as gel electrolyte. The above ASC exhibited a high operating potential up to 1.8?V, a favorable specific capacitance of 93.5?F?g^?1 (2.92?F?cm^?3), long-term stability (91.3% retention of initial value over 5000 cycles), and remarkable mechanical stability and flexibility, suggesting its potential application for wearable electronics.     

Preparation of on chip,flexible supercapacitor with high performance based on electrophoretic deposition of reduced graphene oxide/polypyrrole composites

A new concept is introduced to fabricate flexible, on-chip supercapacitors by electrophoretically depositing highly dispersed reduced graphene oxide/polypyrrole on interdigital-like electrodes. By the unique method, the deposited films could construct on the substrate facilely and uniformly. The prepared all-solid-state device demonstrates high volumetric capacitance (about 147.9 F cm⁻³), high energy density (13.15 mWh cm⁻³ at a power density of 1300 mW cm⁻³) and excellent cycling stability (approximately 71.7% of the initial capacitance retained after 5000 cycles). Compared with other supercapacitor, the device demonstrated here is lightweight, flexible and inexpensive.     

High performance asymmetric supercapacitor based on 3D microsphere-like 1T-MoS2 with high 1T phase content

1T phase molybdenum disulfide (1T-MoS₂) has aroused extensive concern in energy storage devices such as supercapacitors due to its large interlayer spacing, high conductivity and good hydrophilicity. However, it is struggle to synthesize 1T-MoS₂ with stable 1T phase with high content. Herein, Ammonium ion intercalation molybdenum disulfide (A-MoS₂) with high 1T content and stable 3D microsphere structure was successfully synthesized using a facile hydrothermal method. We explained the feasibility of ammonium ion (NH₄⁺) intercalation through density functional theory (DFT) calculations and proved the successful intercalation of NH₄⁺ by XRD and XPS. Through XPS fitting, the 1T phase content is calculated as high as 83.1%. The as-prepared A-MoS₂ presents a stable 3D microsphere structure with the interlayer spacing expanded to 0.93 nm, which provides a wide ion diffusion channel that allows ions to pass through quickly. Moreover, the high 1T content increases the hydrophilicity of MoS₂, thereby improving the wettability of the electrode, which contributes to the interaction between the electrolyte and electrode. In 1 M Na₂SO₄, A-MoS₂ electrode material displays high specific capacitance of 228 F g^?1 at 5 mV s^?1 and retains 127 F g^?1 at 80 mV s^?1, which proves the good rate capability. Furthermore, the assembled α-MnO₂//A-MoS₂ asymmetric supercapacitor (ASC) displayed a wide operating voltage of 2.1 V. The assembled ASC displays a high energy density of 35.8 Wh?kg^?1 at a power density of 525.0 W kg^?1, which indicates excellent energy storage performance.     

Sulfur-incorporated,porous graphene films for high performance flexible electrochemical capacitors

Graphene and its derivatives are considered potential electrode materials for flexible electrochemical capacitors (f-ECs), but their capacitive performances have to be improved for practical applications. Herein, we demonstrate fabrication of flexible sulfur (S)-incorporated reduced graphene oxide (SRGO) electrodes obtained by pyrolyzing free-standing film consisting of benzyl disulfide-functionalized graphene oxides at 900 °C. The effect of S incorporation on morphology and chemical structure of SRGO were investigated by various microscopic and spectroscopic methods. Incorporation of S and the crumpled and porous morphology of SRGO electrodes improve capacitive performance of f-ECs; SRGO f-ECs show a specific capacitance of 140.8 F/g at 1 A/g, rate capability of 91.5% retention, and cyclic performance of 93.4% after 1000 charge/discharge cycles at 4 A/g. Impressively, SRGO f-ECs exhibit excellent electrochemical and mechanical durability after 1000 charge/discharge cycles at a bending angle of 120° with values that greatly exceed those of conventional RGO-based f-ECs. This study provides a fundamental foundation of the correlation between S composition of carbon nanomaterials and their electrochemical (or surface) properties.     

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.     

Alkylated graphene nanosheets for supercapacitor electrodes: High performance and chain length effect

Single electrode materials capable of both electric double-layer and Faradic redox-based pseudo capacitance can be used for fabrication of high performance supercapacitors in an easy way and thus are highly desirable in the energy storage field. This contribution reports a new kind of such materials based on alkylated graphene materials (C_nrGO, n is the carbon number of their alkyl side chains) having different alkyl side chains (n = 4, 8, and 16). These materials were prepared via esterification of KOH-treated GO with the corresponding alkyl bromides in the presence of a phase transfer catalyst. More importantly, water was used as the reaction medium, and thus endowing the preparation method an eco-friend feature. The so-prepared graphene materials displayed chain length-dependent specific surface area and the population of residue CO functionalities, and thus affording vast differences in their supercapacitor behaviors. C₄rGO, the product having butyl side chains, showed the best supercapacitor performance with a capacitance up to 242.2 F g⁻¹ at a scan rate of 100 mV s⁻¹ and a good cycling stability.     

Mechanically strong high performance layered polypyrrole nano fibre/graphene film for flexible solid state supercapacitor

Paper like flexible electrode becomes one of the most important research objects recently in request of the fast expanding market of portable electronics. Flexible solid state supercapacitors are shortlisted as one of the most promising energy devices to power electronics with medium to high power density requirements. In this work, we developed a simple but effective way to produce a mechanically strong and electrochemically active RGO/polypyrrole (PPy) fibre paper. A well-bedded microstructure was created with interlaced polypyrrole fibres evenly distributed between the graphene layers. Such microstructure can create enormous amount of pores and therefore provides larger interfaces for charge carrier storage/release. The effects of polypyrrole fibres on the film’s morphologies, mechanical properties and electrochemical performance were discussed. A solid state supercapacitor was demonstrated using such paper electrodes and a gel type electrolyte – phosphate acid (H₃PO₄) infused polyvinyl alcohol (PVA). It showed a high capacitance (345 F g⁻¹) and an excellent cycling stability (9.4% drop after 1000 cycles).     

氧化石墨烯的酸性还原及其超级电容性能

采用改进的Hummers法制备氧化石墨烯(GO),在酸性条件(pH=5)下以180°C进行水热还原,通过调节水热反应时间来制备不同还原程度的还原氧化石墨烯(RGO)。研究了不同的水热反应时间对RGO结构及超级电容性能的影响。结果表明：控制水热反应时间可以制备出还原程度不同的RGO,在电化学测试中,随着水热反应时间的延长,RGO电极的比电容呈先上升后下降的趋势。当水热反应时间为6 h时,RGO电极表现出最佳的超级电容性能,其在1 A/g电流密度下比电容达到251 F/g,相对于GO电极提高了225%。经过500次充放电循环后,RGO-6电极比电容保持率达到92%,具有优异的循环稳定性。     

柔性固态非对称超级电容器电极材料的研究进展

综述了柔性固态非对称超级电容器关键元器件和材料的研究现状,重点介绍了柔性固态非对称超级电容器体系的材料选择与性能改善方面的研究进展,其中包括碳材料/过渡金属化合物材料和过渡金属氧化物/过渡金属氧化物材料等。同时还综合分析了选择不同材料体系的柔性固态非对称超级电容器结构与性能,并对该领域的发展趋势进行了展望。     

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.     

High-performance supercapacitor electrodes based on highly corrugated graphene sheets

Highly corrugated graphene sheets (HCGS) have been prepared by a rapid, low cost and scalable approach through the thermal reduction of graphite oxide at 900 °C followed by rapid cooling using liquid nitrogen. The wrinkling of the graphene sheets can significantly prevent them from agglomerating and restacking with one another face to face and thus increase the electrolyte-accessible surface area. The maximum specific capacitance of 349 F g^?1 at 2 mV s^?1 is obtained for the HCGS electrode in 6 M KOH aqueous solution. Additionally, the electrode shows excellent electrochemical stability along with an approximately 8.0% increase of the initial specific capacitance after 5000 cycle tests. These features make the present HCGS material a quite promising alternative for next generation of high-performance supercapacitors.     

One-step scalable preparation of graphene nanosheets and high-thermal-conductivity flexible graphene films

It is well known that graphene nanosheets (GNSs) have many excellent properties. However, it has been a difficult thing to exfoliate graphite into GNSs in a controllable and scalable manner. In this research, a new strategy named xylitol-assisted ball milling exfoliation (XABME) was developed for the scalable preparation of GNSs. The experimental results characterized by a series of measurements showed that GNSs were successfully exfoliated by the XABME strategy. The structure of the prepared nanosheets was featured by large lateral size and ultra-small thickness. Furthermore, the prepared GNSs easily achieved high production yield (≈54%). Lastly, the as-obtained GNSs and cellulose nanofibers (CNF) were compounded to form some nanomaterial films. The prepared films exhibited excellent flexibility and higher thermal conductivity, with the in-plane thermal conductivity of 90 wt% GNS film (8.0 W/(m·K)) being 11.4 times higher than that of the film without GNSs. This shows that GNSs could effectively enhance the thermal conductivity of the CNF matrix and indicate that these prepared films have great potentials in the thermal management of portable mobile devices.     

Vertically oriented polyaniline‐graphene nanocomposite based on functionalized graphene for supercapacitor electrode

Polyaniline functionalized reduced graphene oxide (PORGO) is prepared by interfacial polymerization and then vertically oriented polyaniline‐graphene (PANI‐PORGO) nanocomposites based on PORGO are developed successfully by in situ polymerization. The morphology and structure are characterized by field emission scanning electron microscopy (FE‐SEM), transmission electron microscopy (TEM), Fourier transform infrared spectra (FT‐IR), Raman spectra and X‐ray diffraction (XRD). The electrochemical tests indicate that the specific capacitance of PORGO and PANI‐PORGO is as high as 291 and 369 F/g, respectively, at the current density of 1 A/g. PANI—PORGO nanocomposite exhibits high electrochemical activity and enhanced cycle stability with a capacitance retention of 81.2% after 500 cycles at 10 A/g. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44808.     

Direct reduction of graphene oxide films into highly conductive and flexible graphene films by hydrohalic acids

We report a simple but highly-effective hydrohalic acid reducing method to reduce graphene oxide (GO) films into highly conductive graphene films without destroying their integrity and flexibility at low temperature based on the nucleophilic substitution reaction. GO films reduced for 1 h at 100 °C in 55% hydroiodic (HI) acid have an electrical conductivity as high as 298 S/cm and a C/O ratio above 12, both of which are much higher than films reduced by other chemical methods. The reduction maintains good integrity and flexibility, and even improves the strength and ductility, of the original GO films. Based on this reducing method, a flexible graphene-based transparent conductive film with a sheet resistance of 1.6 kΩ/sq and 85% transparency was obtained, further verifying the advantage of HI acid reduction.     

Nanosheet-like MoO3 and conductive PANI electrodeposited on flexible carbon cloth for self-supported solid-state supercapacitor electrode

In this paper, uniformly transition metal oxide (MoO₃) nanosheets were electrochemically deposited on flexible carbon cloth (CC), and then conductive polyaniline (PANI) was orderly wrapped around their surface by electrochemical polymerization. The morphology and structure of as-obtained self-supported PANI/MoO₃/CC electrode were investigated by FTIR, X-ray diffraction, Raman, scanning electron microscope (SEM), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy measurements in detail. Among all PANI/MoO₃/CC electrode, the self-supported PMC-3 (deposition time of 300 s) has high specific capacitance of 841.6 F g⁻¹ at current density of 0.5 A g⁻¹ in the three-electrode system, having specific capacitance of 595.7 F g⁻¹ even at 10 A g⁻¹. Novelty, the as-assembled symmetrical capacitor is flexible and convenient with power density of 199.93 W kg⁻¹ at the energy density of 9.69 Wh kg⁻¹ and the energy density of 3.88 Wh kg⁻¹ at power density of 4000 W kg⁻¹. Thus, the electrochemical properties of the self-supported PANI/MoO₃/CC electrode were significantly improved, and the self-supported electrodes are more competitive than other materials in practical application of clean energy storage systems.     

High power aqueous hybrid asymmetric supercapacitor based on zero-dimensional ZnS nanoparticles with two-dimensional nanoflakes CuSe2 nanostructures

Energy storage materials, particularly chalcogenides, are fascinating electrode materials for supercapacitors (SCs) because of their high capacitance, remarkable electrical conductivity, and multiple oxidation states contributed by numerous metal cations. Herein, a novel nanocomposite based on zinc sulfide and copper diselenide, denoted as (ZnS–CuSe₂), was prepared via a sonochemical-assisted method. The structural analysis revealed the cubic structure for pure ZnS, orthorhombic for CuSe_2, and co-existing cubic and orthorhombic phases for ZnS–CuSe₂ nanocomposites with high purity and crystallinity. The ZnS–CuSe₂ nanocomposite offered exceptional electrochemical performance with redox peaks from the CV analysis, and coupled with plateaus in the charge/discharge profile, confirming the faradaic energy storage properties with functional reversibility. Similarly, a high conductive feature of the ZnS–CuSe₂ composite was revealed by impedance study, with a minor charge transfer resistance than their bulk materials. A hybrid asymmetric supercapacitor (HASCs) composed of ZnS–CuSe₂//AC was constructed, which manifested an enlarged voltage window up to 1.7 V with capacitance of 95 F g⁻¹ and a maximum specific energy of 38 Wh kg⁻¹. Also, high power delivery was attained at 3927 Wkg^-1 when specific energy goes down to 12 Wh kg⁻ at 5 A g⁻¹. Interestingly, only 81.8% retention was left beneath when cycled to 8000 cycles, specifying decent stability of the ZnS–CuSe₂//AC HASCs.     

Room temperature ammonia sensing based on graphene oxide integrated flexible polyvinylidenefluoride/cerium oxide nanocomposite films

ABSTRACT

In this work, novel room temperature (RT) ammonia (NH₃) sensors comprising graphene oxide (GO) integrated polyvinylidenefluoride (PVDF)/cerium oxide (CeO₂) nanocomposite films have been prepared via simple solution casting technique. The structural and morphological characteristics of flexible tertiary PVDF/CeO₂/GO nanocomposite films have been investigated using various analytical techniques and their NH₃ gas-sensing performance was evaluated at RT and the relevant sensing mechanism was established. The flexible PVDF/CeO₂/GO nanocomposite films responded strongly to NH₃ gas with enhanced gas sensing properties at RT as compared with various other volatile organic compounds (VOCs) such as acetone, ethanol, formaldehyde and toluene.     

High-performance supercapacitor of manganese oxide/reduced graphene oxide nanocomposite coated on flexible carbon fiber paper

Although supercapacitors have higher power density than batteries, they are still limited by low energy density and low capacity retention. Here we report a high-performance supercapacitor electrode of manganese oxide/reduced graphene oxide nanocomposite coated on flexible carbon fiber paper (MnO₂–rGO/CFP). MnO₂–rGO nanocomposite was produced using a colloidal mixing of rGO nanosheets and 1.8 ± 0.2 nm MnO₂ nanoparticles. MnO₂–rGO nanocomposite was coated on CFP using a spray-coating technique. MnO₂–rGO/CFP exhibited ultrahigh specific capacitance and stability. The specific capacitance of MnO₂–rGO/CFP determined by a galvanostatic charge–discharge method at 0.1 A g⁻¹ is about 393 F g⁻¹, which is 1.6-, 2.2-, 2.5-, and 7.4-fold higher than those of MnO₂–GO/CFP, MnO₂/CFP, rGO/CFP, and GO/CFP, respectively. The capacity retention of MnO₂–rGO/CFP is over 98.5% of the original capacitance after 2000 cycles. This electrode has comparatively 6%, 11%, 13%, and 18% higher stability than MnO₂–GO/CFP, MnO₂/CFP, rGO/CFP, and GO/CFP, respectively. It is believed that the ultrahigh performance of MnO₂–rGO/CFP is possibly due to high conductivity of rGO, high active surface area of tiny MnO₂, and high porosity between each MnO₂–rGO nanosheet coated on porous CFP. An as-fabricated all-solid-state prototype MnO₂–rGO/CFP supercapacitor (2 × 14 cm) can spin up a 3 V motor for about 6 min.     

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。