Investigation of polymer electrolyte hybrid supercapacitor based on manganese oxide-carbon electrodes

A hybrid supercapacitor based on manganese oxide, activated carbon and polymer electrolyte was developed and electrochemically investigated. The capacitive performance obtained from the polymer electrolyte based supercapacitor was similar to that of an aqueous electrolyte based supercapacitor, tested for comparison in the same operative conditions. A durability test carried out for 2500 cycles showed stable and slowly increasing performance. The specific capacitance of hybrid supercapacitor was 48 F g⁻¹ (192 F g⁻¹ as a mean one electrode capacitance), in which that of the positive electrode was 384 F g⁻¹ of MnO₂ and that of negative electrode 117 F g⁻¹ of carbon. The impedance analysis evidenced that although the polymer electrolyte based hybrid supercapacitor showed higher resistance compared to that of the liquid electrolyte based supercapacitor, this drawback was counterbalanced by better ion transport features, which were evident at lower frequencies, where similar values of capacitances were obtained from the different supercapacitors.     

A study of lithium insertion into MnO2 containing TiS2 additive a battery material in aqueous LiOH solution

The electrochemical behavior and surface characterization of manganese dioxide (MnO₂) containing titanium disulphide (TiS₂) as a cathode in aqueous lithium hydroxide (LiOH) electrolyte battery have been investigated. The electrode reaction of MnO₂ in this electrolyte is shown to be lithium insertion rather than the usual protonation. MnO₂ shows acceptable rechargeability as the battery cathode. The influence of TiS₂ (1, 3 and 5 wt%) additive on the performance of MnO₂ as a cathode has been determined. The products formed on reduction of the cathode material have been characterized by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), secondary ion mass spectrometry (SIMS), fourier transform infrared spectroscopy (IR) and transmission electron microscopy (TEM). It is found that the presence of TiS₂ to ≤3 wt% improves the discharge capacity of MnO₂. However, increasing the additive content above this amount causes a decrease in its discharge capacity.     

木质素基活性炭氮掺杂改性及其电化学性能

以磷酸法木质素基活性炭为原料,三聚氰胺为氮源、KOH为活化剂,采用同步掺杂方式制备了氮掺杂活性炭(NAC)。通过BET、XRD、拉曼光谱和XPS表征手段测试了改性后活性炭的结构及其组分,并通过电化学表征手段,测试了其作为超级电容器电极材料在几种不同性质电解液中的性能,初步探究了电解液对电极材料电化学性能的影响机制。实验结果表明：改性后的活性炭具有丰富的孔结构,比表面积达到2 332 m²/g,微孔孔容为1.37 cm³/g,中孔孔容为0.74 cm³/g,平均孔径为2.79 nm,含氮元素7.5%,其中类石墨型氮(N-Q)结构达到34.6%。丰富的孔结构和氮含量大幅提升了活性炭的电化学性能,其在水系电解液中展现出了高比电容,在1 A/g的电流密度下比电容最高可达424 F/g;在有机系电解液中,尽管其在1 A/g的电流密度下比电容最高仅为87 F/g,由于其工作电压窗口更宽(0～2.5 V),因此具备了更高的能量密度。对结果进行分析,发现：活性炭电极材料在水系电解液中的性能主要受电解液水合离子半径影响,而在有机系电解液中...     

A novel nickel-based mixed rare-earth oxide/activated carbon supercapacitor using room temperature ionic liquid electrolyte

Mesopore nickel-based mixed rare-earth oxide (NMRO) and activated carbon (AC) with rich oxygen-contained groups were prepared as electrode materials in a supercapacitor using room temperature ionic liquid (RTIL) electrolyte. These electrode materials were characterized by XPS, XRD, N₂ adsorption, SEM as well as various electrochemical techniques, and showed good properties and operated well with RTIL electrolyte. A 3 V asymmetrical supercapacitor was fabricated, which delivered a real power density of 458 W kg⁻¹ as well as a real energy density of 50 Wh kg⁻¹, and during a 500-cycle galvanostatic charge/discharge measurement, no capacity decay was visible. Such promising energy-storage performance was to a large extent ascribed to nonvolatile RTIL electrolyte with wide electrochemical windows and high stable abilities worked with both electrode materials.     

Electrochemical behavior of activated-carbon capacitor material loaded with nickel oxide

In order to enhance specific capacitance and energy density of carbon-based supercapacitor, some nanometer-scale amorphous particles of nickel oxide were loaded into activated-carbon by suspending the activated-carbon in a Ni(NO₃)₂ solution followed by neutralization. A hybrid type electrochemical capacitor was made and tested, in which the activated-carbon loaded with nickel oxide was used as cathode material and activated-carbon was used as anode material. Although the BET surface area of the activated-carbon decreased upon nickel oxide loading compared to that of the starting material, its specific capacitance increased 10.84%, from 175.40 to 194.01 F g⁻¹ and the potential of oxygen evolution on the composite material electrode was 0.076 V higher than that of the pure activated-carbon electrode, in the electrolyte of 6 mol/L KOH solution, so the hybrid capacitor had larger energy density. Similar to the pure activated-carbon electrode, no obvious change appears on the specific capacitances of the composite material electrode at various discharge currents and the composite material electrode exhibiting good power characteristics.     

Self-standing manganese dioxide/graphene carbon nanotubes film electrode for symmetric supercapacitor with high energy density and superior long cycling stability

The low capacitance utilization and capacitance fading of manganese dioxide (MnO₂) is mainly due to poor electro-conductivity and irreversible phase transform. This work proposes a new method of designing hierarchical and binder-free electrode based on MnO₂ material for stable supercapacitor with high specific capacitance. Herein, we fabricated the self-standing electrode of MnO₂ on nitrogen-doped graphene and single wall carbon nanotubes (SWCNTs) self-standing film (NGCF) by electrochemical deposition. As a result, as-prepared MnO₂/NGCF cathode showed excellent electrochemical performance of 489.7 F g^-1 at 1 A g^-1. Assembled symmetric aqueous supercapacitor (SC) manifests high voltage of 2.4 V and presents excellent high energy density of 106.7 Wh kg^-1 at 1200 W kg^-1 and outstanding long-life stability without no decay after 10 000 charge-discharge circuits. This work proposes a new view of designing hierarchical and binder-free electrode with high energy density and long cycling stability based on MnO₂ material for stable symmetric supercapacitor.     

Preparation of ordered mesoporous nickel oxide film electrodes via lyotropic liquid crystal templated electrodeposition route

A novel electrochemical route to fabricate ordered mesoporous metal oxide film electrodes has been investigated with particular reference to nickel oxide. Ordered mesoporous nickel oxide films are successfully synthesized by templated electrodeposition of H_I-e nickel hydroxide and followed by heat-treatment in air at various temperatures. The films are characterized physically by thermogravimetry (TG), transmission electron microscopy (TEM) and X-ray diffraction (XRD). The applicability of this film as inexpensive and high-performance supercapacitor electrode material is demonstrated by the electrochemical characterization using cyclic voltammetry (CV) and chronopotentiometry technique. The specific capacitance of the nickel oxide film depends on the annealing temperature, showing a maximum value of 590 F g⁻¹ when the as-deposited film is heat-treated at 250 °C for 1.5 h.     

Supercapacitive behavior of mesoporous carbon CMK-3 in calcium nitrate aqueous electrolyte

Calcium nitrate Ca(NO₃)₂ aqueous solution was found to be an effective aqueous electrolyte for a supercapacitor using ordered mesoporous carbon as the electrode materials. The supercapacitive behavior of ordered mesoporous carbon CMK-3 electrode in Ca(NO₃)₂ aqueous electrolyte was investigated utilizing cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and galvanostatic charge/discharge measurements. CMK-3 electrode shows excellent supercapacitive behavior with wide voltage window, high specific gravimetric capacitance and satisfactory electrochemical stability in Ca(NO₃)₂ aqueous electrolyte. The specific gravimetric capacitance of CMK-3 electrode in Ca(NO₃)₂ aqueous electrolyte reaches 210 F g^?1 at a current density of 1 A g^?1, which is higher than that in conventional aqueous electrolytes NaNO₃ and KOH solution about 40% and 54%, respectively. The high charge density of the electric double layer formed at the interface of the CMK-3 electrode and Ca(NO₃)₂ aqueous electrolyte and the pseudo-capacitive effect originating from the oxygen groups on the surface of CMK-3 were believed to respond for the excellent supercapacitive behavior of CMK-3 electrode in Ca(NO₃)₂ aqueous electrolyte.     

Graphite oxide/polypyrrole composite electrodes for achieving high energy density supercapacitors

Fabrication and characterization of high energy density supercapacitor based on graphite oxide/polypyrrole (GO/PPy) composites is reported. Improvement in charge storage has been obtained by exfoliation of graphite oxide sheets via intercalation of polypyrrole. The formation of composite has been shown by the analysis of X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy, and Fourier transfer of infrared spectroscopy data. Scanning electron and transmission electron microscopy clearly show sheet-like layered structure of graphite oxide surrounded by polypyrrole. Supercapacitors fabricated using this composite system result in a reduced equivalent series resistance value ~1.85 Ω. Such low value can be attributed to the intercalation of conducting polypyrrole into the graphite sheets. A specific capacitance of ~181 F g^?1 in 1 M Na₂SO₄ aqueous electrolyte with a corresponding specific energy density of ~56.5 Wh kg^?1 could be achieved. These values make GO-based materials suitable for their use as electrodes in high performance supercapacitors.     

MnO2基超级电容器电极材料

超级电容器作为一种新型的储能装置,具有长寿命、高功率等特点,在诸多领域内有广泛的应用前景。在影响超级电容器性能的所有因素中,电极材料的性能起着决定性的作用。二氧化锰(MnO₂)具有原料易得,价格低廉,来源广泛,环境友好等优点。综述了MnO₂超级电容器电极材料的储能机理,纳米MnO₂的微观结构与电化学特性之间的关系,并从纳米MnO₂的制备及其综合改性角度,综述其合成、掺杂改性、复合方法在MnO₂基电极材料的新进展,指出了MnO₂基超级电容器电极材料的主要研究方向。     

A high-performance asymmetric supercapacitor based on carbon and carbon–MnO2 nanofiber electrodes

An asymmetric supercapacitor with high energy and power densities has been fabricated using MnO₂/carbon nanofiber composites as positive electrode and activated carbon nanofibers as negative electrode in Na₂SO₄ aqueous electrolyte. Both electrode materials are freestanding in nature without any conductive additives or binders and exhibit outstanding electrochemical performances. The as-assembled asymmetric supercapacitor with optimal mass ratio can be operated reversibly over a wide voltage range of 0–2.0 V, and presents a maximum energy density of 30.6 Wh kg⁻¹, which is much higher than those of symmetric supercapacitors. Moreover, the supercapacitor exhibits excellent rate capability (high power density of 20.8 kW kg⁻¹ at 8.7 Wh kg⁻¹) and long-term cycling stability with only 6% loss of its initial capacitance after 5000 cycles. These attractive results make these freestanding materials promising for applications in aqueous electrolyte-based asymmetric supercapacitors with high energy and power densities delivery.     

A novel LiTi2(PO4)3/MnO2 hybrid supercapacitor in lithium sulfate aqueous electrolyte

In this work, carbon-coated lithium-ion intercalated compound LiTi₂(PO₄)₃ and MnO₂ have been synthesized and they deliver a capacity of 90 and 60 mAh/g in 1 M Li₂SO₄ neutral aqueous electrolyte within safe potentials without O₂ and H₂ evolution, respectively. The novel hybrid supercapacitor in which MnO₂ was used as a positive electrode and carbon-coated LiTi₂(PO₄)₃ as a negative electrode was assembled and the LiTi₂(PO₄)₃/MnO₂ hybrid supercapacitor showed a sloping voltage profile from 0.7 to 1.9 V, at an average voltage near 1.3 V, and delivers a capacity of 36 mAh/g and an energy density of 47 Wh/kg based on the total weight of the active electrode materials. It exhibits a desirable profile and maintains over 80% of its initial energy density after 1000 cycles. The hybrid supercapacitor also exhibit an excellent rate capability, even at a power density of 1000 W/kg, it has a specific energy 25 Wh/kg compared with 43 Wh/kg at the power density about 200 W/kg.     

Carbon nanotubes-polyethylene oxide composite electrolyte for solid-state dye-sensitized solar cells

Novel carbon nanotubes (CNTs)-polyethylene oxide (PEO) composite electrolyte for dye-sensitized solar cell (DSSC) was prepared and characterized for the first time. The strong bonding and interaction between CNTs and PEO in CNTs-PEO composites was observed by the characterization of X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM) and Raman spectra. The introduction of CNTs into PEO matrix significantly improved the electrolyte properties of DSSC such as roughness, amorphicity and ionic conductivity. The solid-state DSSC fabricated with the optimum composite electrolyte (added 1% CNTs in PEO matrix, 1%CNT-PEO) achieved maximum conversion efficiency of 3.5%, an open circuit voltage (V_OC) of 0.589 V, short circuit current density (J_SC) of 10.64 mA/cm² and fill factor (FF) of 56%. The highest IPCE in the DSSC fabricated with 1%CNT-PEO electrolyte is ascribed to the improved ionic conductivity of composite electrolytes and enhanced interfacial contact between electrode and electrolyte.     

有机添加剂对超级电容器中水系电解液理化性能的影响

以6 mol/L KOH水溶液为电解液,高比表面积的活性炭为活性物质,研究了有机添加剂对体系润湿性、电导率、工作电压窗口及阻抗的影响,测试了超级电容器的电化学性能。结果表明,适量添加有机添加剂可明显抑制体系的极化现象,提高超级电容器的工作电压窗口。添加10vol%异丙醇时,电极材料和电解液间的润湿性大幅提高,比电容从79.3 F/g提高至113.2 F/g。添加20vol%异丙醇时,超级电容器的能量密度达19.4 Wh/kg,体系的电荷转移电阻明显降低,在10 A/g电流密度下的比电容比0.5 A/g时下降13.9%,而不加添加剂时下降30.3%。添加30vol%异丙醇时,电解液电导率迅速下降,比电容降低,电导率是影响比电容的关键因素。     

A rechargeable redox battery utilizing ruthenium complexes with non-aqueous organic electrolyte

A new-type redox battery has been developed. Some ruthenium complexes in organic electrolyte solution were utilized as the electrode active materials. A single cell consisting of [Ru(bpy)₃]²⁺ complex in acetonitrile solution had an open circuit voltage of 2.6 V and a discharge current of 5 mA cm^–2 (at a smooth carbon electrode). The characteristics of this type of cell were much influenced by such factors as the diaphragm material and the concentration of the complex. A cell with flowing electrolyte was also constructed and its charge-discharge performance was examined.     

Asymmetric Flexible Supercapacitor Stack

Electrical double layer supercapacitor is very significant in the field of electrical energy storage which can be the solution for the current revolution in the electronic devices like mobile phones, camera flashes which needs flexible and miniaturized energy storage device with all non-aqueous components. The multiwalled carbon nanotubes (MWNTs) have been synthesized by catalytic chemical vapor deposition technique over hydrogen decrepitated Mischmetal (Mm) based AB₃ alloy hydride. The polymer dispersed MWNTs have been obtained by insitu polymerization and the metal oxide/MWNTs were synthesized by sol-gel method. Morphological characterizations of polymer dispersed MWNTs have been carried out using scanning electron microscopy (SEM), transmission electron microscopy (TEM and HRTEM). An assymetric double supercapacitor stack has been fabricated using polymer/MWNTs and metal oxide/MWNTs coated over flexible carbon fabric as electrodes and nafion^® membrane as a solid electrolyte. Electrochemical performance of the supercapacitor stack has been investigated using cyclic voltammetry, galvanostatic charge-discharge, and electrochemical impedance spectroscopy.     

1-Methyl-3-butylimidazolium tetraflouroborate with activated carbon for electrochemical double layer supercapacitors

This article presents the main features of electrochemical double layer supercapacitors, made of nanostructured carbon materials with specially selected and optimized porosity structure and electrolyte based on solvent-free ionic liquid as follows 1-methyl-3-butylimidazolium tetrafluoroborate (1Me3BuImBF₄). The performance of supercapacitor was carried out by cyclic voltammetry and galvanostatic charge/discharge measurements. The main characteristics of stacked supercapacitors exhibit a nominal voltage 3.0 V and a maximum cell voltage 3.5 V as well as a specific capacitance (individual electrode of supercapacitor) of 111 F/g. The specific energy of 4.1 Wh/kg and specific power of 1.7 W/kg for industrial stacked supercapacitor has been achieved.     

Development of new nanocomposite based on nanosized-manganese oxide and carbon nanotubes for high performance electrochemical capacitors

We report the synthesis of a new composite electrode based on nanosized-manganese oxide and carbon nanotubes (CNTs) by electrophoretic deposition of CNTs on a stainless steel (SS) substrate followed by direct spontaneous reduction of MnO₄⁻ ions to MnO₂ to form the multi-scaled SS-CNT-MnO₂ electrode. The resulting material was characterized by scanning electron microscopy, energy dispersive X-ray analysis, cyclic voltammetry and galvanostatic charge-discharge in a 0.65 M K₂SO₄ aqueous solution. The binderless SS-CNT-MnO₂ nanocomposite electrode shows a very high specific capacitance of 869 F/g of CNT-MnO₂ and good stability during long galvanostatic charge-discharge cycling. To the best of our knowledge, this is one of the highest capacitance for manganese oxide electrode ever reported. In addition to its applicability in electrochemical capacitors, this methodology could be extended to develop other high performance nanocomposite material electrodes based on carbon nanotubes and metal oxide for the future generation of electrochemical power sources.     

Preparation and electrochemical performance of composite oxide of alpha manganese dioxide and Li-Mn-O spinel

Nano-sized composite powder which consisted of two manganese-based oxides, alpha manganese dioxide (α-MnO₂) and spinel Li-Mn-O, was successfully formed by intergrowth of the spinel phase inside α-MnO₂. This composite oxide was synthesized by precipitation and heat treatment in air; α-manganese dioxide powder was firstly prepared by oxidative precipitation of Mn(II) with K₂S₂O₈ in an aqueous solution, and then a mixture of the obtained manganese oxide powder and LiOH methanol solution was heat-treated in air. Electron microscopy and diffraction observations confirmed that the manganese oxide composite consisted of nano-sized grains of the spinel LiMn₂O₄ and α-MnO₂ phases. It was found that this α-MnO₂/spinel LiMn₂O₄ composite electrode exhibited highly reversible lithium insertion compared to the pristine α-MnO₂ and conventional LiMn₂O₄, that is, the composite demonstrated high discharge capacity of 148 mAh g⁻¹ as a cathode material of lithium cells in the potential range of 2.5-4.3 V with no significant capacity fading. It was thought that the intimately mixing of two oxides on a nanometer scale helped to maintain structural integrity on charge-discharge cycling, which leads to excellent capacity retention for both of the spinel and alpha-type manganese oxide.