Improved electrochemical properties of amorphous Mg65Ni27La8 electrodes: Surface modification using graphite

Amorphous Mg₆₅Ni₂₇La₈ alloy is prepared by melt-spinning. The alloy surface is modified using different contents of graphite to improve the performances of the Mg₆₅Ni₂₇La₈ electrodes. In detail, the electrochemical properties of (Mg₆₅Ni₂₇La₈) + xC (x = 0–0.4) electrodes are studied systematically, where x is the mass ratio of graphite to alloy. Experimental results reveal that the discharge capacity, cycle life, discharge potential characteristics and electrochemical kinetics of the electrodes are all improved. The surface modification enhances the electrocatalytic activity of the alloy, reduces the contact resistance of the electrodes and obstructs the formation of Mg(OH)₂ on the alloy surface. An optimal content of graphite has been obtained. The (Mg₆₅Ni₂₇La₈) + 0.25 C electrode has the largest discharge capacity of 827 mA h g⁻¹, which is 1.47 times as large as that of the electrode without graphite, and the best electrochemical kinetics. Further increasing of graphite content will lead to the increase of contact resistance and activation energy for charge-transfer reaction of the electrode, resulting in the degradation of electrode performance.     

Fabrication of MnO2-pillared layered manganese oxide through an exfoliation/reassembling and oxidation process

MnO₂-pillared layered manganese oxide has been first fabricated by a delamination/reassembling process followed by oxidation reaction and then by heat treatment. The structural evolution of MnO₂-pillared layered manganese oxide has been characterized by XRD, SEM, DSC-GTA, IR and N₂ adsorption-desorption. MnO₂-pillared layered manganese oxide shows a relative high thermal stability and mesoporous characteristic. The layered structure with a basal spacing of 0.66 nm could be maintained up to 400 °C. The electrochemical properties of the synthesized MnO₂-pillared layered manganese oxide have been studied using cyclic voltammetry in a mild aqueous electrolyte. Sample MnO₂–BirMO (300 °C) shows good capacitive behavior and cycling stability, and the specific capacitance value is 206 F g⁻¹.     

Supercapacitive properties of hybrid films of manganese dioxide and polyaniline based on active carbon in organic electrolyte

This is the first report about supercapacitive performance of hybrid film of manganese dioxide (MnO₂) and polyaniline (PANI) in an organic electrolyte (1.0 M LiClO₄ in acetonitrile). In this work, a high surface area and conductivity of active carbon (AC) electrode is used as a substrate for PANI/MnO₂ film electro-codeposition. The redox properties of the coated PANI/MnO₂ thin film exhibit ideal capacitive behaviour in 1 M LiClO₄/AN. The specific capacitance (SC) of PANI/MnO₂ hybrid film is as high as 1292 F g⁻¹ and maintains about 82% of the initial capacitance after 1500 cycles at a current density of 4.0 mA cm⁻², and the coulombic efficiency (η) is higher than 95%. An asymmetric capacitor has been developed with the PANI/MnO₂/AC positive and pure AC negative electrodes, which is able to deliver a specific energy as high as 61 Wh kg⁻¹ at a specific power of 172 W kg⁻¹ in the range of 0-2.0 V. These results indicate that the organic electrolyte is a promising candidate for PANI/MnO₂ material application in supercapacitors.     

Optimization of MnO2/vertically aligned carbon nanotube composite for supercapacitor application

The optimization strategy for producing manganese oxide supercapacitors based on vertically aligned carbon nanotubes (VACNTs) deposited on large area electrodes is presented. A single sequential process of sputtering, annealing and plasma enhanced chemical vapour deposition (PECVD) is applied to produce dense and uniform VACNTs electrodes. As dielectric layer of the supercapacitor, manganese oxide is electrodeposited lining the surface of the VACNTs electrodes. The control of the growing parameters such as catalyst thickness layer, temperature and deposition time for tuning the density, length and diameter of the VACNTs and their structure are found to be key points for the optimization of the MnO₂ electrodeposition process in view to improve the efficiency of the supercapacitor devices.The electrochemical properties of the obtained electrodes are characterized using cyclic voltammetry and galvanostatic charge-discharge techniques. A specific capacitance of 642 Fg⁻¹ is obtained for MnO₂/VACNTs nanocomposite electrode at a scan rate of 10 mV s⁻¹.     

Carbon-supported,nano-structured,manganese oxide composite electrode for electrochemical supercapacitor

Carbon-supported MnO₂ nanorods are synthesized using a microemulsion process and a manganese oxide/carbon (MnO₂/C) composite is investigated for use in a supercapacitor. As shown by high-resolution transmission electron microscopy the 2 nm × 10 nm MnO₂ nanorods are uniformly dispersed on the carbon surface. Cyclic voltammograms recorded for the MnO₂/C composite electrode display ideal capacitive behaviour between −0.1 and 0.8 V (vs. saturated calomel electrode) with high reversibility. The specific capacitance of the MnO₂/C composite electrode found to be 165 F g⁻¹ and is estimated to be as high as 458 F g⁻¹ for the MnO₂. Based on cyclic voltammetric life-cycle tests, the MnO₂/C composite electrode gives a highly stable and reversible performance for up to 10,000 cycles.     

La substituted Sr2MnO4 as a possible cathode material in SOFC

Sr_2−xLa_xMnO_4+δ (x = 0.4, 0.5, 0.6) oxides were studied as the cathode material for solid oxide fuel cells (SOFC). The reactivity tests indicated that no reaction occurred between Sr_2−xLa_xMnO_4+δ and CGO at annealing temperature of 1000 °C, and the electrode formed good contact with the electrolyte after being sintered at 1000 °C for 4 h. The total electrical conductivity, which has strong effect on the electrode properties, was determined in a temperature range from 100 to 800 °C. The maximum value of 5.7 S cm⁻¹ was found for the x = 0.6 phase at 800 °C in air. The cathode polarization and AC impedance results showed that Sr_1.4La_0.6MnO_4+δ exhibited the lowest cathode overpotential. The area specific resistance (ASR) was 0.39 Ω cm² at 800 °C in air. The charge transfer process is the rate-limiting step for oxygen reduction reaction on Sr_1.4La_0.6MnO_4+δ electrode.     

Low-temperature solid oxide fuel cells with La1−xSrxMnO3 as the cathodes

La_1−xSr_xMnO₃ (LSM) has been widely developed as the cathode material for high-temperature solid oxide fuel cells (SOFCs) due to its chemical and mechanical compatibilities with the electrolyte materials. However, its application to low-temperature SOFCs is limited since its electrochemical activity decreases substantially when the temperature is reduced. In this work, low-temperature SOFCs based on LSM cathodes are developed by coating nanoscale samaria-doped ceria (SDC) onto the porous electrodes to significantly increase the electrode activity of both cathodes and anodes. A peak power density of 0.46 W cm⁻² and area specific interfacial polarization resistance of 0.36 Ω cm² are achieved at 600 °C for single cells consisting of Ni-SDC anodes, LSM cathodes, and SDC electrolytes. The cell performances are comparable with those obtained with cobalt-based cathodes such as Sm_0.5Sr_0.5CoO₃, and therefore encouraging in the development of low-temperature SOFCs with high reliability and durability.     

Electrodeposited manganese oxides on three-dimensional carbon nanotube substrate: Supercapacitive behaviour in aqueous and organic electrolytes

Thin amorphous manganese oxide layers with a thickness of 3–5 nm are electrodeposited on a carbon nanotube (CNT) film substrate that has a three-dimensional nanoporous structure (denoted as MnO₂/CNT electrode). For the purpose of comparison, manganese oxide films are also electrodeposited on a flat Pt-coated Si wafer substrate (denoted as MnO₂ film electrode). The pseudocapacitive properties of the MnO₂ film and MnO₂/CNT electrodes are examined in both aqueous electrolyte (1.0 M KCl) and non-aqueous organic electrolyte (1.0 M LiClO₄ in propylene carbonate). While both types of electrode show pseudocapacitive behaviour in the aqueous electrolyte, only the MnO₂/CNT electrode does so in the organic electrolyte, due to its high oxide/electrolyte interfacial area and improved electron conduction through the CNT substrate. Compared with the MnO₂ film electrode, the MnO₂/CNT electrode shows a much higher specific capacitance and better high-rate capability, regardless of the electrolyte used. Use of the organic electrolyte results in a ∼6 times higher specific energy compared with that obtained with the aqueous electrolyte, while maintaining a similar specific power. The construction of a three-dimensional nanoporous network structure consisting of a thin oxide layer on a CNT film substrate at the nm scale and the use of an organic electrolyte are promising approaches to improving the specific energy of supercapacitors.     

Nickel oxyhydroxide/manganese dioxide composite as a candidate electrode material for alkaline secondary cells

Nickel hydroxide and manganese dioxide are used in alkaline cells as positive electrode materials. Positive electrodes comprising a nickel oxyhydroxide/manganese dioxide composite, with modification by Bi₂O₃, deliver a combined reversible discharge capacity of 2.25e per metal atom (650 mAh g⁻¹ metal content), which is higher than that realized from electrodes of either component taken singly. The composite discharges with two potential plateaux, the first appearing at 325 mV corresponds to the discharge of the nickel component, whereas the second at −600 mV is due to the manganese component. Composites of NiO(OH)/MnO₂ can be used as a new electrode material with higher discharge capacity than conventional electrodes.     

Electrochemical synthesis of birnessite-type layered manganese oxides for rechargeable lithium batteries

Layered manganese dioxide (MnO₂) films intercalated with Li⁺, Na⁺ or Mg²⁺ ions were synthesized by a one-step electrochemical method. The electrodeposition was potentiostatically performed by applying an anodic potential of 1.0 V vs. Ag/AgCl in an aqueous MnSO₄ solution containing a perchlorate salt of the cation. The electrodeposited oxide films have a birnessite-type layered structure with alkali cations and water molecules between manganese oxide layers. The galvanostatic charge–discharge experiments performed in 1 M LiPF₆-DME/PC solution indicated that the Mg²⁺-intercalated MnO₂ electrode exhibits an initial discharge capacity as large as 140 mAh g⁻¹ and it shows a better capacity retention during cycling as compared with the Li⁺- or Na⁺-intercalated MnO₂ electrode.     

(La,Sr)MnO3–(Y,Bi)2O3 composite cathodes for intermediate-temperature solid oxide fuel cells

Yttria-stabilized bismuth oxides (YSB) are cooperated to (La,Sr)MnO₃ (LSM) to form composite cathodes for intermediate-temperature solid oxide fuel cells. The composite electrodes are fabricated with screen-printing technique and characterized using electrochemical impedance spectroscopy. The interfacial polarization resistances (R_p) of the LSM–YSB electrodes on yttria-stabilized zirconia (YSZ), samaria-doped ceria (SDC), and YSB electrolytes are analyzed regarding the electrode composition and operating temperature. R_p decreases with the increase of YSB content up to 80 wt.% in the LSM–YSB composite. When YSZ is used as the electrolyte, the lowest R_p is 0.14 Ω cm² at 700 °C, which is only 1.8% of that for a pure LSM electrode, 5.6% of that reported for LSM–YSZ composites, and 13.2% of that for reported LSM–GDC (gadolinia-doped ceria) electrodes, demonstrating that YSB is very effective to enhance the performance of LSM-based cathodes. The electrode performance is also affected by the electrolyte substrate. LSM electrodes without any YSB exhibit obviously different performance on YSZ, SDC and YSB electrolytes. However, when YSB is cooperated, R_p on different electrolytes tends to become equivalent, especially for electrodes with high YSB content. Further analysis shows that their electrochemical performance is contributed dominantly from the electrode bulk whereas the contribution from the electrode/electrolyte interface is negligible, suggesting weak electrolyte effect on the performance of LSM–YSB composite electrodes.     

Anodic deposition of manganese oxide electrodes with rod-like structures for application as electrochemical capacitors

The electrochemical properties of nanocrystalline manganese oxide electrodes with rod-like structures were investigated to determine the effect of morphology, chemistry and crystal structure on the corresponding electrochemical behavior of manganese electrodes. Manganese oxide electrodes of high porosity composed of 1-1.5 μm diameter rods were electrochemically synthesized by anodic deposition from a dilute solution of Mn(CH₃COO)₂ (manganese acetate) onto Au coated Si substrates without any surfactants, catalysts or templates under galvanostatic control. The morphology of the electrodes depended on the deposition current density, which greatly influenced the electrochemical performance of the capacitor. Electrochemical property and microstructure analyses of the manganese oxide electrodes were conducted using cyclic voltammetry and microstructural techniques, such as scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The synthesized rod-like manganese oxide electrodes at low current densities exhibited a high specific capacitance due to their large surface areas. The largest value obtained was 185 F g⁻¹ for deposits produced at .5 mA cm⁻². Specific capacity retention for all deposits, after 250 charge-discharge cycles in an aqueous solution of 0.5 M Na₂SO₄, was about 75% of the initial capacity.     

Poly(3-methylthiophene)/MnO2 composite electrodes as electrochemical capacitors

Composite electrodes prepared by electrodeposition of manganese oxide on titanium substrates modified with poly(3-methylthiophene) (PMeT) were investigated and compared with Ti/MnO₂ electrodes. The polymer films were prepared by galvanostatic deposition at 2 mA cm⁻² with different deposition charges (250 and 1500 mC cm⁻²). The electrodes were characterized by cyclic voltammetry in 1 mol L⁻¹ Na₂SO₄ and by scanning electron microscopy. The results show a very significant improvement in the specific capacitance of the oxide due the presence of the polymer coating. For Ti/MnO₂ the specific capacitance was of 122 F g⁻¹, while Ti/PMeT₂₅₀/MnO₂ and Ti/PMeT₁₅₀₀/MnO₂ displayed values of 218 and 66 F g⁻¹, respectively. If only oxide mass is considered, the capacitances of the composite electrode increases to 381 and 153 F g⁻¹, respectively. The micrographs of samples show that the polymer coating leads to very significant changes in the morphology of the oxide deposit, which in consequence, generate the improvement observed in the charge storage property.     

Synthesis and pseudocapacitive studies of composite films of polyaniline and manganese oxide nanoparticles

We report the synthesis and pseudocapacitive studies of a composite film (PANI-ND-MnO₂) of polyaniline (PANI) and manganese oxide (MnO₂) nanoparticles. To enhance the interaction of MnO₂ and PANI, the surfaces of MnO₂ nanoparticles were modified by a silane coupling reagent, triethoxysilylmethyl N-substituted aniline (ND42). The composite film was obtained via controlled electro-co-polymerization of aniline and N-substituted aniline grafted on surfaces of MnO₂ nanoparticles (ND-MnO₂) on a carbon cloth in a electrolyte of 0.5 M H₂SO₄ and 0.6 M (NaPO₃)₆. In comparison to similarly prepared PANI film, the incorporation of MnO₂ nanoparticles substantially increases the effective surface area of the film by reducing the size of rod-like PANI aggregates and avoiding the entanglement of these PANI nanorods. Significantly, we observed significant enhancement of specific capacitance in PANI-ND-MnO₂ film compared to PANI-MnO₂ film prepared in a similar condition, indicating that the presence of the coupling reagent can improve the electrochemical performance of PANI composite film. A symmetric model capacitor has been fabricated by using two PANI-ND-MnO₂ nanocomposite films as electrodes. The PANI-ND-MnO₂ capacitor showed an average specific capacitance of ∼80 F g⁻¹ and a stable coulombic efficiency of ∼98% over 1000 cycles. The results demonstrated that PANI-ND-MnO₂ nanocomposites are promising materials for supercapacitor electrode and the importance of designing and manipulating the interaction between PANI and MnO₂ for fundamentally improving capacitive properties.     

Effects of addition of different carbon materials on the electrochemical performance of nickel hydroxide electrode

Nickel hydroxide is used as an active material in positive electrodes of rechargeable alkaline batteries. The capacity of nickel-metal hydride (Ni-MH) batteries depends on the specific capacity of the positive electrode and utilization of the active material because of the Ni(OH)₂/NiOOH electrode capacity limitation. The practical capacity of the positive nickel electrode depends on the efficiency of the conductive network connecting the Ni(OH)₂ particle with the current collector. As β-Ni(OH)₂ is a kind of semiconductor, the additives are necessary to improve the conductivity between the active material and the current collector. In this study the effect of adding different carbon materials (flake graphite, multi-walled carbon nanotubes (MWNT)) on the electrochemical performance of pasted nickel-foam electrode was established. A method of production of MWNT special type of catalysts had an influence on the performance of the nickel electrodes. The electrochemical tests showed that the electrode with added MWNT (110-170 nm diameter) exhibited better electrochemical properties in the chargeability, specific discharge capacity, active material utilization, discharge voltage and cycling stability. The nickel electrodes with MWNT addition (110-170 nm diameter) have exhibited a specific capacity close to 280 mAh g⁻¹ of Ni(OH)₂, and the degree of active material utilization was ∼96%.     

Electrochemical properties of manganese oxide coated onto carbon nanotubes for energy-storage applications

Birnessite-type manganese dioxide (MnO₂) is coated uniformly on carbon nanotubes (CNTs) by employing a spontaneous direct redox reaction between the CNTs and permanganate ions (MnO₄⁻). The initial specific capacitance of the MnO₂/CNT nanocomposite in an organic electrolyte at a large current density of 1 A g⁻¹ is 250 F g⁻¹. This is equivalent to 139 mAh g⁻¹ based on the total weight of the electrode material that includes the electroactive material, conducting agent and binder. The specific capacitance of the MnO₂ in the MnO₂/CNT nanocomposite is as high as 580 F g⁻¹ (320 mAh g⁻¹), indicating excellent electrochemical utilization of the MnO₂. The addition of CNTs as a conducting agent improves the high-rate capability of the MnO₂/CNT nanocomposite considerably. The in situ X-ray absorption near-edge structure (XANES) shows improvement in the structural and electrochemical reversibility of the MnO₂/CNT nanocomposite after heat-treatment.     

Regulation of the discharge reservoir of negative electrodes in Ni-MH batteries by using Ni(OH)x (x = 2.10) and γ-CoOOH

In this paper, a novel strategy to regulate the discharge reservoir of negative electrodes in Ni-MH batteries is introduced by using Ni(OH)_x (x = 2.10) and γ-CoOOH. The electrochemical measurements of these batteries demonstrate that the use of Ni(OH)_x (x = 2.10) and γ-CoOOH can not only successfully regulate the discharge reservoir of negative electrodes in Ni-MH batteries to an adequate quantity, but also effectively improve the electrochemical performance of the batteries. Compared with normal batteries, the in-house prepared batteries with a lower discharge reservoir exhibit an enhanced discharge capacity, improved high-rate discharge ability, higher discharge potential plateau and superior cycle stability. The effect of Ni(OH)_x (x = 2.10) and γ-CoOOH on the electrochemical performance of nickel electrode is also investigated by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The results suggest that the new method is simple and effective for cost reduction of Ni-MH batteries with improved electrochemical performance.     

Nanoporous MnOx thin-film electrodes synthesized by electrochemical lithiation/delithiation for supercapacitors

Nanoporous MnO_x thin-film electrodes are synthesized using a combination of pulsed laser deposition (PLD) and electrochemical lithiation/delithiation methods. A dense Mn₃O₄ thin-film deposited by PLD can transform into a nanoporous MnO_x thin-film after electrochemical lithiation/delithiation. A nanoporous MnO_x thin-film electrode exhibits significantly improved supercapacitive performance compared with an as-deposited Mn₃O₄ thin-film electrode. A MnO_x thin-film finally transforms into a MnO₂ thin-film through an electrochemical oxidation process during continuous cyclic voltammetry scanning.     

Adjustment of electrodes potential window in an asymmetric carbon/MnO2 supercapacitor

The electrodes mass ratio of MnO₂/activated carbon supercapacitors has been varied in order to monitor its influence on the potential window of both electrodes and consequently to optimize the operating voltage. It appeared that the theoretical mass ratio (R = 2), calculated considering an equivalent charge passed across both electrodes, is underestimated. It was demonstrated that R values of 2.5-3 are better adapted for this system; the extreme potential reached for each electrode is close to the stability limits of the electrolyte and active material, allowing a maximum voltage to be reached. During galvanostatic cycling up to 2 V, the best performance was obtained with R = 2.5. The specific capacitance increased from 100 to 113 F g⁻¹ during the first 2000 cycles, then decayed up to 6000 cycles and finally stabilized at 100 F g⁻¹. SEM images of the manganese based electrode after various numbers of thousands cycles exhibited dramatic morphological modifications. The later are suspected to be due to Mn(IV) oxidation and dissolution at high potential values. Hence, the evolution of specific capacitance during cycling of the asymmetric capacitor is ascribed to structural changes at the positive electrode.     

Material design concept for Fe-substituted Li2MnO3-based positive electrodes

Fe-substituted Li₂MnO₃ (Li_1+x(Fe_yMn_1−y)_1−xO₂, 0 ≤ x ≤ 1/3, 0.3 ≤ y ≤ 0.7) was synthesized using a combination of coprecipitation, hydrothermal, and heat-treatment methods. It exhibits high initial specific capacity greater than 200 mAh g⁻¹ and small capacity, which fades up to the 50th cycle (>150 mAh g⁻¹ at the 50th cycle) under electrochemical cycle testing at 60 °C. The attractive electrode properties appeared by controlling the chemical composition (x > 0.05, 0.3 ≤ y ≤ 0.5) and high specific surface area (>20 m² g⁻¹). The Fe-substituted Li₂MnO₃ is an attractive candidate as a novel 3 V-class positive electrode material.