Electrochemical characterization of P2-type layered Na2/3Ni1/4Mn3/4O2 cathode in aqueous hybrid sodium/lithium ion electrolyte

P2-type layered Na_2/3Ni_1/4Mn_3/4O₂ has been synthesized by a solid-state method and its electrochemical behavior has been investigated as a potential cathode material in aqueous hybrid sodium/lithium ion electrolyte by adopting activated carbon as the counter electrode. The results indicate that the Na⁺/Li⁺ ratio in aqueous electrolyte has a strong influence on the capacity and cyclic stability of the Na_2/3Ni_1/4Mn_3/4O₂ electrode. Increase on the Li⁺ content leads to a shift of the redox potential towards a high value, which is favorable for the improvement of the working voltage of the layered material as cathode. It is found that the coexistence of Na⁺ and Li⁺ in aqueous electrolyte can improve the cyclic stability for the Na_2/3Ni_1/4Mn_3/4O₂ electrode. A reversible capacity of 54 mAh g⁻¹ was obtained with a high cyclability as the Na⁺/Li⁺ ratio was 2:2. Furthermore, an aqueous hybrid ion cell was assembled with the as-proposed Na_2/3Ni_1/4Mn_3/4O₂ as cathode and NaTi₂(PO₄)₃/graphite synthesized in this work as anode in 1 M Na₂SO₄/Li₂SO₄ (mole ratio as 2:2) mixed electrolyte. The cell shows an average discharge voltage at 1.2 V, delivering an energy density of 36 Wh kg⁻¹ at a power density of 16 W kg⁻¹ based on the total mass of the active materials.     

Hydrothermal synthesis of reduced graphene oxide-Mn3O4 nanocomposite as an efficient electrode materials for supercapacitors

Mn₃O₄ nanoparticles (NPs) are decorated with reduced graphene oxide nanosheets (rGO-Mn₃O₄) through a facile and eco-friendly hydrothermal method. The as-synthesized composite was characterized by XRD, SEM, TEM and Raman spectroscopy. The electrochemical properties of (rGO-Mn₃O₄) nanocomposite were studied as electrode materials for supercapacitors. The rGO-Mn₃O₄ nanocomposite exhibit high specific capacitance of 457 Fg^?1 at 1.0 A/g in 1 M Na₂SO₄ aqueous electrolyte. The rGO-Mn₃O₄ exhibits good capacitance retention by achieving 91.6% of its initial capacitance after 5000 cycles. The excellent electrochemical performance is attributed to the increased electrode conductivity in the presence of graphene network.     

A green strategy for the synthesis of graphene supported Mn3O4 nanocomposites from graphitized coal and their supercapacitor application

A by-product free strategy based on modified Hummers method was proposed to synthesize graphene/Mn₃O₄ composites without any additional manganese source. Coal-derived graphite (CDG) was used as carbon source instead of conventional natural graphite flakes and MnSO₄ produced from the modified Hummers was in situ transformed into Mn₃O₄ by precipitation in air. After reduction with hydrazine, the reduced coal-derived graphene oxide/Mn₃O₄ (RCDGO/Mn₃O₄) was obtained and employed as the electrode material for the supercapacitors. In addition, K₂SO₄ produced from the modified Hummers was used as electrolyte, as a result, residual-free was achieved during the whole process, and the atom utilization was calculated as high as about 97%. A maximum specific capacitance of 260 F g⁻¹ was achieved for RCDGO/Mn₃O₄ composite with 86% Mn₃O₄ in saturated K₂SO₄ electrolyte solution based on the synergetic effects between coal-derived graphene and attached Mn₃O₄ nanoparticles. Its specific energy density reached 8.7 Wh kg⁻¹ at a current density of 50 mA g⁻¹ when used as a symmetrical supercapacitor. The good capacitance retention (92–94%) was also observed after 1000 continuous cycles of galvanostatic charge–discharge.     

Electrodeposited hybrid films of polyaniline and manganese oxide in nanofibrous structures for electrochemical supercapacitor

Hybrid films of polyaniline (PANI) and manganese oxide (MnO_x) were obtained through potentiodynamic deposition from solutions of aniline and MnSO₄ at pH 5.6. The hybrid films demonstrated characteristic redox behaviors of PANI in acidic aqueous solution. Characterization of the hybrid films by XRD indicated the amorphous nature of MnO_x in the films in which manganese existed in oxidation states of +2, +3 and +4, based on XPS measurement. Hybrid film of PANI and MnO_x, PM120 obtained from the solution of 0.1 M aniline and 120 mM Mn²⁺ displayed a well opened nanofibrous structure which showed an 44% increase in specific capacitance from that of PANI (408 F g^?1) to 588 F g^?1, measured at 1.0 mA cm^?2 in 1 M NaNO₃ (pH 1). The hybrid film kept more than 90% of its capacitance after 1000 charging-discharging cycles, with a coulombic efficiency of 98%. The specific capacitance of a symmetric capacitor using PM120 as the electrodes is 112 F g^?1.     

Electrochemically synthesized graphene/polypyrrole composites and their use in supercapacitor

Composite films consisting of polypyrrole (PPy) and graphene oxide (GO) were electrochemically synthesized by electrooxidation of 0.1 M pyrrole in aqueous solution containing appropriate amounts of GO. Simultaneous chronoamperometric growth profiles and frequency changes on a quartz crystal microbalance showed that the anionic GO was incorporated in the growing GO/PPy composite to maintain its electrical neutrality. Subsequently, the GO was reduced electrochemically to form a reduced GO/PPy (RGO/PPy) composite by cyclic voltammetry. Specific capacitances estimated from galvanostatic discharge curves in 1 M H₂SO₄ at a current density of 1 A g^?1 indicated that values for the RGO/PPy composite were larger than those of a pristine PPy film and the GO/PPy composite. In the case of 6 mg mL^?1 GO for the preparation of GO/PPy, a high specific capacitance of 424 F g^?1 obtained at the electrochemically prepared RGO/PPy composite indicated its potential for use as an electrode material for supercapacitors.     

Optimal synthesis and new understanding of P2-type Na2/3Mn1/2Fe1/4Co1/4O2 as an advanced cathode material in sodium-ion batteries with improved cycle stability

A sol-gel method with ethylene diamine tetraacetic acid and citric acid as co-chelates is employed for the synthesis of P2-type Na_2/3Mn_1/2Fe_1/4Co_1/4O₂ as cathode material for sodium-ion batteries. Among the various calcination temperatures, the Na_2/3Mn_1/2Fe_1/4Co_1/4O₂ with a pure P2-type phase calcined at 900 °C demonstrates the best cycle capacity, with a first discharge capacity of 157 mA h g^?1 and a capacity retention of 91 mA h g^?1 after 100 cycles. For comparison, the classic P2-type Na_2/3Mn_1/2Fe_1/2O₂ cathode prepared under the same conditions shows a comparable first discharge capacity of 150 mA h g^?1 but poorer cycling stability, with a capacity retention of only 42 mA h g^?1 after 100 cycles. Based on X-ray photoelectron spectroscopy, the introduction of cobalt together with sol-gel synthesis solves the severe capacity decay problem of P2-type Na_2/3Mn_1/2Fe_1/2O₂ by reducing the content of Mn and slowing down the loss of Mn on the surface of the Na_2/3Mn_1/2Fe_1/4Co_1/4O₂, as well as by improving the activity of Fe³⁺ and the stability of Fe⁴⁺ in the electrode. This research is the first to demonstrate the origin of the excellent cycle stability of Na_2/3Mn_1/2Fe_1/4Co_1/4O₂, which may provide a new strategy for the development of electrode materials for use in sodium-ion batteries.     

High dispersion of γ-MnO2 on well-aligned carbon nanotube arrays and its application in supercapacitors

The well-aligned carbon nanotube arrays (ACNTs) were used as supporting material and the γ-MnO₂/ACNT electrode with high dispersion of γ-MnO₂ has been prepared by electrochemically induced deposition method. The crystal structure and morphology of the γ-MnO₂/ACNT electrode were investigated by X-ray diffraction, scanning electron microscopy and transmission electron microscopy. The capacitive properties of γ-MnO₂/ACNT electrode were characterized by cyclic voltammetry and galvanostatic charge–discharge method. The specific capacitance of the γ-MnO₂/ACNT electrode is as high as 784 F g^− 1 based on γ-MnO₂ and 234 F g^− 1 based on γ-MnO₂/ACNT composites in 0.1 M Na₂SO₄ aqueous solution from 0 to 1 V when the charge–discharge current density is 1 mA cm^− 2. Additionally, the electrode shows excellent power characteristics, high electrochemical reversibility and excellent long-term charge–discharge cycle stability.     

Facile synthesis of NiMn2O4 nanosheet arrays grown on nickel foam as novel electrode materials for high-performance supercapacitors

Nanostructured spinel NiMn₂O₄ arrays have been fabricated by a facile hydrothermal approach and further investigated as binder-free electrode for high-performance supercapacitors. Compared with Mn₃O₄, NiMn₂O₄ exhibited higher specific capacitances (662.5 F g⁻¹ and 370.5 F g⁻¹ in different electrolytes at the current density of 1 A g⁻¹) and excellent cycling stability (~96% capacitance retention after 1000 cycles) in a three-electrode system. Such a novel microstructure grown directly on the conductive substrate provided sufficient active sites for redox reaction resulting in their enhanced electrochemical behaviors. Their improved performances suggested that ultrathin sheet-like NiMn₂O₄ arrays on Ni foam substrate were a promising electrode material for supercapacitors.     

One-dimensional supramolecular assembly of an Mn12 single molecule magnet by ligand interactions

A new Mn₁₂ complex was synthesized using ligand substitution reaction of Mn₁₂–OAc with 4-(thiophen-3-yl)benzoic acid and complex’s structural and magnetic properties were analysed. [Mn₁₂O₁₂(O₂CC₆H₄C₄H₃S)₁₆(H₂O)₃]·14CH₂Cl₂ (1) crystallized in the P2₁/c space group. Intermolecular π–π interactions between phenyl and thiophene rings of two adjacent Mn₁₂ molecules result in one-dimensional supramolecular assembly of 1 in the crystal. On the other hand, steric repulsion between the neighbouring molecules causes unusual ligand arrangement and coordination geometry of Mn(III) ion with five coordination. The ac magnetic study of 1 gives U_eff = 69.98 K and 1/τ₀ = 1.456 × 10⁸ s^?1 and dc reduced magnetization measurement gives S = 10, g = 1.95 and D = ?0.425 cm^?1 showing that outer ligand distortion has little effect on the magnetic properties.     

High performance MnO2 nanoflower supercapacitor electrode by electrochemical recycling of spent batteries

MnO₂ nanoflower is prepared by electrochemical conversion of Mn₃O₄ obtained by heat treatment of spent zinc‒carbon batteries cathode powder. The heat treated and converted powders were characterized by TGA, XRD, FTIR, FESEM and TEM techniques. XRD analyses show formation of Mn₃O₄ and MnO₂ phases for the heat treated and converted powders, respectively. FESEM images indicate the formation of porous nanoflower structure of MnO_2, while, condensed aggregated particles are obtained for Mn₃O₄. The energy band gap of MnO₂ is obtained from UV‒Vis spectra to be 2.4 eV. The electrochemical properties are investigated using cyclic voltammetry, galvanostatic charge‒discharge and electrochemical impedance techniques using three-electrode system. The specific capacitance of MnO₂ nanoflower (309 F g⁻¹ at 0.1 A g⁻¹) is around six times higher than those obtained from the heat treated one (54 F g⁻¹ at 0.1 A g⁻¹). Moreover, it has high capacitance retention up to 93% over 1650 cycles. Impedance spectra of MnO₂ nanoflower show very small resistances and high electrochemical active surface area (340 m² g⁻¹). The present work demonstrates a novel electrochemical approach to recycle spent zinc-carbon batteries into high value supercapacitor electrode.     

Synthesis of Mn3O4/N-doped graphene hybrid and its improved electrochemical performance for lithium-ion batteries

Mn₃O₄/N-doped graphene (Mn₃O₄/NG) hybrids were synthesized by a simple one-pot hydrothermal process. The scanning electron microscopy (SEM), transition electron microscopy (TEM), X-ray powder diffraction (XRD), Thermogravimetric analysis (TG), Raman Spectroscopy and X-ray photoelectron spectroscopy (XPS) were used to characterize the microstructure, crystallinity and compositions. It is demonstrated that Mn₃O₄ nanoparticles are high-dispersely anchored onto the individual graphene nanosheets, and also found that, in contrast with pure Mn₃O₄ obtained without graphene added, the introduction of graphene effectively restricts the growth of Mn₃O₄ nanoparticles. Simultaneously, the anchored well-dispersed Mn₃O₄ nanoparticles also play a role as spacers in preventing the restacking of graphene sheets and producing abundant nanoscale porous channels. Hence, it is well anticipated that the accessibility and reactivity of electrolyte molecules with Mn₃O₄/NG electrode are highly improved during the electrochemical process. As the anode material for lithium ion batteries, the Mn₃O₄/NG hybrid electrode displays an outstanding reversible capacity of 1208.4 mAh g⁻¹ after 150 cycles at a current density of 88 mA g⁻¹, even still retained 284 mAh g⁻¹ at a high current density of 4400 mA g⁻¹ after 10 cycles, indicating the superior capacity retention, which is better than those of bare Mn₃O₄, and most other Mn₃O₄/C hybrids in reported literatures. Finally, the superior performance can be ascribed to the uniformly distribution of ultrafine Mn₃O₄ nanoparticles, successful nitrogen doping of graphene and favorable structures of the composites.     

Ionic conductivity of Mn2+ doped dense tin pyrophosphate electrolytes synthesized by a new co-precipitation method

Mn²⁺-doped Sn_1−xMn_xP₂O₇ (x = 0–0.2) are synthesized by a new co-precipitation method using tin(II)oxalate as tin(IV) precursor, which gives pure tin pyrophosphate at 300 °C, as all the reaction by-products are vaporizable at <150 °C. The dopant Mn²⁺ acts as a sintering aid and leads to dense Sn_1−xMn_xP₂O₇ samples on sintering at 1100 °C. Though conductivity of Sn_1−xMn_xP₂O₇ samples in the ambient atmosphere is 10⁻⁹–10⁻⁶ S cm⁻¹ in 300–550 °C range, it increases significantly in humidified (water vapor pressure, pH₂O = 0.12 atm) atmosphere and reaches >10⁻³ S cm⁻¹ in 100–200 °C range. The maximum conductivity is shown by Sn_0.88Mn_0.12P₂O₇ with 9.79 × 10⁻⁶ S cm⁻¹ at 550 °C in ambient air and 2.29 × 10⁻³ S cm⁻¹ at 190 °C in humidified air. It is observed that the humidification of Sn_1−xMn_xP₂O₇ samples is a slow process and its rate increases at higher temperature. The stability of Sn_1−xMn_xP₂O₇ samples is analyzed.     

(La,Sr)(Mn,Me)O3 manganites doped with d metals: Study of charge compensation mechanisms by crystallographic and magnetic characterizations

A comparison between theoretically calculated unit cell volume and interatomic distances in the system La_0.7Sr_0.3Mn_1−xMe_xO_3+δ (where Me = Cu, Fe, Cr, Ti) and the experimental data obtained by the full-profile Rietveld X-ray analysis as well as an analysis of magnetic properties allowed us to suggest possible mechanisms of charge compensation occurring when d metals substitute for manganese. It has been shown that in the case when copper, iron, chromium and titanium ions substitute for manganese ions in the system La_0.7Sr_0.3Mn_1−xMe_xO₃ charge compensation is described by the model 2Mn³⁺ → Mn⁴⁺ + Cu²⁺, Mn³⁺ → Fe³⁺, Mn³⁺ → Cr³⁺ and Mn⁴⁺ → Ti⁴⁺, respectively. In the latter case, a decrease in oxygen nonstoichiometry occurs with increasing x.     

Hydrazine hydrate-induced hydrothermal synthesis of MnFe2O4 nanoparticles dispersed on graphene as high-performance anode material for lithium ion batteries

Herein, a MnFe₂O₄/graphene (MnFe₂O₄/G) nanocomposite has been synthesized via a facile N₂H₄·H₂O-induced hydrothermal method. During the synthesis, N₂H₄·H₂O is employed to not only reduce graphene oxide to graphene, but also prevent the oxidation of Mn²⁺ in alkaline aqueous solution, thus ensuring the formation of MnFe₂O₄/G. Moreover, MnFe₂O₄ nanoparticles (5–20 nm) are uniformly anchored on graphene. MnFe₂O₄/G electrode delivers a large reversible capacity of 768 mA h g⁻¹ at 1 A g⁻¹ after 200 cycles and high rate capability of 517 mA h g⁻¹ at 5 A g⁻¹. MnFe₂O₄/G holds great promise as anode material in practical applications due to the outstanding electrochemical performance combined with the facile synthesis strategy.     

Straightforward synthesis of hierarchical Co3O4@CoWO4/rGO core–shell arrays on Ni as hybrid electrodes for asymmetric supercapacitors

Hierarchical Co₃O₄@CoWO₄/rGO core/shell nanoneedles arrays are successfully grown on 3D nickel foam using a simple, effective method. By virtue of its unique structure, Co₃O₄@CoWO₄/rGO demonstrates an enhanced specific capacitance of 386 F g⁻¹ at 0.5 A g⁻¹ current density. It can be used as an integrated, additive-free electrode for supercapacitors that boasts excellent performance. As illustration, we assemble an asymmetric supercapacitor (ASC) using the as-prepared Co₃O₄@CoWO₄/rGO as the positive electrode and activated carbon as the negative electrode. The optimized ASC displays a maximum energy density of 19.99 Wh kg⁻¹ at a power density of 321 W kg⁻¹. Furthermore, the ASC also presents a remarkably long cycle life along with 88.8% specific capacitance retention after 5000 cycles.     

Spark plasma sintering of MgAl2O4–YCr0.5Mn0.5O3 composite NTC ceramics

New high temperature negative temperature coefficient (NTC) thermistor ceramics based on a xMgAl₂O₄–(1 − x)YCr_0.5Mn_0.5O₃ (x = 0.1, 0.4, 0.6) composite system have been successfully fabricated through spark plasma sintering (SPS) with a low sintering temperature and a short sintering period. The X-ray diffraction analysis indicates that the SPS-sintered composite ceramics consist of a cubic spinel MgAl₂O₄ phase and an orthorhombic perovskite YCr_0.5Mn_0.5O₃ phase isomorphic to YCrO₃. The SPS-sintered composite ceramics have high relative density ranging from 94.1 to 97.4% of the theoretical density. X-ray photoelectron spectroscopy analysis corroborates the presence of Cr³⁺, Cr⁴⁺, Mn³⁺, and Mn⁴⁺ ions on lattice sites, which may result in the hopping conduction. The obtained ρ₂₅, B_25–150, and B_700–1000 of the SPS-sintered composite NTC thermistors are in the range of 1.53 × 10⁶–9.92 × 10⁹ Ω cm, 3380–5172 K, and 7239–9543 K, respectively. These values can be tuned by adjusting the MgAl₂O₄ concentration.     

Microwave dielectric properties of Mn-doped BaO–(Nd0.7,Sm0.3)2O3–4TiO2 ceramic sintered in a reducing atmosphere

The effect of MnCO₃ doped from 0 to 55 mol% into BaO–(Nd_0.7Sm_0.3)₂O₃–4TiO₂ (BNST) sintered in a reducing atmosphere on the microstructure and electrical properties was studied. Mn³⁺ completely substituted into Ti⁴⁺-sites of BNST to form a solid solution, so there is no second phase until 42 mol% which is the maximum solubility. Mn (<42 mol%)-doped BNST sintered in a reducing atmosphere is in a semi-conducing state because the concentration of free electron is higher than that of the acceptors. On the other hand, when Mn content doped into BNST exceeds a critical value (>43 mol%), the second Mn-rich phase due to excess of Mn³⁺ substituted into Ti⁴⁺-site, corresponding to original BaO–(Nd_0.7Sm_0.3)₂O₃–4TiO₂ (1 1 4) phase, is formed. Mn (>43 mol%)-doped BNST sintered in a reducing atmosphere is in an insulating state because the concentration of the acceptors is higher than that of liberated free electron, so the insulation resistance becomes high and tan δ becomes low. The formation of the second Mn-rich phase affects Q × f factor and temperature coefficient of capacitance (T.C.C.) of BNST significantly.     

Soot oxidation over K-doped manganese and iron spinels — How potassium precursor nature and doping level change the catalyst activity

This paper describes catalytic investigations into soot oxidation over KOH, K₂CO₃, KNO₃, CH₃COOK and K₂SO₄ doped iron and manganese spinels. For Fe₃O₄ it was found that alkali doping (0.5 monolayer) is confined to the surface and results in the substantial enhancement of its catalytic activity (ΔT_50% ≈ 80 °C for K₂CO₃), depending on the precursor nature. For Mn₃O₄ K-doping at low loading (0.5 ML) has a negative effect, whereas at high loading (9 ML) leads to the formation of a birnessite shell on the Mn₃O₄ core catalyst with a spectacular increase of the soot oxidation rate (ΔT_50% ≈ 150 °C).     

3D network-like porous MnCo2O4 by the sucrose-assisted combustion method for high-performance supercapacitors

3D network-like porous MnCo₂O₄ nanostructures have been successfully fabricated through a facile and scalable sucrose-assisted combustion route followed by calcination treatment. Benefiting from its advantages of the unique 3D network-like architectures with large specific surface area (216.15 m² g⁻¹), abundant mesoporosity (2–50 nm) and high electronic conductivity, the as-prepared MnCo₂O₄ electrode displays a high specific capacitance of 647.42 F g⁻¹ at a current density of 1 A g⁻¹, remarkable capacitance retention rate of 70.67% at current density of 10 A g⁻¹ compared with 1 A g⁻¹, and excellent cycle stability (only 6.32% loss after 3000 cycles). The excellent electrochemical performances coupled with facile and cost effective method will render the as-fabricated 3D network-like porous MnCo₂O₄ as a promising electrode material for supercapacitors.     

Electrochemical evaluation of LiZnxMn2−xO4 (x≤0.10) cathode material synthesized by solution combustion method

The spinel LiZn_xMn_2−xO₄ (x≤0.10) cathode materials have been synthesized by solution combustion method at 600 °C for 3 h. The structure and the morphology of LiZn_xMn_2−xO₄ were characterized by X-ray diffraction (XRD) analysis and scanning electron microscopy (SEM), respectively. All the obtained samples were identified as the spinel structure of LiMn₂O₄, the lattice parameters of samples decreased and the particle size increased as the Zn content increased. The effects of Zn-doping on the electrochemical characteristics of LiMn₂O₄ were investigated by galvanostatic charge–discharge experiments, cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). Among them, LiZn_0.05Mn_1.95O₄ particles presented outstanding cycling stability with a capacity retention of 82.9% at a discharge rate of 1 C (1 C=148 mA h g⁻¹) after 500 cycles. Spinel LiZn_0.05Mn_1.95O₄ had reversible cycling performance, revealing that doping LiMn₂O₄ with Zn improves its electrochemical performance.