Investigation on capacity fading of aqueous MnO2·nH2O electrochemical capacitor

Cycle stability of MnO₂·nH₂O electrochemical capacitors (ECs) has been studied by using galvanostatic tests and electrochemical impedance spectroscopy (EIS). The extent of capacity fading, ranging from 5 to 30% in 1000 cycles, increases with current-rate, and is markedly reduced with increasing binder content. Two fading mechanisms have been identified. With low binder content, and at high current-rate, capacity fading occurs in conjunction with appreciable increase in transmission resistance, suggesting progressively deteriorating electric contacts among the pseudocapacitive oxide particles and conductive carbon. The mechanical failure of the electrode structure may arise from the cyclic volumetric variation of the pseudocapacitive oxide particles as previously reported. With high binder content or at low current-rate, capacity fading is associated with increasing interfacial charge-transfer resistance upon cycling, which has a less pronounced effect than the mechanical failure mechanism.     

New design of electric double layer capacitors with aqueous LiOH electrolyte as alternative to capacitor with KOH solution

Activated carbon (AC) fiber cloths and a hydrophobic microporous polypropylene (PP) membrane, both modified with lithiated acetone oligomers, were used as electrodes and a separator in electric double layer capacitors (EDLCs) with aqueous lithium hydroxide (LiOH) as the electrolyte. Electrochemical characteristics of EDLCs were investigated by cyclic voltammetry (CV), galvanostatic charge-discharge cycle tests and impedance spectroscopy (EIS), compared with a case of the capacitor with aqueous potassium hydroxide (KOH) as an electrolyte. As a result, the capacitor with LiOH aqueous solution and a modified separator and electrodes was found to exhibit higher specific capacitance, maximum energy stored and maximum power than that with KOH aqueous solution.     

Long-term cycling behavior of asymmetric activated carbon/MnO2 aqueous electrochemical supercapacitor

Activated carbon–MnO₂ hybrid electrochemical supercapacitor cells have been assembled and characterized in K₂SO₄ aqueous media. A laboratory cell achieved 195,000 cycles with stable performance. The maximal cell voltage was 2 V associated with 21 ± 2 F g⁻¹ of total composite electrode materials (including activated carbon and MnO₂, binder and conductive additive) and an equivalent serie resistance (ESR) below 1.3 Ω cm². Long-life cycling was achieved by removing dissolved oxygen from the electrolyte, which limits the corrosion of current collectors. Scaling up has been realized by assembling several electrodes in parallel to build a prismatic cell. A stable capacity of 380 F and a cell voltage of 2 V were maintained over 600 cycles. These encouraging results show the interest of developing such devices, including non-toxic and safer components as compared to the current organic-based devices.     

Interfacial properties between LiFePO4 and poly(ethylene oxide)-Li(CF3SO2)2N polymer electrolyte

The interface resistance between Li_xFePO₄ and poly(ethylene oxide) (PEO)-Li(CF₃SO₂)₂N (LiTFSI) was examined by AC impedance measurement of a Li_xFePO₄/PEO-LiTFSI/Li_xFePO₄ cell in the temperature range of 30-60 °C. Four types of resistance, R0, R1, R2 and R3 were proposed according to analysis of the cell impedance using an equivalent circuit. The sum of R0 and R1 in the high frequency range is consistent with the resistance of the PEO electrolyte. R2 in the middle frequency range is related to lithium ion transport to an active point for charge transfer inside the composite electrode, and R3 in the low frequency range is considered to be the charge transfer resistance. The activation energy for R2 was affected by the thickness and composition of the electrode, whereas that for R3 was not.     

Fabrication and electrochemical characterization of two-dimensional ordered nanoporous manganese oxide for supercapacitor applications

A nanoporous manganese oxide (MnO₂) film was fabricated via a polystyrene templated electrodeposition in the solution containing MnSO₄. The nanoporous MnO₂ film obtained has been characterized by field emission scanning electron microscopy, cyclic voltammetry, electrochemical impedance spectroscopy and galvanostatic charge/discharge methods. The specific capacitance of 1018 F g⁻¹ was observed at a low current density of 500 mA g⁻¹. When the current density increased to 30.0 A g⁻¹, the specific capacitance of 277 F g⁻¹ remained. The high capacitance retention at high rates makes the prepared MnO₂ a promising candidate for supercapacitor applications.     

A novel activated mesocarbon microbead(aMCMB)/Mn3O4 composite for electrochemical capacitors in organic electrolyte

A novel activated mesocarbon microbead(aMCMB)/Mn₃O₄ composite is successfully prepared for electrochemical capacitors. The morphology and crystal structure of the composite are investigated by scanning electron microscopy and X-ray diffraction. The electrochemical studies indicate that the aMCMB/Mn₃O₄ composite has ideal capacitive performance in 1.0 mol L⁻¹ LiPF₆(EC + DMC). A maximum specific capacitance of 178 F g⁻¹ is obtained for the composite via galvanostatic charge–discharge at a current density of 330 mA g⁻¹, and the specific capacitance of Mn₃O₄ is estimated to be as high as 445 F g⁻¹. The aMCMB/Mn₃O₄ composite material exhibits ideal capacitive behavior indicating a promising electrode material for electrochemical supercapacitors.     

Multiwall carbon nanotube-poly(4-styrenesulfonic acid) supported polypyrrole/manganese oxide nano-composites for high performance electrochemical electrodes

Poly(4-styrenesulfonic acid) (PSS) dispersed multiwall carbon nanotubes (MWCNTs) are used as a support for polypyrrole (PPy)/MnO₂ in a supercapacitor electrode. Synergetic interaction between polypyrrole and MnO₂ significantly improves the electrical properties and the mechanical stability of the electrode that yields high rate capability. The (–SO₃⁻) surface functionalities on MWCNT-PSS facilitate an ordered growth, and the molecular level dispersion of MnO₂ in PPy matrix enhances the electrode performance. As an electrochemical electrode the MWCNT-PSS/PPy:MnO₂ nano-composite exhibits 268 F g⁻¹ specific capacitance at 5 mV s⁻¹. The excellent rate capability and stability of the electrode is demonstrated by only 7% fade in the specific capacity at 100 mV s⁻¹ (compared to the available capacity at 5 mV s⁻¹) and 10% fade in the same after 5000 CV cycles. Specific capacitance of PPy:MnO₂ component in the nano-composite is as high as 412 F g⁻¹ in 0.5 M Na₂SO₄ electrolyte. Electrical conductivity of the MWCNT-PSS/PPy nano-composite is significantly improved upon inclusion of MnO₂ in molecular level dispersion.     

Electrochemical capacitance of NiO/Ru0.35V0.65O2 asymmetric electrochemical capacitor

A designed asymmetric hybrid electrochemical capacitor was presented where NiO and Ru_0.35V_0.65O₂ as the positive and negative electrode, respectively, both stored charge through reversible faradic pseudocapacitive reactions of the anions (OH⁻) with electroactive materials. And the two electrodes had been individually tested in 1 M KOH aqueous electrolyte to define the adequate balance of the active materials in the hybrid system as well as the working voltage of the capacitor based on them. The electrochemical tests demonstrated that the maximum specific capacitance and energy density of the asymmetric hybrid electrochemical capacitor were 102.6 F g⁻¹ and 41.2 Wh kg⁻¹, respectively, delivered at a current density of 7.5 A cm⁻². And the specific energy density decreased to 23.0 Wh kg⁻¹ when the specific power density increased up to 1416.7 W kg⁻¹. The hybrid electrochemical capacitor also exhibited a good electrochemical stability with 83.5% of the initial capacitance over consecutive 1500 cycle numbers.     

Cu(OH)2 and CuO nanotube networks from hexaoxacyclooctadecane-like posnjakite microplates: Synthesis and electrochemical hydrogen storage

Our recent progress shows that Cu(OH)₂ and CuO nanoribbon arrays exhibit notable electrochemical hydrogen storage capacities of 180 and 160 mAh/g, respectively, which also suggests that porous or tubular nanostructures can have a higher ability of hydrogen uptake. Two dimensional (2D) networks consisting of crossed Cu(OH)₂ nanotubes were prepared by a simple topotactic transformation process, including the fabrication of hexaoxacyclooctadecane-like intermediate posnjakite microplates and their subsequent chemical transformation into Cu(OH)₂ nanotube networks, which further dehydrated to produce CuO nanotube networks with partial morphological preservation. The formation of half-tube and half-ribbon structures, nanoribbons, and nanotubes during the transformation processes revealed that the deformations of corrugated posnjakite sheets to give lamellar Cu(OH)₂ with rolling into tubular structures could be responsible for the growth of Cu(OH)₂ nanotube networks from posnjakite microplates. The Cu(OH)₂ and CuO nanotube networks could electrochemically charge and discharge with higher hydrogen storage capacities of 220 and 188 mAh/g than the Cu(OH)₂ and CuO nanoribbon arrays at room temperature, respectively, which made them promising candidates for hydrogen storage, high-energy batteries and catalytic fields. Based on the rolling mechanism of layered structural materials, this simple topotactic transformation route might be extendable to the preparation of novel nanotube networks with higher capacities of hydrogen storage if appropriate precursors of numerous materials with layered structures were treated in solution.     

A cheap asymmetric supercapacitor with high energy at high power: Activated carbon//K0.27MnO2·0.6H2O

Studies of the electrochemical behavior of K_0.27MnO₂·0.6H₂O in K₂SO₄ show the reversible intercalation/deintercalation of K⁺-ions in the lattice. An asymmetric supercapacitor activated carbon (AC)/0.5 mol l⁻¹ K₂SO₄/K_0.27MnO₂·0.6H₂O was assembled and tested successfully. It shows an energy density of 25.3 Wh kg⁻¹ at a power density of 140 W kg⁻¹; at the same time it keeps a very good rate behavior with an energy density of 17.6 Wh kg⁻¹ at a power density of 2 kW kg⁻¹ based on the total mass of the active electrode materials, which is higher than that of AC/0.5 mol l⁻¹ Li₂SO₄/LiMn₂O₄. In addition, this asymmetric supercapacitor shows excellent cycling behavior without the need to remove oxygen from the electrolyte solution. This can be ascribed in part to the stability of the lamellar structure of K_0.27MnO₂·0.6H₂O. This asymmetric aqueous capacitor has great promise for practical applications due to high energy density at high power density.     

Study of poly(vinyl alcohol)/titanium oxide composite polymer membranes and their application on alkaline direct alcohol fuel cell

The novel poly(vinyl alcohol)/titanium oxide (PVA/TiO₂) composite polymer membrane was prepared using a solution casting method. The characteristic properties of the PVA/TiO₂ composite polymer membrane were investigated by thermal gravimetric analysis (TGA), a scanning electron microscopy (SEM), a micro-Raman spectroscopy, a methanol permeability measurement and the AC impedance method. An alkaline direct alcohol (methanol, ethanol and isopropanol) fuel cell (DAFC), consisting of an air cathode based on MnO₂/C inks, an anode based on PtRu (1:1) black and a PVA/TiO₂ composite polymer membrane, was assembled and examined for the first time. The results indicate that the alkaline DAFC comprised of a cheap, non-perfluorinated PVA/TiO₂ composite polymer membrane shows an improved electrochemical performances. The maximum power densities of alkaline DAFCs with 4 M KOH + 2 M CH₃OH, 2 M C₂H₅OH and 2 M isopropanol (IPA) solutions at room temperature and ambient air are 9.25, 8.00, and 5.45 mW cm⁻², respectively. As a result, methanol shows the highest maximum power density among three alcohols. The PVA/TiO₂ composite polymer membrane with the permeability values in the order of 10⁻⁷ to 10⁻⁸ cm² s⁻¹ is a potential candidate for use on alkaline DAFCs.     

Hybrid supercapacitor based on MnO2 and columned FeOOH using Li2SO4 electrolyte solution

The nano-sized columned β-FeOOH was prepared by the hydrolysis process and its electrochemical capacitance performance was evaluated for the first time in Li₂SO₄ solution. A hybrid supercapacitor based on MnO₂ positive electrode and FeOOH negative electrode in Li₂SO₄ electrolyte solution was designed. The electrochemical tests demonstrated that the hybrid supercapacitor has a energy density of 12 Wh kg⁻¹ and a power density of 3700 W kg⁻¹ based on the total weight of the electrode active materials with a voltage range 0–1.85 V. This hybrid supercapacitor also exhibits a good cycling performance and keeps 85% of initial capacity over 2000 cycles.     

Novel polymer electrolytes based on triblock poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) with ionically active SiO2

A novel polymer electrolyte based on triblock copolymer of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) with ionically active SiO₂ inclusions has been designed. The electrolyte shows favorable features for ion migration such as low glass transition temperature and high concentration of amorphous phase. Combined with the effect of active SiO₂, its ionic conductivity is about 8.0 × 10⁻⁵ S cm⁻¹ at 30 °C, which exceeds that for the PEO-based systems. As applying them to cells with LiFePO₄-type cathodes, a capacity of about 147.0 mAh g⁻¹ is obtained at 60 °C, which is retained by more than 90% after 40 charge/discharge cycles. Moreover, about 100 mAh g⁻¹ could still be delivered as temperature decreases to 30 °C.     

Synthesis of hydrothermally reduced graphene/MnO2 composites and their electrochemical properties as supercapacitors

Hydrothermally reduced graphene/MnO₂ (HRG/MnO₂) composites were synthesized by dipping HRG into the mixed aqueous solution of 0.1 M KMnO₄ and 0.1 M K₂SO₄ for different periods of time at room temperature. The morphology and microstructure of the as-prepared composites were characterized by field-emission scanning electron microscopy, X-ray diffraction, Raman microscope, and X-ray photoelectron spectroscopy. The characterizations indicate that MnO₂ successfully deposited on HRG surfaces and the morphology of the HRG/MnO₂ shows a three-dimensional porous structure with MnO₂ homogenously distributing on the HRG surfaces. Capacitive properties of the synthesized composite electrodes were studied using cyclic voltammetry and electrochemical impedance spectroscopy in a three-electrode experimental setup using 1 M Na₂SO₄ aqueous solution as electrolyte. The main results of electrochemical tests are drawn as follows: the specific capacitance value of HRG/MnO₂-200 (HRG dipped into the mixed solution of 0.1 M KMnO₄ and 0.1 M K₂SO₄ for 200 min) electrode reached 211.5 F g⁻¹ at a potential scan rate of 2 mV s⁻¹; moreover, this electrode shows a good cyclic stability and capacity retention. It is anticipated that the synthesized HRG/MnO₂ composites will find promising applications in supercapacitors and other devices in virtue of their outstanding characters of good cycle stability, low cost and environmentally benign nature.     

Polypropylene-supported and nano-Al2O3 doped poly(ethylene oxide)-poly(vinylidene fluoride-hexafluoropropylene)-based gel electrolyte for lithium ion batteries

A new gel polymer electrolyte (GPE) is reported in this paper. In this GPE, blending polymer of poly(ethylene oxide) (PEO) with poly(vinylidene fluoride-hexafluoropropylene) (P(VdF-HFP)), doped with nano-Al₂O₃ and supported by polypropylene (PP), is used as polymer matrix, namely PEO-P(VdF-HFP)-Al₂O₃/PP. The performances of the PEO-P(VdF-HFP)-Al₂O₃/PP membrane and the corresponding GPE are characterized with mechanical test, CA, EIS, TGA and charge-discharge test. It is found that the performances of the membrane and the GPE depend to a great extent on the content of doped nano-Al₂O₃. With doping 10 wt.% nano-Al₂O₃ in PEO-P(VdF-HFP), the mechanical strength from 9.3 MPa to 14.3 MPa, the porosity of the membrane increases from 42% to 49%, the electrolyte uptake from 176% to 273%, the thermal decomposition temperature from 225 °C to 355 °C, and the ionic conductivity of corresponding GPE is improved from 2.7 × 10⁻³ S cm⁻¹ to 3.8 × 10⁻³ S cm⁻¹. The lithium ion battery using this GPE exhibits good rate and cycle performances.     

Solid-state photoelectrochemical device based on poly(3-hexylthiophene) and an ion conducting polymer electrolyte, amorphous poly(ethylene oxide) complexed with I3/I redox couple

The photoelectrochemical properties of a solid-state photoelectrochemical cell (PEC) based on poly(3-hexylthiophene), P3HT, and an ion-conducting polymer electrolyte, amorphous poly(ethylene oxide), POMOE, complexed with I₃⁻/I⁻ redox couple has been constructed and studied. The current–voltage characteristics in the dark and under white light illumination, transient photocurrent and photovoltage studies, photocurrent action spectra for front and back side illuminations and an open-circuit voltage and short-circuit current dependence on light intensity have been studied. An open-circuit voltage of 130 mV and a short-circuit current of 0.47 μA cm⁻² were obtained at light intensity of 100 mW/cm². IPCE% of 0.024% for front side illumination (ITO/PEDOT) and IPCE% of 0.003% for backside illumination (ITO/P3HT) were obtained.     

Dye-sensitized, nano-porous TiO2 solar cell with poly(acrylonitrile): MgI2 plasticized electrolyte

Dye-sensitized solar cells are promising candidates as supplementary power sources; the dominance in the photovoltaic field of inorganic solid-state junction devices is in fact now being challenged by the third generation of solar cells based on dye-sensitized, nano-porous photo-electrodes and polymer electrolytes. Polymer electrolytes are actually very favorable for photo-electrochemical solar cells and in this study poly(acrylonitrile)-MgI₂ based complexes are used. As ambient temperature conductivity of poly(acrylonitrile)-salt complexes are in general low, a conductivity enhancement is attained by blending with the plasticizers ethylene carbonate and propylene carbonate. At 20 °C the optimum ionic conductivity of 1.9 × 10⁻³ S cm⁻¹ is obtained for the (PAN)₁₀(MgI₂)_n(I₂)_n/10(EC)₂₀(PC)₂₀ electrolyte where n = 1.5. The predominantly ionic nature of the electrolyte is seen from the DC polarization data. Differential scanning calorimetric thermograms of electrolyte samples with different MgI₂ concentrations were studied and glass transition temperatures were determined. Further, in this study, a dye-sensitized solar cell structure was fabricated with the configuration Glass/FTO/TiO₂/Dye/Electrolyte/Pt/FTO/Glass and an overall energy conversion efficiency of 2.5% was achieved under solar irradiation of 600 W m⁻². The I-V characteristics curves revealed that the short-circuit current, open-circuit voltage and fill factor of the cell are 3.87 mA, 659 mV and 59.0%, respectively.     

Performance improvement of polyethylene-supported poly(methyl methacrylate-vinyl acetate)-co-poly(ethylene glycol) diacrylate based gel polymer electrolyte by doping nano-Al2O3

Polyethylene (PE)-supported poly(methyl methacrylate-vinyl acetate)-co-poly(ethylene glycol) diacrylate with and without doping nano-Al₂O₃, namely P(MMA-VAc)-co-PEGDA/PE and P(MMA-VAc)-co-PEGDA/Al₂O₃/PE, are prepared and their performances as gel polymer electrolytes (GPEs) for lithium ion battery are studied by mechanical test, scanning electron microscopy, thermogravimetric analyzer, electrochemical impedance spectroscopy, cyclic voltammetry, and charge/discharge test. It is found that the doping of nano-Al₂O₃ in the P(MMA-VAc)-co-PEGDA/PE improves the comprehensive performances of the GPE and thus the rate performance and cyclic stability of the battery. With doping nano-Al₂O₃, the mechanical and thermal stability of the polymer and the ionic conductivity of the corresponding GPE increases slightly, while the battery exhibits better cyclic stability. The mechanical strength and the decomposition temperature of the polymer increase from 15.9 MPa to 16.2 MPa and from 410 °C to 420 °C, respectively. The ionic conductivity of the GPE is from 3.4 × 10⁻³ S cm⁻¹ to 3.8 × 10⁻³ S cm⁻¹. The discharge capacity of the battery using the GPE with doping nano-Al₂O₃ keeps 90.9% of its initial capacity after 100 cycles and shows good C-rate performance.     

Effect of impurities and moisture on lithium bisoxalatoborate (LiBOB) electrolyte performance in lithium-ion cells

Electrolytes containing LiB(C₂O₄)₂ (LiBOB) salts are of increasing interest for lithium-ion cells for several reasons that include their ability to form a stable solid electrolyte interphase on graphite electrodes. However, cells containing these electrolytes often show inconsistent performance because of impurities in the LiBOB salt. In this work we compare cycling and impedance data from cells containing electrolytes with LiBOB that was obtained commercially and LiBOB purified by a rigorous recrystallization procedure. We relate the difference in performance to a lithium oxalate impurity that may be a residual from the salt manufacturing process. We also examine the reaction of LiBOB with water to determine the effect of salt storage in high-humidity environments. Although LiBOB electrolytes containing trace amounts (∼100 ppm) of moisture appear relatively stable, higher moisture contents (∼1 wt%) lead to observable salt decomposition resulting in the generation of B(C₂O₄)(OH) and LiB(C₂O₄)(OH)₂ compounds that do not dissolve in typical carbonate solutions and impair lithium-ion cell performance.