Increasing ionic conductivity and mechanical strength of a plastic electrolyte by inclusion of a polymer

In this contribution we present a soft matter solid electrolyte which was obtained by inclusion of a polymer (polyacrylonitrile, PAN) in LiClO₄/LiTFSI-succinonitrile (SN), a semi-solid organic plastic electrolyte. Addition of the polymer resulted in considerable enhancement in ionic conductivity as well as mechanical strength of LiX-SN (X = ClO₄, TFSI) plastic electrolyte. Ionic conductivity of 92.5%-[1 M LiClO₄-SN]:7.5%-PAN (PAN amount as per SN weight) composite at 25 °C recorded a remarkably high value of 7 × 10⁻³ Ω⁻¹ cm⁻¹, higher by few tens of order in magnitude compared to 1 M LiClO₄-SN. Composite conductivity at sub-ambient temperature is also quite high. At −20 °C, the ionic conductivity of (100 − x)%-[1 M LiClO₄-SN]:x%-PAN composites are in the range 3 × 10⁻⁵-4.5 × 10⁻⁴ Ω⁻¹ cm⁻¹, approximately one to two orders of magnitude higher with respect to 1 M LiClO₄-SN electrolyte conductivity. Addition of PAN resulted in an increase of the Young's modulus (Y) from Y → 0 for LiClO₄-SN to a maximum of 0.4 MPa for the composites. Microstructural studies based on X-ray diffraction, differential scanning calorimetry and Fourier transform infrared spectroscopy suggest that enhancement in composite ionic conductivity is a combined effect of decrease in crystallinity and enhanced trans conformer concentration.     

Molecular assembled self-doped polyaniline copolymer ultra-thin films

A self-assembly technique and copolymerization were used to buildup a self-doped polyaniline (SPANI) ultra-thin film on an indium-tin oxide (ITO) substrate. The monomers used were aniline and its derivative MSAN (m-aminobenzenesulfonic acid). Successful MSAN/AN copolymerization and film formation were simultaneously performed in aqueous solution with the addition of oxidant (APS, ammonium persulfate). The film deposition rate of a high AN/MSAN ratio system is generally higher than that of a low AN/MSAN ratio system. Cyclic voltammetry, UV-vis spectroscopy, and α-step instruments indicate a systematic dependence of the film thickness of these ultra-thin films on the assembly time and temperatures. The Auger depth profile reveals the elemental distribution in these films and exhibits different deposition rates between AN and MSAN. XPS N_1s spectra also show the variation of the degree of doping. This SPANI film can be used as an electrochromic electrode in a corresponding device. Carboxyl-terminated-butadiene-acrylonitrile (CTBN) blended with LiClO₄ was used as a solid polymer electrolyte. A total solid electrochromic device was assembled as ITO/SPANI/LiClO₄-CTBN/PEDOT:PSS/ITO, where PEDOT:PSS is poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) as the counter complementary electrode. The device was pale gray at −1.5 V and blue at +1.5 V.     

Electrochromic performance of a poly(3,4-ethylenedioxythiophene)-Prussian blue device encompassing a free standing proton electrolyte film

Electrochromic devices incorporating an electropolymerized poly(3,4-ethylenedioxythiophene) (PEDOT) film and a free standing, transparent film of a proton conducting polymer electrolyte with high ambient temperature ionic conductivity of 10⁻² S cm⁻¹ have been fabricated with and without the ion storage electrodeposited Prussian blue (PB) counter electrode layer. While coloration efficiency increases as a function of applied potential in the sole PEDOT device with largest values of CE_(max,VIS) ∼ 120 cm² C⁻¹ and CE_(max,NIR) ∼ 133 cm² C⁻¹ attained at V_c = −1.9 V, the PEDOT:PB device shows a digression from this trend. Much higher coloration efficiencies in the visible (247 cm² C⁻¹ at 570 nm) and NIR (116 cm² C⁻¹ at 1100 nm) regions are achieved for the PEDOT:PB device at a relatively lower reducing voltage of −0.8 V. The PEDOT:PB device shows fast switching redox process (t_c = 2.6 s and t_b = 1.3 s for a 50% optical contrast at 632.8 nm) and a highly reversible charge density as the ratio of Q_inserted to Q_extracted was found to vary between 0.8 and 1.0. When switched between the clear and blue states for 2000 cycles, the insignificant drop in peak current density maxima observed for the PEDOT:PB device, i.e. the good cycling stability, the facile fabrication of device assembly, the ease of scaling up the electrolyte and electrochromic coatings, indicate that this method can be adapted as a simple and inexpensive alternative to conventional electrochromic windows with high cost components.     

Electrocatalytic activity of 2,3,5,6-tetrachloro-1,4-benzoquinone/multi-walled carbon nanotubes immobilized on edge plane pyrolytic graphite electrode for NADH oxidation

This work reports the electrocatalytic activity of 2,3,5,6-tetrachloro-1,4-benzoquinone (TCBQ)/multi-walled carbon nanotubes (MWCNT) immobilized on an edge plane pyrolytic graphite electrode for nicotinamide adenine dinucleotide (NADH) oxidation. Scanning electron microscopy (SEM) and energy dispersive X-ray spectrometry (EDS) were used to confirms the presence of chloro after the nanotube modification with 2,3,5,6-tetrachloro-1,4-benzoquinone. The surface charge transfer constant, k_s, and the charge transfer coefficient for the modified electrode, α, were estimated as 98.5 (±0.6) s⁻¹ and 0.5, respectively. With this modified electrode the oxidation potential of the NADH was shifted about 300 mV toward a less positive value, presenting a peak current much higher than those measured on an unmodified edge plane pyrolytic graphite electrode (EPPG). Cyclic voltammetry and rotating disk electrode (RDE) experiments indicated that the NADH oxidation reaction involves 2 electrons and a heterogenous rate constant (k_obs) of 3.1 × 10⁵ mol⁻¹ l s⁻¹. The detection limit, repeatability, long-term stability, time of response and linear response range were also investigated.     

The conductivity and characterization of the plasticized polymer electrolyte based on the P(AN-co-GMA-IDA) copolymer with chelating group (II): The effect of free ion in the plasticized polymer electrolyte

A new gel-type polymer electrolyte (GPE) was made by the copolymerizing acrylonitrile (AN) and (2-methylacrylic acid 3-(bis-carboxymethylamino)-2-hydroxy-propyl ester) (GMA-IDA). The copolymer mixed with a plasticizer—propylene carbonate (PC) and lithium salt to form GPE. The lithium salts are LiCF₃SO₃, LiBr and LiClO₄. FT-IR spectra show that the lithium ion in the LiClO₄ system has the strongest interaction with the group based on the plasticized polymer. FT-IR spectra also indicate that CF₃SO₃⁻ prefers producing anion-cation association. Moreover, the ¹³C solid state NMR spectra for the carbons attached to the PC of GPE exhibited different level of chemical shift (158.5 ppm) when the different lithium salts were added to the electrolyte. The results of differential scanning calorimeter (DSC) also indicate that the LiClO₄ system has more free lithium ions; therefore, it has the maximum conductivity. In this study, the highest conductivity 2.98 × 10⁻³ S cm⁻¹ exists in AG2/PC = 20/80 wt.% system which contain 3 mmole (g-polymer)⁻¹ LiClO₄. Additionally, the polymer electrolytes, which contain GMA-IDA have better interfacial resistance stability with lithium electrode.     

Characteristics of solubilization and encapsulation of fullerene C60 in non-ionic Triton X-100 micelles

The solubilization and encapsulation of monomeric C₆₀ in Triton X-100 micelles were investigated. Characteristic hydrophobic interactions of the type π-π and CH-π between the Triton X-100 micelle and C₆₀ resulted in stable aqueous dispersions of C₆₀ in the micellar medium, as evidenced from UV-vis, fluorescence emission and micro-Raman spectroscopy. Cyclic voltammetry of C₆₀ encapsulated Triton X-100 in aqueous 5 mM LiClO₄ solution revealed a quasi-reversible one-electron reduction peak with E_1/2 = −0.61 V and a reversible reduction peak at E_1/2 = −1.11 V vs. Ag/AgCl reference electrode at a scan rate of 10 mV s⁻¹, a redox behaviour drifting substantially from that of pure C₆₀. An onset concentration of ∼0.025 mM for C₆₀ aggregation in the micellar core was substantiated from the characteristic absorption spectral broadening and quenching of pyrene fluorescence. The molar solubilization capacity of C₆₀ in aqueous Triton X-100 micellar solution was estimated spectrophotometrically to be 0.22.     

Spray deposited titanium oxide thin films as passive counter electrodes

Titanium dioxide (TiO₂) thin films were deposited from methanolic solution onto fluorine doped tin oxide coated conducting glass substrates by spray pyrolysis technique. The electrochemical properties of TiO₂ thin films were investigated using cyclic voltammetry, chronoamperometry, chronocoulometry and iono-optical studies, in 0.1N H₂SO₄ electrolyte. Performance of the films deposited at three different substrate temperatures, viz. 350, 400 and 450 °C is discussed in view of their utilization in electrochromic devices, as counter electrode. The magnitude of charge storage capacity, Q/t (4.75-6.13 × 10⁻³ mC/(cm² nm)) and colouration efficiency (3.2-4.3 cm²/mC) of TiO₂ rank these films among the promising counter electrodes in electrochromic devices.     

Replies to comments contained in “Conductivity hysteresis in polymer electrolytes incorporating poly(tetrahydrofuran)” by O. Akbulut, et al., Electrochim. Acta 52 (2007) 1983

DSC indicates that first-heating endotherms at 95 and 100-115 °C in poly(tetramethylene oxide)-based polymers with LiClO₄ and LiBF₄, respectively, arise from the decomposition of phase-separated LiClO₄·3H₂O and a pre-melting transition in phase-separated LiBF₄ and not from organized adducts with poly(tetramethylene oxide) as asserted by Akbulut et al. and other literature. Water in the LiClO₄ system, at least (absent in freeze-dried samples), could account for higher conductivities reported by Akbulut et al. than observed by the present authors. Irreversibility of log σ versus1/T in these weakly ionophilic systems apparently arises from slow dissolution of lithium salts together with morphological changes in mixtures of the self-organising systems CmOn (I) with the ‘grain boundary bridging’ copolymer -[-(CH₂)₄-O-]_x-(CH₂)₁₂- (II). A three-component system I:II:LiBF₄ to which 9 wt% of tetrahydrofuran had been purposefully added showed deterioration in conductivity compared with the system without THF addition. This suggests that solvent-inhibition of self-organization is contrary to the suggestion by Akbulut et al. that irreversible transformation to a high ambient conductivity (σ = 10⁻⁴ to 10⁻³ S cm⁻¹) regime arises from plasticization by the 3 wt% of volatiles, generated by thermal decomposition of II in a three-component mixture, that they report. The irreversible transformation to higher conductivities is also observed in systems heated to maximum temperatures between 50 and 80 °C for which degradation was shown to be negligible.     

Preparation of electrochromic Ni1−xO and TiO2 coatings from pigment dispersions and their application in electrochromic foil based devices

Thin (100–400 nm) electrochromic TiO₂ and Ni_1−xO coatings providing transmissive light modulation were made from an anatase pigment dispersion obtained by co-grinding nanocrystalline titanium particles (6–10 nm in size) with trisilanol heptaisobutylsilsesquioxane as dispersant, while Ni_1−xO based pigment dispersions were made by milling pre-prepared Ni_1−xO pigment with nickel oxyhydroxide (NiO_xH_y) dispersant. Dispersions were obtained by milling the pigments with zirconia beads of various sizes (0.1, 0.2 and 0.4 mm) and the particle size was determined with the dynamic light scattering technique (DLS). Pigment dispersions were deposited by spin-coating on glass and plastic (PET) film and thermally treated at 150 °C to obtain thin TiO₂ and Ni_1−xO pigment coatings. SEM and AFM were used for determination of the surface morphology, revealing their homogenous structure and low surface roughness (up to 20 nm). The optical transmittance and haze of the coatings deposited on glass and PET film were determined from the UV–vis spectra. Their electrochromic effect was analyzed by electrochemical charging/discharging the coatings in a LiClO₄/PC electrolyte. The results demonstrated a convenient, simple and robust technique for making “electrochromic paint” coatings. Pre-prepared TiO₂ and pigments were used for construction of foil-based electrochromic devices with transmissive modulation of light.     

A highly conductive organic-inorganic hybrid electrolyte based on co-condensation of di-ureasil and ethylene glycol-containing alkoxysilane

Organic-inorganic hybrid electrolytes based on di-ureasil backbone structures by reacting poly(propylene glycol)-block-poly(ethylene glycol)-block-poly(propylene glycol) bis(2-aminopropyl ether) (ED2000) with 3-(triethoxysilyl)propyl isocyanate (ICPTES), followed by co-condensation with methoxy(polyethylenoxy)propyl trimethoxysilane (MPEOP) in the presence of LiClO₄ were prepared and characterized by a variety of techniques. The hybrid electrolytes showed good resistance to crystallization and excellent conductivity for use in lithium-ion batteries, as determined by differential scanning calorimetry (DSC) and impedance measurements, respectively. The temperature dependence of the ionic conductivity exhibited a VTF (Vogel-Tamman-Fulcher)-like behavior for all the compositions studied and a maximum ionic conductivity value of 6.9 × 10⁻⁵ S cm⁻¹, a relatively high value for solid polymer electrolytes, was achieved at 30 °C for the hybrid electrolyte with a [O]/[Li] ratio of 16. A microscopic view of the dynamic behavior of the polymer chains (¹³C) and the ionic species (⁷Li) was provided by the ¹H and ⁷Li line widths measured from 2D ¹H-¹³C WISE (Wideline Separation) and variable temperature ⁷Li static NMR, respectively, to elucidate the influence of the mobility of the polymer chains and the charge carriers on the observed ionic conductivity. The present salt-free hybrid electrolyte after plasticization with 1 M LiClO₄ in EC/PC solution exhibited a swelling ratio of 275% and reached an ionic conductivity value up to 8.3 × 10⁻³ S cm⁻¹ at 30 °C, which make it a good candidate for the further development of advanced rechargeable lithium-ion batteries.     

Electrochemical behaviour of (111) B-Doped Polycrystalline Diamond: Morphology/surface conductivity/activity assessed by EIS and CS-AFM

Electrochemical activity, morphology and surface electrical conductivity of Boron-Doped Polycrystalline Diamond films prepared by MPCVD have been investigated. Heterogeneous apparent rate constants of three different redox systems, [Fe(CN)₆]^3−/4−, [IrCl₆]^2−/3− and [Ru(NH₃)₆]^3+/2+ have been measured by both Cyclic Voltammetry and Electrochemical Impedance Spectroscopy on < 100 > textured films with a predominance of (111) faces: first measurements have been done with [Fe(CN)₆]^3−/4− only on as grown samples, and secondly after a mild electrochemical pretreatment the three redox systems have been investigated. “As-grown” samples showed a moderate average activity which was related to the presence of a minority of electronically conducting areas among insulating zones. Electrochemical treatment in neutral conditions substantially increased the activity and heterogeneous apparent rate constants k_app for the three couples were measured in the range of 10^− 2 cm s^− 1 with a good stability in time. Current-sensing AFM images performed ex situ showed that the electrochemically pre-treated material presented a high superficial conductivity whereas the grown sample showed major area of low conductivity.     

Electrochromic property of nano-composite Prussian Blue based thin film

In this paper, we present fabrication of a nano-composite Prussian Blue (NPB) film to synchronously improve the contrast and switching time of regular Prussian Blue (PB) film by applying the concept of nano-technology. The NPB consists of indium tin oxide (ITO) nano-particles (3.0 ± 1.0 Ω, 40 ± 5 nm) as a medium layer for PB to gain larger operative reaction surface area in Li⁺ based electrolyte (1 M LiClO₄/PC) system. The procedures for preparation of NPB are: first, a well-dispersed ITO nano-particle solution is sprayed onto ITO glass (30 Ω/sq) at 200 °C; the PB film is then electroplated onto the pre-sprayed ITO nano-particles. Since ITO nano-particles can be well covered with PB, the NPB film forms a nano-porous electrochromic layer. The switching speed and contrast of NPB exhibit much better performances than traditional PB thin films. The structure, morphology, and electrochromic properties were characterized by scanning electron microscopy (SEM), cyclic voltammograms (CV), and UV-vis spectroscopy.     

Synthesis, characterization and electrochemical performance of mesoporous FePO4 as cathode material for rechargeable lithium batteries

Mesoporous FePO₄ could deliver enhanced specific capacity of 160 mAh g⁻¹ at first discharge process, 90% of theoretical capacity of pure FePO₄, and 135 mAh g⁻¹ in the following cycles at 0.1 C rate. At 1 and 3 C rates, the capacities are 110 and 85 mAh g⁻¹, respectively, which is much higher than that of previously reported for modified FePO₄ materials. Electrochemical impedance spectroscopy (EIS) tests proved that mesoporous structure in FePO₄ materials enhanced the lithium ion intercalation/deintercalation kinetics as indicated by smaller charge transfer resistance (R_ct) of these materials. These results revealed that this mesoporous electrode material can be a potential candidate for high-power energy conversion devices.     

Electrochemical and spectroscopic characterization of poly(1,8-diaminocarbazole): Part II. Electrochemical, in situ vis/NIR and Raman studies of redox reaction of PDACz in protic and aprotic media

Electrochemical redox reactions of poly(1,8-diaminocarbazole) (PDACz) films in aqueous (0.1 M HClO₄) and nonaqueous (0.1 M LiClO₄ in acetonitrile) solutions were studied by cyclic voltammetry, in situ vis/NIR and Raman spectroscopy. It has been demonstrated that spectroelectrochemical behavior of the polymer is strongly dependent on the nature of the solution used for doping-undoping but not on the medium used for electropolymerization. A redox couples Fe²⁺/Fe³⁺, Fe(CN)₆^4−/3− and tertrathiafulvalene were used as the probes for the studies of electroactivity of the oxidized polymer films. The results were discussed in terms of different mechanism of deprotonation process of the polymer in aqueous solution of 0.1 M HClO₄ and in 0.1 M LiClO₄ solution in aprotic acetonitrile and the reaction schemes in the two media are proposed.     

Electrical conductivity relaxation in PVOH-LiClO4-Al2O3

We report on electrical conductivity relaxation measurements of solid polymer electrolytes (SPE) based on poly(vinyl alcohol) (PVOH) and LiClO₄ in which nanoporous Al₂O₃ particles with average pore diameter of 58 Å were dispersed. A power law frequency dependence of the real part of the electrical conductivity is observed as a function of temperature and composition. This behaviour is typical of systems in which correlated ionic motions in the SPE bulk material are responsible for ionic conductivity. This variation is well fitted to a Jonscher expression σ′(ω) = σ₀[1 + (ω/ω₀)^p] where σ₀ is the dc conductivity, ω₀ the characteristic angular frequency relaxation and p is the fractional exponent between 0 and 1. For a prototype membrane with composition 0.9PVOH − 0.1LiClO₄ + 7 wt.%Al₂O₃, it was found that the temperature dependence of σ₀ and ω₀, may be described by the VTF relationship, ? = ?₀ exp[−B/(T − T₀)], with approximately the same constant B and reference temperature T₀, indicating that ion mobility is coupled to the motions of the polymer chains. Moreover, p decreased with increasing temperature, from 0.68 at T = 319 K, to 0.4 at T = 437 K, indicating weaker correlation effects among mobile ions when the temperature is increased.     

Ionic liquids in electrochromic devices

The ionic liquid (PYR₁₄TFSI) has proved to be the key material to make a Li-ion conducting element of a complete electrochromic device, when interposed between transparent film electrodes like WO₃ and Li-charged V₂O₅. The key features of this ionic liquid and its mixtures with LiTFSI are the excellent transparency in the visible and NIR optical regions, the good ionic conductivity and the electrochemical compatibility with inorganic Li-intercalation oxide thin film electrodes used in electrochromic devices. The higher optical contrast found during WO₃ colouration with PYR₁₄TFSI-LiTFSI, compared to that in a conventional non-aqueous electrolyte like PC-LiTFSI, was attributed to the larger inertness of the former one (no decomposition reaction at the lowest electrode potential). This highly conductive ionic liquid has been incorporated into a polymer matrix (P(EO)₁₀LiTFSI), in order to obtain a transparent solid electrolyte with high Li ion conductivity and good mechanical stability. Finally this solid PYR₁₄TFSI-P(EO)₁₀LiTFSI transparent ion conductor was interposed between the same electrodes as above in order to yield a fully solid-state, Li-ion electrochromic device. This new solid electrolyte was able to transfer reversibly a Li ionic charge between 5 mC cm⁻² and 10 mC cm⁻² from the lithium storage electrode Li_xV₂O₅ to the WO₃ electrochromic electrode in less than 100 s at room T, darkening the device from an initial 80% to a final 30% transmittance (at 650 nm). Such a device has been tested first under various constant current conditions, and later under potentiostatic control using ±2 V steps. The latter method allows not only for a faster response of the electrochromic system, but provides also an easier life stability test of the device, which withstood 2000 cycles with little changes in its optical contrast.     

Synthesis and characterization of high-density LiFePO4/C composites as cathode materials for lithium-ion batteries

To achieve a high-energy-density lithium electrode, high-density LiFePO₄/C composite cathode material for a lithium-ion battery was synthesized using self-produced high-density FePO₄ as a precursor, glucose as a C source, and Li₂CO₃ as a Li source, in a pipe furnace under an atmosphere of 5% H₂-95% N₂. The structure of the synthesized material was analyzed and characterized by X-ray diffraction (XRD) and scanning electron microscope (SEM). The electrochemical properties of the synthesized LiFePO₄/carbon composite were investigated by cyclic voltammetry (CV) and the charge/discharge process. The tap-density of the synthesized LiFePO₄/carbon composite powder with a carbon content of 7% reached 1.80 g m⁻³. The charge/discharge tests show that the cathode material has initial charge/discharge capacities of 190.5 and 167.0 mAh g⁻¹, respectively, with a volume capacity of 300.6 mAh cm⁻³, at a 0.1C rate. At a rate of 5C, the LiFePO₄/carbon composite shows a high discharge capacity of 98.3 mAh g⁻¹ and a volume capacity of 176.94 mAh cm⁻³.     

Performance evaluation of CNT/polypyrrole/MnO2 composite electrodes for electrochemical capacitors

A ternary composite of CNT/polypyrrole/hydrous MnO₂ is prepared by in situ chemical method and its electrochemical performance is evaluated by using cyclic voltammetry (CV), impedance measurement and constant-current charge/discharge cycling techniques. For comparative purpose, binary composites such as CNT/hydrous MnO₂ and polypyrrole/hydrous MnO₂ are prepared and also investigated for their physical and electrochemical performances. The specific capacitance (SC) values of the ternary composite, CNT/hydrous MnO₂ and polypyrrole/hydrous MnO₂ binary composites estimated by CV technique in 1.0 M Na₂SO₄ electrolyte are 281, 150 and 35 F g⁻¹ at 20 mV s⁻¹ and 209, 75 and 7 F g⁻¹ at 200 mV s⁻¹, respectively. The electrochemical stability of ternary composite electrode is investigated by switching the electrode back and forth for 10,000 times between 0.1 and 0.9 V versus Ag/AgCl at 100 mV s⁻¹. The electrode exhibits good cycling stability, retaining up to 88% of its initial charge at 10,000th cycle. A full cell assembled with the ternary composite electrodes shows a SC value of 149 F g⁻¹ at a current loading of 1.0 mA cm⁻² during initial cycling, which decreased drastically to a value of 35 F g⁻¹ at 2000th cycle. Analytical techniques such as scanning electron microscopy (SEM), X-ray diffraction spectroscopy (XRD), Brunauer-Emmet-Teller (BET) surface area measurement and inductively coupled plasma-atomic emission spectrometry (ICP-AES) are also used to characterize the composite materials.     

Synthesis and characterization of highly stable optically passive CeO2-ZrO2 counter electrode

Transparent and adherent CeO₂-ZrO₂ thin films having film thicknesses ∼543-598 nm were spray deposited onto the conducting (fluorine doped tin oxide coated glass) substrates from a blend of equimolar concentrations of cerium nitrate hexahydrate and zirconium nitrate having different volumetric proportions (0-6 vol.% of Zr) in methanol. CeO₂-ZrO₂ films were polycrystalline with cubic fluorite crystal structure and the crystallinity was improved with increasing ZrO₂ content. Films were highly transparent (T ∼ 92%), showing decrease in band gap energy from 3.45 eV for pristine CeO₂ to 3.08-3.14 eV for CeO₂-ZrO₂ films. The different morphological features of the film obtained at various CeO₂-ZrO₂ compositions had pronounced effect on the ion storage capacity and electrochemical stability. CeO₂-ZrO₂ film prepared at 5 vol.% Zr concentration exhibited higher ion storage capacity of 24 mC cm⁻² and electrochemical stability of 10,000 cycles in 0.5 M LiClO₄ + PC electrolyte due to its film thickness (584 nm) coupled with relatively larger porosity (8%). The optically passive behavior of such CeO₂-ZrO₂ film (with 5 vol.% Zr) is affirmed by its negligible transmission modulation irrespective of repeated Li⁺ and electron insertion/extraction. The coloration efficiency of spray deposited WO₃ thin film is found to enhance from 47 to 107 cm² C⁻¹ when CeO₂-ZrO₂ is coupled as a counter electrode with WO₃ in an electrochromic device (ECD). These films can be used as stable ‘passive’ counter electrodes in electrochromic smart windows as they retain full transparency in both the oxidized and reduced states and ever-reported longevity.     

Modification of glassy carbon electrode with multi-walled carbon nanotubes and iron(III)-porphyrin film: Application to chlorate, bromate and iodate detection

In this study, multi-wall carbon nanotubes (MWCTs) is evaluated as a transducer, stabilizer and immobilization matrix for the construction of amperometric sensor based on iron-porphyrin. 5,10,15,20-Tetraphenyl-21H,23H-porphine iron(III) chloride (Fe(III)P) adsorbed on MWCNTs immobilized on the surface of glassy carbon electrode. Cyclic voltammograms of the Fe(III)P-incorporated-MWCNTs indicate a pair of well-defined and nearly reversible redox couple with surface confined characteristics at wide pH range (2-12). The surface coverage (Γ) and charge transfer rate constant (k_s) of Fe(III)P immobilized on MWCNTs were 7.68 × 10⁻⁹ mol cm⁻² and 1.8 s⁻¹, respectively, indicating high loading ability of MWCNTs for Fe(III)P and great facilitation of the electron transfer between Fe(III)P and carbon nanotubes immobilized on the electrode surface. Modified electrodes exhibit excellent electrocatalytic activity toward reduction of ClO₃⁻, IO₃⁻ and BrO₃⁻ in acidic solutions. The catalytic rate constants for catalytic reduction of bromate, chlorate and iodate were 6.8 × 10³, 7.4 × 10³ and 4.8 × 10² M⁻¹ s⁻¹, respectively. The hydrodynamic amperometry of rotating-modified electrode at constant potential versus reference electrode was used for detection of bromate, chlorate and iodate. The detection limit, linear calibration range and sensitivity for chlorate, bromate and iodate detections were 0.5 μM, 2 μM to 1 mM, 8.4 nA/μM, 0.6 μM, 2 μM to 0.15 mM, 11 nA/μM, and 2.5 μM, 10 μM to 4 mM and 1.5 nA/μM, respectively. Excellent electrochemical reversibility of the redox couple, good reproducibility, high stability, low detection limit, long life time, fast amperometric response time, wide linear concentration range, technical simplicity and possibility of rapid preparation are great advantages of this sensor. The obtained results show promising practical application of the Fe(III)P-MWCNTs-modified electrode as an amperometric sensor for chlorate, iodate and bromate detections.