The cell-impedance-controlled lithium transport through LiMn2O4 film electrode with fractal surface by analyses of ac-impedance spectra, potentiostatic current transient and linear sweep voltammogram

Lithium transport through the fractal LiMn₂O₄ film electrode under the cell-impedance-controlled constraint was investigated by employing ac-impedance spectroscopy, potentiostatic current transient technique and linear sweep voltammetry. For this purpose, the flat and fractal LiMn₂O₄ film electrodes were prepared on the as-deposited Pt/polished Al₂O₃ substrate and the surface modified Pt/unpolished Al₂O₃ substrate, respectively. From the analysis of the ac-impedance spectra obtained from the flat and fractal electrodes, it is found that the apparent self-similar fractal dimension reduces the charge-transfer resistance, and the phase angle of the diffusion impedance under the semi-infinite diffusion condition positively deviates in absolute value from 45° with increasing fractal dimension. All the potentiostatic current transients experimentally measured from the flat and fractal LiMn₂O₄ electrodes showed non-generalised Cottrell behaviour which resulted from the cell-impedance-controlled constraint during lithium transport. In the case of linear sweep voltammogram theoretically calculated and experimentally measured from the flat and fractal LiMn₂O₄ electrodes, the power dependence of the peak current on the scan rate hardly exhibited the generalised Randles-Sev?ik behaviour. From the analyses of the potentiostatic current transients and the linear sweep voltammograms, furthermore, it is experimentally confirmed that the internal cell resistance mainly determining the cell-impedance-controlled lithium transport strongly depends upon the fractal dimension as well as such external parameters as the applied potential step and the amount of lithium transferred during lithium transport.     

A study on lithium transport through fractal Li1−δCoO2 film electrode by analysis of current transient based upon fractal theory

Lithium transport through fractal Li_1−δCoO₂ film electrode was investigated in a 1 M lithium perchlorate (LiClO₄)-propylene carbonate (PC) solution by analysis of current transient based upon fractal theory. For this purpose, two kinds of Li_1−δCoO₂ films were deposited by rf magnetron sputtering method on the substrates with different roughnesses. From the analysis of AFM image by the triangulation method, it was found that two Li_1−δCoO₂ film electrodes have the self-similar scaling properties with different spatial outer cut-off ranges. From the analysis of the potentiostatic current transient, it was recognised that the cell-impedance-controlled constraint at the electrode surface is changed to the real potentiostatic boundary condition (diffusion-controlled constraint) when the applied potential step exceeds a critical value and simultaneously the internal cell resistance is below a certain value in the region of single-β-phase. In addition, from the comparison between the cathodic current transients obtained from two fractal Li_1−δCoO₂ film electrodes, it was experimentally confirmed that the current transient shows the generalised Cottrell behaviour before the temporal outer cut-off of fractality, followed by a linear relationship with the slope of −0.5 after the temporal outer cut-off of fractality, when the real potentiostatic boundary condition is maintained at the electrode surface.     

An experimental study on cell-impedance-controlled lithium transport through Li1−δCoO2 film electrode with fractal surface by analyses of potentiostatic current transient and linear sweep voltammogram

The effect of the surface roughness on the cell-impedance-controlled lithium transport through the Li_1−δCoO₂ film electrode was experimentally investigated in a 1 M LiClO₄-PC solution by the analyses of the potentiostatic current transient (PCT) and the linear sweep voltammogram (LSV). The flat and fractal Li_1−δCoO₂ film electrodes were prepared on the Pt/polished Al₂O₃ substrate and the surface-modified Pt/unpolished Al₂O₃ substrate, respectively. From the ac-impedance spectra obtained from the flat and fractal electrodes, it is found that the apparent self-similar fractal dimension reduces the charge-transfer resistance. All the PCTs did not exhibit the generalised Cottrell behaviour until the characteristic time t_ch and all the power dependence of the peak current on the potential scan rate positively deviated from the generalised Randles-Sevcik behaviour above the characteristic scan rate ν_ch in the LSVs. From the analyses of the PCTs and the LSVs in terms of t_ch and ν_ch, furthermore, it is experimentally confirmed that the surface roughness plays a significant role in the kinetic facilitation of the interfacial charge-transfer reaction during the whole lithium intercalation and deintercalation processes.     

Investigation of lithium transport through LiMn2O4 film electrode in aqueous LiNO3 solution

Lithium transport through LiMn₂O₄ film electrode was investigated in aqueous saturated LiNO₃ solution by analyses of the potentiostatic current transient and ac-impedance spectra. It was found that the current transient hardly shows the Cottrell behaviour, and the initial current is linearly proportional to the potential step. This strongly suggests that lithium transport through the film electrode proceeds in aqueous LiNO₃ solution by the same mechanism involving the cell-impedance-controlled constraint, as does lithium transport in non-aqueous organic solution such as LiClO₄ in propylene carbonate (PC). However, the cell-impedance in aqueous LiNO₃ solution was determined to be much smaller by more than one order in value than that cell-impedance in non-aqueous LiClO₄-PC solution over the whole potential range, indicating lithium transport is markedly enhanced in aqueous electrolyte. From the comparison between the ac-impedance spectra obtained in aqueous and non-aqueous electrolytes, the reduced cell-impedance in aqueous electrolyte can be accounted for by the kinetic facility for the interfacial charge-transfer reaction in the absence of the resistive surface film as well as by the high conductivity of the electrolyte itself.     

Lithium transport through a sol-gel derived LiMn2O4 film electrode: analyses of potentiostatic current transient and linear sweep voltammogram by Monte Carlo simulation

Lithium transport through a sol-gel derived LiMn₂O₄ film electrode was theoretically investigated by analyses of the potentiostatic current transient and the linear sweep voltammogram in consideration of the interactions between lithium ions by using Monte Carlo simulation. The anodic current transients experimentally measured on the film electrode ran with the slope of logarithmic current with logarithmic time flatter than −0.5 in the early stage, and then did in an upward concave shape in the time interval between t_T1 and t_T2. The linear sweep voltammograms experimentally measured on the film electrode showed two anodic peak currents I_p1 and I_p2 which increased linearly with scan rate v to the power of 0.66 and 0.70, respectively, (i.e. I_p1∝v^0.66 and I_p2∝v^0.70) at the scan rates higher than 0.5 mV s⁻¹. Moreover, the higher v was, the larger appeared the positive deviations of the first and second peak potentials E_p1 and E_p2 from the first and the second transition potentials E°_p1 and E°_p2, respectively, in the inverse derivative of the electrode potential curve. The current transients and the linear sweep voltammograms were analyzed in consideration of the interactions between lithium ions in the electrode by using the Monte Carlo simulation under two different constraints of the diffusion-controlled lithium transport and the cell-impedance-controlled lithium transport. The current transients and the linear sweep voltammograms, theoretically calculated under the cell-impedance-controlled constraint in consideration of the interactions between lithium ions, were in good agreement with the experimental results in shape. The disorder to order phase transition in the LiMn₂O₄ film electrode during the cell-impedance-controlled lithium transport at the potential jump and scan was discussed with the aid of the concentration profiles and the local cross-sectional snapshots of the configuration of lithium ions simulated by the Monte Carlo method.     

Theoretical approach to cell-impedance-controlled lithium transport through Li1 − δMn2O4 film electrode with partially inactive fractal surface by analyses of potentiostatic current transient and linear sweep voltammogram

Lithium transport through the partially inactive fractal Li_1 − δMn₂O₄ film electrode under the cell-impedance-controlled constraint was theoretically investigated by using the kinetic Monte Carlo method based upon random walk approach. Under the cell-impedance-controlled constraint, all the potentiostatic current transients calculated from the totally active and partially inactive fractal electrodes hardly exhibited the generalised Cottrell behaviour and they were significantly affected in shape by the interfacial charge-transfer kinetics. In the case of the linear sweep voltammogram determined from the totally active and partially inactive fractal electrodes, all the power dependence of the peak current on the scan rate above the characteristic scan rate deviated from the generalised Randles-Sev?ik behaviour. From the analyses of the current transients and the linear sweep voltammograms simulated with various values of the simulation parameters, it was further recognised that the cell-impedance-controlled lithium transport through the partially inactive fractal Li_1 − δMn₂O₄ film electrode strongly deviates from the generalised diffusion-controlled transport behaviour of the electrode with the totally active surface, which is attributed to the impeded interfacial charge-transfer kinetics governed by the surface inhomogeneities including the fractal dimension of the surface and the surface coverage by active sites and by the kinetic parameters including the internal cell resistance.     

Hydrothermal synthesis of vanadium pentoxide nanostructures and their morphology control

Different morphologies of vanadium pentoxide (V₂O₅) from 1D to 3D, including nanospheres, nanowires, urchin-like and flower-like nanostructures, have been synthetized by a simple hydrothermal method. Some parameters, such as the reaction temperature, the volume of polyvinyl pyrrolidone (PVP) and possible formation mechanisms of different V₂O₅ nanostructures were discussed. The results demonstrate that PVP and the reaction temperature play a critical role on the morphology of vanadium pentoxide.     

An investigation of cell-impedance-controlled lithium transport through LiCoO2/Li1−δMn2O4 bilayer film electrode prepared by rf magnetron sputtering

Lithium transport through LiCoO₂/Li_1−δMn₂O₄ bilayer film electrode prepared by radio-frequency (rf) magnetron sputtering was investigated in a 1 M solution of LiClO₄ in propylene carbonate. From the analyses of the AC-impedance spectra experimentally measured from the Li_1−δMn₂O₄ single-layer and LiCoO₂/Li_1−δMn₂O₄ bilayer film specimens, the internal cell resistance of the LiCoO₂/Li_1−δMn₂O₄ bilayer film electrode was determined to be smaller in value than that of the Li_1−δMn₂O₄ single-layer film electrode over the whole potential range, which can be accounted for by the kinetic facility for the interfacial charge-transfer reaction in the presence of the more conductive LiCoO₂ surface film. Moreover, from the analyses of the anodic current transients measured from both the film specimens, it was suggested that the cell-impedance-controlled constraint at the electrode surface is changed to the diffusion-controlled constraint simultaneously characterised by the large potential step and the small amount of lithium transferred during lithium transport. In addition, in the case of the LiCoO₂/Li_1−δMn₂O₄ bilayer film electrode, it was found that the critical value of the applied potential step needed for the mechanism transition is reduced, which strongly indicates that the internal cell resistance plays a significant role in determining the cell-impedance-controlled lithium transport. Furthermore, from the comparison of the cathodic current transients measured on the Li_1−δMn₂O₄ single-layer film specimens with various thicknesses, it was experimentally verified that the diffusion resistance is explicitly distinguished from the internal cell resistance.     

An investigation of intercalation-induced stresses generated during lithium transport through sol-gel derived LixMn2O4 film electrode using a laser beam deflection method

The stress changes Δσ generated during lithium transport through the sol-gel derived Li_xMn₂O₄ film electrodes annealed at 773 and 873 K were quantitatively determined as a function of the lithium stoichiometry x using a laser beam deflection method (LBDM). Δσ generated during a real potential step between an initial electrode potential and a final applied potential was uniquely specified by the Δσ versus x curve. The Li_xMn₂O₄ film annealed at 773 K for 24 h (low temperature (LT)-Li_xMn₂O₄) showed larger capacity than the Li_xMn₂O₄ film annealed at 873 K for 6 h (high temperature (HT)-Li_xMn₂O₄) and this result is ascribed to the fact that the smaller the grain size is, the more increases the electrochemically active area of the film electrode. From the analysis of the normalised Δσ transient measured simultaneously along with the cyclic voltammogram in the potential range of 2.5-3.4 VLi/Li⁺, it is found that normalised Δσ generated in the LT-Li_xMn₂O₄ was smaller than that in the HT-Li_xMn₂O₄ during the lithium intercalation/de-intercalation around 3.0 VLi/Li⁺ region. This result gives an experimental evidence for the fact that the Jahn-Teller distortion is suppressed by the increase in the average oxidation state of manganese with decreasing in annealing temperature.     

Effect of pore structure on anomalous behaviour of the lithium intercalation into porous V2O5 film electrode using fractal geometry concept

The effect of pore structure on anomalous behaviour of the lithium intercalation into porous V₂O₅ film electrode has been investigated in terms of fractal geometry by employing ac-impedance spectroscopy combined with N₂ gas adsorption method and atomic force microscopy (AFM). For this purpose, porous V₂O₅ film electrodes with different pore structures were prepared by the polymer surfactant templating method. From the analysis of N₂ gas adsorption isotherms and the triangulation analysis of AFM images, it was found that porous V₂O₅ surfaces exhibited self-similar scaling properties with different fractal dimensions depending upon amount of the polymer surfactant in solution and the spatial cut-off ranges. All the ac-impedance spectra measured on porous V₂O₅ film electrodes showed the non-ideal behaviour of the charge-transfer reaction and the diffusion reaction, which resulted from the interfacial capacitance dispersion and the frequency dispersion of the diffusion impedance, respectively. From the comparison between the surface fractal dimensions by using N₂ gas adsorption method and AFM, and the analysis of ac-impedance spectra by employing a constant phase element (CPE), it is experimentally confirmed that the lithium intercalation into porous V₂O₅ film electrode is crucially influenced by the pore surface irregularity and the film surface irregularity.     

Li-intercalation behaviour of vanadium oxide thin film prepared by thermal oxidation of vanadium metal

In order to produce thin films of crystalline V₂O₅, vanadium metal was thermally oxidised at 500 °C under oxygen pressures between 250 and 1000 mbar for 1-5 min. The oxide films were characterised by X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), X-ray diffraction (XRD) and Rutherford backscattering spectrometry (RBS). The lithium intercalation performance of the oxide films was investigated by cyclic voltammetry (CV), chronopotentiometry and electrochemical impedance spectroscopy (EIS). It was shown that the composition, the crystallinity and the related lithium intercalation properties of the thin oxide films were critically dependent on the oxidation conditions. The formation of crystalline V₂O₅ films was stimulated by higher oxygen pressure and longer oxidation time. Exposure for 5 min at 750 mbar O₂ at 500 °C resulted in a surface oxide film composed of V₂O_5, and consisting of crystallites up to 200 nm in lateral size. The thickness of the layer was about 100 nm. This V₂O₅ oxide film was found to have good cycling performance in a potential window between 3.8 and 2.8 V, with a stable capacity of 117 ± 10 mAh/g at an applied current density of 3.4 μA/cm². The diffusion coefficients corresponding to the two plateaus at 3.4 and 3.2 V were determined from the impedance measurements to (5.2 and 3.0) × 10⁻¹³ cm² s⁻¹, respectively. Beneath the V₂O₅ layer, lower oxides (mainly VO₂) were found close to the metal. At lower oxygen pressure and shorter exposure times, the oxide films were less crystalline and the amount of V⁴⁺ increased in the surface oxide film, as revealed by XPS. At intermediate oxygen pressures and exposure times a mixture of crystalline V₂O₅ and V₆O₁₃ was found in the oxide film.     

An investigation of intercalation-induced stresses generated during lithium transport through Li1 − δCoO2 film electrode using a laser beam deflection method

The stress change, Δσ, generated during lithium transport through the rf sputter-deposited Li_{1 − δ}CoO₂ film was exactly determined as a function of the lithium stoichiometry, (1 − δ), using a laser beam deflection method (LBDM) combined with cyclic voltammetry, galvanostatic intermittent titration technique and potentiostatic current transient technique. Tensile and compressive stresses were generated during the lithium intercalation and deintercalation, respectively. Δσ varied remarkably with (1 − δ) in the single-α-phase region as well as in the two-phase region, but it remained almost constant in the single-β-phase region. Δσ generated during a real potential step between an initial electrode potential and a final applied potential was uniquely specified by (1 − δ). The value of Δσ coincided well with that value derived from the Δσ versus (1 − δ) curve (stress transient) measured simultaneously along with the galvanostatic intermittent titration discharge curve. From the comparison between the values of Δσ measured experimentally and calculated theoretically, it was suggested that Δσ in the single-α-phase region and the two-phase region originate from the molar volume change of the α-phase and from the lattice parameter mismatch between the α-phase and β-phase, respectively.     

An XPS study of dispersion and valence state of TiO2 supported vanadium oxide catalysts

Monolayer vanadium species are mainly in the V(V) valence state, but with XPS a small fraction of V⁴⁺ species are identified. Prolonged analysis treatment increases the V⁴⁺ concentration. With increasing vanadium concentration, a monolayer coverage corresponding to 1 mg V₂O₅ per m² develops, and it contains additional layers with a thickness of about 250 Å at 4 mg V₂O₅ per m², covering 3% of its surface area.     

Mechanism transition of cell-impedance-controlled lithium transport through Li1−δMn2O4 composite electrode caused by surface-modification and temperature variation

The mechanism transition of lithium transport through a Li_1−δMn₂O₄ composite electrode caused by the surface-modification and temperature variation was investigated using the galvanostatic intermittent titration technique (GITT), electrochemical impedance spectroscopy (EIS) and the potentiostatic current transient technique. From the analyses of the ac-impedance spectra, experimentally measured from unmodified Li_1−δMn₂O₄ and surface-modified Li_1−δMn₂O₄ with MgO composite electrodes, the internal cell resistance of the MgO-modified Li_1−δMn₂O₄ electrode was determined to be much smaller in value than that of the unmodified electrode over the whole potential range. Moreover, from the analysis of the anodic current transients measured on the MgO-modified Li_1−δMn₂O₄ electrode, it was found that the cell-impedance-controlled constraint at the electrode surface is changed to a diffusion-controlled constraint, which is characterised by a large potential step and simultaneously by a small amount of lithium transferred during lithium transport. This strongly suggests that the internal cell resistance plays a significant role in determining the cell-impedance-controlled lithium transport through the MgO-modified Li_1−δMn₂O₄ electrode. Furthermore, from the temperature dependence of the internal cell resistance and diffusion resistance in the unmodified Li_1−δMn₂O₄ composite electrode measured by GITT and EIS, it was concluded that which mechanism of lithium transport will be operative strongly depends on the diffusion resistance as well as on the internal cell resistance.     

In situ Raman microspectrometry investigation of electrochemical lithium intercalation into sputtered crystalline V2O5 thin films

We report here the first in situ Raman microspectrometry study of the electrochemical lithium insertion and de-insertion reaction into crystalline sputtered Li_xV₂O₅ thin films (0 ≤ x ≤ 0.94) in liquid electrolyte. We show that the orthorhombic Pmmn symmetry of the pristine material is kept upon lithium intercalation in the Li_xV₂O₅ film (0 ≤ x ≤  0.94). In fact, a subsequent and unexpected solid solution behaviour is evidenced, leading to the typical Raman fingerprint of the -LiV₂O₅ phase for the Li₀.₉₄V₂O₅ composition. After the charge, a complete recovery of the local structure is found, in good accord with the excellent electrochemical reversibility exhibited by these thin films. Such limited structural changes differ from that usually observed for the bulk material, which emphasizes the key role of the microstructure and morphology on the nature and magnitude of the structural rearrangements induced by the lithium insertion process.     

Electrochemical preparation and characterization of V2O5/polyaniline composite film cathodes for Li battery

Vanadium pentoxide/polyaniline (V₂O₅/PANi) composite films were prepared by a two-step electrochemical method and evaluated for their application in lithium batteries. As a first step the PANi film was potentiodynamically grown in an acid solution containing aniline monomer, and secondly vanadium oxide was oxidatively deposited on the polyaniline film in a temperature controlled VOSO₄ solution. The increased current efficiency obtained with the larger anodic current in the high temperature solutions results in high contents of V₂O₅ in the composites, even if the oxidative dissolution of PANi also occurs. The large value of the diffusion coefficient estimated from the cyclic voltammograms for the composite film provides evidence for the synergistic effect of the conducting polymer and the inorganic composite. The cell exhibited excellent cycle stability with a high charge storage capacity. The large increase in the specific capacity for the composite film prepared in this work demonstrates that the conducting polymer in the composite acts as a binding and conducting element by contributing its electroactivity. The V₂O₅/PANi composite film cathodes show a large specific capacity (ca. 270 mAh/g) and improved cyclability with an extremely small amount of capacity fading (ca. 3.4%) during repeated charge/discharge cycles.     

Investigation of hydrogen transport through Mm(Ni3.6Co0.7Mn0.4Al0.3)1.12 and Zr0.65Ti0.35Ni1.2V0.4Mn0.4 hydride electrodes by analysis of anodic current transient

Hydrogen transport through such metal-hydride electrodes as Mm(Ni_3.6Co_0.7Mn_0.4Al_0.3)_1.12 and Zr_0.65Ti_0.35Ni_1.2V_0.4Mn_0.4 was investigated in 6 M KOH solution by using potentiostatic current transient technique. From the shape of the anodic current transient and the dependence of the initial current density on the discharging potential, the boundary conditions at the electrode surface were established during hydrogen extraction from the as-annealed and as-surface-treated electrodes. Especially, it was experimentally confirmed that the diffusion-limited boundary condition is no longer valid at the electrode surface during hydrogen transport in case hydrogen diffusion is coupled with either the interfacial charge transfer reaction or the hydrogen transfer reaction between adsorbed state on the electrode surface and absorbed state at the electrode sub-surface. From the transition behaviour of the boundary condition, it was further recognised that the boundary condition at the electrode surface during hydrogen transport is not fixed at the specific electrode/electrolyte system by itself, but it is rather simultaneously determined even at any electrode/electrolyte system by the potential step and the nature of the electrode surface, depending upon e.g. the presence or absence of the surface oxide scales.     

The kinetics of hydrogen transport through amorphous Pd82−yNiySi18 alloys (y=0-32) by analysis of anodic current transient

Hydrogen transport through amorphous Pd_82−yNi_ySi₁₈ alloys (y=0-32) was investigated in 0.1 M NaOH solution by analysis of the anodic current transient. It was found that the anodic current transient shows the non-Cottrell behaviour, but its shape and value remain nearly constant regardless of the hydrogen discharging potential. From the coincidence of the anodic current transient theoretically calculated with that experimentally measured, it is suggested that the change in surface concentration of hydrogen with time is uniquely given by the rate of hydrogen transfer from absorbed state at the electrode sub-surface to adsorbed state on the electrode surface. This means that neither the ‘constraint of constant concentration’ nor the ‘constraint by Butler-Volmer behaviour’ is effective at the electrode surface during hydrogen extraction. On the basis of the theoretical current-time relation under the ‘constraint by hydrogen transfer of absorbed state to adsorbed state’, the hydrogen diffusivity was determined to have an almost constant value of (1.3±0.4)×10⁻⁸ cm² s⁻¹, irrespective of the Ni content and in the absence of Ni. On the other hand, it is inferred that the rate constant of hydrogen transfer decreases markedly with increasing Ni content due to the Ni(OH)₂ layer formed on the electrode surface.