Nucleation and growth of clusters through multi-step electrochemical reactions

Milchev, A.

doi:10.1016/j.jelechem.2007.09.010

Cited by 19 publications

(9 citation statements)

References 20 publications

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“…Increased current density also results in a high over potential, which increases nucleation rate. During deposition, the thickness of the electrodeposit was shown to increase with deposition time [27,28]. NiO deposition on the porous GR/PI working electrode was carried out using two different current densities at varying deposition times.…”

Section: Polyimide/graphene Nanosheet-poly (Acrylic Acid)-nio Hybrid mentioning

confidence: 99%

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Electrochemical Properties of Porous Graphene/Polyimide-Nickel Oxide Hybrid Composite Electrode Material

Okafor

Iroh

2021

Energies

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Polyimide-graphene nanosheet composite electrodes are rigid and dense and, therefore, exhibit moderate electrochemical properties. The electrochemical properties of polyimide-graphene nanosheet electrodes were remarkably improved by creating voids in the composite followed by the insertion of nickel oxide into the composites. Nickel oxide particles were electrodeposited onto the porous graphene/poly(amic acid) composite, containing poly (acrylic resin). The hybrid composite was then subjected to thermal treatment at ≥ 300 °C to simultaneously complete imidization and degrade the poly (acrylic resin). Cyclic Voltammetry (CV) and electrochemical impedance spectroscopy (EIS) were used to study the eletrochemical properties of the composite electrode material. It is shown that remarkable improvement in the electrochemical behavior of the hybrid composite occurred due to the removal of poly(acrylic acid) and the insertion of NiO particles into the polyimide matrix. Fourier Transform Infrared Spectroscopy (FTIR) spectra of the hybrid composites show distinct characteristic peaks for polyimide and NiO in the hybrid composite electrode. Scanning Electron Microscopy, SEM images of the composites, show the presence of NiO aggregates in the composite material. Compared to neat graphene/polyimide composite electrode (GR/PI) composites, the specific capacitance of the hybrid composite electrode increased remarkably by over 250% due to the high interfacial surface area provided by NiO and the concomitant improvement in the electrode–electrolyte interaction.

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Section: Polyimide/graphene Nanosheet-poly (Acrylic Acid)-nio Hybrid mentioning

confidence: 99%

“…where α is the cathodic charge transfer coefficient, η is the over potential, R is the molar gas constant and T is the absolute temperature [25,27,30]. Equation (5) shows a linear relationship between deposition time and size of the aggregates.…”

Section: Polyimide/graphene Nanosheet-poly(acrylic Acid)-nio Hybrid Cmentioning

confidence: 99%

Electrochemical Properties of Porous Graphene/Polyimide-Nickel Oxide Hybrid Composite Electrode Material

Okafor

Iroh

2021

Energies

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“…Approximate models for growing nuclei under mixed kinetic and diffusion control have been derived by Fletcher [33] and Milchev. [34] Ross et al [35] have compared the predictions of the SH model to real-time imaging of growing copper clusters on a gold electrode using a small liquid transmission electron microscopy cell. They showed that the SH model may grossly underestimate the actual nucleus density, and ascribe this to the importance of surface adatom formation and surface diffusion on the gold during the initial stage of the process.…”

Section: Chronoamperometric Transientsmentioning

confidence: 99%

The Effect of Naphthalene‐Based Additives on the Kinetics of Tin Electrodeposition on Boron‐Doped Diamond Electrodes

2021

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The effect of naphthalene-based additives: naphthalene (NPT), naphthalenesulfonate (NPTS) and hydroxynaphthalenesulfonate (HNPTS) on the kinetics of tin electrodeposition on a borondoped diamond (BDD) electrode has been studied by means of chronoamperometry and scanning electron microscopy (SEM). Potentiostatic current transients in the absence and the presence of naphthalene-based additives are analyzed by using the Scharifker-Hills model. A strong decrease of the kinetics of tin nucleation on BDD was observed in the presence of naphthalene-based additives, NPT showing the smallest effect and HNPTS showing the largest effect. From the long-term Cottrell behavior of the transients, similar values of tin(II) diffusion coefficients were obtained for all additives, suggesting that there is no complexation of Sn(II) by the additives and that the charge-transfer kinetics itself is not substantially influenced by the presence of the additives. In the absence of additives, tin deposition on BDD displays a progressive nucleation and growth mechanism at the least negative potentials, switching to instantaneous nucleation and growth at more negative potential. In the presence of NPTS and HNPTS, progressive nucleation and growth transients are observed. The growth mode results are confirmed by the tin features observed in the scanning electron micrographs. In conclusion, NPT, NPTS and HNPTS mainly decrease the rate of the nucleation of tin deposition, most likely by blocking or reducing access to active nucleation sites. In comparison, ethoxylated α-napthalenesulfonic acid (ENSA, a commonly used additive in the tin plating industry) inhibits tin deposition process on BDD even more strongly. These observations show a striking similarity to our previous study of tin deposition on gold electrodes.

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“…An exact solution to the overlap problem can be found only for the case of kinetically controlled growth [ 17 , 18 ], which is relatively rarely realized under ordinary conditions of electrodeposition [ 19 , 20 ]. The growth of a new phase can often occur under mixed (charge transfer and diffusion) control [ 21 , 22 , 23 , 24 , 25 , 26 ]. Taking into account that the overlap significantly complicates the determination of the nucleation and growth parameters in this case, they can be most accurately detected by the analysis of the data on the formation of single nano- and microcrystals or data on the initial stages of growth at multiple nucleation, when the influence of nuclei on each other can be neglected [ 6 , 27 , 28 , 29 , 30 , 31 , 32 , 33 , 34 ].…”

Section: Introductionmentioning

confidence: 99%

Simulation of 3D Electrochemical Phase Formation: Mixed Growth Control

et al. 2021

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Processes of nucleation and growth largely determine the structure and properties of thin films obtained by electrodeposition on foreign substrates. Theoretical aspects of the initial stages of electrochemical phase formation under constant and variable overpotentials are considered in this work. Simulation of multiple nucleation with mixed (charge transfer, and diffusion) controlled growth was performed for three cases (cyclic voltammetry, potentiostatic electrodeposition, and galvanostatic electrodeposition). The influence of the bulk concentration of depositing ions and the exchange current density at the electrolyte/nucleus interface on cyclic voltammograms (CVs), transients of current and overpotential, as well as the number and size of non-interacting new-phase nuclei was analyzed. It is found that, under galvanostatic conditions, the number of nuclei decreases as the concentration of depositing ions increases due to a more rapid decrease in overpotential. The proposed model was applied to determine the diffusion coefficient, exchange current density, and transfer coefficient considering the experimental CV.

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Nucleation and growth of clusters through multi-step electrochemical reactions

Cited by 19 publications

References 20 publications

Electrochemical Properties of Porous Graphene/Polyimide-Nickel Oxide Hybrid Composite Electrode Material

Electrochemical Properties of Porous Graphene/Polyimide-Nickel Oxide Hybrid Composite Electrode Material

The Effect of Naphthalene‐Based Additives on the Kinetics of Tin Electrodeposition on Boron‐Doped Diamond Electrodes

Simulation of 3D Electrochemical Phase Formation: Mixed Growth Control

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