Dynamic electro-chemo-mechanical analysis during cyclic voltammetry

Smetanin, Maxim; Deng, Qibo; Weißmüller, J.

doi:10.1039/c1cp21781j

Cited by 38 publications

(58 citation statements)

References 39 publications

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“…The first approach can be implemented by cantilever bending experiments [19][20][21] or porous metal dilatometry, [22][23][24] while the second requires experiments which cyclically strain a planar electrode simultaneously with electrochemical characterization. 15,25 The numerical values of B emerging from the respective approaches are found in excellent agreement. 15,16,19,20,22,25 Besides the relevance of the above experiments for the physics of adsorption and for catalysis, cantilever bending is also of technological relevance for various sensing schemes, such as DNA detection and analysis.…”

Section: Introductionsupporting

confidence: 61%

“…15,25 The numerical values of B emerging from the respective approaches are found in excellent agreement. 15,16,19,20,22,25 Besides the relevance of the above experiments for the physics of adsorption and for catalysis, cantilever bending is also of technological relevance for various sensing schemes, such as DNA detection and analysis. 26 In view of the significance of experiments probing the variation of surface stress on planar surfaces during electric charging or adsorption and of the complementary experiments measuring the variation of the electrode potential with strain, it is significant that real surface are never perfectly planar and that experiment points at a strong impact of surface corrugation on the experimental phenomena.…”

Section: Introductionsupporting

confidence: 61%

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Electrocapillary coupling at rough surfaces

Deng

Gosslar

Smetanin

et al. 2015

Phys. Chem. Chem. Phys.

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We investigate the impact of the surface roughness on the experimental value of the electrocapillary coupling coefficient, B. This quantity relates the response of electrode potential, E, to tangential elastic strain, e, and also measures the variation of the surface stress, f, with the superficial charge density, q. We combine experiments measuring the apparent coupling coefficient B eff for gold thin film electrodes in weakly adsorbing electrolyte with data for the surface roughness determined by atomic force microscopy and by the capacitance ratio method. We find that even moderate roughness has a strong impact on the value of B eff . Analyzing the mechanics of corrugated surfaces affords a correction scheme yielding values of B that are invariant with roughness and that agree with expectations for the true coupling coefficient on ideal, planar surfaces. The correction is simple and readily applied to experiments measuring B eff from surface stress changes in cantilever bending studies or from the potential variation in dynamic electrochemo-mechanical analysis.

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Section: Introductionsupporting

confidence: 61%

Section: Introductionsupporting

confidence: 61%

Electrocapillary coupling at rough surfaces

Deng

Gosslar

Smetanin

et al. 2015

Phys. Chem. Chem. Phys.

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“…26 is 0.34 at 1% of uniaxial strain, and substrate is the RMS of the uni-axial substrate strain variation. The phase shift of the signal is typically associated with finite transport rates in the electrolyte or slow adsorption or absorption rates 17 and will therefore be neglected.…”

Section: Dynamic Electro-chemo-mechanical Analysis (Decma)-mentioning

confidence: 99%

“…Re(U ac ) (1 − ν substrate ) substrate [17] where Re(U ac ) is the root mean square (RMS) of the potential variation that is in phase with the strain variation, ν substrate is the Poisson's ratio of the substrate, which according to Ref. 26 is 0.34 at 1% of uniaxial strain, and substrate is the RMS of the uni-axial substrate strain variation.…”

Section: Dynamic Electro-chemo-mechanical Analysis (Decma)-mentioning

confidence: 99%

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The Electro-Chemo-Mechanical Coupling in Lithium Alloy Electrodes and Its Origins

Kitzler

Maawad

Többens

et al. 2015

J. Electrochem. Soc.

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A method to identify and separate the influence of changes in the surface stress from the bulk stress in a model lithium-ion battery electrode during electrochemical cycling was developed. The strategy for this separation is based on the different influence of surface and bulk stresses on the coupling between electrode potential and mechanical strain as measured by dynamic electro-chemo-mechanical analysis and the coupling between the transferred electric charge and the elastic strain as determined by wide angle X-ray scattering. Using both methods, it was possible to uncover the behavior of an apparent surface stress evoked by the bulk stress due to grain boundary alloying of lithium in a gold film. Additionally, the analysis allowed for a determination of a range in surface stress due to underpotential deposition of one monolayer of lithium as the interval between −3.1 to Lithium-ion batteries are widely used, though the amount of electric charge they can store is still far away from their theoretical capacity.1,2 In order to increase the capacity of lithium-ion battery anodes, the commonly used graphite needs to be replaced. A very promising alternative are materials which can form alloys with lithium. 3,4 There are several possible candidates. 5 Among the most important ones are silicon, germanium, tin, aluminum, and antimony. The theoretical volumetric lithium storage capacity of these materials is several times higher than that of the currently used anodes. In case of silicon, more than ten times that of graphite relative to the weight of the host material. This storage capability of the afore mentioned materials is based on their ability to store more than one, in case of silicon, germanium, and tin up to 4.4 lithium atoms per host atom. The obvious drawback of these materials is the huge volume change during lithium loading which can easily exceed 100%.If the electrode material is constrained (e.g. by the current collector) or the lithium is inhomogeneously distributed in the host material, the change in volume is accompanied by stresses.6 Possible consequences are the evolution of cracks in the material which can lead to pulverization of the electrode material and consequently loss of capacity. 6 A promising possibility to prevent pulverization is to reduce the structure size of the electrode material and to introduce high porosity. 7,8 High porosity reduces concentration gradients by reducing the diffusion lengths and it weakens the constraints by offering free space in the vicinity of the electrode. However, this strategy also increases the surface to volume ratio, and therefore drastically increases the impact of the surface stress, which can have an important impact on the stability of the electrode material.9 Additionally, the stress interacts with the chemical potential via the strain energy. 10 Therefore, the equilibrium lithium concentration is a function of the stress state which, in general, is inhomogeneous within the electrode material. Recent simulations performed by Gau and Zhou 11 indicat...

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Electrocapillarity of Solids and its Impact on Heterogeneous Catalysis

Weißmüller

2013

Advances in Electrochemical Sciences and Engineering

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Dynamic electro-chemo-mechanical analysis during cyclic voltammetry

Cited by 38 publications

References 39 publications

Electrocapillary coupling at rough surfaces

Electrocapillary coupling at rough surfaces

The Electro-Chemo-Mechanical Coupling in Lithium Alloy Electrodes and Its Origins

Electrocapillarity of Solids and its Impact on Heterogeneous Catalysis

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