Influence of the Composition on the Copper Diffusion in Copper Sulfides Study by Impedance Spectroscopy

Cassaignon, Sophie; Sanchez, Sylvie; Guillemoles, Jean-François; Vedel, J.; Meier, H. Gomez

doi:10.1149/1.1392691

Cited by 15 publications

(19 citation statements)

References 15 publications

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“…41 Titration curves have been recorded, in particular with Cu x S, which allow precise monitoring of the composition by comparison with the potential of Cu/Cu͑I͒ redox couple. [42][43][44][45] Our interpretation is that each plateau is related to the transition between two phases such as CuSe/Cu 3 Se 2 for OCP close to −0.24 V, and the shift of potential would correspond to the transformation in a single phase.…”

Section: Discussionmentioning

confidence: 85%

Electrochemical Cementation Phenomena on Polycrystalline Molybdenum Thin Films from Cu(II)–In(III)–Se(IV) Acidic Solutions

Ramdani

Chassaing

Canava

et al. 2007

J. Electrochem. Soc.

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The electrochemical behavior of polycrystalline molybdenum thin films in contact with acidic aqueous solutions containing Cu͑II͒, In͑III͒, and Se͑IV͒ species was investigated. The substrate and solutions are used for the electrodeposition of CuInSe 2 films in the field of photovoltaics. The chemical interaction between Mo electrode and the electrolyte at the initial steps of immersion is studied by in situ electrochemical measurements of the time evolution of the open-circuit potential. Ex situ field emission gun-scanning electron microscope observations for morphological investigations, X-ray photoelectron spectroscopy for surface composition, and chemical environment analysis was carried out. Raman spectroscopy, X-ray diffraction, and X-ray fluorescence were also performed. It is shown that molybdenum undergoes electrochemical cementation reactions associated with a characteristic potential increase with immersion time. Immediately after immersion, small nuclei of Cu-Se deposits appear on the surface, which then grow to form a quasi-continuous layer after 400 s. The chemical composition of the layer evolves with immersion time. No indium is incorporated. The global composition changes from a Se/Cu atomic ratio close to 0.3 to a ratio close to 0.7. The final layer contains at least two phases, i.e., umangite Cu 3 Se 2 and CuSe. These complex evolutions are discussed in terms of competing electrochemical reactions and thermodynamic considerations.Molybdenum is used as an important metallic alloying element which improves considerably the resistance to pitting corrosion of stainless steels. 1 Molybdenum thin films have a wide variety of applications, such as soft X-ray optics, gas detection, microelectronics, and as back-contact for thin-film solar cells ͑Ref. 2 and 3 and references therein͒. For these applications, properties of the interfaces between the Mo films and the overlayers are a major concern.Cu͑In,Ga͒͑Se,S͒ 2 is among the most promising absorber materials for thin-film solar cells. 4,5 A wide range of methods has been used for their preparation. Most of them use high-cost vacuumbased techniques such as coevaporation and sputtering. 4 However, electrodeposition is a low-cost method which allows large-scale production. 6 Since the pioneering work by Bhattacharya, 7 several investigations have been carried out on photovoltaic devices based on the electrodeposition of CuInSe 2 ͑CIS͒ thin films on glass plates covered by a molybdenum layer prepared by sputtering. 4,[8][9][10][11][12][13][14][15][16] Most of the electrolytes used for this deposition are acidic solutions, and it has been observed that during immersion at open-circuit potential ͑OCP͒ in the electrolyte, the surface of the molybdenumcoated glass substrates evolves and becomes covered with a surface film. 17,18 However, basic studies of these transformations, which are of key importance for the CIS electrodeposition process, are still lacking. The objective of this work is to focus on a precise experimental characterization of these phenomena an...

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Section: Discussionmentioning

confidence: 85%

Electrochemical Cementation Phenomena on Polycrystalline Molybdenum Thin Films from Cu(II)–In(III)–Se(IV) Acidic Solutions

Ramdani

Chassaing

Canava

et al. 2007

J. Electrochem. Soc.

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“…For generation of the interface, synergistic effect between large sodium and high copper diffusivity facilitates multiple phase transitions. Copper ionic diffusivity in CuS is much higher (

{\overset{D}{true}}_{Cu} = 2.5 \times 10^{–12} {cm}^{normal2} {normals}^{–1}

) than other cations in metal sulfides like FeS 2 (

{\overset{D}{true}}_{Fe} = \approx 10^{–17} {cm}^{normal2} {normals}^{–1}

at 100 °C) . Large sodium cannot replace copper atoms unlike lithiation case in CuS due to high formation energy, which engenders formation of Na‐Cu‐S ternary system to generate Na 3 (CuS) 4 /Na 2 S semi‐coherent boundary (Figure S13, Supporting Information).…”

Section: Resultsmentioning

confidence: 99%

Pulverization‐Tolerance and Capacity Recovery of Copper Sulfide for High‐Performance Sodium Storage

et al. 2019

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Finding suitable electrode materials is one of the challenges for the commercialization of a sodium ion battery due to its pulverization accompanied by high volume expansion upon sodiation. Here, copper sulfide is suggested as a superior electrode material with high capacity, high rate, and long‐term cyclability owing to its unique conversion reaction mechanism that is pulverization‐tolerant and thus induces the capacity recovery. Such a desirable consequence comes from the combined effect among formation of stable grain boundaries, semi‐coherent boundaries, and solid‐electrolyte interphase layers. The characteristics enable high cyclic stability of a copper sulfide electrode without any need of size and morphological optimization. This work provides a key finding on high‐performance conversion reaction based electrode materials for sodium ion batteries.

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“…Thus it is called diffusion regime. Here we think that that the thickening of the sulfur containing layer is due to a diffusion of copper cations from the bulk to the surface [29], where they react with the H 2 S [26,27]. Oxygen traces in the bulk might be from water, which can diffuse along the grain boundaries outside.…”

Section: Discussionmentioning

confidence: 96%

“…In copper sulfides with different stoichiometries Cu x S (x between 1 and 2) the main diffusion process is assigned to the motion of copper cations via vacancy mechanisms [29]. However, in phases with higher sulfur content the diffusion coefficient of the cation slows down, being a consequence of a stronger binding of the copper by the sulfur.…”

Section: Diffusion Processesmentioning

confidence: 99%

Copper oxide based H2S dosimeters – Modeling of percolation and diffusion processes

Hennemann

Kohl

Smarsly

et al. 2015

Sensors and Actuators B: Chemical

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Influence of the Composition on the Copper Diffusion in Copper Sulfides Study by Impedance Spectroscopy

Cited by 15 publications

References 15 publications

Electrochemical Cementation Phenomena on Polycrystalline Molybdenum Thin Films from Cu(II)–In(III)–Se(IV) Acidic Solutions

Electrochemical Cementation Phenomena on Polycrystalline Molybdenum Thin Films from Cu(II)–In(III)–Se(IV) Acidic Solutions

Pulverization‐Tolerance and Capacity Recovery of Copper Sulfide for High‐Performance Sodium Storage

Copper oxide based H2S dosimeters – Modeling of percolation and diffusion processes

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