Ex Situ Scanning Electrochemical Microscopy (SECM) Investigation of Bismuth‐ and Bismuth/Lead Alloy Film‐Modified Gold Electrodes in Alkaline Medium

Salles, Maiara Oliveira; Battistel, Dario; Lima, Alex Silva; Bertotti, Mauro; Daniele, Salvatore

doi:10.1002/elan.201000528

Cited by 8 publications

(3 citation statements)

References 50 publications

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“…The interaction of soluble Bi and Cu species is supported by the distribution of Bi throughout the cathode. The formation of high content of Bi particles is only possible upon Bi dissolution when the cathode is oxidized, which is probable given the reports of soluble Bi(III) species and the slight solubility of Bi 2 O 3 in alkaline conditions (solubility = 3 × 10 –4 M in 9 M KOH). − This is further supported by the recent report that upon charging of birnessite-type MnO 2 cathodes with the Bi 2 O 3 additive, Bi does not completely return to Bi 2 O 3 but exists as Bi(III) ions in the oxidized state . With this in mind, CV and RRDE experiments were conducted which support the solid-state conversion of Cu 0 to Cu 2 O as well as the solubility of Bi(III) and Cu(II) upon oxidation (Figures and S14).…”

Section: Resultsmentioning

confidence: 78%

Rechargeable Alkaline Zinc/Copper Oxide Batteries

Schorr

Arnot

Bruck

et al. 2021

ACS Appl. Energy Mater.

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Resurrecting a battery chemistry thought to be only primary, we demonstrate the first example of a rechargeable alkaline zinc/copper oxide battery. With the incorporation of a Bi2O3 additive to stabilize the copper oxide-based conversion cathode, Zn/(CuO–Bi2O3) cells are capable of cycling over 100 times at >124 W h/L, with capacities from 674 mA h/g (cycle 1) to 362 mA h/g (cycle 150). The crucial role of Bi2O3 in facilitating the electrochemical reversibility of Cu2O, Cu(OH)2, and Cuo was supported by scanning and transmission electrochemical microscopy, cyclic voltammetry, and rotating ring-disc electrode voltammetry and monitored via operando energy-dispersive X-ray diffraction measurements. Bismuth was identified as serving two roles, decreasing the cell resistance and promoting Cu(I) and Cu(II) reduction. To mitigate the capacity losses of long-term cycling CuO cells, we demonstrate two limited depth of discharge (DOD) strategies. First, a 30% DOD (202 mA h/g) retains 99.9% capacity over 250 cycles. Second, the modification of the CuO cathode by the inclusion of additional Cu metal enables performance at very high areal capacities of ∼40 mA h/cm2 and unprecedented energy densities of ∼260 W h/L, with near 100% Coulombic efficiency. This work revitalizes a historically primary battery chemistry and opens opportunity to future works in developing copper-based conversion cathode chemistries for the realization of low-cost, safe, and energy-dense secondary batteries.

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Section: Resultsmentioning

confidence: 78%

Rechargeable Alkaline Zinc/Copper Oxide Batteries

Schorr

Arnot

Bruck

et al. 2021

ACS Appl. Energy Mater.

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“…The formation of other hydroxide complexes has also been documented, including polynuclear structures such as Bi 6 (OH) 12 6 + [9]. It is this hydroxide complexation that allows Bi and other metals (such as Pb, Cd, Cu, and Zn) to be measured in alkaline solution [10]. Further ASV research in the pH > 14 regime could prove useful for a variety of applications including alkaline batteries and fuel cells [11].…”

Section: Introductionmentioning

confidence: 99%

Bismuth Detection in Alkaline Electrolyte via Anodic Stripping Voltammetry for Battery Separator Evaluation

Arnot

Lambert

2020

Electroanalysis

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Anodic stripping voltammetry (ASV) has been widely used for the detection of several heavy metal ions in neutral and acidic solution, in many cases employing electrodes and/or solutions incorporating Bi. In this work we demonstrate that Bi(OH)4− ion concentration can be measured in highly alkaline 8.5 M KOH solution using ASV. The addition of Pb in similar concentrations to the Bi(OH)4− being measured is shown to improve both the sensitivity and precision of the method. When the Pb additive is employed, a formal limit of detection of 8.5 ppb is achieved, compared to 17.3 ppb when the Pb additive is not used. Due to the use of Bi additives in alkaline battery chemistries, it follows that separators which limit Bi(OH)4− diffusion into the bulk electrolyte and away from the electrodes are of interest. For this purpose, we utilize ASV to determine Bi(OH)4− diffusion rates through Celgard 3501, cellophane 350P00, and Nafion 211. Bi(OH)4− crossover rates, as determined by ASV, are shown to be repeatable and consistent with expectations from the known separator structure.

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“…However, to the best of our knowledge, only a few papers exist in the literature that deal with the application of Hgcoated Pt SECM tips for investigating the open-circuit release of Cd, Pb, and Bi ions from thin films of the corresponding metals. [47,50] In this paper, we present a study of the corrosion of zinc samples to illustrate the potential of coupling mercury tips and SECM in corrosion science under typical metal-corroding conditions. Naturally aerated aqueous chloride-containing solutions have been employed as the test environment.…”

Section: Introductionmentioning

confidence: 99%

In Situ Scanning Electrochemical Microscopy (SECM) Detection of Metal Dissolution during Zinc Corrosion by Means of Mercury Sphere‐Cap Microelectrode Tips

González-García

Battistel

Daniele

2011

Chemistry A European J

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This work presents a scanning electrochemical microscopy (SECM)‐based in situ corrosion probing methodology that is capable of monitoring the release of zinc species in corrosion processes. It is based on the use of Hg‐coated Pt microelectrodes as SECM tips, which offer a wider negative potential range than bare platinum or other noble‐metal tips. This allows for the reduction of zinc ions at the tip to be investigated with low interference from hydrogen evolution and oxygen reduction from aqueous solutions. The processes involved in the corrosion of zinc during its immersion in chloride‐containing solutions were successfully monitored by scanning the SECM tip, set at an adequate potential, across the sample either in one direction or in the X–Y plane parallel to its surface. In this way, it was possible to detect the anodic and cathodic sites at which the dissolution of zinc and the reduction of oxygen occurred, respectively. Additionally, cyclic voltammetry (CV) or constant potential measurements were used to monitor the release of zinc species collected at the tip during an SECM scan.

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Ex Situ Scanning Electrochemical Microscopy (SECM) Investigation of Bismuth‐ and Bismuth/Lead Alloy Film‐Modified Gold Electrodes in Alkaline Medium

Cited by 8 publications

References 50 publications

Rechargeable Alkaline Zinc/Copper Oxide Batteries

Rechargeable Alkaline Zinc/Copper Oxide Batteries

Bismuth Detection in Alkaline Electrolyte via Anodic Stripping Voltammetry for Battery Separator Evaluation

In Situ Scanning Electrochemical Microscopy (SECM) Detection of Metal Dissolution during Zinc Corrosion by Means of Mercury Sphere‐Cap Microelectrode Tips

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