Porous electrodes for spectroelectrochemistry and x-ray structure analyses

Patent metadata

Field	Value
Publication number	US-2018031496-A1
Application number	US-201615221167-A
Country	US
Kind code	A1
Filing date	Jul 27, 2016
Priority date	Jul 27, 2016
Publication date	Feb 1, 2018
Grant date	—

Abstract

An electrochemical cell that allows for in-situ structural characterization of amorphous thin film materials during the course of electrolysis using high-energy X-ray scattering (>50 keV). The compact and versatile cell, fabricated using a 3 D printer, employs a three-electrode configuration and minimizes X-ray scattering contributions from the cell, reference and counter electrodes, as well as the working electrode support. A large surface area working electrode has a physically robust support and is largely transparent to X-rays. This design, which utilizes a three-dimensional working electrode, also greatly improves the intensity and quality of the scattered signal compared to a two-dimensional working electrode. The in-situ cell can be used not only to investigate structural evolution during electrolysis using X-ray scattering (e.g. pair distribution function), but also to perform electrochemical potential-dependent structural analysis by extended X-ray absorption fine structure. The in-situ electrochemical cell opens new opportunity to characterize amorphous thin films thinner than 70 nm.

First claim

What is claimed is:

1 . An article of manufacture comprising:
an in-situ cell comprising:
at least three electrodes including a working electrode (W.E.), a reference electrode (R.E.), and a cell electrode (C.E.);
an electrolyte system including an electrolyte line and an electrolyte source in fluid communication with the in-situ cell; and
a film over the WE forming an WE electrolyte chamber.

2 . The article of manufacture of claim 1 , wherein the W.E. includes a substrate having a glass capillary array having a conformal conductive layer deposited thereon.

3 . The article of manufacture of claim 1 , wherein the glass capillary array is a microporous glass capillary array having pores with a diameter of 40 μm or less and at least a 20 mm 2 surface area.

4 . The article of manufacture of claim 3 , wherein the conformal conductive layer is less than 70 nm thick.

5 . The article of manufacture of claim 2 , wherein the W.E. further comprises a metallic layer deposited on the glass capillary array opposite the conductive layer.

6 . The article of manufacture of claim 2 , wherein the conformal conductive layer is less than 50 nm thick.

7 . The article of manufacture of claim 2 , further comprising the housing of magnetic stirrer and possesses a tubing and syringe pump for electrolyte flow.

8 . The article of manufacture of claim 1 , wherein the W.E. electrolyte chamber has a cross-section shape selected from half-moon, semi-elliptical, and semi-circular.

9 . The article of manufacture of claim 7 , wherein the film is 7.5 μm thick.

10 . The article of manufacture of claim 1 , wherein the electrolyte system further including a stirrer associated with the electrolyte source and configured to stir electrolyte in the electrolyte source.

11 . The article of manufacture of claim 2 , wherein the electrolyte system further comprises a pump.

12 . A method of characterizing a thin film within an electrochemical cell, the method comprising:
depositing a thin film on a working electrode within the electrochemical cell; controlling the deposition at last in part by application of a current to a cell electrode in electrical contact with the working electrode; interacting the deposited thin film with an incident x-ray beam; measuring background scattering; and collecting CV data for the thin film.

13 . The method of claim 12 , wherein measuring the background scattering is at a distance q.

14 . The method of claim 12 , wherein the deposited thin film is less than 70 nm thick.

15 . The method of claim 14 , wherein the deposited thin film is less than 50 nm thick.

16 . The method of claim 12 , further comprising providing a continuous flow of electrolyte over the working electrode.

17 . The method of claim 15 , wherein providing the continuous flow further includes purging oxygen bubbles from the working electrode.

18 . The method of claim 12 , wherein an interaction volume for interaction for the x-rays with the deposited thin film is at least 1500×10 −6 mm 3 .

19 . The method of claim 11 , wherein the working electrode comprises a microporous glass capillary array having pores with a diameter of 40 μm or less and at least a 20 mm 2 surface area

Assignees

• Uchicago Argonne Llc

Inventors

• Kwon Gihan
• Emery Jonathan D
• Kim In Soo
• Martinson Alex B
• Tiede David M

Classifications

• C25D17/12 Primary

  Shape or form (C25D17/14 takes precedence) · CPC title

• G01N23/203 Primary

  Measuring back scattering · CPC title

• C25B1/04

  by electrolysis of water · CPC title

• G01N2223/61

  thin films, coatings · CPC title

• C25D9/04

  with inorganic materials · CPC title