Reference electrode with SPEEK/IL sandwich structure, and preparation method and use thereof

Patent metadata

Field	Value
Publication number	US-12429452-B2
Application number	US-202318211304-A
Country	US
Kind code	B2
Filing date	Jun 19, 2023
Priority date	Dec 28, 2020
Publication date	Sep 30, 2025
Grant date	Sep 30, 2025

Abstract

A reference electrode with a sulfonated polyether ether ketone/ionic liquid (SPEEK/IL) sandwich structure, and a preparation method and use thereof are provided. In the reference electrode, an end of a reference electrode main body is provided with the SPEEK/IL sandwich structure; the SPEEK/IL sandwich structure includes two layers of SPEEK/IL composite film and one layer of SPEEK film, and the SPEEK film is arranged at an outermost layer of the SPEEK/IL sandwich structure.

First claim

What is claimed is:

1. A reference electrode with a SPEEK/IL sandwich structure, wherein an end of a reference electrode main body is provided with the SPEEK/IL sandwich structure; the SPEEK/IL sandwich structure comprises two layers of SPEEK/IL composite film and one layer of SPEEK film, and the SPEEK film serves as an outermost layer of the SPEEK/IL sandwich structure; an ionic liquid layer is separately filled between the reference electrode main body and an inner layer of SPEEK/IL composite film, between the two layers of SPEEK/IL composite film, and between a SPEEK/IL composite film and the SPEEK film; the SPEEK refers to sulfonated polyether ether ketone, and the IL refers to ionic liquid; and the IL is 1-(2-hydroxyethyl)-3-methylimidazolium chloride ([HOEtMIM][Cl]) with a structural formula as follows:

2. The reference electrode with the SPEEK/IL sandwich structure according to claim 1 , wherein the SPEEK/IL composite film is a SPEEK/SiO x /IL composite film; the SPEEK/IL sandwich structure comprises two layers of SPEEK/SiO x /IL composite film and the one layer of SPEEK film, and the SPEEK film serves as the outermost layer of the SPEEK/IL sandwich structure; the IL layer is separately filled between the reference electrode main body and an inner layer of SPEEK/SiO x /IL composite film, between the two layers of SPEEK/SiO x /IL composite film, and between a SPEEK/SiO x /IL composite film and the SPEEK film.

3. A preparation method of the reference electrode with the SPEEK/IL sandwich structure according to claim 2 , comprising the following steps:
1) pouring polyether ether ketone (PEEK) particles into concentrated sulfuric acid, and dissolving by stirring continuously; after the PEEK particles are completely dissolved, heating a resulting solution to 35° C. to 70° C., and conducting vulcanization for 2 h to 4 h in an inert gas atmosphere;
2) slowly pouring a polymer solution obtained in step 1) into an ice-water mixture to terminate the reaction, collecting formed particles, washing the particles with water until a pH value of a washing solution reaches 6 to 7, and drying the particles in an oven at 50° C. to 70° C. for 12 h to 48 h to obtain SPEEK particles;
3) pouring the SPEEK particles into a solvent, and dissolving by stirring to obtain a 10 wt % SPEEK solution;
4) mixing an inorganic acid, a silicate, deionized water, and an alcohol as raw materials at a molar ratio of (0.01-0.1):1:(2-8):(2-8), and stirring to form a homogeneous solution; pouring the SPEEK solution obtained in step 3) into the homogeneous solution and stirring uniformly, and adding the IL dropwise into a solution and stirring to obtain a SPEEK/SiO x /IL solution;
5) immersing the reference electrode main body into the IL, taking out and drying, such that a surface of the reference electrode is covered with an IL layer; immersing a reference electrode into the SPEEK/SiO x /IL solution, taking out and air-drying upside down to form one layer of SPEEK/SiO x /IL composite film;
6) repeating step 5) once on an electrode obtained in step 5) to obtain the two layers of SPEEK/SiO x /IL composite film; immersing an obtained reference electrode into the IL, taking out and drying, such that a surface of an outer SPEEK/SiO x /IL composite film is covered with an IL layer; and
7) immersing a reference electrode obtained in step 6) into the SPEEK solution, taking out and air-drying upside down to obtain the reference electrode with the SPEEK/IL sandwich structure.

4. The preparation method according to claim 3 , wherein in step 1), the concentrated sulfuric acid has a concentration of 95% to 98%; in step 1), the dissolving is conducted at less than 30° C.; and the PEEK particles and the concentrated sulfuric acid are at a mass ratio of 1:(20-40).

5. The preparation method according to claim 3 , wherein in step 3), the solvent is selected from the group consisting of N,N-dimethylformamide (DMF) and N,N-dimethylaniline (DMA); and
in step 4), the inorganic acid is hydrochloric acid, the silicate is tetraethyl orthosilicate (TEOS), and the alcohol is ethanol.

6. The preparation method according to claim 3 , wherein in step 4), the homogeneous solution and the SPEEK solution are at a volume ratio of 1:(4-7.5); and the IL and the SPEEK solution are at a volume ratio of 1:(1-3.3).

7. The preparation method according to claim 3 , wherein the reference electrode main body is an Ag/AgCl reference electrode; the Ag/AgCl reference electrode is immersed in the SPEEK/SiO x /IL solution or the SPEEK solution for 5 s to 10 s; and the Ag/AgCl reference electrode is immersed in the IL for 1 h to 12 h at 50° C. to 80° C. with help of ultrasonic wave.

8. The reference electrode with the SPEEK/IL sandwich structure according to claim 2 , wherein the reference electrode main body is an Ag/AgCl reference electrode; and the SPEEK/IL sandwich structure completely covers AgCl on a surface of the reference electrode.

9. The reference electrode with the SPEEK/IL sandwich structure according to claim 1 , wherein the reference electrode main body is an Ag/AgCl reference electrode; and the SPEEK/IL sandwich structure completely covers AgCl on a surface of the reference electrode.

10. A use method of the reference electrode with the SPEEK/IL sandwich structure according to claim 1 in pH value detection.

11. The use method according to claim 10 , wherein in the reference electrode with the SPEEK/IL sandwich structure, the SPEEK/IL composite film is a SPEEK/SiO/IL composite film; the SPEEK/IL sandwich structure comprises two layers of SPEEK/SiO x /IL composite film and the one layer of SPEEK film, and the SPEEK film serves as the outermost layer of the SPEEK/IL sandwich structure; the IL layer is separately filled between the reference electrode main body and an inner layer of SPEEK/SiO x /IL composite film, between the two layers of SPEEK/SiO x /IL composite film, and between a SPEEK/SiO x /IL composite film and the SPEEK film.

12. The use method according to claim 10 , wherein in the reference electrode with the SPEEK/IL sandwich structure, the reference electrode main body is an Ag/AgCl reference electrode; and the SPEEK/IL sandwich structure completely covers AgCl on a surface of the reference electrode.

Assignees

• Univ Zhejiang

Inventors

• Pan Yiwen
• Shen Yunwen
• Wang Xiaoping
• Sun Zhentao

Classifications

• Y02E60/50

  Fuel cells · CPC title

• G01N27/307

  Disposable laminated or multilayered electrodes (G01N27/3272 takes precedence) · CPC title

• G01N27/302

  pH sensitive, e.g. quinhydron, antimony or hydrogen electrodes (ion selective electrodes G01N27/333, glass electrodes G01N27/36) · CPC title

• G01N27/3335 Primary

  the membrane containing at least one organic component (G01N27/3271 takes precedence; aspects concerning the enzyme reagent in enzyme electrodes C12Q1/001) · CPC title

• G01N27/301 Primary

  Reference electrodes · CPC title