CA2429360A1 - Electrochemical cell - Google Patents

Electrochemical cell Download PDF

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Publication number
CA2429360A1
CA2429360A1 CA002429360A CA2429360A CA2429360A1 CA 2429360 A1 CA2429360 A1 CA 2429360A1 CA 002429360 A CA002429360 A CA 002429360A CA 2429360 A CA2429360 A CA 2429360A CA 2429360 A1 CA2429360 A1 CA 2429360A1
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CA
Canada
Prior art keywords
working electrode
electrode
counter electrode
working
counter
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Granted
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CA002429360A
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French (fr)
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CA2429360C (en
Inventor
Alastair Hodges
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LifeScan Inc
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Individual
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Classifications

    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28Electrolytic cell components
    • G01N27/30Electrodes, e.g. test electrodes; Half-cells
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28Electrolytic cell components
    • G01N27/30Electrodes, e.g. test electrodes; Half-cells
    • G01N27/327Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
    • G01N27/3271Amperometric enzyme electrodes for analytes in body fluids, e.g. glucose in blood
    • G01N27/3274Corrective measures, e.g. error detection, compensation for temperature or hematocrit, calibration
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/50Fuel cells

Abstract

The present invention relates to electrochemical cells including a first working electrode 32, a first counter electrode 34, a second working electrode 36, and a second counter electrode 38, wherein the electrodes are spaced such that reaction products from the first counter electrode 34 arrive at the first working electrode 32, and reaction products from the first and second counter electrodes 34, 38 do not reach the second working electrode 36. Also provided is a method of using such electrochemical cells for determining the concentration of a reduced or oxidized form of a redox species with greater accuracy than can be obtained using an electrochemical cell having a single working and counter electrode.

Claims (33)

1. A method for determining a concentration of a reduced or oxidized form of a redox species, the method comprising the steps of:

a) providing an electrochemical cell comprising a first working electrode, a first counter electrode, a second working electrode and a second counter electrode;

b) selecting a spacing between the first working electrode and the first counter electrode such that reaction products from the first counter electrode arrive at the first working electrode;

c) selecting a spacing between the first working electrode and the second counter electrode such that a significant amount of reaction products from the second counter electrode do not arrive at the first working electrode;

d) selecting a spacing between the second working electrode and the second counter electrode such that a significant amount of reaction products from the second counter electrode do not arrive at the second working electrode;

e) applying an electric potential difference between the first working electrode and the first counter electrode;

f) applying an electric potential difference between the second working electrode and second counter electrode;

g) selecting a potential of the first working electrode such that a rate of electro-oxidation of a reduced form of a redox species or a rate of electro-reduction of an oxidized form of a redox species is diffusion controlled;

h) selecting a potential of the second working electrode such that a rate of electro-oxidation of the reduced form of a redox species or a rate of electro-reduction of an oxidized from of a redox species is diffusion controlled;

i) subtracting a current flowing between the second working electrode and the second counter electrode from a current flowing between the first working electrode and the first counter electrode, whereby a corrected current is obtained; and j) obtaining from the corrected current a value indicative of the concentration of the reduced form of the redox species or the oxidized form of the redox species.
2. The method according to Claim 1, wherein a surface area of the first working electrode and a surface area of the second working electrode are substantially the same.
3. The method according to Claim 1, wherein a surface area of the first working electrode and a surface area of the second working electrode axe different, wherein step i) comprises:
determining a current flowing between the first working electrode and the first counter electrode;

determining a current flowing between the second working electrode and the second counter electrode;
normalizing the current flowing between the first working electrode and the first counter electrode and the current flowing between the second working electrode and the second counter electrode to a same electrode surface area to yield a normalized current flowing between the first working electrode and the first counter electrode and a normalized current flowing between the second working electrode and the second counter electrode; and subtracting the normalized current flowing between the second working electrode and the second counter electrode from the normalized current flowing between the first working electrode and the first counter electrode, whereby a corrected current is obtained.
4. The method according to Claim 1 wherein the first working electrode and the first counter electrode are separated by less than about 500 µm.
5. The method according to Claim 1 wherein the first working electrode and the first counter electrode are separated by less than about 200 µm.
6. The method according to Claim 1 wherein the second working electrode and the second counter electrode are separated by more than about 500 µm.
7. The method according to Claim 1 wherein the first working electrode and the second counter electrode are separated by more than about 500 µm.
8. The method according to Claim 1 wherein the second working electrode and the second counter electrode are separated by more than about 1 mm.
9. The method according to Claim 1 wherein the first working electrode and the second counter electrode are separated by more than about 1 mm.
10. The method according to Claim 1 wherein the redox species is a mediator and the concentration of the reduced or oxidized form of the mediator is indicative of a concentration of an analyte and wherein a measure of a diffusion coefficient of a reduced or oxidized form of the mediator is determined as a precursor to the determination of the concentration of the analyte.
11. The method according to Claim 1 wherein the redox species is a mediator.
12. The method according to Claim 1 wherein the electrochemical cell additionally comprises a separate reference electrode.
13. The method according to Claim 10 wherein the analyte is glucose.
14. An electrochemical cell comprising a first working electrode, a first counter electrode, a second working electrode and a second counter electrode, the first working electrode being spaced from the first counter electrode by less than about 500 µm, the first working electrode being spaced from the second counter electrode by more than about 500 µm, and the second working electrode being spaced from the second counter electrode by more than about 500 µm.
15. The electrochemical cell according to Claim 14, wherein the first working electrode and the first counter electrode are facing one another.
16. The electrochemical cell according to Claim 14, wherein the first working electrode and the first counter electrode are in a side-by-side configuration.
17. The electrochemical cell according to Claim 14, wherein the second working electrode and the second counter electrode are facing one another.
18. The electrochemical cell according to Claim 14, wherein the second working electrode and the second counter electrode are in a side-by-side configuration.
19. The electrochemical cell according to Claim 14, wherein the first working electrode, the first counter electrode, the second working electrode, and the second counter electrode are in a side-by-side configuration.
20. The electrochemical cell according to Claim 14, wherein the first working electrode and the second working electrode are of substantially corresponding area.
21. The electrochemical cell according to Claim 14, further comprising a separate reference electrode.
22. The electrochemical cell of Claim 14, wherein the electrochemical cell is a hollow electrochemical cell.
23. The electrochemical cell according to Claim 22, having an effective cell volume of less than 1.5 microliters.
24. Apparatus for determining the concentration of a redox species in an electrochemical cell comprising:
an electrochemical cell having a first working electrode, a first counter electrode, a second working electrode and a second counter electrode, characterized in that the first working electrode is spaced from the first counter electrode by less than 500µm, the first working electrode is spaced from the second counter electrode by more than 500 µm, and the second working electrode is spaced from the second counter electrode by more than 500µm;
an electrical circuit capable of applying an electric potential difference between the first working electrode and the first counter electrode; and an electrical circuit capable of applying an electric potential difference between the second working electrode and the second counter electrode.
25. The apparatus according to Claim 28, wherein the apparatus is a glucose meter.
26. An electrochemical cell comprising a first working electrode, a first counter electrode, and a second working electrode, the first working electrode being spaced from the first counter electrode by less than about 500 µm, and the second working electrode being spaced from the first counter electrode by more than about 500 µm.
27. A method for determining the concentration of a reduced or oxidized form of a redox species, the method comprising the steps of:

a) providing an electrochemical cell comprising a first working electrode, a counter electrode, and a second working electrode;

b) selecting a spacing between the first working electrode and the counter electrode such that reaction products from the counter electrode arrive at the first working electrode;

c) providing a redox species, wherein at least a useful fraction of the redox species initially present in a solution above the second working electrode has been reduced or oxidized at the second working electrode;

d) applying an electric potential difference between the first working electrode and the counter electrode;

e) selecting a potential of the first working electrode such that the rate of electro-oxidation of the reduced form or electro-reduction of the oxidized form of the species is diffusion controlled;

f) determining a current flowing between the first working electrode and the counter electrode; and g) obtaining from the current a value indicative of a concentration of a reduced form of the redox species or a concentration of an oxidized form of the redox species.
28. The method according to Claim 27, wherein a surface area of the first working electrode and a surface area of the second working electrode are substantially the same.
29. The method according to Claim 27, wherein a surface area of the first working electrode and a surface area of the second working electrode are substantially different.
30. A method for determining a concentration of a reduced or oxidized form of a redox species, the method comprising the steps of:

a) providing an electrochemical cell comprising a first working electrode, a second working electrode, and a counter electrode;

b) selecting a spacing between the first working electrode and the counter electrode such that reaction products from the counter electrode arrive at the first working electrode;

c) selecting a spacing between the second working electrode and the counter electrode such that a significant amount of reaction products from the counter electrode do not arrive at the second working electrode;

d) applying an electric potential difference between the second working electrode and the counter electrode whereby the second working electrode is substantially charged and whereby surface group reactions are substantially completed;
e) interrupting a circuit between the second working electrode and the counter electrode before a significant amount of the redox species is reacted at the second working electrode;
f) applying an electric potential difference between the first working electrode and the counter electrode;
g) selecting a potential of the first working electrode such that a rate of electro-oxidation of the reduced form of the redox species or a rate of electro-reduction of the oxidized form of the redox species is diffusion controlled;
h) determining a current flowing between the first working electrode and the counter electrode; and i) obtaining from the current a value indicative of a concentration of the reduced form of the redox species or the oxidized form of the redox species.
31. A method for determining a concentration of a reduced or oxidized form of a redox species, the method comprising the steps of:
a) providing an electrochemical cell comprising a first working electrode, a second working electrode, and a counter electrode;
b) selecting a spacing between the first working electrode and the counter electrode such that reaction products from the counter electrode arrive at the first working electrode;
c) selecting a spacing between the second working electrode and the counter electrode such that a significant amount of reaction products from the counter electrode do not arrive at the second working electrode;
d) applying an electric potential difference between the second working electrode and the counter electrode and between the first working electrode and the counter electrode, whereby the second working electrode and first working electrode are substantially charged and whereby surface group reactions are substantially completed;
e) interrupting a circuit between the second working electrode and the counter electrode before a significant amount of the species is reacted at the second working electrode;
f) applying an electric potential difference between the first working electrode and the counter electrode;

g) selecting a potential of the first working electrode such that a rate of electro-oxidation of the reduced foam of the redox species or a rate of electro-reduction of the oxidized form of the redox species is diffusion controlled;
h) determining a current flowing between the first working electrode and the counter electrode; and i) obtaining from the current a value indicative of a concentration of the reduced form of the redox species or the oxidized fore of the redox species.
32. Apparatus for determining a concentration of a redox species in an electrochemical cell comprising:
an electrochemical cell having a first working electrode, a first counter electrode, a second working electrode and a second counter electrode, characterized in that the first working electrode is spaced from the first counter electrode by less than 500 µm, the first working electrode is spaced from the second counter electrode by more than 500 µm, and the second working electrode is spaced from the second counter electrode by more than 500 µm;
means for applying an electric potential difference between the first working electrode and the first counter electrode; and means for applying an electric potential difference between the second working electrode and the second counter electrode.
33. The apparatus according to Claim 32, wherein the apparatus is a glucose meter.
CA2429360A 2001-10-10 2002-10-01 Electrochemical cell Expired - Fee Related CA2429360C (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US32884601P 2001-10-10 2001-10-10
US60/328,846 2001-10-10
PCT/US2002/031289 WO2003032411A2 (en) 2001-10-10 2002-10-01 Electrochemical cell

Publications (2)

Publication Number Publication Date
CA2429360A1 true CA2429360A1 (en) 2003-04-17
CA2429360C CA2429360C (en) 2012-01-24

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CA2429360A Expired - Fee Related CA2429360C (en) 2001-10-10 2002-10-01 Electrochemical cell

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US (3) US7431820B2 (en)
EP (1) EP1442289A2 (en)
JP (2) JP4767493B2 (en)
KR (1) KR100955587B1 (en)
CN (3) CN1232818C (en)
AU (1) AU2002340079A1 (en)
CA (1) CA2429360C (en)
HK (1) HK1066062A1 (en)
IL (2) IL156007A0 (en)
RU (1) RU2297696C2 (en)
TW (1) TWI227066B (en)
WO (1) WO2003032411A2 (en)

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