Novel electrode with switchable and tunable power output and fuel cell using such electrode

• US 20060269826A1
• Filed: 03/02/2004
• Published: 11/30/2006
• Est. Priority Date: 03/03/2003
• Status: Abandoned Application

• Current Assignee: Yissum Research Development Company of the Hebrew University of Jerusalem Ltd. (Hebrew University of Jerusalem)
• Original Assignee: Yissum Research Development Company of the Hebrew University of Jerusalem Ltd. (Hebrew University of Jerusalem)
• Inventors: Willner, Itamar, Katz, Eugenii
• Application Number:
  US10/547,617
• Publication Number:
  US 20060269826A1
• Time in Patent Office: Days
• US Class Current: 429/401
• CPC Class Codes: C12Q 1/001 Enzyme electrodes
• CPC Class Codes: H01M 4/8647 consisting of more than one material, e.g. consisting of composites
• CPC Class Codes: H01M 4/90 Selection of catalytic material
• CPC Class Codes: H01M 4/9008 Organic or organo-metallic compounds
• CPC Class Codes: H01M 8/16 Biochemical fuel cells, i.e. cells in which microorganisms function as catalysts
• CPC Class Codes: Y02E 60/50 Fuel cells

Abstract

The present invention provides a novel electrode carrying on at least a portion of its support surface a hybrid polymer matrix (HPM), a catalyst that can catalyze a redox reaction and an optional electron mediator group that enhances the electrical contact between the HPM and the catalyst, the HPM being capable to be electrochemically changed from a non-conductive state to a conductive state. The electrode of the invention may be used in electrical devices such as fuel cells, thus imparting them switchable and tunable properties. The fuel cell of the invention may be used as a power source or as a self-powered sensor.

Claims

1-44. -44. (canceled)

45. An electrode carrying on at least a portion of its support surface a hybrid polymer matrix (HPM), a catalyst that can catalyze a redox reaction and an optional electron mediator group that enhances electrical contact between the HPM and the catalyst, said HPM being capable to be electrochemically charged from a non-conductive state to a conductive state.

46. The electrode according to claim 45, wherein said HPM in its conductive state enables electrical contact between said electrode and said catalyst.

47. The electrode according to claim 45 wherein said catalyst layer carried on the electrode surface comprises a redox enzyme.

48. The electrode according to claim 45, wherein said HPM comprises in the non-conductive state a polymer carrying negatively charged groups that electrostatically accommodate metal cations.

49. The electrode according to claim 48 wherein said negatively charged groups are selected from carboxyl, sulphonate and phosphate.

50. The electrode according to claim 48 wherein said polymer is selected from polyacrylic acid, polylysine, polystyrene sulfonate and nafion.

51. The electrode according to claim 48 wherein said metal cations are cations of transition metals.

52. The electrode according to claim 51 wherein said metal cations are cations of metals selected from Cu, Ag, Hg, Cr, Fe, Ni and Zn.

53. The electrode of claim 45 having switchable conductivity properties such that in the conductive state of the HPM, the catalyst is electrically contacted with the electrode'"'"' support, while in the non conductive state of the HPM, the catalyst lacks electrical contact with the electrode'"'"' support, thus resulting in high electron transfer resistances.

54. The electrode of claim 45, having tunable conductivity properties such that application of reductive potential for time-intervals that are shorter than that required for full reduction of HPM, results in the partial reduction of the HPM to the conductive state, thus allowing tuning of the electrode'"'"'s output.

55. The electrode of claim 45, wherein said HPM is capable to be changed from a non-conductive to a conductive state and vice versa by reversible application of reductive potential and oxidative potential on the electrode.

56. A fuel cell comprising at least one electrode according to claim 45.

57. The fuel cell according to claim 56 comprising a pair of electrodes, one of the electrodes being an anode and the other a cathode, wherein both electrodes carry on at least a portion of their support surface a hybrid polymer matrix (HPM), a catalyst layer and an optional electron mediator group that enhances the electrical contact between the HPM and the catalyst, said HPM being capable to be electrochemically charged from a non-conductive state to a conductive state such that in its conductive state the catalyst layer is electrically contacted with the electrode that carries it, thus allowing the fuel cell operation.

58. The fuel cell of claim 57, wherein said catalyst layer carried on the anode or cathode surface comprises a redox enzyme.

59. The fuel cell of claim 58, wherein said redox enzyme is cofactor-dependent, the cofactor being selected from flavin adenine dinucleotide phosphate (FAD), pyrroloquinoline quinone (PQQ), nicotinamide adenine dinucleotide (NAD), nicotinamide adenine dinucleotide phosphate (NADP), hemes and iron-sulfur clusters.

60. The fuel cell of claim 58, wherein the enzyme carried on the anode electrode is selected from glucose oxidase (GOx), glucose dehydrogenase, lactate dehydrogenase (LDH), fructose dehydrogenase, cholin oxidase, amino oxidase and alcohol dehydrogenase.

61. The fuel cell of claim 58, wherein the enzyme carried on the cathode electrode is selected from lacase, billirubin oxidase and a complex formed of cytochrome c/cytochrome oxydase (COx).

62. The fuel cell of claim 57, wherein said HPM comprises in the non-conductive state a polymer carrying negatively charged groups that electrostatically accommodate metal cations.

63. The fuel cell of claim 62 wherein said negatively charged groups are selected from carboxyl, sulphonate and phosphate.

64. The fuel cell of claim 62 wherein said polymer is selected from polyacrylic acid, polylysine, polystyrene sulfonate and nafion.

65. The fuel cell of claim 62 wherein said metal cations are cations of transition metals.

66. The fuel cell of claim 65 wherein said metal cations are cations of metals selected from Cu, Ag, Hg, Cr, Fe, Ni and Zn.

67. The fuel cell of claim 56 having switchable conductivity properties such that in the conductive state of the HPM, the catalyst is electrically contacted with the electrode'"'"' support, thus switching on the fuel cell operation, while in the non conductive state of the HPM, the catalyst lacks electrical contact with the electrode'"'"' support, thus resulting in high electron transfer resistances switching off the fuel cell performance.

68. The fuel cell of claim 56, having tunable conductivity properties such that application of reductive potential for time-intervals that are shorter than that required for the full reduction of HPM, results in the partial reduction of the HPM to the conductive state, thus allowing tuning of the fuel cell output.

69. The fuel cell of claim 57, wherein said HPM is capable to be changed from a non-conductive to a conductive state and vice versa by reversible application of reductive potential and oxidative potential on the electrodes.

70. The fuel cell of claim 57, wherein said HPM is bound to a further polymeric layer comprising functional groups capable to bind to the catalyst layer or to the electron mediator group.

71. The fuel cell of claim 70, wherein said further polymeric layer comprises amino groups.

72. The fuel cell of claim 57, wherein the electrode'"'"' support is made of or coated by a material selected from gold, platinum, palladium, silver, carbon, copper, and indium tin oxide.

73. The fuel cell of claim 57, further comprising a membrane between the anode and the cathode.

74. The fuel cell according to claim 56 for use as a switchable and/or tunable power supply.

75. The fuel cell according to claim 56 for use as a biosensor.

76. A system for the determination of an analyte in a liquid medium comprising a biosensor according to claim 75 and a detector for measuring an electrical signal generated by said biosensor while the analyte is being oxidized or reduced, the analyte being capable of undergoing a biocatalytic oxidation or reduction in the presence of an oxidizer or reducer, respectively.

77. The system of claim 76, wherein said analyte is selected from the group consisting of sugar molecules, hydroxy, carbonyl or carboxy compounds and amino acids.

78. A system according to claim 76, wherein the biosensor is adapted for invasive measurements of an analyte in a body fluid of a tested subject.

79. A method for determining an analyte in a liquid medium, said analyte being capable to undergo a biocatalytic oxidation or reduction in the presence of an oxidizer or a reducer, respectively, the method comprising:

(i) providing the system of claim 76;

(ii) activating the biosensor of said system by applying reductive potential to shift the HRM of the biosensor from non-conductive into a conductive state;

(iii) contacting the activated biosensor of said system with the liquid medium;

(iv) measuring the electric signal generated between the cathode and the anode, said electric signal being indicative of the presence and/or the concentration of said analyte;

(v) determining said analyte based on said signal.

80. The method according to claim 79, wherein said liquid medium is a body fluid, said method comprising inserting said biosensor into the body and bringing it into contact with the body fluid and determining said analyte in said body fluid within the body.

81. A method of powering an electrical device comprising the steps of electrically connecting the fuel cell of claim 56 to the device, electrooxidizing the fuel at the anode and electroreducing an electron reducing molecule at the cathode, to generate electrical power.