Actuators using double-layer charging of high surface area materials

• US 6,555,945 B1
• Filed: 08/20/1999
• Issued: 04/29/2003
• Est. Priority Date: 02/25/1999
• Status: Expired due to Fees

• Current Assignee: Alliedsignal Inc. (Honeywell International Inc.)
• Original Assignee: Alliedsignal Inc. (Honeywell International Inc.)
• Inventors: Iqbal, Zafar, Baughman, Ray H., Su, Ji, Zakhidov, Anvar, Cui, Changxing
• Primary Examiner(s): Font, Frank G.
• Assistant Examiner(s): Mooney, Michael P.
• Application Number:
  US09/379,132
• Time in Patent Office: 1,348 Days
• Field of Search: 310/300, 385/22, 385/134, 385/147, 385/15, 385/39, 385/52, 429/9, 429/345, 429/346, 136/291, 216/56, 361/500
• US Class Current: 310/300
• CPC Class Codes: F03G 7/005 Electro-chemical actuators; Actuators having a material for absorbing or desorbing gas, e.g. a metal hydride; Actuators using the difference in osmotic pressure between fluids; Actuators with elements stretchable when contacted with liquid rich in ions, with UV light, with a salt solution
• CPC Class Codes: H02N 11/006 Motors
• CPC Class Codes: Y10S 136/291 Applications
• CPC Class Codes: Y10S 977/725 Nanomotor/nanoactuator

Abstract

Actuators are described that operate as a result of double-layer charge injection in electrodes having very high gravimetric surface areas and gravimetric capacitances. The actuator output of the actuators may be a mechanical displacement that can be used to accomplish mechanical work. As a result of the non-faradaic process and the actuator materials utilized, such as carbon nanotubes, the actuators have improved work capacity, power density, cycle life, and force generation capabilities. Other benefits include low voltage operation and high temperature performance. The actuators also convert a mechanical energy input to an electrical energy output. The actuators may be used to control either thermal, electrical or fluid transport or cause either the switching, phase shift, or attenuation of electromagnetic radiation.

Claims

1. An actuator comprising:

at least one ionically conducting and electronically insulating electrolyte; and

at least two electronically conducting electrodes separated by said at least one electrolyte, at least one electrode of said at least two electronically conducting electrodes being a porous solid with a skeletal density in gm/cm³ of ρ

having an accessible gravimetric surface area of at least 150 ρ

<sup>−

1</sup> m²/gm and an accessible gravimetric capacitance of at least 5 ρ

<sup>−

1</sup> F/gm and having pores containing an electrolyte that is ionically conducting,

the at least one electrode undergoing a response that provides, in whole or in part, an actuator output upon non-faradaic charge injection responsive to application of an electrical voltage between said at least two electronically conducting electrodes.

2. The actuator of claim 1, which provides an actuator output that is one of a mechanical displacement;

control of either thermal, electrical, or fluid transport;

or either switching, phase shift, or attenuation of electromagnetic radiation.

3. The actuator of claim 1, wherein the actuator output substantially originates from either change of dimension, surface energy, an optical property, or an electrical property of the at least one electrode as a result of non-faradaic electrode charging.

4. The actuator of claim 1, wherein the at least one electrode undergoes less than a 5% change in weight upon undergoing the actuator response to provide a useful actuator output.

5. The actuator of claim 4, wherein the at least one electrode has a maximum electronic conductivity that is above 1 S/cm, and wherein a ratio of the maximum electronic conductivity of a highest conductivity electrode to an electronic conductivity of the electrolyte that is ionically conducting and electronically insulating is above 10⁵.

6. The actuator of claim 1, wherein said at least one electrolyte comprises either (a) an aqueous salt solution of an alkali metal cation and a halogen anion, (b) a solid state electrolyte, or (c) an aqueous solution of either sulfuric acid or KOH having a molar concentration above 4 M.

7. The actuator of claim 6, wherein said at least one electrolyte is aqueous NaCl, blood, or seawater.

8. The actuator of claim 1, wherein the at least one electrode comprises an electrode formed by:

(a) crystallizing spheres of a first material into a porous first structure having three-dimensional periodicity and voids between the spheres;

(b) infiltrating the porous first structure with a second material to form a composite structure of the first and second materials; and

(c) removing the first material from the composite structure to form a porous second structure comprising the second material.

9. The actuator of claim 8, wherein the second material is either comprised of graphite or a precursor to graphite.

10. The actuator of claim 2, wherein the at least one electrode is part of either an optical switch in an electroptical circuit, an electrochromic element on a display, or an electrically switchable window.

11. The actuator of claim 3, wherein the at least one electrode is one part of a fluid control valve, wherein valve operation results from an electrically controlled change in surface energy of the at least one electrode that is in a form of either a pipe or a sheet.

12. The actuator of claim 1, wherein the at least one electrode comprises a form of carbon.

13. The actuator of claim 12, wherein the form of carbon comprises either single-wall, multi-wall, or scroll carbon nanotubes.

14. The actuator of claim 12, wherein the at least one electrode is in the form of a sheet comprising single-wall carbon nanotubes.

15. The actuator of claim 12, wherein the form of carbon comprises separated sheets of graphite dispersed in a solid electrolyte and percolated in the solid electrolyte.

16. The actuator of claim 1, wherein one or more of said at least two electronically conducting electrodes comprises a conducting organic polymer.

17. The actuator of claim 1, wherein two electrodes of said at least two electronically conducting electrodes are electrolyte filled porous solids that (a) undergo an actuator response upon non-faradaic charge injection and (b) have an accessible gravimetric surface area of at least 150 ρ

<sup>−

1</sup> m²/gm and an accessible gravimetric capacitance of at least 5 ρ

<sup>−

1</sup> F/g.

18. The actuator of claim 2, that is an electromechanical actuator providing mechanical displacement capable of accomplishing mechanical work in response to application of the electrical voltage between said at least two electronically conducting electrodes.

19. The actuator of claim 18, wherein the at least one electrode is a sheet comprised of carbon single-wall nanotubes, wherein an in-plane Young'"'"'s modulus of the sheet is at least 0.5 GPa.

20. The actuator of claim 18, wherein an electrical energy is generated as an output from said at least two electronically conducting electrodes responsive to one or more time varying mechanical strains on the at least one electrode.

21. The actuator of claim 2, wherein said at least two electronically conducting electrodes each comprise a porous thermoelectric having a thermoelectric coefficient that is electrically switched by substantially non-faradaic charge injection.

22. The actuator of claim 1, wherein said at least two electronically conducting electrodes comprise a working electrode and a counter electrode, the working and counter electrodes and said at least one electrolyte being interpenetrating elements in a single composite structure.

23. The actuator of claim 1, comprising the at least one electrode that operates non-faradaically and a counter electrode that operates faradaically.

24. The actuator of claim 23, wherein the at least one electrode is predominately surface coated with ions during actuation and the counter electrode is a solid electrode that is predominately infiltrated with ions that insert therein during actuation.

25. The actuator of claim 1, wherein above 25% of pore volume of the at least one electrode that is either two-dimensionally accessible or three-dimensionally accessible by the electrolyte that is ionically conducting has an effective radius of above 20 Å

.

26. The actuator of claim 1, wherein an electrical energy is chemically or photochemically generated using said at least two electronically conducting electrodes as one of battery electrodes, fuel cell electrodes, and electrodes of a photo-rechargeable battery.

27. The actuator of claim 26, wherein said at least two electronically conducting electrodes are electrodes of a photo-rechargeable battery, one of said at least two electronically conducting electrodes being a transition metal chalcogenide.

28. The actuator of claim 26, wherein said at least two electronically conducting electrodes are battery electrodes, wherein one of said at least two electronically conducting electrodes is comprised of lithium and another of said at least two electronically conducting electrodes that provides the actuator response is comprised of carbon nanofibers, the electrolyte that is ionically conducting and electronically insulating being comprised of a lithium salt and either thionyl chloride (SOCl₂) or SO₂.

29. The actuator of claim 28, wherein the actuator response is mechanical displacement.

30. An electromechanical actuator comprising:

at least one ionically conducting and electronically insulating electrolyte; and

at least two electronically conducting electrodes separated by said at least one electrolyte, at least one electrode of said at least two electronically conducting electrodes being a porous solid having an accessible gravimetric surface area of at least 150 m²/gm and an accessible gravimetric capacitance of at least 5 F/gm, having a mechanical modulus of at least 0.5 GPa and having pores containing an electrolyte that is ionically conducting,

the at least one electrode undergoing a dimensional change that provides, in whole or in part, an actuator output upon non-faradaic charge injection responsive to application of an electrical voltage between said at least two electronically conducting electrodes.

31. The electromechanical actuator of claim 30, wherein the at least one electrode is comprised of carbon nanotubes having a number-average diameter of less than about 10 nm.

32. The electromechanical actuator of claim 31, wherein the carbon nanotubes are predominately single-wall carbon nanotubes.

33. The electromechanical actuator of claim 32, wherein the single-wall carbon nanotubes are predominately (10, 10) nanotubes.

34. The electromechanical actuator of claim 32, wherein the single-wall carbon nanotubes are made by a laser-based process.

35. The electromechanical actuator of claim 33, wherein either more than 50% of the single-wall carbon nanotubes are non-bundled or the average number of carbon nanotubes in a bundle is less than about 50.

36. The electromechanical actuator of claim 32, wherein a number-average length-to-diameter ratio of the carbon nanotubes is above 1000.

37. The electromechanical actuator of claim 32, wherein the single-wall carbon nanotubes are configured as a sheet.

38. The electromechanical actuator of claim 37, wherein the sheet predominately comprises carbon single-wall nanotubes that are either biaxially oriented in a plane of the sheet or preferentially oriented in a particular in-plane direction.

39. The electromechanical actuator of claim 38, wherein a maximum in-plane electrical conductivity of the sheet is above 1000 S/cm.

40. The electromechanical actuator of claim 37, wherein an average tube length between inter-tube contacts divided by tube diameter for the sheet is below 100.

41. The electromechanical actuator of claim 37, wherein the sheet is formed by either filtration of a dispersion of carbon nanotubes in a carrier fluid or disposition of a mixture of carbon nanotubes and polymeric electrolyte in the carrier fluid, followed by evaporation of the carrier fluid.

42. The electromechanical actuator of claim 41, wherein the sheet is formed by filtration of a dispersion of single-wall nanotubes in the carrier fluid, a concentration of nanotubes in the carrier fluid being below about 0.1 mg/ml.

43. The electromechanical actuator of claim 38, wherein the sheet is annealed at a temperature of at least 400°

C. and less than 2000°

C. under either a substantially inert atmosphere or a hydrogen-containing atmosphere.

44. The electromechanical actuator of claim 31, wherein the at least one electrode is fabricated by applying an electrical voltage between two electrodes immersed in a carrier fluid containing carbon nanotubes.

45. The electromechanical actuator of claim 30, wherein the at least one electrode has an average thickness in a narrowest dimension of less than 0.5 millimeters.

46. The electromechanical actuator of claim 30, wherein a maximum thickness of said at least one electrolyte that separates said at least two electronically conducting electrodes is less than 1 millimeter and said at least one electrolyte is either a solid-state electrolyte or an organic electrolyte.

47. The electromechanical actuator of claim 30, wherein said at least one electrolyte comprises either (a) an aqueous salt solution of an alkali metal cation and a halogen anion, (b) a solid state electrolyte, or (c) an aqueous solution of either sulfuric acid or KOH having a molar concentration above 4 M.

48. The electromechanical actuator of claim 30, wherein said at least one electrolyte is aqueous NaCl, human blood, or seawater.

49. The electromechanical actuator of claim 30, wherein said at least two electronically conducting electrodes comprise more than two current carrying electrodes operable at different voltages.

50. The electromechanical actuator of claim 30, wherein the actuator output is controlled at least in part by determining a voltage of the at least one electrode with respect to one or more other of said at least two electronically conducting electrodes.

51. The electromechanical actuator of claim 50, wherein at least one of the one or more other electronically conducting electrodes transports negligible current.

52. The electromechanical actuator of claim 30, wherein the actuator output is controlled at least in part by determining either a current that flows between said at least two electronically conducting electrodes or an integral of the current over a time period.

53. The electromechanical actuator of claim 30, wherein the actuator output is controlled at least in part by measuring an optical property change of at least one of said at least two electronically conducting electrodes during actuation.

54. The electromechanical actuator of claim 30, wherein mechanical actuation results from charge injection in the at least one electrode, an opposing electrode of said at least two electronically conducting electrodes for current flow having a total surface area larger than a total surface area of the at least one electrode by at least a factor of ten.

55. The electromechanical actuator of claim 30, wherein the at least two electronically conducting electrodes are in sheet electrode form and comprise one or more monomorph or bimorph cantilever devices, wherein a sheet electrode is either (a) mechanically connected on one sheet side with a layer of an electromechanically inactive material or (b) mechanically connected on one sheet side with an electrolyte layer, which is mechanically connected on an opposite electrolyte sheet side with another sheet electrode.

56. The electromechanical actuator of claim 55, comprising more than one interconnected cantilevers.

57. The electromechanical actuator of claim 30, wherein the at least one electrode is mechanically connected to an optical fiber and deflects an end of the optical fiber, responsive to application of the electrical voltage, to move the end of the optical fiber between ends of two or more neighboring optical fibers that are substantially coaxial with the optical fiber.

58. The electromechanical actuator of claim 57, wherein the at least one electrode is adhesively connected to the optical fiber as a semicircular strip that runs approximately parallel to an axis of the optical fiber, a dimensional change of the at least one electrode as a result of non-faradaic charge injection contributing to bending of the optical fiber.

59. The electromechanical actuator of claim 58, wherein said at least two electronically conducting electrodes comprise either two, three, or four electrodes that are adhesively connected to the optical fiber and that run approximately parallel to the axis of the optical fiber, application of differing relative voltages between the plural electrodes that are electrically separated and ionically connected displacing the optical fiber in either one or more directions.

60. The electromechanical actuator of claim 58, wherein the at least one electrode comprises single-wall carbon nanotubes contacted with one or more liquid electrolytes or solid electrolytes that substantially fill pore volume and provide an inter-electrode path for ions.

61. The electromechanical actuator of claim 60, wherein the inter-electrode path for ions is provided by a liquid electrolyte having approximately a same refractive index as a core of the optical fiber at an optical wavelength that can be transmitted along the optical fiber.

62. The electromechanical actuator of claim 30, wherein the actuator output is a mechanical displacement that regulates thermal contact between two bodies, one of which is cooled as a result of the thermal contact.

63. The electromechanical actuator of claim 62, wherein one of said two bodies comprises a thermoelectric having an electrical current pulsed therethrough, said at least two electronically conducting electrodes providing a mechanical displacement opening thermal contact between the two bodies.

64. The electromechanical actuator of claim 30, wherein a mechanical strain applied to at least one of said at least two electronically conducting electrodes generates an inter-electrode voltage change that causes current flow.

65. The electromechanical actuator of claim 64, wherein either said at least one electrolyte causes faradaic charge injection at zero applied potential or a bias voltage is applied between said at least two electronically conducting electrodes.

66. The electromechanical actuator of claim 64, comprising arrays of said at least two electronically conducting electrodes that are electrically connected in series, so as to additively combine the inter-electrode voltages generated in the array by application of the mechanical strain to one or more of said at least two electronically conducting electrodes.

67. The electromechanical actuator of claim 30, wherein the at least one electrode is a sheet that is penetrated on opposite sheet sides by respective materials having different ionic conductivities, wherein a first respective material is solid and a second respective material is liquid.

68. A mechanical actuator for converting chemical energy to electrical energy and converting the electrical energy to a mechanical displacement, comprising:

first and second electrodes that are electronically conductive and contain a catalyst for oxidation or reduction, said first and second electrodes being porous and filled with an electrolyte,

at least one electrode of said first and second electrodes having a gravimetric surface area of at least 150 m²/gm and undergoing a dimensional change responsive to non-faradaic charging;

an electrolyte separating said first and second electrodes, said separating electrolyte being substantially gas impermeable, ionically conductive, and electronically insulating;

means for contacting said first electrode with a first reactant that is oxidizable; and

means for separately contacting said second electrode with a second reactant that is reducible,

the at least one electrode being mechanically displaced responsive to at least one of controlling flow of said first and second reactants to said first and second electrodes and electrically connecting said first and second electrodes either directly or indirectly.

69. The mechanical actuator of claim 68, wherein the electrical energy is generated by supplying one of gaseous hydrogen, methanol, and NH₂NH₂ as said first reactant to said first electrode and oxygen or air as said second reactant to said second electrode.

70. The mechanical actuator of claim 68, wherein the at least one electrode comprises sheets of carbon nanotubes having a number-average diameter of less than about 10 nm.

71. The mechanical actuator of claim 68, wherein said first and second electrodes form a cylindrical shaped object of changeable shape that provides the mechanical displacement, said first reactant being provided at an interior of the mechanical actuator along said first electrode and said second reactant being provided within an exterior of the mechanical actuator along said second electrode.

72. The mechanical actuator of claim 68, wherein said first and second electrodes are hollow, said first reactant being provided to the mechanical actuator through a hollow of said first electrode and said second reactant being provided to the mechanical actuator through a hollow of said second electrode.

73. The mechanical actuator of claim 68, wherein said first and second reactants are gas or liquid.

74. An electromechanical microactuator comprising:

a first electrode that is electronically conducting and having a thickness in a narrowest dimension of less than 10 nm, a gravimetric surface area of at least 150 m²/gm, and a capacitance of at least 5 F/gm;

a second electrode that is electronically conducting serving as a counter electrode to said first electrode; and

an electronically insulating electrolyte providing an ionically conducting path between said first and second electrodes,

said first electrode being mechanically displaced responsive to application of a voltage between said first and second electrodes.

75. The electromechanical microactuator of claim 74, wherein said first electrode comprises at least one carbon nanotube.

76. The electromechanical microactuator of claim 75, wherein said carbon nanotube is a single-wall carbon nanotube.

77. The electromechanical microactuator of claim 74, wherein said second electrode has a total surface area that is at least 100 times larger than a total surface area of said first electrode.