Electrochemical methods, devices, and structures

• US 20060102455A1
• Filed: 06/13/2005
• Published: 05/18/2006
• Est. Priority Date: 06/14/2004
• Status: Active Grant

• Current Assignee: Massachusetts Institute of Technology
• Original Assignee: Chin E. Timothy, Dimitrios Sapnaras, Fernando Tubilla, Kyungyeol Song, Steven R. Hall, Urs Rhyner, Yet-Ming Chiang, Yukinori Koyama
• Inventors: Chiang, Yet-Ming, Tubilla, Fernando, Song, Kyungyeol, Koyama, Yukinori, Rhyner, Urs, Hall, Steven R., Sapnaras, Dimitrios, Chin, E. Timothy
• Granted Patent: US 7,541,715 B2
• Time in Patent Office: Days
• US Class Current: 200/181
• 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: H01M 2004/021 Physical characteristics, e.g. porosity, surface area
• CPC Class Codes: H01M 2010/4292 Aspects relating to capacity ratio of electrodes/electrolyte or anode/cathode
• CPC Class Codes: H01M 4/485 of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy H01M4/505, H01M4/525 take precedence
• CPC Class Codes: H01M 4/505 of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
• CPC Class Codes: H01M 4/525 of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
• CPC Class Codes: H01M 4/587 for inserting or intercalating light metals
• CPC Class Codes: H01M 50/443 Particulate material
• CPC Class Codes: H01M 50/491 Porosity
• CPC Class Codes: H01M 6/30 Deferred-action cells
• CPC Class Codes: Y02E 60/10 Energy storage using batteries
• CPC Class Codes: Y02P 70/50 Manufacturing or production processes characterised by the final manufactured product

Abstract

The present invention provides devices and structures and methods of use thereof in electrochemical actuation. This invention provides electrochemical actuators, which are based, inter-alia, on an electric field-driven intercalation or alloying of high-modulus inorganic compounds, which can produce large and reversible volume changes, providing high actuation energy density, high actuation authority and large free strain.

Claims

1. An electrochemical actuator, comprising:

a. a negative electrode;

b. a positive electrode; and

c. an intercalating species;

wherein said electrochemical actuator is subjected to an applied voltage or current;

whereby application of said voltage or current or cessation thereof induces intercalation of said species in electrodes of said actuator, resulting in a volumetric or dimensional change of said actuator and linear strain is produced, ranging from 1-300%.

2. The electrochemical actuator of claim 1, wherein said volumetric or dimensional change is in said negative electrode or said positive electrode or a combination thereof.

3. The electrochemical actuator of claim 1, wherein said volumetric or dimensional change ranges from 0.1-300%.

5. The electrochemical actuator of claim 1, wherein said negative electrode or positive electrode undergoes a phase change, anisotropic expansion or anisotropic contraction upon intercalation.

6. The electrochemical actuator of claim 1, wherein said negative electrode serves as a donor or acceptor or combination thereof, of said intercalating species.

7. The electrochemical actuator of claim 1, wherein said positive electrode serves as a donor or acceptor or combination thereof, of said intercalating species.

8. The electrochemical actuator of claim 1, wherein said negative electrode may serve as a source for said intercalating species.

9. The electrochemical actuator of claim 1, wherein said positive electrode may serve as a source for said intercalating species.

10. The electrochemical actuator of claim 1, wherein said negative or positive electrode, or combination thereof comprises a high elastic modulus compound.

11. The electrochemical actuator of claim 10, wherein said compound exhibits an elastic modulus ranging between 10-500 GPa.

12. The electrochemical actuator of claim 11, wherein said compound exhibits an elastic modulus ranging between 50-150 GPa.

13. The electrochemical actuator of claim 1, wherein said negative electrode, positive electrode, or combination thereof comprises an ion transition metal oxide.

14. The electrochemical actuator of claim 13, wherein the ion in said ion transition metal oxide is a proton or an alkali metal or an alkaline earth metal.

15. The electrochemical actuator of claim 14, wherein the alkali metal is lithium.

16. The electrochemical actuator of claim 1, wherein said negative electrode, positive electrode, or combination thereof comprises:

LiCoO₂, LiFePO₄, LiNiO₂, LiMn₂O₄, LiMnO₂, LiMnPO₄, Li₄Ti₅O₁₂, TiSi₂, MoSi₂, WSi₂ or modified compositions or solid solutions thereof.

17. The electrochemical actuator of claim 1, wherein said negative electrode, positive electrode, or combination thereof comprises titanium oxide, vanadium oxide, tin oxide, antimony oxide, cobalt oxide, nickel oxide, iron oxide, or a combination thereof.

18. The electrochemical actuator of claim 1, wherein said negative electrode, positive electrode, or combination thereof comprises a metal or intermetallic compound.

19. The electrochemical actuator of claim 1, wherein said negative electrode, positive electrode, or combination thereof is lithium or a lithium-metal alloy, which may be crystalline, nanocrystalline, or amorphous.

20. The electrochemical actuator of claim 1, wherein said negative electrode, positive electrode, or combination thereof comprises aluminum, silver, gold, boron, bismuth, gallium, germanium, indium, lead, antimony, silicon, tin, or a combination thereof.

21. The electrochemical actuator of claim 1, wherein an electrode comprises carbon in the form of graphite, a carbon fiber structure, a glassy carbon structure, a highly oriented pyrolytic graphite, a disordered carbon structure or a combination thereof.

22. The electrochemical actuator of claim 1, wherein the intercalating species is an ion.

23. The electrochemical actuator of claim 1, wherein the intercalating species is a proton or an alkali metal or an alkaline earth metal.

24. The electrochemical actuator of claim 1, wherein said negative electrode, positive electrode, or combination thereof comprises a porous aggregate of particles.

28. The electrochemical actuator of claim 1, wherein said voltage is 0.1-15V.

30. The electrochemical actuator of claim 1, further comprising an electrically conductive current collector, a separator, or a combination thereof.

31. The electrochemical actuator of claim 30, wherein said separator is porous or rigid.

32. The electrochemical actuator of claim 31, wherein said porous separator comprises a microporous polymer or a porous electronically insulating ceramic material.

33. The electrochemical actuator of claim 31, wherein said porous separator comprises a multiplicity of insulating polymer or ceramic particles.

34. The electrochemical actuator of claim 33, wherein said porous electronically insulating ceramic material comprises alumina, an aluminosilicate, cordierite, a silicate glass, or electronically insulating mixed-metal oxides, nitrides or carbides.

35. The electrochemical actuator of claim 1, the electrodes of which further comprise a conductive additive.

36. The electrochemical actuator of claim 1, further comprising an electrolyte.

37. The electrochemical actuator of claim 36, wherein said electrolyte is a solid or liquid electrolyte.

38. The electrochemical actuator of claim 1, further comprising an external packaging layer.

39. The electrochemical actuator of claim 38, wherein said external packaging layer is an electrochemically-insulating layer, a protective layer or a combination thereof.

40. The electrochemical actuator of claim 1, wherein said actuator has a blocked stress of between 1-1000 MPa.

41. An apparatus comprising at least one electrochemical actuator of claim 1.

42. The apparatus of claim 41, wherein said apparatus is adaptive.

43. The apparatus of claim 42, wherein said actuator is used as an element to apply stress at a site on said apparatus distal to said actuator.

44. The apparatus of claim 41, wherein said apparatus amplifies said volumetric or dimensional change induced by said actuator.

45. The apparatus of claim 41, wherein said apparatus is in the form of a woven structure comprising said at least one electrochemical actuator.

46. The apparatus of claim 45, wherein said actuator amplifies stress in said woven structure.

47. The apparatus of claim 45, wherein said apparatus is in the form of a lever and fulcrum mechanism, and said lever comprises said at least one electrochemical actuator.

48. The apparatus of claim 47, wherein said actuator amplifies strain in said apparatus.

86. The electrochemical actuator of claim 1, wherein said actuator is a Rotational Electrochemical Actuator, comprising rolled layers of:

a. said negative electrode;

b. said positive electrode; and

c. said intercalating species

wherein said rolled layers assume a laminate configuration, wherein when said Rotational Electrochemical Actuator is subjected to an applied voltage or current, said rolled laminate configuration winds or unwinds, and torque is produced.

87. The Rotational Electrochemical Actuator of claim 86, wherein when said rolled laminate configuration winds or unwinds, rotary motion is produced.

128. The electrochemical actuator of claim 1, wherein said actuator is a Continuous Fiber Electrochemical Actuator, wherein said negative electrode is a fibrous electrode and said positive electrode is a counter electrode, whereby said volumetric or dimensional change of said actuator results in said fibrous electrode undergoing elongation or contraction.

129. The Actuator of claim 128, wherein said fibrous electrode comprises at least one fibrous layer.

4. (canceled)

25-27. -27. (canceled)

29. (canceled)

49. A Multilayer Stacked Electrochemical Actuator, comprising:

a. two or more negative electrode layers;

b. two or more positive electrode layers; and

c. an intercalating species;

wherein said Multilayer Stacked Electrochemical Actuator is subjected to an applied voltage or current;

whereby application of said voltage or current or cessation thereof induces intercalation of said species in electrodes of said actuator, resulting in a volumetric or dimensional change of said actuator and linear strain is produced, ranging from 0.5—

5%.

50. The Multilayer Stacked Electrochemical Actuator of claim 49, wherein intercalation of said species, in said electrodes, results in a volumetric or dimensional change of said actuator.

51. The Multilayer Stacked Electrochemical Actuator of claim 49, wherein said volumetric or dimensional change ranges from 0.1-300%.

52. The Multilayer Stacked Electrochemical Actuator of claim 49, wherein said negative electrode or positive electrode undergoes a phase change, anisotropic expansion or anisotropic contraction upon intercalation.

53. The Multilayer Stacked Electrochemical. Actuator of claim 49, wherein said negative electrode serves as a donor or acceptor or combination thereof, of said intercalating species.

54. The Multilayer Stacked Electrochemical Actuator of claim 49, wherein said positive electrode serves as a donor or acceptor or combination thereof of said intercalating species.

55. The Multilayer Stacked Electrochemical Actuator of claim 49, wherein said negative electrode may serve as a source for said intercalating species.

56. The Multilayer Stacked Electrochemical Actuator of claim 49, wherein said positive electrode may serve as a source for said intercalating species.

57. The Multilayer Stacked Electrochemical Actuator of claim 49, wherein said positive electrode, said negative electrode, or a combination thereof comprises a metal or intermetallic compound.

58. The Multilayer Stacked Electrochemical Actuator of claim 49, wherein said positive electrode, said negative electrode, or a combination thereof comprises lithium or a lithium-metal alloy.

59. The Multilayer Stacked Electrochemical Actuator of claim 49, wherein said positive electrode, said negative electrode, or a combination thereof comprises carbon, aluminum, silver, gold, boron, bismuth, gallium, germanium, indium, lead, antimony, silicon, tin, or a combination thereof.

60. The Multilayer Stacked Electrochemical Actuator of claim 59, wherein said carbon is graphite, a carbon fiber structure, a glassy carbon structure, a highly oriented pyrolytic graphite, a disordered carbon structure or a combination thereof.

61. The Multilayer Stacked Electrochemical Actuator of claim 49, wherein said positive electrode, said negative electrode, or a combination thereof comprises lithium titanium oxide, titanium oxide, vanadium oxide, tin oxide, antimony oxide, cobalt oxide, nickel oxide, iron oxide, or a combination thereof.

62. The Multilayer Stacked Electrochemical Actuator of claim 49, wherein said positive electrode, said negative electrode, or a combination thereof comprises an ion transition metal oxide.

63. The Multilayer Stacked Electrochemical Actuator of claim 62, wherein said ion of said ion transition metal oxide is a proton or an alkali metal or an alkaline earth metal.

64. The Multilayer Stacked Electrochemical Actuator of claim 63, wherein said alkali metal is lithium.

65. The Multilayer Stacked Electrochemical Actuator of claim 49, wherein said positive electrode, said negative electrode, or a combination thereof comprises LiCoO2, LiFePO4, LiNiO2, LiMn2O4, LiMnPO4, Li₄Ti₅O₁₂, or modified compositions or solid solutions thereof,

66. The Multilayer Stacked Electrochemical Actuator of claim 49, wherein said negative electrode, positive electrode, or combination thereof comprises a porous aggregate of particles of said electrode material.

67. The Multilayer Stacked Electrochemical Actuator of claim 66, wherein said porous aggregate is sintered.

68. The Miltilayer Stacked Electrochemical Actuator of claim 67, wherein said porous sintered aggregate is a composite, further comprising a conductive additive or sintering aid.

69. The Multilayer Stacked Electrochemical Actuator of claim 66, wherein said aggregate comprises crystallites of a compound sharing a common orientation or texture of their crystal axes.

70. The Multilayer Stacked Electrochemical Actuator of claim 49, wherein said intercalating species is an ion.

71. The Multilayer Stacked Electrochemical Actuator of claim 70, wherein said ion is a proton or an alkali metal or an alkaline earth metal.

73. The Multilayer Stacked Electrochemical Actuator of claim 49, wherein said structural change is a result of intercalation of said species in said negative electrode or said positive electrode or a combination thereof.

74. The Multilayer Stacked Electrochemical Actuator of claim 49, wherein said voltage is 0.1-15V.

75. The Multilayer Stacked Electrochemical Actuator of claim 49, further comprising a current collector, a separator or a combination thereof.

76. The Multilayer Stacked Electrochemical Actuator of claim 75, wherein said current collector comprises a conductive material.

77. The Multilayer Stacked Electrochemical Actuator of claim 75, wherein said separator is porous or rigid.

78. The Multilayer Stacked Electrochemical Actuator of claim 77, wherein said porous separator comprises a microporous polymer or a porous electronically insulating ceramic material.

79. The Multilayer Stacked Electrochemical Actuator of claim 77, wherein said porous separator comprises a multiplicity of particles of said polymer or ceamic material.

80. The Multilayer Stacked Electrochemical Actuator of claim 79, wherein said porous electronically insulating ceramic material is alumina, an aluminosilicate, cordierite, a silicate glass, or electronically insulating mixed-metal oxides, nitrides or carbides.

81. The Multilayer Stacked Electrochemical Actuator of claim 49, the electrodes of which further comprise a conductive additive.

82. The Multilayer Stacked Electrochemical Actuator of claim 49, further comprising an electrolyte.

83. The Multilayer Stacked Electrochemical Actuator of claim 82, wherein said electrolyte is a solid or liquid electrolyte.

84. The Multilayer Stacked Electrochemical Actuator of claim 49, further comprising an external packaging layer, which is an electrochemically-insulating layer, a protective layer or a combination thereof.

85. The Multilayer Stacked Electrochemical Actuator of claim 49, wherein said actuator is subjected to a uniaxial or hydrostatic pressure ranging from 10,000-45,000 psi, (69-310 MPa).

88-127. -127. (canceled)

130-172. -172. (canceled)

173. A method of actuation, comprising the step of applying a voltage or current to an actuator comprising a negative electrode, a positive electrode and an intercalating species, wherein applying said voltage or current induces intercalation of said species in said actuator, whereby said intercalation induces a volumetric or dimensional change of said actuator and linear strain is produced;

ranging from 1-300%.

174. The method of claim 173, wherein said voltage or current are varied as a function of time.

175-212. -212. (canceled)

213. A nastic structure comprising at least one electrochemical actuator, comprising an negative electrode, a positive electrode, and an intercalating species, wherein following application of a voltage causing current flow in said actuator, intercalation of said species produces a change in volume in said actuator, such that a bend or other deformity is induced in said nastic structure.

214-215. -215. (canceled)