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1. (WO2019032217) COILED AND TWISTED NANOFIBER YARNS FOR ELECTROCHEMICALLY HARVESTING ELECTRICAL ENERGY FROM MECHANICAL DEFORMATION
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[0246] What is claimed is:

1. A mechanical energy harvester comprising:

(a) a first electrode;

(b) a second electrode; and

(c) an electrolyte, wherein

(i) both the first electrode and the second electrode are immersed in the electrolyte,

(ii) there exists a path for ionic conductivity between the first electrode and the second electrode,

(iii) the energy harvester is operable to generate power without an external bias voltage, and

(iv) at least one electrode comprises a twisted, high-electrochemical-surface- area, conductive yarn.

2. The energy harvester of Claim 1, wherein the twisted yarn is additionally coiled.

3. The coiled energy harvester of Claim 2, wherein the coil spring index is between 0.2 and 0.8.

4. The energy harvester of Claim 1, wherein the energy harvester is operable to convert tensile deformation directly into electrical energy.

5. The energy harvester of Claim 1, wherein the energy harvester is operable to convert torsional deformation directly into electrical energy.

6. The energy harvester of Claim 1, wherein the energy harvester comprises a high-surface-area carbon material.

7. The energy harvester of Claim 6, wherein the high-surface-area carbon material is selected from a group consisting of carbon nanotubes, carbon nanohorns, graphene, fullerene, activated carbon, carbon black, carbon nanofibers, and combinations thereof.

8. The energy harvester of Claim 1, wherein the energy harvester is operable to provide at least 20 W of peak electrical power per kilogram of the twisted, high-electrochemical-surface-area, conductive yarn when stretched at rates above 20 Hz.

9. The energy harvester of Claim 1, wherein the energy harvester is operable to provide at least 10 J of electrical energy per kilogram of the twisted, high-electrochemical-surface-area, conductive yarn per mechanical cycle.

10. The energy harvester of Claim 1, wherein the twisted yarn is selected from a group consisting of cone spun yarns, funnel spun yarns, Fermat spun yarns, and dual-Archimedean spun yarns.

11. The energy harvester of Claim 1 , wherein the twisted yarn has a diameter between 10 μιη and 500 μπι.

12. The energy harvester of Claim 1, wherein the twisted yarn has a diameter between 100 nm and 10 μιη.

13. The energy harvester of Claim 1, wherein at least one electrode comprises an overcoat comprising an elastomeric barrier material.

14. The energy harvester of Claim 13, wherein the elastomeric barrier material comprises polyurethane.

15. The energy harvester of Claim 1, wherein the electrolyte comprises NaCl.

16. The energy harvester of Claim 1, wherein the electrolyte comprises hydrochloric acid.

17. The energy harvester of Claim 1, wherein the electrolyte is a gel electrolyte.

18. The energy harvester of Claim 1, wherein the energy harvester is operable to generate a change of voltage of at least 50 mV during stretch.

19. The energy harvester of Claim 1, wherein the twisted yarn is wrapped around an elastomeric support.

20. The energy harvester of Claim 19, wherein the twisted yarn wrapped around an elastomeric support is wrapped in a helical manner to provide a homochiral coil.

21. The energy harvester of Claim 19, wherein the twisted yarn wrapped around an elastomeric support is wrapped in a helical manner to provide a heterochiral coil.

22. The energy harvester of Claim 1, wherein the harvester comprises a plurality of segments which are electrically connected in series, in parallel, or in combinations thereof.

23. The energy harvester of Claim 1, wherein both the first electrode and the second electrode comprise twisted, high-electrochemical-surface area, conductive yarn.

24. The energy harvester of Claim 23, wherein

(a) the first electrode increases in potential when stretched, and

(b) the second electrode decreases in potential when stretched.

25. The energy harvester of Claim 24, wherein

(a) the first electrode comprises homochiral coils, and

(b) the second electrode comprises heterochiral coils.

26. The energy harvester of Claim 24, wherein the first electrode and the second electrode can both be homochiral or heterochiral and mechanically deformed with opposite phases.

27. The energy harvester of Claim 24, wherein the first energy harvesting electrode and the second energy harvesting electrode comprise twisted yarns wrapped around a stretchable core.

28. The energy harvester of Claim 1, wherein at least one energy harvesting electrode comprises an auxiliary conductor which lowers the impedance of the energy harvester.

29. The energy harvester of Claim 1, wherein the first electrode and second electrode are components of the same yarn.

30. A textile comprising the energy harvester of Claim 1.

31. A method of making an energy harvester comprising the steps of:

(a) spinning sheets of aligned carbon nanotubes into high strength carbon nanotube yarns;

(b) inserting twist into the high strength carbon nanotube yarns that are under tension to yield a twisted yarn;

(c) forming an electrode comprising the twisted carbon nanotube yarn; and

(d) immersing the electrode in an electrolyte.

32. The method of Claim 31 further comprising a step of inserting additional twist until coils spontaneously form.

33. The method of Claim 31 further comprising a step of adding a high-surface-area carbon material to the twisted carbon nanotube yarn electrode.

34. The method of Claim 33, wherein the high-surface-area carbon material is selected from a group consisting of carbon nanotubes, carbon nanohorns, graphene, fullerene, activated carbon, carbon black, carbon nanofibers, and combinations thereof.

35. The method of Claim 31, wherein the electrode is operable to generate an average electrical power of at least 10 W per kilogram of the carbon nanotube yarn, without requiring an external bias voltage.

36. The method of Claim 31, wherein tensile or torsional oscillations of the twisted carbon nanotube yarn are converted directly into electrical energy.

37. The method of Claim 31, wherein the energy harvester is operable to provide at least 20 W of peak electrical power per kilogram of the carbon nanotube yarn when cycled at rates above 20 Hz.

38. The method of Claim 31, wherein the energy harvester is operable to provide at least 10 J of electrical energy per kilogram of the carbon nanotube yarn per mechanical cycle.

39. The method of Claim 31, wherein the step of spinning is selected from a group consisting of cone spinning, funnel spinning, Fermat spinning, tow-spinning, and dual-Archimedean spinning.

40. The method of Claim 39, wherein the step of spinning is cone spinning.

41. The method of Claim 39, wherein the twisted carbon nanotube yarn has a diameter between 10 um and 500 μιη.

42. The method of Claim 31 , wherein the twisted carbon nanotube yarn has a diameter between 100 nm and 10 μιη.

43. The method of Claim 31, wherein the electrode comprises an overcoat comprising an elastomeric barrier material.

44. The method of Claim 43, wherein the elastomeric barrier material comprises polyurethane.

45. The method of Claim 31, wherein the electrolyte comprises NaCl.

46. The method of Claim 31, wherein the electrolyte comprises hydrochloric acid.

47. A method comprising:

(a) selecting a twistron mechanical energy harvester comprising an electrode comprising a twisted, high-electrochemical-surface-area, conductive yarn, wherein the electrode is immersed in an electrolyte, and

(b) applying mechanical energy to deform the yarn by tension, torsion, or combinations thereof, to convert the mechanical energy directly to electrical energy.

48. The method of Claim 47, wherein the minimum applied strain is selected to prevent yarn snarling from occurring.

49. The method of Claim 47, wherein the twisted, high-electrochemical-surface-area, conductive yarn is additionally coiled.

50. The method of Claim 50, wherein the yarn comprises high-surface-area carbon material.

51. The method of Claim 50, wherein the high-surface-area carbon material is selected from a group consisting of carbon nanotubes, carbon nanohorns, graphene, fullerene, activated carbon, carbon black, carbon nanofibers, and combinations thereof.

52. The method of Claim 47, wherein the electrode generates an average electrical power of at least 1 W per kilogram of the twisted, high-electrochemical-surface-area, conductive yarn, without requiring an external bias voltage.

53. The method of Claim 47, wherein the twistron mechanical energy harvester provides at least 20 W of peak electrical power per kilogram of the twisted, high-electrochemical-surface-area, conductive yarn when stretched at rates above 20 Hz.

54. The method of Claim 47, wherein the twistron mechanical energy harvester provides at least 1 J of electrical energy per kilogram of the twisted, high-electrochemical-surface-area, conductive yarn, per mechanical cycle.

55. The method of Claim 47, wherein the twisted yarn is selected from a group consisting of cone spun yarns, funnel spun yarns, Fermat spun yarns, and dual-Archimedean spun yarns.

56. The method of Claim 47, wherein the twisted yarn is a cone spun yarn.

57. The method of Claim 47, wherein the twisted yarn has a diameter between 10 μπι and 500 μιη.

58. The method of Claim 47, wherein the twisted single yarn has a diameter between 100 nm and 10 μιη.

59. The method of Claim 47, wherein the electrode comprises an overcoat comprising an elastomeric barrier material.

60. The method of Claim 59, wherein the elastomeric barrier material comprises polyurethane.

61. The method of Claim 47, wherein the electrolyte comprises NaCl.

62. The method of Claim 47, wherein the twisted yarn is wrapped around a stretchable core.

63. The method of Claim 62, wherein the twist direction and wrapping direction are of the same chirality.

64. The method of Claim 62, wherein the twist direction and the wrapping direction are of opposite chirality.

65. The method of Claim 47, wherein the electrolyte comprises hydrochloric acid.

66. The method of Claim 47, wherein the mechanical energy is supplied by a human body.

67. The method of Claim 47, wherein the mechanical energy is supplied by an oscillating source.

68. The method of Claim 67, wherein the oscillating source is ocean waves.

69. The method of Claim 67, wherein in the oscillating source comprises one or more water wheels.

70. The method of Claim 47 further comprising utilizing the generated electrical energy to power a device selected from a group consisting of sensor nodes, sensors, actuators, transmitters, wearable electronics, and combinations thereof.

71. The method of Claim 47, wherein the energy harvester is incorporated into a textile.

72. An electrochemical mechanical energy harvester comprising:

(a) an electrolyte-containing electronically conducting yarn electrode that is operable to cause a reversible change in electrochemical capacitance when the level of inserted twist is changed, thereby enabling the harvesting of torsional mechanical energy as electrical energy;

(b) a counter electrode; and

(c) an electrolyte that ionically connects said electronically conducting electrode and said counter electrode.

73. The electrochemical mechanical energy harvester of Claim 72, wherein the electrochemical mechanical energy harvester is operable to cause a reversible change in open circuit voltage of at least 20 mV when the level of inserted twist is changed.

74. The electrochemical mechanical energy harvester of Claim 72, wherein the electronically conducting yarn electrode is operable to cause the reversible change in electrochemical capacitance of at least 5% when the level of inserted twist is changed.

75. The electrochemical mechanical energy harvester of Claim 72, wherein the electronically conducting yarn electrode has an electrochemical capacitance of at least 0.5 Farads per gram of electrochemically-active material.

76. An electrochemical mechanical energy harvester comprising:

(a) an electrolyte-containing coiled electronically conducting yarn electrode that is operable to cause reversible changes in electrochemical capacitance when either stretched, twisted, or combinations thereof, thereby enabling the harvesting of either tensile mechanical energy, torsional mechanical energy or a combination of tensile and torsional mechanical energy, as electrical energy;

(b) a counter electrode; and

(c) an electrolyte that ionically connects said coiled electronically conducting electrode and said counter electrode.

77. The electrochemical mechanical energy harvester of Claim 76, wherein the electrochemical mechanical energy harvester is operable to cause a reversible change in open circuit voltage of at least 20 mV when the conducting yarn electrode is either stretched, twisted, or combinations thereof.

78. The electrochemical mechanical energy harvester of Claim 76, wherein the electronically conducting yarn electrode is operable to cause the reversible change in electrochemical capacitance of at least 5% when the conducting yarn electrode is either stretched, twisted, or combinations thereof.

79. The electrochemical mechanical energy harvester of Claim 76, wherein the electronically conducting yarn electrode has an electrochemical capacitance of at least 0.5 Farads per gram of electrochemically-active material.

80. A wearable self-generating and storaging packing comprising:

(a) an electrochemical mechanical energy harvester that is a twistron fiber harvester; and

(b) a stretchable fiber supercapacitor.

81. The wearable self-generating and storaging packing of Claim 80, wherein (a) the twistron fiber harvester comprises

(i) a first fiber that is stretchable,

(ii) a homochiral CNT yarn wrapped about the first fiber,

(iii) a heterochiral CNT yarn wrapped about the first fiber,

(iv) a first solid electrolyte about the first fiber wrapped with the homochiral CNT yarn and the heterochiral CNT yarn, and

(v) a first tube about the first solid electrolyte about the fiber wrapped with the homochiral CNT yarn and the heterochiral CNT yarn, wherein the first tube is stretchable; and

(b) the stretchable fiber supercapacitor comprises

(i) a second fiber that is stretchable,

(ii) an anode comprising a first substantially non-twisted CNT yarn wrapped about the second fiber,

(iii) a cathode comprising a second substantially non-twisted CNT yarn wrapped about the second fiber,

(iv) a second solid electrolyte about the second fiber wrapped with the anode and the cathode, and

(v) a second tube about the second solid electrolyte about the second fiber wrapped with the anode and the cathode, wherein the second tube is stretchable.

82. The wearable self-generating and storaging packing of Claim 81, wherein the first fiber, the second fiber, the first tube, and the second tube are each comprising rubber.

83. The wearable self-generating and storaging packing of Claim 81, wherein the packaging comprises a plurality of twistron fiber harvesters and a plurality of stretchable fiber supercapacitors.