Energy storage devices and methods of production thereof

• US 9,916,931 B2
• Filed: 11/03/2015
• Issued: 03/13/2018
• Est. Priority Date: 11/04/2014
• Status: Active Grant

• Current Assignee: Capacitor Sciences Corp.
• Original Assignee: Capacitor Sciences Corp.
• Inventors: Lazarev, Pavel Ivan
• Primary Examiner(s): Ferguson, Dion R
• Application Number:
  US14/931,757
• Publication Number:
  US 20160314901A1
• Time in Patent Office: 861 Days
• Field of Search: None
• CPC Class Codes: C08L 2203/20 use in electrical or conductive gadgets
• CPC Class Codes: C08L 33/02 Homopolymers or copolymers of acids; Metal or ammonium salts thereof
• CPC Class Codes: C08L 79/00 Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
• CPC Class Codes: H01G 4/14 Organic dielectrics
• CPC Class Codes: H01G 4/18 of synthetic material, e.g. derivatives of cellulose H01G4/16 takes precedence
• CPC Class Codes: H01G 4/20 using combinations of dielectrics from more than one of groups H01G4/02 - H01G4/06 H01G4/12 takes precedence
• CPC Class Codes: H01G 4/30 Stacked capacitors H01G4/33 takes precedence

Abstract

The present disclosure provides an energy storage device comprising a first electrode, a second electrode, and a solid multilayer structure disposed between said first and second electrodes. The solid multilayer structure can be in contact with said first and second electrodes. The solid multilayer structure can include layers disposed parallel to said electrodes, the layers have a sequence (A-B)_m-A, wherein, A is an insulating layer and B is a polarization layer comprising a colloidal composite with a micro-dispersion of electro-conductive nano-particles in an insulator matrix, and ‘m’ is a number greater than or equal to 1. Layer A can have a breakdown voltage of at least about 0.05 volts per nanometer (nm), and layer B can have a dielectric permittivity of at least about 100.

Claims

1. A capacitor comprising

a first electrode;

a second electrode; and

a solid multilayer structure disposed between said first and second electrodes,

wherein the solid multilayer structure is in contact with said first and second electrodes and comprises layers disposed parallel to said electrodes, wherein the solid multilayer structure has a sequence of layers (A-B)_m-A, wherein A is an insulating layer and B is a polarization layer comprising a colloidal composite with a micro-dispersion of electro-conductive nano-particles in an insulator matrix, and m is a number greater than or equal to 1,

wherein A has a breakdown voltage of at least about 0.05 volts (V) per nanometer (nm), and

wherein B has dielectric permittivity of at least about 100.

2. A capacitor according to claim 1, wherein at least one of the insulating layers is crystalline.

3. A capacitor according to claim 1, wherein A has a breakdown voltage of at least about 0.5 V/nm.

4. A capacitor according to claim 1, wherein at least one of the insulating layers comprises a material selected from oxides, nitrides, oxynitrides and fluorides.

5. A capacitor according to claim 4, wherein at least one of the insulating layers comprises a material selected from SiO₂, HfO₂, Al₂O₃ or Si₃N₄.

6. A capacitor according to claim 1, wherein at least one of the insulating layers comprises a modified organic compounds of the general structural formula I:

{Cor}(M)_n, 

 

(I)

wherein Cor is a polycyclic organic compound, each M is independently a modifying functional group; and

n is a number of the modifying functional groups that is greater than or equal to zero.

7. A capacitor according to claim 6, wherein the polycyclic organic compound is selected from the group consisting of oligophenyl, imidazole, pyrazole, acenaphthene, triaizine, indanthrone and structures 1-43:

8. A capacitor according to claim 6 or 7, wherein the modifying functional groups are selected from the group consisting of alkyl, aryl, substituted alkyl, and substituted aryl.

9. A capacitor according to claim 1, wherein at least one of the insulating layers comprises a compound selected from the group consisting of fluorinated alkyls, polyethylene, kevlar, poly(vinylidene fluoride-hexafluoropropylene), polypropylene, fluorinated polypropylene, and polydimethylsiloxane.

10. A capacitor according to claim 1, wherein at least one of the insulating layers comprises a material having a structure selected from the structures 44 to 49:

11. A capacitor according to claim 1, wherein at least one of the insulating layers comprises a material having a structure selected from the structures 50 to 55:

12. A capacitor according to claim 1, wherein at least one of the polarization layers is crystalline.

13. A capacitor according to claim 1, wherein the electro-conductive nano-particles comprise an electro-conductive oligomer.

14. A capacitor according to claim 13, wherein longitudinal axis of the electro-conductive oligomer is directed perpendicularly in relation to an electrode surface.

15. A capacitor according to claim 13, wherein the electro-conductive oligomer is one of structures 57 to 63:

16. A capacitor according to claim 1, wherein the electro-conductive nano-particles comprise a low-molecular weight electro-conductive polymer.

17. A capacitor according to claim 16, wherein the low-molecular weight electro-conductive polymer comprises a monomer corresponding to one of structures 57 to 63:

18. A capacitor according to claim 13, wherein the electro-conductive oligomer is of formula:

(electroconductive oligomer)-R_q 

 

(II)

wherein R_q is a substitute group, and q is a number that is greater than or equal to zero.

19. A capacitor according to claim 18, wherein each R is independently an alkyl, aryl, substituted alkyl, or substituted aryl.

20. A capacitor according to claim 1, wherein a material of the insulator matrix is selected from the group consisting of poly (acrylic acid) (PAA), poly(N-vinylpyrrolidone) (PVP), poly(vinylidene fluoride-hexafluoropropylene) [P(VDF-HFP)], ethylene propylene polymers, which include ethylene propylene rubber (EPR) and ethylene propylene diene monomer (EPDM), and silicone rubber (PDMSO) such as dimethyldicloro siloxane, dimethylsilane diol, and polydimethyl siloxane.

21. A capacitor according to claim 1, wherein at least one of the electrodes comprises Pt, Cu, Al, Ag, Au, Ti, W, Zn, Ni or a low-melting temperature alloy.

22. A capacitor according to claim 1, wherein the thickness of the insulating layer (d_ins) and thickness of the polarization layer (d_pol) and breakdown field strength of the insulating layers E_ins and breakdown field strength of the polarization layers E_pol satisfy the following relations:

d_{ins <}

d_pol, and E_ins >

E_pol.

23. A capacitor according to claim 1, wherein the electrodes comprise copper, m is greater than or equal to 1, a dielectric material of the insulating layers A is polyethylene, a material of the polarization layer B is a micro-dispersion PANI-DBSA/PAA, the ratio of PANI to PAA in the composite is greater than or equal to about 20wt %, a thickness of the insulating layer (d_ins) is at least about 2.5 nm, and a thickness of the polarization layer (d_pol) is at least about 1.0 mm.

24. A capacitor according to claim 1, wherein the electrodes comprise copper, m is greater than or equal to 1, a dielectric material of the insulating layers A is polyethylene, a material of the polarization layer B is colloidal PANI dispersions stabilized with poly(N-vinylpyrrolidone) (PVP), a thickness of the insulating layer (d_ins) is from 2.5 nm to 1000 nm, and a thickness of the polarization layer (d_cond) is from 10 micrometer (μ

m) to 50 μ

m.

25. A capacitor according to claim 1, wherein said polarization layers comprise a surfactant selected from:

dodecylbenzene sulfonate (DBSA), polyoxyethylene glycol alkyl ethers, polyoxypropylene glycol alkyl ethers, polyoxyethylene glycol octylphenol ethers, polyoxyethylene glycol sorbitan alkyl esters, sorbitan alkyl esters, and dobecyldimethylamine oxide.

26. A method of producing a capacitor, comprising:

a) preparing a conducting substrate serving as a first electrode;

b) forming a solid multilayer structure adjacent to the first electrode; and

c) forming a second electrode adjacent to the multilayer structure, wherein formation of the multilayer structure comprises alternating operations of the application of insulating and polarization layers or an operation of coextrusion of the insulating and polarization layers, wherein the polarization layer is a colloidal composite with a micro-dispersion of electro-conductive nano-particles in an insulator matrix, wherein an individual insulating layer has a breakdown voltage of at least about 0.05 volts per nanometer (nm) and an individual polarization layer has dielectric permittivity of at least about 100.

27. A method according to claim 26, wherein forming the solid multilayer structure comprises alternating operations of the application of a solution of an insulating material and the application of a solution of the polarization material, wherein both application operations are followed with an operation of drying to form a solid insulating and polarization layers, the alternating operations are recurred until a formation of the multilayer structure is completed, and the insulating layer is formed as the first and the last layer being in direct contact with the electrodes.

28. A method according to claim 26, wherein forming the solid multilayer structure comprises alternating operations of the application of a melt of an insulating material and the application of a melt of the polarization material, wherein both application operations are followed with an operation of cooling down to form a solid insulating and polarization layers, and wherein the alternating operations are recurred until a formation of the multilayer structure is completed, and the insulating layers are formed as the first and the last layers being in direct contact with the electrodes.

29. A method according to claim 26, wherein forming the solid multilayer structure comprises an operation of coextrusion of at least one set of the layers successively containing alternating polarization materials and insulating dielectric materials onto the substrate, followed by drying to form the solid multilayer structure.

30. A method according to claim 26, wherein forming the solid multilayer structure comprises an operation of coextrusion of set of the layers successively containing alternating melts of polarization materials and insulating dielectric materials, followed with the step of cooling down to form the solid multilayer structure.

31. A method of producing a capacitor, which comprises:

a) coating insulating layers on first and second electrodes; and

b) coating a multilayer structure on an insulating layer on one of the first and second electrodes with the lamination of the other of the first and second electrodes to the multilayer structure,

wherein an individual insulating layer has a breakdown voltage of at least about 0.05 volts per nanometer (nm) and the multilayer structure comprises a polarization layer having a dielectric permittivity of at least about 100,

wherein the polarization layer is a colloidal composite with a micro-dispersion of electro-conductive nano-particles in an insulator matrix.