Multilayered electrode and film energy storage device

• US 10,395,841 B2
• Filed: 12/02/2016
• Issued: 08/27/2019
• Est. Priority Date: 12/02/2016
• Status: Active Grant

• Current Assignee: Capacitor Sciences Incorporated (Bolloré SE)
• Original Assignee: Capacitor Sciences Incorporated (Bolloré SE)
• Inventors: Lazarev, Pavel Ivan, Furuta, Paul T., Sharp, Barry K., Li, Yan
• Primary Examiner(s): Kosack, Joseph R
• Application Number:
  US15/368,171
• Publication Number:
  US 20180158616A1
• Time in Patent Office: 998 Days
• CPC Class Codes: C08G 2261/3142 fluorene-based, e.g. fluorene, indenofluorene, or spirobifluorene
• CPC Class Codes: C08G 2261/3221 containing one or more nitrogen atoms as the only heteroatom, e.g. pyrrole, pyridine or triazole
• CPC Class Codes: C08G 2261/3223 containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
• CPC Class Codes: C08G 2261/3241 containing one or more nitrogen atoms as the only heteroatom, e.g. carbazole
• CPC Class Codes: C08G 2261/3422 conjugated, e.g. PPV-type
• CPC Class Codes: C08G 2261/51 Charge transport
• CPC Class Codes: C08G 73/0266 Polyanilines or derivatives thereof
• CPC Class Codes: C08G 73/0672 with only one nitrogen atom in the ring
• CPC Class Codes: C09D 165/00 Coating compositions based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain C09D107/00 - C09D157/00, C09D161/00 take precedence; Coating compositions based on derivatives of such polymers
• CPC Class Codes: C09D 5/24 Electrically-conducting paints conductive materials H01B1/00
• CPC Class Codes: H01B 1/127 comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
• CPC Class Codes: H01B 1/128 comprising six-membered aromatic rings in the main chain, e.g. polyanilines, polyphenylenes
• CPC Class Codes: H01G 4/008 Selection of materials
• CPC Class Codes: H01G 4/01 Form of self-supporting electrodes
• CPC Class Codes: H01G 4/14 Organic dielectrics
• CPC Class Codes: H01G 4/32 Wound capacitors
• CPC Class Codes: H01G 4/33 Thin- or thick-film capacitors thin- or thick-film circuits H01L27/00; capacitors without a potential-jump or surface barrier specially adapted for integrated circuits, details thereof, multistep manufacturing processes therefor H01L28/40

Abstract

The present disclosure provides a multilayered electrode comprising an electro-conductive layer and at least one protective layer located on one side of the electro-conductive layer and selected from the list comprising a field-planarization layer, a tunneling injection blocking layer and a coulomb blocking layer.

Claims

1. An multilayered electrode comprising an electro-conductive layer and at least one protective layer located on one side of the electro-conductive layer and selected from the list comprising a field-planarization layer configured to minimize electric field enhancement due to geometric curvature on a surface of the electro-conductive layer, a tunneling injection blocking layer including a wide-band gap organic insulating material, a coulomb blocking layer including electron traps, and any combination of two or more of these.

2. The multilayered electrode according to claim 1, comprising one, two or three protective layers which are different and selected from the list consisting of the field-planarization layer, tunneling injection blocking layer and the coulomb blocking layer sandwiched together in any sequence.

3. The multilayered electrode according to claim 1, wherein a material of the electro-conductive layer is selected from the list consisting of metal, an electro-conductive oligomer, an electro-conductive (current-conducting) polymer, a molecular-crystal material, a molecular material.

4. The multilayered electrode according to claim 3, wherein the electro-conductive (current-conducting) polymer is selected from the list consisting of polyacetylene, polypyrrole, polythiophene, polyaniline, poly-p-phenylenesulphide, poly-para-phenylenevinylene, polyindole, polycarbazole, polyazulene, polyfluorene, polynaphthalene.

5. The multilayered electrode according to claim 3, wherein a material of the electro-conductive layer is selected from the list consisting of nickel, gold, platinum, lead, chromium, titanium, copper, aluminium, molybdenum, tungsten, indium, silver, calcium, tantalum, palladium and any combination thereof.

6. The multilayered electrode according to claim 3, wherein the material of the electro-conductive layer comprises an electro-conductive oligomer including a phenylene oligomer and a polyacene quinine radical oligomer.

7. The multilayered electrode according to claim 6, wherein the electro-conductive oligomer is selected from the structures 1 to 9 wherein n=2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12, Z is ═

O, ═

S or ═

NT₁, and T₁ is selected from the group consisting of unsubstituted or substituted C₁-C₁₈alkyl, unsubstituted or substituted C₂-C₁₈alkenyl, unsubstituted or substituted C₂-C₁₈alkynyl, and unsubstituted or substituted C₄-C₁₈aryl

8. The multilayered electrode according to claim 1, wherein protective layer includes the field-planarization layer, wherein the field planarization layer includes a polarizable material deposited from liquid or melt stage (phase), where polarizability of the polarizable material is greater than polarizability of propylene.

9. The multilayered electrode according to claim 1, wherein the protective layer includes the field-planarization layer, wherein the field planarization layer includes an electro-conductive material deposited from liquid or melt stage (phase).

10. The multilayered electrode according to claim 1, wherein the protective layer includes the coulomb blocking layer, wherein the coulomb blocking layer includes tetrapyrrolic macrocyclic fragments having a general structural formula from the group comprising structures 10-14, where M is an atom of metal serving as the electron traps:

11. The multilayered electrode according to claim 1, wherein the protective layer includes the tunneling injection blocking layer including a wide-band gap organic insulating material, wherein the wide-band gap organic insulating material has an energy gap band greater than 4 electron-volts, wherein the energy gap band is an energy difference between an energy level of a lowest unoccupied molecular orbital (LUMO) of the tunneling injection blocking layer and a highest occupied molecular orbital (HOMO) of the tunneling injection blocking layer.

12. The multilayered electrode according to claim 1, wherein the protective layer includes the tunneling injection blocking layer including a wide-band gap organic insulating material, wherein a difference between a lowest unoccupied molecular orbital (LUMO) energy level of the wide-band gap organic insulating material and a work function (Wf) of the electro-conductive layer is not less than 1 electron-volt.

13. The multilayered electrode according to claim 1, wherein the protective layer includes the tunneling injection blocking layer including a wide-band gap organic insulating material, wherein a difference between a work function (Wf) of the electro-conductive layer and a highest occupied molecular orbital (HOMO) energy level of the wide-band gap organic insulating material is not less than 1 electron-volt.

14. The multilayered electrode according to claim 1, wherein the protective layer includes the tunneling injection blocking layer, wherein the tunneling injection blocking layer is monomolecular layer and comprises amphiphilic molecules selected from the list consisting of amines (RNH₃⁺), carboxylates (RCO₂⁻

), sulphates (RSO₄⁻

), sulfonates (RSO₃⁻

), phosphates (RHPO₄⁻

), alcohols (ROH), thiols (RSH), where R is a carbon chain comprising more than ten CH₂- and CF₂-groups.

15. The multilayered electrode according to claim 14, wherein the carbon chains are polymerized by ultraviolet light.

16. The multilayered electrode according to claim 14, wherein a thickness of the tunneling injection blocking layer is not less, than lnm and is defined by the carbon chain length.

17. A multilayered structure for an energy storage device comprising

a dielectric layer, and

the multilayered electrode according to claim 1, located on one surface of the dielectric layer.

18. The multilayered structure according to claim 17, wherein the dielectric layer comprises a material having breakdown field strength greater than 0.5 V/nm, greater than 1.0 V/nm, greater than 5.0 V/nm, greater than 10 V/nm.

19. The multilayered semi-product according to claim 17, wherein a surface of the dielectric layer contains surfactant which is intended to increase wettability of the electro-conductive material in the time of forming the multilayered electrode.

20. The multilayered structure according to claim 17, having a rectangular shape in-plan.

21. The multilayered structure according to claim 17, wherein the dielectric layer comprises a material selected from oxides, nitrides, oxynitrides and fluorides.

22. The multilayered structure according to claim 21, wherein the dielectric layer comprises a material selected from SiO₂, SiO_xN_y, HfO₂, Al₂O₃ or Si₃N₄.

23. The multilayered structure according to claim 17, wherein the dielectric layer comprises an organic compound which is characterized by electronic polarizability and has a following general structural formula:

24. The multilayered structure according to claim 23, wherein R₁ is a group that electrically insulates said organic compound from neighboring compounds and provides solubility of the organic compound in an organic solvent.

25. The multilayered structure according to claim 17, wherein the dielectric layer comprises an electro-polarizable complex compound having the following general formula:

[M⁴⁺(L)_m]^XK_n,

where complexing agent M is a four-valence metal, ligand L comprises at least one heteroatomic fragment comprising at least one metal-coordinating heteroatom (neutral or anionic) and at least one electrically resistive fragment that provides resistivity to electric current, m represents the number of ligands, x represents the oxidative state of the metal-ligand complex, K is a counter-ion or zwitterionic polymer which provides an electro-neutrality of the complex compound, n represents the number of counter-ions, wherein said metal-coordinating heteroatoms form a first coordination sphere, and the number of heteroatoms in this first coordination sphere does not exceed 12.

26. The multilayered structure according to claim 17, wherein the dielectric layer comprises an electro-polarizable compound having the following general formula:

27. A film energy storage device comprising two multilayered structures according to claim 17 laminated with each other, wherein the laminated structure is characterized by the following sequence of layers:

multilayered electrode—

dielectric layer—

multilayered electrode—

dielectric layer.

28. The film energy storage device according to claim 27, wherein the two laminated multilayered structures are wound (coiled) into a spiral.

29. The film energy storage device according to claim 27, wherein the dielectric layer comprises a material having breakdown field strength greater than 0.5 V/nm, greater than 1.0 V/nm, greater than 5.0 V/nm, greater than 10 V/nm.

30. The film energy storage device according to claim 27, wherein a surface of the dielectric layer contains surfactant which is intended to increase wettability of the electro-conductive material in the time of forming the multilayered electrode.

31. The film energy storage device according to claim 27, having a rectangular shape in-plan.

32. The film energy storage device according to claim 27, wherein the dielectric layer comprises a material selected from oxides, nitrides, oxynitrides and fluorides.

33. The film energy storage device according to claim 32, wherein the dielectric layer comprises a material selected from SiO₂, SiO_xN_y, HfO₂, Al₂O₃ or Si₃N₄.

34. The film energy storage device according to claim 27, wherein the dielectric layer comprises an organic compound which is characterized by electronic polarizability and has a following general structural formula:

35. The film energy storage device according to claim 34, wherein R₁ is a group that electrically insulates said organic compound from neighboring compounds and provides solubility of the organic compound in an organic solvent.

36. The film energy storage device according to claim 27, wherein the dielectric layer comprises an electro-polarizable complex compound having the following general formula:

[M⁴⁺(L)_m]^XK_n,

where complexing agent M is a four-valence metal, ligand L comprises at least one heteroatomic fragment comprising at least one metal-coordinating heteroatom (neutral or anionic) and at least one electrically resistive fragment that provides resistivity to electric current, m represents the number of ligands, x represents the oxidative state of the metal-ligand complex, K is a counter-ion or zwitterionic polymer which provides an electro-neutrality of the complex compound, n represents the number of counter-ions, wherein said metal-coordinating heteroatoms form a first coordination sphere, and the number of heteroatoms in this first coordination sphere does not exceed 12.

37. The film energy storage device according to claim 27, wherein the dielectric layer comprises an electro-polarizable compound having the following general formula: