Electro-polarizable compound and capacitor

• US 10,707,019 B2
• Filed: 05/17/2018
• Issued: 07/07/2020
• Est. Priority Date: 04/04/2016
• Status: Active Grant

• Current Assignee: Capacitor Sciences Incorporated (Bolloré SE)
• Original Assignee: Capacitor Sciences Corp.
• Inventors: Lazarev, Pavel Ivan, Furuta, Paul T., Sharp, Barry K., Li, Yan
• Primary Examiner(s): Rozof, Timothy R
• Application Number:
  US15/982,482
• Publication Number:
  US 20190139705A1
• Time in Patent Office: 782 Days
• CPC Class Codes: C07D 471/22 in which the condensed systems contains four or more hetero rings
• CPC Class Codes: C07D 487/22 in which the condensed system contains four or more hetero rings
• CPC Class Codes: C09B 47/00 Porphines; Azaporphines non-dyeing compounds C07D487/22
• CPC Class Codes: C09B 47/04 Phthalocyanines abbreviation: Pc
• CPC Class Codes: C09B 5/008 only N-containing hetero rings
• CPC Class Codes: C09B 5/62 Cyclic imides or amidines of peri-dicarboxylic acids of the anthracene, benzanthrene, or perylene series
• CPC Class Codes: C09B 57/08 Naphthalimide dyes; Phthalimide dyes
• CPC Class Codes: C09B 69/00 Dyes not provided for by a single group of this subclass
• CPC Class Codes: C09K 19/606 Perylene dyes
• 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 4/32 Wound capacitors
• CPC Class Codes: H10K 10/20 Organic diodes
• CPC Class Codes: H10K 85/621 Aromatic anhydride or imide compounds, e.g. perylene tetra-carboxylic dianhydride or perylene tetracarboxylic di-imide
• CPC Class Codes: H10K 85/6572 comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
• CPC Class Codes: Y02E 10/549 Organic PV cells
• CPC Class Codes: Y02T 10/70 Energy storage systems for electromobility, e.g. batteries

Abstract

An electro-polarizable compound has the following general formula:

• • where Core1 is an aromatic polycyclic conjugated molecule having two-dimensional flat form and self-assembling by pi-pi stacking in a column-like supramolecule, which is tetrapirolic macro-cyclic fragment, R1 is an dopant group connected to Core1, m is number of R1 which is equal to 1, 2, 3 or 4, R2 is a substituent comprising one or more ionic groups, p is number of R2 which is equal to 0, 1, 2, 3 or 4. The fragment marked NLE containing the Core1 with at least one R1 has a nonlinear effect of polarization. Core2 is an electro-conductive oligomer self-assembling by pi-pi stacking in a column-like supramolecule, n is number of Core2 which is equal to 2, or 4, R3 is a substituent comprising one or more ionic groups, s is number of R3 which is equal to 0, 1, 2, 3 or 4. R4 is a non-polar resistive substituent, k is a number of R4 which is equal to 0, 1, 2, 3, 4, 5, 6, 7 or 8.

Claims

1. An electro-polarizable compound having the following general formula (I):

2. The electro-polarizable compound according to claim 1, wherein the dopant group (R1) is selected from nucleophilic groups (donors) and electrophilic groups (acceptors).

3. The electro-polarizable compound according to claim 2, wherein the electrophilic groups (acceptors) are selected from —

NO₂, —

NH₃⁺ and —

NR₃⁺ (quaternary nitrogen salts), counterion Cl⁻

or Br⁻

, —

CHO (aldehyde), —

CRO (keto group), —

SO₃H (sulfonic acids), —

SO₃R (sulfonates), SO₂NH₂ (sulfonamides), —

COOH (carboxylic acid), —

COOR (esters, from carboxylic acid side), —

COCl (carboxylic acid chlorides), —

CONH₂ (amides, from carboxylic acid side), —

CF₃, —

CCl₃, —

CN, wherein R is radical selected from the list comprising alkyl (methyl, ethyl, isopropyl, tert-butyl, neopentyl, cyclohexyl etc.), allyl (—

CH₂—

CH═

CH₂), benzyl (—

CH₂C₆H₅) groups, phenyl (+substituted phenyl) and other aryl (aromatic) groups; and

wherein the nucleophilic groups (donors) are selected from —

O⁻

(phenoxides, like —

ONa or —

OK), —

NH₂, —

NHR, NR₂, —

OH, OR (ethers), —

NHCOR (amides, from amine side), —

OCOR (esters, from alcohol side), alkyls, —

C₆H₅, vinyls, wherein R is radical selected from the list comprising alkyl (methyl, ethyl, isopropyl, tert-butyl, neopentyl, cyclohexyl etc.), allyl (—

CH2-CH═

CH2), benzyl (—

CH2C6H5) groups, phenyl (+substituted phenyl) and other aryl (aromatic) groups.

4. The electro-polarizable compound according to claim 1, wherein at least one ionic group R2 or R3 is independently selected from the list comprising [NR₄]⁺, [PR₄]⁺ as cation and [—

CO₂O]⁻

, [—

SO₃]⁻

, [—

SR₅]⁻

, [—

PO₃R]⁻

, [—

PR₅]⁻

as anion, wherein R is selected from the list comprising H, alkyl, and fluorine.

5. The electro-polarizable compound according to claim 1, wherein the at least one connecting group is selected from the list comprising the following structures:

29-45, where W is hydrogen (H) or an alkyl group;

6. The electro-polarizable compound according to claim 1, wherein the at least one connecting group is selected from the group of CH₂, CF₂, SiR₂O, CH₂CH₂O, wherein R is selected from the list comprising H, alkyl, and fluorine.

7. The electro-polarizable compound according to claim 1, wherein the resistive substituent R4 is selected from the group of alkyl, aryl, substituted alkyl, substituted aryl, fluorinated alkyl, chlorinated alkyl, branched and complex alkyl, branched and complex fluorinated alkyl, branched and complex chlorinated alkyl groups, and any combination thereof, and wherein the alkyl group is selected from methyl, ethyl, propyl, n-butyl, iso-butyl and tert-butyl groups, and the aryl group is selected from phenyl, benzyl and naphthyl groups or siloxane, and/or polyethyleneglycol as linear or branched chains.

8. The electro-polarizable compound according to claim 1, wherein the resistive substituent R4 is C_XQ_2X+1, where X≥

1 and Q is hydrogen (H), fluorine (F), or chlorine (Cl).

9. The electro-polarizable compound of claim 1, wherein the aromatic polycyclic conjugated molecule (Core1) and the dopant groups (R1) form a non-centrosymmetric molecular structure.

10. The electro-polarizable compound of claim 1, wherein the aromatic polycyclic conjugated molecule (Core1), the dopant groups (R1) and the resistive substituents (R4) form a non-centrosymmetric molecular structure.

11. An electro-polarizable compound of claim 1, wherein a fragment comprising the aromatic polycyclic conjugated molecule (Core1), dopant groups (R1) and resistive substituents providing solubility of the organic compound in a solvent and electrically insulating the column-like supramolecules from each other (R4) is selected from structures 46 to 97:

12. A solution comprising an organic solvent and at least one type of electro-polarizable compound according to claim 1.

13. The solution according to claim 12, comprising a mixture of different electro-polarizable compounds.

14. The solution according to claim 12, wherein the organic solvent is selected from the list consisting of ketones, carboxylic acids, hydrocarbons, cyclic hydrocarbons, chlorohydrocarbons, alcohols, ethers, esters, acetone, xylene, toluene, ethanol, methylcyclohexane, ethyl acetate, diethyl ether, octane, chloroform, methylene chloride, dichloroethane, trichloroethene, tetrachloroethene, carbon tetrachloride, 1,4-dioxane, tetrahydrofuran, pyridine, triethylamine, nitromethane, acetonitrile, dimethylformamide, dimethyl sulfoxide, and any combination thereof.

15. The solution according claim 12, wherein the solution is a lyotropic liquid crystal solution.

16. A crystal metadielectric layer comprising a mixture of the electro-polarizable compounds according to claim 1, wherein the nonlinearly polarizable fragments comprising an aromatic polycyclic conjugated molecule with at least one dopant group, the electro-conductive oligomers and the ionic groups which have electronic and/or ionic type of polarizability are placed into the resistive dielectric envelope formed by resistive substituents providing solubility of the organic compound in a solvent and electrically insulating the column-like supramolecules from each other.

17. The crystal metadielectric layer according to claim 16, wherein the column-like supramolecules are formed by the electro-polarizable compounds comprising rylene fragments of different length.

18. The crystal metadielectric layer according to claim 16, wherein the layer'"'"'s relative permittivity is greater than or equal to 1000 and the layer'"'"'s resistivity is greater than or equal to 10¹³ ohm/cm.

19. A meta-capacitor comprising two metal electrodes positioned parallel to each other and which can be rolled or flat and planar and metadielectric layer between this electrodes, wherein the layer comprises the electro-polarizable compounds according to any claim 1, wherein the nonlinearly polarizable fragments comprising an aromatic polycyclic conjugated molecule with at least one dopant group, the electro-conductive oligomers and the ionic groups which have electronic and/or ionic type of polarizability are placed into the resistive dielectric envelope formed by resistive substituents providing solubility of the organic compound in a solvent and electrically insulating the column-like supramolecules from each other.