Electro-polarizable compound and capacitor

• US 10,672,560 B2
• Filed: 12/04/2018
• Issued: 06/02/2020
• Est. Priority Date: 04/04/2016
• 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, Kelly-Morgan, Ian S.G.
• Primary Examiner(s): Davis, Zinna Northington
• Application Number:
  US16/208,953
• Publication Number:
  US 20190108944A1
• Time in Patent Office: 546 Days
• Field of Search: None
• CPC Class Codes: C07D 471/22 in which the condensed systems contains four or more hetero rings
• 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: H01G 4/005 Electrodes
• 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

Abstract

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

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 comprising one or more rylene fragments, R1 is an electron donor group connected to Core1 and R1′ is an electron acceptor group connected to the Core1, m is number of acceptor group R1, m′ is a number of donor group R′, m and m′ are equal to 0, 1, 2, 3, 4, 5 or 6, wherein m and m′ are not both equal to 0, R2 is a substituent comprising one or more ionic groups from a class of ionic compounds that form ionic liquids connected to the Core1-directly or via a connecting group, p is a number of ionic groups R2 which is equal to 0, 1, 2, 3 or 4; wherein the fragment marked NLE containing the Core1 with at least one group R1 and/or R1′ has a nonlinear effect of polarization, wherein Core2 is an electro-conductive oligomer, n is a number equal to 0, 2, or 4, R3 is a substituent comprising one or more ionic groups from a class of ionic compounds that form ionic liquids connected to the Core2 directly or via a connecting group, s is a number of the ionic groups R3 which is equal to 0, 1, 2, 3 or 4; wherein R4 is a non-conjugate cyclic or polycyclic resistive substituent electrically insulating the column-like supramolecules from each other and connected to the aromatic polycyclic conjugated molecule (Core1) and/or to the Core2 directly or via a connecting group, k is a number of substituents R4 which is equal to 1, 2, 3, 4, 5, 6, 7 or 8.

Claims

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

2. The electro-polarizable compound according to claim 1, wherein the acceptor groups (R1′

) are selected from —

NO₂, —

NH₃⁺, —

NR₃⁺, Cl⁻

, Br⁻

, —

CHO, —

CRO, —

SO₃H, —

SO₃R, —

SO₂NH₂, —

COOH, —

COOR, —

COCl, —

CONH₂, —

CF₃, —

CCl₃, —

CN, and —

C(CN)₂, wherein R is selected from alkyl, allyl, benzyl groups, phenyl, and aryl groups.

3. The electro-polarizable compound according to claim 1, wherein the donor groups (R1) are selected from —

O—

, —

NH₂, —

NHR, —

NR₂, —

OH, —

OR, —

NHCOR, —

OCOR, alkyls, —

C₆H₅, and vinyls, wherein R is radical selected from alkyl, allyl, benzyl groups, phenyl, and aryl groups.

4. The electro-polarizable compound according to claim 1, wherein the at least one connecting group is a structure selected from structures:

13-22, where X is hydrogen (H) or an alkyl group;

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

6. The electro-polarizable compound according to claim 1, wherein the at least one connecting group is a structure selected from structures 24 to 29:

7. The electro-polarizable compound according to claim 1, wherein the resistive substituent R4 is selected from unsubstituted alkyl, unsubstituted aryl, substituted alkyl, substituted aryl, fluorinated alkyl, chlorinated alkyl, branched alkyl, branched fluorinated alkyl, branched chlorinated alkyl groups, and any combination thereof.

8. The electro-polarizable compound of claim 1, wherein the Core1 and the groups R1 and R1′

form a non-centrosymmetric molecular structure.

9. The electro-polarizable compound of claim 1, wherein the Core1 the groups R1 and R1′

and the resistive substituents (R4) form a non-centrosymmetric molecular structure.

10. The electro-polarizable compound of claim 1 having the following formula (II):

11. The electro-polarizable compound of claim 10, wherein a length of the non-conjugated part of the electro-polarizable compound is selected such that the resistivity of the electro-polarizable compound is greater than 1018 ohm cm.

12. The electro-polarizable compound of claim 10, wherein a length of the non-conjugated part of the electro-polarizable compound is selected such that the resistivity of the electro-polarizable compound is between 1018 ohm·

cm and 1024 ohm·

cm.

13. The electro-polarizable compound of claim 10, wherein the resistive substituent R4 is a polycyclic alkyl group and a polycyclic halo-alkyl group, wherein in the polycyclic halo-alkyl group is connected to the apex of Core1 on which the R1 is connected, or the apex of Core1 on which R1′

is connected, but not both.

14. The electro-polarizable compound of claim 10, wherein the resistive substituent R4 is a resistive polycyclic substituent selected from C₂₅H₃₄, C₂₅H₃₅, C₂₅F₃₄ and C₂₅F₃₅ and located on the apex phenyl, naphthyl, or anthryl rings of Core1.

15. The electro-polarizable compound of claim 10 having the following formula (III):

16. The electro-polarizable compound according to claim 15, wherein the set of the electron donor and acceptor groups consists of two donor groups —

NH₂ and two acceptor groups —

NO₂, wherein m is equal to 4, located on rylene rings, or on apex phenyl, naphthyl, and/or anthryl ring positions of the Core1, or on both rylene rings positions and apex phenyl, naphthyl, and/or anthryl ring positions;

wherein the resistive substituent (R4) is an amine structure having a formula of the type;

17. The electro-polarizable compound of claim 10 having a formula (V):

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

19. The solution according to claim 18, comprising a mixture of different electro-polarizable compounds.

20. The solution according to claim 18, wherein the mixture of the electro-polarizable compounds comprises rylene fragments of different length.

21. The solution according to claim 18, wherein the organic solvent is selected from ketones, carboxylic acids, hydrocarbons, cyclic hydrocarbons, chlorohydrocarbons, alcohols, ethers, esters, and any combination thereof.

22. The solution according to claim 18, wherein the organic solvent is selected from 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.

23. A metadielectric layer comprising the electro-polarizable compounds according to claim 1, wherein the nonlinearly polarizable fragments comprising an aromatic polycyclic conjugated molecule with one or more R1 groups, and wherein the one or more R1 and/or R1′

groups form a resistive envelope and solubilize the organic compound in a solvent and electrically insulating the column-like supramolecules from each other.

24. The metadielectric layer according to claim 23, wherein the column-like supramolecules are formed by the electro-polarizable compounds comprising rylene fragments of different length.

25. The metadielectric layer according to claim 23, wherein the metadielectric layer'"'"'s relative permittivity is greater than or equal to 1000.

26. The metadielectric layer according to claim 23, wherein the layer'"'"'s resistivity is greater than or equal to 1013 ohm/cm.

27. A meta-capacitor comprising two metal electrodes positioned parallel to each other and which can be rolled or flat and planar with said metadielectric layer between said electrodes, wherein the metadielectric layer comprises the electro-polarizable compounds according to claim 1 wherein the nonlinearly polarizable fragments comprising an aromatic polycyclic conjugated molecule with at least one group R1 or R1′

, the electro-conductive oligomers and the ionic groups which have electronic and/or ionic type of polarizability are placed into a resistive dielectric envelope formed by resistive substituents R1 and/or R1′

providing solubility of the organic compound in a solvent and electrically insulating the column-like supramolecules from each other.