WO2019100026A1 - Composé électro-polarisable hein et condensateur de celui-ci - Google Patents

Composé électro-polarisable hein et condensateur de celui-ci Download PDF

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WO2019100026A1
WO2019100026A1 PCT/US2018/061874 US2018061874W WO2019100026A1 WO 2019100026 A1 WO2019100026 A1 WO 2019100026A1 US 2018061874 W US2018061874 W US 2018061874W WO 2019100026 A1 WO2019100026 A1 WO 2019100026A1
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groups
electro
alkyl
polarizable
benzyl
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PCT/US2018/061874
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English (en)
Inventor
Pavel Lazarev
Samuel Hein
Carine Edder
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Capacitor Sciences Incorporated
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Priority claimed from US15/818,474 external-priority patent/US11092142B2/en
Priority claimed from US15/870,504 external-priority patent/US10566138B2/en
Application filed by Capacitor Sciences Incorporated filed Critical Capacitor Sciences Incorporated
Priority to KR1020207017408A priority Critical patent/KR20200123084A/ko
Priority to CA3082828A priority patent/CA3082828A1/fr
Priority to EP18877469.9A priority patent/EP3717485A4/fr
Priority to CN201880075023.5A priority patent/CN111372933A/zh
Priority to JP2020528028A priority patent/JP2021503488A/ja
Priority to SG11202004660VA priority patent/SG11202004660VA/en
Publication of WO2019100026A1 publication Critical patent/WO2019100026A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed systems contains four or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/06—Peri-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains three hetero rings
    • C07D471/16—Peri-condensed systems
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/002—Details
    • H01G4/018—Dielectrics
    • H01G4/06—Solid dielectrics
    • H01G4/14—Organic dielectrics
    • H01G4/18—Organic dielectrics of synthetic material, e.g. derivatives of cellulose
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/32—Wound capacitors

Definitions

  • the present disclosure relates generally to passive components of electrical circuit and more particularly to an electro-polarizable compound and capacitor based on this material and intended for energy storage.
  • a capacitor is a passive electronic component that is used to store energy in the form of an electrostatic field, and comprises a pair of electrodes separated by a dielectric layer. When a potential difference exists between the two electrodes, an electric field is present in the dielectric layer.
  • An ideal capacitor is characterized by a single constant value of capacitance, which is a ratio of the electric charge on each electrode to the potential difference between them. For high voltage applications, much larger capacitors are necessary.
  • the breakdown field corresponds to the value of electric field strength at which the material suffers a catastrophic failure and conducts electricity between the electrodes.
  • the electric field in the dielectric can be approximated by the voltage between the two electrodes divided by the spacing between the electrodes, which is usually the thickness of the dielectric layer. Since the thickness is usually constant it is more common to refer to a breakdown voltage, rather than a breakdown field.
  • the geometry of the conductive electrodes is important factor affecting breakdown voltage for capacitor applications. In particular, sharp edges or points hugely increase the electric field strength locally and can lead to a local breakdown. Once a local breakdown starts at any point, the breakdown will quickly "trace" through the dielectric layer until it reaches the opposite electrode and causes a short circuit.
  • Breakdown of the dielectric layer usually occurs as follows. Intensity of an electric field becomes high enough to "pull" electrons from atoms of the dielectric material and makes them conduct an electric current from one electrode to another. Presence of impurities in the dielectric or imperfections of the crystal structure can result in an avalanche breakdown as observed in semiconductor devices.
  • dielectric permittivity Another important characteristic of a dielectric material is its dielectric permittivity.
  • dielectric materials include ceramics, polymer film, paper, and electrolytic capacitors of different kinds.
  • the most widely used polymer film materials are polypropylene and polyester. Increasing dielectric permittivity allows for increasing volumetric energy density, which makes it an important technical task.
  • NLO nonlinear optical
  • Hyper-electronic polarization of organic compounds is described in greater detail in Roger D. Hartman and Herbert A. Pohl,“Hyper-electronic Polarization in Macromolecular Solids”, Journal of Polymer Science: Part A-l Vol. 6, pp. 1135-1152 (1968). Hyper-electronic polarization may be viewed as the electrical polarization external fields due to the pliant interaction with the charge pairs of excitons, in which the charges are molecularly separated and range over molecularly limited domains. In this article four polyacene quinone radical polymers were investigated. These polymers at 100 Hz had dielectric constants of 1800-2400, decreasing to about 58-100 at 100,000 Hz. Essential drawback of the described method of production of material is use of a high pressure (up to 20 kbars) for forming the samples intended for measurement of dielectric constants.
  • the present disclosure provides an electro-polarizable compound having the following general formula (I):
  • Corel is an aromatic polycyclic conjugated molecule having two-dimensional flat form and self- assembles into supramolecular structures.
  • Rl are electron donor groups connected to the aromatic polycyclic conjugated molecule (Corel) and Rl’ are electron acceptor groups connected to the aromatic polycyclic conjugated molecule (Corel)
  • m is number of acceptor groups Rl
  • m’ is a number of donor groups Rl’
  • 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 are used in ionic liquids connected to the aromatic polycyclic conjugated molecule (Corel) directly or via a connecting group
  • p is number of ionic groups R2 which is equal to 0, 1, 2, 3 or 4.
  • the fragment marked NLE containing the Corel with at least one group Rl and/or Rl’ has a nonlinear effect
  • Core2 is an electro-conductive oligomer and number n of the electro-conductive oligomers is equal to 0, 2, or 4.
  • R3 is a substituent comprising one or more ionic groups from a class of ionic compounds that are used in ionic liquids connected to the electro-conductive oligomer (Core2) directly or via a connecting group, s is number of the ionic groups R3 which is equal to 0, 1, 2, 3 or 4.
  • R4 is a resistive substituent connected to the aromatic polycyclic conjugated molecule (Corel) and/or to the electro-conductive oligomer (Core2) directly or via a connecting group.
  • the resistive substituent R4 provides solubility of the organic compound in a solvent and electrically insulates the supramolecular structures from each other and.
  • the parameter k is a number of substituents R4, which is equal to 1, 2, 3, 4, 5, 6, 7 or 8.
  • the present disclosure provides a solution comprising an organic solvent and at least one disclosed electro-polarizable compound.
  • the present disclosure provides a crystal metadielectric layer comprising a mixture of the electro-polarizable compounds as disclosed above.
  • the nonlinearly polarizable fragments comprising an aromatic polycyclic conjugated molecule with at least one group Rl are placed into the resistive dielectric envelope formed by resistive substituents R4 providing solubility of the organic compound in a solvent and electrically insulating the supramolecular structures, such as supramolecular columns, from each other.
  • the present disclosure provides 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 one or more types of the disclosed electro-polarizable.
  • the nonlinearly polarizable fragments comprising an aromatic polycyclic conjugated molecule with at least one group Rl, 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 supramolecular structures from each other.
  • Figure 1 A schematically shows a capacitor with flat and planar electrodes in accordance with an aspect of the present disclosure.
  • Figure 1B schematically shows a capacitor with rolled (circular) electrodes in accordance with another aspect of the present disclosure.
  • Figure 2 shows a chemical formula that illustrates possible variations on a structure referred to as a rylene fragment that may be included in a Hein Electro-Polarizable compound in accordance with aspects of the present disclosure.
  • the present disclosure provides an electro-polarizable compound.
  • the existence of the electrophilic groups (acceptors) and the nucleophilic groups (donors) in an aromatic polycyclic conjugated molecule (Corel) promotes non-uniform distribution of electronic density in the conjugated molecule: surplus of electrons in one place (in a donor zone) and a shortage of electrons in other place (in an acceptor zone).
  • the influence of external electric field onto non- uniform distribution of electronic density along the conjugated molecule leads to the induced polarization Ri h1 .
  • the induced polarization is nonlinear function of intensity of local electric field Ei oc .
  • An essential feature of the present disclosure is use of rigid non-conjugated limit carbon structures as resistive substituents.
  • Such structures distinguish from the dielectric structures formed by "fat" tails (such as alkyl, aryl, substituted alkyl, substituted aryl, fluorinated alkyl, chlorinated alkyl, branched and complex alkyl) which can be bent (curved) and lead to stochastic distribution of electronic density in the dielectric structure that leads to its electric breakdown.
  • resistive substituent R4 is preferably a non-conjugated compound that minimizes or does not contain voids/empty space; that have dense packing of SP3 carbon with H and F substitutes.
  • friable dielectric structure film, layer, and envelope. It is possible that in friable structure that there will be a local area ("hole") in which electronic density is equal to zero and which can be occupied with a free electron (that leads to electric breakdown). It is possible to enter a concept of a molecular hole when one molecule "is taken out” from the ordered structure (from a crystal lattice). In this case the quantum object (a quantum hole, a quantum point) is formed in which there are empty (non- occupied) energy levels. Set of such objects creates a condition for conductivity of electrons and for electric breakdown of dielectric structure.
  • Resistive substituents are preferentially selected from single and branched chains between 5 and 13 carbon-carbons in length in one direction and non-conjugated fused carbo-cyclic chains greater than 3 rings in length in one direction.
  • the presence of the electro-conductive oligomers leads to increasing polarizability of the disclosed electro-polarizable compound because of electronic super conductivity of the electro- conductive oligomers.
  • Ionic groups increase an ionic component of polarization of the disclosed electro-polarizable compound.
  • the nonlinearly polarizable fragments comprising an aromatic polycyclic conjugated molecule with at least one dopant group, the electro-conductive oligomers and the ionic groups are placed into the resistive dielectric envelope formed by resistive substituents providing solubility of the organic compound in a solvent and electrically insulating the supramolecular structures from each other.
  • the resistive substituents increase the electric strength of these electro-polarizable compounds and breakdown voltage of the dielectric layers made on their basis.
  • the aromatic polycyclic conjugated molecule may comprise rylene fragments, which may be in conjugation with phenyl amides, naphthalene amides, and/or anthracene amides.
  • the rylene fragments are selected from structures from 1 to 17 as given in Table 2.
  • the electron donor and acceptor groups (Rl) may be selected from nucleophilic groups (donors) and electrophilic groups (acceptors) and the set (variety) of groups (Rl) m containing of m elements comprises donors (Rl 1 ) and/or acceptors (Rl).
  • -O phenoxides, like -ONa or -OK
  • the polycyclic aromatic Cores may be similarly expanded in the lateral dimension, herein defined as the direction that is in plane and perpendicular to the length wise dimension which is variable in compounds 1-17, which is herein defined as the longitudinal dimension.
  • lateral dimension herein defined as the direction that is in plane and perpendicular to the length wise dimension which is variable in compounds 1-17, which is herein defined as the longitudinal dimension.
  • Lateral expansion makes the Cores more planar and results in greater surface area for pi-pi interactions to enhance stacking effect. Lateral expansion also prevents the molecules from warping due to steric influences from neighboring molecules or substituents.
  • These embodiments may still possess the electron donor and acceptor groups as described for compounds 1-17 and still possess the essential rigid non- conjugated limit carbon structures as resistive substituents.
  • Ri, R 2 , R 3 , R 4 , R 5 , 3 ⁇ 4 are each independently selected from hydrogen, electrophilic groups, nucleophilic groups, and resistive groups. In some embodiments, the resistive groups are connected via at least one connecting group.
  • the electro-polarizable compound may take the form of the following structure
  • R a is a nucleophile with or without alkyl resistive groups
  • R b and R c are electrophilic groups.
  • a non-limiting example of such a structure includes the structure wherein R and R’ are independently selected from hydrogen, and alkyl groups ranging between Ci-Cig.
  • At least one connecting group is selected from the list comprising structures 18-35 given in Table 4, where X is hydrogen (H) or an alkyl group.
  • the at least one connecting group is selected from the group of CH 2 , CF 2 , SiR 2 0, CH 2 CH 2 0, wherein R is selected from the list comprising H, alkyl, and fluorine.
  • 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, «-butyl, zso-butyl and /er/-butyl groups, and the aryl group is selected from phenyl, benzyl and naphthyl groups or siloxane, and/or polyethylene glycol as linear or branched chains.
  • the resistive substituent R4 is C X Q 2X + I , where X > 1 and Q is hydrogen (H), fluorine (F), or chlorine (Cl).
  • the aromatic polycyclic conjugated molecule (Corel) and the groups (Rl) form a non- centro symmetric molecular structure.
  • the aromatic polycyclic conjugated molecule (Corel), the groups (Rl) and the resistive substituents (R4) form a non- centro symmetric molecular structure.
  • the electro- polarizable compound has the following general formula (II):
  • Corel is the aromatic polycyclic conjugated molecule, as discussed above, the resistive substituent R4 is a non-conjugated part of disclosed compound, which may be saturated and fused cyclo-hydrocarbons or saturated and fused cyclo-halocarbons with rigid spatial structure including, but not limited to cyclohexane, cyclopentane, polycyclic
  • a length of the non-conjugated part is selected such that its resistivity is greater than 10 15 ohm ⁇ cm.
  • the resistive substituent R4 is selected from benzyl groups, benzyl alkoxy groups, benzyl halo-alkoxy groups, alkoxy groups, benzyl alkyl groups, benzyl halo-alkyl groups, alkyl groups, halo-alkoxy groups, halo-alkyl groups, benzyl aryl groups, and benzyl halo-aryl groups, wherein in the R4 substituents are connected to the apex of Corel on which the nucleophilic groups (donor) Rl are connected, or the apex of Corel on which the electrophilic group (acceptor) RT is connected, but not both.
  • the resistive substituent R4 is resistive polycyclic substituents selected from the list comprising long C 25 H 34 and C 25 H 35 or C 25 F 34 and C 25 F 35 and located on the apex phenyl rings of Corel.
  • the electro-polarizable compound has the following general formula (III):
  • the parameters m and m’ are equal to 1, RF is an acceptor group, Rl is a donor group, k and k’ indicate R4 resistive groups are on either end of the molecule.
  • the Corel is rylene fragment having the following structural formula where repetition parameter t is an integer varying from 0 to 5 :
  • resistive substituents (R4) are benzyl alkoxy groups and in some instances are attached via a benzyl group such as:
  • resistive substituents (R4) are branched alkyl or alkoxy groups attached via an alkyne connecting group, for example:
  • the electro-polarizable compound has the following general formula (VI):
  • Corel is the above-described aromatic polycyclic conjugated molecule, m is equal to 6, Rl' is donor group, Rl is acceptor group, k is equal to 2.
  • the Corel is rylene fragment having the following structural formula where repetition parameter t varies from 1 to 5 :
  • resistive substituent (R4) is an amine structure of the following type:
  • resistive substituents are connected via a connecting group.
  • Non-limiting examples of the electro-polarizable cores includes at least two regioisomers selected from the below structures:
  • Ri, R 2 , R 3 , R4, R 5 , R 6 are each independently selected from hydrogen, electrophilic groups, nucleophilic groups, and resistive groups; and n is an integer greater than or equal to 1.
  • Non-limiting examples of such combinations of substituents are listed in Table 5.
  • R and R’ can be the same or independently selected from alkyl, alkene, and substituted alkyl groups; and wherein DB is 3,5-dimethoxyphenyl.
  • the electro-polarizable compounds may be further modified to include resistive substituents connected to the core via DB groups, or connecting groups listed in Table 4.
  • a dielectric layer of electro-polarizable compounds is comprised of more than one regioisomer. In some embodiments, a dielectric layer comprised of electro- polarizable compounds includes a mixture of electro-polarizable compounds. In one embodiment of the present disclosure, the induced polarization Ri h1 of the electro- polarizable compound may be written in the form of decomposition into a series on degrees of intensity of a local electric field Ei oc :
  • the present disclosure provides the organic solvent comprising the disclosed electro-polarizable compound.
  • the solution comprises a mixture of different electro-polarizable compounds.
  • the mixture of the electro-polarizable compounds comprises the rylene fragments of different length.
  • the organic solvent is selected from the list comprising ketones, carboxylic acids, hydrocarbons, cyclic hydrocarbons, chlorohydrocarbons, alcohols, ethers, esters, and any combination thereof.
  • the organic solvent is selected from the list comprising acetone, xylene, toluene, ethanol, methylcyclohexane, ethyl acetate, diethyl ether, octane, chloroform, methylene chloride, dichloroethane, trichloroethene, tetrachloroethene, carbon tetrachloride, l,4-dioxane, tetrahydrofuran, pyridine, triethylamine, nitromethane, acetonitrile, dimethylformamide, dimethyl sulfoxide, and any combination thereof.
  • the solution is a lyotropic liquid crystal solution.
  • aspects of the present disclosure provide a crystal metadielectric layer comprising at least one type of the disclosed electro-polarizable compounds.
  • the crystal metadielectric layers are produced from the disclosed organic compound by Cascade
  • Cascade Crystallization process involves a chemical modification step and four steps of ordering during the crystal metadielectric layer formation.
  • the chemical modification step introduces hydrophilic groups on the periphery of the molecule of the disclosed organic compound in order to impart amphiphilic properties to the molecule.
  • Amphiphilic molecules stack together into supramolecular structures, which is the first step of ordering. At certain concentration, supramolecular structures are converted into a liquid-crystalline state to form a lyotropic liquid crystal, which is the second step of ordering.
  • the lyotropic liquid crystal is deposited under the action of a shear force (or meniscus force) onto a substrate based on a Mayer Rod shearing technique, so that shear force (or the meniscus) direction determines the crystal axis direction in the resulting solid crystal layer.
  • the external alignment upon the lyotropic liquid crystal can be produced using any other means, for example by applying an external electric field at normal or elevated temperature, with or without additional illumination, magnetic field, or optical field (e.g., coherent photovoltaic effect); the degree of the external alignment should be sufficient to impart necessary orientation to the supramolecular structures of the lyotropic liquid crystal and form a structure, which serves as a base of the crystal lattice of the dielectric layer.
  • This directional deposition is third step of ordering, representing the global ordering of the crystalline or polycrystalline structure on the substrate surface.
  • the last fourth step of the Cascade Crystallization process is drying/crystallization, which converts the lyotropic liquid crystal into a solid crystal dielectric layer.
  • the term Cascade Crystallization process is used to refer to the chemical modification and four ordering steps as a combination process.
  • the Cascade Crystallization process is used for production of thin crystalline metadielectric layers.
  • the dielectric layer produced by the Cascade Crystallization process has a global order which means that a direction of the crystallographic axis of the layer over the entire substrate surface is controlled by the deposition process. Molecules of the deposited material are packed into supramolecular structures with a limited freedom of diffusion or motion.
  • the thin crystalline dielectric layer is characterized by an interplanar spacing of 3.4 ⁇ 0.3 Angstroms (A) in the direction of one of the optical axes.
  • the crystal metadielectric layer comprises supramolecular structures such as columns, needles, etc., formed by the electro-polarizable compounds comprising the rylene fragments of different length.
  • the variety of the rylene fragment lengths increases the randomness of the stack.
  • the layer’s relative permittivity is greater than or equal to 1000.
  • the real part of the relative permittivity (e’) of the crystal metadielectric layer comprises first-order (e (1) ) and second-order (e (2) ) permittivities according to follow formula: where Vo is the DC-voltage which is applied to the crystal metadielectric layer, d is the layer thickness.
  • the layer’s resistivity is greater than or equal to 10 13 ohm/cm.
  • the present disclosure provides the metacapacitor comprising two metal electrodes positioned parallel to each other and which can be rolled or flat and planar and metadielectric layer between said electrodes.
  • the layer comprises the electro-polarizable compounds as disclosed above.
  • the metacapacitor comprises a first electrode 1, a second electrode 2, and a metadielectric layer 3 disposed between said first and second electrodes as shown in Figure 1 A.
  • the electrodes 1 and 2 may be made of a metal, such as copper, zinc, or aluminum or other conductive material such as graphite or carbon nanomaterials and are generally planar in shape.
  • the electrodes 1, 2 may be flat and planar and positioned parallel to each other.
  • the electrodes may be planar and parallel, but not necessarily flat, they may be coiled, rolled, bent, folded, or otherwise shaped to reduce the overall form factor of the capacitor. It is also possible for the electrodes to be non-flat, non-planar, or non-parallel or some
  • a spacing d between the electrodes 1 and 2 may range from about 100 nm to about 10,000 pm.
  • the electrodes land 2 may have the same shape as each other, the same dimensions, and the same area A.
  • the area A of each electrode 1 and 2 may range from about 0.01 m 2 to about 1000 m 2 .
  • the capacitance C of the capacitor may be approximated by the formula:
  • the energy storage capacity U is determined by the dielectric constant e, the area A, and the breakdown field E bd.
  • a capacitor or capacitor bank may be designed to have any desired energy storage capacity U.
  • a capacitor in accordance with aspects of the present disclosure may have an energy storage capacity U ranging from about 500 Joules to about 2 ⁇ 10 16 Joules.
  • a capacitor of the type described herein may have a specific energy capacity per unit mass ranging from about 10 W-h/kg up to about 100,000 W-h/kg, though implementations are not so limited.
  • a metacapacitor 20 comprises a first electrode 21, a second electrode 22, and a metadielectric material layer 23 of the type described hereinabove disposed between said first and second electrodes.
  • the electrodes 21 and 22 may be made of a metal, such as copper, zinc, or aluminum or other conductive material such as graphite or carbon nano materials and are generally planar in shape.
  • the electrodes and metadielectric material layer 23 are in the form of long strips of material that are sandwiched together and wound into a coil along with an insulating material, e.g., a plastic film such as polypropylene or polyester to prevent electrical shorting between the electrodes 21 and 22.
  • an insulating material e.g., a plastic film such as polypropylene or polyester to prevent electrical shorting between the electrodes 21 and 22.
  • reaction was placed back on an ice water bath to cool for 10 minutes before 1 mL of methanol was added to quench any unreacted BBr 3 still present.
  • This reaction mixture was washed with aqueous HC1 (2 M) and extracted with EtOAc (3x). The organic fractions were collected and dried with Na 2 S0 3 before being filtered.
  • the crude reaction mixture was concentrated under vacuum and precipitated into hexanes to yield 3,5-dihydroxy- bromobenzene.
  • Example 2 This Example describes synthesis of the disclosed organic compound according following structural scheme:
  • Naphthalene anhydride 16 (1 eq.) and naphthalene 15 (1 eq.) were stirred in imidazole at 130 °C overnight. The mixture was dissolved in THF and washed with water 3 times. The organics were combined and dried over MgS0 4. The solvent was removed under reduced pressure to give 17.
  • Amidine 17 (1 eq.) and Pd/C (20% wt/wt) were stirred in THF in a three-neck flask with a 3 ⁇ 4 balloon attached for 18 h. The mixture was filtered through Diatomaceous earth and the solvents were removed under reduced pressure to give 18.
  • Amidine 17 (1 eq.) was dissolved in THF and stirred at -80 °C. N-butyllithium (1.2 eq., 2.5 M in hexanes) was added dropwise. After 1 h, triisopropylborane was added dropwise and allow to warm to room temperature overnight. The mixture was washed with NaHCCh and brine and dried over MgS0 4. The solvent was removed under reduced pressure to give 19.
  • aspects of the present disclosure provide compounds characterized by highly nonlinear electric polarizability. Such compounds are useful as high dielectric constant metadielectrics for meta- capacitors with extremely high capacitance and extremely high energy storage capacity.

Abstract

La présente invention concerne un composé électro-polarisable de formule générale : (I) une molécule de noyau 1 conjuguée polycyclique aromatique auto-assemblée pour former des structures supramoléculaires ; m groupes donneurs R1 et m' de groupes accepteurs R1' se connectent au noyau 1 ; m et m' = 0, 1, 2, 3, 4, 5 ou 6, mais ne peuvent pas être 0 ; p = 0, 1, 2, 3 ou 4 substituants R2 (un ou plusieurs groupes ioniques) se connectent au noyau 1 directement ou par l'intermédiaire d'un groupe de connexion. Le fragment NLE présente un effet de polarisation non linéaire. Un nombre n d'oligomères de noyau 2 électro-conducteurs auto-assemblés peut être 0, 2 ou 4 ; s = 0, 1, 2, 3, ou 4 groupes ioniques R3 se connectent au noyau 2 ; k = 0, 1, 2, 3, 4, 5, 6, 7 ou 8 substituants résistifs R4 qui isolent électriquement les structures supramoléculaires.
PCT/US2018/061874 2017-11-20 2018-11-19 Composé électro-polarisable hein et condensateur de celui-ci WO2019100026A1 (fr)

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KR1020207017408A KR20200123084A (ko) 2017-11-20 2018-11-19 Hein 전기-분극가능한 화합물 및 그의 커패시터
CA3082828A CA3082828A1 (fr) 2017-11-20 2018-11-19 Compose electro-polarisable hein et condensateur de celui-ci
EP18877469.9A EP3717485A4 (fr) 2017-11-20 2018-11-19 Composé électro-polarisable hein et condensateur de celui-ci
CN201880075023.5A CN111372933A (zh) 2017-11-20 2018-11-19 Hein可电极化化合物及其电容器
JP2020528028A JP2021503488A (ja) 2017-11-20 2018-11-19 Ｈｅｉｎ電子分極性化合物及びそのキャパシター
SG11202004660VA SG11202004660VA (en) 2017-11-20 2018-11-19 Hein electro-polarizable compound and capacitor thereof

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US15/818,474 2017-11-20
US15/818,474 US11092142B2 (en) 2017-11-20 2017-11-20 Plasma electric propulsion device
US15/870,504 2018-01-12
US15/870,504 US10566138B2 (en) 2016-04-04 2018-01-12 Hein electro-polarizable compound and capacitor thereof

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EP (1) EP3717485A4 (fr)
JP (1) JP2021503488A (fr)
KR (1) KR20200123084A (fr)
CN (1) CN111372933A (fr)
CA (1) CA3082828A1 (fr)
SG (1) SG11202004660VA (fr)
WO (1) WO2019100026A1 (fr)

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US20170287637A1 (en) * 2016-04-04 2017-10-05 Capacitor Sciences Incorporated Electro-polarizable compound and capacitor
US20180137978A1 (en) * 2016-04-04 2018-05-17 Capacitor Sciences Incorporated Hein electro-polarizable compound and capacitor thereof

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CA3082828A1 (fr) 2019-05-23
EP3717485A4 (fr) 2021-07-07
CN111372933A (zh) 2020-07-03
EP3717485A1 (fr) 2020-10-07
KR20200123084A (ko) 2020-10-28
JP2021503488A (ja) 2021-02-12

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