Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G4/00—Fixed capacitors; Processes of their manufacture
  • H01G4/002—Details
  • H01G4/005—Electrodes
  • H01G4/012—Form of non-self-supporting electrodes
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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

Definitions

• 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 two electrodes, an electric field is present in the dielectric layer.
• An ideal capacitor is characterized by a single constant value of capacitance. This is a ratio of the electric charge on each electrode to the potential difference between them.
• the dielectric layer between electrodes passes a small amount of leakage current. Electrodes and leads introduce an equivalent series resistance, and dielectric layer has limitation to an electric field strength which results in a breakdown voltage.
• An ideal capacitor is characterized by a constant capacitance C, defined by the formula (1)
• a characteristic electric field known as the breakdown strength i3 ⁇ 4 d is an electric field in which the dielectric layer in a capacitor becomes conductive.
• the voltage at which this occurs is called the breakdown voltage of the device, and is given by the product of dielectric strength and separation between the electrodes,
• V M E M d (2)
• the maximal volumetric energy density stored in the capacitor is limited by the value proportional to ⁇ ⁇ bd , where ⁇ is dielectric permittivity and 3 ⁇ 4 d IS breakdown strength.
• ⁇ is dielectric permittivity and 3 ⁇ 4 d IS breakdown strength.
• Breakdown of the dielectric layer usually occurs when the intensity of the electric field becomes high enough to "pull" electrons from atoms of the energy storage molecular material and make them conduct an electric current from one electrode to another. Presence of impurities in the energy storage molecular material or imperfections of the crystal dielectric layer can result in an avalanche breakdown as observed in capacitor.
• an energy storage molecular material is its dielectric permittivity.
• Different types of energy storage molecular materials are used for capacitors and include ceramics, polymer film, paper, and electrolytic capacitors of different kinds.
• the most widely used film materials are polypropylene and polyester. Increase of dielectric permittivity allows increasing of volumetric energy density which makes it an important technical task.
• the water-soluble PAA served as a polymeric stabilizer, protecting the PANI particles from macroscopic aggregation.
• a very high dielectric constant of ca. 2.0*10 5 (at 1 kHz) was obtained for the composite containing 30% PANI by weight.
• Influence of the PANI content on the morphological, dielectric and electrical properties of the composites was investigated. Frequency dependence of dielectric permittivity, dielectric loss, loss tangent and electric modulus were analyzed in the frequency range from 0.5 kHz to 10 MHz.
• SEM micrograph revealed that composites with high PANI content (i.e., 20 wt%) consisted of numerous nano-scale PANI particles that were evenly distributed within the PAA matrix.
• Single crystals of doped aniline oligomers are produced via a simple solution-based self-assembly method (see, Yue Wang, et. al., "Morphological and Dimensional Control via Hierarchical Assembly of Doped Oligoaniline Single Crystals", J. Am. Chem. Soc. 2012, 134, pp. 9251-9262).
• Detailed mechanistic studies reveal that crystals of different morphologies and dimensions can be produced by a "bottom-up" hierarchical assembly where structures such as one-dimensional (1-D) nanofibers can be aggregated into higher order architectures.
• a large variety of crystalline nanostructures including 1 -D nanofibers and nano wires, 2-D nanoribbons and nanosheets, 3-D nanoplates, stacked sheets, nanoflowers, porous networks, hollow spheres, and twisted coils, can be obtained by controlling the nucleation of the crystals and the non- covalent interactions between the doped oligomers.
• These nanoscale crystals exhibit enhanced conductivity compared to their bulk counterparts as well as interesting structure-property relationships such as shape-dependent crystallinity.
• the morphology and dimension of these structures can be largely rationalized and predicted by monitoring molecule-solvent interactions via absorption studies. Using doped tetra-aniline as a model system, the results and strategies presented in this article provide insight into the general scheme of shape and size control for organic materials.
• electrochemical energy storage e.g. a battery.
• capacitors are able to store energy with very high power density, i.e. charge/recharge rates, have long shelf life with little degradation, and can be charged and discharged (cycled) hundreds of thousands or millions of times.
• capacitors often do not store energy in such little volume or weight as in a battery, or at low cost per energy stored, making capacitors impractical for applications such as in electric vehicles. Accordingly, it would be an advance in energy storage technology to provide storing energy more densely per volume and/or mass.
• aspects of the present disclosure provide solutions to the problem of the further increase of volumetric and mass density of reserved energy of the energy storage device, and at the same time reduces cost of materials and manufacturing process.
• the present disclosure provides an energy storage molecular material, crystal dielectric layer and capacitor which may solve a problem of the further increase of volumetric and mass density of reserved energy associated with some energy storage devices, and at the same time reduce cost of materials.
• the energy storage molecular material is a relatively low molecular weight dielectric crystalline material having a molecular structure.
• Other dielectric materials, e.g. and polymers are also molecular but are characterized by a distribution of molecular weight.
• the present disclosure provides an energy storage molecular material having a general molecular structural formula:
• Cor is a predominantly planar polycyclic molecular system which forms column-like supramolecular stacks by means of ⁇ - ⁇ -interaction
• P is a polarization unit providing polarization
• I is a high-breakdown insulating substituent group
• n is 1 , 2, 3, 4, 5, 6, 7 or 8
• m is 1, 2, 3, 4, 5, 6, 7 or 8.
• the present disclosure provides an energy storage molecular material having a general molecular structural formula: wherein D- moiety is a polarization unit forming column-like supramolecular stacks by means of ⁇ - ⁇ -interaction, I is a high-breakdown insulating substituent group, m is 1, 2, 3, 4, 5, 6, 7 or 8.
• the present disclosure provides a crystal dielectric layer comprising the disclosed energy storage molecular material.
• the present disclosure provides a capacitor comprising a first electrode, a second electrode, and a crystal dielectric layer disposed between said first and second electrodes.
• the electrodes are flat and planar and positioned parallel to each other.
• the crystal dielectric layer comprises the disclosed energy storage molecular material.
• FIG. 1 is a schematic diagram of a capacitor according to an aspect of the present disclosure.
• the present disclosure provides an energy storage molecular material.
• the energy storage molecular material contains three components which carry out different (various) functions.
• the predominantly planar polycyclic molecular systems (Cors) give to the energy storage molecular material an ability to form supramolecules. In turn supramolecules allow forming crystal structure of the crystal dielectric layer.
• the polarization units (P) are used for providing the molecular material with high dielectric permeability.
• polarizability such as dipole polarizability, ionic polarizability, and hyper-electronic polarizability of molecules, monomers and polymers possessing metal conductivity. All polarization units with the listed types of polarization may be used in aspects of the present disclosure.
• the insulating substituent groups (I) provide electric isolation of the supramolecules from each other in the dielectric crystal layer and provide high breakdown voltage of the energy storage molecular material.
• the planar polycyclic molecular system may comprise tetrapirolic macro-cyclic fragments having a general structural formula from the group comprising structures 1-6 as given in Table 1, where M denotes an atom of metal or two protons (2H).
• the planar polycyclic molecular system may comprise planar fused polycyclic hydrocarbons selected from the list comprising truxene, decacyclene, antanthrene, hexabenzotriphenylene, 1.2,3.4,5.6,7.8-tetra-(peri-naphthylene)- anthracene, dibenzoctacene, tetrabenzoheptacene, peropyrene, hexabenzocoronene and has a general structural formula from the group comprising structures 7 - 17 as given in Table 2.
• the planar polycyclic molecular system may comprise coronene fragments having a general structural formula from the group comprising structures 18 - 25 as given in table 3.
• the polarization unit may comprise rylene fragments having a general structural formula from the group comprising structures 33-53 as given in Table 5.
• the polarization unit may be selected from the list comprising doped oligoaniline and p-oligo-phenylene.
• the doped oligoaniline is self-doped oligoaniline with SO3- groups or COO- groups on the phenyl rings of aniline.
• the doped oligoaniline is mix-doped by acid compounds selected from the list comprising alkyl- SO 3 H acid or alkyl-COOH mixed to oligoaniline in oxidized state.
• At least one of the high-breakdown insulating substituent group may be independently selected from the list comprising -(CH 2 ) n -CH 3 ,
• the energy storage molecular material may further comprise at least one linker unit selected from the list comprising the following structures: 54- 63 as given in Table 6, which connect the predominantly planar polycyclic molecular system (Cor) with the polarization units (P).
• the predominantly planar polycyclic molecular system is perylene comprising the polarization units (P) connected to bay positions of perylene structure by linker units (L) where s is equal to 0, 1 , 2, 3, 4, 5, or 6:
• the predominantly planar polycyclic molecular system may be perylene comprising the polarization units (P) connected to apex positions of perylene structure by linker units (L) where s is equal to 0, 1 , 2, 3, 4, 5, or 6:
• the predominantly planar polycyclic molecular system may be perylene of structural formula where P are the polarization units, I are the high-breakdown insulating substituent groups:
• the predominantly planar polycyclic molecular system (Cor) may be perylene of structural formula:
• I are the high-breakdown insulating substituent groups.
• the predominantly planar polycyclic molecular system (Cor) may be perylene of structural formula:
• I are the high-breakdown insulating substituent groups.
• aspects of the present disclosure also include an energy storage molecular material having a general molecular structural formula: wherein D- moiety is a polarization unit forming column-like supramolecular stacks by means of ⁇ - ⁇ -interaction, I is a high-breakdown insulating substituent group, m is 1, 2, 3, 4, 5, 6, 7 or 8.
• D- moiety is a polarization unit forming column-like supramolecular stacks by means of ⁇ - ⁇ -interaction
• I is a high-breakdown insulating substituent group
• m is 1, 2, 3, 4, 5, 6, 7 or 8.
• the D- moiety gives to the energy storage molecular material an ability to form supramolecules. In turn supramolecules allow forming crystal structure of the crystal dielectric layer.
• the D- moiety is used for providing the molecular material with high dielectric permeability.
• the D- moiety may be selected from the list comprising doped oligoaniline and p-oligo-phenylene.
• the doped oligoaniline is self-doped oligoaniline with S03- groups or COO- groups on the phenyl rings of aniline.
• the doped oligoaniline is mix-doped by acid compounds selected from the list comprising alkyl- SO 3 H acid or alkyl-COOH mixed to oligoaniline in oxidized state.
• the energy storage molecular material further comprises at least one linker unit presented in structures 71-80 as given in Table 8, which connect the polarization units (D- moiety) with the high-breakdown insulating substituent group.
• the energy storage molecular material may comprise perylene as the D- moiety and the high-breakdown insulating substituent groups (I) may be connected to bay positions of perylene structure by linker units (L) where s is equal to
• the energy storage molecular material may comprise perylene as the D- moiety and the high-breakdown insulating substituent groups (I) may be connected to apex positions of perylene structure by linker units (L) where s is equal to 0, 1, 2, 3, 4, 5, and 6:
• the energy storage molecular material may have the general structural formula, where m is 1 :
• the energy storage molecular material may have the general structural formula, where m is 2:
• aspects of the present disclosure include a crystal dielectric layer comprising the disclosed energy storage molecular material.
• energy storage molecular material When dissolved in an appropriate solvent, such energy storage molecular material forms a colloidal system (lyotropic liquid crystal) in which molecules are aggregated into supramolecular complexes constituting kinetic units of the system.
• This lyotropic liquid crystal phase is essentially a precursor of the ordered state of the system, from which the crystal dielectric layer is formed during the subsequent alignment of the supramolecular complexes and removal of the solvent.
• a method for making the crystal dielectric layers from a colloidal system with supramolecular complexes may include the following steps: -application of the colloidal system onto a substrate.
• the colloidal system typically possesses thixotropic properties, which are provided by maintaining a preset temperature and a certain concentration of the dispersed phase;
• the degree of the external alignment should be sufficient to impart necessary orientation to the kinetic units of the colloidal system and form a structure, which serves as a base of the crystal lattice of the crystal dielectric layer;
• the molecular planes of the predominantly planar polycyclic molecular system are parallel to each other and the energy storage molecular material forms a three-dimensional crystal structure, at least in part of the crystal. Optimization of the production technology may allow the formation of the single crystal dielectric layer.
• aspects of the present disclosure include a capacitor 100 comprising a first electrode 102, a second electrode 104, and a crystal dielectric layer 106 disposed between said first and second electrodes.
• the crystal dielectric layer 106 comprises the disclosed energy storage molecular material having a general molecular structural formula:
• Such materials may be characterized by a dielectric constant ⁇ between about 100 and about 1,000,000 and a breakdown field E d between about 0.01 V/m and about 2.0 V/nm.
• the electrodes may be made of any suitable conductive material, e.g., metals, such as
• one or both electrodes may be made of a foamed metal, such as foamed Aluminum.
• the electrodes 102,104 may be flat and planar and positioned parallel to each other.
• the electrodes may be planar and parallel, but not necessarily flat, e.g., they may coiled, rolled, bent, folded, or otherwise shaped to reduce the overall form fact of the capacitor. It is also possible for the electrodes to be non-flat, non-planar, or non-parallel or some combination of two or more of these.
• a spacing d between the electrodes 102, 104 which may correspond to the thickness of the crystal dielectric layer 106 may range from about 1 ⁇ to about 10 000 ⁇ .
• the electrodes may have the same shape as each other, the same dimensions, and the same area A.
• the area A of each electrode 102,104 may range from about 0.01 m 2 to about 1000 m 2 .
• electrodes up to, e.g., 1000 m long and 1 m wide are manufacturable with roll-to-roll processes similar to those used to manufacture magnetic tape or photographic film.
• the capacitance C of the capacitor 100 may be approximated by the formula:
• the energy storage capacity U is determined by the dielectric constant ⁇ , 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 2X10 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.
• the example describes a method of synthesis of porphyrin - (phenyl - perylene diimide)4-compound (TPP-PDI4) represented by the general structural formula / and comprising fragments represented by structural formulas 6 and 35 (Tables 1 and 5),
• the method comprises several steps.
• porphyrin - phenyl - perylene diimideV compound (TPP-PDI 4 ) represented by the general structural formula / was carried out.
• TPP-PDI 4 phenyl - perylene diimideV compound represented by the general structural formula /
• 510,15,20-Tetrakis(p-aminophenyl)po hyrin (50 mg, 0.074 mmol), PIA (334 mg, 0.36 mmol) and imidazole (3.0 g) are added to 10 ml of pyridine.
• the reaction mixture was heated to reflux under dry nitrogen for 2 days with stirring.
• the reaction is slow (monitored by MALDI) and additional PIA (252 mg, 0.28 mmol) was added.
• TPP-PDI 4 The synthesis of TPP-PDI 4 have been performed according with known literature procedures (see, 1.) van der Boom, T.; Hayes, R. T.; Zhao, Y.; Bushard, P. J.; Weiss, E. A.; Wasielewski, M. R. J. Am. Chem. Soc. 2002, 124, 9582; 2.) M.J. Ahrens, L.E. Sinks, B. Rybtchinski, W. Liu, B.A. Jones, J.M. Giaimo, A.V. Gusev, A.J. Goshe, D M. Tiede, M R. Wasielewski, J. Am. Chem. Soc, 2004, 126, 8284).

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• Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
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