TW201640536A - Energy storage device - Google Patents

Abstract

Embodiments of a high-permittivity, low-leakage energy storage device, such as a capacitor, and methods of making the energy storage device are disclosed. The disclosed device includes electrically conductive first and second electrodes, and a sterically constrained dielectric film disposed between the first and second electrodes. The sterically constrained dielectric film comprises a plurality of polymeric molecules, and at least some of the polymeric molecules are bound to the first electrode. The disclosed device may include an insulative layer between the first electrode and the dielectric film and/or between the second electrode and the dielectric film.

Description

Energy storage device Cross-reference to related applications

The present application claims the benefit of U.S. Patent Application Serial No. 14/574,175, filed on Dec. 17, 2014, which is incorporated herein by reference. This document is incorporated by reference in its entirety. This application is also a continuation-in-part of U.S. Patent Application Serial No. 14/156,457, filed on Jan. 16, 2014, which is hereby incorporated by reference. The right to incorporate each of the foregoing is incorporated herein by reference. This application is also a continuation of the U.S. Patent Application Serial No. 14/490,873, filed on Sep. 19, 2014, which is incorporated herein by reference. Part of the continuation case, which was filed on November 7, 2012, and is part of the continuation of US Patent Application No. 13/671,546, which was filed on August 30, 2012. Part of the continuation of No. 13/599,996, which was filed on January 21, 2014, is U.S. Patent No. 8,633,289, the entire disclosure of which is incorporated herein by reference.

The present disclosure relates to embodiments of high permittivity, low leakage energy storage devices, such as capacitors, and to methods of fabricating the energy storage devices.

Electrostatic capacitors are an energy storage method that has not been widely used for large amounts of electrical energy storage. In general, the charging and discharging mechanisms of conventional electrostatic energy storage in dielectric materials range from a few picoseconds to hundreds of microseconds in the time domain. More dense energy storage is required in both the energy density per unit mass and the energy density per unit volume.

The present disclosure relates to embodiments of high permittivity, low leakage energy storage devices, such as capacitors, and to methods of fabricating the energy storage devices. An embodiment of the energy storage device includes: a conductive first electrode; a conductive second electrode; and a space-limited dielectric film disposed on the conductive first electrode and the conductive second Between the electrodes, the space constrained dielectric film comprises a plurality of polymeric molecules. The energy storage device has an energy storage capacity, and the energy storage capacity is at least 1 Wh/kg when the energy storage device is not charged and/or discharged, and is only disposed on the conductive first electrodes and the first The weight of the space-limited dielectric film between the two electrodes is based. In some embodiments, an insulating layer is disposed on the conductive first electrode, the conductive second electrode, or both of the conductive first and second electrodes. In any or all of the above embodiments, the polymerizable molecules may have one or more polar functional groups, ionizable functional groups, or a combination of the foregoing. In any or all of the above embodiments, at least 1% of the polymerizable molecules may be bonded to the first electrode or to an insulating layer disposed on the first electrode. In any or all of the above embodiments, the polymerizable molecules may be protein molecules. In any or all of the above embodiments, the polymerizable molecule can be bonded to at least 1% of the surface of the electrically conductive first electrode that is in contact with the dielectric film.

In certain embodiments, the present invention provides a method of fabricating an energy storage device The method comprises: (a) applying a dielectric film to a conductive first electrode, the dielectric film comprising a film material, wherein the film material (i) is electrically insulating and/or exhibits high permittivity And (ii) comprising a plurality of polymerizable molecules; (b) contacting the dielectric film with a conductive second electrode; and (c) applying an electric field across the first electrode, the dielectric film, and the first Two electrodes to manufacture the energy storage device. In a specific embodiment, the method further includes: applying an insulating layer to the conductive first electrode to form a composite first electrode; and coating the dielectric film to the composite first electrode The insulating layer. In any or all of the above embodiments, the electric field can be greater than 100 V/cm. In any or all of the above embodiments, the polymerizable molecules may be protein molecules.

In some embodiments, the present invention provides a method of fabricating an energy storage device comprising: (a) applying a dielectric film to a conductive first electrode, the dielectric film comprising a film material, The film material (i) is electrically insulating and/or exhibits high permittivity and (ii) includes a plurality of polymerizable molecules having one or more polar functional groups, ionizable functional groups, or the foregoing a combination of (b) contacting the dielectric film with a second conductive electrode, and (c) bonding at least some of the polymeric molecules to the conductive first electrode to form a space-receiving The dielectric film is limited to manufacture the energy storage device. Bonding at least some of the polymeric molecules to the electrically conductive first electrode comprises: (i) applying an electric field across the first electrode, the dielectric film, and the second electrode, such that the first The electrode is a positive electrode, the electric field is applied for a period of time effective to bond at least some of the polymeric molecules to the first electrode, and (ii) the dielectric is treated with a chemical agent Membrane, or (iii) a combination of the foregoing.

In any or all of the above embodiments, the electric field can be at least 0.001 V/μm based on the average thickness of the dielectric film. In some embodiments, the electricity The field is 0.005 to 1 V/μm and the effective time period is from 1 second to 30 minutes.

In any or all of the above embodiments, the method may further include: applying an insulating layer to the conductive first electrode to form a composite first electrode; and coating the dielectric film To the insulating layer of the composite first electrode. In one embodiment, bonding at least some of the polymeric molecules includes applying the electric field across the composite first electrode, the dielectric film, and the second electrode for an effective period of time, thereby At least some of the polymeric molecules are bonded to the insulating layer of the composite first electrode. In a separate embodiment, treating the dielectric film with a chemical agent includes applying a radical initiator to the insulating layer before applying the dielectric film to the insulating layer. And activating the radical initiator after applying the dielectric film to the insulating layer, thereby bonding at least some of the polymerizable molecules to the insulating layer of the composite first electrode. In a separate embodiment, treating the dielectric film with a chemical agent comprises: (i) derivatizing the polymerizable molecules with a derivatizing agent to provide an insulating layer capable of crosslinking to the composite first electrode a functional group, (ii) incorporating a crosslinking agent into the film material of the dielectric film, (iii) incorporating a radical initiator into the film material of the dielectric film, and Activating the radical initiator after applying the dielectric film to the insulating layer, (iv) applying a radical initiator to the insulating layer before applying the dielectric film to the insulating layer And activating the radical initiator after applying the dielectric film to the insulating layer, and (v) applying a plasma to the insulating layer before applying the dielectric film to the insulating layer, Or (vi) any combination of the foregoing. In any or all of the above embodiments, the insulating layer may comprise polymerized p-xylylene.

In any or all of the above embodiments, the polymerizable molecules may include: protein, parylene, acrylic acid polymer, methacrylic acid. (methacrylic acid) polymer, polyethylene glycol, urethane polymer, expoxy polymer, silicone polymer, terpenoid A polymer, a naturally occurring resin polymer, a polyisocyanate, or a combination of the foregoing. In any or all of the above embodiments, the polymeric molecules may comprise proteins or derivatized proteins.

In any or all of the above embodiments, the conductive second electrode may be a composite second electrode including an insulating layer, and the composite second electrode is positioned such that the insulating layer contacts the Dielectric film. In any or all of the above embodiments, applying the dielectric film to the conductive first electrode may include: forming the dielectric film on a removable carrier film; removing the Removing the carrier film; and applying the dielectric film to the conductive first electrode.

In any or all of the above embodiments, the polymerizable molecules may be formed in situ. In these embodiments, the method further comprises: coating a composition to the first electrode, the composition comprising a crosslinking agent and a plurality of polymeric molecular precursors, the polymeric molecular precursors comprising one or More polar functional groups, ionizable functional groups, or a combination of the foregoing; and activating the crosslinker to crosslink the polymeric molecular precursors to provide a plurality of polymeric molecules Dielectric film. In certain embodiments, the polymeric molecular precursors comprise: (i) an amino acid molecule, (ii) an oligopeptide, (iii) a polypeptide, or (iv) a combination of the foregoing. In certain embodiments, the polymeric molecular precursors further comprise a para-xylene monomer.

In a separate embodiment, the present invention provides a method of making an energy storage device comprising: (a) providing a first polymer sheet or roll having a metallized surface And including an insulating layer on the metallized surface, wherein the insulating layer does not completely cover the metallized surface, such that an edge portion of the metallized surface is not covered; (b) applying a dielectric film to The insulating layer, the dielectric film comprising a film material (i) being electrically insulating and/or exhibiting high permittivity and (ii) comprising a plurality of polymerizable molecules having one or more polarities a functional group, an ionizable functional group, or a combination of the foregoing; (c) contacting a second metallized polymer sheet or roll with the dielectric film, the second sheet or roll having a metallized surface comprising an insulating layer on the metallized surface, wherein the insulating layer does not completely cover the metallized surface, such that an edge portion of the metallized surface is not covered, wherein the second thin sheet or The roll is oriented such that the insulating layer contacts the dielectric film and the uncovered edge portion of the second sheet or roll is adjacent to the uncovered edge portion of the first sheet or roll In order to form a composite a layered surface; (d) winding the composite multilayer surface into a rolled configuration, or cutting and stacking portions of the composite multilayer surface to form a stacked configuration; (e) the first The uncovered edge portion of the sheet or roll and the uncovered edge portion of the second sheet or roll are bonded to a conductor cover or a non-conductor support having an electrical connection a conductor polymer; (f) electrically connecting the composite multilayer surface to a positive electrode and a negative electrode; and (g) applying an electric field to the multilayer composition, the electric field being applied to maintain an effective period a time period for bonding at least some of the polymeric molecules to the insulating layer of the first sheet or roll, the insulating layer of the second sheet or roll, or both.

In a separate embodiment, the present invention provides a method of fabricating an energy storage device comprising: (a) providing a first electrode in a containment device having an upper surface including an insulating layer; Positioning a perforated non-conductor separator sheet at the first electrode (c) positioning a second electrode on the separator sheet, the second electrode having a lower surface including an insulating layer, such that the insulating layer of the second electrode contacts the separator sheet; Adding a dielectric material for filling a space inside the apertured separation sheet and for contacting the first electrode and the second electrode, wherein the dielectric material (i) is electrically insulating and/or presenting High permittivity and (ii) comprising a plurality of polymeric molecules having one or more polar functional groups, ionizable functional groups, or a combination of the foregoing; and (e) spanning by application of an electric field The first electrode, the dielectric material, and the second electrode are such that the first electrode is a positive electrode and at least some of the polymerizable molecules are bonded to an insulating layer of the first electrode. The application is maintained for an effective period of time to bond at least some of the polymeric molecules to the insulating layer of the first electrode.

The foregoing and other objects, features and advantages of the present invention will become more apparent from the <RTIgt;

100‧‧‧ energy storage device

110‧‧‧ positive electrode

112‧‧‧ outer surface of the first/positive electrode

115‧‧‧Conductor wire

120‧‧‧ Space-constrained dielectric layer

122‧‧‧ Polymeric molecules

124‧‧‧ Attachment

126‧‧‧ Attachment

130‧‧‧negative electrode

132‧‧‧ outer surface of the second/negative electrode

135‧‧‧Conductor wire

140‧‧‧Insulation

150‧‧‧Insulation

200‧‧‧ energy storage device

210‧‧‧ positive electrode

215‧‧‧Conductor wire

220‧‧‧ Space-constrained dielectric layer

222‧‧‧ Polymeric molecules

223‧‧‧ Polymeric molecules

224‧‧‧ Polymeric molecules

225‧‧‧ Attachment

226‧‧‧ Attachment

230‧‧‧negative electrode

235‧‧‧Conductor wire

240‧‧‧Insulation

250‧‧‧Insulation

300‧‧‧ energy storage device

310‧‧‧electrode

320‧‧‧ Space-constrained dielectric layer

325‧‧‧Substrate

326‧‧‧The edge of the substrate

330‧‧‧Conductor polymer

340‧‧‧Cover/bracket

345‧‧‧Electrical cable

350‧‧‧Cover/bracket

355‧‧‧Electrical cable

400‧‧‧ energy storage device

410‧‧‧electrode

412‧‧‧Insulation

415‧‧‧Conductor wire

420‧‧‧electrode

422‧‧‧Insulation

425‧‧‧Conductor wire

430‧‧‧Non-conductor separator

440‧‧‧ dielectric materials

450‧‧‧protection box

1 is a schematic diagram of an exemplary energy storage device.

2 is a schematic cross-sectional view of an exemplary energy storage device.

3 is a schematic illustration of another exemplary energy storage device.

Figure 4 is a schematic exploded view of an exemplary energy storage device having a rolled configuration.

Figure 5 is a schematic exploded view of an exemplary energy storage device including a perforated divider.

Figure 6 is a cross-sectional side view of the energy storage device of Figure 5.

Figure 7 is an energy storage device made by an embodiment of the method disclosed by the present invention. Optical micrograph of the negative electrode in the middle.

Figure 8 is an optical photograph of a positive electrode in the energy storage device of Figure 7.

Fig. 9 is an optical photograph of the negative electrode of Fig. 7 after washing with tap water.

Fig. 10 is an optical photograph of the positive electrode of Fig. 8 after washing with tap water.

Figure 11 is an optical photograph of the negative electrode of Figure 9 taken from a certain angle.

Figure 12 is an optical photograph of the positive electrode of Figure 10 taken from a certain angle.

Figure 13 is an optical photograph of the positive electrode of Figure 10 after manual scraping to remove the bonded polymeric molecules.

The present disclosure relates to an embodiment of an energy storage device comprising a dielectric material comprising a polymerizable molecule, wherein at least some of the polymeric molecules are bonded to an electrode of the energy storage device And the present disclosure is also related to methods of making such energy storage devices. The energy storage devices store energy through an electrostatic type of charging/discharging mechanism, for example, similar to an electrostatic capacitor. Embodiments of such energy storage devices can be used in the electronics field, in bulk electrical storage, and any other device that may or may not use to store electrical energy.

I. Definition

The following terms and abbreviations are provided to better explain the present disclosure and to guide those skilled in the art to practice the present disclosure. As used herein, unless expressly stated otherwise, the meaning of "include" is "include" and the singular "a" or "the" includes the plural. Unless otherwise expressly stated in the text, the word "or" is used. A single element of a plurality of the alternative elements or a combination of two or more elements is indicated.

Unless otherwise explained, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art. Methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present disclosure; however, suitable methods and materials are described below. The materials, methods, and examples are illustrative only and are not intended to be limiting. Other features of the present disclosure will become apparent from the following detailed description and claims.

Unless otherwise indicated, all numbers expressing quantities of devices, voltages, temperatures, <RTI ID=0.0> </ RTI> </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> in the specification or claims are to be understood as being modified by the term "about." Accordingly, the numerical parameters set forth are approximations, which may be dependent upon the desired characteristics sought and/or standard test conditions known to those skilled in the art, unless otherwise indicated. The detection limit under the specification of the method. When the embodiments of the present invention and the prior art discussed above are directly and clearly distinguished, the embodiment number is not an approximation unless the term "about" is used.

To assist in reviewing various embodiments of the present disclosure, the present invention provides an explanation of the following specific terms:

Capacitor: An energy storage device comprising two conductor plates separated by a substantially non-conducting material, the substantially non-conductor material being referred to as a dielectric. The value of the capacitance of the capacitor, or the value of the storage capacity, depends on the size of the plates, the distance between the plates, and the characteristics of the dielectric. The relationship is shown in Equation 1 below: Where e0 = vacuum permittivity (8.8542x10 ^-12 F/m), er = relative permittivity (defined below), A = plate surface area (two plates have the same size), and d = two plates the distance between.

Dielectric material: An electrical insulator that can be polarized by an applied electric field. As used herein, the term "dielectric material" means a material comprising a plurality of polymeric molecules comprising one or more polar functional groups and/or ionizable functional groups.

Dielectric breakdown voltage: The dielectric material will "crash" at this point and turn on the current. The dielectric breakdown voltage is an indicator of the dielectric strength of a material.

Derivatized: As used herein with reference to a polymer, the term "derivatization" refers to a polymer to which a functional group has been added via chemical modification. For example, the protein can be derivatized with maleic anhydride to impart a maleic acid functional group to the protein.

Electrical Insulation or Insulator: Insulation is a material in which the internal charge does not flow arbitrarily, and therefore, the material conducts only little or no current. A well-established system, a perfect insulator does not exist. As used herein, the term "electrically insulating material" refers to a material that is primarily insulating, that is, a critical collapse electric field that exceeds that applied across the material during normal use as a capacitor. The material of the electric field, therefore, can avoid electrical collapse during normal use.

Electrode: As used herein, the term "electrode" refers to an electrical conductor (for example, metal); or, it refers to a "composite" electrode that includes an electrical conductor and is located on the surface of the electrical conductor. Non-conductor material.

Functional group: A specific atomic group within a molecule that is responsible for the characteristic chemical reactions and/or electrostatic interactions of the molecule. Exemplary functional groups include, but are not limited to, halogen (fluoro, chloro, bromo, iodo) groups, epoxides, hydrozyl, carbonyls (ketones) , formaldehyde group, carbonate ester, carboxylate, ether, ester, peroxy, peroxidation Hydroperoxy, carboxamide, amine (primary, secondary, tertiary), ammonium, amide, sulfhydryl Imide, azide, cyanate, isocyanate, thiocyanate, nitrate, nitrite group (nitrite), nitrile group, nitroalkane, nitroso group, pyridyl group, phosphate group, sulfonyl group, sulfur Sulfide, thiol (sulfhydryl), and disulfide. Polar functional groups do not form ions in the environment of use, but instead, they provide partial separation of positive and negative electrical charges within the molecule. The ionizable functional group is then a functional group in an ionized state in the environment (for example, -COOH relative to -COO ^- , -NH ₃ relative to NH ₄ ⁺ ).

Insulation/Coating or Non-Conductor/Coating: As used herein, the terms “insulating layer”, “insulating coating”, “non-conducting layer”, and “non-conducting coating” mean a kind of From the standpoint of ohmic conductivity, it is an electrically insulating material layer or coating, that is, the material has an ohmic conductivity of less than 1 x 10 ^-1 S/m (1 x 10 ^-1 Siemens per meter).

Parylene (parylene): poly-p-xylene (polymerized p-xylylene), also known as Puralene ^TM polymer, a poly-substituted or p-xylene. Polyparaxylene conforms to the following chemical formula:

Permittivity : As used herein, the term "permittivity" refers to the ability of a material to become polarized, thereby changing the "dielectric constant" of its spatial volume to a value above vacuum. Measuring a value of the relative permittivity of the dielectric constant of the material divided by its dielectric constant static vacuum, as shown in Equation 2 below: Where e _r = relative permittivity, e _s = measured permittivity, and e ₀ = vacuum permittivity (8.8542x10 ^-12 F/m). The relative permittivity of the vacuum is 1, while the relative permittivity of water is 80.1 (at 20 ° C), and the organic coating typically has a relative permittivity of 3 to 8. In general, the term "high permittivity" means a material having a relative permittivity of at least 3.3. As used herein, the term "high permittivity" also refers to a material whose permittivity is increased by at least 10% using a permittivity enhancement technique, for example, immersed in an electric field.

Oligo: A preface with a "small". For example, an oligopeptide may comprise from 2 to 20 amino acids joined together via a guanamine group linkage, while a polypeptide may contain more than 20 amino acids. The oligopeptide comprises a dipeptide, a tripeptide, a tetrapeptide, a pentapeptide, ... and the like.

Polarity: The term "polarity" means a compound or a functional group in a compound in which electrons are not equally shared among the atoms, that is, a region of positively charged charge and a region of negatively charged charge. Being permanently separated.

Polypeptide: A polymer having more than 20 amino acids bonded together via a guanamine group bond. The term polypeptide is intended to encompass naturally occurring polypeptides as well as synthetically produced polypeptides.

Polymer/Polymerizable Molecule: A molecule having a plurality of repeating structural units (for example, monomers) formed by a chemical reaction (i.e., multimerization).

Space-constrained dielectric film: As used herein, the term "space-constrained dielectric film" refers to an electrically insulating and/or high-permittivity dielectric film comprising a plurality of polymeric molecules. , having one or more polar functional groups, ionizable functional groups, or a combination of the foregoing, wherein the space of at least some of the polymeric molecules is limited, that is, the polymerizations At least some of the molecules are restricted such that the entire polymerizable molecule cannot physically move within the dielectric material. A space limitation occurs when a portion of the polymerizable molecule is bonded to the surface of the electrode in contact with the dielectric film. The polymeric molecule can be bonded to the electrode surface by an embodiment of the methods disclosed herein.

II. Energy storage device with space-limited dielectric film

An embodiment of an energy storage device includes two conductor surfaces (electrodes) that are substantially parallel to each other and a space-limited dielectric film between the conductor surfaces. The device can further include an insulating layer or coating on one or both of the electrodes. The dielectric material includes a plurality of polymeric molecules, at least some of which are bonded to one of the electrodes or an insulating layer bonded to the electrode.

A. Electrode

In some embodiments, the electrodes are planar or substantially planar. Each electrode can independently have a smooth surface or a rough surface. For example, a rough electrode can be prepared with carbon particles that give the electrode a surface area that is much higher than a smooth electrode (eg, an electrode made of polished metal). The amount of surface roughness selected may depend, at least in part, on the desired external electrical parameters of a given energy storage device or capacitive device. Compared to an energy storage device including a smooth electrode, a similar energy storage device including a rough electrode will have a faster charging and discharging ampere in a short period of time (for example, several microseconds to milliseconds). The number (for example, 100 times faster) will then have a slower discharge rate that is similar to the discharge rate provided by the energy storage device with smooth electrodes.

B. Insulation

Each of the electrodes may be coated with an insulating (non-conducting) layer or coating on one or more surfaces. An electrode with an insulating coating will be referred to as a "composite electrode." In the energy storage device, the composite electrode is oriented such that the insulating layer contacts the dielectric material. The insulating layer provides high insulating properties to the electrode and provides a bonding site for the dielectric material to be added. The insulating layer has an ohmic conductivity of less than 1 x 10 ^-1 S/m. In certain embodiments, the insulating layer has an ohmic conductivity of less than 1 x 10 ^-2 S/m, less than 1 x 10 ^-5 S/m, or less than 1 x ^{10 -10} S/m. In a particular embodiment, the ohmic conductivity is from 1 x 10 ^-25 S/m to 1 x 10 ^-1 S/m, from 1 x ^{10 -10} S/m to 1 x 10 ^-1 S/m or from 1 x 10 ^-5 S/m to 1 x 10 ^-1 S/m. The thickness of the coating can range from a few nanometers to greater than 10 microns. In some embodiments, the insulating layer has an average thickness of from 5 nm to 10 μm, for example, from 0.1 to 10 μm, from 0.3 to 10 μm, from 0.3 to 5 μm, or from 0.3 to 2 μm. In one embodiment, the outer surface of the second electrode is measured from the outer surface of the first electrode, the coating having an average thickness that is less than 10% of the total thickness of the capacitor. The insulative coating can be applied by any convenient means including, but not limited to, vapor deposition, liquid spray, and other techniques known to those skilled in the art of coating. An exemplary insulating coating is a polymeric para-xylene, such as the Puralene ^(TM) polymer coating as disclosed in US 2014/0139974.

The insulating layer can be modified with a suitable comonomer to provide a high permittivity and/or to provide an attachment site for the polymerizable molecules of the dielectric material. In certain embodiments, the comonomers comprise one or more unsaturated bonds. For example, one that includes poly-p-xylene The edge layer may be modified by incorporating a comonomer comprising, but not limited to, an olefin, an ethylene derivative, an alkynyl derivative, a propylene compound, An allyl group compound, a carbonyl group, a cyclic ether, a cyclic acetal, a cyclic amide, an oxazoline, and combinations thereof. In certain embodiments, the comonomers are: acrylic acid (for example, 2-carboxylethyl acrylate), methyl acrylate (for example, 3-trimethyloxane) 3-(trimethoxysilyl)propyl methacrylate), α-pinene, R-(-) carvone (R-(-)carvone), linalool , cyclohexene, dipentene, α-terpinene, R-(+)-limonene (R-(+)-limonene), and combinations of the foregoing. The copolymers may comprise alternating monomers or may be in the form of a block copolymer.

C. Dielectric material including polymerizable molecules

Some embodiments of the energy storage device comprise a dielectric film comprising a single layer of dielectric material, while other embodiments comprise a dielectric film comprising a plurality of layers of dielectric material. The multilayer dielectric material can be formed using a single material that is deposited multiple times with or without surface modification between the depositions. Alternatively, each layer can have a different chemical composition. In some embodiments, the device is constructed to have a dielectric film comprising two or more dielectric layers having different permittivity. The dielectric film may have an average thickness ranging from a few microns to a few millimeters. In certain embodiments, the dielectric film has an average thickness of from 10 μm to 5 mm, for example, from 10 μm to 1 mm, from 10 μm to 500 μm, or from 50 μm to 250 μm. In certain embodiments, the dielectric film has an average thickness of from 80 μm to 120 μm, for example, an average thickness of 100 μm.

In certain embodiments, the dielectric material has a liquid character and is viscous similar to honey or larger. In a particular embodiment, the dielectric material has a viscosity from 10,000 cP to 250,000 cP. In a separate embodiment, the dielectric material is a solid.

The dielectric material may be substantially free of any conductivity; in other words, the dielectric material does not undergo any oxidation/reduction at or near any of the electrodes and does not exhibit ohmic conductivity. Therefore, the embodiments of the energy storage device disclosed by the present invention are not conventional electrochemical cells, and conversely, they are similar in relation to electrostatic capacitors. However, the dielectric material can store a greater amount of specific energy than a conventional electrochemical cell or electrostatic capacitor for a long period of time.

In some embodiments, the energy storage device comprises a non-conducting high permittivity dielectric material. Two non-limiting examples of non-conducting high permittivity dielectrics are the zein in the shellac matrix and the protein derived from maleic anhydride. In other embodiments, the dielectric material is a conductor; in such embodiments, the electrodes are typically coated with an insulating layer as described above to reduce or prevent ohmic conduction. For example, an insulating layer can be used when the dielectric material has a resistance of less than 2.5 MΩ per square centimeter. In some embodiments, the energy storage device comprises a dielectric material having a permittivity of at least 10 to 2,000,000 and an ohmic conductor coefficient of from 1 S/m to 1 x 10 ^-25 S/m.

Embodiments of the energy storage device disclosed herein comprise a dielectric material comprising polymerizable molecules having polar and/or ionizable functional groups leading to intramolecular dipoles and dipole moments . The polymeric molecules may further comprise one or more double bonds. In some embodiments, the dielectric material is a thin film that contacts the two electrodes of the energy storage device. Generally, the contact can be described as a direct physical contact between the film and the entire contact surface of the electrode. The dielectric material can be in contact with a "naked" metal or a carbon-based electrode surface or an insulating layer of a composite electrode.

In certain embodiments, the polymeric molecules are polar polymers. Proteins are inexpensive polar polymers that are readily available and have low toxicity. Low toxicity is an important advantage over other polymers and allows these energy storage devices to be recycled or incinerated. The protein molecule comprises an amino acid having a polar and/or ionizable functional group. Other suitable polymers include, but are not limited to, substituted (fluorinated) and unsubstituted para-xylene polymers, acrylic polymers, methacrylic polymers, polyethylene glycols, urethanes Polymers, epoxy polymeres, oxime polymers, organic terpene polymers, natural organic polymers (for example, resins such as shellac), polyisocyanates, and combinations of the foregoing. Copolymers such as the following are also within the scope of the disclosure: acrylic copolymers, for example, copolymers having ethylene butyl acrylate, copolymers having ethyl acrylate, and copolymerization with methacrylate And a parylene copolymer, for example, a para-xylene copolymer having acrylic acid (for example, 2-carboxyethyl acrylate), a para-xylene copolymer having methacrylic acid (for example) , 3-trimethyloxonium propyl methacrylate), α-pinene, R-(-) carvone, linalool, cyclohexene, dipentene, α-terpinene, R- (+) - Lemon olein, and combinations of the foregoing. Non-limiting examples of polar polymers include: maize protein, hemp protein, wheat gluten, polyacrylic acid-maleic acid copolymer, polyacrylic acid, whey protein isolated (whey protein) Isolates, soy protein isolates, pea protein extracts, shellac, and combinations of the foregoing.

In certain embodiments, the polymeric molecules are derivatized to attach additional functional groups, for example, to help bond the polymeric molecules to a bare electrode surface (ie, bare metal or carbon). Surface) or a functional group that is bonded to the surface of a composite electrode. Exemplary derivatizing agents include, but are not limited to, anhydrides; carbonized diimine (carbodiimide); imidoester; and a reagent comprising the following combination: N-hydroxysuccinimide and maleimide, aromatic stack An aryl azide or a diazide group. In certain instances, the polymer is derivatized with an anhydride, for example, maleic anhydride, itaconic anhydride, cis-4-cyclohexene-1,2-dicarbonic anhydride (cis 4-cyclohexene-1,2-dicarboxylic anhydride), or cis-5-norbornene-end-2,3-dicarboxylic anhydride. A derivatized polymerizable molecule can be bonded to the surface by crosslinking or other reaction with the surface of the electrode. For example, when a polymerizable molecule is derivatized with maleic anhydride, the derivatized polymerizable molecule is crosslinked via the double bonds. Crosslinking can be carried out by any convenient means, for example, a chemical agent (for example, a free radical initiator), ultraviolet light activation, or heat activation.

The inventors of the present invention unexpectedly found that although the polymerizable molecules are not free to move between the electrodes; however, the polymerizable molecules having the above characteristics can be used for energy storage when space is limited. The polymerizable molecule may bond the polymerizable molecules to a bare electrode by any means before charging and/or discharging an energy storage device including the composite electrode and the dielectric material including the polymerizable molecules. The surface is either space-limited to the non-conductor or insulating coating of the electrode, and the means include: covalent bonds (single or multiple bonds), van der Waals forces, or Hydrogen bonding. In certain embodiments, the polymeric molecules are bonded to a positive electrode. When the energy storage device is charged and discharged during subsequent use, the polymeric molecules remain bonded to the electrode, for example, when the energy storage device is subsequently used in an electronic circuit.

In an energy storage device comprising a dielectric material, one is added from the electrode The external electric field can cause disintegration of the lowest energy state that can be obtained from the current position of an ion or dipole in the layer of dielectric material. Therefore, when the electric field is applied, the dipole or ion is moved from its resting position (that is, its position before the electric field is applied), and then it causes the material to be Rearrangement of charge distribution. This causes other rearrangements of all other dipoles to continue throughout the dielectric material. Energy that is not converted to heat is absorbed by the dielectric material. When this energy is released, the reverse process of this process occurs, provided that the stored energy is not released via other mechanisms (eg, elevated thermal motion (which is a random molecular motion proportional to temperature)) .

Because it does not want to be bound by any special theory of operation, it is said that in a large molecule, only a part of the movement of the molecule will occur, and the other parts of the molecule are firmly restrained in the original place. Avoid moving all to a lower energy level and subsequent release of potential energy will be coupled to the electrode without being released into thermal motion. This movement limiting condition reduces the degree of freedom in the dielectric molecule and, as a result, reduces the ability of the molecule to dissipate energy absorbed from the electric field into heat. Therefore, a bonded polymerizable molecule is coupled to the electric field such that the polymerizable molecule cannot release energy in the form of heat because of its low degree of freedom. The movement of specific parts of a giant molecule is related and similar to the electrophoretic movement known to those who use such techniques to analyze biological giant molecules.

Because it is not intended to be bound by any particular theory of operation, it is believed that when a portion of the polymer is bonded to the electrode (or a coating that is bonded to the electrode), it is polar and/or ionizable. When the functional group realigns in response to an electric field, the remainder of the polymer may stretch, twist, or bend within the dielectric film. Changes in these configurations and locations store energy in the energy storage device. When the energy storage device is discharged, it has been stored The energy is released as electrical energy when the bonded polymer molecules return to the lower order configuration. When at least some of the polymerizable molecules in a dielectric material comprising a polymerizable molecule have a low degree of freedom, the dielectric material is referred to as a "space-constrained dielectric film."

Accordingly, embodiments of the energy storage device disclosed herein comprise a space constrained dielectric material comprising polymerizable molecules. In certain embodiments, at least 1%, at least 10%, at least 25%, at least 50%, at least 80%, or at least 90% of the polymeric molecules in the space constrained dielectric material It will be bonded to an electrode, and in a particular embodiment, at least some of the polymeric molecules are bonded to the positive electrode. When the electrode is a composite electrode, the polymerizable molecules are bonded to the insulating layer of the composite electrode. The percentage of bond can be predicted by measuring the amount of polymerizable molecules that are washed out of the electrode after at least some of the polymerizable molecules are bonded to the electrode.

In certain embodiments, the polymeric molecule will be bonded to at least 1%, at least 25%, at least 50%, at least 80%, or at least 90% of the surface of the positive electrode contacting the dielectric material. The percentage of the surface covered by the bonded polymer can be visually predicted, for example, by optical microscopy. After the energy storage device is manufactured, the device can be disassembled for inspection. The positive electrode will be rinsed, for example, by exposure to tap water to remove unbonded material and then inspected by an optical microscope. The area of the surface covered by the bonding polymer and the area without the bonding polymer can be easily distinguished.

The bond between the polymerizable molecule and the electrode is very strong enough to withstand sporadic damage. For example, the use of tap water to rinse the electrode and the bonded polymerizable molecule is equivalent to water falling from a height of one meter. Or, manually scrubbing the bonded polymeric molecules under tap water will have a force of less than 20N. Bonds with this strength are only making an energy store An electric field has been applied across the device to observe the device. In some embodiments, at least some of the bonds can be interrupted by applying an external voltage of opposite polarity to the device such that the positive electrode becomes negative.

D. Exemplary energy storage device

In some embodiments, an energy storage device 100 includes a positive electrode 110, a space-limited dielectric layer 120, and a negative electrode 130 (FIGS. 1, 2). The positive electrode 110 and the negative electrode 130 may independently be a conductor metal, a semiconductor, a conductor polymer, or other conductive material. In certain cases, this material may be advantageous for a high surface area conductor, such as a carbon based or graphene type electrode. The space constrained dielectric layer 120 includes a film material (i) that is electrically insulating and/or exhibits high permittivity and (ii) includes a plurality of polymerizable molecules 122 that contain polar functionalities a group and/or an ionizable functional group. The polymeric molecules may also contain one or more double bonds. Optionally, an insulating layer 140, 150 may be disposed between the positive electrode 110 and the dielectric layer 120 and/or between the dielectric layer 120 and the negative electrode 130. In some embodiments, the outer surface 132 of the second electrode 130 is measured from the outer surface 112 of the first electrode 110, and the thickness of the insulating layer 140, 150 may be less than 10 of the total thickness of the energy storage device 100. %. An insulating layer can be incorporated to prevent Joule heat and/or ohmic conductor loss during use of the device. At least some of the polymeric molecules 122 are bonded to the positive electrode 110 (or insulating layer 140, if present) through attachment points 124. Each attachment point 124 can be a covalent bond (single bond, double bond, or triple bond), hydrogen bond, van der Waals force, or other bonding force, assuming that the positive electrode 110 remains The strength of the force is sufficient to prevent the polymerizable molecule 122 from being detached from the positive electrode 110 at a positive charge relative to the negative electrode 130. One of the polymerizable molecules 122 Portions may be bonded to the negative electrode 130 (or insulating layer 150, if present) through attachment points 126. Each of the attachment points 126 can be a covalent bond (single bond, double bond, or triple bond), hydrogen bond, van der Waals force, or other bonding force, assuming that the negative electrode 130 remains in a The force is strong enough to prevent the polymerizable molecule 122 from being detached from the negative electrode 130 relative to the negative charge of the positive electrode 110. The positive and negative electrodes 110 and 130 may be attached to a voltage source through conductor leads 115, 135 (for example, conductor wires or other lines).

In a separate embodiment, an energy storage device 200 includes a positive electrode 210, a space-limited dielectric layer 220, and a negative electrode 230 (FIG. 3). The space constrained dielectric layer 220 includes a film material (i) that is electrically insulating and/or exhibits high permittivity and (ii) includes a plurality of polymerizable molecules 222, 223, 224, the polymeric molecules A polar functional group and/or an ionizable functional group is included. The polymeric molecules may also contain one or more double bonds. An insulating layer or non-conductor layer 240, 250 is disposed between the positive electrode 210 and the dielectric layer 220 and between the dielectric layer 220 and the negative electrode 230. A portion of the polymerizable molecules 222 have a polarity and/or ionizable functional group that is a negative or partial negative charge and is bonded to the insulating layer 240 through the attachment point 225. A portion of the polymerizable molecule 223 has a polarity or ionizable functional group that is a positive electric quantity or a partial positive electric quantity, and is bonded to the insulating layer 250 through the attachment point 226. A portion of the polymerizable molecule 224 has at least one polarity or ionizable functional group that is positively charged or partially positively charged and at least one polar or ionizable functional group is a negative or partial negative charge. The polymerizable molecules 224 having a sufficient length may span the distance between the insulating layers 240 and 250 and may be bonded to the two insulating layers. The positive electrode 210 and the negative electrode 230 can be attached through the conductor wires 215 and 235. Connected to a voltage source.

In one exemplary embodiment, an energy storage device has a rolled or stacked dielectric layer configuration. 4 is an exemplary energy storage device 300 having a roll-on configuration of an electrode 310 that includes a space-limited dielectric layer 320 on a substrate 325. A second substrate (not shown) may be positioned at the top end of the dielectric layer 320 such that the space-limited dielectric layer 320 is sandwiched between the two substrates. As shown in FIG. 4, the space constrained dielectric layer 320 does not extend to one of the edges 326 of the substrate 325. The top and bottom of the roll-rolled electrode 310 are bonded to a conductor polymer 330, which may be contained within a cover having electrical connections 345, 355 or a bracket. An optional cuff (not shown) can be placed around the device 300 to provide mechanical and electrical protection during use.

In a separate embodiment shown in FIGS. 5 and 6, an exemplary energy storage device 400 includes two electrodes 410, 420. The electrodes 410, 420 may be conductor sheets. In some examples, the conductor sheets are metal (for example, aluminum) and have a size of about 500 mm ² and a thickness of about 2 mm. Each sheet is covered by a insulating layer are 412, 422 (e.g., Puralene ^TM polymer coating), for generating an electrode. A conductor wire 415, 425 is attached to each of the electrodes 410, 420 and insulated to prevent unwanted conduction in the area in contact with a dielectric material. A non-conductor spacer sheet 430 of approximately the same size as the electrodes is perforated to provide a path for a dielectric material 440 to fill and contact the electrodes 410, 420. In some examples, the separator sheet 430 has a thickness of about 0.5 mm, but depending on the applied voltage, it can also accept a thickness of up to 2 mm and above. The separator sheet prevents the two electrodes 410, 420 from contacting each other and provides a constant separation distance for the two electrodes. The electrodes are assembled into a protective case 450 as shown in FIG. A solid dielectric material or liquid dielectric material 440 is added to fill the space between the electrodes 410, 420. Alternatively, the dielectric material can be applied to the electrodes in advance. Dielectric material 440 includes a plurality of polymeric molecules comprising polar functional groups and/or ionizable functional groups. These polymeric molecules may also contain one or more double bonds. A voltage is applied to the two electrodes to bond at least some of the polymeric molecules to the positive electrode, thereby creating a space constrained dielectric material.

In some embodiments, a similar energy storage device that is not bonded to the first electrode is compared to the polymeric molecules (ie, the dielectric material has no space prior to charging and/or discharging the energy storage device) a limited similar energy storage device) prior to charging and/or discharging the energy storage device (ie, after the energy storage device is manufactured, prior to use of the device, for example, in an electronic circuit) An electric field and/or treatment with a chemical agent to bond at least some of the polymeric molecules to the first electrode improves the permittivity of the space-constrained dielectric material by at least 50%, for example, from 50% to 10,000%, from 50% to 100,000%, from 50% to 1,000,000%, or even from 50% to 10,000,000% and higher. Space-limited control energy compared to a polymer comprising substantially the same chemical composition but without polymer bonding at least some of the polymers to an electrode surface prior to charging and/or discharging the energy storage device Storage Device, embodiments of the energy storage device disclosed herein are capable of storing an amount of energy of at least 100X, 1000X, 10,000X, or even 100,000X. In certain embodiments, the energy storage device disclosed herein can store an energy amount from 100X to 100,000X, for example, from 100X to 10,000X, from 100X to 20,000X, or from 100X, to the comparison energy storage device. To 100,000X. Certain embodiments of the energy storage device disclosed herein have an energy storage capacity of at least 1 Wh/kg, at least 10 Wh/kg, or at least 100 Wh/kg when the energy storage device is not charged and/or discharged. Only to be disposed on the electrically conductive first electrodes and The weight of the dielectric material between the second electrodes is based on, for example, an energy storage capacity of from 1 Wh/kg to 1300 Wh/kg, from 10 Wh/kg to 1300 Wh/kg, or from 100 Wh/kg to 1300 Wh/kg. In a particular embodiment, the energy storage capacity falls within the range of 100 Wh/kg to 1300 Wh/kg. Certain embodiments of the energy storage device disclosed herein have an energy loss of less than 10% per hour, less than 1% per hour, less than 0.5% per hour, or even less than 0.1% per hour. Accordingly, the energy storage device disclosed herein is a durable high energy density capacitor. This high energy density also allows the devices to be fabricated with a dielectric film thicker than other capacitors without sacrificing energy storage.

III. Method of manufacturing an energy storage device

An embodiment of a method for fabricating an energy storage device includes: (a) applying a dielectric film to a conductive first electrode, the dielectric film comprising a film material, the film material (i) being electrically insulated And/or exhibiting a high permittivity and (ii) comprising a plurality of polymeric molecules having one or more polar functional groups, ionizable functional groups, or a combination of the foregoing; (b) The dielectric film contacts a conductive second electrode; and (c) applies an electric field across the first electrode, the dielectric film, and the second electrode to fabricate the energy storage device. When the energy storage device is fabricated, at least some of the polymerizable molecules are bonded to the first electrode by applying the electric field across the first electrode, the dielectric film, and the second electrode, thereby Generating a space-limited dielectric film, wherein at least some of the plurality of polymerizable molecules are bonded to a surface of the first electrode, a surface of the second electrode, or the first electrode and the The surface of both the second electrodes. In some embodiments, a space-limited dielectric film is produced by: (i) applying an electric field across the first electrode, the dielectric film, and the second electrode, such that The first electrode is a positive electrode, and the electric field is applied for a period of time effective for the polymerization At least some of the molecules are bonded to the first electrode, (ii) the chemical film is treated with a chemical agent, or (iii) the combination described above.

A. Dielectric film formation

A dielectric film comprising a film material can be prepared by any suitable means and applied to a conductive first electrode, including: vapor deposition, liquid spray, screen printing, spin coating, or Other methods known to those skilled in the art of film formation. In one embodiment, the conductive first electrode is a bare electrode or a composite electrode including an insulating layer, and the dielectric film is directly formed on the surface of the bare electrode or formed thereon. The insulating layer of the composite electrode. Next, the dielectric film is dried at a low temperature (for example, 25 to 60 ° C) before or after the dielectric film contacts a conductive second electrode. In a separate embodiment, the dielectric film is formed on a removable carrier film (for example, a polytetrafluoroethylene film), dried, and then transferred to the electrode surface.

In certain embodiments, the film material is prepared using a liquid or slurry comprising a solvent and a plurality of polymeric molecules. Suitable solvents include, but are not limited to, alkanol, alkylene glycol, water, and combinations of the foregoing. Exemplary solvents include: ethanol, ethylene glycol, water, and combinations of the foregoing. In certain embodiments, the polymeric molecules have one or more polar functional groups, ionizable functional groups, or a combination of the foregoing. The polymeric molecules may likewise comprise one or more double bonds. Suitable polymeric molecules have been described above. In a particular embodiment, the undissolved polymerizable molecules are removed from the mixture, for example, by filtration or centrifugation to separate the mixture.

The liquid or slurry may further comprise a crosslinking agent. Suitable crosslinker package Containing, but not limited to, anhydrides; carbodiimide; quinone imide; borax salt; sodium borohydride; and reagents comprising the following combinations: N- Hydroxybutadiene imide and maleimide, aryl azide, or diazocyclopropene group. Commonly used crosslinking agents include: triallyltriazinetrione and other triallyl reagents or trivinyl reagents known to those skilled in the art of polymer chemistry. Exemplary anhydrides include: maleic anhydride, itaconic anhydride, cis-4-cyclohexene-1,2-dicarbonic anhydride, cis-5-norbornene-endo-2,3-dicarbonate Anhydride, and combinations of the foregoing.

In certain embodiments, the liquid or slurry may further comprise a starter, such as a free radical initiator, to catalyze the crosslinking between the polymeric molecules. Exemplary initiators include thermally activated as well as photoactivated chemical initiators, including, but not limited to, azobisisobutyronitrile; 1,1'-azobiscyclohexanecarbonitrile (1) , 1'-azobis (cyclohexanecarbonitrile); dicumyl peroxide; 2-hydroxy-2-methylpropiophenone; camphorquinone; phenanthrenequinone Phannathrenequinone); and combinations of the foregoing. In one of the examples, itaconic acid anhydride and dicumyl peroxide are used to crosslink the maize protein molecules.

One or more salts may be added to the liquid or slurry prior to completion of the crosslinking, for example, a salt capable of forming an organic salt with the polymerizable molecules and/or a salt neutralizing the film material. Carbonates (for example, guanidine carbonate, cesium carbonate, strontium carbonate, or a combination of the foregoing) may be used in certain embodiments because the reaction releases carbon dioxide and No undesirable counterion contamination of the dielectric film is produced. In one embodiment, barium titanate is added to the liquid or slurry. In a separate embodiment, a voltage adjuvant (voltage Adjuvant) (for example, a non-conducting polymer) will be added.

The liquid or slurry is applied to the electrically conductive first electrode by any convenient means. In one embodiment, the slurry is applied to a stationary or continuously moving strip of an electrode. In another embodiment, the liquid or slurry may be poured onto a statically positioned electrode plate via any number of means, including but not limited to: pressure from a container or Water is poured from the mixing container. In another embodiment, the liquid or slurry is applied to the electrode by spin coating. It is also contemplated to use other methods to move the liquid or slurry from the mixing vessel to the electrode. The liquid or slurry can be dispersed, extruded, rolled to cover the surface of the electrode and ensure that the liquid or slurry has a uniform thin coating on the surface of the electrode. A variety of means for performing this step can be considered, including, but not limited to, the use of a smear blade, roller, or other means. Vapor deposition of the slurry can be accomplished by atomization of the slurry or chemical vapor deposition as is known to those skilled in the art of film formation.

In one embodiment, a sufficient amount of liquid or slurry is applied to the surface of the electrode to produce a dielectric film having a desired thickness when dried. In another embodiment, two or more layers of liquid or slurry may be applied to the surface of the electrode to provide the desired thickness. Each layer can be dried before the other layer is applied; alternatively, continuous deposition of the liquid or slurry can be carried out, and drying is performed after all layers have been applied. When two or more layers are applied, the layers may have the same or different chemical compositions.

The electrode and dielectric material can be heated to remove solvent and form a dielectric film on the surface of the electrode. Heating can be performed before or after the dielectric material contacts the electrically conductive second electrode. In some embodiments, the assembly is clamped or squeezed for application. Pressure is applied to the dielectric material and any air or gas is forced away from the liquid or slurry such that the first and second electrodes are in full and intimate contact with the inwardly facing surfaces of the electrodes. In a particular embodiment, the assembly is heated to a temperature of from 150 ° C to 300 ° C to remove the solvent. Other temperature ranges may also apply depending on the particular solvent.

In a separate embodiment, the polymeric molecules of the dielectric film are formed in situ. The liquid or slurry comprises a crosslinking agent and a plurality of polymerizable molecular precursors, the polymerizable molecular precursor comprising one or more polar functional groups, ionizable functional groups, or the foregoing combination. In some examples, the precursors are amino acid molecules, oligopeptides, polypeptides, or a combination of the foregoing. In a particular embodiment, the polymeric molecular precursors further comprise a para-xylene monomer. The liquid or slurry is applied to the first electrode as previously described. After coating, the crosslinking agent is activated to crosslink the polymeric molecular precursors to provide a dielectric film comprising a plurality of polymeric molecules. The crosslinking process may also bond a portion of the polymerizable molecules to the electrode surface, for example, when the electrode is a composite electrode including an insulating layer.

B. Insulation layer formation

In some embodiments, the method further includes applying an insulating layer to the first electrode to form a composite first electrode, and then applying the dielectric film to the composite first electrode Insulation. In one embodiment, the insulating layer comprises a poly-p-xylene. In another embodiment, the insulating layer comprises a copolymer of p-xylene and other comonomers as described above. The insulating layer is applied by any convenient means including vapor deposition, liquid spraying, screen printing, spin coating, or other methods known to those skilled in the art of film formation.

In some embodiments, the insulating layer is applied by vapor deposition. When the insulating layer comprises poly-p-xylene, xylene can be reacted with a single atomic source of oxygen to produce para-xylene in monomer form. For example, the monoatomic source of oxygen can include nitrous oxide or ionized diatomic oxygen. In certain embodiments, the step of reacting xylene with a source of monoatomic oxygen to produce para-xylene in monomer form is in the environment heated to 450 ° C to 800 ° C at atmospheric pressure with xylene and The stoichiometric ratio of monoatomic oxygen sources is implemented. The reaction can be carried out in an electrically heated thermal cracking reaction tube, for example, an Inconel (nickel alloy 600) thermal cracking reaction tube. An inert gas flowing gas stream (for example, only argon or nitrogen; or, with a reactive compound such as nitrous oxide) is supplied to the thermal cracking reaction tube. A starting material (for example, xylene vapor) is introduced into the thermal cracking reaction tube and reacted with monoatomic oxygen in the reaction tube. Since the reaction is easy and short-lived, the monoatomic oxygen must be able to react with the volatile mixture in the reaction chamber. As discussed above, the source of monoatomic oxygen can be a gaseous compound supplied with the carrier gas, or can be a separately supplied gaseous compound, or can be another source (eg, a plasma generator). A monoatomic oxygen plasma can be produced by exposing oxygen (O ₂ ) to an ionizing energy source (eg, an RF discharge) that ionizes the gas. Alternatively, a compound such as nitrous oxide (N ₂ O) may supply a single atom of oxygen to the reaction via thermal, catalytic, and/or other decomposition. Thus, a single atomic oxygen plasma generator, or a single atomic oxidizing compound (for example, N ₂ O), or other suitable source of monoatomic oxygen will be provided. A plasma gas can be used in the aforementioned starting materials for forming an intermediate oxidation product, which can then be reacted to form a reaction product in the oxidized form of the starting materials, which may be monomeric, dimeric, Trisomy, oligomer, or polymer. At a temperature of 300 ° C to 800 ° C, the output of the reaction tube will be very hot enough to maintain the monomer p-xylene in a monomeric form. Rapid cooling of the monomer on the surface of an electrode causes the liquid of the monomer to condense and rapidly polymerize the monomer into a polymer. A means for mixing a plurality of low temperature non-conducting gases into the hyperthermal reaction gas stream can be used to lower the temperature and aid in condensing the reaction intermediates exiting the reaction tube. Optionally, an expansion valve can be used at the outlet of the reaction tube to provide Joule-Thomson cooling of the hot gas. Optionally, the deposited mixture can be exposed to light-inducing light energy and/or permittivity increasing fields (eg, magnetic fields and/or electric fields).

The method can be extended to other substituents including, but not limited to, 2-chloro-1,4-dimethylbenzene; 2,5-dichloro- 2,5-dichloro-p-xylene; 2,5-dimethylanisole; tetrafluoro-p-xylene; 2,4-trimethyl benzene. The meta orientation and ortho orientation of the substituents on the aromatic ring are also viable reaction starting materials. The reaction can be generally characterized as comprising reacting with monoatomic oxygen generated from a plasma or reacting with a decomposed oxygen-containing substance or a monoatomic oxygen generated in a reaction product thereof and further containing the aromatic ring The presence of all compounds that stabilize the hydrogen atoms. Generally, these hydrogen atoms are located at the alpha position of the phenyl ring (the position of the benzyl group). It is well known to those skilled in the art of organic synthesis that the Michael structure removed from the alpha aromatic ring position is known to provide the same reactivity as the hydrogen radical at the alpha position of the aromatic ring. However, the reactivity of such hydrogen atoms is not limited to an aromatic ring or an alpha and/or a Michael position of an aromatic ring such as benzene. Those familiar with organic chemistry know the many aromatic stabilizing effects of many different rings, fused rings, and acyclic systems. Preferably, the starting materials are two hydrogen atoms which can be removed to form a partially oxidized starting material. These comparisons Good materials may have the ability to dimerize, trimerize, oligomerize, or multimerize depending on the situation.

When the insulating layer comprises a copolymer comprising para-xylene, xylene can be reacted with a single atomic oxygen source to produce para-xylene in monomer form. For example, the single atomic oxygen source can include nitrous oxide or ionized diatomic oxygen. A monoatomic oxygen plasma can be produced by exposing oxygen (O ₂ ) to an ionizing energy source (eg, an RF discharge) that ionizes the gas. Alternatively, a compound such as nitrous oxide (N ₂ O) may supply a single atom of oxygen to the reaction via thermal, catalytic, and/or other decomposition. In a preferred embodiment, the step of reacting xylene with a source of monoatomic oxygen to produce para-xylene in monomer form is carried out at atmospheric pressure in an environment heated to 350 ° C to 800 ° C. A stoichiometric ratio of toluene to monoatomic oxygen source is used. The reaction can be carried out in an electrically heated thermal cracking reaction tube, for example, an Inconel (nickel alloy 600) thermal cracking reaction tube. The monomeric form of p-xylene is mixed with a copolymerized compound (comonomer), that is, the copolymerized compound is a compound copolymerized with p-xylene in the form of the monomer. The monomeric form of para-xylene and the copolymerized compound are in a gaseous state upon mixing. A plasma gas can be used in the aforementioned starting materials to form an intermediate oxidation product which can then be reacted to form a reaction product which is an oxidized form of the starting materials. After mixing the monomeric form of p-xylene with a copolymerized compound, the resulting mixture can be captured in a condenser. The temperature of the condenser is at a temperature at which the mixture will condense. A temperature of at least -30 ° C (for example, in the range of -30 ° C to 400 ° C) can condense most of these mixtures. The condenser contains a solvent to aid in capture. Optionally, the captured mixture can be combined with a tertiary material (for example, another monomer), a reactive material, or an inert material. After mixing the monomeric form of p-xylene with a copolymerized compound, the resulting mixture can be deposited on an electrode. The temperature of the electrode can be controlled to promote solidification of the deposition mixture. Rapid cooling of the monomers (whether modified or unmodified) upon directing the monomers on the surface of an electrode results in condensation of the liquids of the monomers and rapid multimerization of the monomers into a polymer. Optionally, the deposited mixture can be exposed to light-inducing light energy and/or permittivity increasing fields (eg, magnetic fields and/or electric fields).

C. Bonding polymeric molecules to the electrodes

In some embodiments, an electric field is applied across the first electrode, the dielectric film, and the second electrode. The advantage is that the electric field is a constant current electric field. The electric field will be applied such that the first electrode acts as a positive electrode and the second electrode acts as a negative electrode. The electric field strength may be greater than 100 V/cm, or at least 0.001 V/μm, based on the average thickness of the dielectric film. In a particular embodiment, the electric field strength is from 0.005 to 1 V/μm, from 0.01 to 1 V/μm, from 0.1 to 1 V/μm, or from 0.4 to 0.6 V/μm.

The electric field can be applied for a period of time effective to bond at least some of the polymeric molecules in the dielectric film to the first electrode to produce a space-limited dielectric film . The effective time period is based on at least a portion of the electric field strength and can range from one second to several minutes, for example, from 30 seconds to 60 minutes, from 5 minutes to 30 minutes, and from 5 minutes to 15 minutes. In certain embodiments, the electric field strength is from 0.005 to 1 V/μm and the effective time period is from 1 second to 30 minutes. In one embodiment, the electric field strength is maintained from 0.005 to 0.5 V/μm for 20 minutes to bond more than 50% of the protein molecules to a composite electrode surface comprising poly-p-xylene. In another embodiment, the electric field strength is maintained from 0.5 to 1 V/μm for 5 to 15 minutes to bond more than 90% of the protein molecules to a composite electrode surface comprising poly-p-xylene.

In some embodiments, the first conductive electrode, the dielectric film is assembled, And after the second conductive electrode, the dielectric film is treated with a chemical agent for bonding at least some of the polymerizable molecules to the first electrode to generate a space-limited dielectric Plasma membrane. In a particular embodiment, an electric field is applied across the first electrode, the dielectric film, and the second electrode and the chemical film is treated with a chemical.

In one embodiment, the first electrode is a composite electrode, and treating the dielectric film with a chemical agent comprises applying a radical before applying the dielectric film to the insulating layer. The initiator is applied to the insulating layer, and then the radical initiator is activated to bond at least some of the polymerizable molecules to the insulating layer and to produce a space-limited dielectric film. Exemplary free radical initiators include: azobisisobutyronitrile; 1,1'-azobiscyclohexanecarbonitrile; dicumyl peroxide; 2-hydroxy-2-methylpropiophenone; camphorquinone; Phenanthrenequinone; combinations of the foregoing; and other free radical initiators known to those skilled in the art of polymerization. The free radical initiator will be activated by oxidation-reduction, photoinitiation, thermal initiation, or other methods known to those skilled in the art of polymerization, thereby at least some of the polymerizable molecules. Junction to the insulating layer.

In a separate embodiment, the first electrode is a composite electrode, and processing the dielectric film with a chemical agent comprises incorporating a radical initiator into the film material of the dielectric film. And activating the radical initiator after applying the dielectric film to the insulating layer.

In a separate embodiment, the first electrode is a composite electrode, and treating the dielectric film with a chemical agent comprises derivatizing the polymerizable molecules with a derivatizing agent to provide cross-linking a functional group to the insulating layer of the composite first electrode, and then crosslinking the functional groups to the insulating layer by using a radical initiator, ultraviolet light, heat activation, or a combination thereof Layers, thereby creating a space-limited dielectric film. Exemplary derivatizing agents include: anhydrides; carbodiimide; quinone imine; and anti-inclusions comprising the following combinations Reagents: N-hydroxybutadienimide and maleimide, aryl azide, or diazocyclopropene groups. In certain embodiments, the derivatizing agent is an anhydride, such as maleic anhydride, itaconic anhydride, cis-4-cyclohexene-1,2-dicarbonic anhydride, or cis-5-norbornene. - Inner-2,3-dicarbonic anhydride.

In a separate embodiment, the first electrode is a composite electrode, and treating the dielectric film with a chemical agent comprises applying a plasma to the dielectric film before applying the dielectric film to the insulating layer. The surface of the insulating layer. The plasma is achieved by conducting an aerobic carrier gas (for example, nitrogen or argon) through a high voltage "spark" plasma. The voltage drop across the spark is about 100V to 1000V at 250kHz. Alternatively, it is also possible to make high frequency plasma (for example, 13.6 MHz and <100 V) at a lower voltage using the same gas mixture. The plasma produces monoatomic oxygen which lasts long enough (for example, a few milliseconds) to oxidize p-xylene. A polymerizable molecule in the dielectric film reacts with the plasma to bond at least some of the polymerizable molecules to the insulating layer and form a space-limited dielectric film.

One or more of the embodiments above using a chemical to treat the dielectric film can be used in combination. For example, the polymeric molecules can be derivatized with a derivatizing agent, a crosslinking agent can be incorporated into the film material, and a free radical initiator can be incorporated into the film material. Or it is applied to the insulating layer before being applied to the dielectric film and then activated.

D. Method of manufacturing an alternative assembly

In one embodiment, a method for making an energy storage device as shown in FIG. 4 comprises: (i) providing a first polymer sheet or roll having a metallized surface and metallizing The surface includes an insulating layer as disclosed herein, wherein the insulating layer has no Fully covering the metallized surface such that an edge portion of the metallized surface is not covered; (ii) applying a dielectric film as disclosed herein to the insulating layer; (iii) allowing a second metal The polymer sheet or roll contacts the dielectric film, the second sheet or roll having a metallized surface and including an insulating layer on the metallized surface, wherein the insulating layer does not completely cover the metal a surface such that an edge portion of the metallized surface is not covered, wherein the second sheet or web is oriented such that the insulating layer contacts the dielectric film and the second sheet or roll The uncovered edge portion is adjacent to the uncovered edge portion of the first sheet or web to form a composite multilayer surface; (iv) winding the composite multilayer surface into a rolled configuration, Or cutting and stacking portions of the composite multilayer surface to form a stacked configuration; (v) uncovered edge portions of the first sheet or roll and the second sheet or roll Covered edge Bonding to a conductor cover or a conductor polymer contained in a non-conductor support bracket having an electrical connection; (vi) electrically connecting the composite multilayer surface to a positive electrode and a negative electrode; And (vii) applying an electric field to the multilayer composition, the electric field being applied for an effective period of time for bonding at least some of the polymeric molecules of the dielectric film to the first An insulating layer of a sheet or roll, an insulating layer of the second sheet or roll, or both.

In a separate embodiment, a method for fabricating an energy storage device as shown in FIGS. 5 and 6 includes: (i) providing a first electrode in a containment device, having one comprising The upper surface of the disclosed insulating layer; (ii) positioning a perforated non-conductor separator sheet on the insulating layer of the first electrode; (iii) positioning a second electrode on the separator sheet, the The two electrodes have a lower surface comprising an insulating layer as disclosed herein such that the insulating layer of the second electrode contacts the separator sheet; (iv) incorporating a dielectric material as disclosed herein, a space for filling the porous separator sheet and for contacting the first electrode and the second electrode; and (v) spanning the first electrode, the dielectric material, and the second by applying an electric field And bonding at least some of the polymerizable molecules of the dielectric material to the insulating layer of the first electrode, the electric field being applied for maintaining for an effective period of time to at least one of the polymerizable molecules Some are bonded to the insulating layer of the first electrode.

IV. Examples Example 1

Preparation of dielectric film

material:

Protein/Polymer/Amino Acid: Zeain Protein (CAS # 9010-66-6 by Sigma-Aldrich), Hemp Protein (Hemp, produced by Manitoba Harvest Hemp Foods, Winnipeg, Manitoba, Canada) Pro 70), wheat gluten (produced by John & Jennie's Gourmet Kitchen Center in Salt Lake City, Utah, USA, jandjkitchen.com), polyacrylic acid-maleic acid copolymer (CAS # by Sigma-Aldrich) 52255-49-9), polyacrylic acid (CAS # 9003-01-4 by Sigma-Aldrich), separating whey protein (Purebulk.com Lot # 20131025-07-1000g), separating soy protein (located in Utah, USA) Item # 30-066-904 produced by Honeyville Food Products of Honeywell, Gamma amino butyric acid (GABA) (Purebulk.com Lot # 20130722-01), pea protein extract (Purebulk.com Lot # 20140226-06-1000g), L-lysine HCI (Purebulk.com Lot # 20131125-01-1000g), L-serine (L-serine) (Purebulk.com Lot # 20130606-04), L-glutamine (Purebulk.com Lot # 20130912), L- L-tryptophan (Purebulk.com Lot # 20131015-04-100g), L-tyrosine (Purebulk.com Lot # 20131016-08-1000g), aspartic acid (Aspartic) Acid)(Purebulk.com Lot # 20130122-06).

Anhydrides: maleic anhydride (CAS # 108-31-6 by Sigma-Aldrich), itaconic anhydride (CAS # 2170-03-8 by Alfa Aesar), cis-4-cyclohexene - 1,2-dicarbonic anhydride (CAS # 935-795 by Alfa Aesar), cis-5-norbornene-endo-2,3-dicarbonic anhydride (CAS # 129-64-6 by Alfa Aesar) ).

Salts: Barium carbonate (CAS # 593-85-1 by Sigma-Aldrich), Barium carbonate (CAS # 534-17-8 by Alfa Aesar), Barium carbonate (CAS # 1633 by Sigma-Aldrich) -05-2), rubidium carbonate (CAS # 584-09-8 produced by Alfa Aesar).

Solvent: ethanol, ethylene glycol (CAS # 107-21-1 produced by Sigma-Aldrich).

Exemplary dielectric layer preparation procedure

In a 50 mL Erlenmeyer flask, 1 gram of maize protein and 1.14 grams of itaconic anhydride were dissolved in 10 mL of absolute ethanol by heating to 65 ° C for 15 minutes under argon atmosphere. Once the dissolution was completed and the reaction temperature reached 65 ° C, 0.035 g of dicumyl peroxide was added to a portion thereof, and the mixture was continuously stirred under argon for 1 hour. Next, the hot plate was turned off and the mixture was allowed to cool to room temperature. Once cooled, the pH of the mixture (pH ~ 3) was tested using a universal pH indicator paper and 1 gram of cesium carbonate was added to a small portion until the pH was measured to ~7. Care must be taken when adding cesium carbonate to ensure that excessive effervescence (and bubbling over) due to carbon dioxide generation from the reaction is avoided. Some cesium carbonate can be used to achieve neutralization, depending on the degree of completion of the protein/anhydride reaction. However, the anhydrides that are usually added do not significantly exceed 1 mole equivalent. The final pH of the dielectric can range from 5 to 10.

Remarks: a) The protein contains additional intrinsic functional groups capable of reacting with cesium carbonate, therefore, the protein requires more than one equivalent; b) the amount of anhydride used is based on maize and maleic anhydride (Mole weight 98.06 g/mol) is determined on the basis of a weight ratio of 1:1. The molar equivalent of the substituted anhydride (Ikonic anhydride) is calculated based on the molar weight of maleic anhydride.

Example 2

Preparation of poly-p-xylene coating

Coatings comprising Puralene ^(TM) polymers (poly-p-xylene) with and without comonomers were prepared using several procedures.

material:

Starting agent: azobisisobutyronitrile (AIBN) (CAS # 78-67-1 by Sigma-Aldrich), 1,1'-azobiscyclohexanecarbonitrile (ACHN) (Sigma-Aldrich) CAS # 2094-98-6), dicumyl peroxide (CAS # 80-43-3 by Sigma-Aldrich), 2-hydroxy-2-methylpropiophenone (CAS # by Sigma-Aldrich) 7473-98-5), camphor sputum (CAS # 10373-78-1 produced by Sigma-Aldrich), phenanthrenequinone (CAS # 84-11-7 produced by Sigma-Aldrich).

Initiation source: heat from the heated evaporator block attached to the reactor output (>65 ° C), 254 nm light (Philips TUV 15W G15t8 UV-C Long Life), 354 nm light (Sylvania 350 Blacklight F15T8/350BL ).

Comonomer: 3-trimethyloxonium propyl methacrylate (CAS # 2530-85-0 by Sigma-Aldrich), vinyl acetate (CAS # 108-05 by Alfa Aesar) -4), 2-carboxyethyl acrylate (CAS # 24615-84-7 by Sigma-Aldrich), (+)-α-pinene (CAS # 7785-70-8 by Alfa Aesar), (-)-α-terpinene (CAS # 7785-26-4 by Alfa Aesar), R-(-)-carvone (CAS # 6485-40-1 by Alfa Aesar), 樟Alcohol (CAS # 78-70-6 by Alfa Aesar), cyclohexene (CAS # 110-83-8 by Alfa Aesar), dipentene (CAS # 138-86-3 by Alfa Aesar) ), CAS # 99-86-5), R-(+)-limonin (CAS # 5989-27-5 produced by Alfa Aesar) produced by α-terpinene Alfa Aesar.

Production of Puralene ^(TM) polymer using a chemical initiator , Procedure A: This procedure utilizes the reactor described in U.S. Patent No. 8,633,289, without any modification. A 5% hot starter solution was applied to the surface of a circular 1⁄2" copper substrate without oxide supported by an 11⁄2" square FR4 glass filled epoxy board. This solution was sonicated by dissolving 0.05 g of a solid starter (AIBN, ACHN, or dicumyl peroxide) in 10 mL of absolute ethanol until complete/almost complete dissolution. After dissolution, 20 μL of the starter solution was applied to the metal surface and the solvent was evaporated under ambient atmosphere. This process leaves a thin layer of fine particle starter solids on the metal surface. These substrates are then placed in a frozen (~13 ° C) aluminum block that is attached to the robotic arm. The substrates are then uniformly coated with monomeric p-xylene for a minimum of three times and a maximum of ten times. Between coatings, the substrates may be allowed to stand on the frozen block for two minutes to enhance the chemical reaction. This produces a poly-p-xylene conformal coating ranging in thickness from 300 nm to 1000+ nm.

Using chemical initiators Puralene ^TM polymer production, program B: This program uses the reactor No. 8,633,289 U.S. Patent No. case of no correction. A 5% UV active initiator solution was applied to the surface of the previously described copper substrate without oxide. This solution was sonicated by dissolving 0.05 g of a solid starter (camphorin or phenanthrenequinone) in 10 mL of absolute ethanol until complete/almost complete dissolution. After dissolution, 20 μL of the starter solution was applied to the metal surface and the solvent was evaporated under ambient atmosphere. This process leaves a thin layer of fine particle starter solids on the metal surface. These substrates are then placed in a frozen (~13 ° C) aluminum block that is attached to the robotic arm. Next, the substrates are uniformly coated with p-xylene for a minimum of three times and a maximum of ten times. Between coatings, the substrates were exposed to 254/350 nm UV light for two minutes by two lamps placed side by side in the same housing. After irradiation, the substrates can be allowed to stand on the frozen block for an additional two minutes to enhance the chemical reaction. This produces a poly-p-xylene conformal coating ranging in thickness from 300 nm to 1000+ nm.

Production of Puralene ^(TM) polymer using a chemical initiator , Procedure C: This procedure utilizes the reactor described in U.S. Patent No. 8,633,289, but with the following modifications. Attached to the top of the Inconel reaction tube is a heated stainless steel evaporator block, nitrogen (carrier gas) and 2-hydroxy-2-methylpropiophenone (UV active initiator, no dilution) will be fed to the Heated stainless steel evaporator block. Next, the previously described copper substrate without oxide will be placed in a frozen (~13 ° C) aluminum block that is attached to the robotic arm. Next, the substrates are uniformly coated with p-xylene for a minimum of three times and a maximum of ten times. Between coatings, the substrates were exposed to 254/350 nm UV light for two minutes by two lamps placed side by side in the same housing. After irradiation, the substrates can be allowed to stand on the frozen block for an additional two minutes to enhance the chemical reaction. This produces a poly-p-xylene conformal coating ranging in thickness from 300 nm to 1000+ nm.

Puralene ^TM Copolymer Production, Procedure A: 5 μL of a 5% starter solution (described above) or 5 μL of net 2-hydroxy- on the surface of the previously described oxide-free copper electrode 2-methylpropiophenone and 20 μL of one of the comonomers listed above. The substrates may be slightly dried so that the liquid materials do not drip from the surface when the substrates are vertically disposed. The prepared substrates can then be coated by the methods described in the above Puralene ^(TM) Polymer Production Procedures A through C (related to the starter). This produces copolymer films of various thicknesses that can be analyzed using energy dispersive X-ray spectroscopy.

Puralene ^TM Copolymer Production, Procedure B: 20 μL of a 5% starter solution (described above) or 20 μL of net 2-hydroxy- on the surface of the previously described copper-free electrode without oxide 2-methylpropiophenone. Once the carrier solvent has evaporated and the substrates have been placed, a liquid comonomer is applied to the surface of the substrate using a spray gun prior to coating. Then, they use production Puralene ^TM polymer using a chemical initiator, the coating technique according to Procedure A.

Puralene ^TM copolymer production procedure C: This program uses the reactor No. 8,633,289 U.S. Patent No. case in, but after the following correction. A heated stainless steel evaporator block is attached to the top of the Inconel reaction tube, and nitrogen (carrier gas) and liquid comonomer (without dilution) are fed into the heated stainless steel evaporator block. On the surface of the previously described oxide-free copper electrode, 20 μL of a 5% starter solution (described above) or 20 μL of neat 2-hydroxy-2-methylpropiophenone was applied. Once the carrier solvent evaporates, the substrates are placed on the frozen block. In this process, the comonomer is vaporized in the evaporator block, heated to a specific boiling temperature of the monomer, and then the evaporated monomer is added to the main paraxylene stream. Among them, ruthenium allows both the monomer and xylene to be simultaneously applied to the surface of the substrate. Next, the prepared substrates were coated by the method described in the above Puralene ^(TM) Polymer Production Procedures A to C (related to the starter).

Puralene ^TM copolymer production procedure D: This program uses the reactor No. 8,633,289 U.S. Patent No. case in, but after the following correction. A heated stainless steel evaporator block is attached to the top of the Inconel reaction tube, and nitrogen (carrier gas) and liquid comonomer (without dilution) are fed into the heated stainless steel evaporator block. A second evaporator block is positioned above it for transporting nitrogen and a liquid initiator (2-hydroxy-2-methylpropiophenone). In this process, both the comonomer and the starter are vaporized and passed into the paraxylene stream, causing all three materials to contact the substrates simultaneously. No copper oxide substrate is disposed on the frozen block using Puralene ^TM and polymer production using a chemical initiator in the above, the method described in Procedure C was coated.

Example 3

Preparation of energy storage device

A metallized polymer sheet or roll (for example, the pattern treated aluminum polyethylene terephthalate (polyethylene terephthalate, PET) (Mylar ® polyester film)) is an insulating layer (e.g. Including the Puralene ^(TM) polymer coating described in US 2014/0139974 A1. In some examples, the metallized polymer sheet or web has a thickness of about 6 [mu]m and a width of about 50 mm. The non-conductor coating is applied to the metallized surface and may not completely cover the metallized surface. A bare conductor surface of approximately 6 mm will be exposed to one of the edges. The coated metallized material is then spray coated onto the top end of the non-conducting polymer surface using a dielectric material as described in US 2013/0224397 A1. A sufficient dielectric material will be deposited to provide a dielectric layer having a thickness of about 100 μm after drying at 60 ° C for 10 minutes. Another metallized polymer sheet or roll that has been coated with a non-conducting polymer in the same manner as the first substrate will then be flipped such that the uncoated edges are opposite to the first substrate. The coated edges and the two aluminized surfaces will face each other. The polymer coated side of the second substrate contacts the dielectric coated side of the first substrate. The composite multilayer surface is then wound into a roll (which can be flattened later) or stacked into multiple plates to provide a larger device with a larger energy storage amount. The uncoated electrode edges electrically connected to the reel or stack are bonded to a conductor multimeric blend by the edges of the conductor electrodes (e.g., conductor epoxy resins known to those skilled in the art). ) to provide. The conductor polymer is contained within a cover of a mechanically substantial conductor or other non-conductor support bracket having electrical connections (eg, wires) and/or mechanical strength sufficient for extrusion electrical connection . An optional cuff will be placed around the entire device to provide mechanical and electrical protection to the film and the device itself when it is intended for use.

The energy storage device will be attached to a DC voltage supply. The device is powered by a current of 0.001 to 100 mA/cm ² . At an electric field strength of greater than 0.001 V per micron thickness of the dielectric film, current can flow for an effective period of time to bond at least some of the polymerizable molecules of the dielectric film to the non-conductor coating. In some embodiments, the electric field strength is greater than 0.01 V/μm, for example, from 0.05 to 1 V/μm or from 0.1 to 1 V/μm. The effective time period can range from a few seconds to a few minutes. In some embodiments, the voltage is from 0.1 to 1 V/[mu]m and the effective time period is from 5 minutes to 30 minutes. The calculation of the energy absorbed by the device is determined by methods known to those skilled in the art of manufacturing energy storage devices. The discharge system that has absorbed energy is determined by integrating the differential voltage discharged to the ground via a resistor.

In a working example, disassembling the device and performing a microscopic examination reveals that the dielectric material is firmly and mechanically bonded to the surface of the non-conducting polymer coated electrode.

Example 4

Preparation of a copolymer layer using a radical initiator and a crosslinking agent

In the energy storage device shown in any of Figures 1 to 6, a monomer molecule (preferably, a para-xylene monomer) is deposited on a conductor electrode serving as a removable carrier film. Or a non-conductor sheet (for example, a polytetrafluoroethylene sheet). The comonomer molecules can be any molecule that has the ability to multimerize, dimerize, or form an extended structure that may be a conductor or insulation. In addition to this, the added comonomer species may also have a structure possessing several reaction functions that can act as a crosslinking agent. Alternatively, a crosslinking agent as known above or known to those skilled in the art of polymerization or film formation may be added in conjunction with the deposited monomers. The free radical initiator as known above or known to those skilled in the art of polymerization or film formation will be incorporated with the deposited monomers or added in separate deposition steps. The film can be deposited by vapor deposition, liquid spraying, screen printing, or other methods known to those skilled in the art of film formation. Activation of the free radical initiator is provided by oxidation-reduction, photoinitiation, thermal initiation, or other methods known to those skilled in the art of film formation. An exemplary method for making a polymeric film is described in U.S. Patent No. 8,633,289, the disclosure of which is incorporated herein by reference. An electric field, a magnetic field, or both may be applied to the polymer film during formation of the polymer film to modify the mechanical and electrical properties of the film, for example, to make the film more viscous or It is more solid.

Then, a dielectric layer can be deposited as a separate step, if formed The film thereon is not the complete dielectric material of the device. The counter electrode will then be added as described in the previous examples and the device will be placed as previously described.

Example 5

Polymer bonding

An insulating layer made of a polymer will use Puralene ^TM "produced by chemical Puralene ^TM polymer initiator, Procedure C 'in the process of being applied to a first electrode surface. A dielectric film comprising a maize protein is applied to the insulating layer. Puralene ^TM comprises a polymer made of the insulating layer contacting the second electrode will dielectric film. An electric field of 20 V is applied across the first electrode, the dielectric film, and the second electrode for 5 minutes to bond the maize protein polymer to the insulating layer on the first (positive) electrode. The energy storage device is disassembled and inspected to determine the extent and strength of the protein bond.

Optical micrographs of the negative and positive electrodes, respectively, shown in Figures 7 and 8 after disassembly. As seen in Figure 8, the positive electrode contains a conformal protein coating on its surface. The electrodes are washed with tap water and checked again. Optical images of the negative and positive electrodes, respectively, after washing, are shown in Figures 9 and 10. As seen in Figure 10, the protein remains bonded to the surface of the positive electrode.

11 and 12 are optical photographs of a negative electrode and a positive electrode, respectively. These photos are taken at an angle to give a clearer view of the surface details. Figure 12 shows the substantial intact coverage of the electrode surface with protein molecules. Figure 13 is an optical photograph of the washed positive electrode after manually scraping the dielectric film with a blade. The brighter area (indicated by the arrow) is the area where the bonded protein molecules are removed by scraping and the display is displayed The surface of the electrode under the protein layer. The photograph shows that considerable force is required to remove the bound protein molecules from the electrode surface.

In view of the many possible embodiments in which the principles of the disclosed invention may be employed, it is understood that the embodiments described herein are merely preferred examples of the invention and should not be construed as limiting the scope of the invention. Rather, the scope of the invention is defined by the scope of the following claims. Therefore, the inventors of the present invention claim that the present invention falls within the scope and spirit of the scope of such patent application.

100‧‧‧ energy storage device

110‧‧‧ positive electrode

112‧‧‧ outer surface of the first/positive electrode

115‧‧‧Conductor wire

120‧‧‧ Space-constrained dielectric layer

122‧‧‧ Polymeric molecules

124‧‧‧ Attachment

126‧‧‧ Attachment

130‧‧‧negative electrode

132‧‧‧ outer surface of the second/negative electrode

135‧‧‧Conductor wire

140‧‧‧Insulation

150‧‧‧Insulation

Claims (25)

A method comprising: fabricating an energy storage device by: applying a dielectric film to a conductive first electrode, the dielectric film comprising a film material, (i) being electrically insulating And/or exhibiting a high permittivity and (ii) comprising a plurality of polymerizable molecules having one or more polar functional groups, ionizable functional groups, or a combination of the foregoing; allowing the dielectric film Contacting a conductive second electrode; and bonding at least some of the polymerizable molecules to the conductive first electrode by forming a space-constrained dielectric film: (i) applying a An electric field spans the first electrode, the dielectric film, and the second electrode, such that the first electrode is a positive electrode, and the electric field is applied for an effective period of time to be used in the polymerizable molecules At least some of the energy storage device is bonded to the first electrode, (ii) the chemical film is treated with a chemical agent, or (iii) the combination described above. The method of claim 1, wherein the electric field is at least 0.001 V/μm based on the average thickness of the dielectric film. The method of claim 2, wherein the electric field is 0.005 to 1 V/μm, and the effective time period is from 1 second to 30 minutes. The method of claim 1, further comprising: applying an insulating layer to the conductive first electrode to form a composite first electrode; and coating the dielectric film to the composite The insulating layer of an electrode. The method of claim 4, wherein the insulating layer comprises polymerized para-xylene. The method of claim 4, wherein bonding at least some of the polymerizable molecules comprises applying the electric field across the composite first electrode, the dielectric film, and the second electrode for an effective period of time a period whereby at least some of the polymeric molecules are bonded to the insulating layer of the composite first electrode. The method of claim 4, wherein the treating the dielectric film with a chemical agent comprises: applying a radical initiator to the insulating layer before applying the dielectric film to the insulating layer And activating the radical initiator after applying the dielectric film to the insulating layer, thereby bonding at least some of the polymerizable molecules to the insulating layer of the composite first electrode. The method of claim 4, wherein the treating the dielectric film with a chemical agent comprises: (i) deriving the polymerizable molecules with a derivatizing agent to provide crosslinkability to the composite first a functional group of the insulating layer of the electrode; (ii) incorporating a crosslinking agent into the film material of the dielectric film; (iii) incorporating a radical initiator into the dielectric film In the film material, and after applying the dielectric film to the insulating layer, the radical initiator is activated; (iv) applying a radical before applying the dielectric film to the insulating layer Activating agent to the insulating layer, and activating the radical initiator after applying the dielectric film to the insulating layer; (v) coating a dielectric film before applying the dielectric film to the insulating layer Plasma to the insulation; or (vi) any combination of the foregoing. The method of claim 1, wherein the polymerizable molecules include protein, parylene, acrylic polymer, methacrylic polymer, polyethylene glycol, urethane polymer, epoxy Resin polymer, neodymium polymer, terpene polymer, naturally occurring resin polymer, polyisocyanate or a combination of the foregoing. The method of claim 1, wherein the polymerizable molecules comprise a protein or a derivatized protein. The method of claim 1, wherein the electrically conductive second electrode is a composite second electrode comprising an insulating layer, and the composite second electrode is positioned such that the insulating layer contacts the dielectric Plasma membrane. The method of claim 1, wherein the applying the dielectric film to the electrically conductive first electrode comprises: forming the dielectric film on a removable carrier film; removing the removable film a carrier film; and coating the dielectric film to the conductive first electrode. The method of claim 1, wherein the polymerizable molecules are formed in situ, the method further comprising: coating a composition to the first electrode, the composition comprising a crosslinking agent and a plurality of polymerizations a precursor of a molecular molecule comprising one or more polar functional groups, an ionizable functional group or a combination of the foregoing; and activating the crosslinking agent to crosslink the polymerizable properties A molecular precursor to provide a dielectric film comprising a plurality of polymeric molecules. The method of claim 13, wherein the polymerizable molecular precursor comprises: (i) an amino acid molecule, (ii) an oligopeptide, (iii) a polypeptide, or (iv) a combination of the foregoing. The method of claim 13, wherein the polymerizable molecular precursor further comprises a p-xylene monomer. A method of making an energy storage device, comprising: providing a first polymer sheet or roll having a metallized surface and including an insulating layer on the metallized surface, wherein the insulating layer does not completely cover the Metallized surface, such that an edge portion of the metallized surface is not covered; a dielectric film is applied to the insulating layer, the dielectric film includes a film material, and the film material (i) is electrically insulating And/or exhibiting a high permittivity and (ii) comprising a plurality of polymerizable molecules having one or more polar functional groups, ionizable functional groups or a combination of the foregoing; allowing a second metallization polymerization a sheet or roll contacting the dielectric film, the second sheet or roll having a metallized surface and including an insulating layer on the metallized surface, wherein the insulating layer does not completely cover the metalized surface俾 such that an edge portion of the metallized surface is uncovered, wherein the second sheet or web is oriented such that the insulating layer contacts the dielectric film and the second sheet or roll is not The edge portion of the cover is adjacent to the uncovered portion of the first sheet or roll to form a composite multilayer surface; the composite multilayer surface is wound into a rolled configuration, Or cutting and stacking portions of the composite multilayer surface to form a stacked configuration; uncovered the edge portion of the first sheet or web and the uncovered portion of the second sheet or web The edge portion is bonded to a conductor cover or a conductor polymer contained in a non-conductor support bracket having an electrical connection; Electrically connecting the composite multilayer surface to a positive electrode and a negative electrode; and applying an electric field to the multilayer composition, the electric field being applied for an effective period of time for use in the polymerizable molecules At least some of the insulating layer bonded to the first sheet or web, the insulating layer of the second sheet or web, or both. A method of fabricating an energy storage device, comprising: providing a first electrode in a containment device having an upper surface including an insulating layer; positioning a perforated non-conductor separator sheet on the first electrode Disposing a second electrode on the separator sheet, the second electrode having a lower surface including an insulating layer, such that the insulating layer of the second electrode contacts the separator sheet; adding a dielectric a material for filling a space inside the apertured separation sheet and for contacting the first electrode and the second electrode, wherein the dielectric material (i) is electrically insulating and/or exhibits a high permittivity and Ii) comprising a plurality of polymeric molecules having one or more polar functional groups, ionizable functional groups or a combination of the foregoing; and spanning the first electrode, the dielectric material by applying an electric field And the second electrode is such that the first electrode is a positive electrode and at least some of the polymerizable molecules are bonded to the insulating layer of the first electrode, and the electric field is applied to maintain an effective period Cycle, so the junction of these polymerizable bond in the molecule at least some of the insulating layer to the first electrode. An energy storage device comprising: a conductive first electrode; a conductive second electrode; and a space-limited dielectric film disposed on the conductive first electrode and the conductive Between the second electrodes, the space-constrained dielectric film comprises a plurality of polymerizable molecules having one or more polar functional groups, ionizable functional groups or a combination of the foregoing, the energy storage The device has an energy storage capacity, and the energy storage capacity is at least 1 Wh/kg when the energy storage device is not charged and/or discharged, and is disposed only on the electrically conductive first electrode and the second electrode The space is limited by the weight of the dielectric film. The energy storage device according to claim 18, wherein the polymerizable molecules are protein molecules. The energy storage device of claim 18 or 19, wherein at least 1% of the plurality of polymerizable molecules are bonded to the conductive first electrode. The energy storage device of claim 20, wherein the energy storage device has an energy storage capacity at least 100X greater than an energy storage capacity of the energy storage device: (i) a conductive first electrode; (ii) a conductive second electrode; and (iii) an electrically insulating and/or high permittivity dielectric film disposed between the electrically conductive first electrode and the electrically conductive second electrode, the dielectric The film includes a plurality of polymerizable molecules having one or more polar functional groups, ionizable functional groups, or a combination of the foregoing, wherein the polymerizable molecules are not bonded to the first of the conductive electrode. The energy storage device of claim 20, wherein the space-limited dielectric film has a permittivity greater than 50% to 10,000,000% of a permittivity of the underlying dielectric film: the dielectric film includes a plurality A polymerizable molecule having one or more polar functional groups, ionizable functional groups, or a combination of the foregoing, wherein the polymeric molecules are not bonded to the electrically conductive first electrode. An energy storage device according to claim 18 or 19, wherein the polymerization At least some of the molecules are bonded to the surface of the electrically conductive first electrode that contacts the space constrained dielectric film such that the polymerizable molecules are bonded to at least 1% of the surface. The energy storage device of claim 18 or 19, further comprising: an insulating layer disposed between the electrically conductive first electrode and the space constrained dielectric film; An insulating layer between the second electrode and the dielectric film; or a first insulating layer disposed between the conductive first electrode and the dielectric film and a first electrode disposed on the conductive film a second insulating layer between the second electrode and the space-limited dielectric film. The energy storage device of claim 24, wherein at least 1% of the plurality of polymerizable molecules are bonded to the first insulating layer.