KR102561229B1 - Method for chemical binding of the dielectric to the electrode after their assembly - Google Patents

Abstract

The present invention discloses a high permittivity and low leakage energy storage device such as a capacitor and a method for manufacturing the energy storage device. The disclosed device includes electrically conductive first and second electrodes and a three-dimensionally confined dielectric film disposed between the first and second electrodes. The three-dimensionally confined dielectric film includes a plurality of polymer molecules, and at least some of the polymer molecules are bonded to the first electrode. The disclosed device may include an insulating layer between the first electrode and the dielectric film and/or between the second electrode and the dielectric film.

Description

Method for chemical binding of the dielectric to the electrode after their assembly

This application claims priority to U.S. Patent Application Serial No. 14/574,175, filed on December 17, 2014, which is a continuation-in-part of U.S. Patent Application Serial No. 14/499,028, filed on September 26, 2014, which The entire contents are incorporated herein by reference. This application is also a continuation-in-part of U.S. patent application Ser. No. 14/156,457, filed on Jan. 16, 2014, which claims priority to U.S. Provisional Application No. 61/808,733, filed on Apr. 5, 2013, each of which is incorporated herein by reference in its entirety. This application is also a continuation-in-part of US patent application Ser. No. 13/671,546, filed on Nov. 7, 2012, now abandoned, and filed on Aug. 30, 2012, filed on Jan. 21, 2014 as U.S. Patent No. 8,633,289. Continuing-in-part of U.S. Patent Application Serial No. 13/599,996 filed on March 29, 2013, U.S. Patent Application Serial No. 14/490,873 filed on September 19, 2014 , each of which is incorporated herein by reference in its entirety.

The present disclosure relates to a high permittivity and low leakage energy storage device, such as a capacitor, and a method of manufacturing the energy storage device.

Electrostatic capacitance is an energy storage method that has not been widely used for mass electrical energy storage. Typically, charge and discharge mechanisms for conventional electrostatic energy storage in dielectric materials are in the time domain ranging from picoseconds to hundreds of microseconds. Higher density energy storage in both energy density per unit mass and energy density per unit volume is needed.

The present disclosure relates to a high permittivity and low leakage energy storage device, such as a capacitor, and a method of manufacturing the energy storage device. An embodiment of the energy storage device includes an electrically conductive first electrode, an electrically conductive second electrode, and a sterically constrained dielectric film disposed between the electrically conductive first electrode and the electrically conductive second electrode. And, the three-dimensionally confined dielectric film includes a plurality of polymer molecules. wherein the energy storage device stores energy of at least 1 Wh/kg based solely on the weight of the sterically confined dielectric film disposed between the electrically conductive first and second electrodes, in the absence of a charged and/or discharged energy storage device; have capacity In some embodiments, an insulating layer is disposed on the electrically conductive first electrode, on the electrically conductive second electrode or on the electrically conductive first and second electrodes. In any one or all of the above embodiments, the polymer molecule can have one or more polar functional groups, ionizable functional groups, or combinations thereof. In any one or all of the above embodiments, at least 1% of the polymer molecules may be bound to the first electrode or to an insulating layer disposed on the first electrode. In any one or all of the above embodiments, the polymeric molecule can be a protein molecule. In any one or all of the above embodiments, the polymer molecule can be bound to at least 1% of the surface of the electrically conductive first electrode in contact with the dielectric film.

In some embodiments, a method includes fabricating an energy storage device, wherein (a) applying a dielectric film to an electrically conductive first electrode, wherein the dielectric film is i) electrically insulative and/or intrinsic ii) comprising a film material comprising a plurality of polymer molecules, (b) contacting said dielectric film with an electrically conductive second electrode, and (c) said first electrode, said dielectric film and applying an electric field across the second electrode, thereby fabricating the energy storage device. In certain embodiments, the method further comprises applying an insulating layer to the electrically conductive first electrode to form a composite first electrode, and applying the dielectric film to the insulating layer of the composite first electrode. . In any one or all of the above embodiments, the electric field can be greater than 100 V/cm. In any one or all of the above embodiments, the polymeric molecule can be a protein molecule.

In some embodiments, a method includes fabricating an energy storage device, wherein (a) applying a dielectric film to an electrically conductive first electrode, wherein the dielectric film is i) electrically insulative and/or intrinsic comprising a film material comprising a plurality of polymer molecules exhibiting a translucency and ii) having one or more polar functional groups, ionizable functional groups, or combinations thereof; (b) contacting the dielectric film with an electrically conductive second electrode; and (c) forming a three-dimensionally confined dielectric film by bonding at least a portion of the polymer molecules to the electrically conductive first electrode, thereby manufacturing the energy storage device. bonding at least a portion of the polymer 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 electrode becomes an anode; , wherein the electric field is applied for a time effective to couple at least a portion of the polymer molecules to the first electrode; ii) treating the dielectric film with a chemical agent, or iii) a combination thereof.

In any one 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 electric field is 0.005 to 1 V/μm and the effective time is 1 second to 30 minutes.

In any one or all of the above embodiments, the method further comprises applying an insulating layer to the electrically conductive first electrode to form a composite first electrode, and applying the dielectric film to the insulating layer of the composite first electrode. An application step may be further included. In an embodiment, bonding at least some of the polymer molecules comprises applying an electric field across the composite first electrode, the dielectric film and the second electrode for the effective time, whereby the polymer molecules At least some of the molecules bond to the insulating layer of the composite first electrode. In one independent embodiment, treating the dielectric film with a chemical agent comprises applying a radical initiator to the insulating layer prior to applying the dielectric film to the insulating layer, and applying the dielectric film to the insulating layer. and later activating the radical initiator, thereby binding at least a portion of the polymer molecules to the insulating layer of the composite first electrode. In one independent embodiment, treating the dielectric film with a chemical agent comprises (i) derivatizing the polymer molecules with a derivatizing agent to provide functional groups capable of cross-linking to the insulating layer of the composite first electrode; (ii) including a crosslinking agent in the film material of the dielectric film, (iii) including a radical initiator in 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, (v) step of activating the radical initiator, (v) the insulating layer and (vi) applying plasma to the insulating layer prior to applying the dielectric film thereto, or (vi) any combination thereof. In any one or all of the above embodiments, the insulating layer may include polymerized p-xylylene.

In any one or all of the above embodiments, the polymer molecule is a protein, parylene, acrylic acid polymer, methacrylic acid polymer, polyethylene glycol, urethane polymer, epoxy polymer, silicone polymer, terpenoid polymer, natural resin polymer, polyisocyanates or combinations thereof. In any one or all of the above embodiments, the polymeric molecule may comprise a protein or a derivatized protein.

In any one or all of the above embodiments, the electrically conductive second electrode can be a composite second electrode comprising an insulating layer, the composite second electrode positioned such that the insulating layer contacts the dielectric film. . In any one or all of the above embodiments, applying the dielectric film to the electrically conductive first electrode comprises forming a dielectric film on a removable carrier film, removing the removable carrier film, and and applying the dielectric film to the electrically conductive first electrode.

In any one or all of the above embodiments, the polymer molecule may be formed in situ . In this embodiment, the method includes applying to the first electrode a composition comprising a crosslinking agent and a plurality of polymer molecular precursors comprising one or more polar functional groups, ionizable functional groups, or combinations thereof, and activating the crosslinking agent. and cross-linking the polymer molecule precursors thereby providing a dielectric film including a plurality of polymer molecules. In some embodiments, the polymer molecule precursor comprises (i) an amino acid molecule, (ii) an oligopeptide, (iii) a polypeptide, or (iv) a combination thereof. In some embodiments, the polymer molecular precursor further comprises a p-xylylene monomer.

In one independent embodiment, a method of making an energy storage device includes (a) providing a first sheet or roll of polymer having a metallized surface and comprising an insulating layer on the metallized surface, the insulating layer comprising: the layer does not completely cover the metallized surface such that edge portions of the metallized surface are exposed; (b) applying a dielectric film to the insulating layer, wherein the dielectric film i) is electrically insulating and/or exhibits a high permittivity, and ii) comprises a plurality of polar functional groups, ionizable functional groups, or combinations thereof. comprising a film material comprising polymer molecules; (c) contacting a second sheet or roll of metallized polymer with the dielectric film, the second sheet or roll having a metallized surface and comprising an insulating layer on the metallized surface; The insulating layer does not completely cover the metallized surface such that an edge portion of the metallized surface is exposed, and the second sheet or roll is such that the insulating layer contacts the dielectric film and the exposed portion of the second sheet or roll. orienting the edge portion to proximate the exposed edge portion of the first sheet to form a composite multilayer surface; (d) winding the composite multi-layer surface into a rolled form or cutting and laminating portions of the composite multi-layer surface to form a laminated form; (e) bonding exposed edge portions of the first sheet or roll and the second sheet or roll to a conductive polymer contained within a conductive cap or non-conductive holder having electrical connections; (f) electrically connecting the composite multilayer surface to an anode and a cathode; and (g) applying an electric field to the multilayer composite, wherein the electric field causes at least some of the polymer molecules to bond to the insulating layer of the first sheet or roll, the insulating layer of the second sheet or roll, or both. It includes a step of applying for an effective time for

In one independent embodiment, a method of manufacturing an energy storage device includes (a) providing a first electrode in a containment device having a top surface comprising an insulating layer; (b) placing a perforated non-conductive separator sheet on the insulating layer of the first electrode; (c) positioning a second electrode having a lower surface including an insulating layer on the separator sheet so that the insulating layer of the second electrode contacts the separator sheet; (d) adding a dielectric material to fill the space in the perforated separator sheet and bring the first and second electrodes into contact, wherein the dielectric material is i) electrically insulative and/or exhibits a high permittivity, and ii) one or more polarities comprising a plurality of polymer molecules having a functional group, an ionizable functional group, or a combination thereof; and (e) coupling at least some of the polymer molecules to the insulating layer of the first electrode by applying an electric field across the first electrode, the dielectric material and the second electrode such that the first electrode becomes an anode. , the electric field is applied for an effective time to couple at least some of the polymer molecules to the insulating layer of the first electrode.

The above and other objects, features and advantages of the present invention will become more apparent from the following detailed description taken with reference to the accompanying drawings.

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 cross-sectional view of another exemplary energy storage device.
4 is a schematic exploded view of an exemplary energy storage device having a rolled form.
5 is a schematic exploded view of an exemplary energy storage device including a perforated separate plate.
6 is a cross-sectional side view of the energy storage device of FIG. 5;
7 is an optical micrograph of a cathode from an energy storage device made by one embodiment of the disclosed method.
8 is an optical picture of an anode from the energy storage device of FIG. 7;
Figure 9 is an optical photograph of the cathode of Figure 7 after rinsing with running water.
10 is an optical photograph of the anode of FIG. 8 after rinsing with running water.
11 is an optical photograph of the cathode of FIG. 9 taken at an angle.
FIG. 12 is an optical photograph of the anode of FIG. 10 taken from a predetermined angle.
13 is an optical photograph of the anode of FIG. 10 after manual scraping to remove bound polymer molecules.

The present disclosure relates to an energy storage device comprising a dielectric material comprising polymer molecules and a method of manufacturing the energy storage device, wherein at least a portion of the polymer molecules are bonded to electrodes of the energy storage device. The energy storage device stores energy through, for example, an electrostatic type charge/discharge mechanism similar to an electrostatic capacitor. Embodiments of energy storage devices are useful in the fields of electronic devices, bulk electrical storage, and any other device that uses or requires storage of electrical energy.

I. Definition

The following explanations of terms and abbreviations are provided to better describe the present disclosure and guide those skilled in the art in the practice of the present disclosure. As used herein, “comprising” means “including” and the singular form or “the” refers to plural references unless the context clearly dictates otherwise. include The term “or” refers to a single element or a combination of two or more of the recited alternative elements, unless the context dictates otherwise.

Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. Although methods and materials similar or equivalent to those described herein may be used in the practice or testing of the present disclosure, 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 are apparent from the following detailed description and claims.

Unless otherwise indicated, all numbers expressing quantities of components, voltages, temperatures, times, etc., used in the specification or claims are to be understood as being modified by the term "about." Thus, unless otherwise indicated, implicitly or explicitly, numerical parameters presented are approximations that may depend on the desired property sought and/or limits of detection under standard test conditions/methods known to those skilled in the art. Where the prior art discussed is directly and explicitly distinguished from an embodiment, the number of an embodiment is not an approximation unless the word "about" is recited.

To facilitate review of various embodiments of the present disclosure, explanations of certain terms are provided below:

Capacitor : An energy storage device comprising two conductive plates separated by a substantially non-conductive material called a dielectric . The capacitance value or storage capacity of a capacitor depends on the size of the plates, the distance between the plates and the characteristics of the dielectric. This relationship is shown in Equation 1:

Equation 1: C = (e ₀ e _r A)/d

where e ₀ = electric permittivity of vacuum (8.8542 × 10 ^-12 F/m), e _r = relative permittivity (defined below), A = surface area of one plate (of equal size), and d = distance between two plates .

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

Dielectric breakdown voltage: The voltage at which the dielectric material “breaks down” and conducts current. Dielectric breakdown voltage is an indicator of the dielectric strength of a material.

Derivatized : The term “derivatized,” as used herein with reference to polymers , refers to polymers to which functional groups have been added through chemical transformation. For example, proteins can be derivatized with maleic anhydride to provide proteins with maleic acid functionality.

Electrically insulative material or insulator : An insulator is a material through which internal charge does not flow freely, and therefore it conducts little or no current. Recognizing that no perfect insulator exists, the term "electrically insulating material" as used herein refers to a material that is primarily insulating, i.e., a capacitor, which has a threshold breakdown field that exceeds the electric field applied across the material during normal use. ), which means a material capable of avoiding electrical breakdown during normal use.

Electrode: As used herein, the term “electrode” refers to an electrical conductor (eg, metal) or a “composite” electrode comprising an electrical conductor and a non-conductive material on the surface of the electrical conductor.

Functional group: A specific group of atoms within a molecule that is responsible for specific chemical reactions and/or electrostatic interactions of molecules. Exemplary functional groups include, without limitation, halo (fluoro, chloro, bromo, iodo), epoxide, hydroxyl, carbonyl (ketone), aldehyde, carbonate ester, carboxylate, ether, ester, peroxy, hydro Peroxy, carboxamide, amine (primary, secondary, tertiary), ammonium, amide, imide, azide, cyanate, isocyanate, thiocyanate, nitrate, nitrite, nitrile, nitroalkane, nitro bovine, pyridyl, phosphate, sulfonyl, sulfide, thiol (sulfohydryl) and disulfide groups. Polar functional groups do not form ions in the environment of use, but instead provide partial separation of positive and negative charges within a molecule. Ionizable functional groups are those that may be in an ionized state in the environment of use (eg, -COOH to COO-, -NH ₃ to NH ₄ ⁺ ).

Insulative or non - conductive layer/coating : As used herein, the terms “insulative layer,” “insulating coating,” “non-conductive layer,” and “non-conductive coating” refer to an electrically insulative property in terms of ohmic conductivity. refers to a layer or coating of a phosphorus material, ie the material has an ohmic conductivity of less than 1×10 ⁻¹ Siemens per meter (S/m).

Parylene : Also known as polymerized p-xylylene (also known as Puralene ^™ polymer), or polymerized substituted p - xylylene. Polymerized p-xylylene satisfies the formula:

.

Permittivity : As used herein, the term "permittivity" refers to the ability of a material to change the "dielectric constant" of its spatial volume to be higher than the permittivity of vacuum by being polarized. The relative permittivity of a material is the measured static permittivity constant divided by the dielectric constant of vacuum , as shown in Equation 2.

Equation 2: e _r = e _s /e ₀

where: e _r = relative permittivity, e _s = measured permittivity and e ₀ = electric permittivity of vacuum (8.8542 × 10 ^-12 F/m). Vacuum has a relative permittivity of 1, whereas water has a relative permittivity of 80.1 (at 20°C) and organic coatings generally have a relative permittivity of 3 to 8. Generally, the term "high permittivity" refers to a material having a relative permittivity of at least 3.3. As used herein, the term “high permittivity” also refers to a material that has a permittivity that is increased by at least 10% using permittivity enhancement techniques such as immersion in an electric field.

Oligo : A prefix meaning "a few". For example, an oligopeptide may contain 2 to 20 amino acids linked via amide bonds, whereas a polypeptide contains more than 20 amino acids. Oligopeptides include dipeptides, tripeptides, tetrapeptides, pentapeptides and the like.

Polar: The term “polar” refers to a compound or functional group within a compound in which electrons are not shared equally between atoms, ie regions of positive and negative charge are permanently separated.

Polypeptide: More than 20 amino acids or polymers joined via amide linkages. The term polypeptide includes natural as well as synthetic polypeptides.

Polymer / polymeric molecule: A molecule of repeating structural units (eg monomers) formed through a chemical reaction, i.e. polymerization.

Sterically constrained dielectric film: As used herein, the term "sterically constrained dielectric film" is an electrically insulating and/or comprising a plurality of polymer molecules having one or more polar functional groups, ionizable functional groups or combinations thereof. As a high permittivity dielectric film, at least some of the polymer molecules are sterically confined, that is, at least some of the polymer molecules are constrained in physical motion of the entire polymer molecule within the dielectric material. Steric confinement occurs when some of the polymer molecules are bonded to the electrode surface in contact with the dielectric film. The polymer molecules may be bonded to the electrode surface by embodiments of the methods disclosed herein.

II. Energy storage device with three-dimensionally confined dielectric film

An embodiment of an energy storage device includes two conductive surfaces (electrodes) substantially parallel to each other and a three-dimensionally confined dielectric film between the conductive surfaces. The device may further include an insulating layer or coating over one or both of the electrodes. The dielectric material includes a plurality of polymer molecules, at least some of which are bonded to one of the electrodes or to an insulating layer on the electrode.

A. electrode

In some embodiments, the electrode is planar or substantially planar. Each electrode may independently have a smooth or rough surface. Rough electrodes can be made, for example, from carbon particles, which provide the electrode with much more surface area than smooth electrodes, such as electrodes made of polished metal. The amount of surface roughness selected may depend, at least in part, on external electrical parameters that may be required for a given energy storage or capacitive device. Compared to energy storage devices that include smooth electrodes, similar energy storage devices that include rough electrodes have much faster charge and discharge currents (e.g., 100 times faster) for shorter time periods, such as a few microseconds to milliseconds. , followed by a slow discharge rate similar to that provided by energy storage devices with smooth electrodes.

B. insulation layer

Each electrode may be covered with an insulating (non-conductive) layer or insulating coating on one or more surfaces. An electrode with an insulating coating is referred to as a “composite electrode”. In the energy storage device, the composite electrode is oriented such that the insulating layer is in contact with the dielectric material. The insulating layer provides increased insulating properties for the electrodes as well as bonding sites for the dielectric material to be added. The insulating layer has an ohmic conductivity of less than 1×10 ⁻¹ S/m. In some embodiments, the insulating layer has an ohmic conductivity of less than 1×10 ⁻² S/m, less than 1×10 ⁻⁵ S/m, or less than 1×10 ⁻¹⁰ S/m. In certain embodiments, the ohmic conductivity is between 1 x 10 ^-25 S/m and 1 x 10 ^-1 S/m, between 1 x 10 ^-10 S/m and 1 x 10 ^-1 S/m, or 1 x 10 ^-5 S/m to 1 × 10 ^-1 S/m. The coating can range in thickness from a few nm to more than 10 μm. In some embodiments, the insulating layer has an average thickness of 5 nm to 10 μm, such as 0.1 to 10 μm, 0.3 to 10 μm, 0.3 to 5 μm or 0.3 to 2 μm. In one embodiment, the coating has an average thickness that is less than 10% of the total thickness of the capacitor measured from the outer surface of the first electrode to the outer surface of the second electrode. The insulative coating may be applied by any suitable means including, but not limited to, vapor deposition, liquid spraying, and other techniques known to those skilled in the art of coating application. Exemplary insulating coatings are polymerized p-xylylene, such as Puralene ^™ polymer coatings, for example as disclosed in US 2014/0139974.

The insulating layer may be modified with suitable comonomers to provide increased permittivity and/or attachment sites for polymer molecules of the dielectric material. In some embodiments, the comonomer contains one or more unsaturated bonds. The insulating layer containing polymerized p-xylylene is, for example, olefin, vinyl derivative, alkynyl derivative, acryl compound, allyl compound, carbonyl, cyclic ether, cyclic acetal, cyclic amide, oxazoline and these may be modified by the inclusion of comonomers, including but not limited to combinations. In some embodiments, the comonomer is an acrylate (eg, 2-carboxyethyl acrylate), a methacrylate (eg, 3-(trimethoxysilyl)propyl methacrylate), α-pinene, R-(- ) carvone, linalool, cyclohexene, dipentene, α-terpinene, R-(+)-limonene, and combinations thereof. Copolymers may include alternating monomers or may be in the form of block copolymers.

C. polymer Dielectric material containing molecules

Some embodiments of the energy storage device include a dielectric film comprising a single dielectric material layer, and other embodiments include a dielectric film comprising multiple layers of dielectric material. The multilayer dielectric material may be formed from a single material that is deposited multiple times, with or without surface modification between depositions. Alternatively, each layer may have a different chemical composition. In some embodiments, the device is composed of a dielectric film comprising two or more dielectric layers having different electrical permittivities. The dielectric film may have an average thickness ranging from several μm to several mm. In some embodiments, the dielectric film has an average thickness such as 10 μm to 5 mm, such as 10 μm to 1 mm, 10 μm to 500 μm, or 50 μm to 250 μm. In some embodiments, the dielectric film has an average thickness between 80 and 120 μm, for example an average thickness of 100 μm.

In some embodiments, the dielectric material has liquid properties and has a viscosity similar to or greater than that of honey. In certain embodiments, the dielectric material has a viscosity of 10,000 cP to 250,000 cP. In one independent embodiment, the dielectric material is a solid.

The dielectric material may be substantially non-conductive: that is, the dielectric material is not oxidized/reduced at or near the positive electrodes and exhibits no ohmic conductivity. Thus, embodiments of the disclosed energy storage devices are more closely related to electrostatic capacitors, rather than conventional electrochemical cells. However, the dielectric material can store a greater amount of specific energy for a longer period of time than a conventional electrochemical cell or electrostatic capacitor.

In some embodiments, the energy storage device includes a high-k dielectric material that is non-conductive. Two non-limiting examples of non-conductive high-k dielectrics are proteins derivatized with zein and maleic anhydride in a shellac matrix. In another embodiment, the dielectric material is conductive; In this embodiment, the electrode is typically coated with an insulating layer described above to mitigate or prevent ohmic electrical conduction. If the dielectric material has a resistance of less than 2.5 MΩ/cm 2 , an insulating layer may be used. In some embodiments, the energy storage device includes a dielectric material having a permittivity of at least 10 to 2,000,000 and an ohmic conductance of 1 S/m to 1 x 10 ⁻²⁵ S/m.

Embodiments of the disclosed energy storage devices include dielectric materials comprising polymer molecules having polar functional groups and/or ionizable functional groups, resulting in intramolecular dipoles and dipole moments. The polymer molecule may further include one or more double bonds. In some embodiments, the dielectric material is a film that contacts the two electrodes of the energy storage device. Typically, contact can be described as direct physical contact between the film and the entire contact surface of the electrode. The dielectric material may be in contact with the “bare” metal or carbon-based electrode surface, or with the insulating layer of the composite electrode.

In some embodiments, the polymer molecule is a polar polymer. Proteins are readily available and inexpensive polar polymers with low toxicity. Low toxicity is a great advantage over other polymers, allowing the energy storage device to be recycled or incinerated. Protein molecules include amino acids with polar functional groups and/or ionizable functional groups. Other suitable polymers include substituted (eg fluorinated) and unsubstituted parylene polymers, acrylic acid polymers, methacrylic acid polymers, polyethylene glycols, urethane polymers, epoxy polymers, silicone polymers, organic terpenoid polymers, natural organic polymers. (resins such as shellac), polyisocyanates, and combinations thereof. Also copolymers such as acrylate copolymers (e.g. copolymers with ethylenebutyl-, ethyl- and methyl-acrylates) and parylene copolymers (e.g. p-xylylene with acrylates (e.g. 2- carboxyethyl acrylate), methacrylates (e.g. 3-(trimethoxysilyl)propyl methacrylate), α-pinene, R-(-)carvone, linalool, cyclohexene, dipentene, α-ter copolymers with pinene, R-(+)-limonene, and combinations thereof) are within the scope of this disclosure. Non-limiting examples of polar polymers include zein, hemp protein, wheat gluten, poly(acrylic acid-co-maleic acid), poly(acrylic acid), whey protein isolate ), soy protein isolate, pea protein extract, shellac, and combinations thereof.

In certain embodiments, the polymer molecule is derivatized to attach additional functional groups, such as functional groups that promote subsequent incorporation of the polymer molecule to the bare electrode surface (ie, bare metal surface or carbon surface) or composite electrode surface. Exemplary derivatizing agents include, but are not limited to, anhydrides, carbodiimides, imidoesters, and reagents comprising a combination of N-hydroxysuccinimide and maleimide, arylazide, or diazirine groups. In some embodiments, the polymer is an anhydride such as maleic anhydride, itaconic anhydride, cis-4-cyclohexene-1,2-dicarboxylic anhydride or cis-5-norbornene-endo-2,3-dicarboxylic anhydride. is derivatized with The derivatized polymer molecule can be bound to the electrode surface by cross-linking or other reaction with the electrode surface. When a polymer molecule is derivatized with maleic anhydride, for example the derivatized polymer molecule can be cross-linked via a double bond. Crosslinking may be effected by any suitable means such as chemical agents (eg radical initiators), ultraviolet light activation or thermal activation.

The present inventors have surprisingly found that polymer molecules having the above properties can be used for energy storage when sterically confined, even though the polymer molecules cannot move freely between electrodes. Any means including covalent bonding (single or multiple), van der Waals forces or hydrogen bonding prior to charging and/or discharging the energy storage device comprising an electrode and a dielectric material comprising the polymer molecule. It can be sterically constrained by binding the polymer molecule to the surface of the bare electrode of the composite electrode or to the non-conductive or insulating coating of the composite electrode. In some embodiments, the polymer molecule is bonded to an anode. The polymer molecules remain bound to the electrodes as the energy storage device is charged and discharged during subsequent use, such as when the energy storage device is subsequently used in an electronic circuit.

In an energy storage device comprising a dielectric material, the imposition of an external electric field from the electrode induces the collapse of the lowest energy state of the ion or dipole obtainable from its present position in the dielectric material layer. Thus, when an electric field is applied, the dipoles or ions move from their resting position (i.e., the position before the electric field is applied), which in turn induces a rearrangement of the charge distribution within the material. This leads to a different rearrangement of all other dipoles that continues throughout the dielectric material. Energy not converted to heat is absorbed by the dielectric material. When energy is released, the reverse of this process can occur if the stored energy is not released through some other mechanism, such as increased thermal motion (random molecular motion proportional to temperature).

While not wishing to be bound by any particular theory, within a large molecule, different parts of the molecule are bonded in place resulting in global motion to lower energy levels and subsequent potential energy bonded to the electrodes and not released in the form of thermal motion. It is believed that motion of only a portion of the molecule can occur, sufficiently preventing enemy emission. This restraint of motion reduces the degree of freedom of the dielectric molecules and consequently reduces the ability of the molecules to dissipate the energy absorbed as heat in the electric field. Thus, bound polymer molecules bind to the electric field such that the polymer molecules cannot release energy in the form of heat due to the reduced degree of freedom. The motion of certain parts of macromolecules can be related to, and similar to, electrophoretic motion known to those who use such techniques to analyze biological macromolecules.

While not wishing to be bound by any particular theory, when a portion of the polymer is bonded to an electrode (or coating on an electrode), the remainder of the polymer reacts to an electric field to reorient the polar and/or ionizable functional groups while making the dielectric dielectric It is believed that the polymer can be stretched, twisted or bent within the film. These changes in conformation and position store energy within the energy storage device. When the energy storage device is discharged, the stored energy is released as electrical energy as the bound polymer molecules revert to a less regular three-dimensional structure. A dielectric material comprising polymer molecules, in which at least some of the polymer molecules have a reduced degree of freedom, is referred to as a "sterically constrained dielectric film".

Accordingly, embodiments of the disclosed energy storage devices include a sterically confined dielectric material comprising polymer molecules. In some embodiments, at least 1%, at least 10%, at least 25%, at least 50%, at least 80%, or at least 90% of the polymer molecules in the sterically constrained dielectric material are bound to electrodes. In certain embodiments, at least some of the polymer molecules are bonded to the positive electrode. When the electrode is a composite electrode, the polymer molecules are bonded to the insulating layer of the composite electrode. The percentage of binding can be evaluated by measuring the amount of polymer molecules washed off the electrode after binding at least some of the polymer molecules to the electrode.

In some embodiments, the polymer molecules are bound to at least 1%, at least 25%, at least 50%, at least 80% or at least 90% of the anode surface in contact with the dielectric material. The percentage of surface covered by the bound polymer can be assessed visually, for example by light microscopy. After manufacturing the energy storage device, the device can be disassembled and inspected. The anode is washed by exposing it to running water to remove unbound material and then examined under an optical microscope. Areas of the surface covered by bound polymers can be easily distinguished from areas without bound polymers.

The bonding between the polymer molecules and the electrodes is such as washing the electrodes and bonded polymer molecules with running water having a force equivalent to that of water falling from a height of 1 meter, or manually rubbing the bonded polymers under running water with a force of less than 20 N. , strong enough to withstand everyday breakdowns. Such strong coupling is only observed when an electric field is applied to the energy storage device during fabrication of the device. In some embodiments, at least some bonds can be broken by applying an external voltage of reverse polarity to the device such that the positive electrode becomes negative.

D. Exemplary Energy Storage Devices

In some implementations, energy storage device 100 includes an anode 110, a sterically confined dielectric layer 120 and a cathode 130 (FIGS. 1 and 2). Anode 110 and cathode 130 may independently be a conductive metal, semiconductor, conductive polymer, or other electrically conductive material. In certain cases, it is advantageous for this material to be a high surface area conductor, such as a carbon- or graphene-based electrode. The sterically constrained dielectric layer 120 comprises a film material comprising a plurality of polymer molecules 122 that (i) are electrically insulative and/or have a high permittivity and (ii) contain polar functional groups and/or ionizable functional groups. The polymer molecule may also contain one or more double bonds. Optionally, insulating layers 140 and 150 are disposed between anode 110 and dielectric layer 120 and/or between dielectric layer 120 and cathode 130 . In some implementations, the insulating layer 140, 150 is the total thickness of the energy storage device 100 measured from the outer surface 112 of the first electrode 110 to the outer surface 132 of the second electrode 130. It may have a thickness of less than 10% of An insulating layer may be included to prevent Joule heating and/or ohmic conduction losses occurring during use of the device. At least some of the polymer molecules 122 are bonded to the anode 110 (or to the insulating layer 140 if present) via attachment points 124 . Each attachment point 124 is a covalent bond (single, double, or triple), hydrogen bond, van der Waals forces, or an anode, assuming that the anode 110 retains a positive charge relative to the cathode 130. Another bonding force strong enough to prevent dissociation of the polymer molecules 122 from (110) may be. Some of the polymer molecules 122 may be bonded to the negative electrode 130 (or to the insulating layer 150 if present) via attachment points 126 . Each attachment point 126 is a covalent bond (single, double, or triple), hydrogen bond, van der Waals forces 130, or negative electrode 130, assuming that negative electrode 130 retains a negative charge relative to positive electrode 110. may be another binding force strong enough to prevent dissociation of the polymer molecule 122 from Anodes and cathodes 110, 130 may be attached to a voltage source via conductive leads 115, 135 (eg, conductive wire leads, traces, or other pathways).

In one stand-alone implementation, energy storage device 200 includes an anode 210, a sterically constrained dielectric layer 220, and a cathode 230 (FIG. 3). The sterically confined dielectric layer 220 is a film material comprising a plurality of polymer molecules 222, 223, 224 that (i) are electrically insulative and/or exhibit high permittivity and (ii) contain polar functional groups and/or ionizable functional groups. include The polymer molecule may also contain one or more double bonds. Insulating or non-conductive layers 240 and 250 are disposed between the anode 210 and the dielectric layer 220 and between the dielectric layer 220 and the cathode 230 . Some of the polymer molecules 222 have polar and/or ionizable functional groups that have a negative charge or partially negative charge and are bonded to the insulating layer 240 via attachment points 225 . Some of the polymer molecules 223 have a polar or ionizable functional group with a positive charge or a partial positive charge, and are bonded to the insulating layer 250 via an attachment point 226 . Some of the polymer molecules 224 have at least one polar functional group or ionizable functional group having a positive or partial positive charge, and at least one polar functional group or ionizable group having a negative or partial negative charge. Polymer molecules 224 of sufficient length can extend the distance between insulating layers 240 and 250 and can bond to both insulating layers. Anodes and cathodes 210 and 230 may be attached to a voltage source via conductive leads 215 and 235 .

In one exemplary embodiment, the energy storage device has a rolled or stacked form of dielectric layers. FIG. 4 shows an exemplary energy storage device 300 having an electrode 310 having a rolled form that includes a three-dimensionally confined dielectric layer 320 on a substrate 325 . A second substrate (not shown) may be positioned on top of the dielectric layer 320 such that the three-dimensionally confined dielectric layer 320 is sandwiched between the two substrates. As shown in FIG. 4 , the sterically confined dielectric layer 320 does not extend to one edge 326 of the substrate 325 . The upper and lower portions of the rolled electrode 310 are bonded to a conductive polymer 330, which is contained within caps or holders 340, 350 having electrical contacts 345, 355. An optional sleeve (not shown) may be placed around the device 300 to provide mechanical and electrical protection during use.

In one stand-alone implementation shown in FIGS. 5 and 6 , the exemplary energy storage device 400 includes two electrodes 410 and 420 . The electrodes 410 and 420 may be conductive sheets. In some embodiments, the conductive sheet is metal (eg, aluminum) and may have a size of about 500 mm ² with a thickness of about 2 mm. Each sheet is covered with an insulating layer 412, 422 such as a Puralene ^™ polymer coating to create an electrode. Electrically conductive leads 415 and 425 are attached to respective electrodes 410 and 420 and are insulated to prevent unwanted conduction in areas in contact with the dielectric material. A non-conductive separator sheet 430 of approximately the same size as the electrodes is perforated to provide a path for dielectric material 440 to fill and contact the electrodes 410 and 420 . In some embodiments, the separator sheet 430 has a thickness of about 0.5 mm, and a greater thickness of up to 2 mm or more is allowed depending on the applied voltage. The separator sheet prevents the two electrodes 410 and 420 from contacting each other and provides a constant distance between the two electrodes. The electrodes are assembled into containment device 450 as shown in FIG. 6 . A solid dielectric or liquid dielectric material 440 is added to fill the space between electrodes 410 and 420 . Alternatively, the dielectric material may be pre-coated on the electrode. Dielectric material 440 includes a plurality of polymer molecules that include polar functional groups and/or ionizable functional groups. The polymer molecule may also contain one or more double bonds. A three-dimensionally confined dielectric material is prepared by applying a voltage to two electrodes to couple at least a portion of the polymer molecules to the anode.

In some embodiments, by application of an electric field and/or treatment with a chemical agent prior to charging and/or discharging the energy storage device (i.e., after the device is manufactured, prior to using the energy storage device in an electronic circuit, etc.) When at least a portion of the polymer molecules are bonded to the first electrode, a similar energy storage device in which the polymer molecules are not bonded to the first electrode, i.e., before charging and/or discharging the energy storage device, the dielectric material is not sterically constrained. Compared to the permittivity of dielectric materials in similar energy storage devices, the permittivity of the sterically constrained dielectric material is at least 50%, for example 50% to 10,000%, 50% to 100,000%, 50% to 1,000,000%, or even 50% to 10,000,000% or more. Embodiments of the disclosed energy storage device include dielectric materials having substantially the same chemical composition, but binding at least some of the polymers to electrode surfaces prior to charging and/or discharging the energy storage device so that the polymers are not sterically constrained to provide a comparable material. It may store at least 100 times, 1000 times, 10,000 times or even 100,000 times the amount of energy stored by the energy storage device. In some embodiments, the disclosed energy storage devices can increase the amount of energy stored by comparable energy storage devices by a factor of 100 to 100,000, such as 100 to 10,000, 100 to 20,000, or 100 to 100,000 times. can be saved Some embodiments of the disclosed energy storage devices provide at least 1 Wh/kg, at least 10 Wh, based solely on the weight of the dielectric material disposed between the electrically conductive first and second electrodes, in the absence of a charged and/or discharged energy storage device. /kg, or an energy storage capacity of at least 100 Wh, for example 1 Wh/kg to 1300 Wh/kg, 10 Wh/kg to 1300 Wh/kg or 100 Wh/kg to 1300 Wh/kg. . In certain embodiments, the energy storage capacity is in the range of 100 Wh/kg to 1300 Wh/kg. Some embodiments of the disclosed energy storage devices have an energy loss of less than 10% per hour, less than 1% per hour, less than 0.5% per hour, or less than 0.1% per hour. Thus, the disclosed energy storage device is a robust high energy density capacitor. Because of their high energy density, devices can be fabricated with thicker dielectric films than other capacitors without sacrificing energy storage.

III. How to make an energy storage device

Embodiments of a method of fabricating an energy storage device include (a) applying a dielectric film to an electrically conductive first electrode, wherein the dielectric film (i) is electrically insulative and/or exhibits a high permittivity and (ii) has one or more polarities. comprising a film material comprising a plurality of polymer molecules having a functional group, an ionizable functional group, or a combination thereof; (b) contacting the dielectric film with an electrically conductive second electrode; and (c) applying an electric field across the first electrode, the dielectric film and the second electrode, thereby fabricating the energy storage device. By applying an electric field across the first electrode, the dielectric film and the second electrode, at least some of the polymer molecules are bonded to the first electrode, whereby at least some of the polymer molecules are bonded during fabrication of an energy storage device. To prepare a three-dimensional confinement type dielectric film bonded to the surface of the first electrode, the second electrode, or both the first electrode and the second electrode. In some embodiments, the three-dimensionally constrained dielectric film is prepared by (i) applying an electric field across the first electrode, the dielectric film, and the second electrode such that the first electrode becomes an anode, wherein the electric field is applied to a polymer molecule. is applied for an effective time to bond at least a portion of to the first electrode, (ii) treating the dielectric film with a chemical agent, or (iii) a combination thereof.

A. Dielectric Film Formation

A dielectric film comprising a film material is prepared by any suitable means including vapor deposition, liquid spray, screening, spin-coating or other methods known to those skilled in the art of film formation and applied to the electrically conductive first electrode. . In one embodiment, the electrically conductive first electrode is a bare electrode or a composite electrode including an insulating layer, and the dielectric film is directly formed on a surface of the bare electrode or an insulating layer of the composite electrode. The dielectric film is then dried at a low temperature (eg, 25 to 60° C.) before or after contacting the dielectric film with the electrically conductive second electrode. In one stand-alone embodiment, the dielectric film is formed on a removable carrier film (eg, polytetrafluoroethylene film), dried, and then transferred to an electrode surface.

In some embodiments, the film material is prepared from a liquid or slurry comprising a solvent and a plurality of polymer molecules. Suitable solvents include, but are not limited to, alkanols, alkylene glycols, water, and combinations thereof. Exemplary solvents include ethanol, ethylene glycol, water and combinations thereof. In some embodiments, the polymer molecule has one or more polar functional groups, ionizable functional groups, or combinations thereof. The polymer molecule may also contain one or more double bonds. Suitable polymer molecules are described above. In certain embodiments, undissolved polymer molecules are removed from the mixture, for example, by filtering or centrifuging the mixture.

The liquid or slurry may further include a crosslinking agent. Suitable crosslinking agents include anhydrides, carbodiimides, imidoesters, borax salts, sodium borohydride, and reagents comprising a combination of N-hydroxysuccinimide and maleimide, aryl azide or diazirine groups, but Not limited. Common crosslinkers include triallyltriazinetriones and other triallyl 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-dicarboxylic anhydride, cis-5-norbornene-endo-2,3-dicarboxylic anhydride, and combinations thereof do.

In some embodiments, the liquid or slurry further comprises an initiator, such as a radical initiator, to catalyze cross-linking between the polymer molecules. Exemplary initiators include azo bisisobutyronitrile, 1,1'-azobis(cyclohexanecarbonitrile), dicumylperoxide, 2-hydroxy-2-methylpropiophenone, camphorquinone, phenanthrenequinone, and thermal and light activated chemical initiators, including but not limited to combinations. In one embodiment, itaconic anhydride and dicumyl peroxide were used to cross-link the zein molecule.

One or more salts, such as those capable of forming organic salts with polymer molecules and/or neutralizing film materials, may be added to the liquid or slurry before crosslinking is complete. In some embodiments, carbonates (eg, guanidine carbonate, cesium carbonate, strontium carbonate, or combinations thereof) may be used since the reaction releases carbon dioxide and does not result in undesirable counter ion contamination of the dielectric film. In one embodiment, barium titanate is added to the liquid or slurry. In one independent embodiment, a voltage aid such as a non-conductive polymer is added.

The liquid or slurry is applied to the electrically conductive first electrode by any suitable means. In one embodiment, the slurry is coated onto a stationary or continuously moving strip of electrodes. In other embodiments, the liquid or slurry is poured onto the fixedly positioned electrode plate via any number of means, such as, but not limited to, pressure sprayed from a vessel or poured from a mixing vessel. In another embodiment, the liquid or slurry is applied to the electrode by spin coating. Other methods for transferring the liquid or slurry from the mixing vessel to the electrode are envisaged. The liquid or slurry may be spread, pressed, or rolled to cover the electrode surface to ensure a uniform thin film coating of the liquid or slurry on the electrode surface. A plurality of means for performing this step are envisioned, including but not limited to the use of spreading blades, rollers or other means. Vapor deposition of the slurry may be accomplished through atomization or chemical vapor deposition of the slurry, as 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 and when dried to produce a dielectric film of the desired thickness. In other embodiments, two or more liquid or slurry layers may be applied to the electrode surface to provide the desired thickness. Each layer may be dried before the other layers are applied, or sequential deposition of the liquid or slurry may be performed with drying after all layers have been applied. When two or more layers are applied, the layers may have the same or different chemical composition.

The electrode and dielectric material may be heated to remove the solvent and form a dielectric film on the surface of the electrode. Heating may be performed before or after contacting the dielectric material with the electrically conductive second electrode. In some embodiments, the assembly is clamped or pressurized to apply pressure to the dielectric material and extrude air or gas from the liquid or slurry to bring the first and second electrodes into full and intimate contact with the inward facing surfaces of the electrodes. In certain embodiments, the assembly is heated to a temperature of 150° C. to 300° C. to remove the solvent. Other temperature ranges may be appropriate depending on the particular solvent.

In one independent embodiment, the polymer molecules of the dielectric film are formed in situ . The dielectric material liquid or slurry includes a crosslinking agent and a plurality of polymer molecular precursors comprising one or more polar functional groups, ionizable functional groups, or combinations thereof. In some embodiments, the precursor is an amino acid molecule, oligopeptide, polypeptide or combination thereof. In certain embodiments, the polymer molecular precursor further comprises a p-xylylene monomer. The liquid or slurry is applied to the first electrode as described above. After application, the crosslinking agent is activated to crosslink the polymer molecule precursors to provide a dielectric film comprising a plurality of polymer molecules. The cross-linking process can also bind some of the polymer molecules to the electrode surface 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 first composite electrode and then applying a dielectric film to the insulating layer of the first composite electrode. In one embodiment, the insulating layer includes polymerized p-xylylene. In another embodiment, the insulating layer comprises a copolymer of p-xylylene and other comonomers as described above. The insulating layer is applied by any suitable means including vapor deposition, liquid spraying, screening, spin-coating or other methods known to those skilled in the art of film formation.

In some embodiments, the insulating layer is applied using vapor deposition. When the insulating layer includes polymerized p-xylylene, monomeric p-xylylene may be produced by reacting the xylene with a monoatomic oxygen source. As an example, the source of monoatomic oxygen may include nitrous oxide or ionized diatomic oxygen. In some embodiments, the step of reacting xylene with the monoatomic oxygen source to produce p-xylylene in monomeric form is from 450° C. to 800° C. at atmospheric pressure, at a stoichiometric ratio of xylene to monoatomic oxygen source. It is performed in a heated environment. The reaction may occur in an electrically heated pyrolysis reaction tube, such as an Inconel (nickel alloy 600) pyrolysis reaction tube. A flow stream of an inert gas such as argon or nitrogen gas alone or containing a reactive compound such as nitrous oxide is fed to the pyrolysis reaction tube. A starting material, for example xylene vapor, is introduced into a pyrolysis reaction tube and reacts with monoatomic oxygen in the reaction tube. Being highly reactive and ephemeral, monoatomic oxygen must be able to react with the volatile mixture within reaction chamber 215. As described above, the source of monoatomic oxygen may be a gas compound supplied together with a carrier gas, or a gas compound supplied separately, or may include another source such as a plasma generator. A monoatomic oxygen plasma can be created by exposing oxygen (O ₂ ) gas to a source of ionizing energy, such as, for example, an RF discharge that ionizes the gas. Alternatively, a compound such as nitrous oxide (N ₂ O) may supply monoatomic oxygen for the reaction via thermal decomposition, catalyzed decomposition and/or other decomposition. Accordingly, a monoatomic oxygen plasma generator, or a monoatomic oxygen compound (eg, N ₂ O) feed or other suitable monoatomic source is provided. Plasma gases can be used with the aforementioned starting materials to form oxidized intermediates, which are subsequently reacted to form reaction products in oxidized forms of the starting materials, which can be monomers, dimers, trimers, oligomers or polymers. can form At temperatures between 300° C. and 800° C., the output of the reaction tube is sufficiently hot to retain the monomeric p-xylylene in its monomeric form. Rapid cooling of the monomers on the electrode surface results in liquid condensation of the monomers and rapid polymerization of the monomers into polymers. Devices for mixing cooled non-reactive gases with the hot reaction stream may be used to reduce the temperature of the reactive intermediate exiting the reaction tube and promote condensation. Optionally, an expansion valve may be used at the outlet of the reaction tube to provide Joule-Thomson cooling of the hot gases. Optionally, the deposited mixture may be exposed to permittivity enhancing fields such as photoinitiated light energy and/or magnetic and/or electric fields.

The method is 2-chloro-1,4-dimethylbenzene, 2,5-dichloro-p-xylene, 2,5-dimethylanisole, tetrafluoro-p-xylene and 1,2,4-trimethyl benzene Can be extended to other substituents, including but not limited to. Those with meta or ortho orientation of substituents on the aromatic ring are also acceptable reaction starting materials. The reaction is generalized to all compounds which can react with monoatomic oxygen prepared from plasma or decomposed oxygenates or intermediate reaction products thereof, and which also contain hydrogen atoms stabilized by the presence of an aromatic ring. It can be. Typically, this hydrogen atom is located at the α position (benzyl position) of the phenyl ring. Michael structures removed from the alpha aromatic ring position are known to impart similar reactivity to the hydrogen at the alpha position to the aromatic ring, as is well known to those skilled in organic synthesis. However, the reactivity of these hydrogen atoms is not limited to the alpha and/or Michael positions of aromatic rings or to aromatic rings such as benzene. As is known to those skilled in the art of organic chemistry, other aromatic stabilizations are known for many different ring, fused ring and non-ring systems. This starting material may preferably have the presence of two hydrogen atoms which can be removed to form a partially oxidized starting material. These preferred materials may optionally have the ability to dimerize, trimerize, oligomerize or polymerize.

When the insulating layer includes a copolymer containing p-xylene, xylene may react with a monoatomic oxygen source to produce p-xylylene in monomeric form. As an example, the monoatomic oxygen source may include nitrous oxide or ionized diatomic oxygen. A monoatomic oxygen plasma can be created by exposing oxygen (O ₂ ) gas to a source of ionizing energy, such as, for example, an RF discharge that ionizes the gas. Alternatively, a compound such as nitrous oxide (N ₂ O) may supply monoatomic oxygen for the reaction through thermal decomposition, catalyzed decomposition, and/or other decomposition. In a preferred embodiment, the step of reacting xylene with a monoatomic oxygen source to produce p-xylylene in monomeric form is a chemical reaction of xylene with respect to a monomeric oxygen source in a heated environment at atmospheric pressure, 350° C. to 800° C. It is carried out in a stoichiometric ratio. The reaction may occur in an electrically heated pyrolysis reaction tube, such as an Inconel (nickel alloy 600) pyrolysis reaction tube. Monomer form of p-xylylene is mixed with a copolymerization compound (comonomer), that is, a compound that copolymerizes with monomer form of p-xylylene. The monomeric form of p-xylylene and the copolymerized compound are in gaseous form during mixing. Plasma gases can be used with the aforementioned starting materials to form intermediate oxidation products, which can subsequently react to form reaction products that are oxidized forms of the starting materials. After mixing p-xylylene in monomeric form with the copolymerization compound, the resulting mixture can be trapped in a condenser. The condenser has a temperature at which condensation of the mixture occurs. Temperatures in the range of at least -30°C, eg -30°C to 400°C, allow condensation for most mixtures. The condenser contains solvent to facilitate trapping. Optionally, the trapped mixture may be mixed with a third material, such as another monomer, reactive material or inert material. After mixing the monomeric form of p-xylylene with the copolymerized compound, the resulting mixture can be deposited on an electrode. The temperature of the electrode can be controlled to promote solidification of the deposited mixture. The monomer (modified or unmodified) is rapidly cooled while directing it onto the electrode surface to condense the monomer into a liquid and rapidly polymerize the monomer into a polymer. Optionally, the deposited mixture may be exposed to permittivity enhancing fields such as photoinitiated light energy and/or magnetic and/or electric fields.

C. polymer bind molecules to electrodes

In some embodiments, an electric field is applied across the first electrode, the dielectric film and the second electrode. Preferably, the electric field is a direct current electric field. The electric field is applied such that the first electrode functions as an anode and the second electrode functions as a cathode. 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 certain embodiments, the electric field strength is 0.005 to 1 V/μm, 0.01 to 1 V/μm, 0.1 to 1 V/μm, or 0.4 to 0.6 V/μm.

The electric field may be applied for an effective time to manufacture a three-dimensionally confined dielectric film by binding at least some polymer molecules in the dielectric film to the first electrode. The effective time is based at least in part on the electric field strength and may range from 1 second to several minutes, such as from 30 seconds to 60 minutes, from 5 minutes to 30 minutes, or from 5 minutes to 15 minutes. In some embodiments, the electric field is 0.005 to 1 V/μm and the effective time is 1 second to 30 minutes. In one embodiment, an electric field strength of 0.005 to 0.5 V/μm for 20 minutes is effective to bind 50% or more of the protein molecules to the surface of the composite electrode comprising polymerized p-xylylene. In another embodiment, an electric field strength of 0.5 to 1 V/μm for 5 to 15 minutes is effective to bind more than 90% of the protein molecules to the composite electrode surface comprising polymerized p-xylylene.

In some embodiments, after assembling the electrically conductive first electrode, the dielectric film and the electrically conductive second electrode, by treating the dielectric film with a chemical agent to bond at least some of the polymer molecules to the first electrode. Create a three-dimensionally confined dielectric film. In certain embodiments, the electric field is applied across the first electrode, the dielectric film and the second electrode, and the dielectric film is treated with a chemical agent.

In one embodiment, the first electrode is a composite electrode and the step of treating the dielectric film with a chemical agent applies a radical initiator to the insulating layer before applying the dielectric film to the insulating layer, and then activates the radical initiator. to bond at least a portion of the polymer molecules to the insulating layer to create a three-dimensionally constrained dielectric film. Exemplary radical initiators are azobisisobutyronitrile, 1,1'-azobis(cyclohexanecarbonitrile), dicumyl peroxide, 2-hydroxy-2-methylpropiophenone, camphorquinone, phenanthrenequinone, combinations thereof, and other radical initiators known to those skilled in the art of polymerization. The radical initiator is activated by oxidation-reduction, photoinitiation, thermal initiation or other methods known to those skilled in the art of polymerization to bind at least a portion of the polymer molecules to the insulating layer.

In one independent embodiment, the first electrode is a composite electrode, and the step of treating the dielectric film with a chemical agent includes a radical initiator in the film material of the dielectric film, and applies the dielectric film to the insulating layer after and activating the radical initiator.

In one independent embodiment, the first electrode is a composite electrode, and the step of treating the dielectric film with a chemical agent derivatizes the polymer molecules with a derivatizing agent to form functional groups capable of cross-linking to the insulating layer of the first composite electrode. providing, and subsequently cross-linking the functional group to the insulating layer using a radical initiator, ultraviolet light, thermal activation, or a combination thereof to prepare a three-dimensionally constrained dielectric film. Exemplary derivatizing agents include anhydrides, carbodiimides, imidoesters, and reagents comprising a combination of N-hydroxysuccinimide and maleimide, arylazide, or diazirine groups. In some embodiments, the derivatizing agent is maleic anhydride, itaconic anhydride, cis-4-cyclohexene-1,2-dicarboxylic acid anhydride or cis-5-norbornene-endo-2,3-dicarboxylic acid anhydride. It is anhydrous.

In one independent embodiment, the first electrode is a composite electrode, and treating the dielectric film with a chemical agent includes applying a plasma to a surface of the insulating layer prior to applying the dielectric film to the insulating layer. . The plasma is produced by passing a carrier gas (eg, nitrogen or argon) along with oxygen through a high voltage “spark” plasma. The voltage drop across the spark is about 100V to 1000V at 250 kHz. Alternatively, a high-frequency plasma can be generated at a much lower voltage (eg, 13.6 MHz and <100V) using the same gas mixture. The plasma produces monoatomic oxygen that is long enough to oxidize p-xylene (e.g., several milliseconds). The polymer molecules in the dielectric film react with the plasma to bond at least a portion of the polymer molecules to the insulating layer and form a three-dimensionally confined dielectric film.

One or more of the above embodiments may be used in combination to treat the dielectric film with a chemical agent. For example, the polymer molecule may be derivatized with a derivatizing agent, a crosslinking agent may be included in the film material, and a radical initiator may be included in the film material prior to application of the dielectric film or applied to an insulating layer and subsequently activated. can

D. Methods of Manufacturing Substitute Assemblies

In one embodiment, a method of fabricating an energy storage device as shown in FIG. 4 includes (i) a polymer having a metallized surface and comprising an insulating layer as disclosed herein on the metallized surface. providing a first sheet or roll of, wherein the insulating layer does not completely cover the metallized surface such that edge portions of the metallized surface are exposed; (ii) applying a dielectric film as disclosed herein to the insulating layer; (iii) contacting the dielectric film with a second sheet or roll of metallized polymer, the second sheet or roll having a metallized surface and comprising an insulating layer on the metallized surface; The insulating layer does not completely cover the metallized surface such that an edge portion of the metallized surface is exposed, and the second sheet or roll is such that the insulating layer is in contact with the dielectric film and the second sheet or roll is in contact with the dielectric film. orienting an exposed edge portion proximate to the exposed edge portion of the first sheet to form a composite multilayer surface; (iv) winding the composite multi-layer surface into a rolled form or cutting and laminating portions of the composite multi-layer surface to form a laminated form; (v) bonding exposed edge portions of the first sheet or roll and the second sheet or roll to a conductive polymer contained within a conductive cap or non-conductive holder having an electrical connection; (vi) electrically connecting the composite multilayer surface to an anode and a cathode; and (vii) applying an electric field to the multilayer composite, wherein the electric field causes at least some of the polymer molecules of the dielectric film to be in the insulating layer of the first sheet or roll, the insulating layer of the second sheet or roll, or both. and applying for an effective time for binding.

In one independent embodiment, a method of manufacturing an energy storage device as shown in FIGS. 5 and 6 includes (i) providing a first electrode having a top surface comprising an insulating layer disclosed herein in a containment device. step; (ii) placing a perforated non-conductive separator sheet on the insulating layer of the first electrode; (iii) positioning a second electrode having a lower surface comprising an insulating layer as disclosed herein on the separator sheet such that the insulating layer of the second electrode contacts the separator sheet; (iv) adding a dielectric material as disclosed herein to fill the space in the perforated separator sheet and bring the first and second electrodes into contact; and (v) applying an electric field across the first electrode, the dielectric material, and the second electrode for an effective time to couple at least some of the polymer molecules to the insulating layer of the first electrode, thereby causing the dielectric material to be oxidized. bonding at least a portion of the polymer molecules to the insulating layer of the first electrode.

IV. Example

Example One

Manufacturing of Dielectric Films

ingredient:

Proteins/ Polymers / Amino Acids : Zein (Sigma-Aldrich CAS # 9010-66-6), Hemp Protein (Manitoba Harvest Hemp Foods, Winnipeg, Manitoba, Canada, Hemp Pro 70), Vital Wheat Gluten (John &Jennie's Gourmet Kitchen Center, Salt Lake City, UT, jandjkitchen.com), Poly(Acrylic Acid-Co-Maleic Acid) (Sigma-Aldrich CAS # 52255-49-9), Poly(Acrylic Acid) (Sigma-Aldrich CAS # 9003- 01-4), Whey Protein Isolate (Purebulk.com Lot # 20131025-07-1000g), Soy Protein Isolate (Honeyville Food Products, Honeyville, UT Item # 30-066-904), Gamma Aminobutyric Acid (GABA) ( Purebulk.com Lot # 20130722-01), Pea Protein Extract 85% (Purebulk.com Lot # 20140226-06-1000g), L-Lysine HCl (Purebulk.com Lot # 20131125-01-1000g), L-Serine (Purebulk .com Lot # 20130606-04), L-Glutamine (Purebulk.com Lot # 20130912), L-Tryptophan (Purebulk.com Lot # 20131015-04-100g), L-Tyrosine (Purebulk.com Lot # 20131016-08- 1000 g), aspartic acid (Purebulk.com Lot # 20130122-06)

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

Salts: Guanidine Carbonate (Sigma-Aldrich CAS # 593-85-1), Cesium Carbonate (Alfa Aesar CAS # 534-17-8), Strontium Carbonate (Sigma-Aldrich CAS # 1633-05-2), Rubidium Carbonate (Alfa Aesar CAS#584-09-8)

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

Exemplary dielectric preparation procedure : In a 50 mL Erlenmeyer flask, 1 g of zein and 1.14 g of itaconic anhydride were dissolved in 10 mL of absolute ethanol by heating to 65° C. with stirring under an argon atmosphere for 15 minutes. Once complete dissolution occurred and the reaction temperature reached 65° C., 0.035 g of dicumyl peroxide was added in one portion, and the mixture was continued to stir under argon for 1 hour. The hot plate was then turned off and the mixture cooled to room temperature. Once cooled, the pH of the mixture was tested with universal indicator pH paper (pH about 3) and 1 gram of guanidine carbonate was added in small portions until the pH was about 7. When adding guanidine carbonate, care was taken to avoid excessive foaming (and bubbling) due to carbon dioxide production during the reaction. Depending on the degree of completion of the protein/anhydride reaction, more or less guanidine carbonate can be used to achieve neutralization, but usually not significantly more than 1 molar equivalent of added anhydride. The final pH of the dielectric may be between 5 and 10.

Notes: a) Potential need to exceed 1 equivalent as proteins contain additional intrinsic functional groups that can react with guanidine carbonate; b) The amount of anhydride used was determined based on a 1:1 weight/weight ratio of zein to maleic anhydride (molecular weight 98.06 g/mol). Equimolar amounts of the substituted anhydride (itaconic acid) were calculated based on the molecular weight of the maleic anhydride.

Example 2

polymerized p- xylylene manufacture of coatings

Coatings comprising Puralene™ polymer (polymerized xylylene) with and without comonomers have been prepared by several routes.

ingredient:

Initiators: Azobisisobutyronitrile (AIBN) (Sigma-Aldrich CAS # 78-67-1), 1,1'-Azobis(cyclohexanecarbonitrile) (ACHN) (Sigma-Aldrich CAS # 2094-98- 6), dicumyl peroxide (Sigma-Aldrich CAS # 80-43-3), 2-hydroxy-2-methylpropiophenone (Sigma-Aldrich CAS # 7473-98-5), camphorquinone (Sigma-Aldrich CAS # 10373-78-1), phenanthrenequinone (Sigma-Aldrich CAS # 84-11-7)

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

Comonomers: 3-(trimethoxysilyl)propyl methacrylate (Sigma-Aldrich CAS # 2530-85-0), vinyl acetate (Alfa Aesar CAS # 108-05-4), 2-carboxyethyl acrylate (Sigma -Aldrich CAS # 24615-84-7), (+)-α-pinene (Alfa Aesar CAS # 7785-70-8), (-)-α-pinene (Alfa Aesar CAS # 7785-26-4), R -(-)-Carvone (Alfa Aesar CAS # 6485-40-1), Linalool (Alfa Aesar CAS # 78-70-6), Cyclohexene (Alfa Aesar CAS # 110-83-8), Dipentene ( Alfa Aesar CAS # 138-86-3), α-Terpinene (Alfa Aesar CAS # 99-86-5), R-(+)-Limonene (Alfa Aesar CAS # 5989-27-5)

Puralene ^TM with chemical initiator Polymer Preparation, Route A: This route used the reactor described in US Pat. No. 8,633,289 without modification. A 5% solution of thermal initiator was applied to the surface of an oxide-free round copper ½" substrate supported with a 1½" square FR4 glass filled epoxy board. This solution was prepared by dissolving 0.05 g of a solid initiator (AIBN, ACHN, or dicumyl peroxide) in 10 mL absolute ethanol and sonicating until complete/near complete dissolution occurred. Once dissolved, 20 μL of the initiator solution was applied to the metal surface and the solvent was evaporated under ambient air. This process left a thin layer of particulate initiator solids on the metal surface. The board was then mounted on a cooling aluminum block (~13°C) attached to a robotic arm. The substrate was then coated with the monomer p-xylylene at least 3 times and at most 10 times. Between each coating, the substrate was placed on a cooling block for 2 minutes to intensify the chemical reaction. This resulted in a conformal coating of polymerized p-xylylene with a thickness ranging from 300 nm to 1000+ nm.

Puralene ^TM with chemical initiator Polymer Preparation, Route B: This route used the reactor described in US Pat. No. 8,633,289 without modification. A 5% solution of a UV active initiator was applied to the surface of the aforementioned oxide-free copper substrate. This solution was prepared by dissolving 0.05 g of a solid initiator (camphorquinone or phenanthrenequinone) in 10 mL absolute ethanol and sonicating until complete/near complete dissolution occurred. Once dissolved, 20 μL of the initiator solution was applied to the metal surface and the solvent evaporated under ambient air. This process left a thin layer of particulate initiator solids on the metal surface. The substrate was then mounted on a cooling aluminum block (~13°C) attached to a robotic arm. The substrate was then coated with p-xylylene at least 3 times and at most 10 times. Between each coating, the substrate was exposed to 254/350 nm ultraviolet light for 2 minutes using two lamps placed side by side in the same housing. After irradiation, the substrate was placed on a cooled block for an additional 2 minutes to intensify the chemical reaction. This resulted in conformal coatings of polymerized p-xylylene with thicknesses ranging from 300 nm to 1000+ nm.

Preparation of Puralene ™ Polymer Using Chemical Initiator , Route C: This route used the reactor described in US Pat. No. 8,633,289 with the following modifications: Nitrogen (carrier gas) and 2-hydroxy-2 on top of Inconel reactor tubes. - A heated stainless steel evaporator block supplied with methylpropiophenone (UV active initiator, stock solution) was attached. The aforementioned oxide-free copper substrate was mounted on a cooling aluminum block (~13 °C) attached to a robotic arm. The substrate was then coated with p-xylylene at least 3 times and at most 10 times. Between each coating, the substrate was exposed to 254/350 nm ultraviolet light for 2 minutes using two lamps placed side by side in the same housing. After irradiation, the substrate was placed on a cooled block for an additional 2 minutes to intensify the chemical reaction, resulting in a conformal coating of polymerized p-xylylene with a thickness ranging from 300 nm to 1000+ nm.

Preparation of Puralene ™ copolymer , route A: 5 μL of the above 5% initiator solution (see details above) or 5 μL of pure 2-hydroxy-2-methylpropiophenone, and 20 μL of the above on the surface of an oxide-free copper electrode as described above. One of the comonomers was applied. The substrate was slightly dried so that the liquid material did not drip off the surface when the substrate was mounted vertically. The prepared substrates were coated using the method described in Puralene ^™ Polymer Preparation Routes A to C above (initiator dependent). This produced copolymer films of various thicknesses that could be analyzed using energy dispersive X-ray spectroscopy.

Preparation of Puralene ™ copolymer , route B: 20 μL of a 5% initiator solution (see details above) or 20 μL of pure 2-hydroxy-2-methyl propiophenone were applied to the surface of an oxide-free copper electrode as described above. Once the carrier solvent had evaporated and the substrate was mounted, a liquid comonomer was applied to the surface of the substrate using an airbrush prior to coating. This was followed by the coating technique described in Preparation of Puralene™ Polymers Using Chemical Initiators, Route A.

Puralene ™ Copolymer Preparation, Route C: This route used the reactor described in U.S. Pat. No. 8,633,289 with the following modification: Nitrogen (carrier gas) and liquid comonomer (stock solution) were introduced into the top of the Inconel reactor tubes. A supplied heated stainless steel evaporator block was attached. 20 μL of a 5% initiator solution (see details above) or 20 μL of pure 2-hydroxy-2-methyl propiophenone were applied to the surface of the aforementioned oxide-free copper electrode. Once the carrier solvent has evaporated, the substrate is mounted on a cooling block. In this process, the comonomer was vaporized in an evaporator block, heated to the monomer boiling point, and the evaporated monomer was added to the p-xylylene main flow to simultaneously apply both the monomer and xylylene to the substrate surface. Afterwards, the manufactured substrate is treated with the Puralene ^TM Coating was performed using the method described in Polymer Preparation Routes A to C (initiator dependent).

Preparation of Puralene ™ Copolymer , Route D: This route used the reactor described in U.S. Patent No. 8,633,289 with the following modifications: a heated stainless steel evaporator block at the top of the Inconel reactor tubes into which nitrogen (carrier gas) and liquid comonomer (stock solution) were fed. Attached. A second evaporator block was placed above to deliver nitrogen and liquid initiator (2-hydroxy-2-methyl propiophenone). In this process, both comonomer and initiator are vaporized into the p-xylylene stream so that all three materials contact the substrate simultaneously. An oxide-free copper substrate was mounted on a cooling block and coated using the method described in Preparation of Puralene ^™ Polymer Using Chemical Initiator, Route C.

Example 3

Manufacture of energy storage devices

Sheets or rolls of metallized polymer, for example patterned aluminized polyethylene terephthalate (PET) (Mylar® polyester film), such as coatings comprising Puralene ^™ polymers as described in US 2014/0139974 A1 coated with an insulating layer. In some embodiments, the sheet or roll of metallized polymer has a thickness of about 6 μm and a width of about 50 mm. A non-conductive coating is applied to the metallized surface, but does not completely cover the surface. Approximately 6 mm of conductive bare surface is exposed at one edge. The coated metallized material is then coated by spraying a dielectric material described in US 2013/0224397 A1 onto the non-conductive polymer surface. Enough dielectric material is deposited to provide a dielectric layer having a thickness of about 100 μm after drying at 60° C. for 10 minutes. Invert the other sheet or roll of metallized polymer coated with the non-conductive polymer in a manner similar to the first substrate so that the uncoated edge faces the uncoated edge of the first substrate and the two aluminized surfaces face each other. let it do The polymer coated side of the second substrate is brought into contact with the dielectric coated side of the first substrate. The composite multilayer surface is then wound into a roll (which can later be flattened) or laminated into a plate to provide a larger device with greater energy storage. Bonding the conductive electrode edge to a conductive polymer blend (such as a conductive epoxy known to those of ordinary skill in the art) provides an electrical connection to a roll or stack of uncoated electrode edges. The conductive polymer is incorporated within a mechanically substantial electrically conductive cap or electrical connection such as a wire and/or other non-conductive holder having sufficient mechanical strength to permit compression electrical connection. Optionally, a sleeve may be placed around the entire device to provide mechanical and electrical protection to the membrane and the device itself when used as intended.

Connect the energy storage device to a DC voltage supply. The device is powered with a current of 0.001 to 100 mA/cm 2 . At an electric field greater than 0.001 V per micron thickness of the dielectric film, current is passed for a time effective to bond at least some polymer molecules of the dielectric film to the non-conductive coating. In some embodiments, the electric field strength is greater than 0.01 V/μm, such as 0.05 to 1 V/μm or 0.1 to 1 V/μm. The effective time can be from a few seconds to several minutes. In some embodiments, the voltage is between 0.1 and 1 V/μm and the effective time is between 5 minutes and 30 minutes. Calculation of the energy absorbed by the device is determined by methods known to those skilled in the art of energy storage device manufacturing. The release of absorbed energy is determined by integrating the differential voltage discharge across the resistor to ground.

In one working embodiment, disassembly and microscopic examination of the device revealed that the dielectric material was strongly mechanically bonded to the electrode surfaces coated with the non-conductive polymer.

Example 4

radical initiator and with a crosslinking agent of the copolymer layer manufacturing

In the energy storage device shown in any one of FIGS. 1 to 6, monomer molecules (preferably p-xylylene monomer) are used as a conductive electrode or a non-conductive sheet (e.g., polytetrafluoroethylene) to act as a removable carrier film. sheet). A comonomer molecule can be any molecule that has the ability to polymerize, dimerize, or form an extended structure that can be conductive or insulating. Additionally, the added comonomer species can have structures with several reactive functional groups that can act as crosslinkers. Alternatively, a crosslinking agent as described above or a crosslinking agent known to those skilled in the art of polymerization or film formation may be added together with the deposited monomers. A radical initiator as described above or known to a person skilled in the art of polymerization or film formation is added together with the deposited monomers or in a separate deposition step. The film may be deposited by vapor deposition, liquid spraying, screening, or other methods known to those skilled in the art of film formation. Activation of the radical initiator is provided by oxidation-reduction, photoinitiation, thermal initiation, or other methods known to those skilled in the art of film formation. Exemplary methods for making polymeric films are described in US Pat. No. 8,633,289, incorporated herein by reference. An electric field, a magnetic field, or both can be applied to the polymer film during fabrication to modify the mechanical and electrical properties of the film, for example making the film more viscous or solid.

A dielectric layer may then be deposited as a separate step if the formed film is not a complete dielectric material for the device. A counter electrode is added as described in the previous embodiments, and the device is mounted as described above.

Example 5

polymer Combination

An insulating layer of Puralene ^™ polymer was applied to the surface of the first electrode using the method described in “Puralene ^™ polymer prepared using chemical initiator , route C” . A dielectric film containing zein was applied on the insulating layer. A second electrode comprising an insulating layer of Puralene ^™ polymer was brought into contact with the dielectric film. An electric field of 20V was applied across the first electrode, the dielectric film and the second electrode for 5 minutes to bond the zein polymer to the insulating layer on the first electrode (anode). The energy storage devices were disassembled and examined to determine the extent and strength of protein binding.

7 and 8 are optical micrographs of the cathode and anode after disassembly, respectively. As shown in Figure 8, the anode contains a conformal coating of protein on its surface. The electrodes were rinsed with running water and inspected again. 9 and 10 are optical photographs of each of the cathode and anode after rinsing. As shown in Figure 10, the protein remained bound to the anodic surface.

11 and 12 are optical photographs of the cathode and anode, respectively. These photos were taken at an angle to show surface details more clearly. 12 shows substantially complete covering of the electrode surface with protein molecules. 13 is an optical photograph of an anode after manually scraping the dielectric film with a knife and then rinsing. The bright area (indicated by the arrow) is the area where the scraping removed bound protein molecules and showing the electrode surface underneath the protein layer. The picture shows that significant force is required to remove bound protein molecules from the electrode surface.

In view of the many possible implementations to which the principles of the disclosed invention may be applied, the illustrated implementations are only preferred examples of the invention and should not be regarded as limiting the scope of the invention. Rather, the scope of the present invention is defined by the following claims. Accordingly, we claim as our invention all that comes within the scope and spirit of these claims.

Claims (25)

A method comprising manufacturing an energy storage device, said step comprising:
Forming a composite first electrode by applying a first insulating layer to the electrically conductive first electrode, wherein the first insulating layer is a polymerized p-xylylene insulating layer, or an acrylate, methacrylate, α-pinene, prepared from p-xylylene and one or more comonomers selected from R-(-)carvone, linalool, cyclohexene, dipentene, α-terpinene, R-(+)-limonene, or any combination thereof a copolymer insulating layer that becomes;
Applying a dielectric film to the first insulating layer of the composite first electrode, wherein the dielectric film (i) is electrically insulating, exhibits a high dielectric constant, or is electrically insulating and exhibits a high dielectric constant, and (ii) one comprising a film material comprising a plurality of polymer molecules having at least one polar functional group, at least one ionizable functional group, or a combination of a polar functional group and an ionizable functional group;
contacting the dielectric film with an electrically conductive second electrode; and
(i) applying an electric field across the composite first electrode, the dielectric film and the electrically conductive second electrode such that the composite first electrode is an anode, wherein the electric field is at least 1% of the plurality of polymer molecules. applied for an effective time to bond to the first insulating layer of the composite first electrode, or
(ii) treating the dielectric film with a chemical agent;
By bonding at least 1% of the plurality of polymer molecules to the composite first electrode to form a sterically constrained dielectric film, thereby manufacturing an energy storage device. 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 is 1 second to 30 minutes. delete The method of claim 1 wherein said first insulating layer is a polymerized p-xylylene insulating layer. 2. The method of claim 1 , wherein binding at least 1% of the polymer molecules comprises applying the electric field for the effective time across the composite first electrode, the dielectric film, and the electrically conductive second electrode, and , whereby at least 1% of the polymer molecules are bonded to the first insulating layer of the composite first electrode. The method of claim 1 , wherein treating the dielectric film with a chemical agent comprises:
applying a radical initiator to the first insulating layer before applying the dielectric film to the first insulating layer; and
activating the radical initiator after applying the dielectric film to the first insulating layer, thereby bonding at least 1% of the plurality of polymer molecules to the first insulating layer of the composite first electrode. . The method of claim 1 , wherein treating the dielectric film with a chemical agent comprises:
(i) derivatizing the polymer molecules with a derivatizing agent to provide a cross-linkable functional group to the first insulating layer of the composite first electrode;
(ii) including a cross-linking agent in the film material of the dielectric film;
(iii) including a radical initiator in the film material of the dielectric film and activating the radical initiator after applying the dielectric film to the first insulating layer;
(iv) applying a radical initiator to the insulating layer before applying the dielectric film to the first insulating layer, and activating the radical initiator after applying the dielectric film to the first insulating layer;
(v) applying plasma to the first insulating layer before applying the dielectric film to the first insulating layer; or
(vi) a method comprising any combination thereof. The method according to any one of claims 1 to 3, wherein the polymer molecule is a protein, parylene, acrylic acid polymer, methacrylic acid polymer, polyethylene glycol, urethane polymer, epoxy polymer, silicone polymer, terpenoid polymer, natural resin Methods involving polymers, polyisocyanates, or combinations thereof. 4. The method according to any one of claims 1 to 3, wherein the polymeric molecule comprises a protein or a derivatized protein. 4. The method according to any one of claims 1 to 3, wherein the electrically conductive second electrode is a composite second electrode including an insulating layer, and the composite second electrode is positioned such that the insulating layer contacts the dielectric film. method. The method of any one of claims 1 to 3, wherein the step of applying the dielectric film to the first insulating layer of the composite first electrode,
forming the dielectric film on a removable carrier film;
removing the removable carrier film; and
and applying the dielectric film to the first insulating layer of the composite first electrode. 4. The method according to any one of claims 1 to 3, wherein the polymer molecules are formed in situ and the method
applying a composition comprising a crosslinking agent and a plurality of polymer molecular precursors including one or more polar functional groups, ionizable functional groups, or combinations thereof to the first electrode; and
activating the crosslinking agent, thereby crosslinking the polymer molecule precursor to provide a dielectric film comprising a plurality of polymer molecules. 14. The method of claim 13, wherein the polymer molecule precursor comprises (i) an amino acid molecule, (ii) an oligopeptide, (iii) a polypeptide, or (iv) a combination thereof. 14. The method of claim 13, wherein the polymer molecular precursor further comprises a p-xylylene monomer. A method of manufacturing an energy storage device comprising:
providing a first sheet or roll of polymer having a metallized surface and comprising an insulating layer on the metallized surface, wherein the insulating layer is exposed such that an edge portion of the metallized surface is exposed; A p-xylylene insulating layer in which the insulating layer is polymerized without completely covering the surface, or an acrylate, methacrylate, α-pinene, R-(-)carbon, linalool, cyclohexene, dipentene, α -A step of a copolymer insulating layer prepared from p-xylylene and at least one comonomer selected from terpinene, R-(+)-limonene, or any combination thereof;
applying a dielectric film to the insulating layer, wherein the dielectric film (i) is electrically insulative, exhibits a high dielectric constant, or is electrically insulative and exhibits a high dielectric constant, and (ii) one or more polar functional groups, ionizable functional groups, or comprising a film material comprising a plurality of polymer molecules having a combination of a polar functional group and an ionizable functional group;
contacting a second sheet or roll of metallized polymer with the dielectric film, the second sheet or roll having a metallized surface and comprising an insulating layer on the metallized surface, the insulating layer comprising: It does not completely cover the metallized surface such that the edge portion of the metallized surface is exposed, and the second sheet or roll is such that the insulating layer is in contact with the dielectric film and the exposed edge portion of the second sheet or roll is orienting the first sheet or roll to proximate the exposed edge portion to form a composite multilayer surface;
winding the composite multi-layer surface into a rolled form or cutting and laminating portions of the composite multi-layer surface to form a laminated form;
bonding exposed edge portions of the first sheet or roll and the second sheet or roll to a conductive polymer contained within a conductive cap or non-conductive holder having an electrical connection;
electrically connecting the composite multilayer surface to an anode and a cathode; and
applying an electric field to the composite multilayer surface, wherein the electric field is effective to bind at least 1% of the polymer molecules to the insulating layer of the first sheet or roll, the insulating layer of the second sheet or roll, or both A method comprising applying for a period of time. A method of manufacturing an energy storage device comprising:
A step of providing, within a containment device, a first electrode having an upper surface comprising an insulating layer, wherein the insulating layer is a polymerized p-xylylene insulating layer, or an acrylate, methacrylate, α-pinene, R-( -) A copolymer prepared from p-xylylene and one or more comonomers selected from carvone, linalool, cyclohexene, dipentene, α-terpinene, R-(+)-limonene, or any combination thereof an insulating layer;
placing a perforated non-conductive separator sheet on the insulating layer of the first electrode;
positioning a second electrode having a lower surface including an insulating layer on the separator sheet so that the insulating layer of the second electrode contacts the separator sheet;
adding a dielectric material to fill the space in the perforated separator sheet and bringing the first electrode and the second electrode into contact, wherein the dielectric material (i) is electrically insulating, exhibits a high permittivity, or is electrically insulating and has a high dielectric constant; (ii) comprising a plurality of polymer molecules comprising one or more polar functional groups, ionizable functional groups, or combinations thereof; and
bonding at least 1% of the polymer molecules to the insulating layer of the first electrode by applying an electric field across the first electrode, the dielectric material and the second electrode such that the first electrode becomes an anode; and applying an electric field for a period of time effective to bind at least 1% of the polymer molecules to the insulating layer of the first electrode. As an energy storage device,
an electrically conductive first electrode;
an electrically conductive second electrode;
A sterically constrained dielectric film disposed between the electrically conductive first electrode and the second electrode, wherein the sterically constrained dielectric film comprises a plurality of polymer molecules having at least one polar functional group, an ionizable functional group, or a combination of a polar functional group and an ionizable functional group. A three-dimensionally confined dielectric film comprising; and
A first insulating layer disposed between the electrically conductive first electrode and the three-dimensionally constrained dielectric film, wherein the first insulating layer is a polymerized p-xylylene insulating layer, or acrylate, methacrylate, α-pinene, R -(-)carvone, linalool, cyclohexene, dipentene, α-terpinene, R-(+)-limonene, or one or more comonomers selected from any combination thereof and p-xylylene a first insulating layer that is a copolymer insulating layer;
including,
The energy storage device is disposed between the electrically conductive first electrode and the second electrode when there is no charged energy storage device, when there is no discharged energy storage device, or when there is no charged and discharged energy storage device. Having an energy storage capacity of at least 1 Wh/kg based only on the weight of the three-dimensionally confined dielectric film;
the electrically conductive first electrode and the first insulating layer together form a composite first electrode; and
wherein at least 1% of the plurality of polymer molecules are bonded to the first insulating layer of the composite first electrode, thereby sterically constraining the dielectric film. 19. The energy storage device of claim 18, wherein the polymer molecules are protein molecules. delete 19. The energy storage device of claim 18, wherein the energy storage device comprises (i) an electrically conductive first electrode, (ii) an electrically conductive second electrode, and (iii) an electrically insulating dielectric disposed between the electrically conductive first and second electrodes. A film, a dielectric film having a high dielectric constant, or a dielectric film having an electrically insulating and high dielectric constant, wherein the dielectric film includes a plurality of polymer molecules having one or more polar functional groups, ionizable functional groups, or a combination thereof, wherein the An energy storage device having an energy storage capacity at least 100 times greater than an energy storage capacity of an energy storage device in which the polymer molecules are not bonded to the electrically conductive first electrode. 19. The method of claim 18, wherein the three-dimensionally constrained dielectric film includes a plurality of polymer molecules having one or more polar functional groups, ionizable functional groups, or combinations thereof, and the polymer molecules are bonded to the first insulating layer of the composite first electrode. An energy storage device having a permittivity that is 50% to 10,000,000% greater than the permittivity of an uncoated dielectric film. 23. The energy storage device of any one of claims 18, 19, 21 and 22, wherein the polymer molecule is bonded to at least 1% of the surface of the first electrode in contact with the sterically constrained dielectric film. . According to claim 18,
The energy storage device further comprising an insulating layer disposed between the electrically conductive second electrode and the three-dimensionally confined dielectric film. delete