JP2018503243A - Energy storage device - Google Patents

Abstract

Embodiments of a high dielectric constant, low leakage energy storage device such as a capacitor and a method of manufacturing such an energy storage device are described. The disclosed apparatus includes conductive first and second electrodes and a sterically constrained dielectric film disposed between the first and second electrodes. The sterically constrained dielectric film includes a plurality of polymers, and at least a part of the polymers is bonded to the first electrode. The disclosed apparatus may include an insulating layer between the first electrode and the dielectric film and / or between the second electrode and the dielectric film. [Selection] Figure 2

Description

[Cross-reference of related applications]
This application is a continuation-in-part of U.S. Patent Application No. 14 / 499,028, filed on September 26, 2014, and U.S. Patent Application No. 14 / 574,175, filed on December 17, 2005. Which is hereby incorporated by reference in its entirety. This application also claims US Provisional Patent Application No. 14/156, filed Jan. 16, 2014, which claims priority from US Provisional Patent Application No. 61 / 808,733, filed April 5, 2013. No. 457, a continuation-in-part application, which is incorporated herein by reference in its entirety. This application is also a continuation of US Patent Application No. 13 / 853,712 filed on March 29, 2013, which is a continuation of US Patent Application No. 14 / 490,873 filed on September 19, 2014. A continuation-in-part of U.S. Patent Application No. 13 / 671,546 filed abandoned on November 7, 2012, and as U.S. Patent No. 8,633,289 in 2014 U.S. Patent Application No. 13 / 599,996, patented on January 21, which is hereby incorporated by reference in its entirety.

  The present disclosure relates to an embodiment of a high dielectric constant, low leakage energy storage device such as a capacitor and a method of manufacturing such an energy storage device.

  Capacitance is one method of storing energy, but is not widely used for storing large amounts of electrical energy. In general, conventional charge and discharge cycles in storing electrostatic energy in a dielectric material are in the time range of picoseconds to hundreds of microseconds. There is a need to store energy by increasing the energy density in both the energy density per unit mass and the energy density per unit volume.

  The present disclosure relates to an embodiment of a high dielectric constant, low leakage energy storage device such as a capacitor and a method of manufacturing such an energy storage device. The energy storage device according to the embodiment includes a conductive first electrode, a conductive second electrode, and a three-dimensionally constrained dielectric film. The three-dimensionally constrained dielectric film is disposed between the conductive first electrode and the conductive second electrode, and includes a plurality of polymers. The energy storage device is at least 1 Wh / based only on the weight of the dielectric material disposed between the conductive first electrode and the second electrode when the energy storage device is charged and / or not charged. Has an energy storage capacity of kg. In some embodiments, the insulating layer is disposed on the first conductive electrode, the second conductive electrode, or both the first and second conductive electrodes. In any or all of the above embodiments, the polymer may have one or more polar functional groups, ionizable functional groups, or combinations thereof. In any or all of the above embodiments, the macromolecule may be a protein molecule. In any or all of the above embodiments, the polymer may bind to at least 1% of the surface of the conductive first electrode in contact with the dielectric film.

  In one embodiment, a method for manufacturing an energy storage device includes the step (a) of applying a dielectric film comprising a dielectric material to a conductive first electrode. The dielectric material (i) exhibits electrical insulation and / or high dielectric constant, and (ii) includes a plurality of polymers. The manufacturing method further includes a step (b) of bringing the dielectric film into contact with the conductive second electrode, and a step (c) of applying an electric field across the first electrode, the dielectric film, and the second electrode. In this way, an energy storage device is manufactured. In certain embodiments, the manufacturing method includes applying an insulating layer to the conductive first electrode to form a first composite electrode, and applying a dielectric film to the insulating layer of the first composite electrode. Further included. In any or all of the above embodiments, the electric field may be greater than 100 V / cm. In any or all of the above embodiments, the macromolecule may be a protein molecule.

  In one embodiment, a method for manufacturing an energy storage device includes the step (a) of applying a dielectric film comprising a dielectric material to a conductive first electrode. The dielectric material includes a plurality of polymers that (i) exhibit electrical insulation and / or high dielectric constant, and (ii) have one or more polar functional groups, ionizable functional groups, or combinations thereof. The manufacturing method includes the step (b) of bringing the dielectric film into contact with the conductive second electrode, and forming at least a part of the polymer on the conductive first electrode in order to form a sterically constrained dielectric film. Combining (c). In this way, an energy storage device is manufactured. The step of bonding at least a part of the polymer to the conductive first electrode includes the following step (i), step (iii) or step (iii). In step (i), the first electrode, the dielectric film and the first electrode are applied so that the first electrode becomes a positive electrode and an electric field is applied for a time effective for at least a portion of the polymer to bind to the first electrode. Applying an electric field across two electrodes. Step (ii) is a step of treating the dielectric film with a chemical agent. Step (iii) is a step combining the step (i) and the step (ii).

  In any or all of the above embodiments, the electric field may be at least 0.001 V / m based on the average thickness of the dielectric film. In certain embodiments, the electric field is 0.005 to 1 V / μm and the effective time is 1 second to 30 minutes.

  In any or all of the above-described embodiments, the manufacturing method includes the steps of applying an insulating layer to the conductive first electrode to form a first composite electrode, and forming a dielectric film on the insulating layer of the first composite electrode. A step of assigning. In one embodiment, coupling a portion of the polymer includes applying an electric field across the first composite electrode, the dielectric film, and the second electrode for an effective time, thereby providing at least one of the polymers. The portion is coupled to the insulating layer of the first composite electrode. In an independent embodiment, treating the dielectric film with a chemical agent comprises applying a radical initiator to the insulating layer before applying the dielectric film to the insulating layer, and adding the dielectric film to the insulating layer. Activating the radical initiator later, whereby at least a part of the polymer is bonded to the insulating layer of the first composite electrode. In an independent embodiment, the step of treating the dielectric film with a chemical agent comprises the following step (i), step (ii), step (iii), step (iv), step (v) or step (vi): including. The step (i) is a step of derivatizing the polymer with a derivatizing agent to generate a crosslinkable functional group in the insulating layer of the first composite electrode. The step (ii) is a step of adding a crosslinking agent to the film material of the dielectric film. The step (iii) is a step in which a radical initiator is included in the film material of the dielectric film, and the radical initiator is activated after the dielectric film is applied to the insulating layer. The step (iv) is a step of 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. The step (v) is a step of applying plasma to the insulating layer before applying the dielectric film to the insulating layer. The step (vi) is a step obtained by combining any of the above-mentioned step (i), the above-mentioned step (ii), the above-mentioned step (iii), the above-mentioned step (iv), or the above-mentioned step (v). . In any or all of the above embodiments, the insulating layer may include p-xylylene.

  In any or all of the above embodiments, the polymer is a protein, parylene, acrylic acid polymer, methacrylic acid polymer, polyethylene glycol, urethane polymer, epoxy polymer, silicone polymer, terpenoid polymer, natural resin polymer, polyisocyanate or the like May be included. The macromolecule may comprise a protein or derivatized protein.

  In any or all of the above embodiments, the conductive second electrode may be a second composite electrode comprising an insulating layer, the second composite electrode being arranged such that the insulating layer is in contact with the dielectric film. Is done. In any or all of the embodiments described above, the step of applying the dielectric film to the conductive first electrode includes the steps of forming the dielectric film on the removable carrier film, and removing the carrier film. And transferring the dielectric film to the first conductive electrode.

  In any or all of the above embodiments, the polymer is formed in situ. In such an embodiment, the manufacturing method includes applying a composition including a cross-linking agent and a plurality of polymer precursors to the first electrode, and activating the cross-linking agent, thereby forming the polymer precursor. Cross-linking to produce a dielectric film containing a plurality of polymers. Here, the polymer precursor includes one or more polar functional groups, ionizable functional groups, or a combination thereof. In certain embodiments, the polymeric precursor comprises (i) an amino acid molecule, (ii) an oligopeptide, (iii) a polypeptide or (iv) a combination thereof. In certain embodiments, the polymeric precursor further comprises a p-xylylene monomer.

  In an independent embodiment, the method of manufacturing an energy storage device comprises step (a) of providing a first sheet or roll of polymer having a metallized surface, wherein the first sheet or roll is insulated from the metallized surface. A layer, wherein the insulating layer does not completely coat the metallized surface such that the edges of the metallized surface are exposed; and a dielectric film comprising a film material is applied to the insulating layer. Applying (b), wherein the film material (i) exhibits electrical insulation and / or high dielectric constant, and (ii) one or more polar functional groups, ionizable functional groups or combinations thereof A step (b) comprising a plurality of polymers having: a step (c) of bringing a second sheet or roll of metallized polymer into contact with the dielectric film, wherein the second sheet or roll is metallized Have surface , An insulating layer on the metal surface. The insulating layer does not completely coat the metallized surface such that the end of the metallized surface is exposed, where the insulating layer contacts the insulator film and the uncoated end of the second sheet or roll. The second sheet or roll is oriented so that the portion is in close proximity to the uncoated end of the first sheet or roll to form a composite multilayer surface; and winding the composite multilayer surface into a roll Or cutting and laminating a portion of the composite multilayer surface to form a laminated structure; and the uncoated ends of the first sheet or roll and the second sheet or roll are electrically conductive caps Or (e) bonding to a conductive polymer housed in a non-conductive holder having an electrical connection; and a step of electrically connecting the composite multilayer surface to the positive and negative electrodes. Flop and (f); a step (g) applying an electric field to the composite multi-layer surface. The electric field is applied for a time effective for at least a portion of the dielectric film polymer to bond to the insulating layer of the first sheet or roll, the insulating layer of the second sheet or roll, or both. Step (g).

  In an independent embodiment, the method for manufacturing an energy storage device comprises a step (a) of providing a first electrode having an upper surface with an insulating layer on a receiving device, and perforating non-conductive on the insulating layer of the first electrode. A step (b) of disposing the separator sheet, and a step (c) of disposing the second electrode having a lower surface including the 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 a space in the perforated separate sheet and to contact the first electrode and the second electrode (d). The dielectric material includes (i) a plurality of polymers that exhibit electrical insulation and / or high dielectric constant, and (ii) have one or more polar functional groups, ionizable functional groups, or combinations thereof. Further, the manufacturing method applies an electric field across the first electrode, the dielectric material, and the second electrode for a period of time effective for at least a portion of the polymer to bond to the insulating layer of the first electrode. Coupling at least a portion to the insulating layer of the first electrode.

  The foregoing and other details, features and advantages of the present invention will be described and elucidated with reference to the accompanying drawings.

It is a figure which shows an example of an energy storage device. It is sectional drawing of an example of an energy storage device. It is sectional drawing of another example of an energy storage device. It is an exploded view of an example of the energy storage device which has a winding structure. 1 is an exploded view of an example of an energy storage device that includes a perforated separator plate. FIG. It is sectional drawing of the energy storage apparatus of FIG. It is an optical micrograph of the negative electrode of the energy storage device manufactured by the method of the disclosed embodiment. It is an optical photograph of the positive electrode of the energy storage device of FIG. FIG. 8 is an optical photograph of the negative electrode of FIG. 7 after rinsing with running water. 9 is an optical photograph of the positive electrode of FIG. 8 after rinsing with running water. FIG. 10 is an optical photograph of the negative electrode of FIG. 9 taken obliquely. FIG. 11 is an optical photograph of the positive electrode in FIG. 10 taken obliquely. FIG. 11 is an optical photograph of the positive electrode of FIG. 10 after the bonded polymer is scraped off by hand.

[Detailed description]
The present disclosure relates to an energy storage device having a dielectric material including a polymer and a method for manufacturing the energy storage device. Here, at least a portion of the polymer binds to the electrode of the energy storage device. The energy storage device stores energy by an electrostatic method of a charge / discharge mechanism, for example, similarly to a capacitance. The energy storage device according to the embodiments is useful in the fields of electronics, bulk electrical storage and any other device. Such other devices are those in which electrical energy needs to be stored or stored electrical energy can be used.

[I. Definition]
The terms and abbreviations are then described to provide those skilled in the art with more details of the disclosure and to guide the practice of the disclosure. “Providing” as described herein means “including”. Also, the singular forms “a”, “an”, and “the” include plurals unless the context clearly dictates otherwise. The term “or” means a single element of stated alternative elements or a combination of two or more elements, unless the context clearly indicates otherwise.

  Unless defined otherwise, all technical and chemical terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. Although methods and materials similar or equivalent to those described herein can 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 not intended to be limiting. Other features of the disclosure will be apparent from the following detailed description and claims.

  Unless otherwise indicated, all numbers representing quantities of components, voltages, temperatures, times, etc. as used in the specification and claims are understood to be modified by the term “about”. Should be. Thus, unless otherwise stated, implicitly or explicitly, numerical parameters, etc. are the desired characteristics and / or detection limits required under standard test conditions / methods as known to those skilled in the art. Approximate value depending on. Where an embodiment is directly and explicitly distinguished from the prior art described above, the numerical value of the embodiment is not an approximation unless the language “about” is stated.

  Subsequently, certain terms are described to facilitate review of various embodiments of the present disclosure.

Capacitor: An energy storage device comprising two conductive plates separated by a substantially non-conductive material (referred to as a “dielectric”). The capacitance value or storage performance of the capacitor depends on the size of the plate, the distance between the plates, and the dielectric properties. The relationship is given by equation (1).

C = (e ₀ · _er · A) / d Formula (1)

In the formula (1), _{e 0} is the vacuum dielectric constant ^{(8.8542 × 10 -12 F / m} ). _er is a non-dielectric constant (described later). A is the surface area of one plate (if both are the same size). d is the distance between the two plates.

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

  Dielectric breakdown voltage: A voltage at which an insulating material “breaks down” and causes a current to flow. The breakdown voltage is an index of the dielectric strength of a material.

  Derivatization: As used herein with respect to macromolecules, the term “dielectricization” refers to macromolecules to which functional groups are added by chemical modification. For example, the protein can be derivatized with maleic anhydride, which produces a protein with maleic acid functionality.

  Electrical insulating material or insulator: An insulator is a material having an internal charge. The internal charge of the insulator does not flow freely. For this reason, the insulator hardly flows current. In view of the absence of a perfect insulator, the term “electrically insulating material” as used herein primarily means an insulating material. That is, the term “electrically insulating material” has a threshold that breaks down when the applied electric field across the material exceeds its value during normal use as a capacitor, thereby causing the material to break down during normal use. It means a material that avoids this.

  Electrode: As used herein, the term “electrode” means a conductor (eg, metal) electrode or a “composite” electrode. A “composite” electrode comprises a conductor and a non-conductive material on the surface of the conductor.

Functional group: A specific group of atoms in a molecule that is responsible for the characteristic chemical reaction and / or electrostatic interaction of the molecule. Examples of functional groups include, but are not limited to, halogen groups (fluoro, chloro, bromo, iodo), epoxide groups, hydroxyl groups, carbonyl (ketone) groups, aldehyde groups, carbonate ester groups, carboxylate groups, ether groups, esters. Group, peroxy group, hydroperoxy group, carboxamide group, amine group (primary, secondary, tertiary), ammonium group, amide group, imide group, azide group, cyanate group, isocyanate group, thiocyanate group, nitrate Groups, nitrito groups, nitrile groups, nitroalkane groups, nitroso groups, pyridyl groups, phosphate groups, sulfonyl groups, sulfide groups, thiol (sulfhydryl) groups, and disulfide groups. Polar functional groups do not form ions in the environment of use, but instead cause partial separation of positive and negative charges in the molecule. An ionizable functional group is one that can be in an ionized state in the environment of use (eg, COO ⁻ for COOH, NH ₄ ⁺ for NH ₃ ).

Insulating or non-conducting layer / coating: As used herein, the terms “insulating layer”, “insulating coating”, “non-conducting layer” and “non-conducting coating” are electrically insulative in terms of ohmic conductivity. It means a layer or coating of a material. That is, the ohmic conductivity of the material is less than 1 × 10 ⁻¹ S / m (Siemens per meter).

Parylene: polymerized p-xylylene known as Puralen® polymer or polymerized substituted p-xylylene. The polymerized p-xylylene satisfies the following formula.

Dielectric constant: As used herein, the term “dielectric constant” means the ability of a material to polarize. Depending on the dielectric constant, the dielectric constant of the space volume is changed to a value higher than the dielectric constant of the vacuum. The relative dielectric constant of the material is given by dividing the measured value of its static dielectric constant by the dielectric constant of the vacuum, as shown in equation (2).

_{e r} = e s / e ₀ formula (2)

In the formula (2), _er is a relative dielectric constant. e _s is the measured dielectric constant. e ₀ is the vacuum dielectric constant (8.8542 × 10 ⁻¹² F / m). The relative permittivity of vacuum is 1, whereas the relative permittivity of water is 80.1 (at 20 ° C.), and the relative permittivity of typical organic coatings is 3 to 8. Generally speaking, the term “high dielectric constant” means a material having a relative dielectric constant of at least 3.3. The term “high dielectric constant” as used herein refers to a material having a dielectric constant increased by at least 10% using dielectric constant increasing techniques such as application of an electric field.

  Oligo: A prefix meaning “a few”. For example, an oligopeptide can contain 2 to 20 amino acids linked by amide bonds, whereas a polypeptide can contain more than 20 amino acids. Oligopeptides include dipeptides, tripeptides and polypeptides.

  Polarity: The term “polarity” means a compound or a functional group within a compound in which electrons are not equally shared between atoms, ie, a positively charged region and a negatively charged region are permanently separated. .

  Polypeptide: More than 20 amino acids linked by polymer or amide bonds. The term “polypeptide” is intended to encompass naturally occurring polypeptides as well as artificially produced polypeptides.

  Polymer / polymer: A molecule composed of repeating structural units (eg, monomers) formed by a chemical reaction (ie, polymerization).

  Sterically constrained dielectric film: As used herein, the term “sterically constrained dielectric film” is an electrically insulating and / or high dielectric constant dielectric film comprising one or more polar functional films. A group including a plurality of macromolecules having a group, an ionizable functional group, or a combination thereof. Here, at least some of the polymers are sterically constrained. That is, the physical movement of the entire polymer in the dielectric film is limited by at least a part of the polymer. When a part of the polymer is bonded to the electrode surface in contact with the dielectric film, a steric constraint occurs. The polymer may be bound to the electrode surface according to embodiments of the disclosed method.

[II. Energy storage device having steric constrained dielectric film]
The energy storage device according to the embodiment includes two conductive surfaces (electrodes) and a three-dimensionally constrained dielectric film. The two conductive surfaces are substantially parallel to each other, and the sterically constrained dielectric film is located between the two conductive surfaces. The device further comprises an insulating layer or coating on one or both of the electrodes. The dielectric material includes a plurality of polymers. At least a portion of the plurality of polymers is bonded to one of the electrodes or to an insulating layer on the electrode.

[A. electrode]
In certain embodiments, the electrodes are planar or substantially planar. Each electrode may independently have a smooth surface or a rough surface. The rough surface electrode may be made of carbon particles, for example. A rough surface electrode has a larger surface area than a smooth electrode, such as an electrode made from polished metal. Depending on at least some of the external electrical parameters desired for a given energy storage device or capacitance device, the amount of surface roughness may be selected. Compared to an energy storage device with a smooth electrode, a similar energy storage device with a rough electrode has faster (eg, 100 times faster) charge and discharge currents in a short period of time, such as a few microseconds to milliseconds. And has a gradual discharge rate similar to that provided by energy storage devices with smooth electrodes.

[B. Insulation layer]
Each electrode may be coated on one or more surfaces with an insulating layer or coating. An electrode having an insulating coating is also referred to as a “composite electrode”. In the energy storage device, the composite electrode is oriented so that the insulating layer contacts the dielectric material. The insulating layer provides a bonding site for the added dielectric material and improves the insulating properties of the electrode. The insulating layer has an ohmic conductivity of less than 1 × 10 ⁻¹ S / m. In some embodiments, the insulating layer has a 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 1 × 10 ⁻²⁵ S / m to 1 × 10 ⁻¹ S / m, 1 × 10 ⁻¹⁰ S / m to 1 × 10 ⁻¹ S / m, 1 × 10. ^-5 S / m to 1 × 10 ^-1 S / m. The coating may range from a thickness of a few nanometers to a thickness greater than 10 micrometers. In some embodiments, the insulating layer has an average thickness of 5 nm to 10 μm, for example, an average thickness of 0.1-10 μm, 0.3-10 μm, or 0.3-2 μm. In one embodiment, it has an average thickness of less than 10% of the total capacitor thickness. The thickness of the entire capacitor is a thickness measured from the outer surface of the first electrode to the outer surface of the second electrode. The insulating coating may be applied by any suitable means. Any suitable means include, but are not limited to, other techniques known to those skilled in the art of vapor deposition, liquid spraying and coating. The insulating coating includes polymerized p-xylylene, such as, for example, a Puralen® polymer coating, as disclosed, for example, in US Patent Publication No. 2014/0139974.

  The insulating layer may be modified with a suitable comonomer to improve the dielectric constant and / or provide an attachment site for the polymer of dielectric material. In certain embodiments, the comonomer includes one or more unsaturated bonds. Insulating layers comprising polymerized p-xylylene may be modified, for example, by the inclusion of a copolymer. Such copolymers include, but are not limited to, olefins, vinyl derivatives, alkynyl derivatives, acrylic compounds, allyl compounds, carbonyls, cyclic ethers, cyclic acetals, cyclic amides, oxazolines and combinations thereof. In some embodiments, the comonomer is an acrylate (eg, 2-carboxyethyl acrylate), methacrylate (eg, 3- (trimethoxysilyl) propyl methacrylate), α-pinene, R-(−) carvone, linalool, cyclohexene, dipentene. , Α-terpinene, R-(+)-limonene and combinations thereof. The copolymer may alternately contain monomers or may be a block copolymer type.

[C. Dielectric material containing polymer]
In certain embodiments, the energy storage device includes a single dielectric material layer. In other embodiments, the energy storage device includes a dielectric film comprising multiple layers of dielectric material. The multi-layer dielectric material may be formed by depositing a single dielectric material multiple times, with or without surface modification between depositions. Alternatively, each layer may have a different chemical composition. In some embodiments, the device is constituted by a dielectric film comprising two or more dielectric layers having different electrical dielectric constants. The average thickness of the dielectric film may range from a few micrometers to a few millimeters. In some embodiments, the average thickness of the dielectric film is in the range of 10 μm to 5 mm, in the range of 10 μm to 1 mm, in the range of 10 μm to 500 μm, or in the range of 50 μm to 250 μm. In some embodiments, the average thickness of the dielectric film ranges from 80 μm to 120 μm, for example, the average thickness is 100 μm.

  In some embodiments, the dielectric material has fluid properties and has a viscosity greater than honey. In certain embodiments, the dielectric material has a viscosity of 10,000 cP to 250,000 cP. In a separate embodiment, the dielectric material is a solid.

  The dielectric material may not be substantially conductive. In other words, the dielectric material is not oxidized / reduced or exhibits ohmic conductivity at or near any electrode. Thus, in the disclosed embodiment, the energy storage device is more closely associated with an electrostatic capacitor than a conventional electrochemical battery. However, the dielectric material can store a greater amount of specific energy over a longer period of time than either a conventional electrochemical battery or electrostatic capacitor.

In some embodiments, the energy storage device comprises a dielectric material that is non-conductive and has a high dielectric constant. Two non-limiting examples of non-conductivity and high dielectric constant include shellac matrix zein and proteins derivatized with maleic anhydride. In other embodiments, the dielectric material is electrically conductive. In such embodiments, the electrodes are typically coated with an insulating layer as described above that mitigates or prevents ohmic electrical conduction. For example, an insulating layer may be used when the resistance value of the dielectric material is less than 2.5 MΩ per square centimeter. In some embodiments, the energy storage device comprises a dielectric material having a dielectric constant of at least 10 to 2,000,000 and an ohmic conductivity of 1 S / m to 1 × 10 ⁻²⁵ S / m.

  In an embodiment of the present disclosure, the energy storage device includes a dielectric material comprising a polymer having polar functional groups and / or ionizable functional groups, resulting in dipoles and dipole moments in the molecules. The polymer may further comprise 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, the contact can be described as a direct physical contact between the membrane and the entire surface coating of the electrode. The dielectric material may be in contact with the “bare” metal or carbon-based electrode surface, or the insulating layer of the composite electrode.

  In certain embodiments, the macromolecule is a polar polymer. Protein is an inexpensive polar polymer with low toxicity and is readily available. Low toxicity is a significant advantage over other polymers and allows energy storage devices to be recycled or incinerated. Protein molecules include amino acids having polar functional groups and / or ionizable functional groups. Other suitable polymers include, but are not limited to, substituted (eg, fluorinated) and unsubstituted parylene polymers, acrylic acid polymers, methacrylic polymers, polyethylene glycols, urethane polymers, epoxy polymers, silicone polymers, organic terpenoid polymers, Includes natural organic polymers (eg, resins such as shellac), polyisocyanates, and combinations thereof. Acrylate copolymers (eg, copolymers with ethylene butyl-, ethyl- and methyl-acrylate), and parylene copolymers (eg, p-xylylene, acrylates (eg, 2-carboxyethyl acrylate), methacrylates (eg, 3- (tri Copolymers such as (methoxysilyl) propyl methacrylate), α-pinene, R-(−)-carvone, linalool, cyclohexene, dipentene, α-terpinene, R-(+)-limonene, and combinations thereof) Is also within the scope of this disclosure. Non-limiting examples of polar polymers include wheat protein, wheat gluten, poly (acrylic acid-co-maleic acid)), poly (acrylic acid), whey protein isolate, soy protein isolate, pea protein Includes extracts, shellac, and combinations thereof.

  In certain embodiments, the polymer is derivatized to attach additional functional groups. The functional group facilitates subsequent binding of the polymer to, for example, a bare electrode surface (ie, bare metal or carbon surface) or a composite electrode surface. Non-limiting derivatizing agents include anhydrides, carbodiimides, imide esters and reagents, which include a combination of N-hydroxysuccinimide and a maleimide, arylazide or diazirine group. In one example, the polymer is derivatized with an anhydride. The anhydride is maleic anhydride, itaconic anhydride, cis-4-cyclohexene-1,2-dicarboxylic anhydride, cis-5-norbornene-terminated-2,3-dicarboxylic anhydride, or the like. The derivatized polymer can be bound to the electrode surface by crosslinking or other reaction with the surface. When the polymer is derivatized with maleic anhydride, for example, the derivatized polymer can be cross-linked by a double bond. Crosslinking can be performed by any suitable means such as chemical agents (eg, radical initiators), UV activation or heat activation.

  The inventors have made the surprising discovery that when a polymer having the above properties is sterically constrained, it can be used for energy storage even if the polymer cannot move freely between the electrodes. Before charging and / or discharging an energy storage device comprising an electrode and a dielectric material comprising a polymer, any means may be used to couple the polymer to the bare electrode surface or to insulate non-conductive or composite electrodes By bonding to the coating, the polymer can be sterically constrained. Such optional means include covalent bonds (single or multiple bonds), van der Waals forces or hydrogen bonds. In certain embodiments, the polymer binds to the positive electrode. When the energy storage device charges and discharges during subsequent use, such as when the energy storage device is subsequently used in an electronic circuit, the polymer remains attached to the electrode.

  In an energy storage device comprising a dielectric material, an external electric field is applied from the electrode, thereby disrupting the lowest energy state of ions or dipoles reachable from the current position in the dielectric material layer. Thus, when an electric field is applied, the dipole or ion moves from a rest position (ie, the position of the dipole or ion before the electric field is applied), which results in a rearrangement of charge distribution in the material. This can subsequently rearrange all other dipoles throughout the dielectric material. Energy that is not converted to heat is absorbed by the dielectric material. When energy is released, the reverse of this process can occur unless the stored energy is released by other mechanisms such as an increase in thermal motion (random molecular motion proportional to temperature).

  While not wishing to be bound by any particular theory of action, within a large molecule, the rest of the molecule binds to a location sufficient to prevent overall transfer to lower energy, but Only a part is thought to move. Furthermore, it is considered that the potential energy is released after being coupled to the electrode, but not as thermal motion. This movement constraint reduces the degree of freedom of the molecules of the dielectric, and as a result, reduces the movement of the molecules that dissipate the energy absorbed from the electric field as heat. Thus, the binding polymer binds to the electric field in such a way that it cannot release energy in the form of heat due to its reduced degree of freedom. The movement of a particular part of the macromolecule can be related and is similar to the electrophoretic movement known in the field of biological macromolecule analysis.

  While not wishing to be bound by any particular theory of action, if a portion of the polymer is bound to the electrode (or to the coating of the electrode), the remainder of the polymer depends on the electric field in the dielectric film The polar functional group and / or the ionizable functional group may stretch, twist or bend as it reorients. Energy is stored in the energy storage device by these three-dimensional structure change and position change. When the energy storage device is discharged, the storage energy is released as electric energy by the binding polymer returning to a three-dimensional structure with less regularity. A dielectric material containing a polymer whose degree of freedom is at least partially reduced is referred to as a “stereoconstrained dielectric film”.

  Thus, in the disclosed embodiments, the energy storage device includes a sterically constrained dielectric material that includes a polymer. In certain embodiments, in the steric constraint dielectric material, at least 1%, at least 10%, at least 25%, at least 50%, at least 80%, or at least 90% of the polymer is bound to the electrode. In certain embodiments, at least a portion of the polymer is bound to the positive electrode. When the electrode is a composite electrode, the polymer binds to the insulating layer of the composite electrode. After binding at least a portion of the polymer to the electrode, the rate of binding can be estimated by measuring the amount of polymer rinsed from the electrode.

  In certain embodiments, the polymer binds to at least 1%, at least 25%, at least 50%, at least 80% or at least 90% of the positive electrode surface in contact with the dielectric material. The percentage of the surface coated with the binding polymer may be estimated visually, for example by optical microscopy. After manufacture of the energy storage device, the device may be disassembled for inspection. To remove unbound material, the positive electrode is washed, such as by exposure to running water, and then examined by optical microscopy. The surface area coated with the binding polymer is easily distinguishable from the area without the binding polymer.

  The bond between the polymer and the electrode is strong enough to withstand light breakage. The light breakage may occur, for example, by washing the electrode and the binding polymer with running water having a force equivalent to water falling from a height of 1 meter, or under running water having a force of less than 20N. This may be caused by rubbing the binding polymer by hand. Only during application of the electric field across the energy storage device while manufacturing the device, a bond with such strength is observed. In some embodiments, at least a portion of the coupling may be broken by applying an external voltage of the opposite polarity to the device that makes the positive electrode negative.

[D. Example of energy storage device]
In an embodiment, the energy storage device 100 includes a positive electrode 110, a three-dimensionally constrained dielectric layer 120, and a negative electrode 130 (FIGS. 1 and 2). The positive electrode 110 and the negative electrode 130 may independently be a conductive metal, a semiconductor, a conductive polymer, or other conductive material. In certain cases, high surface area conductors such as carbon-based or graphene-type electrodes are advantageous as this material. The three-dimensionally constrained dielectric layer 120 includes a film material. The film material includes a plurality of polymers 122 that exhibit (i) electrical insulation and / or high dielectric constant, and (ii) include polar functional groups and / or ionizable functional groups. Furthermore, the polymer may contain one or more double bonds. As required, the insulating layer 140 is disposed between the positive electrode 110 and the dielectric layer 120 and / or the insulating layer 150 is disposed between the dielectric layer 120 and the negative electrode 130. In some embodiments, the insulating layers 140 and 150 may have a thickness that is less than 10% of the total thickness of the energy storage device 100. The thickness of the entire energy storage device 100 is, for example, a thickness measured from the outer surface 112 of the first electrode 110 to the outer surface 132 of the second electrode 130. An insulating layer may be included to prevent Joule heat and / or ohmic conduction losses from occurring during use of the device. At least a portion of the polymer 122 is bonded to the positive electrode 110 (the insulating layer 140, if present) by the attachment point 124. Each attachment point 124 may be a covalent bond (single bond, double bond or triple bond), hydrogen bond, van der Waals force or other bonding force. The other binding force is sufficient to prevent the polymer 122 from dissociating from the positive electrode 110, assuming that the positive electrode 110 is maintained at a positive charge with respect to the negative electrode 130. A portion of the polymer 122 may be bonded to the negative electrode 130 (the insulating layer 150, if present) by the attachment point 126. Each attachment point 126 may be a covalent bond (single bond, double bond or triple bond), hydrogen bond, van der Waals force, or other bonding force. The other binding force is sufficient to prevent dissociation of the polymer 122 from the negative electrode 130 on the assumption that the negative electrode 130 is maintained at a negative charge with respect to the positive electrode 110. The positive electrode 110 and the negative electrode 130 may be attached to the voltage source by conductive leads 115, 135 (eg, conductive wire leads, traces or other paths).

  In an independent embodiment, the energy storage device 200 includes a positive electrode 210, a three-dimensionally constrained dielectric layer 220, and a negative electrode 230 (FIG. 3). The three-dimensionally constrained dielectric layer 220 includes a film material. The film material includes (i) a plurality of polymers 222 and 223 that exhibit electrical insulation and / or high dielectric constant, and (ii) include polar functional groups and / or ionizable functional groups. Furthermore, the polymer may contain one or more double bonds. An insulating or non-conductive layer 240 is disposed between the positive electrode 210 and the dielectric layer 220. In addition, an insulating or non-conductive layer 250 is disposed between the dielectric layer 220 and the negative electrode 230. A part of the polymer 222 has a polar functional group and / or an ionizable functional group having a negative charge or a partial negative charge, and is bonded to the insulating layer 240 by an attachment point 225. A part of the polymer 223 has a polar functional group and / or an ionizable functional group having a positive charge or a partial positive charge, and is bonded to the insulating layer 250 by an attachment point 226. A portion of the polymer 224 includes at least one of a polar functional group or an ionized functional group having a positive charge or a partial positive charge and at least one of a polar functional group or an ionized functional group having a negative charge or a partial negative charge. Have one. The polymer 224 may be long enough to span the distance between the insulating layer 240 and the insulating layer 250 and may be bonded to both insulating layers. The positive electrode 210 and the negative electrode 230 may be attached to the voltage source by conductive leads 215 and 235.

  In an example embodiment, the energy storage device has a structure in which an insulating layer is wound or laminated. FIG. 4 shows an example of an energy device 300 including an electrode 310 having a winding structure. The winding structure includes a three-dimensionally constrained dielectric layer 320 on a substrate 325. A second substrate (not shown) may be disposed on the dielectric layer 320, whereby the steric constraining dielectric layer 320 is sandwiched between the two substrates. As shown in FIG. 4, the three-dimensionally constrained dielectric 320 does not extend to one end 326 of the substrate 325. The top and bottom of roll electrode 310 are bonded to conductive polymer 330. The conductive polymer 330 may be housed in holders 340, 350 having caps or electrical connections 345, 355. An optional sleeve (not shown) may be placed around the device 300 to provide mechanical and electrical protection during use.

In the independent embodiment shown in FIGS. 5 and 6, the exemplary energy storage device 400 includes two electrodes 410, 420. The electrodes 410 and 420 may be conductive sheets. In one example, the conductive sheet is metal (eg, aluminum) and may have a thickness of about ² mm and a size of about 500 mm ² . Each sheet is coated with an insulating layer, such as a Puralen® polymer coating, to create an electrode. Conductive leads 415, 425 are attached to each electrode 410, 420 and insulated to prevent undesired conduction in the area in contact with the insulating material. A non-conductive separator sheet 430 approximately the same size as the electrodes is perforated to provide a path for the filled dielectric material 440 to contact the electrodes 410,420. In one example, separator sheet 430 has a thickness of about 0.5 mm, but has a thickness of up to 2 mm, and a thickness of 2 mm or more is acceptable depending on the applied voltage. The separator sheet prevents the two electrodes 410 and 420 from contacting each other and provides a constant spacing between the two electrodes. As shown in FIG. 6, the electrodes are incorporated in a storage box 450. A solid dielectric material or a liquid dielectric material 440 is added to fill the space between the electrodes 410, 420. Alternatively, a dielectric material may be precoated on the electrodes. The dielectric material 440 includes a plurality of macromolecules including polar functional groups and / or other ionizable functional groups. Furthermore, the polymer may contain one or more double bonds. A voltage is applied to the two electrodes where at least a portion of the polymer is bonded to the positive electrode, thereby producing a sterically constrained dielectric material.

  In certain embodiments, prior to charging and / or discharging the energy storage device (ie, after manufacturing the energy storage device, for example, before using the energy storage device in an electronic circuit), applying an electric field and / or chemistry. By binding at least a part of the polymer to the first electrode by treatment with an agent, the dielectric constant of the sterically constrained dielectric material is improved. A similar energy storage device in which no polymer is bonded to the first electrode (ie, in a similar energy storage device, the dielectric material is not sterically constrained before charging and / or discharging the energy storage device). Compared to the dielectric constant of the dielectric material, the dielectric constant of the sterically constrained dielectric material is at least 50%, such as 50% to 10,000%, 50% to 100,000%, or 50%. From 1 to 1,000,000% or from 50% to 10,000,000%. An energy storage device comprising a dielectric material having a substantially similar chemical composition, but before charging and / or discharging the energy storage device, at least a part of the polymer is bonded to the electrode surface to form the polymer in three dimensions. Compared to an unconstrained energy storage device, the energy storage device according to the disclosed embodiments can store at least 100 times, 1000 times, 10,000 times, or 100,000 times the amount of energy. In an embodiment of the present disclosure, when the energy storage device is not charged and / or discharged, the energy storage capacity of the energy storage device is a dielectric disposed between the conductive first electrode and the second electrode. Based on the weight of the body material alone, it is at least 1 Wh / kg, at least 10 Wh / kg or at least 100 Wh / kg, for example, the energy storage capacity is from 1 Wh / kg to 1300 Wh / kg, 10 Wh / kg to 1300 Wh / kg Or from 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. In certain embodiments of the present disclosure, the energy loss of the energy storage device is 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 rugged and high energy density capacitor. High energy density allows devices to be fabricated using a thicker dielectric film than other capacitors without sacrificing energy storage.

[III. Manufacturing method of energy storage device]
The manufacturing method of the energy storage device according to the embodiment is a step (a) of applying a dielectric film containing a dielectric material to the conductive first electrode, the dielectric material comprising: (i) electrical insulation And (ii) comprising a plurality of polymers having one or more polar functional groups, ionizable functional groups, or a combination thereof, exhibiting properties and / or high dielectric constants; Contacting (b) the second electrode; and (c) applying an electric field across the first electrode, the dielectric film and the second electrode. In this way, an energy storage device is manufactured. By applying an electric field across the first electrode, the dielectric film, and the second electrode, at least a portion of the polymer binds to the first electrode during manufacture of the energy storage device. As a result, a sterically constrained dielectric film in which at least a part of the plurality of polymers is bonded to the first electrode, the second electrode, or both the first electrode and the second electrode is produced. In some embodiments, the sterically constrained dielectric film comprises: (i) a first effective period of time to bind at least a portion of the polymer to the first electrode such that the first electrode is a positive electrode. It is created by applying an electric field across the electrode, dielectric film and second electrode, (ii) treating the dielectric film with a chemical agent, or (iii) a combination thereof.

[A. Shape of dielectric film]
The dielectric film comprising the film material is prepared by any suitable means including methods known to those skilled in the art of vapor deposition, liquid spraying, screening, spin coating or film formation, and the conductive first Applied to the electrode. In one embodiment, the conductive first electrode is a bare electrode or a composite electrode including an insulating layer. The dielectric film is formed directly on the bare electrode surface or directly on the insulating layer of the composite electrode. Thereafter, the dielectric film is dried at a low temperature (for example, 25 ° C. to 60 ° C.) before bringing the dielectric film into contact with the conductive second electrode. In a separate embodiment, the dielectric film is formed on a removable carrier film (eg, polytetrafluoroethylene film), dried, and then transferred to the electrode surface.

  In certain embodiments, the membrane material is prepared from a liquid or slurry comprising a solvent and a plurality of polymers. 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 has one or more polar functional groups, ionizable functional groups, or combinations thereof. Furthermore, the polymer may have one or more double bonds. Suitable polymers are as described above. In certain embodiments, undissolved macromolecules are removed from the mixture, for example, by filtration or centrifugation of the mixture.

  The liquid or slurry may further contain a crosslinking agent. Suitable crosslinking agents include, but are not limited to, acid anhydrides, carbodiimides, imide esters, borax salts, sodium borohydride, and reagents that include N-hydroxymaleimide, aryl azide, or diazirine groups. Includes combinations. Typical cross-linking agents include triallyltriazinetrione and other triallytrivinyls or reagents known to those skilled in the art of polymer chemistry. Exemplary acid anhydrides include maleic anhydride, itaconic anhydride, cis-4-cyclohexene-1, 2-dicarboxylic acid anhydride, cis-5-norbornene-endo-2,3-dicarboxylic acid anhydride, and Including combinations thereof.

  In certain embodiments, the liquid or slurry further comprises an initiator, such as a radical initiator that catalyzes cross-linking between polymers. Exemplary initiators include heat and light activated chemical initiators, including but not limited to azobisisobutyronitrile, 1,1′-azobis (cyclohexanecarbonitrile), dicumyl peroxide, 2-hydroxy-2-methylpropiophenone, camphorquinone, phenanthrenequinone, and combinations thereof. In one example, itaconic anhydride and dicumyl peroxide were used to crosslink zein molecules.

  One or more salts, such as salts capable of forming organic salts with polymers and / or neutralizing membrane 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. This is because carbon dioxide is released by the reaction and undesirable counter ion contamination of the dielectric film does not occur. In some embodiments, barium titanate is added to the liquid or slurry. In a separate embodiment, a voltage adjuvant such as a non-conductive polymer is added.

  The liquid or slurry is applied to the conductive first electrode by any suitable means. In one embodiment, the slurry is coated on a fixed strip of electrodes or on a continuously moving strip. In another embodiment, the liquid or slurry is poured onto the statically placed electrode plate by any number of means. The arbitrary number of means is, but is not limited to, for example, the pressure released from the container or the pressure injected from the mixing container. In another embodiment, the liquid or slurry is applied to the electrode by spin coating. Other ways of moving the liquid or slurry from the mixing vessel to the electrode are also conceivable. The liquid or slurry may be spread, pressed, or stretched to coat the electrode surface to ensure a thin and uniform coating of liquid or slurry on the electrode surface. Multiple means of performing this step are contemplated and include, but are not limited to, the use of spreading blades, rollers or other means. Vapor deposition of the slurry can also be achieved by atomization of the slurry or chemical vapor deposition, as is known to those skilled in the art of forming films.

  In some embodiments, a sufficient amount of liquid or slurry is applied to the electrode surface to form a desired thickness of dielectric film when dried. In another embodiment, two or more layers of liquid or slurry may be applied to the electrode surface to obtain the desired thickness. Each layer may be dried before another layer is applied. Alternatively, a continuous deposition of liquid or slurry may be performed and may be dried after all layers have been applied. When two or more layers are applied, the chemical composition of these layers may be the same or different.

  The electrode and dielectric material may be heated to remove the solvent and form a dielectric film on the electrode surface. Heating may be performed before contacting the dielectric material with the conductive second electrode, or may be performed after. In certain embodiments, the assembly is clamped or pressed to apply pressure to the dielectric material and push air or gas out of the liquid or slurry. As a result, the first electrode and the second electrode are in close contact with the inner surface of the electrode. In certain embodiments, the assembly is heated at a temperature of 150 ° C. to 300 ° C. to remove the solvent. Other temperature ranges may be suitable depending on the solvent.

  In an independent embodiment, the dielectric film polymer is formed in situ. The liquid or slurry of dielectric material includes a cross-linking agent and a plurality of polymer precursors. The polymeric precursor includes one or more polar functional groups, ionizable functional groups, or combinations thereof. In certain examples, the precursor is an amino acid molecule, oligopeptide, polypeptide or a combination thereof. In certain embodiments, the polymeric precursor further comprises p-xylylene monomer. The liquid or slurry is applied to the first electrode as described above. After application, the crosslinking agent is activated, whereby the polymer precursor is crosslinked, and a dielectric film including a plurality of polymers is generated. For example, when the electrode is a composite electrode including an insulating layer, a part of the polymer may be bonded to the electrode surface.

[B. Formation of insulating layer]
In one embodiment, the manufacturing method includes a step of applying an insulating layer to the first electrode to form a composite electrode, and a step of applying a dielectric film to the insulating layer of the composite electrode. In one embodiment, the insulating layer comprises 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 appropriate means. Any suitable means include vapor deposition, liquid spray, screening, spin coating, or other methods known to those skilled in the art of film formation.

In certain embodiments, the insulating layer is applied using vapor deposition. When the insulating layer contains polymerized p-xylylene, the xylylene may be reacted with a monoatomic oxygen source to produce monomeric p-xylylene. As an example, the monoatomic oxygen source may comprise nitrous oxide or ionized diatomic oxygen. In one embodiment, the step of reacting xylene to produce mono-p-type p-xylylene with a monoatomic oxygen source is performed in a heating environment between 450 ° C. and 800 ° C. with a stoichiometric ratio of xylene to monoatomic oxygen. It may be performed at atmospheric pressure. The reaction may be carried out in a pyrolysis reaction tube, such as an electrically heated Inconel (nickel alloy 600) pyrolysis reaction tube. A flow of only an inert gas such as argon gas or nitrogen gas or a flow of a reactive compound such as nitrous oxide is supplied to the thermal decomposition reaction tube. A starting material, such as xylene vapor, is introduced into the pyrolysis reaction tube and reacts with monoatomic oxygen in the reaction tube. In order to react with a volatile mixture, monoatomic oxygen must be available in the reaction chamber 215 to react with the volatile mixture because it is very reactive and transient. As noted above, the monoatomic oxygen source may be a gaseous compound supplied with the carrier gas, a separately supplied gaseous compound, or another source such as a plasma generator. It may be a source. The monoatomic oxygen plasma may be generated by exposing oxygen (O ₂ ) gas to an ionization energy source such as an RF discharge that ionizes the gas. Alternatively, a compound such as nitrous oxide (N ₂ O) may be decomposed by thermal decomposition, catalytic decomposition and / or other methods to supply monoatomic oxygen for reaction. Thus, a monoatomic oxygen plasma generator or a monoatomic oxygen compound (eg, N ₂ O) is provided, or another suitable monoatomic oxygen source is provided. To form the intermediate oxidation product, a plasma gas can be used with the starting materials described above. The intermediate oxidation product may then react to form a reaction product that is an oxidized form of the starting material (which may be a monomer, dimer, trimer, oligomer or polymer). The temperature of 300 ° C. to 800 ° C. is high enough to keep the monomer p-xylylene in monomer form at the outlet of the reaction tube. When the monomer on the electrode surface is rapidly cooled, the monomer is liquid condensed and the monomer is rapidly polymerized to form a polymer. An apparatus that mixes the cooled non-reactive gas into the hot reaction stream may be used to reduce the temperature and promote condensation of the reaction intermediate exiting the reaction tube. If desired, an expansion valve may be used at the outlet of the reaction tube to provide Joule Thomson cooling of the hot gas. If desired, the deposition mixture may be exposed to a photoinitiator light energy and / or a dielectric enhancement field such as a magnetic and / or electric field.

  The above method may be extended to other substituents. Such other substituents include, but are not limited to, 2-chloro-1,4-dimethylbenzene, 2,5-dichloro-p-xylene, 2,5-dimethylani, tetrafluoro-p-xylene, and 1, Contains 2,4 trimethylbutadiene. The meta and ortho orientations of substituents on the aromatic ring are feasible starting materials for the reaction. To include all compounds containing hydrogen atoms that are capable of reacting with monoatomic oxygen produced from plasma or from decomposed oxygen-containing materials and that are stabilized by the presence of aromatic rings, or intermediate reaction products thereof. In addition, the above reaction can be generalized. Typically, such a hydrogen atom is located in the alpha position (benzyl position) of the phenyl ring. The Michael structure removed from the alpha aromatic ring position is known to provide reactivity similar to alpha hydrogen to the aromatic ring position, as is well known to those familiar with organic synthesis. ing. However, the reactivity of such hydrogen atoms is not limited to alpha and / or Michael positions from aromatic rings such as benzene. As other aromatic stabilization, many different rings, fused rings and acyclic systems are known, as is known to those skilled in the art of organic chemistry. Such starting materials preferably have two hydrogen atoms that can be removed to form a partially oxidized starting material. These suitable materials have the property of dimerizing, trimerizing, oligomerizing or polymerizing as required.

When the insulating layer includes a copolymer containing p-xylene, xylene may be reacted with a monoatomic oxygen source to produce monomeric p-xylylene. As an example, the monoatomic oxygen source may comprise nitrous oxide or ionized diatomic oxygen. The monoatomic oxygen plasma may be generated by exposing oxygen (O ₂ ) gas to an ionization energy source such as an RF discharge that ionizes the gas. Alternatively, a compound such as nitrous oxide (N ₂ O) may be decomposed by thermal decomposition, catalytic decomposition and / or other methods to supply monoatomic oxygen for reaction. In a preferred implementation, the step of reacting xylene with a monoatomic oxygen source to produce monomeric p-xylylene is a large stoichiometric ratio of xylene to monoatomic oxygen in a heating environment of 350 ° C to 800 ° C. It may be performed at atmospheric pressure. The reaction may be carried out in a pyrolysis reaction tube, such as an electrically heated Inconel (nickel alloy 600) pyrolysis reaction tube. The monomer type p-xylylene is mixed with a copolymer compound (comonomer), that is, a compound copolymerized with the monomer type p-xylylene. The monomeric p-xylylene and copolymer compound become gaseous while being mixed. A plasma gas may be used with the starting materials described above to form an intermediate oxidation product. The intermediate oxidation product may then react to form a reaction product that is an oxidized form of the starting material. After mixing the monomeric p-xylylene and the copolymer compound, the resulting product may be trapped in a condenser. At temperatures of at least −30 ° C. (eg in the range of −30 ° C. to 400 ° C.), most of such mixtures can condense. The condenser contains a solvent that facilitates trapping. If desired, the trapped mixture may be mixed with a tertiary material. The tertiary substance is, for example, another monomer, a reactant or an inert material. After mixing the monomeric p-xylylene and the copolymer compound, the resulting product may be deposited on the electrode. The temperature of the electrode may be controlled to promote solidification of the deposited mixture. While the monomer is being applied onto the electrode surface, rapid cooling of the monomer results in liquid condensation of the monomer, resulting in rapid polymerization of the monomer to polymer. If desired, the deposition mixture may be exposed to a photoinitiator light energy and / or a dielectric enhancement field such as a magnetic and / or electric field.

[C. Polymer binding to electrode]
In some embodiments, an electric field is applied across the first electrode, the dielectric film, and the second electrode. Advantageously, the electric field is a direct current electric field. The electric field is applied so that the first electrode functions as a positive electrode and the second electrode functions as a negative electrode. The electric field strength may be greater than 100 V / cm or at least 0.001 V / μm based on the average thickness of the dielectric film. In 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.

  An electric field may be applied for a time effective to couple at least a portion of the polymer in the dielectric film to the first electrode. Thereby, a three-dimensionally restricted dielectric film is generated. The effective time may be in the range of 1 second to several minutes based at least in part on the electric field strength, for example in the range of 30 seconds to 60 minutes, 5 minutes to 30 minutes, or 5 minutes to 15 minutes. It may be. 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 0.005-0.5 V / μm over 20 minutes is effective to bind more than 50% protein molecules to a composite electrode surface comprising polymerized p-xylylene. In another embodiment, an electric field strength of 0.5-1 V / μm over 5-15 minutes is effective to bind more than 90% protein molecules to a composite electrode surface comprising polymerized p-xylylene.

  In some embodiments, after assembling the conductive first electrode, the dielectric film, and the conductive second electrode, the first electrode is bonded with a chemical agent to bind at least a portion of the polymer to the first electrode. In this way, a three-dimensionally constrained dielectric film is generated. In certain embodiments, an electric field across the first electrode, the dielectric film and the second electrode is applied 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 the chemical agent comprises applying a radical initiator to the insulating layer before applying the dielectric film to the insulating layer, and thereafter Activating the radical initiator. In the step of activating the radical initiator, at least a part of the polymer is bonded to the insulating layer, and a sterically constrained dielectric film is generated. Exemplary radical initiators include azobisisobutyronitrile, 1,1′-azobis (cyclohexanecarbonitrile), dicumyl peroxide, 2-hydroxy-2-methylpropiophenone, camphorquinone, phenanthrenequinone, and the like And other radical initiators known to those skilled in the art of polymerization. The radical initiator is activated by redox, photoinitiator, thermal initiator or other methods known to those skilled in the art of polymerization, thereby binding at least a portion of the polymer to the insulating layer.

  In an independent embodiment, the first electrode is a composite electrode, and the step of treating the dielectric film with the chemical agent includes the step of including a radical activator in the film material of the dielectric film, and the dielectric film on the insulating layer. Activating the radical activator after the application.

  In an independent embodiment, the first electrode is a composite electrode, and the step of treating the dielectric film with a chemical agent derivatizes the polymer with a derivatizing agent and crosslinks the insulating layer of the first electrode that is the composite electrode. Generating a possible functional group and then crosslinking the functional group to the insulating layer using a radical initiator, ultraviolet light, thermal activation or a combination thereof, thereby providing a sterically constrained dielectric. A body membrane is produced. Exemplary derivatizing agents include anhydrides, carbodiimides, imide esters and reagents that include a combination of N-hydroxymaleimide, aryl azide or diazirine groups. In certain embodiments, the derivatizing agent is an anhydride that is, for example, maleic anhydride, itaconic anhydride, cis-4-cyclohexene-1,2-dicarboxylic anhydride, or cis-5. -Norbornene-endo-2,3-dicarboxylic anhydride.

  In an independent embodiment, the first electrode is a composite electrode and the step of treating the dielectric film with the chemical agent includes applying a plasma to the surface of the insulating layer prior to applying the dielectric film to the insulating layer. . The plasma is generated by passing a carrier gas (eg, nitrogen or argon) with oxygen through a high voltage “spark plasma”. The voltage drop across the spark is about 100V to 1000V at 250kHZ. Alternatively, a radio frequency plasma can be generated at a lower voltage (eg, 13.6 MHz and <100 V) using a similar gas mixture. The plasma produces monoatomic oxygen that lasts long enough to oxidize p-xylene (eg, 2-3 milliseconds). The polymer of the dielectric film reacts with the plasma, whereby at least a part of the polymer is bonded to the insulating layer, and a steric constraint type dielectric film is formed.

  One or more of the above-described embodiments of treating the dielectric film with a chemical agent may be combined. For example, the polymer may be derivatized with a derivatizing agent, the cross-linking agent may be included in the dielectric film, the radical initiator may be included in the dielectric film, or the dielectric It may be applied to the insulating layer before applying the film, and may be activated after that.

[D. Alternative assembly manufacturing method]
In one embodiment, the method of manufacturing an energy storage device shown in FIG. 4 provides step (i) of providing a first sheet or roll of polymer having a metallized surface, wherein the first sheet or roll is a metallized surface. Comprising an insulating layer as disclosed herein. Wherein the insulating layer does not completely coat the metallized surface such that the edges of the metallized surface are exposed; and the dielectric layer as disclosed herein is applied to the insulating layer; Applying (ii); bringing a second sheet or roll of metallized polymer into contact with the dielectric film (iii), wherein the second sheet or roll has a metallized surface; And the insulating layer does not completely coat the metallized surface so that the edges of the metallized surface are exposed, the insulating layer contacts the insulator film, and the second sheet or roll is not coated. The second sheet or roll is oriented and a composite multilayer surface is formed such that the end is in close proximity to the uncoated end of the first sheet or roll; and (iii) winding the composite multilayer surface into a roll Or Or cutting and laminating a portion of the composite multi-layer surface to form a laminate structure; and the uncoated ends of the first sheet or roll and the second sheet or roll are electrically conductive caps or electrical Bonding to a conductive polymer housed in a non-conductive holder having a connection; electrically connecting the composite multilayer surface to the positive and negative electrodes (vi); Applying an electric field to the composite (vii), wherein at least a portion of the dielectric film polymer is applied to the insulating layer of the first sheet or roll, the insulating layer of the second sheet or roll, or both Applied for a time effective to bind (vii).

  In an independent embodiment, the method of manufacturing the energy storage device shown in FIGS. 5 and 6 includes the step (i) of providing a storage device with a first electrode having a top surface with an insulating layer as disclosed herein. Disposing a perforated non-conductive separator sheet on the insulating layer of the first electrode; and (ii) on the separator sheet such that the insulating layer of the second electrode contacts the separator. Placing a second electrode having a lower surface with an insulating layer as described above (iii) and filling the space in the perforated separate sheet and contacting the first electrode and the second electrode Adding a dielectric material as disclosed herein (iv) and for a time effective for at least a portion of the polymer to bond to the insulating layer of the first electrode, the first electrode, the dielectric material, and First By applying an electric field across the electrodes, and a step (v) to be bonded to the insulating layer of the first electrode at least part of the polymer.

[IV. Example]
<Example 1>
Preparation of dielectric film Material:
Protein / polymer / amino acid: 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 # 20131025-07-1000 g), 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-trypto § emissions (Purebulk.com Lot # 20131015-04-100g), L- tyrosine (Purebulk.com Lot # 20131016-08-1000g), 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 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 cein and 1.14 g of itaconic anhydride are heated to 65 ° C. with stirring for 15 minutes under argon atmosphere to 10 mL of anhydrous Dissolved in ethanol. When complete dissolution occurred and the reaction temperature reached 65 ° C., 0.035 g of dicumyl peroxide was added in one portion and the mixture continued to stir for 1 hour under argon. The hot plate was turned off and the mixture was cooled to room temperature. After cooling, the pH of the mixture was tested with universal indicator pH paper (pH˜3) and 1 gram of guanidine carbonate was added in small portions until the pH was about 7. Care was taken when adding guanidine carbonate to ensure that excessive boiling (and bubbling) due to the carbon dioxide formation reaction was avoided. Some guanidine carbonate can be used to achieve neutralization depending on the degree of protein / anhydride reaction completion, but typically does not significantly exceed one molar equivalent of the added anhydride. The final pH of the dielectric may be 5-10.

  Note: a) The protein further contains a unique functional group that can react with guanidine carbonate. Therefore, potentially 1 equivalent or more is necessary. 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). Based on the molecular weight of maleic anhydride, an equimolar equivalent of substituted anhydride (itaconic acid) was calculated.

<Example 2>
Preparation of Polymerized p-Xylylene Coating A coating comprising Puralene® polymer with a comonomer (polymerized p-xylylene) and Puralene® polymer without a comonomer was prepared by several routes.

material:
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 No. 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).

  Starting source: heat from a heated evaporator block attached to the outlet of the reactor (> 65 ° C.), 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) -847), (+)-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 ™ polymer production using chemical initiator (Route A): This route was utilized without modification to the reactor described in US Pat. No. 8,633,289. A 5% solution of thermal initiator was applied to an oxide free round copper ^{1/2 "} substrate supported by a 1 ^1/2" square FR4 glass filled epoxy substrate. This solution was prepared by dissolving 0.05 g of solid initiator (AIBN, ACHN or dicumyl peroxide) in 10 mL of absolute ethanol and sonicating until complete / almost complete dissolution. Once dissolved, 20 μL of initiator solution was applied to the metal surface and the solvent was evaporated under ambient atmosphere. This process left a thin layer of particulate initiator solid on the metal surface. These substrates were attached to a cooled aluminum block (about 13 ° C.) attached to the robot arm. The substrate was then coated with p-xylylene monomer at least 3 times and up to 10 times. Between coatings, the substrate was placed on a cooling block for 2 minutes to promote the chemical reaction. This produced a conformal coating of polymerized p-xylylene having a thickness in the range of 300 nm to 1000 nm.

  Puralene® polymer production with chemical initiator (Route B): This route was utilized without modification to the reactor described in US Pat. No. 8,633,289. A 5% solution of the UV active initiator was applied to the surface of the copper substrate not containing the oxide described above. This solution was prepared by dissolving 0.05 g of solid initiator (camphorquinone or phenanthrenequinone) in 10 mL of absolute ethanol and sonicating until complete / almost complete dissolution. Once dissolved, 20 μL of initiator solution was applied to the metal surface and the solvent was evaporated under ambient atmosphere. This process left a thin layer of particulate initiator solid on the metal surface. These substrates were then attached to a cooled aluminum block (about 13 ° C.) attached to the robot arm. The substrate was then uniformly coated with p-xylylene at least 3 times and up to 10 times. Between coatings, the substrate was exposed to 254/350 nm UV light for 2 minutes using two lamps placed side by side in the same housing. After irradiation, the substrate was placed on a cooling block for an additional 2 minutes to promote the chemical reaction. This produced a conformal coating of polymerized p-xylylene having a thickness in the range of 300 nm to 1000 nm.

  Puralene® polymer production with chemical initiator (Route C): This route utilized the reactor described in US Pat. No. 8,633,289 with the following modifications: Inconel reaction A heated stainless steel evaporator block supplied with nitrogen (carrier gas) and 2-hydroxy-2-methylpropiophenone (UV active initiator, undiluted) was attached to the top of the tube. Next, the copper substrate not containing the oxide was attached to a cooled aluminum block (about 13 ° C.) attached to the robot arm. The substrate was then uniformly coated with p-xylylene at least 3 times and up to 10 times. Between coatings, the substrate was exposed to 254/350 nm UV light for 2 minutes using two lamps placed side by side in the same housing. After irradiation, the substrate was placed on a cooling block for an additional 2 minutes to promote the chemical reaction. This produced a conformal coating of polymerized polyxylene with a thickness in the range of 300 nm to 1000 nm.

  Puralene® copolymer production (Route A): 5 μL of 5% initiator solution (as described above) or pure 2-hydroxy-2-methylpropio on the surface of the copper electrode without the oxide described above 5 μL of phenone and one of the above comonomers were applied. The substrate was allowed to dry slightly to prevent the liquid material from dripping from the surface when the substrate was mounted vertically. The prepared substrate was then coated using the method described in Routes A to C (depending on initiator) for Puralene® polymer preparation above. This produced copolymer films of various thicknesses that could be analyzed using energy dispersive X-ray spectroscopy.

  Puralene® copolymer production (Route B): 20 μL of 5% (as described above) initiator solution or pure 2-hydroxy-2-methylpropiophenone on the surface of the previously described oxide-free copper electrode 20 μL was applied. After the carrier solvent evaporated, the substrate was attached. Prior to coating, a liquid comonomer was applied to the substrate surface using an air brush. Next, the coating technique described in Puralene® polymer production (Route A) using a chemical initiator was used.

  Puralene® copolymer production (Route C): This route utilized the reactor described in US Pat. No. 8,633,289 with the following modifications: Nitrogen at the top of the Inconel reaction tube A heated stainless steel evaporator block fed with (carrier gas) and (undiluted) liquid comonomer was attached. 20 μL of 5% (as described above) initiator solution or 20 μL of pure 2-hydroxy-2-methylpropiophenone was applied to the surface of the copper electrode without the oxide described above. After the carrier solvent evaporated, the substrate was attached to a cooling block. In this process, the comonomer was vaporized in the evaporator block, heated at the monomer's characteristic boiling temperature, the evaporated monomer was added to the main p-xylylene stream, and both the monomer and xylylene were applied to the substrate surface simultaneously. The prepared substrate was then coated using the method described in the above-mentioned Puralene® polymer manufacture (Route AC) (based on initiator).

  Puralene® Copolymer Production (Route D): This route utilized the reactor described in US Pat. No. 8,633,289 with the following modifications: Nitrogen at the top of the Inconel reaction tube A heated stainless steel evaporator block fed with (carrier gas) and (undiluted) liquid comonomer was attached. A second evaporator block was placed on top to deliver nitrogen and liquid initiator (2-hydroxy-2-methylpropiophenone). In this process, both the comonomer and initiator were vaporized and placed in a p-xylylene stream so that all three materials were in contact with the substrate simultaneously. An oxide-free copper substrate was placed on the cooling block and coated using the method described in Vapor Puralene® Polymer Production (Route C) with a chemical initiator.

<Example 3>
Fabrication of energy storage devices Sheets or rolls of metallized polymers, such as patterned aluminized polyethylene terephthalate (PET) (Mylar® polyester membrane), as described in US Patent Application Publication No. 2014/0139974. Coated with an insulating layer, such as a coating comprising a Puralene ™ polymer. 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 cannot completely coat the surface. An approximately 6 mm bare conductive surface remains exposed at one end. Thereafter, the coated metallized material is coated onto the non-conductive polymer surface by spraying a dielectric material as described, for example, in US 2013/0224397. After drying at 60 ° C. for 10 minutes, enough dielectric material is deposited to provide a dielectric layer having a thickness of about 100 μm. In the same manner as the first substrate, the sheet or roll of metallized polymer coated with a non-conductive polymer has an uncoated end opposite the uncoated end of the first substrate and two aluminum The plated surfaces are inverted so that they face each other. The polymer coating side of the second substrate is in contact with the dielectric coating side of the first substrate. The composite multilayer surface is then rolled into a roll (which may then be flattened) or laminated as a plate to obtain a larger device with greater energy storage. Electrical connections to the uncoated electrode ends of the roll or laminate are provided by joining the conductive electrode ends to a conductive polymer blend (such as a conductive epoxy known to those skilled in the art). The conductive polymer is housed mechanically in a substantially conductive cap or in another non-conductive holder. Such other non-conductive holders have sufficient mechanical strength to allow electrical connections such as wires and / or compression electrical connections. An optional sleeve can be placed throughout the device to protect the membrane and the device itself mechanically and electrically during the intended use.

The energy storage device is connected to a DC voltage source. The apparatus is supplied with a current of 0.001 to 100 mA / cm ² . With an electric field strength greater than 0.001 V per micron thickness of the dielectric film, it is possible to pass an electric current for a time effective to bond at least a portion of the dielectric film polymer 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 may be from a few seconds to a few minutes. In some embodiments, the voltage is 0.1-1 V / μm and the effective time is 5-30 minutes. The calculation of the energy absorbed by the device is determined by methods known to those skilled in the art of manufacturing energy storage devices. The discharge of absorbed energy is determined by the integration of the differential voltage of the discharge to ground through a resistor.

  In the examples, disassembly and microscopic examination of the device revealed that the dielectric material was strongly and mechanically bonded to the non-conductive polymer coated electrode surface.

<Example 4>
Preparation of Copolymer Layer with Radical Initiator and Crosslinking Agent In the energy storage device shown in any one of FIGS. 1-6, a conductive electrode or non-conductive sheet (eg, polytetra On the fluoroethylene sheet), monomer molecules (preferably p-xylylene monomer) are deposited. The comonomer molecule may be any molecule, and the any molecule may have the ability to polymerize, dimerize, or form an elongated structure that may be conductive or insulating. Furthermore, the added comonomer species may have a structure with several reactive functional groups that can serve as a crosslinker. Alternatively, the cross-linking agents described above or cross-linking agents known to those skilled in the art of polymerization or film formation may be added along with the deposition monomer. The radical initiators mentioned above or radical initiators known to those skilled in the art of polymerization or film formation are added together with the deposition monomers or in a separate deposition step. The film may be deposited by vapor deposition, liquid spray, screening or other methods known to those skilled in the art of film formation. Activation of the radical initiator is carried out by redox, photoinitiator, thermal initiator or other methods known to those skilled in the art of film formation. An exemplary method of making a polymer membrane is described in US Pat. No. 8,633,289, which is incorporated herein by reference. To modify the mechanical and electrical properties of the film, for example to make the film more viscous or hard, an electric field, a magnetic field, or both may be applied to the polymer film during formation.

  The dielectric layer may then be deposited as a separate step if the film formed thereon is not a complete dielectric material for the device. Thereafter, a counter electrode is added as described in the previous embodiment, and the device is attached as described above.

<Example 5>
Polymer bonding
An insulating layer of Puralene® polymer was applied to the surface of the first electrode using the method described in “Puralene® Polymer Production Using a Chemical Initiator (Route C)”. A dielectric film comprising 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. In order to bond the zein polymer to the insulating layer on the first electrode (positive electrode), an electric field of 20 V was applied to the first electrode, the dielectric film, and the second electrode for 5 minutes. The energy storage device was disassembled and examined to determine the extent and strength of protein binding.

  7 and 8 are optical micrographs of the negative electrode and the positive electrode after decomposition. As can be seen from FIG. 8, the positive electrode includes a conformally coated protein on its surface. The electrode was rinsed with running water and examined again. 9 and 10 are optical micrographs of the negative electrode and the positive electrode, respectively, after rinsing. As can be seen from FIG. 10, the protein remains bound to the surface of the positive electrode.

  11 and 12 are optical micrographs of the negative electrode and the positive electrode, respectively. These photographs were taken at an angle that more clearly shows the details of the surface. FIG. 12 shows an electrode surface that is substantially completely coated with protein molecules. FIG. 13 is an optical photograph of the rinsed positive electrode after the dielectric film is manually shaved with a knife. The brighter area (indicated by arrows) is the area rubbed to remove the bound protein molecules and shows the electrode surface under the protein layer. This photograph shows that considerable force is required to remove the bound protein molecules from the electrode surface.

  In view of the many possible embodiments to which the disclosed principles of the invention may be applied, the illustrated embodiments are preferred examples of the invention and should not be construed as limiting the scope of the invention. Should be recognized. Rather, the scope of the present invention is defined by the appended claims. We therefore claim as our invention all that comes within the scope of the appended claims and their gist.

Claims (25)

Applying a dielectric film comprising a film material to the conductive first electrode, wherein the film material exhibits (i) electrical insulation and / or high dielectric constant; (ii) one or more, Comprising a plurality of macromolecules having polar functional groups, ionizable functional groups, or combinations thereof;
Contacting the dielectric film with a conductive second electrode;
Bonding at least a portion of the polymer to the conductive first electrode to form a sterically constrained dielectric film,
The combining step includes
An electric field over the first electrode, the dielectric film and the second electrode for a time effective for at least a portion of the polymer to bind to the first electrode such that the first electrode becomes a positive electrode. Applying step (i),
Treating the dielectric film with a chemical agent (ii), or
Step (iii) combining step (i) and step (ii);
The manufacturing method of the energy storage device performed by.   The manufacturing method according to claim 1, wherein the electric field is at least 0.001 V / μm based on an average thickness of the dielectric film.   The manufacturing method according to claim 2, wherein the electric field is 0.005 to 1 V / μm, and the effective period is 1 second to 30 minutes. It is a manufacturing method as described in any one of Claim 1 to 3,
Providing an insulating layer on the conductive first electrode to form a first composite electrode;
Applying the dielectric film to the insulating layer of the first composite electrode.   The manufacturing method according to claim 4, wherein the insulating layer includes polymerized p-xylylene. It is a manufacturing method of Claim 4 or 5,
The coupling step includes applying the electric field across the first composite electrode, the dielectric film, and the second electrode for the effective time, whereby at least a portion of the polymer is 1. A manufacturing method for bonding to an insulating layer of a composite electrode. 6. The manufacturing method according to claim 4, wherein the step of treating the dielectric film with the chemical agent comprises:
Applying a radical initiator to the insulating layer before applying the dielectric film to the insulating layer;
And subsequently activating a radical initiator, thereby binding at least a portion of the polymer to the insulating layer of the first composite electrode. 6. The manufacturing method according to claim 4, wherein the step of treating the dielectric film with the chemical agent comprises:
Derivatizing the polymer with a derivatizing agent to generate a crosslinkable functional group in the insulating layer of the first composite electrode (i),
Including a cross-linking agent in the film material of the dielectric film (ii),
Adding a radical initiator to the film material of the dielectric film, and activating the radical initiator after applying the dielectric film to the insulating layer (iii);
Adding a radical initiator to the insulating layer before adding the dielectric film to the insulating layer, and activating the radical initiator after applying the dielectric film to the insulating layer (iv);
Applying plasma to the insulating layer before applying the dielectric film to the insulating layer (v), or
A manufacturing method comprising the step (vi), which is a combination of any one of the step (i), the step (ii), the step (iii), the step (iv), and the step (v).   The production method according to claim 1, wherein the polymer is a protein, parylene, acrylic acid polymer, methacrylic acid polymer, polyethylene glycol, urethane polymer, epoxy polymer, silicone polymer, terpenoid polymer. , A natural resin polymer, a polyisocyanate or a combination thereof.   The manufacturing method according to claim 1, wherein the polymer includes a protein or a derivatized protein.   11. The manufacturing method according to claim 1, wherein the conductive second electrode is a second composite electrode including an insulating layer, and the second composite electrode is the insulating layer. Is disposed so as to be in contact with the dielectric film. The manufacturing method according to any one of claims 1 to 11, wherein the step of applying the dielectric film to the conductive first electrode includes:
Forming the dielectric film on a removable carrier film;
Removing the removable carrier film;
Applying the dielectric film to the conductive first electrode. The manufacturing method according to any one of claims 1 to 11, wherein the polymer is formed in situ, and the manufacturing method includes:
Applying a composition comprising a crosslinking agent and a plurality of polymer precursors to the first electrode;
Activating the cross-linking agent, thereby cross-linking the polymer precursor to form a dielectric film comprising a plurality of polymers, and
The polymer precursor includes one or more polar functional groups, ionizable functional groups, or a combination thereof.   14. The production method according to claim 13, wherein the polymer precursor comprises (i) an amino acid molecule, (ii) an oligopeptide, (iii) a polypeptide or (iv) a combination thereof.   The manufacturing method according to claim 13, wherein the polymer precursor further includes a p-xylylene monomer. Providing a first sheet or roll of polymer having a metallized surface, wherein the first sheet or roll comprises an insulating layer on the metallized surface, wherein the insulating layer comprises the metallized surface; Not completely coating the metallized surface so that the ends of
Applying a dielectric film comprising a film material to the insulating layer, wherein the film material exhibits (i) electrical insulation and / or high dielectric constant; (ii) one or more polar functional groups; Comprising a plurality of macromolecules having ionizable functional groups or combinations thereof;
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, wherein The insulating layer does not completely coat the metallized surface such that an end of the metallized surface is exposed, wherein the insulating layer contacts the insulator film and the second sheet or roll The second sheet or roll is oriented so that the uncoated end of the first sheet or roll is proximate to the uncoated end of the first sheet or roll to form a composite multilayer surface;
Winding the composite multilayer surface in a roll shape, or cutting and laminating a part of the composite multilayer surface to form a laminated structure; and
Bonding the uncoated ends of the first sheet or roll and the second sheet or roll to a conductive polymer housed in a non-conductive holder having a conductive cap or electrical connection. When,
Electrically connecting the composite multilayer surface to a positive electrode and a negative electrode;
Applying an electric field to the surface of the composite multilayer, wherein the electric field is such that at least part of the polymer of the dielectric film is the insulating layer of the first sheet or roll, the second sheet or roll. Applying for a time effective to bond to the insulating layer or both. Providing a receiving device with a first electrode having an upper surface with an insulating layer;
Disposing a perforated non-conductive separator sheet on the insulating layer of the first electrode;
Disposing a second electrode having a lower surface with an insulating layer on the separator sheet such that an insulating layer of the second electrode contacts the separator sheet;
Adding a dielectric material to fill a space in the separate sheet of the perforations and to contact the first electrode and the second electrode, the dielectric material comprising: (i) (Ii) comprising a plurality of macromolecules that exhibit electrical insulation and / or high dielectric constant and have one or more polar functional groups, ionizable functional groups, or combinations thereof;
Applying an electric field across the first electrode, the dielectric material, and the second electrode for a time effective for at least a portion of the polymer to bond to the insulating layer of the first electrode; Coupling at least a portion of the first electrode to the insulating layer of the first electrode. A conductive first electrode;
A conductive second electrode;
A sterically constrained dielectric film disposed between the conductive first electrode and the conductive second electrode;
The sterically constrained dielectric film includes a plurality of polymers having one or more polar functional groups, ionizable functional groups, or a combination thereof, and the energy storage device is charged and / or charged by the energy storage device. An energy storage device having an energy storage capacity of at least 1 Wh / kg based solely on the weight of the dielectric material disposed between the conductive first electrode and the second electrode when not charged.   The energy storage device according to claim 18, wherein the polymer is a protein molecule.   20. The energy storage device according to claim 18 or 19, wherein at least 1% of the plurality of polymers are coupled to the conductive first electrode.   21. The energy storage device according to claim 20, wherein the energy storage device has an energy storage capacity that is at least 100 times greater than the energy storage capacity of the energy storage device, the energy storage device comprising: A conductive first electrode, (ii) a conductive second electrode, and (iii) an electrically insulating and / or high dielectric constant dielectric film, wherein the dielectric film includes the first electrode and the second electrode. Energy storage device comprising a plurality of macromolecules disposed between and having one or more polar functional groups, ionizable functional groups, or combinations thereof.   The energy storage device according to claim 20 or 21, wherein the sterically constrained dielectric film includes a plurality of polymers having one or more polar functional groups, ionizable functional groups, or a combination thereof. And an energy storage device having a dielectric constant 50% to 10,000,000% higher than a dielectric constant of the dielectric film in which the polymer is not bonded to the conductive first electrode.   23. The energy storage device according to any one of claims 18 to 22, wherein at least a part of the polymer is bonded to at least 1% of the surface of the first electrode. An energy storage device coupled to a surface of the conductive first electrode in contact with a three-dimensionally constrained dielectric film. The energy storage device according to claim 18 or 19,
An insulating layer disposed between the conductive first electrode and the three-dimensionally constrained dielectric film;
An insulating layer disposed between the conductive second electrode and the dielectric film, or
A first insulating layer disposed between the conductive first electrode and the dielectric film, and a first insulating layer disposed between the conductive second electrode and the three-dimensionally constrained dielectric film. 2 insulation layers,
An energy storage device further comprising: The energy storage device according to claim 24, comprising:
The energy storage device, wherein at least 1% of the plurality of polymers are bonded to the first insulating layer.