Energy Storage Media for Ultracapacitors

Abstract

An ultracapacitor having a high mass output power density is provided. [Solution] An ultracapacitor having a mass output power density of at least about 12 kW / kg for multiple charge / discharge cycles, comprising a housing including at least one multi-foam electrode 3 disposed therein, a first layer (current collector 2) including an elongated nanofoam material disposed on the surface of the current collector, the multi-foam electrode 3 including at least a second layer (adhesion layer 34) including nanofoam carbon disposed on the surface of the first layer, and an electrolyte that provides ion transport within the ultracapacitor.

Description

[Technical Field]

[0001] [Declaration of Federally Sponsored Research] This invention was made with government support under Grant DE-AR0000035 / 0001 awarded by the U.S. Department of Energy (ARPA-E). The U.S. Government has certain rights in this invention. [Background technology]

[0002] The present invention relates generally to capacitors, and more particularly to carbon nanotubes used in capacitors.

[0003] Carbon nanotubes (hereafter referred to as "CNTs") are carbon structures that exhibit a variety of properties. Many of these properties suggest opportunities for improvement in a variety of technologies. For example, technologies that benefit from increased strength, conductivity, or capacitance would benefit from the use of CNTs. Advances in CNT technology are therefore of great interest to those working with capacitors.

[0004] Capacitors are one of the important components in various electrical systems. Their functions include power buffering, energy storage, and voltage smoothing. Various industries place strict requirements on capacitors.

[0005] For example, consider that industries such as automotive, manufacturing, aerospace, aircraft, medical, and military have several applications requiring capacitors to provide energy or power support for electric drives, pulse power, or process operations. Energy capacity and power capability are key requirements for typical applications in these industries. Applications such as torque assist in electric drivetrains, power assist for motor drives in manufacturing plants, or providing voltage support during high power load demands require significant energy and power. Some applications exhibit limited physical space or weight limits. Some applications require long cycle life.

[0006] Therefore, capacitors used in industrial environments must meet performance requirements while meeting physical constraints. One of the attendant challenges for ultracapacitor designers and manufacturers is obtaining electrodes that function at the desired power output.

[0007] Therefore, there is a need for a method and apparatus for fabricating high-power electrodes based on carbon nanotubes. Preferably, the method and apparatus are simple to implement, thereby providing reduced manufacturing costs and increased production rates. Preferably, the method and apparatus provide electrodes for ultracapacitors that perform well in demanding situations. Preferably, the electrodes provide stable conductivity and low internal resistance over a wide temperature range. Summary of the Invention

[0008] A method and apparatus for producing carbon nanotubes is provided. The method and apparatus provide carbon nanotubes that exhibit superior properties and therefore superior performance when used in a variety of applications. Various configurations of electrodes and ultracapacitors can be realized as a result.

[0009] In one embodiment, a method for producing an aggregate of vertically aligned carbon nanotubes is provided, the method comprising: mounting a substrate in a substantially oxygen-free environment; disposing a catalyst on the substrate to provide a substrate; exposing the substrate to a source gas and heating at least one of the source gas and the substrate to grow an aggregate on the substrate; and cooling the aggregate in the substantially oxygen-free environment.

[0010] In another embodiment, an apparatus for producing aggregates of vertically aligned carbon nanotubes is provided, the apparatus including: a loader section for loading a substrate into a substantially oxygen-free environment; a sputtering section for disposing a catalyst on the substrate to provide a substrate; a carbon deposition section for exposing the substrate to a source gas and heating at least one of the source gas and the substrate to grow aggregates on the substrate; and a cooling section for cooling the aggregates in the substantially oxygen-free environment.

[0011] In another embodiment, a method for fabricating an electrode for an ultracapacitor is provided, wherein the electrode comprises an aggregate of vertically aligned carbon nanotubes. The method includes mounting a substrate in a substantially oxygen-free environment; disposing a catalyst on the substrate to provide a substrate; exposing the substrate to a source gas and heating at least one of the source gas and the substrate to grow aggregates on the substrate; and selecting aggregates produced by cooling the aggregates in the substantially oxygen-free environment, and one of bonding the aggregates with a current collector, removing the aggregates from the substrate and placing a current collector on the aggregates, and combining the aggregates with other carbonaceous materials and bonding the combination with a current collector.

[0012] In another embodiment, a method for fabricating an electrode for an energy storage system is provided. The method includes selecting a substrate having a thickness of vertically aligned carbon nanotubes (CNTs) disposed thereon; disposing a tie layer on the CNTs of the thickness; bonding the tie layer to a current collector; and removing the substrate from the CNTs to provide an electrode.

[0013] In another embodiment, a method for manufacturing an ultracapacitor is provided, the ultracapacitor comprising at least one electrode comprising an aggregate of vertically aligned carbon nanotubes. The method includes: mounting a substrate in a substantially oxygen-free environment; disposing a catalyst on the substrate to provide a substrate; exposing the substrate to a feedstock gas and heating at least one of the feedstock gas and the substrate to grow aggregates on the substrate; and selecting aggregates produced by cooling the aggregates in the substantially oxygen-free environment, and selecting an electrode produced by one of transferring the aggregates onto a current collector, removing the aggregates from the substrate and disposing a current collector on the aggregates, and combining the aggregates on the current collector with other carbonaceous materials to provide an electrode; and incorporating the electrode into an ultracapacitor.

[0014] In another embodiment, a method for manufacturing an electrode for an energy storage system is provided. The method includes selecting a base including a current collector and a first bonding layer disposed on a surface of the current collector; and bonding a second bonding layer to the first bonding layer, the second bonding layer including a carbonaceous layer disposed thereon, the carbonaceous layer including a material for storing electric charge.

[0015] In another embodiment, an electrode is provided that includes a base including a current collector and a first bonding layer disposed on a surface of the current collector, and a second bonding layer bonded to the first bonding layer, the second bonding layer including a carbonaceous layer disposed thereon, the carbonaceous layer including a material for storing electric charge.

[0016] In another embodiment, a capacitor is provided that includes a housing with at least one electrode including a base including a current collector and a first bonding layer disposed on a surface of the current collector, and a second bonding layer bonded to the first bonding layer, the second bonding layer including a carbonaceous layer disposed thereon, the carbonaceous layer including a material for storing charge in the capacitor; and at least one of an electrolyte and a dielectric material disposed within the housing, wherein the at least one electrode is coupled to an output electrode of the housing.

[0017] In another embodiment, a method for providing a multi-form electrode for an energy storage device is provided, the method comprising: selecting an electrode comprising an aggregate of carbon nanotubes in electrical contact with a current collector; disposing at least one nanoform carbon dispersed in a carrier material on the aggregate; and releasing the carrier material to provide the multi-form electrode.

[0018] In another embodiment, a multiform electrode for an energy storage device is provided, the electrode comprising an aggregate of carbon nanotubes disposed on a surface of a current collector, the aggregate further comprising at least one additional layer of nanoform carbon disposed on the aggregate as a solution comprising nanoform carbon dispersed in a carrier material.

[0019] In another embodiment, an ultracapacitor is provided that includes a housing including at least a multi-form electrode disposed therein, the multi-form electrode including an aggregate of carbon nanotubes disposed on a surface of a current collector, the aggregate further including at least one additional layer of nano-form carbon disposed on the aggregate as a solution including nano-form carbon dispersed in a carrier material, and an electrolyte that provides ion transport within the ultracapacitor.

[0020] In another embodiment, a method for providing a carbonaceous aggregate is provided, the method including dispersing aggregates of aligned carbon nanotubes in a first solution, dispersing a carbon additive in a second solution, ultrasonically mixing the first solution and the second solution, mixing the combined first solution and the combined second solution to provide a mixed solution, ultrasonically mixing the mixed solution, and obtaining the carbonaceous aggregate from the combined mixed solution.

[0021] In another embodiment, an electrode is provided comprising an energy storage medium comprising a carbonaceous aggregate, the electrode comprising a current collector having a carbonaceous aggregate disposed thereon, the aggregate comprising a combination of ultrasonically treated carbon nanofoam.

[0022] In another embodiment, an ultracapacitor is provided that includes at least one electrode with an energy storage medium comprising a carbonaceous aggregate, the electrode including a current collector having the carbonaceous aggregate disposed thereon, the aggregate including a combination of ultrasonically treated carbon nanofoam.

[0023] In another embodiment, a method for manufacturing an electrode component is provided, the method including selecting a substrate having a collection of carbon nanotubes disposed thereon; depositing a layer of conductive material over the collection; and removing the collection and conductive material from the substrate.

[0024] In another embodiment, an electrode is provided that includes a plurality of electrode components, each component including a collection of carbon nanotubes and a layer of conductive material disposed thereon, each of the components being coupled to another one of the components, and at least one coupling including a bond of the component to the conductive material.

[0025] In another embodiment, an ultracapacitor is provided that includes at least one electrode including a plurality of electrode components, each component including a collection of carbon nanotubes and a layer of conductive material disposed thereon, each of the components coupled to another one of the components, at least one coupling including a bond between the component and the conductive material; a housing that encases the at least one electrode; and an electrolyte that provides transport of ions within the ultracapacitor.

[0026] In another embodiment, a method for manufacturing an electrode is provided, the method including obtaining a layered stack of carbon nanotubes (CNTs), wetting the layered stack with a solution, compressing the layered stack, drying the compressed layered stack, and applying a current collector to the compressed layered stack.

[0027] In another embodiment, an ultracapacitor is provided that includes at least one electrode including a compressed layered stack of carbon nanotubes (CNTs) and a current collector disposed on the stack; and an electrolyte for transporting energy stored in the electrode to at least one terminal of the ultracapacitor.

[0028] In another embodiment, a method of using an ultracapacitor is provided. The method includes obtaining an ultracapacitor including an electrolyte and two electrodes, each of the electrodes in electrical communication with a current collector and separated from the other electrode by a separator; and cycling the ultracapacitor by alternatively charging and discharging the ultracapacitor, wherein the power density output by the ultracapacitor is at least 12 kW / kg and at most about 250 kW / kg for each cycle.

[0029] In another embodiment, a method of using an ultracapacitor is provided. The method includes obtaining an ultracapacitor including an electrolyte and two electrodes, each of the electrodes in electrical communication with a current collector and separated from the other electrode by a separator; and cycling the ultracapacitor by alternatively charging and discharging the ultracapacitor, wherein the ultracapacitor has an output energy density of at least 1 Wh / kg and at most about 35 Wh / kg for each cycle.

[0030] In another embodiment, a method of using an ultracapacitor is provided. The method includes obtaining an ultracapacitor including an electrolyte and two electrodes, each of the electrodes in electrical communication with a current collector and separated from the other electrode by a separator; and cycling the ultracapacitor by alternatively charging and discharging the ultracapacitor at least three times while maintaining a voltage across the ultracapacitor between a maximum voltage and about half of the maximum voltage, wherein the charging and discharging results in an output of energy from the ultracapacitor of at least 3.75 Wh / kg per charge or discharge.

[0031] Additional embodiments will become apparent in light of the description provided below.

[0032] The present invention will be more fully understood by reference to the following detailed description taken in conjunction with the drawings in which: [Brief explanation of the drawings]

[0033] [Figure 1] FIG. 1 is a schematic diagram of an ultracapacitor. [Figure 2] FIG. 2 is a block diagram schematically illustrating one embodiment of the functional configuration of a manufacturing apparatus. [Figure 3] FIG. 3 is a block diagram schematically showing another embodiment of the functional configuration of the manufacturing apparatus. [Figure 4] FIG. 4 is a block diagram of an embodiment of a manufacturing apparatus. [Figure 5] FIG. 5 is a block diagram showing an embodiment of a control system for a manufacturing apparatus. [Figure 6] FIG. 6 is a block diagram illustrating a current collector and a substrate having a plurality of carbon nanotubes (CNTs) formed thereon. [Figure 7] FIG. 7 is a block diagram showing the placement of the CNT of FIG. 6 on a current collector. [Figure 8] FIG. 8 is a block diagram illustrating the loaded current collector of FIG. 7 and another substrate fabricated for transferring additional CNTs onto the loaded current collector. [Figure 9] FIG. 9 is a block diagram illustrating the loading of additional CNTs onto a loaded current collector. [Figure 10] FIG. 10 is a block diagram showing a high-power electrode obtained by passing CNTs multiple times over the current collector of FIG. [Figure 11] 11A and 11B (collectively referred to herein as FIG. 11) represent transmission electron micrographs of uncompressed and compressed carbon nanotubes, respectively. [Figure 12] 12A and 12B (collectively referred to herein as FIG. 12) show the comparative performance of an activated carbon-based ultracapacitor and a carbon nanotube-based ultracapacitor, respectively. [Figure 13] 13A and 13B (collectively referred to as FIG. 13) are block diagrams depicting aspects of an embodiment of an electrode base structure and an electrode process structure. [Figure 14] FIG. 14 is a block diagram illustrating one embodiment of a functionally stacked electrode. [Figure 15] FIG. 15 is a block diagram illustrating an electrode having a carbon substrate disposed on a current collector. [Figure 16] FIG. 16 is a block diagram illustrating an apparatus for depositing additional carbon nanofoam onto the electrode of FIG. [Figure 17] FIG. 17 is a block diagram illustrating a multi-form electrode. [Figure 18] FIG. 18 is a block diagram illustrating another apparatus for depositing additional carbon nanofoam onto the electrode of FIG. [Figure 19] FIG. 19 is a flowchart presenting an exemplary method for providing a multi-form electrode. [Figure 20] 20A and 20B (collectively referred to herein as FIG. 20) are diagrams depicting vertically aligned carbon nanotubes and carbon additive fragments, respectively, dispersed in a solvent. [Figure 21] FIG. 21 is a diagram depicting the sonication of the solution depicted in FIG. [Figure 22] FIG. 22 depicts the carbonaceous aggregates resulting from the process depicted in FIG. [Figure 23] FIG. 23 illustrates one embodiment of the treatment of the carbonaceous aggregates depicted in FIG. [Figure 24] FIG. 24 depicts the treated carbonaceous aggregate of FIG. 23 disposed in an electrode suitable for use in the ultracapacitor of FIG. [Figure 25] FIG. 25 is a block diagram illustrating a plurality of carbon nanotubes (CNTs) grown on a substrate. [Figure 26] FIG. 26 is a block diagram illustrating the deposition of a current collector onto the CNTs of FIG. 25 to provide an electrode component. [Figure 27] FIG. 27 is a block diagram illustrating the addition of a transfer tape to the electrode components of FIG. [Figure 28] FIG. 28 is a block diagram representing the electrode components during the transfer process. [Figure 29] FIG. 29 is a block diagram showing the electrode components after movement. [Figure 30] FIG. 30 is a block diagram depicting an exemplary electrode fabricated from multiple electrode components. [Figure 31]FIG. 31 is a flow chart depicting an exemplary process for fabricating an electrode from multiple electrode components. [Figure 32] 32A and 32B (collectively referred to herein as FIG. 32) are graphs depicting power density as a function of frequency response for one exemplary embodiment of an ultracapacitor including electrodes fabricated in accordance with the teachings herein. FIG. 32B provides an expanded view of the initial portion of the curve presented in FIG. 32A. [Figure 33] FIG. 33 is a graph illustrating the voltage response of a discharge cycle for an exemplary ultracapacitor. [Figure 34] FIG. 34 is a graph illustrating the voltage response to charge and discharge cycling of an exemplary ultracapacitor. [Figure 35] FIG. 35 depicts the combined power and energy performance for a series of exemplary ultracapacitors. [Figure 36] FIG. 36 depicts the combined power and energy performance for a series of exemplary ultracapacitors. DETAILED DESCRIPTION OF THE INVENTION

[0034] Disclosed herein are methods and apparatus for providing carbon nanotubes (CNTs). Carbon nanotubes (CNTs) are particularly well suited for use in ultracapacitors. When used in ultracapacitors, the carbon nanotubes (CNTs) disclosed herein provide high power output and reliable operation. Before presenting aspects of the carbon nanotubes (CNTs), some background is first provided.

[0035] As shown in FIG. 1 , one exemplary embodiment of an “ultracapacitor 10” is shown. In this case, the ultracapacitor 10 is an electric double layer capacitor (EDLC). The EDLC includes at least one electrode 3 (in some cases, such as when two electrodes 3 are present, the electrodes may be referred to as a negative electrode 3 and a positive electrode 3). When installed within the ultracapacitor 10, each electrode 3 provides a double layer of charge at the electrolyte interface. In some embodiments, multiple electrodes 3 are included, although for purposes of discussion, only two electrodes 3 are shown. As is conventional herein, at least one of the electrodes 3 uses a carbon-based energy storage medium 1 (discussed further herein) to provide energy storage.

[0036] Each of the electrodes 3 includes a current collector 2 (also called a "charge collector"). The electrodes 3 are separated by separators 5. Typically, separators 5 are thin structural materials (usually sheets or plates) used to separate the electrodes 3 into two or more compartments.

[0037] At least one form of electrolyte 6 is contained in and fills the void spaces in and between the electrodes 3 and separator 5. Generally, the electrolyte 6 is a substance that dissociates into charged ions. In some embodiments, a solvent that dissolves the substance may be included. The resulting electrolyte conducts electricity by ion transport.

[0038] Typically, the combination of electrode(s) 3 and separator 5 is then formed into either a wound or prismatic shape and then packaged into a cylindrical or prismatic housing 7. Once the electrolyte 6 is added, the housing 7 is sealed. In various examples, the package is sealed using laser, ultrasonic, and / or welding techniques. The housing 7 (also referred to as an "enclosing body" or "case" or other similar terminology) includes at least one terminal 8. Each terminal 8 provides electrical access to the energy stored in the energy storage medium 1, typically through a conductor (not shown) coupled to the energy storage medium 1.

[0039] That is, in some embodiments, multiple leads (not shown) are electrically coupled to each of the current collectors 2. Each of the multiple leads is grouped together (and thus relative to the polarity of the ultracapacitor 10) and coupled to a respective terminal 8 of the housing 7.

[0040] In the exemplary EDLC, the energy storage medium 1 is formed from carbon nanotubes. The energy storage medium 1 may include other carbonaceous materials, including, for example, activated carbon, carbon fiber, rayon, graphene, aerogel, carbon cloth, and multiple forms of carbon nanotubes. An activated carbon electrode can be fabricated, for example, by carbonizing a carbon compound to produce a carbon base material through a first activation process, adding a binder to the carbon base material to produce a compact, carbonizing the compact, and finally, performing a second activation process on the carbonized compact to produce an activated carbon electrode. A carbon fiber electrode can be fabricated, for example, by using a paper- or cloth-like base material (or preform) with high-surface-area carbon fibers. The fabrication of carbon nanotubes and their application in the ultracapacitor 10 are discussed in further detail herein.

[0041] Thus, in some embodiments, the materials used to form energy storage medium 1 may include materials other than pure carbon (and various forms of carbon that may currently exist or may later be devised). That is, various blends of other materials may be included in energy storage medium 1. More specifically, and in a non-limiting example, at least one binder material may be used in energy storage medium 1, although the addition of other materials (such as binder materials) is not recommended or required. However, generally, energy storage medium 1 is formed substantially from carbon and, therefore, may be referred to herein as a “carbonaceous material,” “carbonaceous layer,” and other similar terms. In short, energy storage medium 1 is formed primarily from carbon, but may include any form of carbon (and any additives or impurities deemed appropriate or acceptable) to provide the desired functionality as energy storage medium 1.

[0042] Several embodiments of various forms of carbonaceous materials suitable for use in energy storage medium 1 are presented herein as examples. These embodiments discussed below provide robust energy storage and are well suited for use in electrode 3. It should be noted that these examples are illustrative and not limiting of the embodiments of carbonaceous materials suitable for use in energy storage medium 1.

[0043] The electrolyte 6 includes a pair of cations 9 and anions 11 and may include a solvent. Various combinations of each may be used. In an exemplary EDLC, the cations 9 may include at least one of 1-(3-cyanopropyl)-3-methylimidazolium, 1,2-dimethyl-3-propylimidazolium, 1,3-bis(3-cyanopropyl)imidazolium, 1,3-diethoxyimidazolium, 1-butyl-1-methylpiperidinium, 1-butyl-2,3-dimethylimidazolium, 1-butyl-3-methylimidazolium, 1-butyl-4-methylpyridinium, 1-butylpyridinium, 1-decyl-3-methylimidazolium, 1-ethyl-3-methylimidazolium, 3-methyl-1-propylpyridinium, and combinations thereof, as well as other equivalents deemed appropriate.

[0044] Additional exemplary cations 9 include imidazolium, pyrazinium, piperidinium, pyridinium, pyrimidinium, and pyrrolidinium. Generally, these cations 9 were selected to exhibit high thermal stability, low glass transition temperatures (Tg), and high conductivity, and have demonstrated good electrical performance over a wide temperature range. Thus, other embodiments of cation 9 exhibiting desired properties may be used as well, or in conjunction with any of the above.

[0045] In an exemplary EDLC, anion 11 may include at least one of bis(trifluoromethanesulfonate)imide, tris(trifluoromethanesulfonate)methide, dicyanamide, tetrafluoroborate, hexafluorophosphate, trifluoromethanesulfonate, bis(pentafluoroethanesulfonate)imide, thiocyanate, trifluoro(trifluoromethyl)borate, and combinations thereof and other equivalents deemed appropriate.

[0046] The solvent may include acetonitrile, amides, benzonitrile, butyrolactone, cyclic ethers, dibutyl carbonate, diethyl carbonate, diethyl ether, dimethoxyethane, dimethyl carbonate, dimethylformamide, dimethyl sulfone, dioxane, dioxolane, ethyl formate, ethylene carbonate, ethyl methyl carbonate, lactones, linear ethers, methyl formate, methyl propionate, methyl tetrahydrofuran, nitriles, nitrobenzene, nitromethane, n-methylpyrrolidone, propylene carbonate, sulfolane, sulfones, tetrahydrofuran, tetramethylene sulfone, thiophene, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, carbonate esters, gamma-butyrolactone, nitriles, tricyanohexane, any combination thereof, or other material(s) that exhibit suitable performance characteristics.

[0047] Separator 5 may be made from nonwoven glass. Separator 5 may also be made from glass fibers, ceramics, and fluoropolymers such as polytetrafluoroethylene (PTFE), commonly available as TEFLON® by DuPont Chemicals (Wilmington, Delaware). For example, by using nonwoven glass, separator 5 may include main fibers and binder fibers, each of which has a smaller fiber diameter than each of the main fibers, enabling the main fibers to bond together.

[0048] In general, the term "electrode" refers to an electrical conductor used to contact another material, often a non-metal, in a device that may be incorporated into an electrical circuit. Exemplary second materials in an energy storage medium may be in various forms, including solids, liquids, and gases. Energy storage medium 1 materials may include conductive materials, semiconductors, electrolytes, and the like. In general, the term "electrode," as used herein, relates to the energy storage medium 1 and additional components that may be associated with the energy storage medium 1 to provide desired functionality (e.g., a current collector 2 integral with the energy storage medium 1).

[0049] Referring now to Figures 2-5, embodiments of a method and apparatus for producing carbon nanotubes (CNTs) are shown. The disclosed techniques provide a high degree of control over the production process, resulting in CNTs that can be fully adapted (i.e., designed for) a particular application, such as use in an ultracapacitor 10. In summary, a substrate is provided. A catalyst material is then placed on the substrate, and a carbonaceous material is deposited on the catalyst. When production is performed in a substantially oxygen-free environment, problems associated with oxidation and the need for reduction are avoided. When implementing various embodiments of the techniques, CNT manufacturers will understand an effective method for producing high-quality CNTs.

[0050] The techniques disclosed herein may be adjusted as needed to provide CNTs with desired properties, i.e., the methods may be controlled to take into account advantageous properties such as density, surface area, length, number of walls, composition (i.e., metallic or non-metallic), end properties (i.e., open or closed ends), etc.

[0051] Reference may be made to FIG. 2 for an overview of an exemplary embodiment. In FIG. 2, a non-limiting aspect of a method for CNT production 120 is presented. In this embodiment, the method for production 120 includes a first step (substrate loading 121) in which a substrate is loaded into a fabrication machine (also referred to as a "fabrication apparatus" and other similar terms). In a second step, a layer of catalyst is applied to the substrate (catalyst application 122). In a third step, carbonaceous material is gradually deposited on the catalyst to grow CNTs (carbon deposition 123, also referred to as a "deposition step," "growth step," or other similar terms). In a fourth step, the CNTs are cooled for removal and subsequent use (CNT cooling 124). In some embodiments, a buffer step 125 is also included, as discussed further herein.

[0052] Exemplary apparatus embodiments for the mass production of CNTs are provided. In various embodiments, the apparatus is arranged (or configured) to provide strict environmental control (e.g., control of temperature, atmospheric content, and / or pressure, etc.). In some embodiments, CNT products are produced in a continuous (i.e., uninterrupted or continuous) process. By controlling the production environment throughout the process, and by varying aspects of the production environment as needed during the process, it is possible to produce CNTs that exhibit desired properties.

[0053] As can be imagined, the method requires a great deal of equipment and control, and therefore, the description of these four steps is overly simplified. To provide some context and additional embodiments to more fully describe each step in the method for fabrication 120, some definitions, parameters, characteristics, etc. are provided.

[0054] A machine, whether referred to as a "manufacturing apparatus," "fabrication machine," or other similar term(s), typically includes components (or parts) as needed or required for the production of CNTs. Exemplary components included in a manufacturing apparatus include components that perform the described functions as needed. Illustrative, non-limiting examples that may be included include at least one pump, valve, electrical conduit, gas pipe, power supply (or power source), gas supply (including supplies of inert gases, carbonaceous gases, etc.), water supply, nozzle, inlet, outlet, vent, exhaust, fan, material movement device (e.g., conveyor belt, drive system, etc.), heating element (resistive heating element, etc.), heat exchanger (or other form of cooling), shutter, door, servo motor (or automatic control device, servo), motor, sensor (electrical, temperature, pressure, gas, optical, etc.), transducer (or transducer), control device (or controller), human interface, computer interface, processing device (or processor), data storage device, memory, bus, computer executable code for managing the operation of the machine, and other components that may be required by a machine operator, manufacturer, or designer. In short, various technologies supporting and enabling the methods described herein are believed to be well known and are not generally part of the invention disclosed herein. Thus, in considering various embodiments and variations of apparatus for practicing the teachings herein, the discussion of such apparatus is generally limited to some of the aspects that can affect the generation of CNT aggregates.

[0055] As used herein, "aligned CNT aggregate," "CNT aggregate," "vertically aligned carbon nanotubes (VCNTs)," and similar terms generally refer to a structure in which a large number of CNTs are aligned or oriented in a common manner. In some embodiments, the specific surface area SA of the aligned CNT aggregate is 300 m 2 / g or greater (e.g., when the CNTs are mostly closed). In other embodiments, the surface area SA is 1,300 m 2 / g or more (e.g., when the CNTs are mostly open). "Aggregates of CNTs" generally refers to multiple vertically aligned CNT structures. In some embodiments, the weight density (ρ w ) is 0.002g / cm 3 ~0.2g / cm 3 In general, the CNT embodiments discussed herein relate to vertically aligned carbon nanotubes, VCNTs, although in some embodiments, such as those in which the CNTs are mixed with other nanoforms of carbon, this is not a requirement or even true.

[0056] It should be recognized that the term "vertically aligned" in reference to nanotubes and other nanostructures generally refers to the orientation of the nanotubes at the time of fabrication. However, this terminology is not meant to be limiting. That is, when considering an assembly of "vertically aligned nanotubes," it should be recognized that the term "vertical" may not be significant or may be misleading. Accordingly, it should be recognized that, as discussed herein, an assembly and other forms of "vertically aligned nanotubes" generally refer to an assembly that includes a substantially parallel, repeating, or organized structure.

[0057] For the CNT aggregates to exhibit common orientation and a large specific surface area (SA), the height of the CNT aggregates may range from 10 μm to 1 cm. Generally, a height of 10 μm or greater improves orientation. Alternatively, a height of 1 cm or less can improve the specific surface area (SA) because such a height allows for rapid growth and thus controls the deposition of carbonaceous impurities.

[0058] In various embodiments, carbon nanotubes typically exhibit certain properties. In particular, in some embodiments, the produced carbon nanotubes exhibit lengths of about 50 μm to about 5 mm (or longer). In some embodiments, the carbon nanotubes are about 200 μm to about 2 mm. In some embodiments, the carbon nanotubes may include, for example, 1 to 10 walls. In some embodiments, the carbon nanotubes may include, for example, 1 to 5 walls. The carbon nanotubes may have diameters of, for example, about 0.7 nm to 10 nm. When considered as an array of vertically aligned carbon nanotubes, the density is about 10 CNT / cm. 2 ~About 1013CNT / cm 2 In some embodiments, the density may be about 10 CNT / cm 2 ~About 1012CNT / cm 2 It may be.

[0059] The carbon nanotubes used in electrode 3 may be treated or otherwise engineered to achieve specific properties. Exemplary properties and physical characteristics of carbon nanotubes when included in an electrode include an active material thickness of about 30 μm to 500 μm, and in some cases about 100 μm to about 200 μm; 3 ~about 0.8g / cm 3 , in some cases about 0.5 g / cm 3 ~about 0.6g / cm 3 Carbon nanotubes generally do not contain any type of binder. Energy storage media may include vertically aligned carbon nanotubes, entangled carbon nanotubes, other forms of carbon, and any combination of materials deemed suitable. Generally, carbon nanotubes have a volume density of about 500 m. 2 / g ~ approx. 2,200m 2The surface area SA is given as 1 / g (which may be the increase in surface area of ​​the untreated CNTs as a result of the formation of holes and / or pores in the walls of the CNTs). When shaped as an energy storage medium, the carbon nanotubes may have a compressibility ratio (when vertically aligned) of about 10:1 to about 100:1.

[0060] Thus, when used in an ultracapacitor 10, the carbon nanotube-based electrodes 3 described herein may also exhibit certain advantageous properties. For example, the performance of the ultracapacitor 10 may include a mass-specific capacitance (at maximum operating voltage) of about 100 F / g to about 200 F / g; a volume-specific capacitance (at maximum operating voltage) of about 50 F / cc to about 100 F / cc; and a maximum operating voltage of about 3 V to 4.5 V. For example, the ultracapacitor 10 may have a resistance of about 0.5 Ω / cm 2 ~Approx. 1Ω / cm 2 The equivalent series resistance (ESR) of

[0061] The term "substrate" generally refers to a material capable of supporting a catalyst for carbon nanotubes on its surface and capable of maintaining its shape even at high temperatures (e.g., temperatures of 400°C or higher). Any type of substrate proven to be usable for CNT production may be used. Non-limiting examples of materials include: metals such as iron, nickel, chromium, molybdenum, tungsten, titanium, aluminum, manganese, cobalt, copper, silver, gold, platinum, niobium, tantalum, lead, zinc, gallium, germanium, arsenic, indium, phosphor, and antimony; alloys and oxides containing these or other suitable materials; nonmetals such as silicon, quartz, glass, mica, graphite, and diamond; and ceramics. Metal materials are generally less expensive than silicon and ceramics. In particular, Fe-Cr (iron-chromium) alloys, Fe-Ni (iron-nickel) alloys, and Fe-Cr-Ni (iron-chromium-nickel) alloys are suitable. The substrate may be in the form of a thin film, block (or lump), powder, or flat plate. However, a shape in which the substrate has a large surface area relative to its volume is particularly suitable for mass production.

[0062] The term "carburization prevention layer" generally refers to a layer on a substrate. The substrate may have a carburization prevention layer formed on either its front or back surface. In some embodiments, the substrate includes a carburization prevention layer formed on each of its front and back surfaces. Formation may be achieved by techniques such as sputtering. The carburization prevention layer is generally a protective layer that prevents the substrate from carburizing and thereby deforming during the carbon nanotube generation process. The carburization prevention layer may vary in thickness. In various embodiments, the thickness of the carburization prevention layer is from about 1 nm to about 500 nm, and in some cases from about 5 nm to about 100 nm.

[0063] In some embodiments, the carburization prevention layer is composed of a metal or a ceramic material (ceramic materials are effective in preventing carburization). Examples of suitable metals include copper and aluminum. Examples of suitable ceramic materials include oxides such as aluminum oxide, silicon oxide, zirconium oxide, magnesium oxide, titanium oxide, silica, alumina, chromium oxide, boron oxide, calcium oxide, and zinc oxide; and nitrides such as aluminum nitride and silicon nitride. Note that both aluminum oxide and silicon oxide are very effective in preventing carburization.

[0064] As used herein, a "catalyst" may be provided on the substrate or the carburization prevention layer. Any type of catalyst proven to be usable in CNT production can be used. Non-limiting examples of catalysts include iron, nickel, cobalt, molybdenum, their chlorides, their alloys, and composites or layers of these with aluminum, alumina, titania, titanium nitride, or silicon oxide. Other non-limiting examples include iron-molybdenum thin films, alumina-iron thin films, alumina-cobalt thin films, alumina-iron-molybdenum thin films, aluminum-iron thin films, and aluminum-iron-molybdenum thin films. The catalyst can be used in an amount range proven to be usable in CNT production. For example, in some embodiments using iron, the thickness of the thin film formed can range from 0.1 nm to 100 nm. In some other embodiments, the thickness of the iron can be from 0.5 nm to 5 nm. In some further embodiments, the thickness of the iron can be from 0.8 nm to 2 nm.

[0065] The catalyst may include multiple layers. The catalyst may be continuous over another (or other) layer, such as a layer of substrate or a carburization protection layer, or may be at least partially discontinuous. In some embodiments, another layer, such as an additional carburization protection layer, may be disposed on the surface of the catalyst. In some embodiments, the catalyst may include a metal deposited on the surface of another material, such as an oxide. The deposition results in "clusters" or a discontinuous layer. As used herein, the term "continuous" generally refers to "wetting" or substantially complete coverage of the underlying material.

[0066] Dry methods can be used to form the catalyst on the surface of the substrate. For example, sputtering evaporation can be used. Other techniques, such as cathodic arc deposition, sputter deposition, ion beam assisted deposition, ion beam induced deposition, and / or electrospray ionization, can also be used if necessary. Furthermore, the catalyst can be formed into any shape by combining patterning obtained by well-known applications of photolithography, nanoprinting, etc.

[0067] In one embodiment, the shape of the aligned CNT aggregate can be appropriately controlled. This can be achieved, for example, by patterning the catalyst formed on the substrate and controlling the CNT growth time. As a result, the aligned CNT aggregate can take on any of a thin film shape, a cylindrical shape, a prismatic shape, or other complex shape. In particular, in the thin film shape, the aligned CNT aggregate has a thickness (height) that is very small compared to its length and width; however, the length and width can be appropriately controlled by patterning the catalyst and by controlling the growth time of the CNTs that make up the aligned CNT aggregate. In some embodiments, the morphology of the catalyst can be tailored, for example, by varying or controlling the particle size in the catalyst, thereby adjusting the diameter of the CNTs grown on the catalyst.

[0068] Generally, a "reducing gas" is not required by the teachings herein. Reducing gases are commonly used in the prior art to effect reduction of the catalyst. Reducing gases may include any material that is in a gaseous state at the growth temperature. Reducing gases may be used to stimulate the catalyst to become fine particles suitable for CNT growth and to improve the activity of the catalyst. Examples of reducing gases are gases with reducing capabilities, such as hydrogen gas, ammonium, water vapor, or mixtures thereof. While reducing gases are commonly used to overcome oxidation, the methods disclosed herein are substantially oxidation-free (or oxidation-free).

[0069] A "feedstock gas" is generally used to provide the raw material (i.e., carbonaceous material) for generating CNTs. Any type of raw material that has been proven to be usable for CNT production can be used. Generally, a feedstock carbon source that is gaseous at the growth temperature can be used. Among them, hydrocarbons such as methane, ethane, ethylene, propane, butane, pentane, hexane, heptane, propylene, and acetylene are suitable. In addition, lower alcohols such as methanol and ethanol, acetone, low-carbon oxygen-containing compounds such as carbon monoxide, and mixtures thereof can be used. Furthermore, the feedstock gas may be diluted with an inert gas.

[0070] Generally, an "inert gas" is a gas that may be included in the manufacturing process; it need only be a gas that is inert at the temperature at which CNTs are grown. Generally, "inert" is considered to be the property of a gas that does not substantially react with CNT growth. Any type of inert gas that has been proven to be usable in CNT manufacturing can be used. Non-limiting examples of inert gases are helium, argon, hydrogen, nitrogen, neon, krypton, carbon dioxide, chlorine, and mixtures thereof.

[0071] A "catalytically activating material" may be used in various embodiments. The addition of a catalytically activating material can improve the efficiency of carbon nanotube production and the purity of the carbon nanotubes. Generally, a catalytically activating material may be characterized as an oxygen-containing substance that does not substantially damage CNTs at growth temperatures. Thus, in some respects, this embodiment may be considered a "substantially oxygen-free environment." Useful examples other than water include: low-carbon oxygen-containing compounds such as hydrogen sulfide, oxygen, ozone, acid gases, nitrogen oxides, carbon monoxide, and carbon dioxide; alcohols such as ethanol and methanol; ethers such as tetrahydrofuran; ketones such as acetone; aldehydes; esters; nitrogen oxides; and mixtures thereof.

[0072] Generally, only a small amount of catalytically active material needs to be added, but there is no particular limit to the amount to be added. As an example, in some embodiments, when the catalytically active material is water, the catalytically active material is added in an amount ranging from about 10 ppm to about 10,000 ppm, in some of these embodiments, from 50 ppm to 1,000 ppm, and in some of these embodiments, from 100 ppm to 700 ppm.

[0073] The addition of catalytically activating materials enhances the activity of the catalyst and extends its lifespan. When catalytically activating materials are added, CNT growth continues for a longer period of time, and the growth rate increases as well. This results in CNT aggregates with significantly increased height.

[0074] A "high carbon concentration environment" refers to a growth atmosphere in which the ratio of source gas to total flow (or flow) is about 2% to about 20%. This generally refers to an environment in which excess carbon is present, which can result in inefficient growth of CNT aggregates. For example, a high carbon concentration environment can cause catalyst deactivation.

[0075] Because the activity of the catalyst is enhanced by the catalytically activating material, the activity of the catalyst will persist even in some environments with high carbon concentrations, and therefore the growth rate of CNTs can be significantly enhanced.

[0076] Regarding the reactor pressure, in various embodiments, the reactor pressure is 10 2 Pa or more and 10 7 In some embodiments, the pressure in the furnace is 10 Pa or less (100 atmospheres). 4 Pa or more and 3×10 5 Pa or less (3 atmospheres).

[0077] The reaction temperature at which CNTs are synthesized may be determined by considering various parameters such as the characteristics of the metal catalyst, the raw carbon source, and the furnace pressure, etc. In embodiments using a catalytically activated material, the reaction temperature is generally set within a temperature range in which the catalytically activated material functions properly.

[0078] In particular, when water is used as the catalytically activating material, the reaction temperature is preferably 400°C to 1,000°C. Below 400°C, the catalytically activating material does not exert its effect. Above 1,000°C, the catalytically activating material may react with CNTs.

[0079] Alternatively, when carbon dioxide is used as the catalytically activating material, the reaction temperature is preferably about 400°C to about 1,100°C. Generally, at temperatures below 400°C, the catalytically activating material does not exert its effect. At temperatures above 1,100°C, the catalytically activating material reacts with the CNTs.

[0080] As used herein, the terms "growth process," "deposition process," and other similar terms refer to a synthesis process for CNT aggregates. This process generally involves providing an environment around a catalyst that includes a carbonaceous component, such as a feedstock gas, and heating at least one of the environment, the feedstock gas, and the catalyst. This results in a CNT aggregate.

[0081] As used herein, the "cooling step" (also referred to as "CNT cooling 124" and other similar terms) generally refers to the step of cooling the CNT aggregate, catalyst, and substrate. In some embodiments, the cooling step is performed in the presence of an inert gas. That is, after the growth step, the CNT aggregate, catalyst, and substrate are at high temperatures and would themselves be oxidized if placed in the presence of oxygen. Oxidation is substantially prevented by cooling the CNT aggregate, catalyst, and substrate to a temperature at which the oxidation process is substantially limited. In some examples, cooling stops at a temperature of about 200°C or less.

[0082] A "mounting section" generally includes a series of devices for preventing outside air from flowing into the manufacturing equipment. That is, in operation, the mounting section includes components for mounting the substrate. Generally, the substrate is mounted on a transport device. Once mounted, oxygen is released from the mounting section (by at least one of negative pressure exhaust and pressurization with an inert gas). In some embodiments, the mounting section is isolated by at least one of a gas curtain, a door, a shutter, or other such device.

[0083] Once environmental control is established at the loading section (i.e., the loading section is substantially or sufficiently free of oxygen), the substrate is advanced to the catalyst application section to complete catalyst application 122. Like the loading section, the catalyst application section of the manufacturing equipment is subject to environmental control (i.e., is substantially or sufficiently free of oxygen). Once the substrate is positioned in the catalyst application section, the catalyst is applied to the substrate. One embodiment for applying the catalyst includes sputtering the catalyst onto the substrate.

[0084] As used herein, the term "substantially oxygen-free" refers to an environment in which oxygen does not disrupt the intended functionality. For example, in a substantially oxygen-free environment, the substrate will experience only a negligible amount of oxidation.

[0085] When a layer of a suitable catalyst is applied to the substrate (which may include an overlying carburization protection layer), a CNT substrate is achieved. The substrate may be characterized as a substrate having a layer of catalytic material disposed thereon. Advantageously, the substrate was fabricated in a substantially or substantially oxygen-free environment, so that the catalyst has not been subjected to significant oxidation. In this manner, the substrate is prepared for CNT growth.

[0086] Once the substrate is prepared, in some embodiments, the substrate is moved into a buffer section to complete buffering step 125. In various embodiments, the buffer section provides for adjustment and / or modification of pressure, temperature, and / or gas in the environment surrounding the substrate. The buffer section may also provide other functionality, such as mounting or repositioning of the substrate.

[0087] The substrate may then be moved to a carbon deposition section to complete carbon deposition 123. The deposition section functions to synthesize CNT aggregates by changing the environment around the catalyst to a raw material gas environment and by heating at least one of the catalyst and the raw material gas. Specific examples of deposition sections include a furnace in which the raw material gas environment is maintained, a raw material gas injection section for injecting the raw material gas, and a heater for heating at least one of the catalyst and the raw material gas. The heater may be any type of heater capable of appropriate heating. In some embodiments, the heater heats to a temperature in the range of about 400°C to about 1,100°C. Non-limiting examples of heaters include a resistance heater, an infrared heater, and an electromagnetic induction heater.

[0088] In some embodiments, the deposition section also includes a subsection for adding catalytically active material. Typically, the subsection for adding catalytically active material is configured to directly add the catalytically active material to the feed gas or to the environment surrounding the catalyst within the deposition section. The catalytically active material may be added in various ways, including by adding the catalytically active material via a bubbler, by vaporizing a solution containing the catalytically active material, by adding the catalytically active material in a gaseous state, or by liquefying or vaporizing a solid catalytically active material. The subsection may include a supply system using various devices, such as at least one of a vaporizer, a mixer, an agitator, a diluter, a pump, and a compressor. Some embodiments include a device for measuring the concentration of the catalytically active material in the subsection. Feedback and engineering control can ensure a steady supply of the catalytically active material.

[0089] After growth of the CNTs and while the CNT aggregates remain at or near the temperature range used in manufacturing, oxidation of the CNT aggregates remains a concern. Therefore, the CNT aggregates are moved from the deposition section to a cooling section.

[0090] The cooling section is provided to cool the CNT aggregate and the substrate on which the CNT aggregate is grown. The cooling section functions to act as an antioxidant and has a cooling effect on the CNT aggregate, catalyst, and substrate after deposition is completed. An exemplary device for the cooling section includes a receiving area for receiving the substrate and CNT aggregate, the receiving area being disposed within a volume in which an inert gas is held. The volume may include, for example, an inlet (and outlet) for supplying a flow of a lower temperature inert gas, at least one cooling pipe disposed within the volume for carrying a cooling liquid (such as water), and other similar devices suitable for carrying a coolant. Additional devices may be included outside the cooling section, such as at least one heat exchanger capable of dissipating heat transferred from the cooling unit.

[0091] By introducing the various components of the manufacturing apparatus in this manner, certain additional aspects will now be discussed.

[0092] The manufacturing techniques disclosed herein generally do not require the use of reducing gases. That is, the manufacturing techniques result in catalyst materials prepared substantially without oxidation. Therefore, operation of the manufacturing equipment is typically carried out in a manner that limits the ingress of oxygen (such as in the form of ambient air) into the manufacturing area. Accordingly, the various steps discussed herein may be carried out in the presence of at least an inert gas (particularly provided to replace oxygen).

[0093] Thus, the manufacturing equipment may be configured to ensure a relatively oxygen-free environment. That is, various engineering controls (many of which are introduced above) may be arranged (or configured) to ensure the desired environment is maintained. As with Figure 2, the discussion of Figure 3 is in functional terms.

[0094] Referring now to FIG. 3, aspects of one additional embodiment of a manufacturing apparatus are shown. In this embodiment, an intermediate step is included. That is, after the catalyst is disposed on the substrate (catalyst application 122) and before carbon deposition 123, another step is performed. In some embodiments of the another step, a plasma is provided. More specifically, the substrate (i.e., the substrate on which the catalyst is disposed) is subjected to catalyst finishing 126, for example, by plasma treatment. Similar to catalyst application, catalyst finishing 126 is performed without the need to create a reducing atmosphere, such as by adding a reducing gas. The morphology of the catalyst may be adjusted by controlling the plasma time and power. In particular, in this step, the plasma may be controlled to produce desired changes in the catalyst. Exemplary changes include altering the particle size and particle density in the catalyst. After catalyst finishing 126, in which a surface treatment of the catalyst is performed, the substrate proceeds to carbon deposition 123. Although not shown in FIG. 3, some embodiments may include at least one buffer section to provide a buffering step 125.

[0095] Generally, in the embodiments shown in Figures 2 and 3, the method begins and ends with human interaction (e.g., loading the substrate, removing the finished product), although in other embodiments, additional automated steps or functions may be performed.

[0096] FIG. 4 illustrates one embodiment of a manufacturing apparatus 40. In this example, the manufacturing apparatus 40 includes a loader section 41, a sputtering section 42, a plasma section 43, a carbon deposition section 44, and a cooler section 45. During operation, a substrate 49 is loaded into the manufacturing apparatus via the loader section 41. The substrate 49 travels on a conveyor belt through the sputtering section 42, the plasma section 43, the carbon deposition section 44, and the cooler section 45 until a finished product emerges. That is, the substrate 49 emerges from the manufacturing apparatus 40 with a catalyst layer 46 disposed thereon and carbon nanotube aggregates 47 disposed on the catalyst layer 46. In some of these embodiments, the conveyor belt (not shown) is actually multiple conveyor belts, thereby allowing for fine adjustment of the speed at which the substrate 49 is transported through each section (or portion) of the manufacturing apparatus 40.

[0097] Each of the above sections of the production apparatus 40 may be configured with any particular type of equipment deemed appropriate, limited only by practical considerations such as the ability to operate at elevated (or high) temperatures. For example, a "gas shower" may be used in the carbon deposition section 44 to provide a uniform distribution of the carbonaceous material.

[0098] Generally, the term "gas shower" refers to a volume into which at least one gaseous material is introduced, such as by gas injection. Generally, a gas shower serves a purpose, such as isolating a first volume in a manufacturing apparatus 40 from a second volume in the manufacturing apparatus 40. A gas shower may include a "drain" (i.e., exhaust system). The drain may be under negative pressure and adapted to substantially withdraw at least one gaseous material from the gas shower volume. A gas shower may use known components to achieve the intended design and / or functionality as determined by any one of a designer, manufacturer, and user.

[0099] The carbon nanotube aggregates 47 may be recovered by a variety of methods, some of which are presented herein. After recovery, in some embodiments, the catalyst layer 46 may be removed from the substrate 49 using etching or other methods. The substrate 49 may then be appropriately prepared and recycled for manufacturing.

[0100] Referring now to FIG. 5, an embodiment of an exemplary control system 50 for a manufacturing device is shown. In this example, the control system 50 includes a plurality of sensors 58. The sensors 58 may include measuring devices for temperature, gas, feed rate (or feed rate), optical properties, etc.—briefly, any process dynamic useful for controlling a manufacturing process. The sensors 58 communicate with at least one processing device 53 through a communication link 56. Any type of communication link 56 may be used, including wired and wireless links. The at least one processing device 53 in turn communicates with computing components 54 (such as memory, data storage, power supply, clock, machine-executable program instructions stored on a machine-readable medium in the form of software, and other such components) and at least one interface 55. The at least one interface 55 may include a keyboard, video display, mouse, network adapter, printer, and other similar interface elements. These components of the control system 50 provide inputs to controllers 52 (such as servo motors, motors, valves, heaters, gas supplies, operators and any other type of process control device) to modify the manufacturing process.

[0101] The control system 50 may be used to manage (or control) a manufacturing apparatus 40, such as the apparatus of the embodiments described herein and other manufacturing apparatuses. For example, the control system 50 may be used with a system including a formation unit and a separate growth unit and a transfer mechanism. In short, the control system 50 is customizable and may be used to control virtually any system designed for the production of carbon nanotube aggregates. Aspects that may be controlled by the control system 50 include, but are not limited to, temperature, flow rate, conveyor speed, processes related to layering (such as controlling layer thickness, material (e.g., gas) combinations, etc.), etc.

[0102] Operable, the control system 50 provides in-line (i.e., real-time) quality management (or quality control). By way of example, the control system 50 may include an optical metrology system that measures at least one property of at least one of the catalyst layer 46 and the carbon nanotube aggregates 47. Exemplary properties include thickness, density, appearance (or surface condition), etc. When included in the manufacturing tool 40, the optical metrology system may provide information or other similar output to a user to ensure proper deposition of materials, early rejection of defective materials, etc.

[0103] Examples of materials for the components of the manufacturing apparatus 40 include materials that can withstand high temperatures, such as quartz, heat-resistant ceramics, and heat-resistant alloys. However, heat-resistant alloys are preferred from the standpoints of processing accuracy, processing flexibility, and cost. Examples of heat-resistant alloys include heat-resistant steel, stainless steel, and nickel-based alloys. Generally, the term "heat-resistant steel" refers to steel containing Fe as a major component and other alloys at a concentration of 50 percent or less, while "stainless steel" refers to steel containing Cr at a concentration of about 12 percent or more. Further, examples of nickel-based alloys include alloys obtained by adding Mo, Cr, Fe, etc. to Ni. Considering heat resistance, mechanical strength, chemical stability, and low cost, SUS 310, Inconel® 600, Inconel® 601, Inconel® 625, Incoloy® 800, MC alloy, and Haynes® 230 alloy may be particularly useful.

[0104] The presence of carbon contaminants adhering to the walls and other components of the manufacturing apparatus 40 during CNT synthesis can be reduced by various techniques. For example, interior-facing components, such as the interior walls of the furnace, and / or components used in the furnace may be made from metal (e.g., heat-resistant alloys and those with surface treatments for interior-facing surfaces, etc.). This, among other things, provides for continuous production yields while limiting degradation in the quality of the resulting aligned CNT aggregates.

[0105] By convention and for clarity, components of manufacturing equipment may be finished by a treatment process (referred to as "passivation"). Components of manufacturing equipment that may be finished by passivation are generally referred to as "items." For purposes of discussion, an "item" is considered to include, but is not limited to, a component that may have at least one surface, and the surface of the item may be at least one of smooth, rough, irregular, and discontinuous. The item may have an interior and an exterior or outer surface. Passivation of each item may provide resistance to or prevention of hydrogen permeation by applying a coating to the interior of the item that is subjected to a vacuum. Passivation may provide resistance to or prevention of hydrogen permeation by applying a coating to the exterior of the article that is subjected to a vacuum. Alternatively, for example, passivation may be provided on the interior and exterior surfaces of the article. Passivation may be useful for providing enhanced properties to the surface of the article. Additionally, passivation can play an important role in limiting the penetration (or intrusion) of carbonaceous materials (such as those resulting from the decomposition of feedstock gases) into components of the production equipment 40, thus limiting degradation of the production equipment 40 and thereby extending the life of the production equipment 40.

[0106] Limiting the accumulation of contaminants on surfaces may be achieved by passivating articles incorporated into manufacturing equipment. One non-limiting example involves using a method for passivating the surface of a particular article to protect at least one surface of the article from corrosion, the effects of the surface in a vacuum environment, or both. Generally, each article to be passivated is placed in a processing environment, which is first dehydrated and then evacuated. Silicon hydride gas is introduced into the processing environment, which may be heated before the gas is introduced. If the processing environment was not already heated before the gas was introduced, the article and the silicon hydride gas contained therein are heated and pressurized to decompose the gas. A layer of silicon is deposited on the surface of the article. The duration of the silicon deposition step is controlled to prevent the formation of silicon dust in the processing environment. The article is then cooled and held at the cooling temperature to prepare the surface for subsequent deposition, and the processing environment is purged with an inert gas to remove the silicon hydride gas. The article is then cycled through the silicon deposition step until the surface of the article is coated with a layer of silicon. The processing environment is then evacuated and the article is allowed to cool to room temperature.

[0107] In another example, the surface of an article is passivated to protect it from corrosion, undesirable effects in a vacuum environment, or both. Chemical vapor deposition is performed to coat the article with silicon to provide properties for application in a corrosive and / or vacuum environment. It has been found that using single to multiple deposition layers with intermediate variations in process temperature, pressure, and time provides the treated article with a coating that provides enhanced properties, including, but not limited to, application in a corrosive environment for improved resistance, and application in a vacuum environment for reduced off-gassing, outgassing, and hydrogen permeation of the article. The article can be applied to, for example, a low vacuum (10 5 ~3.3×10 3 Pa), medium vacuum (3.3×10 3 ~10 -1 Pa), high vacuum (10 -1 ~10 -4 Pa), very high vacuum (10 -4 ~10-7 Pa), ultra-high vacuum (10 -7 ~10 -10 Pa) and ultra-high vacuum (10 -10 The material may have enhanced properties against a vacuum environment, such as 0.1 MPa (less than 1000 MPa).

[0108] Surfaces that may be coated may include interior surfaces and / or alternatively any other surface of the article. Articles having contact surfaces passivated by these techniques generally exhibit properties for improved resistance to corrosion and reduced outgassing of gas molecules when subjected to a vacuum environment.

[0109] In another example, the article is placed in an environment, such as a processing chamber, that may be controlled to perform a passivation process. Passivation may be performed on the article itself or on the article housed in the processing chamber. In some embodiments, the surface of each article is first pretreated by dehydrating the surface of the article. In the dehydration process, the article is heated to a temperature ranging from about 20°C to 600°C for a duration of about 10 to 240 minutes. The article may be heated in an inert gas or in a vacuum.

[0110] In this example, after the surface of the article is dehydrated, the environment around the surface of the article or the processing chamber is evacuated. Silicon hydride gas may be introduced into the environment around the article or the processing chamber. The article and gas are heated and pressurized to decompose the silicon hydride gas in the processing chamber. The silicon hydride gas may be heated before, during, or after the gas is introduced into the processing chamber. The processing chamber may be heated, and then the silicon hydride gas may be introduced. As the gas decomposes, a layer of silicon is deposited on the surface of the article.

[0111] The duration of the silicon deposition step and the gas pressure are controlled to prevent the formation of silicon dust on the article or in the processing chamber. At the end of silicon deposition, the environment or processing chamber is cooled, held at a temperature for a period of time, and purged with an inert gas to remove the silicon hydride gas. Purging may occur before, after, or while the article is cooling. In some embodiments, purging occurs while the article is cooling. If the silicon layer completely covers the surface of the article, the article is removed and cooled to room temperature. If the silicon layer does not completely cover the surface of the article, the silicon deposition step may be repeated until the surface is completely covered and thereby passivated.

[0112] In some embodiments, the silicon hydride gas is SiH4 and Si n H n+2 The silicon hydride gas may be heated to a temperature approximately equal to the decomposition temperature of the gas, such as a temperature in the range of about 300° C. to about 600° C. In some embodiments, the silicon hydride gas is selected from the group consisting of about 1×10 -7 The pressure may be in the range of from about 100 Torr to 2500 Torr, particularly from about 100 Torr to 250 Torr.

[0113] The technology also provides corrosion-resistant substrates or components having passivated surfaces. For example, the substrates may include metals (ferrous and non-ferrous), glass, carbon, copper, quartz, nickel-containing iron alloys, titanium, aluminum, and ceramics. Conventionally, the surface of the substrate has an average surface roughness (or roughness) RA. A silicon layer is formed on the substrate surface to passivate the surface. The silicon layer may be formed from multiple layers of silicon and is substantially free of silicon dust. In some embodiments, 1 to 10 layers of silicon may be applied.

[0114] It should be understood that passivation techniques may be used to passivate components or specific articles, and in particular surfaces of articles that exhibit undesirable properties when exposed to vacuum conditions, corrosive substances, carbon-rich gases, or that would otherwise benefit from passivation. For example, techniques may be used to passivate surfaces of substrates composed of metals (ferrous and non-ferrous), glass, carbon, copper, quartz, nickel-containing iron alloys, titanium, aluminum, and ceramics. Passivation of surfaces that would be exposed to corrosive substances or molecules, such as organic sulfur, hydrogen sulfide, alcohols, acetates, metal hydrides, hydrochloric, nitric, or sulfuric acid, and aqueous salts, serves to protect the surface from corrosion. Surface passivation also benefits substrates in vacuum environments by reducing undesirable effects, including off-gassing, outgassing, hydrogen penetration, and especially corrosion or contaminant condensation, on the respective surfaces.

[0115] The passivation techniques will now be presented in more detail.

[0116] First, the surface to be passivated is pretreated. Successive layers of silicon are then applied to the surface under controlled conditions, with the surface being cooled and held at a temperature for a period of time between successive deposition layers. In some embodiments, silicon deposition layers are applied until the silicon layers cover the entire surface area of ​​the article. The method may be performed on or within the article itself, or by placing the article in a controlled environment, such as a processing chamber.

[0117] Each surface for passivation is first pretreated by removing water adsorbed on the surface. In the dehydration step, the vessel is heated to a temperature ranging from about 20°C to about 600°C for a duration of about 10 minutes to 240 minutes (4 hours). During the dehydration step, the process chamber containing the substrate to be passivated is evacuated or filled with an inert gas (noble gas or nitrogen). At the end of the dehydration process, the process chamber is evacuated to remove vaporized water.

[0118] After dehydrating and evacuating the processing chamber, SiH4 or Si n H n+2 In some embodiments, a silicon hydride gas, such as a silicon hydride gas, is introduced to the surface or into a processing chamber containing the article. In some embodiments, the pressure of the silicon hydride gas is about 1×10 -7 The pressure is preferably in the range of about 100 Torr to 2500 Torr, more preferably about 100 Torr to 250 Torr. If not already at the decomposition temperature of the gas as a result of the dehydration step, the article and the gas contained in the processing chamber are heated to a temperature approximately equal to the decomposition temperature of the gas. In some embodiments, the article and gas are heated to a temperature in the range of about 300°C to about 600°C. The silicon hydride gas may be introduced under heat or may be introduced at room temperature and then heated. At these pressures and temperatures, the silicon hydride gas decomposes at or near the surface into silicon and hydrogen gas. The silicon formed during the decomposition process adheres to the surface of the article being processed.

[0119] Generally, the duration of the silicon deposition process is controlled. Under the above conditions, the decomposition of the silicon hydride gas in the processing chamber, as a result of pressure, time, and temperature, can eventually form an undesirable by-product, referred to herein as silicon dust. Silicon dust is the result of the silicon hydride gas reacting with itself to produce silicon and hydrogen gas. This gas-phase nucleation forms silicon dust that will deposit by gravity on the surface of the article or in the processing chamber, reducing the integrity of the silicon layer formed on the surface. Silicon dust can also form a physical barrier between successive layers of silicon in the passivating layer.

[0120] The formation of silicon dust can be affected by the duration of the deposition process, the gas pressure, the presence of contaminants on the substrate surface, or a combination of any or all of these. To help prevent the formation of silicon dust, the duration of the silicon deposition process is controlled to a time ranging from about 1 minute to a maximum of about 480 minutes (8 hours). The silicon deposition process may be omitted as a method of preventing the formation of silicon dust. However, the silicon layer may not completely cover the entire surface after a single silicon deposition cycle. Therefore, the silicon deposition cycle may be repeated multiple times to build up a silicon passivation layer of a desired thickness. However, passivation effectiveness can be achieved with a single deposited layer. In some embodiments, effectiveness can be improved by depositing 1 to 10 layers of silicon on the surface, regardless of the surface roughness (or roughness) RA. In some cases, it may be particularly preferable to have six silicon layers deposited on the surface to improve performance.

[0121] After the first silicon deposition cycle, the process chamber containing the article may be purged with an inert gas to remove the silicon hydride gas. If the layer of silicon does not completely cover the surface of the article, the silicon deposition cycle may be repeated. Before depositing the next silicon layer, the surface of the article is cooled and left at a low temperature to establish surface properties for the formation of the next silicon layer deposition. In some embodiments, the surface is cooled to a temperature in the range of about 50°C to about 400°C and left at the cooled temperature for about 5 minutes to about 100 minutes.

[0122] As an example, rough or smooth (electropolished or polished) surfaces having a surface roughness RA of less than about 20 microinches can benefit from the passivation described herein with a single deposition cycle. The number of layers selected to increase the effectiveness of passivation may be selected independently of the surface roughness RA. The number of layers selected to improve resistance to corrosion may be selected independently of the surface roughness RA.

[0123] After forming the silicon passivation layer, the process chamber containing the article is cooled to a temperature in the range of about 50°C to about 400°C, held for a duration of about 5 minutes to about 100 minutes, and purged with an inert gas to remove reactive silicon hydride gas. This inert gas purging ensures that the silicon hydride decomposition reaction is stopped and reduces unwanted gas-phase nucleation problems that arise due to the silicon hydride component reacting with itself rather than with the surface of the article or the process chamber. After the final purging step, the process chamber containing the article may be evacuated and cooled to room temperature.

[0124] In some embodiments, the passivated silicon layer deposited on the surface may be between about 100 Å and 50,000 Å thick.

[0125] The above-described techniques for passivation have particular application to passivating articles that may be contained within manufacturing equipment 40 and that may be subjected to corrosive components and / or gaseous environments (such as the environment of raw material gases). More specifically, the passivation techniques presented herein provide for surface treatment of the articles, with the resulting effect of substantially limiting the accumulation of carbonaceous materials and carbon forms on the surfaces. This effectively provides manufacturing equipment 40 that incorporates at least one design element to ensure manufacturing hygiene.

[0126] Passivation can be used, inter alia, to provide resistance properties to each surface, thereby minimizing the undesirable effects of corrosive substances, such as chemisorption of other molecules; reversible and irreversible physisorption of other molecules; catalytic activity with other molecules; attack from unrelated species resulting in surface and / or bulk molecular, structural, and / or superficial destruction; or any combination of the above. In addition, the presented techniques are particularly useful for passivating articles that may be used in vacuum or low-pressure environments. Passivation techniques can also provide various other benefits, such as providing chemical resistance, limiting the effects of outgassing of materials, and simplifying cleaning.

[0127] The method may be used to impart chemically resistant properties to the substrate to minimize undesirable surface effects on the substrate in a vacuum environment, such as off-gassing or outgassing of volatile materials (e.g., water vapor and organics) from the substrate in a vacuum environment that results in an extended time required to reach the desired vacuum and / or makes it impossible to reach and / or maintain the desired vacuum; hydrogen permeation of the substrate in a vacuum environment through a coating on the inside and / or outside while the interior portion is subjected to a vacuum; or any combination of the above.

[0128] Although the methods may be carried out using a processing chamber configured to house each article during processing steps, it will be understood that the article itself, depending on its configuration, may function as its own processing chamber and the method may be carried out within the article. For example, the passivation process may be carried out in an oven (or dryer) in some embodiments, resulting in surface treatment (i.e., passivation) within the oven.

[0129] Briefly, furnace component(s) may be passivated or otherwise appropriately treated prior to fabrication. In the examples presented, the term "passivation" may be considered to generally refer to treatment methods suitable for limiting the buildup of contaminants (i.e., tramp carbon or carbonaceous residue) and the attendant drop in partial pressure of the feedstock gas during the fabrication process. While the methods presented involve silicon and silicon-containing materials, the term "passivating material" may be considered to encompass these materials and any other embodiments of materials suitable for limiting the buildup of carbonaceous residue.

[0130] Components may be periodically evaluated for their ability to limit contaminant buildup, and users may renew or replace components as needed to ensure continued performance.

[0131] Thus, having described techniques for producing assemblies that exhibit superior properties, additional techniques are now presented for using the assemblies and other forms of carbonaceous materials (alone or in conjunction with assemblies). Generally, these additional techniques are directed to providing superior electrodes 3 for use in ultracapacitors 10, although electrodes 3 may be incorporated into other energy storage devices as desired.

[0132] Advantageously, the electrodes 3 may be fabricated from mass-produced CNTs 47 and, among other things, exhibit higher gravitational power density (power as a function of weight) and volumetric power density (power as a function of volume) than previously achievable. Furthermore, high-power electrodes 3 exhibit low internal resistance and can be configured to provide high voltages (such as about 4 volts or greater).

[0133] In some embodiments of the exemplary methods and apparatus for providing high power electrodes, the electrode 3 includes at least one layer of a carbon-based energy storage medium 1 and may include one to many additional layers.

[0134] Various exemplary embodiments of carbonaceous material manufacturing techniques and electrodes made from carbonaceous materials are presented herein. Exemplary embodiments include high-power (or high-output) electrodes made from at least one layer of compressed carbon nanotubes; functionally stacked electrodes; multi-form electrodes; electrodes made from shaped carbonaceous aggregates; electrodes made from multiple electrode components; and densified electrodes. The exemplary embodiments provide multiple embodiments of techniques for manipulating carbonaceous materials used in energy storage medium 1. The examples should not be considered limiting. For example, aspects of one embodiment may be used, at least in part, with another one of various embodiments. Further techniques will become apparent from review of the various embodiments.

[0135] In one embodiment of electrode 3, at least one layer of compressed carbon nanotubes is used as the energy storage medium. Reference is now made to FIGS. 6-10 to introduce aspects of this embodiment of electrode 3. In this example, the electrode 3 presented may include multiple layers of compressed carbon nanotubes and / or other forms of carbon. Reference is made to FIG. 6, where assembly of electrode 3 begins with the deposition of a current collector 2 and a carbonaceous material. In the embodiment discussed with reference to FIGS. 6-10, the carbonaceous material is a collection of CNTs 47. However, the embodiment discussed with reference to FIGS. 6-10 is not limited to the use of CNTs 47, and the carbonaceous material may assume other forms, such as those shown elsewhere herein.

[0136] FIG. 6 illustrates an embodiment of a current collector 2. Generally, current collector 2 includes a conductor layer 61 and may include a tie layer 62. The conductor layer 61 may be made of any material suitable for conducting an electric charge in the intended application. Exemplary materials include aluminum. The conductor layer 61 may be in the form of a foil, a mesh, multiple wires, or other forms. Generally, the conductor layer 61 is selected for properties such as conductivity and electrical inertness. In some embodiments, the conductor layer 61 is created by removing an oxide layer from the conductor layer 61. The oxide may be removed, for example, by etching the conductor layer 61 with KOH.

[0137] In some embodiments, bonding layer 62 is disposed on conductor layer 61. Bonding layer 62 may appear as a thin layer, such as a layer applied by sputtering, e-beam, or another suitable technique. In various embodiments, bonding layer 62 is from about 10 nm to about 500 nm thick. Generally, bonding layer 62 is selected for its properties, such as conductivity, electrical inertness, and compatibility with the material of conductor layer 61. Some exemplary materials include aluminum, gold, silver, palladium, tin, and platinum, as well as alloys or combinations of materials such as Fe-Cr-Ni.

[0138] The second component includes a substrate 65 that serves as a host for the carbon nanotube aggregates (CNTs) 47. In the embodiment shown in Figure 6, the substrate 65 includes a base material 49 having a thin layer of catalyst 46 disposed thereon. Generally, the substrate 65 is at least somewhat flexible (i.e., the substrate 65 is not brittle) and is made from components that can withstand the environment for depositing the CNTs 47 (e.g., a high-temperature environment of about 400°C to about 1,100°C).

[0139] Once the CNTs 47 are fabricated, another bonding layer 62 is disposed thereon. In some embodiments, the another bonding layer 62 is about 10 nm to about 500 nm thick. The bonding layer 62 of the current collector 2 is then combined with the another bonding layer 62 disposed on the CNTs 47, as shown in FIG.

[0140] FIG. 7 illustrates an embodiment in which CNTs 47 are combined with a current collector 2. Pressure is applied to a substrate 49, as indicated by the downward arrow. Application of the CNTs 47 may involve heating the components. As an example, when platinum is used in the bonding layer 62, heating to about 200° C. to about 250° C. is typically appropriate. The CNTs 47 and catalyst 46 are then separated, resulting in a layer of CNTs 47 disposed on the current collector 2.

[0141] Various post-production processes may be completed to facilitate separation of the CNTs 47 from the catalyst 46. For example, after deposition is completed, the substrate 65 having the CNTs 47 thereon may be exposed to room air, a carbon dioxide environment, or another suitable environment (e.g., heated in the environments described above). Generally, post-production treatment of the CNTs 47 involves gradually ramping the CNTs 47 to an elevated temperature and then holding the CNTs 47 at a temperature under reduced pressure (i.e., pressure less than about 1 atmosphere) for several hours.

[0142] As shown in Figure 8, the process of moving the CNTs 47 onto the current collector 2 by applying pressure results in a layer of compressed CNTs 81. The compressed CNTs 81 may now contain physical defects such as windows and cracks, which generally provide a larger surface area for charge storage than the uncompressed CNTs 47, while occupying a smaller volume than the uncompressed CNTs 47. The addition of another layer of CNTs 47 is also shown in Figure 8.

[0143] As shown in FIG. 9, another layer of CNTs 47 may be applied on top of the compressed CNTs 81. In some embodiments, this step involves applying a nominal amount of pressure (e.g., by hand). It is generally believed that the other layer of CNTs 47 is transferred (i.e., adhered) to the compressed CNTs 81 by van der Waals forces between the carbon nanotubes. This advantageously results in another layer of compressed CNTs 81 (i.e., another thickness of compressed CNTs 81) on top of the current collector 2, as shown in FIG. 10. A high-power, high-energy electrode 3 can be achieved by applying multiple layers of compressed CNTs 81.

[0144] This method may be repeated to provide multiple thicknesses of compressed CNTs 81 on the current collector 2. However, it is generally expected that certain practical limitations will be recognized, i.e., for example, compound defects in the transfer of each layer may result in a layer of compressed CNTs 81 that does not exhibit the desired performance for storing charge. However, it is also expected that as transfer protocols continue to improve, the addition of even greater numbers of layers will be possible.

[0145] Thus, a current collector 2 having at least one layer of compressed CNTs 81 to multiple layers of compressed CNTs 81 disposed thereon may be used as a charge storage device (i.e., an embodiment of electrode 3). In general, such an embodiment of electrode 3 is particularly well suited for use in ultracapacitor 10. In addition to some of the advantages discussed above (higher mass and volumetric power densities, lower internal resistance and higher voltages, and higher energy densities), less electrolyte 6 is required. Thus, users are provided with improved energy storage that is less expensive to manufacture than some similar embodiments of energy storage.

[0146] A comparative example of CNT47 and compressed CNT81 is presented in Figure 11. That is, Figures 11A and 11B (collectively referred to herein as Figure 11) represent transmission electron micrographs of uncompressed CNT47 and compressed CNT81, respectively.

[0147] As shown in FIG. 11A, the CNTs 47 are relatively straight and parallel along the Y direction. As shown in FIG. 11B, the compressed CNTs 81 exhibit periodic deformation (or distortion) (like a "wave"). That is, while the compressed CNTs 81 remain generally parallel to one another, the compressed CNTs 81 are not straight (compared to the uncompressed CNTs 47). That is, in some embodiments, the shape of the compressed CNTs 81 may be represented by a function such as a sinusoidal (or sine-like) function. In other embodiments, the periodicity of the waveform may be expressed or quantified in other ways. In some further embodiments, the compressed CNTs 81 do not exhibit a repeating shape (or deformation). In short, the compressed CNTs 81 may be the result of compression of the CNTs 47 (uncompressed CNTs) such that certain properties of the CNTs 47 are improved or enhanced. The enhancement may be the result of any one or more of certain phenomena, such as increased density, increased defects, etc.

[0148] A comparative evaluation was conducted as a demonstration of the benefits of carbon nanotubes as taught herein. In this evaluation, two ultracapacitors 10 were assembled. The first of the ultracapacitors 10 included electrodes 3 made from activated carbon. The second of the ultracapacitors 10 included electrodes 3 based on carbon nanotubes in accordance with the teachings herein. The results are shown in FIG. 12. Otherwise, the ultracapacitors 10 were identical in all respects.

[0149] In Figures 12A and 12B (collectively referred to herein as Figure 12), Nyquist plots showing comparative performance are presented. Figure 12A represents a (prior art) capacitor with activated carbon electrodes, while Figure 12B represents an ultracapacitor 10 with carbon nanotube-based electrodes. A traditional assessment of electrode resistance is the resistance at the 3 dB point on the Nyquist plot. Figure 12A shows that the total cell resistance of the prior art capacitor is approximately 4 Ω / cm 2 , while FIG. 12B shows that the overall cell resistance of the carbon nanotube-based capacitor is about 1 Ω / cm 2 Furthermore, it can be seen that the electrode contact resistance in the activated carbon embodiment (FIG. 12A) is substantial (as indicated by the semicircles in the Nyquist plot), while it is virtually nonexistent in the CNT embodiment (FIG. 12B).

[0150] In some embodiments, the particular characteristics of substrate 49, catalyst 46, conductor layer 61, and bonding layer 62 may be taken into consideration. That is, it is anticipated that other materials and processes may be used (or omitted) to provide current collector 2 comprising at least one layer of compressed CNTs 81 to multiple layers of compressed CNTs 81, for example, when the above-described fabrication is completed in a substantially oxygen-free environment. Accordingly, these and other embodiments are within the scope of the present invention and the teachings herein, as may be devised by one of ordinary skill in the art.

[0151] We now consider an additional embodiment of electrode 3, which is commonly referred to as a "functionally stacked electrode."

[0152] Referring now to FIG. 13 , aspects of an exemplary embodiment of a functionally laminated electrode 3 are shown. Generally, a functionally laminated electrode 3 may be fabricated from two separate structures: an electrode base structure 26 and an electrode process structure 28. In the example shown in FIG. 13A , the electrode base structure 26 (which may provide the structure upon which a fabricated electrode will reside) may include one embodiment of a current collector 2 fabricated from, for example, aluminum (Al) foil or copper (Cu) foil. The exemplary electrode process structure 28 shown in FIG. 13B includes a process substrate layer 35 (including, for example, tungsten (W) or stainless steel (SS) or aluminum (Al) foil) and a carbonaceous layer 32 formed from a carbonaceous material that may be used in the energy storage medium 1. Generally, the electrode process structure 28 provides the structure upon which the carbonaceous material is formed.

[0153] One goal is to form the carbonaceous layer 32 on the process substrate layer 35, but to effectively transfer the carbonaceous layer 32 to the current collector 2, for example, so that the carbonaceous layer 32 is connected via an intermediate material. The material constituting the process substrate layer 35 may be different from the material constituting the current collector 2. The material may be selected taking into consideration aspects such as the manufacturing requirements of the carbon material and the effectiveness of the current collector 2. Decoupling the design constraints between the selection of materials for the process substrate layer 35 and the current collector 2 has significant advantages in performance, cost, reliability, etc.

[0154] In some embodiments, the electrode base structure 26 may include three layers. For example, a current collector 2 may be provided as the first of the three layers. Because the current collector 2 ultimately transfers the operating current from the capacitor terminals to the carbonaceous material, the material used should be selected for good electrical conductivity. Because the current collector 2 will be exposed to the electrolyte in which the electrode will ultimately be immersed, the material for the current collector 2 should be selected for good electrochemical compatibility, typically a suitably low reaction rate (or percentage) with the given electrolyte. For practical reasons, such as ease of thermal bonding under mechanical compression, the material and thickness of the material for the current collector 2 should be selected for mechanical flexibility. Examples of materials that may be included in the current collector 2 include aluminum (Al), stainless steel, nickel (Ni), copper (Cu), iron (Fe), tantalum (Ta), conductive oxides (e.g., indium-tin-oxide (ITO)), or combinations of these materials. Generally, the thickness of the current collector 2 may vary between about 1 micrometer (μm) and 100 μm.

[0155] If desired, the current collector 2 may first be immersed in a basic etchant such as potassium hydroxide (KOH, which may be useful for electrode embodiments including aluminum) and / or backsputtered to remove any oxide films (e.g., aluminum oxide (Al2O3)). If the method for fabricating the electrode base structure 26 is performed in a low-oxygen environment, such as required for magnetron sputtering, the etching, backsputtering, or other removal of the oxide layer may be performed in the same chamber. The second and third layers, if deposited in the same chamber, form a protective barrier useful for preventing further oxidation when the electrode base structure 26 is subsequently removed from the low-oxygen environment.

[0156] A second layer (referred to as "adhesion layer 34") may be used to improve adhesion between current collector 2 and a third layer (referred to as "first bonding layer 36"). Adhesion layer 34 may be deposited on current collector 2 using magnetron sputtering or a similar method. Typical materials included in adhesion layer 34 are titanium (Ti), chromium (Cr), titanium-tungsten (Ti-W), or combinations of these materials. If the conductivity of the material comprising adhesion layer 34 is relatively low, its thickness should be limited to achieve adequate current handling performance. Typically, the thickness of this adhesion layer 34 varies between about 1 nanometer (nm) and about 100 nm.

[0157] The first bonding layer 36 is useful for bonding the electrode base structure 26 to the electrode process structure 28. If the electrode base structure 26 and the electrode process structure 28 are to be thermally bonded using moderate (or intermediate) temperatures and mechanical pressure, a soft metal may be most useful for the first bonding layer 36. The first bonding layer 36 may be deposited on the adhesion layer 34 using magnetron sputtering or a similar method. If the material of the first bonding layer 36 has relatively low conductivity, the thickness of the first bonding layer 36 should be limited to achieve adequate current handling capabilities. Exemplary materials for the first bonding layer 36 include platinum (Pt), gold (Au), silver (Ag), palladium (Pd), tin (Sn), nickel (Ni), copper (Cu), or combinations of these materials. Typically, the thickness of this first bonding layer 36 varies between about 1 nm and about 10 μm.

[0158] In some embodiments, the electrode process structure 28 includes four layers. The first layer of the electrode process structure 28 is a process substrate layer 35 on which the active electrode material may be formed. An exemplary process substrate layer 35 is a substructure including tungsten (W) foil, iron (Fe) particles, and an intermediate layer of aluminum (Al). The layer thicknesses in this exemplary process substrate layer 35 may vary from approximately 5 μm to 1 mm, 0.5 nm to 5 nm, and 2 nm to 100 nm for the three sublayers, respectively. This exemplary process substrate layer is useful for fabricating certain carbon electrode materials, including vertically aligned carbon nanotubes (VACNTs) by chemical vapor deposition. For practical reasons, such as ease of thermal bonding under mechanical compression, the process substrate material and thickness should be selected for mechanical flexibility. Other exemplary process substrate materials include stainless steel, nickel (Ni), or a combination of these materials.

[0159] The carbonaceous layer 32 of the electrode process structure 28 comprises the material ultimately responsible for storing charge in the fabricated capacitor. Exemplary materials suitable for use in the carbonaceous layer 32 include activated carbon, carbon fiber, rayon, graphene, aerogel, carbon cloth, carbon nanohorns, carbon nanotubes (CNTs), and combinations of these materials. Other carbonaceous materials disclosed herein may be used in the carbonaceous layer 32. The materials used in the carbonaceous layer 32 may be fabricated by chemical vapor deposition (CVD), among others, and may be deposited or pressed onto the process substrate layer 35. Generally, the thickness of the carbonaceous layer 32 may vary from about 1 μm to about 10 mm.

[0160] An ohmic contact layer 30 may be included in the electrode process structure 28 and is useful for achieving ohmic contact with the carbonaceous layer 32. Since the ohmic contact layer 30 is exposed through the porous carbonaceous layer 32 to the electrolyte in which the electrode will ultimately be immersed, the material for the ohmic contact layer 30 should be selected for good electrical compatibility, typically a suitably low reaction rate with the electrolyte of that particular embodiment. The ohmic contact layer 30 may be deposited on the carbonaceous layer 32 using magnetron sputtering, thermal evaporation, or similar methods. Exemplary materials that may be used in the ohmic contact layer 30 are aluminum (Al), tantalum (Ta), and palladium (Pt). Typically, the thickness of the ohmic contact layer 30 varies from about 1 nm to about 10 μm.

[0161] The electrode process structure 28 also includes a second bonding layer 38. The second bonding layer 38 is useful for bonding the electrode base structure 26 to the electrode process structure 28. If the electrode base structure 26 and the electrode process structure 28 are to be thermally bonded using moderate (or intermediate) temperatures and mechanical pressure, a soft metal is useful for the second bonding layer 38. The second bonding layer 38 may be deposited on the ohmic contact layer 30 using magnetron sputtering, thermal evaporation, or a similar process. If the conductivity of the material for the second bonding layer 38 is relatively low, its thickness should be limited to achieve adequate current handling performance. Exemplary materials useful for the second bonding layer 38 include platinum (Pt), gold (Au), silver (Ag), palladium (Pd), tin (Sn), nickel (Ni), copper (Cu), or combinations of these materials. Typically, the thickness of this second bonding layer 38 varies between about 1 nm and about 10 μm.

[0162] The electrode base structure 26 and the electrode process structure 28 may be bonded by any method at the interface between the first bonding layer 36 and the second bonding layer 38. One exemplary method is thermal bonding, in which the two structures are simultaneously heated and pressed together. For platinum (Pt) bonding layer materials, the temperature range useful for thermal bonding varies from about 150°C to about 600°C.

[0163] Once the electrode base structure 26 and the electrode process structure 28 are joined, the process substrate layer 35 may be simply peeled or otherwise removed to expose the surface of the carbonaceous layer 32 .

[0164] As shown in FIG. 14, an exemplary functionally laminated electrode 3 includes a current collector 2, an adhesive layer 34, a first bonding layer 36, a second bonding layer 38, an ohmic contact layer 30, and a carbonaceous layer 32.

[0165] In further embodiments, at least one other layer may be included. For example, an ohmic contact layer may be included to enhance ohmic contact between another bonding layer 62, the compressed CNTs 81 (which may be referred to as an "energy storage layer," "active layer," and other similar terms), or another layer. In another example, an adhesion layer may be included to enhance adhesion between another bonding layer 62 and the compressed CNTs 81 or another layer. The material in the additional or optional layer may be selected according to at least one characteristic, such as electrical conductivity, compatibility, etc.

[0166] The functionally layered electrode 3 is generally in a layered form. The layers shown herein are not limiting of the electrode 3 but are merely illustrative. Other combinations may be implemented. Such other combinations may consider, for example, combining aspects of one layer with aspects of another layer. Other aspects may be considered, and some aspects may not be included at all. In short, the specific configuration of the electrode 3 may be determined when considering the requirements of the designer, manufacturer, user and / or operator, and any of the functional constraints of the materials and manufacturing process, or any of other similar parameter(s).

[0167] A further embodiment of the electrode 3 is presented as a "multi-form" electrode 3, which is introduced as a manufacturing method starting from FIG.

[0168] Referring now to FIG. 15 , an embodiment of a basic electrode 3 is shown. In this non-limiting example, electrode 3 includes a current collector 2 that carries (or supports) a base layer 15. In some embodiments, current collector 2 is about 0.5 micrometers (μm) to about 25 micrometers (μm) thick. Current collector 2 may appear as a thin layer, such as a layer applied by chemical vapor deposition (CVD), sputtering, e-beam (or electron beam), thermal evaporation, or another suitable technique. Generally, current collector 2 is selected for its properties, such as conductivity, electrical inertness, and compatibility with base layer 15. Some exemplary materials include aluminum, platinum, gold, tantalum, titanium, and may include other materials and various alloys.

[0169] In the exemplary embodiment, the substrate 15 is formed from vertically aligned carbon nanotubes (VACNTs) 47. Non-limiting examples of nanoforms of carbon that may be included in the substrate 15 include, but are not limited to, single-walled nanotubes and multi-walled nanotubes.

[0170] Referring now to FIG. 16, one embodiment of adding nanoform carbon 16 to a substrate 15 is shown. In this example, the electrode 3 is immersed in a bath 17 of carrier material. In some embodiments, the bath 17 includes a solvent. The nanoform carbon 16 is provided in the bath 17 and is typically suspended in the bath 17. Generally, the nanoform carbon 16 includes at least one of nanotubes, nanohorns, nanoonions, carbon black, fullerenes, graphene, and graphene oxide. Once the addition is complete, the bath 17 is removed by venting the vapor 19 and / or carrier material. This results in a multiform electrode 3, as shown in FIG. 17. That is, the resulting electrode is referred to as a "multiform" electrode 3 because it includes multiple nanoforms of carbon.

[0171] That is, the step of removing the bath 17 results in another layer of nanoform carbon 16 being disposed on the base layer 15. The multiform electrode 3 may thus be manufactured in various stages.

[0172] Another embodiment of applying nanofoam carbon 16 onto a substrate 15 is shown in FIG. 18 . In FIG. 18 , multiple applicators (or coating or spraying devices) 13 apply nanofoam carbon 16 to the substrate 15 of each electrode 3. Each applicator 13 may be supplied with nanofoam carbon 16 from one of multiple supplies of nanofoam carbon 16. Thus, various forms of nanofoam carbon 16 may be provided. In this example, each applicator 13 includes a device that provides a suitable spray of nanofoam carbon 16 onto the substrate 15. Thus, the nanofoam carbon 16 may be mixed with a solvent or other carrier material. The carrier material provides distribution (or dispersion) of the nanofoam carbon 16 onto the substrate 15. In some embodiments, the carrier material exhibits a high vapor pressure. Thus, the nanofoam carbon 16 will quickly solidify to form a multiform electrode 3.

[0173] Generally, the nanofoam carbon 16 may be considered to be distributed (or dispersed) on the base layer 15 as another layer. By applying the another layer as a mixture or solution of the nanofoam carbon 16 in a carrier material, certain advantages may be realized. For example, the overall arrangement of the nanofoam carbon 16 may be controlled to at least some extent. For example, multiple stacks may be performed. The concentration of the nanofoam carbon 16 may be controlled, as may the combination of nanofoam carbon 16 used. Thus, certain aspects of the multi-foam electrode 3 may be generally controlled (such as the density of the energy storage medium 1). At a microscopic level, this may be the result of incorporating entanglements, voids, packed spaces, etc.

[0174] Other embodiments for providing the nanofoam carbon 16 on the substrate 15 may be used, such as techniques used in the manufacture of paper. More specifically, the nanofoam carbon 16 may be mixed with a carrier material and applied onto the substrate 15 in a manner similar to the way pulp is applied.

[0175] Exemplary carrier materials include ethanol, isopropyl alcohol, deionized water, acetone, dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and other similar materials.

[0176] Optionally, post-fabrication processing may be performed. An exemplary method for post-fabrication processing includes heating the multi-form electrode 3. For example, the multi-form electrode 3 may be appropriately heated to substantially release the remaining carrier material from the nanofoam carbon 16. The method (e.g., heating) may be performed in a controlled environment, such as a substantially oxygen-free environment.

[0177] 19, an exemplary method 190 for providing a multi-form electrode 3 is presented. In a first step, a base electrode 3 is selected and provided (electrode selection 191). In a second step, nanofoam carbon 16 is applied to the base electrode 3 (nanofoam application 192). In a third step, the multi-form electrode 3 is recovered from the bath 17 or the like (electrode recovery 193). In an optional fourth step, post-processing of the multi-form electrode 3 is performed (electrode post-processing 194).

[0178] A further embodiment of an electrode 3 is provided as an electrode 3 comprising a shaped carbonaceous aggregate and is introduced as a manufacturing process beginning with Figure 20. This embodiment of an electrode 3 may be referred to as comprising an "ultrasonicated" material and, therefore, may be referred to as an "ultrasonicated" electrode 3 or other similar terminology.

[0179] 20A and 20B (collectively referred to herein as FIG. 20), an embodiment of a solution is shown. In FIG. 20A, a first solution 66 includes a solvent 68 and a dispersion of a collection of vertically aligned carbon nanotubes (VCNTs) 47. In FIG. 20B, a second solution 67 includes a solvent 68 and a carbon additive 27 dispersed in the solvent. The carbon additive 27 includes at least one form of a material consisting essentially of carbon. Exemplary forms of the carbon additive 27 include, for example, at least one of activated carbon, carbon powder, carbon fiber, rayon, graphene, aerogel, nanohorns, carbon nanotubes, and the like. While in some embodiments the carbon additive 27 is formed substantially from carbon, it is understood that the carbon additive 27 may intentionally or unintentionally include at least some impurities. In short, the material(s) selected for carbon additive 27 may include any material suitable for carrying out the teachings herein as deemed appropriate by a designer, manufacturer, or other similarly situated person.

[0180] Typically, the solvent 68 is an anhydrous solvent, although this is not a requirement. For example, the solvent 68 may include at least one of ethanol, methanol, DMSO, DMF, acetone, etc. Typically, the dispersion of the vertically aligned carbon nanotube aggregates 47 includes pieces (or fragments) of the vertically aligned carbon nanotubes 47 produced by the production cycle. That is, the vertically aligned carbon nanotube aggregates 47 may be broken into pieces (or fragments) when recovered from the substrate 65.

[0181] Reference is now made to FIG. 21, which illustrates that each of first solution 66 and second solution 67 is subjected to "sonication" (a physical effect achieved in an ultrasonic field, e.g., provided by ultrasonic device 78). With respect to first solution 66, sonication is generally performed for a time sufficient to tease out, fluff, or otherwise parse the carbon nanotubes. With respect to second solution 67, sonication is generally performed for a time sufficient to ensure good dispersion or mixing of the carbon additive within solvent 68.

[0182] Once the first solution 66 and the second solution 67 have been properly sonicated, the first solution 66 and the second solution 67 are mixed together to form a mixed solution 69 (see FIG. 22) and sonicated again. Typically, the mixture of the first solution 66 and the second solution 67 is sonicated for a time sufficient to ensure good mixing of the vertically aligned carbon nanotube aggregates (VCNTs) 47 and the carbon additive 27. This second mixing results in carbonaceous aggregates 51.

[0183] The carbonaceous aggregates 51 are then removed from the mixed solution 69 and processed. As shown in Figure 23, the carbonaceous aggregates 51 may be shaped to provide shaped carbonaceous aggregates 51. This process may be aided by placing the carbonaceous aggregates 51 on a suitable surface 48. Any material deemed suitable may be used for the surface 48, but an exemplary material includes PTFE, as its surface properties facilitate its subsequent removal from the surface.

[0184] In some embodiments, the carbonaceous mass 51 is formed in a press to provide a formed carbonaceous mass 51 exhibiting a desired thickness, area, and density. These embodiments are particularly useful in the case of electrode 3 embodiments for ultracapacitor 10.

[0185] 24, which illustrates one embodiment of an electrode 3. In this example, the electrode 3 includes an energy storage medium 1 made from a formed carbonaceous aggregate 51. The current collector 2 shown may be coupled to the formed carbonaceous aggregate 51 by a variety of techniques, including, for example, by depositing the current collector 2 onto the formed carbonaceous aggregate 51.

[0186] Having thus disclosed aspects of the shaped carbonaceous aggregates 51, additional aspects are presented. In summary, the fabrication of the energy storage medium 1 in each instance generally begins with a suspension of pieces (or fragments) of vertically aligned carbon nanotubes (VCNTs) 47 in a solvent 68. The suspension is then "sonicated" or gently mixed, for example, using a conventional ultrasonic device 78. In some embodiments, other forms of carbon are sonicated separately in the solvent 68, while in other embodiments, the other forms of carbon are then added to the solution containing the VCNTs 47. These latter embodiments offer the advantage that a limited amount of solvent 68 can be used.

[0187] The VCNT47 and additional carbon forms are mixed by the ultrasonic field. After a suitable time interval, the VCNT47 and various forms of carbon in suspension assemble into a foam-like carbonaceous material. The foam may then be removed from the solvent 68 and then dried, flattened, compressed, heated, treated, or shaped in any one or more of a variety of ways to provide the energy storage medium 1.

[0188] Generally, VCNT47 includes relatively long nanotubes (e.g., longer than about 300 μm). Various forms of the carbon additive may include at least one of activated carbon, carbon fiber, rayon, graphene, aerogel, nanohorns, carbon nanotubes, etc. The carbon nanotube additive may include multi-walled carbon nanotubes (MWNTs) and single-walled carbon nanotubes (SWNTs). Generally, the nanotubes included in the carbon additive are relatively shorter than the nanotubes in VCNT47.

[0189] Further embodiments of the electrode 3 include techniques for assembling multiple electrode components into a larger electrode 3. By way of introduction, a description of the technique is presented starting with Figure 25. It should be noted that while the embodiments disclosed with respect to Figures 25-31 include techniques for assembling multiple electrode components into a larger electrode 3, additional aspects are included.

[0190] 25, there is shown a substrate 65 that is a host for carbon nanotube aggregates (VCNTs) 47. In the embodiment shown in FIG. 25, the substrate 65 comprises a base material 49 having a thin layer of catalyst 46 disposed thereon.

[0191] Generally, substrate 65 is at least somewhat flexible (i.e., substrate 65 is not brittle) and is made from components that can withstand the environment for depositing energy storage medium 1 (e.g., VCNT) (e.g., a high temperature environment of about 400° C. to about 1,100° C.), although various materials may be used for substrate 65 as appropriately determined.

[0192] Referring now to FIG. 26, once the energy storage medium 1 (e.g., CNTs) is fabricated on the substrate 65, a current collector 2 is disposed thereon. In some embodiments, the current collector 2 is about 0.5 micrometers (μm) to about 25 micrometers (μm) thick. The current collector 2 may appear as a thin layer, such as a layer applied by chemical vapor deposition (CVD), sputtering, e-beam, thermal evaporation, or another suitable technique. Generally, the current collector 2 is selected for its properties, such as conductivity, being electrically inert, and being compatible with the energy storage medium 1 (e.g., CNTs). Some exemplary materials include aluminum, platinum, gold, tantalum, titanium, and may include other materials and various alloys.

[0193] The current collector 2 is disposed on the energy storage medium 1 (e.g., CNTs) to provide an electrode component 20. Each electrode component 20 may be used individually as an electrode 3 or may be coupled (i.e., joined) with at least one other electrode component 20 to provide an electrode 3.

[0194] Optionally, post-fabrication processing is performed before the current collector 2 is fabricated according to desired standards. Exemplary post-processing includes heating and cooling the energy storage medium 1 (e.g., CNTs) in a slightly oxidizing environment. After fabrication (and optional post-processing), a transfer tool is applied to the current collector 2. See FIG. 27.

[0195] FIG. 27 illustrates the application of a transfer tool 63 to a current collector 2. In this example, the transfer tool 63 is a thermal release (or thermal desorption) tape used in a "dry" transfer method. Exemplary thermal release tapes are manufactured by NITTO DENKO CORPORATION (Fremont, California, and Osaka, Japan). One suitable transfer tape is commercially available as REVALPHA®. This release tape may be characterized as an adhesive tape that adheres firmly at room temperature and can be peeled off by heating. This tape and other suitable embodiments of thermal release tapes will peel off at a predetermined temperature. Advantageously, the release tape does not leave any chemically active residue on the electrode component 20.

[0196] Another process, called "wet" transfer, may use a tape designed for chemical stripping (or desorption). Once applied, the tape is removed by immersion in a solvent designed to dissolve the adhesive.

[0197] In other embodiments of the transfer implement 63, suction may be applied to the current collector 2. The suction may be applied, for example, via a slightly oversized paddle with multiple perforations to dispense (or distribute) the suction. In another example, the suction is applied via a roller with multiple perforations to distribute the suction. Suction-driven embodiments (i.e., air-powered tools) offer the advantages of being electrically controlled and economical since no consumables are used as part of the transfer process. Other embodiments of the transfer implement 63 may be used.

[0198] Once the transfer device 63 is temporarily coupled to the current collector 2, the electrode component 20 is gradually removed from the substrate 65 (see FIGS. 27 and 28). The removal typically involves peeling the energy storage medium 1 (e.g., CNTs 47) from the substrate 65, starting at one end of the substrate 65 and the energy storage medium 1 (e.g., CNTs 47).

[0199] The transfer tool 63 may then be separated from the electrode component 20 (see FIG. 29). In some embodiments, the transfer tool 63 is used to attach the electrode component 20. For example, the transfer tool 63 may be used to place the electrode component 20 directly onto the separator 5. Generally, once removed from the substrate 65, the electrode component 20 is ready for use.

[0200] In cases where a larger electrode 3 is desired, multiple electrode components 20 may be joined together. See FIG. 30. As shown in FIG. 30, multiple electrode components 20 may be joined, for example, by connecting links 59 to each electrode component 20 of the multiple electrode components 20. The combined electrode components 20 represent another embodiment of the electrode 3.

[0201] In some embodiments, the connection 59 is connected to each of the electrode components 20 at a joint 57. Each of the joints 57 is created by ultrasonic welding 57. Ultrasonic welding techniques have been found to be particularly well suited for creating each joint 57. That is, the mass of energy storage medium 1 (e.g., CNT47) is generally not amenable to welding, and only a nominal current collector 2, such as the current collectors disclosed herein, is utilized. As a result, many techniques for joining the electrode components 20 are destructive and result in damage to the components 20. However, in other embodiments, other forms of connection are used, and the connection 59 includes bonding, crimping, or other such types of connections.

[0202] Interconnect 59 may be a foil, a mesh, multiple wires, or may be realized in other forms. Generally, interconnect 59 is selected for properties such as conductivity and electrochemical inertness. In some embodiments, interconnect 59 is made from the same material(s) as the material(s) present in current collector 2.

[0203] In some embodiments, link 59 is prepared by removing an overlying oxide layer. The oxide may be removed, for example, by etching link 59 prior to providing bond 57. Etching may be accomplished, for example, with KOH.

[0204] The electrode 3 may be used in a variety of applications. For example, the electrode 3 may be rolled up into a "jelly roll" type energy store.

[0205] Referring now to Figure 31, an exemplary method 170 for fabricating an electrode is presented. In this exemplary method 170, the first step directs CNT growth 171. The second step involves depositing a current collector 172 over the aligned CNT assembly. The third optional step involves CNT post-treatment 173 to facilitate removal from the substrate. The fourth step places a transfer tool over the current collector (174), and in the fifth step, retrieves the electrode component from the substrate (175). In the sixth step, removal 176 of the transfer tool from the electrode component occurs. In the seventh step, the electrode components are joined together to provide a larger, higher power electrode (177).

[0206] Further embodiments of the electrode 3 include techniques for assembling the electrode 3 and performing various post-assembly processes to result in a "densified" electrode 3, or an electrode 3 that exhibits "densification." Regarding techniques for providing a densified electrode 3, reference may be made generally to the previous figures to ensure understanding of the techniques.

[0207] Techniques for densifying electrode 3 include aspects of some of the embodiments described above. In one example of densification, multiple layers of CNTs 47 are removed from their respective substrates 65. Each of the layers of CNTs 47 is removed by techniques such as those described above (e.g., by using heat release tape, blades, air tools, and other such techniques).

[0208] Each layer of CNTs 47 is then stacked to provide a layered stack of CNTs 47. Reference may be made to FIG. 9 and the techniques discussed therein. Once the layered stack of CNTs 47 is assembled, the layered stack of CNTs 47 is then wetted. The wetting may be provided with a solution, such as a solvent. Exemplary embodiments of solvents include isopropyl alcohol, deionized water, acetone, dimethylformamide (DMF), dimethyl sulfoxide (DMSO), suitable combinations, and any other suitable or similar materials.

[0209] Wetting may be accomplished by a suitable spray, bath, or other similar technique as deemed appropriate.

[0210] Once the CNT47 layered stack is properly wetted, the CNT47 layered stack is then compressed. One exemplary device for providing proper compression is a "calender" machine (i.e., a machine with opposing rollers). Any solvent remaining in the CNT47 layered stack is then removed by evaporation, evacuation in a vacuum, or other similar techniques. Heating the CNT47 layered stack may be used to facilitate the removal of the solvent.

[0211] Upon drying, the resulting compressed layered stack of CNTs 47 is typically flexible and mechanically durable (or robust). Typically, a current collector 2 is applied to the compressed layered stack of CNTs 47 at this point in the process (although this is not necessary, as current collector 2 may be applied, for example, during lamination). In some embodiments, current collector 2 is deposited onto the compressed layered stack of CNTs 47 using chemical vapor deposition (CVD), sputtering, e-beam, thermal evaporation, or another suitable technique.

[0212] In another embodiment, a solution of solvent and carbon nanoform is dispersed between layers of CNTs 47.

[0213] The resulting electrode 3 exhibits a high energy density. Generally, increasing the number of layers of CNTs 47 leads to increased energy density. The resulting electrode 3 also exhibits a high power density, even when ionic liquids are used (in the ultracapacitor 10 incorporating the resulting electrode 3).

[0214] Performance aspects of exemplary ultracapacitors are now presented. In some embodiments, the total weight of the ultracapacitor was 2.25 mg and the total volume of the ultracapacitor was 2 cc. The mass peak power density was calculated according to the following equations (1) and (2): VM 2 / (4*R*W) Equation (1); and VM 2 / (4*R*V) formula (2); Where Vm = rated voltage, R = equivalent series resistance (ESR), W = total weight, and V = total volume.

[0215] In summary, the disclosed technology provides a robust energy storage system. Performance data representing the power density of exemplary embodiments of ultracapacitor 10 are presented in Table 1 and also depicted in FIG.

[0216] [Table 1]

[0217] Figures 32A and 32B (collectively referred to herein as Figure 32) are graphs depicting power density as a function of frequency response for one embodiment of an ultracapacitor including electrodes fabricated in accordance with the teachings herein. Figure 32B provides an expanded view of the initial portion of the curve presented in Figure 32A.

[0218] 33 shows the voltage response to discharge of an exemplary ultracapacitor. The discharge curve was evaluated at a current of 0.5 A. Further aspects of the discharge evaluation are presented in Table 2.

[0219] [Table 2]

[0220] 34 shows the voltage response to charge / discharge cycling of an exemplary ultracapacitor. Further aspects of the discharge evaluation are presented in Table 3.

[0221] [Table 3]

[0222] Having thus disclosed various embodiments, it should be understood that the power density and energy density of ultracapacitor 10 can be controlled by varying the energy storage medium loading (i.e., the weight of carbonaceous material placed on the current collector).

[0223] That is, the higher the weight ratio of the energy storage medium to the total weight (of the ultracapacitor), the higher the energy density. In contrast, power density depends substantially on the Euclidean surface area of ​​the electrodes. Therefore, the lower the weight ratio of the energy storage medium to the total weight (of the ultracapacitor) (because the total surface area of ​​the electrodes remains the same but the total weight of the ultracapacitor is lower), the higher the power density.

[0224] In some embodiments, the loading of the energy storage medium is 0.1 mg / cm 2 ~30mg / cm 2 The loading of the energy storage medium can be in the range of 0.1 mg / cm 2 , the ultracapacitor will exhibit very high power densities, such as above about 250 kW / kg, in which case the energy density will be about 1 Wh / kg. 2 If so, the device will exhibit a very high energy density, such as over 30 Wh / kg, in which case the power density would be about 12 kW / kg.

[0225] The performance of the ultracapacitor in terms of combined power and energy output is presented in FIGS.

[0226] As a rule, it should be considered that the term "may" as used herein should be interpreted as optional (or optional); that "comprises" should be interpreted as not excluding other options (i.e., steps, materials, components (or parts or ingredients), compositions, etc.); and that "should" does not imply a requirement, but rather merely a preference depending on the case or circumstances. Other similar terminology is generally used in a similar manner.

[0227] Generally, power output and energy output can be expressed in various ways herein. For example, power density can be expressed in kW / kg. Similarly, energy density can be expressed in Wh / kg. In both cases, the mass used to normalize the output is the mass of the energy storage (e.g., ultracapacitor) being evaluated. Another expression of power density and energy density can be, for example, the volume of the energy storage, and can be taken into account.

[0228] Although the present invention has been described with reference to exemplary embodiments, those skilled in the art will recognize that various modifications may be made and equivalents may be substituted for elements of the present invention without departing from the scope of the invention. Numerous modifications will be apparent to those skilled in the art to adapt a particular arrangement or material to the teachings of the present invention without departing from the essential scope of the invention.

[0229] It should be recognized that the teachings herein are for illustrative purposes only and are not limiting of the present invention. Moreover, one skilled in the art will recognize that additional components, configurations, arrangements, etc. may be realized while remaining within the scope of the present invention. For example, layer configurations, layer content, etc. may vary from the embodiments disclosed herein. Layers may be added, additional functionality may be provided, functionality may be reduced, or some layers may be omitted. In general, the design and / or application of electrodes and ultracapacitors using the electrodes is limited only by the needs of the system designer, manufacturer, operator, and / or user and the requirements present in any particular situation.

[0230] Moreover, various other components may be included and called upon to provide aspects of the teachings herein. For example, additional materials, combinations of materials, and / or omissions of materials may be used to provide additional embodiments that are within the scope of the teachings herein.

[0231] When introducing elements of the invention or embodiment(s) of the invention, the articles "a," "an," and "the" are intended to mean that there are one or more elements. Similarly, the adjective "another," when used to introduce an element, is intended to mean one or more elements. The terms "comprise" and "have" are intended to be inclusive so that additional elements may be present other than the listed elements.

[0232] Various variables are described herein, including, but not limited to, components (e.g., electrode material, electrolyte, etc.), states (or conditions) (e.g., temperature, absence of various impurities at various levels), and performance characteristics (e.g., post-cycling capacity compared to initial cycles, low leakage current, etc.). It should be understood that any combination of these variables may define an embodiment of the present invention. For example, a combination of a specific electrode material with a specific electrolyte, containing less than a specific amount of impurities, operating at a specific post-cycling capacity and leakage current under a specific temperature range (although these variables are included as possibilities, the specific combination may not be explicitly presented) is an embodiment of the present invention. As will be apparent to one of ordinary skill in the art, other combinations of items, components, states, and / or methods may also be specifically selected from among the variables listed herein to define other embodiments.

[0233] It will be recognized that various components or techniques may provide certain necessary or beneficial functionality or features, and as such, these functions and features may be necessary to support the appended claims and variations thereof, and are understood to be inherently included as part of the teachings herein and as part of the disclosed invention.

[0234] While the present invention has been described with reference to illustrative embodiments, it will be understood that various modifications may be made and equivalents may be substituted for elements of the invention without departing from the scope of the invention. In addition, many modifications will be understood to adapt a particular equipment, situation, or material to the teachings of the invention without departing from the essential scope of the invention. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed as the best mode contemplated for carrying out this invention, but rather be understood in accordance with the scope of the claims appended hereto. The present invention includes the following aspects. (Aspect 1) A method for producing an aggregate of vertically aligned carbon nanotubes, comprising: Mounting the substrate in a substantially oxygen-free environment; disposing a catalyst on a substrate to provide a substrate; subjecting the substrate to the source gas and heating at least one of the source gas and the substrate to grow aggregates on the substrate; and Cooling the assembly in a substantially oxygen-free environment A method comprising: (Aspect 2) 2. The method of embodiment 1, wherein the substrate comprises at least one of iron, nickel, chromium, molybdenum, tungsten, titanium, aluminum, manganese, cobalt, copper, silver, gold, platinum, niobium, tantalum, lead, zinc, gallium, germanium, arsenic, indium, phosphors, and antimony; alloys of the foregoing, oxides of the foregoing, silicon, quartz, glass, mica, graphite, diamond, and ceramic. (Aspect 3) The method of embodiment 1, wherein disposing the catalyst comprises using at least one of sputter evaporation, cathodic arc deposition, sputter deposition, ion beam assisted deposition, ion beam induced deposition, and electrospray ionization. (Aspect 4) The method of embodiment 1, wherein disposing the catalyst comprises disposing a thickness of any one of about 0.1 nm to about 100 nm, about 0.5 nm to about 5 nm, and about 0.8 nm to about 2 nm. (Aspect 5) 4. The method of embodiment 3, further comprising patterning the catalyst to control shaping of the aggregates. (Aspect 6) The method of embodiment 1, wherein disposing the catalyst comprises disposing a layer that is one of a discontinuous and a substantially continuous layer. (Aspect 7) The method of embodiment 1, further comprising subjecting the substrate to a catalytically activating material during growth of the aggregates. (Aspect 8) 8. The method of embodiment 7, further comprising adding a catalytically activating material to the feed gas. (Aspect 9) 2. The method of embodiment 1, wherein the feedstock gas comprises at least one of methane, ethane, ethylene, propane, butane, pentane, hexane, heptane, propylene, and acetylene. (Aspect 10) 10. The method of embodiment 9, wherein the feedstock gas further comprises at least one of methanol and ethanol, acetone, carbon monoxide, and low-carbon oxygen-containing compounds. (Aspect 11) 10. The method of embodiment 1, further comprising selecting a manufacturing device comprising components that are treated to limit contaminant accumulation. (Aspect 12) 12. The method of embodiment 11, wherein treating the component comprises passivating the component with at least one passivation material. (Aspect 13) 13. The method of embodiment 12, wherein the passivation material comprises a silicon-containing material. (Aspect 14) Once grown, the aggregates grow to approximately 300m 2 / g ~ approx. 2,200m 2 2. The method of embodiment 1, having a specific surface area SA of 1 / g. (Aspect 15) Once grown, the aggregates have a mass of approximately 0.002 g / cm 3 ~about 0.2g / cm 3 Weight density (ρ w 2. The method of embodiment 1, comprising: (Aspect 16) The method of embodiment 1, wherein once grown, the aggregates have a height of about 50 μm to about 5 mm. (Aspect 17) The method of embodiment 1, wherein once grown, the carbon nanotubes in the assembly comprise about 1-10 walls. (Aspect 18) The method of embodiment 1, wherein once grown, the carbon nanotubes in the assembly have a diameter of about 0.7 nm to about 10 nm. (Aspect 19) Once grown, the aggregates are approximately 10 3 CNT / cm 2 ~about 10 12 CNT / cm 2 2. The method of embodiment 1, wherein the density of the (Aspect 20) 2. The method of embodiment 1, wherein the catalyst comprises at least one of iron, nickel, cobalt, molybdenum, chlorides thereof, alloys thereof, and complexes thereof with at least one of aluminum, alumina, titania, titanium nitride, and silicon oxide; an iron-molybdenum film, an alumina-iron film, an alumina-cobalt film, an alumina-iron-molybdenum film, an aluminum-iron film, and an aluminum-iron-molybdenum film. (Aspect 21) 10. The method of embodiment 1, wherein the catalyst comprises multiple layers. (Aspect 22) 10. The method of embodiment 1, further comprising disposing a carburization prevention layer on at least one of the substrate and the catalyst. (Aspect 23) 23. The method of embodiment 22, wherein the carburization prevention layer comprises at least one of a metal and a ceramic material. (Aspect 24) 23. The method of embodiment 22, wherein the carburization prevention layer is about 1 nm to about 500 nm thick. 2. The method of embodiment 1. (Aspect 25) 23. The method of embodiment 22, wherein the carburization prevention layer comprises at least one of copper, aluminum, aluminum oxide, silicon oxide, zirconium oxide, magnesium oxide, titanium oxide, silica, alumina, chromium oxide, boron oxide, calcium oxide, zinc oxide, aluminum nitride, and silicon nitride. (Aspect 26) An apparatus for producing an aggregate of vertically aligned carbon nanotubes, comprising: Loader section for loading substrates into a substantially oxygen-free environment: a sputtering section for disposing a catalyst on a substrate to provide a substrate; a carbon deposition section for subjecting the substrate to a source gas and heating at least one of the source gas and the substrate to grow aggregates on the substrate; and Cooling section for cooling the assembly in a substantially oxygen-free environment 1. An apparatus comprising: (Aspect 27) 27. The apparatus of embodiment 26, wherein the loader portion comprises a controller for providing a substantially oxygen-free environment. (Aspect 28) 27. The apparatus of embodiment 26, wherein the sputtering portion comprises an apparatus for at least one of sputter evaporation, cathodic arc deposition, sputter deposition, ion beam assisted deposition, ion beam induced deposition, and electrospray ionization. (Aspect 29) 27. The apparatus of embodiment 26, further comprising a catalyst finisher adapted to adjust the morphology of the catalyst. (Aspect 30) 30. The apparatus of embodiment 29, wherein the catalyst finishing portion comprises a glow discharge unit. (Aspect 31) 27. The apparatus of embodiment 26, wherein the carbon deposition unit comprises a chemical vapor deposition apparatus. (Aspect 32) 27. The apparatus of embodiment 26, wherein the carbon deposition unit comprises a gas injector. (Aspect 33) 27. The device of embodiment 26, wherein at least one component of the device is passivated. (Aspect 34) A method for manufacturing an electrode of an ultracapacitor, the electrode comprising a collection of vertically aligned carbon nanotubes, the method comprising: a substrate in a substantially oxygen-free environment; a catalyst disposed on the substrate to provide a substrate; a substrate being exposed to a feed gas and heating at least one of the feed gas and the substrate to grow aggregates on the substrate; and a method of manufacturing an aggregate by cooling the aggregates in the substantially oxygen-free environment; one of joining the aggregate with a current collector, removing the aggregate from the substrate and placing a current collector on the aggregate, and combining the aggregate with another carbonaceous material and joining the combination with a current collector. A method comprising: (Aspect 35) 35. The method of embodiment 34, further comprising adding at least one of additional aggregates and additional carbonaceous material to the electrode. (Aspect 36) 35. The method of embodiment 34, wherein the transferring comprises forming a bonding layer on the surface of the assembly and bonding the assembly to a current collector. (Aspect 37) 35. The method of embodiment 34, wherein the detaching comprises treating the assemblage in a post-manufacturing process to facilitate separation of the assemblage from the substrate. (Aspect 38) 38. The method of embodiment 37, wherein disposing the current collector comprises depositing a layer on the assembly. (Aspect 39) 35. The method of embodiment 34, wherein the combining comprises disposing the assemblies on a surface of another layer of the assemblies. (Aspect 40) 35. The method of embodiment 34, wherein the combining comprises disposing the aggregates on a surface of a layer of another carbonaceous material. (Aspect 41) 35. The method of embodiment 34, wherein the other carbonaceous materials comprise at least one of activated carbon, carbon fiber, rayon, graphene, aerogel, carbon cloth, and multiple forms of carbon nanotubes. (Aspect 42) 35. The method of embodiment 34, further comprising treating the aggregate to increase the surface area SA of the carbon nanotubes. (Aspect 43) 43. The method of embodiment 42, wherein the treating comprises oxidizing the aggregates. (Aspect 44) 1. A method for manufacturing an electrode for an energy storage system, comprising: selecting a substrate having a thickness of vertically aligned carbon nanotubes (CNTs) disposed thereon; disposing a tie layer on the CNTs of said thickness; bonding the bonding layer to the current collector to compress the CNTs to the thickness; and Removing the substrate from the CNT to provide an electrode A method comprising: (Aspect 45) 45. The method of embodiment 44, wherein the compressed CNTs exhibit periodic deformation. (Aspect 46) 45. The method of embodiment 44, further comprising disposing at least another layer of CNTs on the electrode. (Aspect 47) 47. The method of embodiment 46, further comprising compressing at least one more layer of the CNTs. (Aspect 48) 45. The method of embodiment 44, wherein the selecting comprises selecting a substrate that has been treated to promote separation of the CNTs from the substrate. (Aspect 49) 49. The method of embodiment 48, wherein the treating comprises heating the substrate and the CNTs. (Aspect 50) 1. An electrode for an energy storage system, comprising: a current collector including a bonding layer disposed thereon; at least one layer of compressed vertically aligned carbon nanotubes (CNTs) with a binder layer disposed thereon; Including, An electrode in which a tie layer of a current collector is bonded to a tie layer of a layer of compressed CNTs. (Aspect 51) at least one electrode comprising a current collector having a bonding layer disposed thereon and at least one layer of compressed vertically aligned carbon nanotubes (CNTs) having a bonding layer disposed thereon, wherein the bonding layer of the current collector is bonded to the bonding layer of the compressed layer of CNTs; and An electrolyte that wets at least one electrode , including an ultracapacitor. (Aspect 52) 52. The ultracapacitor of embodiment 51, wherein the housing of the ultracapacitor is one of a prismatic and a cylindrical shape. (Aspect 53) 1. A method for manufacturing an ultracapacitor, the ultracapacitor comprising at least one electrode comprising a collection of vertically aligned carbon nanotubes, the method comprising: selecting an assemblies produced by mounting a substrate in a substantially oxygen-free environment; disposing a catalyst on the substrate to provide a substrate; subjecting the substrate to a feed gas and heating at least one of the feed gas and the substrate to grow assemblies on the substrate; and cooling the assemblies in the substantially oxygen-free environment, and selecting an electrode produced by one of transferring the assemblies onto a current collector, removing the assemblies from the substrate and disposing a current collector on the assemblies, and combining the assemblies on the current collector with other carbonaceous material to provide an electrode; and Incorporating electrodes into ultracapacitors A method comprising: (Aspect 54) 54. The method of embodiment 53, further comprising incorporating at least one of the electrolyte and the separator into an ultracapacitor. (Aspect 55) 54. The method of embodiment 53, further comprising sealing the ultracapacitor. (Aspect 56) 1. A method for manufacturing an electrode for an energy storage system, comprising: selecting a base including a current collector and a first bonding layer disposed on a surface of the current collector; and bonding a second bonding layer to the first bonding layer, the second bonding layer including a carbonaceous layer disposed thereon, the carbonaceous layer including a material for storing electric charges; A method comprising: (Aspect 57) 57. The method of embodiment 56, wherein the bonding comprises at least one of heating the bonding layers and pressing the bonding layers together. (Aspect 58) 55. The method of embodiment 54, wherein the heating temperature ranges from about 150°C to about 600°C. (Aspect 59) 57. The method of embodiment 56, further comprising removing the substrate layer from the carbonaceous layer to expose the carbonaceous layer. (Aspect 60) 57. The method of embodiment 56, further comprising removing oxide from the current collector when fabricating the base. (Aspect 61) 57. The method of embodiment 56, wherein the carbonaceous layer is deposited by chemical vapor deposition (CVD). (Aspect 62) 57. The method of embodiment 56, wherein at least one of the bonding layers is deposited by one of magnetron sputtering and thermal evaporation. (Aspect 63) a base including a current collector and a first bonding layer disposed on a surface of the current collector; and a second bonding layer bonded to the first bonding layer, the second bonding layer including a carbonaceous layer disposed thereon, the carbonaceous layer including a material for storing electric charges; an electrode. (Aspect 64) 64. The electrode of embodiment 63, wherein the carbonaceous layer comprises at least one of activated carbon, carbon fiber, rayon, graphene, aerogel, carbon cloth, carbon nanohorns, etched aluminum, carbon nanotubes (CNTs), and combinations thereof. (Aspect 65) 64. The electrode of embodiment 63, wherein the current collector comprises at least one of aluminum, copper, stainless steel, nickel, iron, tantalum, a conductive oxide, and combinations thereof. (Aspect 66) 64. The electrode of embodiment 63, wherein the current collector exhibits a low reaction rate with the electrolyte of the capacitor. (Aspect 67) 64. The electrode of embodiment 63, wherein the current collector is substantially oxide-free. (Aspect 68) 64. The electrode of embodiment 63, further comprising at least one of an adhesion layer disposed between the current collector and the first bonding layer, an ohmic layer disposed between the carbonaceous layer and the second bonding layer, and a substrate layer with the carbonaceous layer disposed thereon. (Aspect 69) 69. The electrode of embodiment 68, wherein the adhesion layer improves adhesion between the current collector and the first bonding layer. (Aspect 70) 69. The electrode of embodiment 68, wherein the adhesion layer comprises one of titanium, tungsten, chromium, and combinations thereof. (Aspect 71) 69. The electrode of embodiment 68, wherein the ohmic layer exhibits a low reaction rate with an electrolyte of the capacitor. (Aspect 72) 69. The electrode of embodiment 68, wherein the ohmic layer comprises at least one of aluminum, tantalum, and platinum. (Aspect 73) 69. The electrode of embodiment 68, wherein the substrate layer is selected as a host for the material in the carbonaceous layer and is selected for mechanical flexibility. (Aspect 74) 64. The electrode of embodiment 63, wherein one of the first bonding layer and the second bonding layer comprises at least one of platinum, gold, silver, palladium, tin, nickel, copper, and combinations thereof. (Aspect 75) a housing comprising at least one electrode including a base including a current collector and a first bonding layer disposed on a surface of the current collector, and a second bonding layer bonded to the first bonding layer, the second bonding layer including a carbonaceous layer disposed thereon, the carbonaceous layer comprising a material for storing charge for the ultracapacitor; and An ultracapacitor including at least one of an electrolyte and a dielectric material disposed within a housing, with at least one electrode coupled to an output electrode of the housing. (Aspect 76) 76. An ultracapacitor according to embodiment 75, wherein a housing of the ultracapacitor is one of a prismatic and a cylindrical shape. (Aspect 77) 1. A method of providing a multi-form electrode for an energy storage device, comprising: selecting an electrode comprising an assembly of carbon nanotubes in electrical contact with a current collector; disposing at least one nanoform carbon dispersed in a carrier material on the assembly; and Releasing carrier material to provide a multi-form electrode A method comprising: (Aspect 78) 78. The method of embodiment 77, wherein the assembly comprises vertically aligned carbon nanotubes. (Aspect 79) 78. The method of embodiment 77, wherein the current collector comprises at least one of aluminum and an aluminum alloy. (Aspect 80) 78. The method of embodiment 77, wherein the placing comprises immersing the electrode in a bath comprising nanoform carbon. (Aspect 81) 81. The method of embodiment 80, further comprising retrieving the electrode from the bath. (Aspect 82) 81. The method of embodiment 80, further comprising evaporating the bath for said releasing. (Aspect 83) 78. The method of embodiment 77, wherein the placing comprises applying nanofoam carbon with an applicator. (Aspect 84) 78. The method of embodiment 77, wherein the releasing comprises heating an electrode comprising nanofoam carbon disposed thereon. (Aspect 85) 78. The method of embodiment 77, wherein the disposing comprises mixing at least one form of single-walled nanotubes, multi-walled nanotubes, nanohorns, nano-onions, carbon black, fullerenes, graphene, graphene oxide, metal nanoparticles, metal oxide nanoparticles, conductive polymers, and processed forms of the foregoing, into the carrier material. The method of embodiment 77. (Aspect 86) 78. The method of embodiment 77, further comprising controlling the positioning to achieve desired properties of the energy storage medium in the multiform electrode. (Aspect 87) 87. The method of embodiment 86, wherein the characteristic comprises a density of the energy storage medium. (Aspect 88) 1. A multi-form electrode for an energy storage device, comprising: A collection of carbon nanotubes disposed on a surface of a current collector, the collection further comprising at least one additional layer of nanoform carbon disposed on the collection as a solution comprising nanoform carbon dispersed in a carrier material. Multiform electrodes, including: (Aspect 89) 89. The multiform electrode of embodiment 88, wherein the aggregates comprise vertically aligned carbon nanotubes. (Aspect 90) 90. The multi-form electrode of embodiment 89, wherein the current collector comprises at least one of aluminum and an aluminum alloy. (Aspect 91) a housing including at least a multiform electrode disposed therein; a multi-foam electrode comprising an aggregate of carbon nanotubes disposed on a surface of a current collector, the aggregate further comprising at least one additional layer of nano-foam carbon disposed on the aggregate as a solution comprising nano-foam carbon distributed in a carrier material; and An electrolyte that provides ion transport within the ultracapacitor , including an ultracapacitor. (Aspect 92) 92. An ultracapacitor according to embodiment 91, wherein the housing of the ultracapacitor is one of a prismatic and a cylindrical shape. (Aspect 93) 92. The ultracapacitor of embodiment 91, wherein the electrolyte comprises at least one of 1-(3-cyanopropyl)-3-methylimidazolium, 1,2-dimethyl-3-propylimidazolium, 1,3-bis(3-cyanopropyl)imidazolium, 1,3-diethoxyimidazolium, 1-butyl-1-methylpiperidinium, 1-butyl-2,3-dimethylimidazolium, 1-butyl-3-methylimidazolium, 1-butyl-4-methylpyridinium, 1-butylpyridinium, 1-decyl-3-methylimidazolium, 1-ethyl-3-methylimidazolium, 3-methyl-1-propylpyridinium, and combinations thereof. (Aspect 94) 92. An ultracapacitor according to embodiment 91, wherein the electrolyte comprises at least one of bis(trifluoromethanesulfonate)imide, tris(trifluoromethanesulfonate)methide, dicyanamide, tetrafluoroborate, hexafluorophosphate, trifluoromethanesulfonate, bis(pentafluoroethanesulfonate)imide, thiocyanate, trifluoro(trifluoromethyl)borate, and combinations thereof. (Aspect 95) 92. The ultracapacitor of embodiment 91, wherein the nanoform carbon comprises at least one form of single-walled nanotubes, multi-walled nanotubes, nanohorns, nano-onions, carbon black, fullerenes, graphene, graphene oxide, metal nanoparticles, metal oxide nanoparticles, conductive polymers, and processed forms of the foregoing. (Aspect 96) 92. The ultracapacitor of embodiment 91, wherein the electrolyte comprises at least one of acetonitrile, amide, benzonitrile, butyrolactone, cyclic ether, dibutyl carbonate, diethyl carbonate, diethyl ether, dimethoxyethane, dimethyl carbonate, dimethylformamide, dimethyl sulfone, dioxane, dioxolane, ethyl formate, ethylene carbonate, ethyl methyl carbonate, lactone, linear ether, methyl formate, methyl propionate, methyl tetrahydrofuran, nitrile, nitrobenzene, nitromethane, n-methylpyrrolidone, propylene carbonate, sulfolane, sulfone, tetrahydrofuran, tetramethylene sulfone, thiophene, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, carbonate ester, gamma-butyrolactone, nitrile, tricyanohexane, or any combination thereof. (Aspect 97) 1. A method for providing a carbonaceous aggregate, comprising: dispersing an aggregate of aligned carbon nanotubes in a first solution; dispersing a carbon additive in the second solution; ultrasonically mixing the first solution and the second solution; mixing the mixed first solution and the mixed second solution to provide a mixed solution; ultrasonically mixing the mixed solution; Obtaining carbonaceous aggregates from the mixed solution A method comprising: (Aspect 98) 98. The method of embodiment 97, further comprising incorporating the carbonaceous aggregates into an electrode of an ultracapacitor as an energy storage medium. (Aspect 99) 98. The method of embodiment 97, further comprising incorporating the carbonaceous aggregate into an electrode of an energy storage cell as an energy storage medium. (Aspect 100) 98. The method of embodiment 97, wherein the incorporating comprises controlling at least one of the density, thickness, and area of ​​the energy storage medium. (Aspect 101) 98. The method of embodiment 97, wherein dispersing the carbon additive comprises dispersing at least one of activated carbon, carbon powder, carbon fiber, rayon, graphene, aerogel, nanohorns, and carbon nanotubes. (Aspect 102) 98. The method of embodiment 97, wherein ultrasonically mixing the solution comprises mixing the carbon for a time sufficient to at least one of draw out, swell, and decompose the carbon in the solution. (Aspect 103) 98. The method of embodiment 97, further comprising at least one of drying, flattening, compressing, heating, treating, and shaping the carbonaceous aggregate. (Aspect 104) An electrode comprising an energy storage medium including a carbonaceous aggregate, a current collector comprising a carbonaceous aggregate disposed thereon, the aggregate comprising a combination of ultrasonically treated carbon nanofoam; an electrode. (Aspect 105) 105. The electrode of embodiment 104, wherein at least one of the carbon nanoforms comprises activated carbon, carbon powder, carbon fiber, rayon, graphene, aerogel, nanohorns, and carbon nanotubes. (Aspect 106) At least one electrode comprising an energy storage medium comprising a carbonaceous aggregate, the electrode including a current collector having the carbonaceous aggregate disposed thereon, the aggregate comprising a combination of sonicated carbon nanofoam. , including an ultracapacitor. (Aspect 107) 107. The ultracapacitor of embodiment 106, further comprising an electrolyte. (Aspect 108) 1. A method for manufacturing an electrode component, comprising: selecting a substrate having a collection of carbon nanotubes disposed thereon; depositing a layer of conductive material over the assembly; and Removing the assembly and conductive material from the substrate A method comprising: (Aspect 109) 109. The method of embodiment 108, further comprising treating the assemblies to weaken bonds between the assemblies and the substrate. (Aspect 110) 110. The method of embodiment 109, wherein the treating comprises oxidizing the bond. (Aspect 111) 110. The method of embodiment 109, wherein the treating comprises heating at least one of the assemblage and the substrate. (Aspect 112) 109. The method of embodiment 108, wherein the removing comprises applying a transfer tool to the conductive material and lifting the assemblage from the substrate. (Aspect 113) The method of embodiment 112, wherein the transfer tool comprises one of a heat release tape and an air-powered tool. (Aspect 114) 109. The method of embodiment 108, further comprising coupling a lead to the conductive material as an electrical connection. (Aspect 115) 115. The method of embodiment 114, further comprising removing the oxide layer to provide the coupling. (Aspect 116) 116. The method of embodiment 115, wherein the joining comprises ultrasonic welding. (Aspect 117) 109. The method of embodiment 108, further comprising a plurality of components coupled together to provide the electrode. (Aspect 118) a plurality of electrode components, each comprising a collection of carbon nanotubes and a layer of conductive material disposed thereon; An electrode comprising: Each of the components is coupled to another one of the components, and at least one coupling includes bonding with the conductive material of the component, the electrode. (Aspect 119) 119. The electrode of embodiment 118, wherein at least one of the links comprises a junction. (Aspect 120) 119. The electrode of embodiment 118, wherein the carbon nanotubes comprise vertically aligned carbon nanotubes. (Aspect 121) 119. The electrode of embodiment 118, wherein the conductive material comprises one of aluminum and an aluminum alloy. (Aspect 122) at least one electrode including a plurality of electrode components, each component including a collection of carbon nanotubes and a layer of conductive material disposed thereon; each of the components being coupled to another one of the components, at least one coupling including a bond of the component to the conductive material; a housing containing at least one electrode; and An electrolyte that provides ion transport within the ultracapacitor an ultracapacitor including: (Aspect 123) A method for manufacturing an electrode, comprising: Obtaining layered stacks of carbon nanotubes (CNTs); wetting the layered stack with the solution; compressing the layered stack; drying the compressed layered stack; and Applying a current collector to the compressed layered stack A method comprising: (Aspect 124) 124. The method of embodiment 123, wherein wetting comprises using at least one of a bath and a spray of the solution. (Aspect 125) 124. The method of embodiment 123, wherein the compressing comprises applying pressure using a calender. (Aspect 126) 124. The method of embodiment 123, wherein the drying comprises at least one of evaporating the solution, applying a vacuum to the compressed layered stack, and heating the compressed layered stack. (Aspect 127) 124. The method of embodiment 123, further comprising disposing the solution of solvent and carbon nanofoam between at least two of the layers of CNT in the layered stack. (Aspect 128) The method of embodiment 123, wherein the solution comprises at least one of ethanol, isopropyl alcohol, deionized water, acetone, dimethylformamide (DMF), and dimethyl sulfoxide (DMSO). (Aspect 129) 1. An electrode for energy storage, comprising: A compressed layered stack of vertically aligned carbon nanotubes (CNTs) and a current collector disposed on the stack. an electrode. (Aspect 130) 130. The electrode of embodiment 129, wherein the current collector is disposed on the CNT by at least one of chemical vapor deposition (CVD), sputter evaporation, cathodic arc deposition, sputter deposition, ion beam assisted deposition, ion beam induced deposition, and electrospray ionization. (Aspect 131) at least one electrode comprising a compressed layered stack of carbon nanotubes (CNTs) and a current collector disposed on the stack; and an electrolyte for transporting energy stored in the electrodes to at least one terminal of the ultracapacitor; an ultracapacitor including: (Aspect 132) 1. A method of using an ultracapacitor, comprising: Obtaining an ultracapacitor including an electrolyte and two electrodes, each of the electrodes in electrical communication with a current collector and separated from the other electrode by a separator; and Cycling the ultracapacitor by alternatively charging and discharging the ultracapacitor, wherein the power density output by the ultracapacitor is at least 12 kW / kg for each cycle and up to about 250 kW / kg. A method comprising: (Aspect 133) 133. The method of embodiment 132, wherein the ultracapacitor is adapted to be cycled approximately 10 million times. (Aspect 134) 1. A method of using an ultracapacitor, comprising: Obtaining an ultracapacitor including an electrolyte and two electrodes, each of the electrodes in electrical communication with a current collector and separated from the other electrode by a separator; and Cycling the ultracapacitor by alternatively charging and discharging the ultracapacitor, wherein the output energy density of the ultracapacitor is at least 1 Wh / kg for each cycle and up to about 35 Wh / kg. A method comprising: (Aspect 135) 135. The method of embodiment 134, wherein the ultracapacitor is adapted to be cycled approximately 10 million times. (Aspect 136) 1. A method of using an ultracapacitor, comprising: Obtaining an ultracapacitor including an electrolyte and two electrodes, each of the electrodes in electrical communication with a current collector and separated from the other electrode by a separator; and cycling the ultracapacitor by alternatively charging and discharging the ultracapacitor while maintaining the voltage across the ultracapacitor between a maximum voltage and approximately half of the maximum voltage, the charging and discharging resulting in an output from the ultracapacitor of at least 3.75 Wh / kg of energy per charge or discharge; A method comprising: (Aspect 137) 137. The method of embodiment 136, wherein the ultracapacitor is adapted to be cycled approximately 10 million times. (Aspect 138) The method of embodiment 136, wherein the maximum voltage is about 4 volts. (Aspect 139) 1. A method of using an ultracapacitor, said method comprising: To obtain an ultracapacitor including an electrolyte and two electrodes, each of the electrodes being in electrical communication with a current collector and separated from the other electrode by a separator. Including, One of the ultracapacitors charges and discharges at approximately 7Wh-kW / kg 2 ~About 250Wh-kW / kg 2 wherein the power product is divided by the mass of the ultracapacitor and the energy product is divided by the mass of the ultracapacitor. (Aspect 140) Range: approximately 25Wh-kW / kg 2 ~About 250Wh-kW / kg 2 140. The method of claim 139, wherein (Aspect 141) Range: approximately 50Wh-kW / kg 2 ~About 250Wh-kW / kg 2 140. The method of claim 139, wherein (Aspect 142) Range: approximately 100Wh-kW / kg 2 ~About 250Wh-kW / kg 2 140. The method of claim 139, wherein (Aspect 143) Range: approximately 150Wh-kW / kg2 ~About 250Wh-kW / kg 2 140. The method of claim 139, wherein (Aspect 144) Range: approximately 200Wh-kW / kg 2 ~About 250Wh-kW / kg 2 140. The method of claim 139, wherein (Aspect 145) Range is approximately 7Wh-kW / kg 2 ~About 200Wh-kW / kg 2 140. The method of claim 139, wherein (Aspect 146) Range: approximately 25Wh-kW / kg 2 ~About 200Wh-kW / kg 2 140. The method of claim 139, wherein (Aspect 147) Range: approximately 50Wh-kW / kg 2 ~About 200Wh-kW / kg 2 140. The method of claim 139, wherein (Aspect 148) Range: approximately 100Wh-kW / kg 2 ~About 200Wh-kW / kg 2 140. The method of claim 139, wherein (Aspect 149) Range: approximately 150Wh-kW / kg 2 ~About 200Wh-kW / kg 2 140. The method of claim 139, wherein (Aspect 150) Range is approximately 7Wh-kW / kg 2 ~About 150Wh-kW / kg 2 140. The method of claim 139, wherein (Aspect 151) Range: approximately 25Wh-kW / kg 2 ~About 150Wh-kW / kg 2 140. The method of claim 139, wherein (Aspect 152) Range: approximately 50Wh-kW / kg 2 ~About 150Wh-kW / kg 2 140. The method of claim 139, wherein (Aspect 153) Range: approximately 100Wh-kW / kg 2 ~About 150Wh-kW / kg 2 140. The method of claim 139, wherein (Aspect 154) Range is approximately 7Wh-kW / kg 2 ~approx. 100Wh-kW / kg 2 140. The method of claim 139, wherein (Aspect 155) Range: approximately 25Wh-kW / kg 2 ~approx. 100Wh-kW / kg 2 140. The method of claim 139, wherein (Aspect 156) Range: approximately 50Wh-kW / kg 2 ~approx. 100Wh-kW / kg 2 140. The method of claim 139, wherein (Aspect 157) Range is approximately 7Wh-kW / kg 2 ~About 50Wh-kW / kg 2 140. The method of claim 139, wherein (Aspect 158) Range: approximately 25Wh-kW / kg 2 ~About 50Wh-kW / kg 2 140. The method of claim 139, wherein (Aspect 159) 1. A method of using an ultracapacitor, said method comprising: To obtain an ultracapacitor including an electrolyte and two electrodes, each of the electrodes being in electrical communication with a current collector and separated from the other electrode by a separator. Including, One of the charging and discharging of the ultracapacitor while maintaining the voltage across the ultracapacitor between the maximum voltage and approximately half the maximum voltage is approximately 7Wh-kW / kg. 2 ~About 250Wh-kW / kg 2 wherein the power product is divided by the mass of the ultracapacitor and the energy product is divided by the mass of the ultracapacitor. (Aspect 160) Range is approximately 5Wh-kW / kg 2 ~approx. 190Wh-kW / kg 2 160. The method of claim 159, wherein (Aspect 161) Range: approximately 19Wh-kW / kg 2 ~approx. 190Wh-kW / kg 2 160. The method of claim 159, wherein (Aspect 162) Range: approximately 38Wh-kW / kg 2 ~approx. 190Wh-kW / kg 2 160. The method of claim 159, wherein (Aspect 163) Range: approximately 75Wh-kW / kg 2 ~approx. 190Wh-kW / kg 2 160. The method of claim 159, wherein (Aspect 164) Range: approximately 112Wh-kW / kg 2 ~approx. 190Wh-kW / kg 2 160. The method of claim 159, wherein (Aspect 165) Range: approximately 150Wh-kW / kg 2 ~approx. 190Wh-kW / kg 2 160. The method of claim 159, wherein (Aspect 166) Range: approximately 5Wh-kW / kg 2 ~About 150Wh-kW / kg 2 160. The method of claim 159, wherein (Aspect 167) Range: approximately 19Wh-kW / kg 2 ~About 150Wh-kW / kg 2 160. The method of claim 159, wherein (Aspect 168) Range: approximately 38Wh-kW / kg 2 ~About 150Wh-kW / kg 2 160. The method of claim 159, wherein (Aspect 169) Range: approximately 75Wh-kW / kg 2 ~About 150Wh-kW / kg 2 160. The method of claim 159, wherein (Aspect 170) Range: approximately 112Wh-kW / kg 2 ~About 150Wh-kW / kg 2 160. The method of claim 159, wherein (Aspect 171) Range is approximately 5Wh-kW / kg 2 ~Approx. 112Wh-kW / kg 2 160. The method of claim 159, wherein (Aspect 172) Range: approximately 19Wh-kW / kg 2 ~Approx. 112Wh-kW / kg 2 160. The method of claim 159, wherein (Aspect 173) Range: approximately 38Wh-kW / kg 2 ~Approx. 112Wh-kW / kg 2 160. The method of claim 159, wherein (Aspect 174) Range: approximately 75Wh-kW / kg 2 ~Approx. 112Wh-kW / kg 2 160. The method of claim 159, wherein (Aspect 175) Range: approximately 5Wh-kW / kg 2 ~about 75Wh-kW / kg 2 160. The method of claim 159, wherein (Aspect 176) Range: approximately 19Wh-kW / kg 2 ~about 75Wh-kW / kg 2 160. The method of claim 159, wherein (Aspect 177) Range: approximately 38Wh-kW / kg 2 ~about 75Wh-kW / kg 2 160. The method of claim 159, wherein (Aspect 178) Range is approximately 5Wh-kW / kg 2 ~About 38Wh-kW / kg 2 160. The method of claim 159, wherein (Aspect 179) Range: approximately 19Wh-kW / kg 2 ~About 38Wh-kW / kg 2 160. The method of claim 159, wherein

Claims

1. a housing including at least one multi-form electrode disposed therein, The at least one multi-form electrode is a first layer made of an aggregate of carbon nanotubes disposed on a surface of a bonding layer included in the electrode current collector; and at least a second layer comprising nanofoam carbon disposed on a surface of the first layer; a housing, wherein the nanoform carbon in the second layer comprises at least one nanoform carbon other than carbon nanotubes, and the first layer is a compressed layer; and An electrolyte that provides ion transport within the ultracapacitor An ultracapacitor comprising: The ultracapacitor is configured to have a mass output power density of at least 12 kW / kg for multiple charge / discharge cycles.

2. The ultracapacitor of claim 1 , wherein the housing of the ultracapacitor is one of a prismatic and a cylindrical shape.

3. 10. The ultracapacitor of claim 1, wherein the electrolyte comprises at least one of 1-(3-cyanopropyl)-3-methylimidazolium, 1,2-dimethyl-3-propylimidazolium, 1,3-bis(3-cyanopropyl)imidazolium, 1,3-diethoxyimidazolium, 1-butyl-1-methylpiperidinium, 1-butyl-2,3-dimethylimidazolium, 1-butyl-3-methylimidazolium, 1-butyl-4-methylpyridinium, 1-butylpyridinium, 1-decyl-3-methylimidazolium, 1-ethyl-3-methylimidazolium, 3-methyl-1-propylpyridinium, and combinations thereof.

4. 10. The ultracapacitor of claim 1, wherein the electrolyte comprises at least one of bis(trifluoromethanesulfonate)imide, tris(trifluoromethanesulfonate)methide, dicyanamide, tetrafluoroborate, hexafluorophosphate, trifluoromethanesulfonate, bis(pentafluoroethanesulfonate)imide, thiocyanate, trifluoro(trifluoromethyl)borate, and combinations thereof.

5. 10. The ultracapacitor of claim 1, wherein the nanoform carbon comprises at least one of nanohorns, nano-onions, carbon black, fullerenes, graphene, graphene oxide, and processed forms of the foregoing.

6. 10. The ultracapacitor of claim 1, wherein the electrolyte comprises at least one of acetonitrile, amide, benzonitrile, butyrolactone, cyclic ether, dibutyl carbonate, diethyl carbonate, diethyl ether, dimethoxyethane, dimethyl carbonate, dimethylformamide, dimethyl sulfone, dioxane, dioxolane, ethyl formate, ethylene carbonate, ethyl methyl carbonate, lactone, linear ether, methyl formate, methyl propionate, methyl tetrahydrofuran, nitrile, nitrobenzene, nitromethane, N-methylpyrrolidone, propylene carbonate, sulfolane, sulfone, tetrahydrofuran, tetramethylene sulfone, thiophene, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, carbonate ester, gamma-butyrolactone, tricyanohexane, and any combination thereof.

7. 10. The ultracapacitor of claim 1, wherein the ultracapacitor is configured to have a mass output power density of at least 250 kW / kg for multiple charge / discharge cycles.

8. 10. The ultracapacitor of claim 7, wherein the ultracapacitor is configured to have a mass output energy density of at least 1 Wh / kg for multiple charge / discharge cycles.

9. 9. The ultracapacitor of claim 8, wherein the plurality of charge / discharge cycles comprises at least 1,000 cycles.

10. 9. The ultracapacitor of claim 8, wherein the plurality of charge / discharge cycles comprises at least 2,000 cycles.

11. The ultracapacitor has a capacity of at least 19 Wh-kW / kg. ２ 10. The ultracapacitor of claim 1, configured to be operated at a voltage of at least half of the maximum rated voltage with a mass output power density having a product equal to

12. 12. The ultracapacitor of claim 11, wherein the maximum rated voltage is at least 4V.

13. The ultracapacitor has a capacity of at least 38 Wh-kW / kg. ２ 10. The ultracapacitor of claim 1, configured to be operated at a voltage of at least half of the maximum rated voltage with a mass output power density having a product equal to

14. 14. The ultracapacitor of claim 13, wherein the maximum rated voltage is at least 4V.

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