Improved lithium ion battery using high surface area nano-tube

Abstract

To provide a high surface area carbon nano-tube containing a desired or selected oxidation level and / or amount in the inside and in the outside of a tube layer.SOLUTION: The nano-tube has little or no oxidations in the inner surface of the tube, and alternately can have different amounts and / or different types of oxidations between the inner surface and the outer surface of the tube. Also, the high surface area carbon nano-tube has a larger length and a larger diameter, and can form useful mechanical, electrical, and thermal characteristics.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to an improved energy storage device comprising a novel carbon nanotube composition having an increased surface area, a targeted oxidation level and / or content, and a formulation thereof.

Background Art

[0002] Many energy storage devices, such as batteries, capacitors, and solar cells, can utilize particle size adjustment techniques to provide improved performance, improved conductivity of the powder used in the cathode or electrode, and ion transport in materials and electrolytes having electronic or photoactivity, as well as binders and / or electrolytes and separator films.

[0003] Lithium-ion batteries are widely used for portable electronic devices, and batteries such as lithium-ion and lead-acid are increasingly used to provide electrical backup for wind and solar energy. Salts for cathode materials in lithium-ion batteries generally have low electrical conductivity and low electrochemical stability, which results in a low cycle (charge / discharge) capacity. Both the cathode and anode materials in many battery types, such as those using lithium ions, exhibit swelling and deswelling as the battery is charged and discharged. This spatial movement results in further separation of some of the particles and an increase in electrical resistance. Specifically, the high internal resistance of the battery in a large array of lithium-ion batteries, such as those used in electric vehicles, results in excessive heat generation, which can lead to a runaway chemical reaction and fire due to the organic liquid electrolyte.

[0004] ​​​​​​​​​​​​​​Primary lithium batteries, for example, contain lithium together with a solvent such as γ-butyrolactone as an electrolyte , poly(carbon monofluoride), and lithium tetrafluoroborate . These primary lithium batteries have an excellent shelf life but can supply only a low current , and the capacity is about one-tenth of what is theoretically possible. This is due to the low electrical conductivity of poly(carbon monofluoride). In some cases, a portion of manganese dioxide is added to assist with the electrical conductivity and power of the lithium battery . Attempts to overcome the drawback of low adhesiveness to the current collector and prevent microcracks during expansion and contraction of rechargeable batteries involve the development of binders. Binders such as polyacrylic acid (PAA) for the cathode, poly(styrene-butadiene) for the anode, carboxymethyl cellulose (CMC), styrene-butadiene (SBR), and particularly polyvinylidene fluoride (PVDF) for both the cathode and anode are used in lithium-based batteries to join the active material particles and maintain contact with the current collector, i.e., aluminum (

[0005] Al) or copper (Cu) foil. PAA and SBR are used as aqueous suspensions or solutions and are considered to be more environmentally friendly than organic solvent-based systems such as n-methyl-2-pyrrolidone (NMP) with PVDF . The cathode electrode of a lithium-ion battery usually consists of an active material powder such as lithium iron phosphate , a binder powder, i.e., high molecular weight PVDF, and, when using PVDF, a solvent such as NMP , and an additive such as carbon black are mixed into a slurry (paste), and this slurry is used to coat the current collector, i.e., aluminum ( Al) or copper (Cu) foil, to maintain contact . PAA and SBR are used as aqueous suspensions or solutions and are considered to be more environmentally friendly than organic solvent-based systems such as n-methyl-2-pyrrolidone (NMP) with PVDF

[0006] The cathode electrode of a lithium-ion battery usually consists of an active material powder such as lithium iron phosphate , a binder powder, i.e., high molecular weight PVDF, and, when using PVDF, a solvent such as NMP whatever the solvent, and an additive such as carbon black are mixed into a slurry (paste), and this slurry It is produced by feeding the slurry into a coater. The anode electrode for a lithium-ion battery is usually similarly produced by mixing an active material such as graphite, or other materials such as silicon, together with a binder, a solvent, and an additive. The coater spreads a mixed slurry (paste) on both sides of the Al foil of the cathode and the Cu foil of the anode. The coated foil is subsequently polished to make the electrode thickness more uniform and then slit for proper electrode sizing and drying. For a zinc-carbon battery, the positive electrode can consist of a wet powder mixture of manganese dioxide, powdered carbon black, and an electrolyte such as ammonium chloride and water. The carbon black can add electrical conductivity to the manganese dioxide particles, but is required in a high weight percentage in the range of about 10 to 50 wt% of the manganese dioxide. These large amounts of carbon black required for improving electrical conductivity or reducing the impedance of the battery result in less manganese dioxide being employed per unit volume of the positive paste mixture, which reduces the capacity per unit volume of the battery. Therefore, generally, it is necessary to improve the impedance of the battery while maximizing the amount of active material per unit volume. For a lead-acid battery, the anode is made from carbon particles together with a binder, which can result in a higher specific capacity (capacity per unit weight). The anode of a zinc-carbon battery is often a carbon rod usually made from a binder such as compressed carbon particles, graphite, and pitch. The anode of carbon particles can cause damage under conditions of vibration and mechanical shock. It is made by feeding the slurry into a coater. The anode electrode for a lithium-ion battery is usually similarly made by mixing an active material such as graphite, or other materials such as silicon, together with a binder, a solvent, and an additive. The coater spreads a mixed slurry (paste) on both sides of the Al foil of the cathode and the Cu foil of the anode. The coated foil is subsequently polished to make the electrode thickness more uniform and then slit for proper electrode sizing and drying. For a zinc-carbon battery, the positive electrode can consist of a wet powder mixture of manganese dioxide, powdered carbon black, and an electrolyte such as ammonium chloride and water. The carbon black can add electrical conductivity to the manganese dioxide particles, but is required in a high weight percentage in the range of about 10 to 50 wt% of the manganese dioxide. These large amounts of carbon black required for improving electrical conductivity or reducing the impedance of the battery result in less manganese dioxide being employed per unit volume of the positive paste mixture, which reduces the capacity per unit volume of the battery. Therefore, generally, it is necessary to improve the impedance of the battery while maximizing the amount of active material per unit volume. For a lead-acid battery, the anode is made from carbon particles together with a binder, which can result in a higher specific capacity (capacity per unit weight). The anode of a zinc-carbon battery is often a carbon rod usually made from a binder such as compressed carbon particles, graphite, and pitch. The anode of carbon particles can cause damage under conditions of vibration and mechanical shock.

[0007] For a zinc-carbon battery, the positive electrode can consist of a wet powder mixture of manganese dioxide, powdered carbon black, and an electrolyte such as ammonium chloride and water. The carbon black can add electrical conductivity to the manganese dioxide particles, but is required in a high weight percentage in the range of about 10 to 50 wt% of the manganese dioxide. These large amounts of carbon black required for improving electrical conductivity or reducing the impedance of the battery result in less manganese dioxide being employed per unit volume of the positive paste mixture, which reduces the capacity per unit volume of the battery. Therefore, generally, it is necessary to improve the impedance of the battery while maximizing the amount of active material per unit volume. For a lead-acid battery, the anode is made from carbon particles together with a binder, which can result in a higher specific capacity (capacity per unit weight). The anode of a zinc-carbon battery is often a carbon rod usually made from a binder such as compressed carbon particles, graphite, and pitch. The anode of carbon particles can cause damage under conditions of vibration and mechanical shock. For a zinc-carbon battery, the positive electrode can consist of a wet powder mixture of manganese dioxide, powdered carbon black, and an electrolyte such as ammonium chloride and water. The carbon black can add electrical conductivity to the manganese dioxide particles, but is required in a high weight percentage in the range of about 10 to 50 wt% of the manganese dioxide. These large amounts of carbon black required for improving electrical conductivity or reducing the impedance of the battery result in less manganese dioxide being employed per unit volume of the positive paste mixture, which reduces the capacity per unit volume of the battery. Therefore, generally, it is necessary to improve the impedance of the battery while maximizing the amount of active material per unit volume. For a lead-acid battery, the anode is made from carbon particles together with a binder, which can result in a higher specific capacity (capacity per unit weight). The anode of a zinc-carbon battery is often a carbon rod usually made from a binder such as compressed carbon particles, graphite, and pitch. The anode of carbon particles can cause damage under conditions of vibration and mechanical shock. For a zinc-carbon battery, the positive electrode can consist of a wet powder mixture of manganese dioxide, powdered carbon black, and an electrolyte such as ammonium chloride and water. The carbon black can add electrical conductivity to the manganese dioxide particles, but is required in a high weight percentage in the range of about 10 to 50 wt% of the manganese dioxide. These large amounts of carbon black required for improving electrical conductivity or reducing the impedance of the battery result in less manganese dioxide being employed per unit volume of the positive paste mixture, which reduces the capacity per unit volume of the battery. Therefore, generally, it is necessary to improve the impedance of the battery while maximizing the amount of active material per unit volume. For a lead-acid battery, the anode is made from carbon particles together with a binder, which can result in a higher specific capacity (capacity per unit weight). The anode of a zinc-carbon battery is often a carbon rod usually made from a binder such as compressed carbon particles, graphite, and pitch. The anode of carbon particles can cause damage under conditions of vibration and mechanical shock. For a zinc-carbon battery, the positive electrode can consist of a wet powder mixture of manganese dioxide, powdered carbon black, and an electrolyte such as ammonium chloride and water. The carbon black can add electrical conductivity to the manganese dioxide particles, but is required in a high weight percentage in the range of about 10 to 50 wt% of the manganese dioxide. These large amounts of carbon black required for improving electrical conductivity or reducing the impedance of the battery result in less manganese dioxide being employed per unit volume of the positive paste mixture, which reduces the capacity per unit volume of the battery. Therefore, generally, it is necessary to improve the impedance of the battery while maximizing the amount of active material per unit volume. For a lead-acid battery, the anode is made from carbon particles together with a binder, which can result in a higher specific capacity (capacity per unit weight). The anode of a zinc-carbon battery is often a carbon rod usually made from a binder such as compressed carbon particles, graphite, and pitch. The anode of carbon particles can cause damage under conditions of vibration and mechanical shock.

[0008] For a lead-acid battery, the anode is made from carbon particles together with a binder, which can result in a higher specific capacity (capacity per unit weight). The anode of a zinc-carbon battery is often a carbon rod usually made from a binder such as compressed carbon particles, graphite, and pitch. The anode of carbon particles can cause damage under conditions of vibration and mechanical shock. For a lead-acid battery, the anode is made from carbon particles together with a binder, which can result in a higher specific capacity (capacity per unit weight). The anode of a zinc-carbon battery is often a carbon rod usually made from a binder such as compressed carbon particles, graphite, and pitch. The anode of carbon particles can cause damage under conditions of vibration and mechanical shock. For a lead-acid battery, the anode is made from carbon particles together with a binder, which can result in a higher specific capacity (capacity per unit weight). The anode of a zinc-carbon battery is often a carbon rod usually made from a binder such as compressed carbon particles, graphite, and pitch. The anode of carbon particles can cause damage under conditions of vibration and mechanical shock. For a lead-acid battery, the anode is made from carbon particles together with a binder, which can result in a higher specific capacity (capacity per unit weight). The anode of a zinc-carbon battery is often a carbon rod usually made from a binder such as compressed carbon particles, graphite, and pitch. The anode of carbon particles can cause damage under conditions of vibration and mechanical shock. ​Tends to have low mechanical strength.

[0009] The properties of the binder material are important for both the manufacture and performance of the battery. Some of these related properties are electrical and ionic conductivity, tensile strength and extensibility, adhesion to particles as well as to the foil, and swelling of the electrolyte. Improvement of electrical and ionic conductivity is required for improvement of battery capacity and power. Materials such as lithium manganese oxide for the cathode and silicon particles for the anode exhibit significantly lower actual specific capacities than those that are theoretically effective. Binder materials with higher electrical and ionic conductivity can be most beneficial in achieving specific capacities closer to their theoretical values. It is desirable to improve the tensile and adhesive strength of the binder, thereby employing less binder material and also improving the cycle life of the battery. Addition of conductive particles such as carbon black reduces the tensile strength and extensibility of the binder. Control of the swelling of the binder in the electrolyte is also important. Excessive swelling causes the particles to separate, significantly increasing the ohmic resistance between the particles. Also, since the anode or cathode particles are coated with the binder, the layer thickness of the binder can be 50 to 100 nanometers thick. This layer thickness hinders the uniform distribution of particles of sizes larger than the layer thickness of the binder. For example, multi-walled carbon nanotubes generally produced in a gas phase reactor consist of bundles with diameters in the range of about 50 to 500 microns and thus will only be present in the inter-lattice spaces between the particles. Examples of binders include, but are not limited to, non-lithium salts, metals such as iron and manganese and so on. For example, multi-walled carbon nanotubes generally produced in a gas phase reactor consist of bundles with diameters in the range of about 50 to 500 microns and thus will only be present in the inter-lattice spaces between the particles. For example, multi-walled carbon nanotubes generally produced in a gas phase reactor

[0010] Examples of binders include, but are not limited to, non-lithium salts, metals such as iron and manganese Impurities can be quite harmful to the performance of batteries. Usually, high-purity binder materials, and other additives such as carbon black that improve electrical conductivity are important elements for minimizing unfavorable side reactions in electrochemistry ical processes. For example, in an alkaline -manganese dioxide battery, the iron in manganese dioxide should be less than 100 ppm in total to prevent hydrogen gas from generating at the anode. Commercially available carbon nanotubes such as NC7000 (trademark) (Nan ocyl) or Graphistrength (registered trademark) (Arkema) contain more than 10 weight percent of residual metal catalysts, and at these impurity levels, they are not considered effective for batteries. Generally, the impurity residues of the nanotubes adopted here should be less than about 5 weight percent, less than about 2 weight percent, or less than about 1 weight percent. For solar cells, the lines of conductive paste ink made from solvents, binders, metal powders, and glass frit are screen-printed onto solar panel modules. The binder is generally a polymer-based one with improved printability such as ETHOCEL (trademark) (Dow Chemical Company). During the dissipation and cooling of the polymer, the lines will crack due to the shrinkage force, increasing the impedance. To prevent cracking during heating and cooling, it is highly desirable to have a more robust conductive paste ink. Efforts to improve the safety of lithium-ion batteries sometimes involve additional additives, for example, polyethylene oxides with titanium dioxide nanoparticles, or glass-ceramic tie

[0011] For solar cells, the lines of conductive paste ink made from solvents, binders, metal powders, and glass frit are screen-printed onto solar panel modules. The binder is generally a polymer-based one with improved printability such as ETHOCEL (trademark) (Dow Chemical Company). During the dissipation and cooling of the polymer, the lines will crack due to the shrinkage force, increasing the impedance. To prevent cracking during heating and cooling, it is highly desirable to have a more robust conductive paste ink. For solar cells, the lines of conductive paste ink made from solvents, binders, metal powders, and glass frit are screen-printed onto solar panel modules. The binder is generally a polymer-based one with improved printability such as ETHOCEL (trademark) (Dow Chemical Company). During the dissipation and cooling of the polymer, the lines will crack due to the shrinkage force, increasing the impedance. To prevent cracking during heating and cooling, it is highly desirable to have a more robust conductive paste ink. The binder is generally a polymer-based one with improved printability such as ETHOCEL (trademark) (Dow Chemical Company). During the dissipation and cooling of the polymer, the lines will crack due to the shrinkage force, increasing the impedance. To prevent cracking during heating and cooling, it is highly desirable to have a more robust conductive paste ink. During the dissipation and cooling of the polymer, the lines will crack due to the shrinkage force, increasing the impedance. To prevent cracking during heating and cooling, it is highly desirable to have a more robust conductive paste ink. During the dissipation and cooling of the polymer, the lines will crack due to the shrinkage force, increasing the impedance. To prevent cracking during heating and cooling, it is highly desirable to have a more robust conductive paste ink. To prevent cracking during heating and cooling, it is highly desirable to have a more robust conductive paste ink. To prevent cracking during heating and cooling, it is highly desirable to have a more robust conductive paste ink.

[0012] Efforts to improve the safety of lithium-ion batteries sometimes involve additional additives, for example, polyethylene oxides with titanium dioxide nanoparticles, or glass-ceramic tie Inorganic solid electrolyte such as ceramic or glass Li 1 +x+yTi 2 -xAl x S i y P 3 -yO 12 (LTAP), together with ionic liquids, e.g., ethyl-methyl-imide Dazolium-bis-(trifluoromethanesulfonyl)-imide (EMI-TFSI) and This includes the use of non-flammable liquids such as organic liquid electrolytes and solid polymers. The conductivity value is 10 -2 ~10 -1 The polymer electrolyte is in the approximate range of 100 S / cm. Depends on about 10 -7 ~10 -4 Although it has electrical conductivity values ​​in the range of S / cm, inorganic solid electrolytes The solution is generally 10 -8 ~10 -5 Most polymer electrodes have values ​​in the range of S / cm. At room temperature, the solution is about 10 -5 It has an electrical conductivity value of 1.0 S / cm. Energy storage and The low performance of polymer and inorganic solid electrolytes for their general use in collection devices is The ionic conductivity is currently the limit. Therefore, the conductivity of the electrolyte is specifically Enhanced with polymer and inorganic electrolytes due to their enhanced flammability characteristics relative to organic liquids. It is highly desirable to have a high level of durability in environments with high vibration or mechanical shock. The mechanical properties of solid electrolytes are advantageous in battery applications and in the ease of device manufacture. It is desirable to improve the target strength.

[0013] In alkaline batteries, the electrolyte is usually potassium hydroxide. Alkaline batteries have a low current It is known that zinc anolytes have a lower capacity at higher current discharges than zinc anolytes. The limit of electrolyte ion transport, similar to the polarization of the cathode, is known for this reason. The increase in electrolyte ion transport is highly desirable.

[0014] Among the new generation of thin-film solar cell technologies, dye-sensitized solar cells (DSSCs) have one of the most promising future possibilities in terms of their cost-performance ratio. One of the most serious drawbacks of this DSSC technology is the use of liquid and corrosive electrolytes that severely limit their commercial development. An example of an electrolyte currently used in DSSCs is potassium iodide / iodine. Although replacement of the currently used electrolyte is desirable, the candidate electrolytes have poor ion transport.

[0015] Typical electrolytic capacitors are made of tantalum, aluminum, or ceramics together with an electrolyte system such as boric acid or sulfuric acid, or any solid electrolyte such as polypyrrole. Desired improvements include speeding up the charge and discharge rates limited by the ion transport of the electrolyte.

[0016] Separator films are often added to batteries or capacitors with liquid electrolytes to perform the electrical insulation function between electrodes and to enable ion transport. Usually, in lithium batteries, the separator film is a porous polymer film, and the polymer is, for example, polyethylene, polypropylene, or polyvinylidene fluoride. Porosity can be introduced, for example, by using a mat of spun fibers or by solvent and / or film stretching techniques. In lead-acid batteries, the separator film used is customarily a glass fiber mat. The polymer separator provided with the high surface area carbon nanotubes of the present invention The separator film can still provide the necessary electrical insulation between the electrodes while improving ion transport.

[0017] Carbon nanotubes can be classified into single-layer, bilayer, and multi-layer according to the number of tube layers. Currently, carbon nanotubes are produced as balls, bundles, or forests of aggregated nanotubes attached to a substrate. When the produced nanotubes are removed from the substrate, they often form a rigid "trunk" - like arrangement. The use of carbon nanotubes as a reinforcing agent in composites is an area where carbon nanotubes are predicted to be very useful. However, the utilization of carbon nanotubes in these applications has been hindered by the property of generally being unable to reliably produce high-surface-area carbon nanotubes and the performance of dispersing carbon nanotubes in a matrix.

[0018] The present invention provides improved binders, electrolyte separator films, and composites for energy storage and collection devices such as batteries, capacitors, and solar cells comprising high-surface-area carbon nanotubes, methods for their production, and products obtained therefrom. High-surface-area carbon nanotubes are formed by fibrillating the nanotubes produced or purchased. This fibrillation of the nanotubes is caused by a combination of targeted oxidation and shear forces such as those generated by sonication. By fibrillating the trunk aggregates, the nanotubes are liberated, exposing the surface of the nanotubes or a larger number of nanotubes and / or more portions of the nanotube surface to the surrounding environment. ​​​​​​​​​​​​​Thereby, the interaction between the surrounding materials and the exposed surface of the nanotubes can be increased. It is possible.

Brief Description of the Drawings

[0019]

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Modes for Carrying Out the Invention

[0020] In the following description, specific details are provided to give a thorough understanding of the embodiments disclosed herein. For this purpose, they are described as specific amounts, sizes, etc. However, it will be apparent to those skilled in the art that the present disclosure can be practiced without such specific details. In many cases, details regarding such considerations, etc., are omitted as they are not necessary for a complete understanding of the present disclosure and are within the scope of understanding of those skilled in the art.

[0021] Many of the terms used herein will be recognizable to those skilled in the art, but unless otherwise specified, the terms should be construed to adopt the meanings currently accepted by those skilled in the art. It should be understood that this is the case. If the construction of a term can render it meaningless or substantially meaningless, the definition should be adopted from Webster's Dictionary, 3rd Edition, 2009. Definitions and / or interpretations should not be incorporated from other related or unrelated patent specifications, patents or publications.

[0022] The functionalized carbon nanotubes of the present disclosure generally refer to any chemical modification of the above carbon nanotube types. Such modifications can involve the ends, sidewalls or both of the nanotubes. Chemical modifications can include, but are not limited to, covalent bonds, ionic bonds, chemical adsorption, intercalation, surfactant interactions, polymer wrapping, cutting, solvent sorption and combinations thereof. In certain embodiments, the carbon nanotubes can be functionalized before, during and after being partially or fully exfoliated.

[0023] In various embodiments, at least about 50, at least about 100, at least about 250, ​​At least about 500, at least about 700, at least about 1000, at least about 150 0, at least or about 2000, up to about 6000 or up to about 5000 aspect ratio, and from about 0.1 weight percent to about 15 weight percent, preferably from about 0.5 weight percent to about 10 weight percent, more preferably from about 1 weight percent to 5 weight percent, more preferably from about 1 weight percent to 3 weight percent, or from about 0.1 weight percent to 5 weight percent total oxidation level, of a single layer, bilayer or multilayer of carbon nanotubes is disclosed. The oxidation level is defined as the weight of oxygen-containing species covalently bonded to the carbon nanotube. In certain embodiments, the oxidation level can be 0 or at least about 0.01 weight percent up to about 2 weight percent. In other embodiments, the oxidation level can be from at least about 2 weight percent up to about 5 weight percent. The thermogravimetric method for determining the weight percent of oxygen-containing species in the carbon nanotube involves using about 7 - 15 mg of dry oxidized carbon nanotubes and heating at 5°C / min from 100°C to 700°C in a dry nitrogen atmosphere. The weight loss percent from 200°C to 600°C is obtained as the weight loss percent of the oxygen-containing species. The oxygen-containing species can also be specifically quantified using Fourier transform infrared spectroscopy FTIR in the wavelength range 1730 - 1680 cm In certain embodiments, the oxidation level can be 0%. -1 to The carbon nanotubes can have oxygen-containing species including carboxylic acids or derivative carbonyl-containing species. The derivative carbonyl species include phenols, ketones, quaternary amines, amides, esters,

[0024] and the like.​​ It may include acyl halides and monovalent metal salts, etc., and can be changed on the inner and outer surfaces of the tube. It can be changed.

[0025] For example, one or more types of acids are used to oxidize the outer surface of the tube, followed by water washing and shearing, thereby being able to break and / or partially separate the tube. If desired, nanotubes or high-surface-area bundles that are essentially formed without (or zero) oxidation on the inner tube wall may be further oxidized with different oxidizing agents or at different concentrations that are equivalent to those used on the outer layer surface of the tube, resulting in different amounts of - and / or different types of - oxidation on the inner and surface. The as-produced carbon nanotubes are treated with shear force and / or oxidation to at least partially defibrillate the "trunk" of the tightly bundled nanotubes. This treatment exposes more of the individual nanotube surface area to the surrounding environment. In certain embodiments, the high-surface-area nanotubes have a surface area that is at least about 10% larger after treatment than before treatment. In other embodiments, the high-surface-area nanotubes have a surface area that is at least about 20%, at least about 30%, at least about 50%, at least about 75%

[0026] or at least about 100% larger after treatment than before treatment. In certain embodiments, the high-surface-area nanotubes have a surface area that is at least about 2.5 times, at least about 3 times, at least about 5 times, at least about 7 times, at least about 10 times or at least about 20 times larger after treatment than before treatment. The BET surface area of the nanotubes is determined by N according to ASTM D6556-16 In certain embodiments, the high-surface-area nanotubes have a surface area that is at least about 20%, at least about 30%, at least about 50%, at least about 75% or at least about 100% larger after treatment than before treatment. In certain embodiments, the high-surface-area nanotubes have a surface area that is at least about 2.5 times, at least about 3 times, at least about 5 times, at least about 7 times, at least about 10 times or at least about 20 times larger after treatment than before treatment. 5 times, at least about 7 times, at least about 10 times or at least about 20 times larger after treatment than before treatment. It has.

[0027] The BET surface area of the nanotubes is N according to ASTM D6556-162 BET isotherm of can be measured using the line. The BET surface area of the nanotubes here can vary depending on the nanotubes, the treatment method and the type of desired application. Generally, the single- and bilayer nanotubes treated by shear, oxidation or both described herein generally have a BET surface area of at least about 400 m 2 / g, at least about 500 m 2 / g, at least about 550 m 2 / g, at least about 600 m 2 / g, at least about 650 m 2 / g, at least about 700 m 2 / g, at least about 7 50 m 2 / g, at least about 800 m 2 / g, at least about 850 m 2 / g, at least about 900 m 2 / g, at least about 1000 m 2 / g, at least about 1100 m 2 / g, at least at least about 1200 m 2 / g, at least about 1300 m 2 / g, at least about 1400 m 2 / g, at least about 1500 m 2 / g or at least about 1600 m 2 / g and have a BET surface area of up to about 2000 m 2 / g, up to about 2000 m 2 / g, up to about 1900 m 2 / g, up to about 1 800 m 2 / g or up to about 1700 m 2 / g.

[0028] The surface area of the nanotubes includes, but is not limited to, known methods such as BET analysis and gas adsorption techniques such as the adsorption of nitrogen, argon and / or carbon dioxide and is measured using It can be determined. These measurements can be carried out isothermally. In certain embodiments, high surface area nano tubes have a measured surface area that is about 25%, about 40%, about 55%, about 80 %, or about 95% larger after treatment than before treatment. In other embodiments, the high surface area nanotubes have a measured surface area that is about 2 times, about 3 times, about 4 times, about 5 times, about 7 times, about 10 times or about 15 times larger after treatment than before treatment.

[0029] In certain embodiments, the high surface area carbon nanotubes are about 300 m 2 / g, about 500 m 2 / g, about 700 m 2 / g, about 1000 m 2 / g, about 1500 m 2 / g, about 2000 m 2 / g, about 2500 m 2 / g, about 3000 m 2 / g, about 4000 m 2 / g, about 5000 m 2 / g, about 7000 m 2 / g or about 10000 m 2 / g or have a larger surface area. In other embodiments, the high surface area carbon nanotubes are about 500 m 2 / g, about 700 m 2 / g, about 1000 m 2 / g, about 1500 m 2 / g, about 2000 m 2 / g, about 2500 m 2 / g, about 3000 m 2 / g, about 4000 m 2 / g, about 5000 m 2 / g, about 7000 m 2 / g or about 10000 m 2 / g or have a smaller surface area.

[0030] As-prepared carbon nanotubes made using a metal catalyst such as iron, aluminum or cobalt can hold a significant amount of catalyst, on the order of 5 weight percent or more, bound or encapsulated within the structure of the carbon nanotubes. These residual metals can be detrimental in applications such as electronic devices due to accelerated corrosion or can inhibit vulcanization of elastomeric composites. Further, these divalent or multivalent metal ions can bind to carboxylic acid groups on the carbon nanotubes and inhibit liberation and / or dispersion processes. In one embodiment, the oxidized carbon nanotubes have a residual metal concentration of less than about 10,000 parts per million (ppm), less than about 5,000 ppm, less than about 3,000 ppm or less than about 1,000 ppm, or are substantially free of residual metals. The metals can be determined as appropriate using energy dispersive X-ray analysis or thermogravimetric methods. In certain embodiments, the present invention is distinct from that of earlier Bosnyak et al. applications and disclosures. The present invention describes a composition of high surface area carbon nanotubes having a targeted or selective oxidation level and / or content on the outer and / or inner sides of the tube layer. Such promote corrosion or can inhibit vulcanization of elastomeric composites. Further, these divalent or multivalent metal ions can bind to carboxylic acid groups on the carbon nanotubes and inhibit liberation and / or dispersion processes. In one embodiment, the oxidized carbon nanotubes have a residual metal concentration of less than about 10,000 parts per million (ppm), less than about 5,000 ppm, less than about 3,000 ppm or less than about 1,000 ppm, or are substantially free of residual metals. The metals can be determined as appropriate using energy dispersive X-ray analysis or thermogravimetric methods. sulfur treatment during curing. Further, these divalent or multivalent metal ions can bind to carboxylic acid groups on the carbon nanotubes and inhibit liberation and / or dispersion processes. In one embodiment, the oxidized carbon nanotubes have a residual metal concentration of less than about 10,000 parts per million (ppm), less than about 5,000 ppm, less than about 3,000 ppm or less than about 1,000 ppm, or are substantially free of residual metals. The metals can be determined as appropriate using energy dispersive X-ray analysis or thermogravimetric methods. A composition of high surface area carbon nanotubes having a targeted or selective oxidation level and / or content on the outer and / or inner sides of the tube layer is described. Such carbon nanotubes can hold a significant amount of catalyst, on the order of 5 weight percent or more, bound or encapsulated within the structure of the carbon nanotubes. These residual metals can be detrimental in applications such as electronic devices due to In one embodiment, the oxidized carbon nanotubes have a residual metal concentration of less than about 10,000 parts per million (ppm), less than about 5,000 ppm, less than about 3,000 ppm or less than about 1,000 ppm, or are substantially free of residual metals. The metals can be determined as appropriate using energy dispersive X-ray analysis or thermogravimetric methods. Bosnyak et al. have made discrete carbon nanotubes through the careful and substantially simultaneous use of oxidation and shear forces in various patent applications (e.g., U.S. Patent Application Publication No. 2012-0183770 and U.S. Patent Application Publication No. 2011-0294013), thereby oxidizing both the inner and outer surfaces of the nanotubes to generally comparable oxidation levels on the inner and outer surfaces, resulting in individual or discrete tubes. In many embodiments, the present invention is distinct from that of earlier Bosnyak et al. applications and disclosures. The present invention describes a composition of high surface area carbon nanotubes having a targeted or selective oxidation level and / or content on the outer and / or inner sides of the tube layer. Such

[0031] carbon nanotubes can hold a significant amount of catalyst, on the order of 5 weight percent or more, bound or encapsulated within the structure of the carbon nanotubes. These residual metals can be detrimental in applications such as electronic devices due to oxidation and shear forces in various patent applications (e.g., U.S. Patent Application Publication No. 2012-0183770 and U.S. Patent Application Publication No. 2011-0294013), thereby oxidizing both the inner and outer surfaces of the nanotubes to generally comparable oxidation levels on the inner and outer surfaces, resulting in individual or discrete tubes. In many embodiments, the present invention is distinct from that of earlier Bosnyak et al. applications and disclosures. The present invention describes a composition of high surface area carbon nanotubes having a targeted or selective oxidation level and / or content on the outer and / or inner sides of the tube layer. Such carbon nanotubes can hold a significant amount of catalyst, on the order of 5 weight percent or more, bound or encapsulated within the structure of the carbon nanotubes. These residual metals can be detrimental in applications such as electronic devices due to oxidation and shear forces in various patent applications (e.g., U.S. Patent Application Publication No. 2012-0183770 and U.S. Patent Application Publication No. 2011-0294013), thereby oxidizing both the inner and outer surfaces of the nanotubes to generally comparable oxidation levels on the inner and outer surfaces, resulting in individual or discrete tubes.

[0032] In many embodiments, the present invention is distinct from that of earlier Bosnyak et al. applications and disclosures. The present invention describes a composition of high surface area carbon nanotubes having a targeted or selective oxidation level and / or content on the outer and / or inner sides of the tube layer. Such oxidation levels and / or contents. oxidation levels and / or contents. The novel carbon nanotubes have little or no oxidation on the inner surface of the tube or may have different amounts and / or types of oxidation between the inner and outer surfaces of the tube. These new nanotubes are for energy storage devices for improving mechanical, electrical, and thermal properties useful in a number of applications including binder materials, electrolyte materials, separator film materials, and / or compositions.

[0033] One embodiment of the present invention is a composition comprising a plurality of high surface area carbon nanotubes, the high surface area carbon nanotubes having inner and outer surfaces, each surface having an inner surface oxidation species content and an outer surface oxidation species content, the inner surface oxidation species content being at least 20%, preferably about 100% different from the outer surface oxidation species content, and the inner surface oxidation species content being less than the outer surface oxidation species content as well.

[0034] The inner surface oxidation species content is at most 3 weight percent based on the weight of the carbon nanotubes preferably about 0.01 to about 3 weight percent based on the weight of the carbon nanotubes, more preferably about 0.01 to about 2, most preferably about 0.01 to about 1. Particularly preferred inner surface oxidation species content is from zero to about 0.01 weight percent based on the weight of the carbon nanotubes

[0035] The outer surface oxidation species content is about 1 to about 6 weight percent based on the weight of the carbon nanotubes preferably about 1 to about 4, more preferably about 1 to about 2 weight percent based on the weight of the carbon nanotubes. This is determined by comparing the outer oxidation species content of a given plurality of nanotubes to the total weight of those plurality of nanotubes.

[0036] ​​​ The total of the inner and outer surface oxidation species content may be about 1 to about 9 weight percent based on the weight of the carbon nanotubes.

[0037] Another embodiment of the present invention is a composition comprising a plurality of high surface area carbon nanotubes wherein the high surface area carbon nanotubes have inner and outer surfaces, each surface having an inner surface oxidation species content and an outer surface oxidation species content, the inner surface oxidation species content being about 0.01 to less than about 1 percent based on the weight of the carbon nanotubes, and the outer surface oxidation species content being more than about 1 to about 3 percent based on the weight of the carbon nanotubes.

[0038] In one embodiment, the present invention is a composition comprising a plurality of high surface area carbon nanotubes wherein at least a portion of the high surface area carbon nanotubes are open-ended, and the composition comprises a binder material, an electrolyte material, a separator film or a composite material for an energy storage and collection device.

[0039] In other embodiments, the composition comprises a plurality of high surface area carbon nanotubes wherein at least a portion of the carbon nanotubes are open-ended and ion-conductive. The composition may further comprise at least one polymer. The polymer includes vinyl polymers and preferably functionalized poly(styrene-butadiene) copolymers such as poly(styrene-butadiene), partially or fully hydrogenated poly(styrene-butadiene), carboxylated poly(styrene-butadiene), poly(styrene-isoprene), poly(methacrylic acid), poly(acrylic acid), poly(vinyl alcohol), and poly(vinyl acetate) and the like. nil), a fluorinated polymer, preferably poly(vinylidene difluoride) and poly(vinylidene difluoride) copolymer, a conductive polymer, preferably poly(acetylene), poly(phenylene), poly(pyrrole) and poly(acrylonitrile), a polymer derived from natural sources, preferably alginate, polysaccharide, lignosulfonate and cellulose-based materials, a polyether, a polyolefin, a polyester, a polyurethane, a polyamide, a homopolymer, graft, block or random copolymer or terpolymer, and a copolymer and mixture thereof. Other polymers that can be employed include, for example, alkali metal salts or alkaline earth metal salts, and in particular, carboxymethyl cellulose or its salts such as sodium salts, cellulose-based polymers, hydrophilic polymers with a water solubility greater than 1% w / v, alkali metal salts or alkaline earth metal salts, and in particular, polystyrene sulfonic acid or its salts such as sodium salts. Hydrophilic polymers may be suitable in certain embodiments. fluoride), a conductive polymer, preferably poly(acetylene), poly(phenylene), poly(pyrrole) and poly(acrylonitrile), a polymer derived from natural sources, preferably alginate, polysaccharide, lignosulfonate and cellulose-based materials, a polyether, a polyolefin, a polyester, a polyurethane, a polyamide, a homopolymer, graft, block or random copolymer or terpolymer, and a copolymer and mixture thereof. Other polymers that can be employed include, for example, alkali metal salts or alkaline earth metal salts, and in particular, carboxymethyl cellulose or its salts such as sodium salts, cellulose-based polymers, hydrophilic polymers with a water solubility greater than 1% w / v, alkali metal salts or alkaline earth metal salts, and in particular, polystyrene sulfonic acid or its salts such as sodium salts. Hydrophilic polymers may be suitable in certain embodiments. (phenylene), poly(pyrrole) and poly(acrylonitrile), a polymer derived from natural sources, preferably alginate, polysaccharide, lignosulfonate and cellulose-based materials, a polyether, a polyolefin, a polyester, a polyurethane, a polyamide, a homopolymer, graft, block or random copolymer or terpolymer, and a copolymer and mixture thereof. Other polymers that can be employed include, for example, alkali metal salts or alkaline earth metal salts, and in particular, carboxymethyl cellulose or its salts such as sodium salts, cellulose-based polymers, hydrophilic polymers with a water solubility greater than 1% w / v, alkali metal salts or alkaline earth metal salts, and in particular, polystyrene sulfonic acid or its salts such as sodium salts. Hydrophilic polymers may be suitable in certain embodiments. (acrylonitrile), a polymer derived from natural sources, preferably alginate, polysaccharide, lignosulfonate and cellulose-based materials, a polyether, a polyolefin, a polyester, a polyurethane, a polyamide, a homopolymer, graft, block or random copolymer or terpolymer, and a copolymer and mixture thereof. Other polymers that can be employed include, for example, alkali metal salts or alkaline earth metal salts, and in particular, carboxymethyl cellulose or its salts such as sodium salts, cellulose-based polymers, hydrophilic polymers with a water solubility greater than 1% w / v, alkali metal salts or alkaline earth metal salts, and in particular, polystyrene sulfonic acid or its salts such as sodium salts. Hydrophilic polymers may be suitable in certain embodiments. materials, a polyether, a polyolefin, a polyester, a polyurethane, a polyamide, a homopolymer, graft, block or random copolymer or terpolymer, and a copolymer and mixture thereof. Other polymers that can be employed include, for example, alkali metal salts or alkaline earth metal salts, and in particular, carboxymethyl cellulose or its salts such as sodium salts, cellulose-based polymers, hydrophilic polymers with a water solubility greater than 1% w / v, alkali metal salts or alkaline earth metal salts, and in particular, polystyrene sulfonic acid or its salts such as sodium salts. Hydrophilic polymers may be suitable in certain embodiments. a polyamide, a homopolymer, graft, block or random copolymer or terpolymer, and a copolymer and mixture thereof. Other polymers that can be employed include, for example, alkali metal salts or alkaline earth metal salts, and in particular, carboxymethyl cellulose or its salts such as sodium salts, cellulose-based polymers, hydrophilic polymers with a water solubility greater than 1% w / v, alkali metal salts or alkaline earth metal salts, and in particular, polystyrene sulfonic acid or its salts such as sodium salts. Hydrophilic polymers may be suitable in certain embodiments. selected from the group consisting of a copolymer and mixture thereof. Other polymers that can be employed include, for example, alkali metal salts or alkaline earth metal salts, and in particular, carboxymethyl cellulose or its salts such as sodium salts, cellulose-based polymers, hydrophilic polymers with a water solubility greater than 1% w / v, alkali metal salts or alkaline earth metal salts, and in particular, polystyrene sulfonic acid or its salts such as sodium salts. Hydrophilic polymers may be suitable in certain embodiments. employed include, for example, alkali metal salts or alkaline earth metal salts, and in particular, carboxymethyl cellulose or its salts such as sodium salts, cellulose-based polymers, hydrophilic polymers with a water solubility greater than 1% w / v, alkali metal salts or alkaline earth metal salts, and in particular, polystyrene sulfonic acid or its salts such as sodium salts. Hydrophilic polymers may be suitable in certain embodiments. such as sodium salts, cellulose-based polymers, hydrophilic polymers with a water solubility greater than 1% w / v, alkali metal salts or alkaline earth metal salts, and in particular, polystyrene sulfonic acid or its salts such as sodium salts. Hydrophilic polymers may be suitable in certain embodiments. greater than 1% w / v, alkali metal salts or alkaline earth metal salts, and in particular, polystyrene sulfonic acid or its salts such as sodium salts. Hydrophilic polymers may be suitable in certain embodiments. salts such as sodium salts. Hydrophilic polymers may be suitable in certain embodiments. Hydrophilic polymers may be suitable in certain embodiments.

[0040] In still other embodiments of the present invention, the plurality of high surface area carbon nanotubes are further functionalized, preferably with a molecule having a mass greater than 50 g / mol of a functional group, more preferably with a functional group having a carboxylate, hydroxyl, ester, ether or amide moiety, or a mixture thereof. In still other embodiments of the present invention, the plurality of high surface area carbon nanotubes are further functionalized, preferably with a molecule having a mass greater than 50 g / mol of a functional group, more preferably with a functional group having a carboxylate, hydroxyl, ester, ether or amide moiety, or a mixture thereof. In still other embodiments of the present invention, the plurality of high surface area carbon nanotubes are further functionalized, preferably with a molecule having a mass greater than 50 g / mol of a functional group, more preferably with a functional group having a carboxylate, hydroxyl, ester, ether or amide moiety, or a mixture thereof. or a mixture thereof.

[0041] A further embodiment of the present invention comprising a plurality of high surface area carbon nanotubes further comprises at least one dispersing aid. A further embodiment of the present invention comprising a plurality of high surface area carbon nanotubes further comprises at least one dispersing aid.

[0042] In still further embodiments of the present invention, the plurality of carbon nanotubes are from the periodic table of the elements It further comprises an additional inorganic structure comprising elements of Groups 2 to 14. These inorganic structures can be in the form of particles, layers or continuous media. Suitable inorganic structures include, but are not limited to, electrically conductive inorganic structures such as silver or copper, magnetic inorganic structures such as, but not limited to, iron oxide, and low melting point inorganic structures such as, but not limited to, indium-tin alloys, including .

[0043] Another embodiment of the invention comprises a plurality of carbons, and the composition has a flexural strength that is at least about 10 percent higher than that of a comparative composition made without a plurality of high surface area carbon nanotubes.

[0044] Yet another embodiment of the invention is a binder, electrolyte or separator film composition comprising a plurality of high surface area carbon nanotubes having a portion of an open-ended carbon nanotube with ion conductivity. In certain embodiments, the composition further comprises other carbon structures. The other carbon structures can comprise components selected from the group consisting of carbon black, graphite, graphene, graphene oxide, fullerenes, and mixtures thereof. Preferably, the graphene or graphene oxide has at least a portion of the high surface area carbon nanotubes dispersed between platelets of the graphene or graphene oxide.

[0045] Still further embodiments of the invention are compositions comprising a plurality of high surface area carbon nanotubes wherein the binder material has an impedance of about 1 billion (1×10 9 ) ohm -m or less and the electrolyte material has a charge transfer resistance of about 10 million (1×10 7 ) ohm-m or less.​​ .

[0046] Other embodiments of this invention include an electrolyte comprising a plurality of high surface area carbon nanotubes or a separator film composition, with the carbon nanotubes being oriented. The orientation can be achieved by manufacturing techniques such as coating, micro-layer, micro-layer with vertical film orientation, film, molding, extrusion, or spinning processes. The orientation can also be made through post-manufacturing methods such as flaring, uniaxial stretching, biaxial stretching and thermoforming. The orientation can also be introduced by 3-D printing technology. The oriented carbon nanotubes of this invention can be extracted from oriented fibers or sheets containing the oriented carbon nanotubes by, but not limited to, the use of a liquid solvent that dissolves the polymer matrix or an auxiliary agent that dissolves the inorganic matrix, or the removal of the matrix material such as the degradation of the matrix by chemical means.

[0047] A further embodiment of this invention is a composition comprising a plurality of high surface area carbon nanotubes, wherein the tube portion with open ends can comprise an electrolyte. For an electrolyte comprising a polymer, the polymer preferably has a polymer molecular weight of less than 10,000 Daltons, by which the polymer can enter the tube. The electrolyte can contain a liquid.

[0048] An additional embodiment of this invention comprises a composition containing a plurality of high surface area carbon nanotubes, wherein at least a portion of the high surface area carbon nanotubes have open ends. The disclosed high surface area nanotubes include bundles with increased length and diameter, with at least about 5% of the nanotubes having a portion of their outer surface exposed to the ambient environment. Such high surface area nanotubes The nanotubes include defibrillated bundles. The bundles can have an average length of at least about 400 nm, about 800 nm, about 1 μm, about 10 μm, about 50 μm, about 100 μm, about 500 μm, about 1 000 μm, about 1250 μm, about 1400 μm, about 1500 μm, about 1600 μm, about 1 800 μm, about 2000 μm, about 3000 μm or about 5000 μm. Such bundles can have a diameter of about 1 μm, about 3 μm, about 5 μm, about 7 μm, about 8 μm, about 9 μm , about 10 μm or about 12 μm. In a preferred embodiment, the high surface area carbon nanotubes are bundles of single-walled nanotubes with an aspect ratio of at least about 50, at least about 100, at least about 300, at least about 500, at least about 700, at least about 900, at least about 1000, at least about 1200, at least about 1500 or at least about 2000.

[0049] In statistics, a bimodal distribution is a continuous probability distribution with two different modes. These appear as distinct peaks (maxima) in the probability density function. More generally, a multimodal distribution is a continuous probability distribution with two or more modes. High surface area carbon nanotubes can have a unimodal, bimodal or multimodal distribution of diameters and / or lengths for both the individual nanotubes that make up the high surface area bundles, and for the high surface area bundles themselves. These compositions are useful in the binders and electrolytes of the present invention.

[0050] In yet other embodiments, the present invention is an electrode paste for a lead-acid battery, preferably an anode paste, wherein the paste has a particle size of at least about 1 μm, about 5 μm, about 10 μm, about 50 μ m, about 100 μm, about 500 μm, about 1000 μm, about 1250 μm, about 1400 μm or has a high surface area carbon nano tube with an average length and / or high surface area bundle length of about 1500 μm. Embodiments further comprise a dispersion aid such as, but not limited to, polyvinyl alcohol, water, lead oxide and / or sulfuric acid. Preferably, the carbon nanotubes , the dispersion aid and water form a dispersion, and the dispersion contacts lead oxide and then sulfuric acid to form an electrode paste. Other suitable solvents include, for example, renewable solvents such as silene (dihydrolevoglucosenone), or solvents miscible with, for example, deionized water.

[0051] Another embodiment of the present invention is a composition consisting of high surface area carbon nanotubes, where the high surface area carbon nanotubes are coated with water, oil, wax, nitric acid or sulfuric acid. This coating reduces and / or prevents the formation of van der Waals forces, electrical forces or electrostatic forces between the carbon nanotubes, thereby preventing the high surface area carbon nanotubes from aggregating into hard bundles and reducing the exposed surface area of the carbon nanotubes CNT.

[0052] In certain embodiments, the composition comprises about 99 wt% of the composite material and about 0.025 wt% of a small amount of carbon nanotubes or about 1 wt% of a small amount of carbon nanotubes. In other embodiments, the composition comprises a greater amount of CNTs such as about 2 wt%, about 3 wt%, about 5 wt%, about 7 wt%, about 10 wt% of CNTs, about 15 wt% of CNTs or about 25 wt% of CNTs. It is possible. By removing water or other coating materials from the composition by drying, the formation of anhydride bonds, van der Waals bonds, electrostatic bonds or other bonds between carbon nanotubes can be brought about. The formation of these bonds can lead to re-aggregation and arrest of the CNTs to result in high surface area carbon nanotubes. Surprisingly, the use of surfactants may not be required for the formation of the disclosed composition, so there is little or no surfactant in the composition. This reduces the connectivity or cross-linking of the matrix, or uses surfactants that can inhibit the desired mechanical properties of the matrix,

[0053] The high surface area carbon nanotubes of any of the above-described composition embodiments preferably comprise a plurality of open-ended tubes, and more preferably, the plurality of high surface area carbon nanotubes comprise a plurality of open-ended tubes. The high surface area carbon nanotubes of any of the above-described composition embodiments are particularly

[0054] suitable, and the difference in oxidation between the inner and outer surfaces is at least about 0.2 weight percent.

[0055] The compositions described herein can be used as ion transporters. Various

[0056] species or classifications of compounds / drugs / chemical substances that exhibit this ion transport effect, including ionic compounds, some non-ionic compounds, It can also be used as a component in or as a sensor.

[0057] The compositions disclosed herein can also be used as components in drug delivery or controlled release formulations or as drug delivery or controlled release formulations.

[0058] The compositions disclosed herein can be used as a structural scaffold for catalysts. As contemplated, catalysts, enzymes, proteins, peptides or other small or large molecules can attach to the outside of the disclosed carbon nanotubes. The scaffold of the disclosed nanotubes can be useful for positioning catalysts that attach within a matrix, positioning multiple catalytic proteins or molecules relative to each other.

[0059] Magnetic particles can bind or attach to the carbon nanotubes disclosed herein. The magnetic particles that are bound can be used to affect the orientation, location or position of the carbon nanotubes to which the magnetic particles attach. By applying a magnetic field to carbon nanotubes bound to magnetic particles, the carbon nanotubes can be made movable to a specific location. The magnetic field can be generated by a natural magnet or an electromagnetic device including at least an MRI, fMRI or pulsed electromagnetic field generator. Furthermore, a single magnetic field generator may be utilized or multiple magnetic field generators may be used. In certain embodiments, an array of EMF generators can be used to move CNTs bound to magnetic particles and / or to vibrate, rotate, oscillate such CNTs, or to direct CNTs from one particular location to another.

[0060] ​​Two or more species of magnetic particles can be attached to a single carbon nanotube. In certain embodiments the other species of magnetic particles behave differently in the same magnetic field, thus providing increased diverse possibilities to affect the behavior of the carbon nanotubes to which the two or more species of magnetic particles are attached.

[0061] The magnetic particles attached to the carbon nanotubes may comprise about 0.001 weight percent relative to the carbon nanotube weight, or about 0. 01 weight percent relative to the carbon nanotube weight, or about 0.1 weight percent relative to the carbon nanotube weight, or about 1 weight percent relative to the carbon nanotube weight, or about 10 weight percent relative to the carbon nanotube weight, or about 50 weight percent relative to the carbon nanotube weight, or about 90 weight percent relative to the carbon nanotube weight.

[0062] The carbon nanotubes attached to the magnetic particles may further contain payload molecules as described above, or may have peptides, small molecules, nucleic acids or other agents, or molecules attached to their outer surface. These combinations can enable the nanotubes to be directed to specific locations where the payload molecules of the attached molecules, together with the attached payload or substantially non-magnetically attached molecules, are desired. In this way, the targeted molecules can be delivered to specific locations using a controlled magnetic field.

[0063] In certain embodiments, the magnetic field is applied to the carbon nanotubes, or to a network of carbon It can be used to bend or deform a workpiece, matrix or scaffold. Nanoch When the open-end payload that transports the ube is bent or deformed as described, this increases the rate at which the inner payload molecules flow into the surrounding environment, thereby enabling a controlled, targeted and / or timed slow release of the payload molecules. Similarly, the described bending of the carbon nanotube network increases the rate at which payload molecules are loaded inside the open-ended nanotubes, or enables molecules to be enclosed within the inner space of the nanotube network itself while remaining outside any particular nanotube. It can be enclosed within the inner space of the nanotube network itself while remaining outside any particular nanotube.

[0064] Batteries comprising the compositions disclosed herein are also useful. Such batteries include lithium, nickel-cadmium, or lead-acid types.

[0065] Formulations comprising the compositions disclosed herein may further comprise molecules having epoxy moieties, urethane moieties, ether moieties, amide moieties, alkane moieties or vinyl moieties. The molecules can be in a rigid, elastomeric or fluid state at room temperature and such formulations may be in the form of a dispersion. The formulations may also include nanoplate structures. They may also include nanoplate structures.

[0066] The composition may further comprise at least one hydrophobic material in contact with at least one inner surface and may further comprise at least one hydrophobic material in contact with at least one inner surface.

[0067] The present invention relates to a composition comprising a plurality of high surface area carbon nanotubes and a plasticizer, the high surface area carbon nanotubes being functionalized by oxygen species at their outermost surface and the high surface area carbon nanotubes having inner and outer surfaces, each surface being an inner surface and and an outer surface oxidation species content, wherein the inner surface oxidation species content is less than about 0.01 to about 1 percent based on the weight of the carbon nanotubes, and the outer surface oxidation species content is more than about 1 to about 3 percent based on the weight of the carbon nanotubes. The oxygen species may comprise carboxylic acids, phenols, or combinations thereof.

[0068] The composition may further comprise a plasticizer selected from the group consisting of dicarboxylic acid / tricarboxylic acid esters, trimellitates, adipates, sebacates, maleates, glycols and polyethers, polymeric plasticizers, plasticizers from biological sources, and mixtures thereof. The composition may comprise a plasticizer comprising a process oil selected from the group consisting of naphthenic oils, paraffinic oils, parabens, aromatic oils, vegetable oils, seed oils, and mixtures thereof.

[0069] The composition may further comprise a plasticizer selected from the group of water-insoluble solvents consisting of, but not limited to, xylene, pentane, methyl ethyl ketone, hexane, heptane, ethyl acetate, ether, dichloromethane, dichloroethane, cyclohexane, chloroform, carbon tetrachloride, butyl butanol acetate, benzene, cresol, or mixtures thereof.

[0070] In yet other embodiments, the composition further comprises an inorganic filler selected from the group consisting of silica, nanoclay, carbon black, graphene, glass fibers, and mixtures thereof.

[0071] In other embodiments, the composition is in the form of free-flowing particles.

[0072] In other embodiments, the composition comprises a plurality of high surface area carbon nanotubes and a plasticizer.​​​​​​​​​​​ , The high surface area carbon nanotubes contain about 10 wt% to about 90 wt%, preferably suitably 10 wt% to 40 wt%, and most preferably 10 to 20 wt%.

[0073] Another embodiment is a composition of high surface area carbon nanotubes in a plasticizer further mixed with at least one rubber. The rubber can be natural or synthetic rubber, preferably , natural rubber, polyisobutylene, polybutadiene, and styrene-butadiene rubber, butyl rubber, polyisoprene, styrene-isoprene rubber, styrene-isoprene rubber, ethylene , propylene diene rubber, silicone, polyurethane, polyester-polyether, hydrogenated and non-hydrogenated nitrile rubber, halogen-modified elastomer, fluoro-elastomer and combinations thereof.

[0074] Another embodiment is a composition of high surface area carbon nanotubes in a plasticizer further mixed with at least one thermoplastic polymer or at least one thermoplastic elastomer. The thermoplastics can be selected from, but not limited to, acrylic, polyamide, polyethylene, poly styrene, polycarbonate, methacryl, phenol, polypropylene, polyolefin such as plastomers and elastomers, EPDM, and copolymers of ethylene and , propylene, and functional monomers.

[0075] Still another embodiment is a composition of high surface area carbon nanotubes in a plasticizer further mixed with at least one thermosetting polymer, preferably epoxy or polyurethane. It is. Thermosetting polymers include, but are not limited to, epoxy resins, polyurethane resins or unsaturated polyester resins.

[0076] General process for generating high - surface - area carbon nanotubes with targeted oxidation Disclosed are embodiments of compositions comprising high surface area carbon nanotubes for improved performance of energy storage devices, including, but not limited to, lithium ion battery technology. In certain embodiments of the disclosure, single layer pouch cells in silicon comprising anodes are treated according to a process in which carbon nanotubes such as those produced by OCSiAl are disclosed to form high surface area single layer nanotubes, showing a significant improvement in cycle life. Other manufacturers of nanotubes suitable for use in the applications described herein include, for example, South west Nanotechnologies, Zeonano or Zeon, CN ano Technology, Nanocyl, ACS Materials, Ame rican Elements, Chasm Technologies, Haoxin Technology, Hanwha Nanotech Group, Hyperi on Catalysis, KH Chemical, Klean Commoditi es, LG Chem, Nano-C, NTP Shenzhen Nanotech Port, Nikkiso, Raymor, Saratoga Energy, SK G lobal, Solid Carbon Products, Sigma Aldric h, Sun Nanotech, Thomas Swan, TimesNano, To kyo Chemical Industry, XF Nano, and including OCSiAl among others.

[0077] The following data shows details of both the oxidation treatment of the tubes and subsequent shear or disruptive force treatment. Samples may be subjected to intense disruptive forces generated by shear (turbulent flow) and / or cavitation by a processing device capable of generating an energy density of about 10 to 10 6 to 8 Joules / m 3 of a relatively high energy density. Suitable devices include, but are not limited to, ultrasonic processors, cavitators, mechanical homogenizers, pressure homogenizers, and microfluidizers (Table 3). One such homogenizer is shown in U.S. Patent No. 756953, the disclosure of which is incorporated herein by reference. Further shear devices include, but are not limited to, HAAKE (trademark) mixers, Brabender mixers, Omni mixers, Silverson mixers, Gaullin homogenizers, and / or twin screw extruders. Bundles of carbon nanotubes, upon shear treatment, are released, thereby exposing more surfaces and / or more portions of the nanotube surfaces to the surrounding environment. Typically, based on a given starting amount of as-received and as-fabricated entangled carbon nanotubes, a plurality of high surface area carbon nanotubes will preferably be produced by this process, at least about 60%, more preferably at least about 75%, most preferably at least about 95%, and on the order of 100% of the tubes on the low side, generally the tightly bundled large number of tubes on the low side, and the surfaces of the substantially non-usable nanotubes so tightly bundled.

[0078] Example 1 - Oxidation of Tuball™ (OCSiAl) ​​​​​​​​​​​​​​​Heat 35 grams of nitric acid (>64%) to 95 °C. Add 15 grams of as-received single-walled carbon nanotubes (Tuball (trademark)) to the acid. The as-received nanotubes have the form of tightly bundled tree trunks. The mixture of acid and carbon nanotubes is mixed while maintaining the solution at about 95 degrees for 5 hours and is labeled "oSWCNT82-2". At the end of the reaction period, the oSWCNT82-2 is filtered to remove the acid and washed with reverse osmosis (RO) water to a pH of 3 - 4. The resulting CNTs were oxidized to about 3.6% and contained about 4.4% metal residue. The deformations in this process were also carried out using slightly different parameters as shown in Table 1 below. Samples oxidized by MAO treatment: For example, 35 g of HNO (65%) / 15 g of Tuball (trademark), oxidation at 95 °C. 23.33 g of HNO (65%) + 10.01 g of CNT. T = 95 °C, large initial plume of NO

[0079] when adding CNT. 3 3 X

Table 1

[0080] Sample 82 - 2 3 34.98 g of HNO

Table 2

[0081] Sample 82 - 3 23.3 g of HNO 3 , 10 g of Tuball™ CNT. Oxidation for 5 hours = 2. 5% Ox, 9.95% residue, 20.2% solids. Recover 31 g at solids @ 20.2% .

[0082] Example 2 - Shearing treatment of oxidized and unoxidized OCSiAl tubes

[0083] Example 2A - Shearing treatment of oxidized OCSiAl tubes Sample volume ~1200 mL. Use a 1.5 L stainless steel container for rotor / stator (R / S) operation . Oxidation of OCSiAl ~0.15% OCSiAl oxidation source: 82 - final product (pH 3.61, 27.1% solids) 1200 g × 0.15% = 1.8 g dry equivalent = 6.64 g wet cake. Use 6.6 5 g of wet cake. Check the viscosity through the rotor - stator R / S as shown below.

Table 2 - 1

Table 2 - 2

[0084] The optical microscope measurement shown in Figure 1 shows the progression of the rotor through 8 cycles of shear on the wet cake with a high - shear rate mixer . The R / S performs an initial breakdown of the bundle, which is greatly facilitated by passing through the shear device. The experimental results described throughout are those described in Table 3, as well as those for HAAKE™ mixers, Brabender mixers , Omni mixers, Silverson mixers, Gaullin homogenizers, twin - screw extruders, Notzch Omcga® Economic Dispersio It is considered to be obtainable using a shear device including a nionizer and / or a Sonolator by Sonic Corp.

Table 3

[0085] Example 2B - Shearing treatment of unmodified OCSiAl tubes 600 mL of solids @ 0.4% = 2.4 g of OCSiAl. OCSiAl source: Single-walled carbon nanotubes of Tuball (trademark). Batch number 01 RW01.N1.257, Manufacturing date: December 20, 2016.

Table 3-1

Table 3-2

[0086] Example 2C - Oxidized OCSiAl / MA14 by a shearing device MA14 / oxidized OCSiAl at a ratio of 80 / 20 was prepared. This was performed to collect wet cakes of both of these components and pass them through a rotor / stator, followed by a shear treatment to check whether the initial-stage product could be generated. Thus, oxidized O CSiAl is being decomposed while being converted to o-CNT to Molecular Rebar (registered trademark) to further improve the performance of the lithium-ion battery. . 600 mL sample size, 1.5% MR. MA-14 (solids 12.95%) of Molecular Rebar (registered trademark ) source. Oxidized OCSiAl (“82-final product”, solids 27.1%) 600 × 0.015 = 9 g / 0.1295 = 69.498 g of MA14. 0.8 g of MA-14 / 0.02 g of OCSiAl oxide = 9 g of MA-14 / 0.22 5 g of OCSiAl oxide. 0.225 g of OCSiAl oxide = 0.225 / 0.271 = 0.83 g of 82 - final product.

Table 3 - 3

Table 3 - 4

[0087] Example 3 - Performance in a Li - ion battery pouch cell Oxidized and unoxidized OCSiAl cells are formed in a Li - ion battery single - layer pouch cell - The following are the cell details: NCM523 cathode / / anode Details of the anode: 20% of SiOx + 71% of graphite + 1% of CMC + 1.5% of SBR + 1% of C65 + % of XP shown in Figure 2. Loading: ~10 mg / cm 2 Cathode loading: 4.2 mAh / cm 2 Separator: Glass fiber - Whatmann GF / F Housing: 40 mAh single - layer pouch

[0088] Figure 2 shows a comparison of the effects of oxidation and treatment (shearing, sonication, etc.) on a control versus an OCSiAl Tuball (trademark) Batt product (PVP dispersion). The control (without carbon nanotubes) shows a very low cycle life. The end of cycle life in the industry

[0089] is generally considered to be the point where the capacity has weakened to less than 80% of its original capacity, i.e., the cell can now be charged to only 80% of its initial capacity and , it no longer accepts further charging. There are many reasons for this, but in the case of a silicon-based anode it does not, and the main cause is the loss of electrical connectivity due to cracking of silicon particles that swell in response to charging (lithium is loaded from the cathode) and discharging (Li moves back to the cathode). When they swell, they press graphite particles closer to each other but they do not move back as they deswell, resulting in electrically separated gaps and particles here.

[0090] Passing OCSiAl through a shearing treatment clearly improves the cycle life compared to untreated OCSiAl. Further improvement is achieved by oxidation and shearing. This is due to fibrillation and an increase in surface area that can expand the above mentioned gaps. Due to fibrillation, there are more connected particles than in the non-fibrillated state.

[0091] Figure 3 shows optical microscope measurements (all images are at approximately the same magnification). The central electron micrograph shows the "as-received" dry powder of OCSiAl. It is a very small amount of fibrillation and low surface area ribbons, i.e., a trunk-type structure. In this structure most of the tube surface area is not exposed as it is protected by the surrounding tubes. The upper left image shows the effect of passing a dilute solution in water (about 0.15%) through a rotor / stator at 9900 rpm for 10 minutes. Clearly this treatment has some effect on the decomposition of the ribbons and causes a certain level of fibrillation, increasing the surface area (SA).

[0092] The lower left image in Figure 3 shows the effect of the above material through a shearing treatment, with further fibrillation Increasing the fibrillation increases the exposed surface area. The upper right shows OCSiAl oxidized through a shearing treatment, which also results in fibrillation and an increase in surface area as a result. Oxidation introduces functionality to the material and significantly reduces the amount of residual metal contaminants. The lower right shows the effect of adding a surfactant to the oxidized and sheared material followed by sonication. Sonication resulted in further fibrillation and an increase in surface area. The electron micrographs of FIGS. 4A and 4B show a side-by-side comparison of oxidized and sheared OCSiAl and unoxidized OCSiAl. FIG. 4A shows a magnification of 2500x, while FIG. 4B shows a magnification of

[0093] 25000x. At both levels of magnification, the oxidized material shows significantly more fibrillation compared to the unoxidized and sheared material. FIG. 5 shows a comparison between a PPS (polystyrene sulfonic acid) dispersion of oxidized OCSiAl and dry powder of OCSiAl. FIG. 6 shows that in one example, it is possible to defibrillate a ribbon into a single tube.

[0094] The electron micrograph of FIG. 7 shows oxidized carbon nanotubes and O-OCSiAl that were mixed and subjected to a shearing treatment together to form a close Molecular Rebar® (MR ) mixture. This micrograph shows that the MR of the "tree trunk" Ox-OCSiAl is long enough to extend along the length of the SiOx particles and is long enough to extend into an overly large gap for crosslinking of the MR, while at the same time the MR forms a coating on the SiOx particles.

[0095]

[0096] ​​​​​​​, shows a synergistic effect that interacts closely with carbon black. Figure 7 shows the length of the SiOx particles shows the trunk of the tree covering the whole. Such a length can easily spread into the gap between SiOx and graphite. MR particles may be too short to achieve this, but as shown in Figure 7, the MR particles cover the surface of SiOx in a "cage type" structure . The oxidized OCSiAl structure can have an electroactive material, for example, Li attached to a functional group . The electroactive material includes, but is not limited to, graphite, lithium cobalt oxide , lithium iron phosphate and / or lithium manganese oxide.

[0097] Example 4 - Electrical property test: The following Tables 4 and 5 show a summary of the readings collected using a parallel plate apparatus.

Table 4

Table 5

[0098] Example 5 - Measurement of BET surface area The BET surface area is measured using the N 2 BET isotherm according to ASTM D6556-16 and the results are given below.

Table 6

[0099] Example 6 - SWCNT of high - purity OCSiAl Tuball through a shearing device The SWCNT of high-purity OCSiAl was measured by TGA analysis and received as-received low purity OC with an oxidation level of 0.6% and a residue (metallic impurities) of 17.7% ​It had an oxidation level of 1.3% and a residue of 0.6% compared to SiAl SWCNTs. High A 2.8 g sample of high-purity OCSiAl SWCNTs was diluted to a total of 650 g with deionized water (solid content 0.43%) and treated for 10 minutes using a rotor / stator. Then, this material was subjected to a shear force of 2000 psi for a single pass through the apparatus. The pressure was increased to 8 000 psi and passed through the shear device 8 more times. Optical images after rotor / stator treatment of the sheared material are shown in Figure 8 showing high-purity OCSiAl SWCNTs before shear, and Figure 9 showing high-purity OCSiAl SWCNTs after wide-area shear. Figures 8 and 9 are both at a magnification of 112.5 times. 8 and 9 are both at a magnification of 112.5 times. 8 and 9 are both at a magnification of 112.5 times.

[0100] Example 7 - Oxidation of SWCNT of high - purity OCSiAl Tuball A total of 15 grams of high-purity grade OCSiAl SWCNTs were added to 35 grams of a 65% nitric acid aqueous solution and heated at 90 °C for 5 hours in a round-bottom flask connected to a condenser cooled by deionized water. Samples were taken from the flask every 30 minutes and 1 hour, washed with deionized water to pH 3.9 and dried. Then, the samples were analyzed by TGA for oxidation level and residue (metallic impurities). The results are given in the following table. impurities). The results are given in the following table. impurities). The results are given in the following table. impurities). The results are given in the following table. Table of TGA results for high-purity OCSiAl Tuball SWCNTs after oxidation

Table 7

[0101] Following the same procedure, a series of different SWCNTs were oxidized, and the oxidation level and residue were measured by the same TGA procedure. The starting materials before oxidation were also evaluated. The results of these experiments are given in the following table. Oxidation levels and residue levels of various SWCNTs before and after acid treatment

Table 8

[0102] Example 8 - SWCNT of high - purity OCSiAl Tuball and sodium carboxymethyl cellulose aqueous dispersion A total of 2 grams of high-purity OCSiAl Tuball SWCNTs were diluted to a solids content of 0.4% with deionized water The mixture was rotor / stator treated at 10,000 rpm for 5 minutes The sample was diluted to 0.2% and sheared twice through a shear device at 8500 - 9000 psi At that point, 105 grams of Walocel CRT 30 PA carboxymethyl cellulose sodium (CMC) with a solids content of 3.79% in deionized water was added And the mixture was passed through the shear device 8 more times while maintaining the mixture at a temperature below 40 °C Optical micrographs of the SWCNTs passed through the rotor / stator compared to the final dispersion are shown in Figures 10 - 11 Figure 10 shows the high-purity OCSiAl Tuball SWCNT before shearing Figure 11 shows the high-purity OCSiAl Tuball SWCNT after the shear device and CMC addition Both are at a magnification of 11.25 times. The absence of any obvious particles in the optical image after dispersion means that the fibril size is less than 1 millimeter ( The scale bar is 1 millimeter). The absence of any obvious particles in the optical image after dispersion means that the fibril size is less than 1 millimeter ( The scale bar is 1 millimeter).

[0103] Example 9 - Aqueous dispersion of oxidized Zeonano SWCNT and sodium carboxymethyl cellulose Example 10 - Aqueous dispersion of unoxidized Zeonano SWCNT and sodium carboxymethyl cellulose An aqueous mixture of 0.77% oxidized Zeonano SWCNTs in deionized water was treated using a rotor / stator at 10,000 rpm for 25 minutes The oxidation was as described above. The mixture was The temperature was maintained at 27-31°C during processing. The material was diluted to 0.17% solids. The mixture was diluted five times. The sample was then passed through a shearing device. The first pass was sheared at 6000 psi, and the subsequent passes at 80 The mixture was sheared at 00-9000 psi. The pH was adjusted to pH 7 after the fourth pass. After the fifth pass, Walocel CR was applied with a mass ratio of 1:1 SWCNT to CMC. T 30 PA sodium carboxymethylcellulose (CMC) was added. The mixture is heated at 8000-9000 psi while maintaining the temperature of the mixture below 40°C. The material was passed through the shearing device 11 times. In the 14th pass, the SWC was 2.25, compared to the CMC of 2.25. Additional surfactant was added at a ratio of 1:1 of NT. At the 16th pass, the CMC was 2.75. Additional surfactant was added at a ratio of 1:1 of SWCNTs to oxidized Zeolite before shearing. Figure 13 shows the SWCNTs in onano and after the addition of shear device and CMC (fold increase) rate 11.25 times).

[0104] Example 11 - Dispersion of high - purity OCSiAl in silene Embodiment A total of 2 g of as-received unoxidized Zeonano SWCNTs were obtained, with 698 g Mix with 100% deionized water and process using a rotor / stator at 10,000 rpm for 20 min. An additional 195 ml of deionized water was then added. The mixture was pressurized at 8000-9000 psi. The mixture was passed through the shearing device six times at 1000 rpm for a total of 105.8 grams of Walnut pulp at 3.78% solids. Add ocel CRT 30 PA sodium carboxymethylcellulose solution to the mixture. The mixture was then stirred for an additional 14 minutes while maintaining the temperature of the mixture below 40°C. Figure 14 shows the S of unoxidized Zeonano after five passes through the shearing device. The WCNT is shown (magnification 35 times), and Fig. 15 shows after 20 passes through the shearing device and addition of CMC. It is shown (magnification 140 times).

[0105] ​ High-purity OCSiAl with a concentration of 0.3% was added to silene and sonicated in an ultrasonic bath for 150 minutes to produce a dispersion of SWCNT in silene. Fig. 16 shows the SWCNT of high-purity OCSiAl after 30 minutes of sonication (magnification 169 times). Fig. 17 shows the SWCNT of high-purity OCSiAl after 150 minutes of sonication (magnification 169 times). Fig. 16 shows the SWCNT of high-purity OCSiAl after 30 minutes of sonication (magnification 169 times). Fig. 17 shows the SWCNT of high-purity OCSiAl after 150 minutes of sonication (magnification 169 times). Fig. 16 shows the SWCNT of high-purity OCSiAl after 30 minutes of sonication (magnification 169 times). Fig. 17 shows the SWCNT of high-purity OCSiAl after 150 minutes of sonication (magnification 169 times). Fig. 17 shows the SWCNT of high-purity OCSiAl after 150 minutes of sonication (magnification 169 times).

[0106] ​ 1. A composition for use as a binder material, electrolyte material or separator film material in an energy storage or collection device, comprising a plurality of high surface area carbon nanotubes, at least a part of the high surface area carbon nanotubes having an open end. A composition for use as a binder material, electrolyte material or separator film material in an energy storage or collection device, comprising a plurality of high surface area carbon nanotubes, at least a part of the high surface area carbon nanotubes having an open end. A composition for use as a binder material, electrolyte material or separator film material in an energy storage or collection device, comprising a plurality of high surface area carbon nanotubes, at least a part of the high surface area carbon nanotubes having an open end.

[0107] 2. The composition of embodiment 1, wherein the plurality of high surface area carbon nanotubes are single-walled nanotubes. The composition of embodiment 1, wherein the plurality of high surface area carbon nanotubes are single-walled nanotubes.

[0108] 3. The composition of embodiment 1, further comprising at least one polymer.

[0109] 4. The composition of embodiment 1, wherein the carbon nanotubes are further functionalized.

[0110] 5. The composition of embodiment 1, further comprising at least one dispersion aid.

[0111] 6. The polymer is a vinyl polymer, poly(styrene-butadiene), a copolymer of partially or fully hydrogenated poly(styrene-butadiene), carboxylated poly(styrene-butadiene), carboxylated Functionalized poly(styrene-butadiene) copolymers such as poly(styrene-butadiene), poly(styrene-isoprene), poly(methacrylic acid), poly(methyl meth acrylate), poly(acrylic acid), poly(vinyl alcohol), poly(vinyl acetate), fluorinated polymers, polyvinylpyrrolidone, conductive polymers, polymers derived from natural sources, poly ethers, polyesters, polyurethanes and polyamides, and homopolymers, grafts, block or random copolymers or terpolymers, and mixtures thereof, selected from the group consisting of the composition of Embodiment 3.

[0112] 7. The composition of Embodiment 2 further comprising an additional inorganic structure comprising elements of Groups 2-14 of the periodic table of elements. The composition of Embodiment 2.

[0113] 8. The battery composition of Embodiment 2 further comprising a carbon structure selected from the group consisting of carbon black, graphite, graphene, graphene oxide, fullerenes, and mixtures thereof. The battery composition of Embodiment 2.

[0114] 9. The composition of Embodiment 1 further comprising at least a portion of discrete carbon nanotubes.

[0115] 10. The composition of Embodiment 1, wherein the binder material has an impedance of about 1 billion ohm-m or less. The composition of Embodiment 1.

[0116] 11. The composition of Embodiment 1, wherein the electrolyte material or separator film has a charge transfer resistance of about 10 million ohm-m or less. The composition of Embodiment 1.

[0117] 12. An electrode paste for a lead-acid battery, having an average length of about 1 μm to about 1500 μm. A high surface area carbon nanotube and a polymer surfactant containing polyvinyl alcohol An electrode paste for a lead-acid battery comprising an agent.

[0118] 13. In a composition comprising a plurality of high surface area carbon nanotubes, said carbon nano Tubes have inner and outer surfaces, and the improvement comprises said inner Surface with an inner surface oxidation species content and said outer surface with an outer surface oxidation species content, said inner surface oxidation species content Is at least about 20% and about 100% different from said outer surface oxidation species content.

[0119] 14. The improvement of embodiment 13, wherein said inner surface oxidation species content is less than said outer surface oxidation species content. Of embodiment 13.

[0120] 15. The improvement of embodiment 13, wherein said outer surface oxidation species content comprises from about 1 to about 6 weight Percent based on the weight of the carbon nanotubes.

[0121] 16. The improvement of embodiment 13, wherein said oxygen species are selected from the group consisting of carboxylic acids, phenols, aldehydes, ketones, ether linkages and Combinations thereof.

[0122] 17. A composition for use as a binder material, electrolyte material or separator fleece material in an energy storage or collection device, comprising a plurality of high surface area carbon nanotube bunches Dles, said plurality of high surface area bundles comprising individual carbon nanotubes, said individual The aspect ratio of the nanotubes is from about 700 to about 1500, and the average length of said high surface area carbon nano Tube bundles is from about 800 microns to about 1500 microns. Composition.

[0123] 18. The composition of embodiment 17, wherein said nanotubes are oxidized.

[0124] 19. The composition of embodiment 18, wherein the carbon nanotube is further functionalized.

Claims

1. 1. A composition for use as a binder material, electrolyte material, or separator film material in an energy storage or collection device, the composition comprising: a plurality of high surface area carbon nanotubes; and at least one dispersing aid; at least a portion of the high surface area carbon nanotubes are open-terminated; the plurality of high surface area carbon nanotubes are oxidized single-walled carbon nanotubes; The plurality of high surface area carbon nanotubes have a BET specific surface area of ​​700 m according to ASTM D6556-16. ２ / g~1500m ２ / g, The composition, wherein the energy storage or collection device is a lithium ion battery.

2. The composition of claim 1 further comprising at least one polymer.

3. 3. The composition of claim 2, wherein the polymer is selected from the group consisting of vinyl polymers, poly(styrene-butadiene), partially or fully hydrogenated poly(styrene-butadiene) including copolymers, functionalized poly(styrene-butadiene) copolymers such as carboxylated poly(styrene-butadiene), poly(styrene-isoprene), poly(methacrylic acid), poly(methyl methacrylate), poly(acrylic acid), poly(vinyl alcohol), poly(vinyl acetate), fluorinated polymers, polyvinylpyrrolidone, conductive polymers, polymers derived from natural sources, polyethers, polyesters, polyurethanes, and polyamides, as well as homopolymers, graft, block, or random copolymers or terpolymers, and copolymers and mixtures thereof.

4. 10. The composition of claim 1, further comprising a carbon structure selected from the group consisting of carbon black, graphite, graphene, graphene oxide, fullerenes, and mixtures thereof.

5. The composition of claim 1 further comprising at least a portion of discrete carbon nanotubes.

6. The composition of claim 1 further comprising a cellulose-based polymer or a salt thereof.

7. The composition of claim 1 further comprising polystyrene sulfonic acid or a salt thereof.

8. The composition of claim 1 further comprising a hydrophilic polymer.

9. 10. The composition of claim 1, wherein at least a portion of the plurality of high surface area carbon nanotubes comprises high surface area single-walled carbon nanotubes having an oxidation level of 0.01 to 2 weight percent as measured by thermogravimetry (TGA).

10. 10. The composition of claim 1, wherein at least a portion of the plurality of high surface area carbon nanotubes comprises high surface area single-walled carbon nanotubes having an oxidation level of 2 to 5 weight percent as measured by thermogravimetry (TGA).

11. 10. The composition of claim 1, wherein the plurality of high surface area carbon nanotubes has less than about 25 weight percent impurity residue.

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