KR20160011558A - Electrode Composition for Battery - Google Patents

Abstract

Disclosed are a carbon nanotube-based composition and a producing method of an electrode for a battery. In addition, disclosed is a composition for a battery electrode where carbonaceous materials of a three dimensional network comprising: carbon nanotube (CNT(A) and CNT(B)) of bi-modal diameter distribution; graphene; carbon black; and a selective carbon-based paste of another shape are mixed.

Description

[0001] Electrode Composition for Battery [

This patent application claims priority benefit from U.S. Serial No. 14 / 338,325, filed on April 22, 2014, which is incorporated herein by reference in its entirety.

This application is a CIP application and claims priority to U.S. Patent Application Serial No. 13 / 437,205, filed April 4, 2012, which is incorporated herein by reference in its entirety.

This application is related to U.S. Patent Nos. 7,563,427, U.S. Patents Nos. 2009/0208708 and 2009/0286675; U.S. Patent Application No. 12 / 516,166, and U.S. Patent Application No. 13 / 006,321, filed December 13, 2011, and U.S. Patent Application No. 13 / 285,243, filed on October 31, 2011, , Which are incorporated herein by reference in their entirety.

The present disclosure relates to a three-dimensional network carbonaceous material, a carbon enhanced electrode composition, and a carbon nanotube composition comprising CNT (A), CNT (B), graphene, carbon black, and optionally other types of carbon- And a method of manufacturing an electrode for a battery.

Carbon nanotubes (CNTs) have a number of peculiar physical properties due to their small size, cylindrical graphite structure and high aspect ratio. Single-walled carbon nanotubes (SWCNTs) are made of a single graphite or graphene sheet wrapped around to form a cylindrical tube. Multiwall carbon nanotubes (MWCNTs) include a concentric set of single-walled nanotubes located along a fiber axis with an interstitial distance of 0.34 nanometers. Carbon nanotubes have extremely high tensile strength (~ 150 GPa), high modulus (~ 1 TPa), good chemical and environmental stability, and high thermal and electrical conductivity. Carbon nanotubes have been applied in many fields including conductive, electromagnetic and microwave absorptive and high strength composites, fibers, sensors, field emission displays, inks, energy storage and energy conversion devices, radiation sources and nanometer- Size semiconductor devices, probes and interconnects, and the like. Carbon nanotubes are often characterized by tube diameter. Materials with smaller diameters exhibit higher surface area and fiber strength; Nanotubes with larger diameters have a smaller volume-to-surface area; And less accessibility than nanotubes with smaller surface area due to less entanglement. Also, large diameter nanotubes are often more linear than smaller ones, so large diameter nanotubes extend through larger spaces or volumes within the composite matrix.

Carbon nanotubes have excellent material properties, but are difficult to process and insoluble in most solvents. Historically, poly (vinyl pyrrolidone; PVP), poly (styrenesulfonate; PSS), poly (phenylacetylene; PAA), poly (metaphenylene vinylene; PmPV), polypyrrole (PPy) - Phenylenebenzobisoxazole, PBO) and natural polymers were used to pack or coat carbon nanotubes and to be soluble in water or organic solvents. Previous studies have also shown that single-walled carbon nanotubes (SWCNTs) can be used in aqueous solutions to deliver (i) anionic aliphatic surfactant, sodium dodecyl sulfate (SDS), (ii) cyclic lipoprotein livestock surfactant and sulfactin, And (iii) amphiphilic materials of three types of water-soluble polymers and polyvinylpyrrolidone (PVP).

Conventional electroconductive pastes or inks have the same conductivity as microparticulated particles of a metal (e.g., silver, gold, copper, nickel, palladium or platinum) and / or carbonaceous materials (e.g. carbon black or graphite) A polymer binder containing a smaller amount of filler or a mixed polymer, and a liquid vehicle. The polymeric binder may attach the conductive filler to the substrate and / or support the electrically conductive filler in a conductive pattern that acts as a conductive circuit. The liquid vehicle includes a solvent (for example, a liquid for dissolving a solid component) and a non-solvent (a liquid for dissolving the solid component). The liquid vehicle acts as a carrier to assist in applying or adhering the polymeric binder and conductive filler onto a specific substrate. Conductive pastes in which carbon nanotubes are dispersed inside are versatile materials in which carbon nanotubes form a conductive network of low resistance.

The technical background and the technical information supporting this are described in the following documents, all of which are incorporated herein by reference in their entirety:

U.S. Patent Nos. 4,427,820, 5,098,711, 6,528,211, 6,703,163, 7,008,563, 7,029,794, 7,365,100, 7,563,427, 7,608,362, 7,682,590, 7,682,750, 7,781,103 , U.S. Patent Application Publication Nos. 2004/0038251, 2007/0224106, 2008/0038635, 2009/0208708, 2009/0286675, 2010/0021819, 2010/0273050, 2010 / 0026324, 2010/0123079, 2010/0143798, 2010/0176337, 2010/0300183, 2011/0006461, 2011/0230672, 2011/0171371, 2011/0171364 , 2014/0045065, 2014/0079991 and 2014/0154577.

The present specification discloses a composition for a carbon nanotube-based composition and a battery, and a method for selectively manufacturing an electrode for a lithium ion battery.

The technology disclosed herein is a composition for manufacturing lithium ion battery electrodes incorporating carbon nanotubes with more active material by having less conductive filler loading and less binder loading to improve battery performance. In one embodiment, the reinforced electrode composition uses fewer binders (e.g., PVDF) and thus allows for more electrode material in the composition, both in absolute and in weight percent, thereby improving the capacity. The technology disclosed herein provides a composition for a cathode and an anode of a lithium ion battery incorporating carbon nanotubes with improved battery performance by allowing less conductive filler loading, less binder loading, and more active material do.

The present technique involves carbon nanotubes having large (large) diameter and small (small) diameter combinations (large and small diameter) combined with other types of carbon, optionally with different cathodes and anode materials of varying sizes to provide. In general, cathode and / or anode materials with smaller particle size have a smaller pore size under compression, while larger particles have a tendency to have larger forerun volume. Small diameter carbon nanotubes fit well into small spaces between small cathodes and / or anode particles. When large diameter particles are present in the electrode, smaller diameter nanotubes can not easily fill the void. Alternatively, the combination of large and small carbon nanotubes, combined with other forms of carbon, provides a way to handle a variety of cathode and anode materials of different particle sizes. The ratio of large (large) diameter nanotubes to small (small) diameter nanotubes can be selected by selecting the cathode and / or anode material (e.g., size, electrical characteristics, etc.) It depends on the compressive force used to collect.

As described in U.S. Provisional Patent Application No. 61 / 294,537, conductive pastes based on carbon nanotubes are composed of carbon nanotubes and a liquid vehicle in a desired amount as a dispersant and / or a binder. In the inspection process, it has been found that surprisingly, when combined with other types of carbon (e.g., CNT, graphene and carbon black) at various weight ratios, additional binder loading requirements can be reduced.

1A is a schematic view of a coating made of an active material, a carbon nanotube and a binder on an aluminum film as an electrode of a lithium battery, FIGS. 1B and 1C show a large (small) and small (small) cathode in the electrode layer and / Lt; / RTI >
2 shows the cycle performance of a lithium ion battery comprising carbon nanotubes;
And Figure 3 shows a conductive network formed by the CNT coating on the LiFePO ₄ observed under a scanning electron microscope (SEM);
4 is a schematic view of a lithium ion battery showing components,
Figure 5 is an electron micrograph of large and small diameter carbon nanotubes intrapenetrating each other;
6A is an electron micrograph of an intrapenetrating graphene sheet and carbon nanotube of a first example, and FIG. 6B is an electron micrograph of an intrapenetrating graphene sheet and carbon nanotube of a first example lithium ion battery, Performance; And
FIG. 7A is an electron micrograph of an intrapenetrating graphene sheet and carbon nanotube of a second example, and FIG. 7B is a cross-sectional view of a second lithium ion battery including a mixture of graphene sheet and carbon nanotube of the second example Performance.

Justice

As used herein, the term " carbonaceous material in a three dimensional network "refers to the fiber structure and other carbon structures of carbon nanotubes, for example, in some embodiments, the three dimensional network comprises carbon nanotubes (CNTs) ;

Optionally, the CNT comprises a first diameter range (A) and a second diameter range (B);

Optionally, the carbonaceous material of the three-dimensional network comprises carbon nanotubes and graphene, and sheet material;

Optionally, the carbonaceous material of the three-dimensional network comprises carbon nanotubes, graphene and carbon black, spherical material;

Optionally, the carbonaceous material of the three-dimensional network comprises at least two carbonaceous materials selected from CNT (A), CNT (B), graphene, carbon black and other forms of carbon. In some embodiments, the electrode material may have carbonaceous materials in a plurality of three-dimensional networks.

As used herein, "carbon nanotubes" means a hollow carbon structure having a diameter of about 2 to 100 nm; For the purposes of this specification, refers to multi-walled nanotubes that exhibit little or no chirality. To distinguish between different diameter carbon nanotubes, the term "CNT (A)" refers more specifically to a nanotube having a diameter of about 4 to 15 nm, and the term "CNT To < RTI ID = 0.0 > 100 nm < / RTI > diameter.

The term "multi-walled carbon nanotubes ", i.e., MWNTs, refers to carbon nanotubes that form more than one concentric cylinder in which the graphene layer is located along the fiber axis.

The term "carbon nanotube-based paste" refers to a conductive composite in which the electro-conductive filler is a carbonaceous material of a three-dimensional network.

The term "composite" means a material comprising at least one polymer and at least one carbonaceous material.

The term "dispersant" refers to an agent that aids in dispersing and stabilizing a carbonaceous material in a three-dimensional network within the composite.

"Carbon nanotube network" refers to a nanotube having a "bi-modal" distribution, two different single-mode uni-modal diameter distributions or a mixture of distributions with only a narrow range of diameters Refers to a structure such as a carbonaceous material of a three-dimensional network, including a tube. Large (diameter) carbon nanotubes (CNT (B)) act as backbone of various conductive paths while small (small) diameter nanotubes (CNT (A) . In some embodiments, the diameter range for small (small) carbon nanotubes (CNT (A)) is about 4-15 nm and the diameter range for large (large) carbon nanotubes (CNT To 100 nm.

The electrode composition refers to an electrode active material, and any matrix or composite composition that surrounds the electrode active material. When the battery is in an active, discharging, or charging state as schematically shown in FIG. 4, the material of the specific "electrode composition" is a metal that collects or dispenses electrons or & Coated or adhered to the conductor plate.

The term "carbon black" is defined as in Wikipedia (http://en.wikipedia.org/wiki/Carbon_black; Carbon black (the subtype is acetylene black, channel black, furnace black, lamp black and thermal black) are FCC tar, coal tar, ethylene cracking Heavy petroleum products such as tar, and small amounts of incomplete combustion from vegetable oils. Carbon black is in a paracrystalline form with a lower surface-area-to-volume ratio than that of activated carbon. Is much different from soot in that it has a much higher surface area to volume ratio and a significantly lower (polyhydroxyhydrocarbon) content of PAH (less bioavailable).

The term "graphene" is defined as in Wikipedia (http://en.wikipedia.org/wiki/Graphene; Graphene is a crystalline allotrope of carbon with two-dimensional properties. In graphene, carbon atoms are tightly packed in a regular sp ² -bonded atom-scale chicken wire (hexagonal) pattern. Graphene can be described as a 1-atom thick layer of graphite. Graphene is the basic structural element of other alloys, including graphite, charcoal, carbon nanotubes, and fullerenes. Graphene may also be considered as an infinitely large aromatic molecule, which is a limited case of a family of flat polycyclic aromatic hydrocarbons. The term "graphene" as used herein refers to graphene ribbons or nanoribbons, graphene formed from cutting open carbon nanotubes, multiple layers of graphene sheets, and as a powder or as a polymer Matrix or other form of graphene such as an adhesive, elastomer, oil, graphene formed as a dispersion of aqueous or non-aqueous solution.

Carbon nanotube

Various types of carbon nanotube structures have been reported in the art, including single-walled nanotubes, multi-walled nanotubes, and vapor-grown carbon fibers (VGCF). The distinction is that the diameter is 0.4 to 1.2 nm for SWCNT, 2 to 100 nm for MWCNT, and> 100 nm for VGCF. 1A is a schematic view of a coating made of an active material 1, a CNT (A) 2 and a binder 3 on an aluminum film 4 as an electrode of a lithium battery. The carbon nanotube 2 acts as a conductive filler as shown to form a conductive path across the active material particles, thereby increasing the overall conductivity.

FIG. 1B shows a schematic cross-sectional view of a mixed, homogeneous, and uniformly dispersed carbon nanotube network forming large (large) and small (small) cathode particles 1 in the electrode layer and a carbon nanotube network, (Large) CNT (B) 5 and small (small) CNT (A) (2) diameter carbon nanotubes and a binder 3.

Fig. 1C shows a large (large) CNT (B) 5 and a small (small) CNT (A) 2, which form a carbon nanotube network that enables a packing structure different from the conventional one and provides alternative conduction paths. (Large) and small (small) graphite anode carbonaceous particles in the electrode layer mixed with a diameter of carbon nanotubes and binder 3. [ 5 is a 5000 x SEM showing exemplary intra-penetrating CNT (A) 505 and CNT (B) 510 in a carbonaceous material of a three dimensional network.

The preparation of carbon nanotubes is widely known in the literature. Generally, the catalyst is used in a heated reactor below carbonaceous reagents. At elevated temperature, the catalyst will decompose the carbon precursor and the resulting carbon species will precipitate in nanotube form on the catalyst particles. Continuous mass production of a carbon nanotube network can be achieved using a mixed gas of hydrogen, nitrogen, and hydrocarbons in the fluidized bed at low space velocities, as described in U.S. Patent No. 7,563,427. The carbon nanotubes formed often form entanglement known as a three-dimensional network. U.S. Patent No. 7,563,427, which is incorporated herein by reference in its entirety, discloses that such an entangled structure comprises a plurality of transition metal nanoparticles, a solid support, wherein the plurality of metal nanoparticles and the support are combined to form a plurality of catalyst nano- Forming a tangled structure); And a plurality of multi-wall carbon nanotubes attached on the plurality of catalyst nano entangled structures. The entangled structure has a size of about 0.5 to 10,000 mu m, wherein the carbon nanotubes are in the form of a multi-walled nanotube having a diameter of 4 to 100 nm. The size of the manufactured entangled structure can be reduced by various means. A typical characteristic of such a tangled structure is its tap density, and the tap density of the produced tangled structure may vary from 0.02 g / cm3 to 0.20 g / cm < 3 > depending on the catalyst, growth conditions, process design and the like. Rigid entanglement structures have a high tap density, while fluffy entanglement structures and single wall nanotubes exhibit a tendency to have a low tap density.

Dispersant

The dispersant acts as an aid to disperse the carbon nanotubes in the solvent. The dispersing agent may be a polar polymer compound, a surfactant, or a high viscosity liquid (for example, a mineral oil or a wax). The dispersant used in the present invention may be at least one selected from the group consisting of poly (vinylpyrrolidone), poly (styrene sulfonate), poly (phenylacetylene), poly (metaphenylene vinylene) , Poly (p-phenylenebenzobisoxazole), natural polymers, amphiphilic materials in aqueous solutions, anionic aliphatic surfactants, sodium dodecylsulfate (SDS), lignocyclic lipopeptide livestock (SDS), n-methyl pyrrolidone, polyoxyethylene surfactant, poly (vinylidene fluoride) (PVdF), polyvinylidene fluoride (PVDF), polyvinylidene fluoride , Carboxymethylcellulose (CMC), hydroxylethylcellulose (HEC), polyacrylic acid (PAA), polyvinyl chloride (PVC), and combinations thereof. Polymeric binder selection is polyethylene. The above-mentioned dispersants including polypropylene, polyamide, polyurethane, polyvinyl chloride, polyvinylidene fluoride, thermoplastic polyester resin, and combinations thereof.

Polyvinylpyrrolidone (PVP) binds polar molecules very well. When used as a binder or as a dispersant such as a thickener, PVP has different physical properties depending on the molecular weight. In some embodiments of the present invention, the molecular weight for the dispersant and / or the binder is in the range of about 9,000 to 1,800,000 Daltons; In some embodiments about 50,000 to 1,400,000 daltons is preferred; In some embodiments, a range of from 5,5000 to 80,000 Daltons is preferred.

Liquid phase Vehicle

A liquid vehicle (water or non-aqueous) can act as a carrier for the denitrifying material. A liquid vehicle can be a solvent or a cost daily depending on whether it solubilizes the solids to be mixed therein. The volatility of the liquid vehicle should not be so high as to readily vaporize at relatively low temperatures and pressures, such as room temperature and atmospheric pressure (e.g., 25 ° C and 1 atm). However, the volatility should not be so low that the solvent in the paste manufacturing process does not vaporize to a degree. As used herein, the term "dry ", or removal of excess liquid vehicle, refers to baking, or vacuum baking, or centrifugation or some other demineralization at a temperature of below 100 ° C to 200 ° C lt; RTI ID = 0.0 > de-liquefying < / RTI > process.

In one embodiment, the liquid vehicle is used to dissolve the polymeric dispersant to entrain the carbonaceous material such that the composition is readily applied (applied) to the substrate. Examples of liquid vehicles include, but are not limited to, water, alcohols, ethers, aromatic hydrocarbons, esters, ketones, n-methyl pyrrolidone, and mixtures thereof. In some cases, water is used as a solvent to dissolve the polymer to form a liquid vehicle. In combination with certain polymers, such aqueous systems can replace solvent based inks while maintaining designated thixotropic properties as described in U.S. Patent No. 4,427,820, which is incorporated herein by reference in its entirety It is included as data.

Nanotubes Dispersion

Dispersing carbon nanotubes and carbonaceous materials in liquids is difficult because nanotubes are entangled with a large network. In some embodiments, the means for reducing the size of the megabit network to an entangled structure of acceptable size is to apply a shear force to the entangled structure; Shear force is a kind of technique to assist dispersion. Means for applying the shear force may include, but are not limited to, milling, sand milling, ultrasonic, grinding, cavitation, or other means known to those of ordinary skill in the art. In one embodiment, the carbon nanotubes are first reduced in size using a jet-miller. The tap density may be reduced to 0.06 g / cm3 in some embodiments, or 0.04 g / cm3 in some embodiments, or 0.02 g / cm3 in some embodiments, by selective milling after dispersion. In some embodiments, a colloid mill or sand mill or other technique is then used to provide sufficient shear force to further comminute the nanotube entanglement structure required in the present invention.

Manufacture of carbonaceous material network

Carbon nanotubes with diameters of about 50 nm, but less than about 100 m, are known to be linear compared to smaller nanotubes, and smaller nanotubes often exist in the form of tangled networks. In one embodiment, a small (small) diameter nanotube (CNT (A)), a carbon nanotube network with a "bi-mode" nanotube distribution, is first introduced into a liquid suspension (eg, NMP or water) And then the large (large) diameter nanotube material (CNT (B)) is added directly to the liquid suspension at a desired ratio for the small (small) diameter nanotubes, and then vigorously stirred and mixed. The resulting paste then includes a mixture of large (large) and small (small) nanotubes that cross each other in a new paste to form the desired network. Optionally, additional carbonaceous material is added into the liquid suspension.

Exemplary lithium ion battery active materials are selected from the group consisting of lithium based compounds and / or lithium and a group consisting of oxygen, phosphorus, sulfur, nitrogen, nickel, cobalt, manganese, vanadium, silicon, carbon, aluminum, niobium, zirconium, And mixtures comprising at least one element. Typical cathode materials include lithium-metal oxides such as LiCoO ₂ , LiMn ₂ O ₄ and Li (Ni _x Mn _y Co _z ) O ₂ ], vanadium oxides, olivines such as LiFePO ₄ , and rechargeable lithium oxides . Layered oxides including cobalt and nickel are also materials for lithium-ion batteries.

Exemplary anode materials are silicon and silicon-based compounds such as lithium, carbon, graphite, lithium-alloy materials, intermetallics, and silicon dioxide. A carbonaceous anode comprising silicon and lithium is also used as the anode material. For example, a method of coating a battery material in combination with a carbon nanotube network on an anode or cathode backing plate such as aluminum or copper is described as an alternative embodiment of the present invention.

Example 1

Dispersion of carbon nanotubes (CNT (A)) in n-methylpyrrolidone

30 g of FloTube ™ 9000 carbon nanotubes manufactured by CNano Technologies, Inc., which was pulverized by jet-milling, was charged into a 2 L beaker. The tap density of the material was 0.03 g / ml. In another 500 mL beaker, 6 g of PVP k90 (manufactured by BASF) was dissolved in 100 g of n-methylpyrrolidone. The PVP solution was then transferred to nanotubes with 864 g of n-methyl pyrrolidone. After stirring for 1 hour, the mixture was transferred to a colloid mill and grounded at a speed of 3,000 rpm. Test samples were taken out every 30 minutes and evaluated. Viscosities were recorded for each sample by measuring at 25 DEG C using a Brookfield viscometer. At the same time, it was recorded on the Hegman scale. Maximum dispersion was observed after milling for 90 minutes. The fineness of these pastes reached well below 10 [mu] m after 60 minutes of milling. The sample was named Sample A.

Example 2

Electrode paste production

10 g of PVDF (HSV 900) and 100 g of n-methylpyrrolidone were placed in a 500 ml beaker under constant stirring to prepare a PVDF solution. After all of the PVDF had dissolved, the specified amounts of the Paste (Sample A) and PVDF solution prepared from Example 1 were mixed for 30 minutes under vigorous stirring at 500-1000 rpm. The resulting mixture was designated Sample B.

In a separate container, the desired amount of active material (e.g., LiFePO ₄ or LiCoO ₃ ) was weighed under a nitrogen blanket. A selected amount of Sample B was also added to the active material, and the mixture was stirred for 5 hours at a high speed, for example, 5000 to 7000 rpm. The resulting viscosity, as measured by a Brookfield viscometer, should be adjusted to 3,000 to 8,000 cps for LFP or 7,000 to 15,000 cps for LiCoO ₃ . Mixing and stirring were carried out in a nitrogen atmosphere and at temperatures not exceeding 40 占 폚. The resulting sample was named Sample C.

Example 3

Electrode Manufacturing

A clean aluminum foil was selected as the cathode current collector and placed on a flat plexiglass. A doctor blade was applied to adhere the thin film coating of Sample C to the surface of the aluminum foil to a thickness of about 40 mu m. The coated foil was then placed in a drying oven at 100 DEG C for 2 hours. The cathode plate was then roll-pressed to form a sheet. A rounded disc of coated foil was punched out of the foil and placed in a coin battery cell. A lithium metal anode was used, the cathode / separator / anode was assembled, the electrolyte was injected, and the coin cell was sealed. The manufactured battery was then tested for various charging and discharging performance.

Example 4

Commercial electrode and disclosed inter-electrode composition comparison

Various samples containing different cathode materials were prepared using the methods described in Examples 1-3. The electrode compositions are listed in Table 1. Cell capacity was measured for different electrode compositions.

Cathode
material
electrode
Electrode composition (% by weight) Capacity (mAh / g) Active substance CNT (A) Dispersant Carbon black PVDF LFP
Containing CNT 93 3 0.75 3 139.9 Commercial 89 6 5 133.5 LCO
Containing CNT 98 0.75 0.19 0.75 145.6 Commercial 97 2 1.5 140.9 NCM
Containing CNT 97 One 0.25 1.5 139.1 Commercial 96 3 1.5 135.4

 Example 5

Comparison of mechanical properties of electrode (crease test)

The coated aluminum (Al) foil from Example 3 was further tested for adhesion and anti-crease properties. The foil was folded several times until the coating was cracked or the surface peeled off. Table 2 describes how the coated Al foil can withstand multiple folding operations. The number indicates the number of folds before failure occurs.

Conductive additive PVF (%) The electrode resistivity (ohm · cm) Wrinkle recovery
2% SP
One% 13.0 / 9.8
3 2 2% 13.9 / 13.3 One
1% CNT


0.75% 11 / 14.58 4 2 One% 9.6 / 12.2
One One

Example 6

Application of carbon nanotube paste on lithium-ion battery cathode material

To prepare a lithium ion coin battery, a CNT (A) paste containing 2% CNT and 0.4% PVF k30 was selected. LiFePO ₄ (manufactured by Phostech / Sud Chemie) was used as a cathode material, and lithium foil was used as an anode. The cathode material contained LiFePO ₄ , CNT, PVP, and PVDF and was prepared by mixing a suitable amount of LiFePO ₄ , CNT paste, PVP, and PVDF together with n-methyl pyrrolidone in a warren blender. A coating of this paste was prepared using a doctor blade on an Al foil, followed by drying and compression (compression). As a comparative example, electrodes were prepared by replacing CNTs with Super-P carbon black (CB) in a manner similar to that described above. The compositions and bulk resistivities of the two battery electrodes are summarized in the following table. Obviously, the CNT-added electrode exhibited much lower resistivity than the carbon black-modified sample with the same concentration.

Content CNT (A) CB LiFePO ₄ 86.8% 88% Carbon additive 2% 2% PVP 0.4% - PVDF 5% 5% Bulk resistivity (ohm-cm) 3.1 31

Example 7

Life evaluation

Batteries assembled using the method described in Example 3 were tested for cycle life performance at different charge rates. Figure 2 shows that an electrode embedded with carbon nanotubes (CNT (A)) exhibits excellent cycle life performance at various charging rates. However, when the multi-walled carbon nanotube of the present invention is used as a conductive filler and various polymers such as polyvinyl pyrrolidone (PVP) as a dispersant, the present inventors have found that when a required amount of a polymeric binder is contained in a conductive paste Can be removed or significantly reduced. As a result, the present inventors have found that the conductivity of the conductive paste can be remarkably improved.

In some embodiments, the electrode composition comprises a carbon nanotube network, a dispersant, and a liquid vehicle, wherein the carbon nanotube network is dispersed as defined by a Hegman scale value of 7 or greater;

Optionally, the carbon nanotubes are multi-wall carbon nanotubes;

Optionally, the carbon nanotubes are present in a spherical network;

Alternatively, the electrode composition may be a poly (vinylpyrrolidone), a poly (styrene sulfonate), a poly (phenylacetylene), a poly (meta-phenylenevinylene; PmPV), a polypyrrole (PPy) (PBO), a natural polymer, an amphiphilic substance in an aqueous solution, an anionic aliphatic surfactant, sodium dodecyl sulfate (SDS), a cyclic lipopeptide livelihood surfactant, sulfictin, a water-soluble polymer, (SDS), polyoxyethylene surfactant, poly (vinylidene fluoride) PVdF, carboxymethylcellulose (CMC), polyvinyl alcohol, polyvinyl alcohol, A dispersant selected from the group consisting of hydroxyethyl cellulose (HEC), polyacrylic acid (PAA), polyvinyl chloride (PVC), and combinations thereof;

Optionally, the dispersant is poly (vinylpyrrolidine);

Optionally, the electrode composition comprises a liquid vehicle selected from the group consisting of water, alcohols, ethers, aromatic hydrocarbons, esters, ketones, n-methyl pyrrolidone, and mixtures thereof;

Optionally, the electrode composition has a solid phase bulk electrical resistivity of less than 10 < ^-1 > -cm and a viscosity of greater than 5,000 cps;

Optionally, the electrode composition comprises a carbon nanotube network having a maximum dimension of from about 0.5 to about 1,000 micrometers;

Optionally, the electrode composition has carbon nanotubes having a diameter of about 4 to 100 nm;

Optionally, the electrode composition comprises a carbon nanotube network fabricated in a fluidized bed reactor;

Alternatively, the electrode composition may be one or more selected from the group consisting of a jet-mill, an ultrasonicator, ultrasonics, a colloid-mill, a ball-mill, a bead-mill, a sand- A carbon nanotube network reduced in size by a further process;

Optionally, the electrode composition has a tap density of the carbon nanotube network of greater than about 0.02 g / cm3;

Optionally, the electrode composition comprises a carbon nanotube network present in the range of about 1 to 15 weight percent of the paste;

Optionally, the electrode composition comprises a dispersant present in the paste in the range of about 0.2 to 5 weight percent;

Optionally, the electrode composition has a weight ratio of the dispersant to the carbon nanotube network of less than one.

In some embodiments, a method of making an electrode composition comprises:

Selecting a carbonaceous material network;

Adding the carbonaceous material network to a liquid vehicle to form a suspension;

Dispersing the carbonaceous material in the suspension;

Reducing the size of the network to a Hegman scale of 7 or less; And

A portion of the liquid vehicle is removed from the suspension to have a carbonaceous material in which the electrode composition is present in the range of about 1 to 10 weight percent, a bulk electrical resistivity of less than about 10 < ^-1 > Forming an electrode composition;

Lt; / RTI >

Optionally, the method further comprises mixing the liquid vehicle and the dispersant prior to adding the carbonaceous material network;

Alternatively, the step of dispersing in the process may be carried out from the group consisting of a jet-mill, an ultrasonicator, ultrasonics, a colloid-mill, a ball-mill, a bead-mill, a sand mill, a dry mill and a roll- And can be performed by a dispersing means selected.

In some embodiments, the electrode composition comprises a multiwalled carbon nanotube of diameter greater than 4 nm; (Polyvinylidene fluoride), poly (vinylidene fluoride), poly (vinyl pyrrolidone), poly (styrene sulfonate), poly (phenylacetylene) (PBO), a natural polymer, an amphiphilic substance in an aqueous solution, an anionic aliphatic surfactant, sodium dodecyl sulfate (SDS), a cyclic lipopeptide livelihood surfactant, sufactin, a water-soluble polymer, a carboxymethylcellulose, (SDS), polyoxyethylene surfactant, poly (vinylidene fluoride) PVdF, carboxymethylcellulose (CMC), hydroxylethylcellulose (hydroxyethylcellulose HEC), polyacrylic acid (PAA), polyvinyl chloride (PVC), and combinations thereof; And a liquid vehicle selected from the group consisting of water, alcohols, ethers, aromatic hydrocarbons, esters, ketones, n-methyl pyrrolidone, and mixtures thereof, and wherein the electrode composition comprises about 1 to 10% A vat material network, a bulk electrical resistivity of less than about 10 < ^-1 > ohm-cm and a viscosity greater than 5,000 cps;

Optionally, the electrode composition further comprises a lithium ion battery electrode material selected from the group consisting of lithium, oxygen, phosphorous, sulfur, nitrogen, nickel, cobalt, manganese, vanadium, silicon, carbon, aluminum, niobium and zirconium and iron , Wherein the electrode composition is present in the range of about 30 to 50 weight percent and the viscosity is greater than about 5,000 cps;

Optionally, the electrode composition further comprises a polymeric binder;

Optionally, the electrode composition is contacted with a metal surface to form an electrode for a lithium ion battery, and the liquid vehicle is removed.

In some embodiments, a method of making a battery electrode coating using the paste composition described herein,

Mixing the paste composition with a lithium ion oxide compound material;

Coating the paste on a metal film to form an electrode for a lithium ion battery and removing at least a portion of the excess liquid or liquid from the coating;

/ RTI >

Optionally, the method further comprises mixing the polymeric binder with a liquid vehicle prior to mixing the paste composition with the lithium ion battery material;

Optionally, the method is a polyethylene. A polymer binder selected from the group consisting of polypropylene, polyamide, polyurethane, polyvinyl chloride, polyvinylidene fluoride, thermoplastic polyester resin, and mixtures thereof, is used in an amount of about 5 wt% / RTI >

Alternatively, the process may be carried out in a fluidized bed reactor, as described in the applicant's U.S. Patent No. 7,563,427 and U.S. Patent Publication Nos. 2009/0208708, 2009/0286675, and U.S. Patent Application Serial No. 12 / 516,166, Lt; RTI ID = 0.0 > carbon nanotube entanglement < / RTI >

Alternatively, the paste compositions described herein can be prepared as described in U.S. Patent No. 7,563,427 and U.S. Patent Nos. 2009/0208708, 2009/0286675, and U.S. Patent Application No. 12 / 516,166, , Use a small portion of the carbonaceous material network produced in the fluidized bed reactor.

In some embodiments, an electrode material composition or electrode material for coating with a metal current collector or metal conductor for a lithium battery comprises a multi-walled carbon nanotube in a bi-mode distribution within the network; An electrode active material selected from the group consisting of lithium, oxygen, phosphorous, nitrogen, nickel, cobalt, manganese, vanadium, silicon, carbon, graphite, aluminum, niobium, titanium and zirconium and iron; (Polyvinylidene fluoride), poly (vinylidene fluoride), poly (vinyl pyrrolidone), poly (styrene sulfonate), poly (phenylacetylene) (PBO), a natural polymer, an amphiphilic substance in an aqueous solution, an anionic aliphatic surfactant, sodium dodecyl sulfate (SDS), a cyclic lipopeptide livelihood surfactant, sufactin, a water-soluble polymer, a carboxymethylcellulose, Polyvinylidene fluoride (PVdF), carboxymethylcellulose (CMC), polyvinylidene fluoride (PVDF), polyvinylidene fluoride (PVDF) ), Hydroxyethylcellulose (HEC), polyacrylic acid (PAA), polyvinyl chloride (PVC), and combinations thereof; And polyethylene. Polymeric binder selected from the group consisting of polypropylene, polyamide, polyurethane, polyvinyl chloride, polyvinylidene fluoride, thermoplastic polyester resin, and mixtures thereof (less than about 0.5 wt% to less than 5 wt% Wherein the electrode active material is present in an amount of 30 to 50 weight percent and the carbonaceous material network is present in a range of about 1 to 10 weight percent prior to coating with the metal current collector, %; After coating and drying, the electrode active material is greater than 80 weight percent (in some spheres greater than 90 weight percent);

Optionally, the electrode material composition comprises a carbon nanotube network fabricated in a fluidized bed reactor;

Optionally, the electrode material composition comprises a carbon nanotube network having a maximum dimension of about 0.5 to 1,000 microns;

Optionally, the electrode material composition comprises carbon nanotubes having a diameter of about 4 to 100 nm;

Optionally, the electrode material comprises carbon nanotubes, wherein the tap density of the carbon nanotube entanglement structure is greater than about 0.02 g / cm < 3 >;

Optionally, the electrode material comprises a carbonaceous material network wherein the bulk resistivity of the material is less than 10 ohm-cm, alternatively less than 1 ohm-cm, alternatively less than 0.1 ohm-cm, alternatively 0.05 ohm-cm .

In some embodiments, a method of making an electrode material using the electrode material composition described herein,

Forming a paste composition comprising a carbonaceous material network, a dispersant, and a polymeric binder;

Mixing the paste composition with a lithium ion battery active material, wherein the paste composition is in the range of about 30 to 50 weight percent of the blended composition;

Coating the mixed paste composition and the active material composition on a metal conductor or electrode; And

Removing excess volatile components to form a battery, optionally an electrode for lithium ion; after the excess volatile component removal, the active material composition is greater than about 80 weight percent of the coated paste and battery material composition;

;

Optionally, in the method, the active material composition comprises greater than about 90% by weight of the coated paste and battery material composition after removal of the excess volatile component;

Optionally, the method includes mixing the liquid vehicle and the polymeric binder prior to mixing the paste composition with the lithium ion battery material;

Optionally, in the method, the polymeric binder is polyethylene. Selected from the group consisting of polypropylene, polyamide, polyurethane, polyvinyl chloride, polyvinylidene fluoride, thermoplastic polyester resin, and mixtures thereof; less than about 5% by weight of the paste composition;

Alternatively, the active material of the lithium ion battery electrode may be selected from the group consisting of lithium, oxygen, phosphorous, nitrogen, nickel, cobalt, manganese, vanadium, silicon, carbon, graphite, aluminum, niobium, titanium and zirconium and iron Selected;

Optionally, in the process, the carbonaceous material network, the dispersant and the polymeric binder are formed into a dry pellet prior to mixing with the active material composition of the lithium ion battery. In some embodiments, a dry pellet comprising a carbonaceous material network, a dispersant, and a polymeric binder is molded to form a liquid vehicle or an additional dispersant prior to coating the electrode composition onto a metal conductor or base electrode prior to re- Lt; / RTI > can be performed).

Example 8

Preparation of large (large) diameter CNT (B) on Ni / SiO ₂ catalyst

The preparation of large (large) diameter carbon nanotubes has been carried out by catalytic decomposition of hydrocarbons such as propylene in the presence of catalysts. The catalyst was prepared using silica gel having an average particle size of 5 mu m. Nickel nitrate was impregnated on these silica particles in a ratio of about 1 part by weight of nickel to 1.5 parts by weight of silica. The resulting particles were calcined in air at 400 < 0 > C for 2 hours thereafter. A 2 inch quartz reactor tube was heated to about 600 ° C while purging with nitrogen. A mixed flow of hydrogen (1 L / min) and nitrogen (1 L / min) was fed to the hot tube for 5 minutes, at which time the catalyst was introduced into the reactor tube. The reduction was performed for about 10 minutes before the propylene / nitrogen (1: 1) mixture passed through the reactor at 2 L / min. The reaction lasted for 0.5 hour, after which the reactor was allowed to cool to room temperature under argon. The resulting nanotubes were recovered and showed a yield of more than 15 times the weight of the catalyst. The final product was recovered as a black fluffy powder. The diameter of the carbon nanotubes was found to be 50 to 70 nm by a scanning electron microscope.

Example 9

Production of large (large) diameter CNTs (B) on Cu-Ni-Al catalysts

The catalyst was prepared through coprecipitation of copper nitrate, nickel nitrate and aluminum nitrate. In a round bottom flask, three nitrates were weighed and dissolved in deionized water to a molar ratio of Cu: Ni: Al of 3: 7: 1. The 20% ammonium bicarbonate containing solution was then slowly added under continuous stirring. After the pH reached 9 (the point at which precipitation ceased), the resulting suspension was allowed to digest under constant agitation for 1 hour. The precipitate was then washed with deionized water and then filtered, dried, and calcined. The resulting catalyst contained 50 wt% Ni, 24 wt% Cu, and 3.5 wt% Al. The nanotubes were prepared at 680 ° C using 1 g of catalyst according to the procedure described in Example 8. A total of 30 g of nanotubes were isolated in a weight yield of 29 times the catalyst. According to the scanning electron microscope photograph, the nanotubes produced from the above process have an average diameter of 80 nm.

Example 10

Mixing and electrode manufacturing of large (large) and small (small) nanotubes

CNT (B) was blended for 5 hours in a Ross mixer with a conductive paste containing 5% of small (small) nanotubes (CNT (A)) prepared from Example 1 and a weight ratio of 3: 140 , Wherein "140" is the mass of the conductive paste containing 5% CNT (A), so that the mass ratio (I: II) in the mixture of the two distinct carbon nanotubes (A) 3; The fraction of large (large) diameter nanotubes to total nanotube content was 30 weight percent. The electrode coating composition was then prepared by mixing large (large) and small (small) nanotubes with graphite particles having a mean diameter of 20 μm and with other necessary binders (eg PVDF). The coating formulations were then applied (applied) to a copper foil for use as a Mylar sheet and a battery anode for resistivity measurements. The coated sheet was further compressed under constant pressure, for example 10 kg / cm ² pressure.

The bulk resistivity was measured using a 4-point probe, and the results are shown in Table 4 below.

Bulk resistivity (Ohm-cm) CNT (A) / graphite CNT (I & II) / graphite No compression 0.33 0.38 After compression 0.012 0.0086

The data show that mixed large (large) and small (small) nanotubes provide better electrical contact within the graphite particle matrix, and as a result, compared to using small (small) carbon nanotubes of a single size And showed much reduced bulk resistivity. The conductivity was good, but it was not optimized for the large pore volume present in large graphite particles.

Example 11

Manufacture of electrodes using graphene and carbon nanotubes

5 g of polyvinylpyrrolidone (PVP) powder was added to 470 g of n-methylpyrrolidone (NMP) solvent and stirred until completely dissolved. The PVP / NMP solution was added to a colloid mill with 20 g of Crushed FloTube ™ 9000 multiwalled carbon nanotubes and 5 g of graphene powder of the first type (specific surface area 150 m ² / g) and grounded at a rate of 3,000 rpm Respectively. Test samples were taken out every 30 minutes and evaluated. The viscosity was measured and recorded at 25 DEG C using a Brookfield viscometer for each sample. At the same time, the Hegman scale was recorded. Maximum dispersion was observed after milling for 180 minutes. The fineness of these pastes reached well below 10 [mu] m after 60 minutes of milling. The sample was named Sample A1. SEM photographs are shown in Fig. 6A. It appears that there is some curled graphene sheet due to the very thin sheet. A somewhat thick graphene sheet type was used in Example 12 below.

Paste Sample A1 containing 4% CNT and 1% graphene was used to make a lithium ion coin battery. LiFePO ₄ manufactured by POSTECH / Sud KEMIS Co., Ltd. was used as a cathode material, and lithium foil was used as an anode. The cathode material contained LiFePO ₄ , CNT, PVP and PVDF and was prepared by mixing a suitable amount of LiFePO ₄ , CNT paste and PVDF with n-methyl pyrrolidone at a rate of 3,000 rpm in a high speed blender. A coating of this paste was prepared using a doctor blade on an Al foil, followed by drying and compression (compression). SEM photographs are shown in Fig. 6A. The assembled battery using the method described in Example 3 was tested for cycle life performance at different discharge rates as shown in FIG. 6B. It has been found that an embedded electrode with a mixture of graphene sheets and carbon nanotubes has excellent cycle life performance at various fill rates.

Example 12

Mixing of graphene and carbon nanotubes and electrode manufacturing

A second paste, Sample A2, was prepared according to the same procedure as in Example 11 except that a second type of graphene (specific surface area of 50 m ² / g) was used. SEM photographs are shown in Fig. 7A. A lithium ion coin battery was prepared using the paste Sample A2 according to the same procedure as in Example 11 and tested for cycle life performance at different discharge rates as shown in FIG. 7B. It has been found that electrodes embedded with a mixture of graphene sheets and carbon nanotubes have excellent cycle life performance at various fill rates.

In some embodiments, an electrode composition comprising a portion of a large (large) diameter carbon nanotube and a portion of a small (small) diameter carbon nanotube is advantageous. For some embodiments herein, a "large diameter" CNT (CNT (B)) is defined as a nanotube whose diameter is about 40 to 100 nm; A "small (small) diameter" CNT (CNT (A)) is defined as a nanotube whose diameter is about 4 to 15 nm. Large (large) diameter nanotubes, defined as 30 to 100 nm, are typically much longer (at least 1 to 10 micrometers or longer) longer than small (small) diameter nanotubes and form main conductive pathways do. Small (small) diameter CNTs act as "local pathways" or networks. In some embodiments, the weight fraction of the small (small) diameter nanotube (A) ranges from about 50 to 95%. In Example 10, the ratio of "A" / ("A" + "B") corresponds to about 70%.

In some embodiments, the electrode material composition for coating applied to (applied to) the conductive electrode (either the cathode for the battery or the anode) comprises a first portion of a large (large) diameter carbon nanotube (CNT (B) Walled carbon nanotubes in the form of entanglement comprising a second portion of a small (small) diameter carbon nanotube (CNT (A)), wherein the ratio of the weight of the first portion to the weight of the second portion The weight ratio of the two parts is about 0.05 to 0.50); Electrode active material; Dispersing agent; Wherein the polymeric binder is in the range of from less than about 0.5% to 5% by weight of the electrode material composition, and the electrode active material comprises from about 30% to 60% by weight of the electrode material composition, The total carbon nanotubes range from about 0.2 to 5 weight percent, and the dispersant ranges from about 0.1 to 2 weight percent;

Optionally, the carbon nanotube entanglement structure is fabricated in a fluid bed reactor;

Optionally, the carbon nanotube entanglement structure has a maximum dimension of about 0.5 to 1,000 [mu] m;

Optionally, the large (large) diameter carbon nanotubes have a diameter in the range of about 40 to 100 nm, the small (small) diameter carbon nanotubes have a diameter in the range of about 5 to 20 nm;

Optionally, the tap density of the carbon nanotube entanglement structure is about 0.02 g / cm < ³ > Bigger;

Optionally, the bulk resistivity of the electrode coating is less than 10 Ohm-cm for the cathode and less than 1 Ohm-cm for the anode.

In some embodiments, a method of making an electrode coating material comprises:

Forming a paste composition comprising a carbon nanotube entanglement structure, a dispersant, and a polymeric binder;

Mixing the paste composition with a battery active material composition, wherein the paste composition ranges from about 1 to 25 weight percent of the blended composition;

Coating the mixed paste composition and the active material composition on an electrical conductor; And

Removing excess volatile components to form an electrode for a battery, wherein after removal of excess volatile components, the active material composition is greater than about 80 weight percent of the coated paste and battery material composition, and the bulk resistivity of the coating is Less than about 10 Ohm-cm for the cathode and less than about 1 Ohm-cm for the anode;

Lt; / RTI >

Optionally, after removal of the excess volatiles, the active material composition may comprise greater than about 90 weight percent of the coated paste and battery material composition;

Optionally, the method further comprises mixing the polymeric binder with a liquid vehicle prior to mixing the paste composition with a lithium ion battery material;

Optionally, the polymeric binder is polyethylene. Selected from the group consisting of polypropylene, polyamide, polyurethane, polyvinyl chloride, polyvinylidene fluoride, thermoplastic polyester resins, and mixtures thereof; less than about 5% by weight of the paste composition;

Alternatively, the battery electrode active material is selected from the group consisting of lithium, oxygen, phosphorous, nitrogen, nickel, cobalt, manganese, vanadium, silicon, carbon, graphite, aluminum, niobium, titanium and zirconium and iron;

Optionally, the multiwall carbon nanotube entanglement structure, dispersant and polymeric binder are formed into a dry pellet prior to mixing with the battery active material composition.

In some embodiments, the material composition for the conductive collector or for the conductive layer on the battery electrode comprises a first diameter carbon nanotube (CNT (A)), a second diameter carbon nanotube (CNT (B)), A conductive additive comprising at least two carbonaceous materials of a three-dimensional network selected from the group consisting of graphene and carbon black; Electrode material; Dispersing agent; And a polymeric binder, wherein the polymeric binder is present in a proportion of from about 0.005 to about 0.10 parts by weight of the material composition; The electrode material is in the range of about 0.30 to 0.90 weight fraction; The carbonaceous material is present in the range of about 0.01 to 0.20 weight fraction;

Optionally, the carbonaceous material is present in a proportion of about 0.01 to 0.10 parts by weight;

The dispersing agent is present in a weight fraction from less than about 0.001 to about 0.10 prior to being coated on the collector;

Optionally, the carbonaceous material is present in an amount of about 0.05 to 0.20 parts by weight;

Optionally, the bulk resistivity of the material composition ranges from about 0.01 to 10 Ohm-cm;

Optionally, the dispersant is selected from the group consisting of polyvinylpyrrolidone and Hypermer KD-1 and is stable at a voltage of about 4.4 volts;

Optionally, the polymeric binder is PVDF;

Optionally, the electrode material is selected from the group consisting of Li cobalt oxide, Li iron phosphate, Li nickel oxide, Li manganese oxide, Li nickel-cobalt-manganese complex oxide, Li-S, Li nickel-cobalt-aluminum oxide and combinations thereof Being;

Alternatively, the carbonaceous material of the three-dimensional network may be a first portion of a small (small) diameter carbon nanotube (CNT (A)) and a second portion of a large (large) diameter carbon nanotube (CNT Wherein the weight ratio of the first portion (CNT (A)) to the combined weight of the first portion and the second portion is in the range of about 0.50 to 0.95;

Optionally, the carbonaceous material of the three-dimensional network further comprises graphene, the weight ratio of graphene to CNT (A + B) is 0.05 to 0.5;

Optionally, the carbonaceous material of the three-dimensional network further comprises graphene and carbon black, wherein the carbonaceous content (by weight) of the conductive additive is about 70% 10% CNT (A + B) 20% 5% graphene, and about 10% 5% carbon black.

In some embodiments, a method of manufacturing a material composition for coating a conductive collector, or as a conductive layer on a battery electrode,

Forming a first composition comprising a carbonaceous material, a dispersant and a polymeric binder in a three-dimensional network;

Dispersing the three-dimensional network in the first composition into a liquid vehicle;

Mixing the first composition and the liquid vehicle with a battery material composition to produce a material composition wherein the first composition ranges from about 0.01 to 0.50 weight percent of the material composition;

Coating the mixed material composition on a conductive collector; And

Removing excess components to form an electrode for the battery; after removal of the excess component, the battery material composition is greater than about 80% by weight of the blended composition;

/ RTI >

Optionally, the polymeric binder is polyethylene. Selected from the group consisting of polypropylene, polyamide, polyurethane, polyvinyl chloride, polyvinylidene fluoride, thermoplastic polyester resins, and mixtures thereof (less than about 5% by weight of the total material composition);

Optionally, the battery material composition is selected from the group consisting of lithium, oxygen, phosphorous, sulfur, nitrogen, nickel, cobalt, manganese, vanadium, silicon, carbon, graphite, aluminum, niobium, titanium and zirconium and iron;

Optionally, the first composition is formed into a dry pellet prior to mixing with the battery material composition;

Optionally, the carbonaceous material of the three-dimensional network is selected from the group consisting of at least two different diameter carbon nanotubes, wherein the weight fraction of the smaller diameter CNT (A) to the combined weight of the two diameter CNTs Is in the range of about 0.50 to 0.95;

Optionally, the carbonaceous material of the three-dimensional network additionally contains graphene, wherein the weight ratio of graphene to the combined weight of two diameters of CNTs is about 0.05 to 0.5 parts by weight;

Optionally, the carbonaceous material of the three-dimensional network additionally contains carbon black, and the combined weight is about 70% 10% of two diameters of CNT, about 20% 5% graphene, and about 10% 5% carbon black;

Alternatively, the dispersant may be selected from the group consisting of poly (vinylpyrrolidone; PVP), poly (styrenesulfonate; PSS), poly (phenylacetylene; PAA), poly (metaphenylene vinylene; PmPV), polypyrrole (PBO), a natural polymer, an amphiphilic substance in an aqueous solution, an anionic aliphatic surfactant, sodium dodecyl sulfate (SDS), a cyclic lipopeptide livelihood surfactant, sulfictin, a water-soluble polymer, Polyvinyl alcohol (PVA), sodium dodecyl sulfate (SDS), n-methyl pyrrolidone, polyoxyethylene surfactant, poly (vinylidene chloride) (PVDF), carboxymethyl cellulose (CMC), hydroxyl ethyl cellulose (HEC), polyacrylic acid (PAA), polyvinyl chloride (PVC), and combinations thereof, On the voltage of the bolt It is stable.

While the present invention has been described by way of examples and embodiments, it is to be understood that the invention is not limited to the disclosed embodiments. On the contrary, it is intended to cover various modifications and similar arrangements, which are obvious to those skilled in the art. Accordingly, the claims are to be accorded the broadest interpretation so as to encompass all such modifications and similar arrangements. All publications, patents, and patent applications cited herein are incorporated by reference in their entirety.

All members, portions and steps described in this specification are preferably included. Any of such members, portions, and steps may be replaced or eliminated altogether by other elements, parts, and steps that will be apparent to those skilled in the art.

Broadly, the disclosure discloses the following. A carbon nanotube-based composition and a method for manufacturing an electrode for a battery are disclosed. Dimensional network carbonaceous material comprising carbon nanotubes (CNT (A) and CNT (B)), grafts, carbon black, and optionally other types of carbon- A composition for a battery electrode is disclosed.

concept

This specification discloses the following concepts.

Concept 1: As a material composition for a conductive layer on a battery electrode,

At least two carbonaceous materials of a three-dimensional network selected from the group consisting of first diameter carbon nanotubes (CNT (A)), second diameter carbon nanotubes (CNT (B)), graphene and carbon black A conductive additive comprising;

Electrode material;

Dispersing agent; And

Polymer binder;

/ RTI >

Wherein the weight fraction of the components in the material composition is about 0.01 to 0.05 for a polymeric binder, about 0.30 to 0.90 for an electrode material, about 0.005 to 0.10 for a carbonaceous material, and about 0.001 to 0.005 for a dispersant.

Concept 2: As a material composition of Concept 1, the bulk resistivity of the material composition is about 0.01 to 10 ohm-cm.

Concept 3: As a material composition of Concept 1 or 2, the dispersant is selected from the group consisting of polyvinylpyrrolidone and Hypermer KD-1 and is stable at a voltage of about 4.4 volts.

Concept 4: A material composition according to any of the preceding concepts, wherein the polymeric binder is PVDF.

Concept 5: A material composition according to any of the preceding concepts, wherein the electrode material is selected from the group consisting of Li cobalt oxide, Li iron phosphate, Li nickel oxide, Li manganese oxide, Li nickel-cobalt-manganese complex oxide, - cobalt-aluminum oxide and combinations thereof.

Concept 6: A material composition according to any of the preceding concepts, wherein the carbonaceous material of the three-dimensional network comprises a first portion of a small (small) diameter carbon nanotube (CNT (A) (CNT (B)) with respect to the combined weight of the first portion (CNT (A)) and the second portion (CNT (B)) and the second portion of the carbon nanotube )) Is in the range of about 0.50 to 0.95.

Concept 7: A material composition according to any of the preceding concepts, wherein the carbonaceous material of the three-dimensional network additionally comprises graphene and the weight ratio of graphene to CNT (A + B) is from about 0.05 to 0.5 .

Concept 8: In the material composition of Concept 7, the carbonaceous material of the three-dimensional network additionally comprises carbon black, wherein the carbonaceous content (by weight) of the conductive additive is about 70% 10% CNT (A + B), about 20% ± 5% graphene, and about 10% ± 5% carbon black.

Concept 9: A method for producing a material composition for a conductive layer on a battery electrode,

Forming a first composition comprising a carbonaceous material, a dispersant and a polymeric binder in a three-dimensional network;

Dispersing the three-dimensional network in the first composition into a liquid vehicle;

Mixing the first composition and the liquid vehicle with a battery material composition to produce a material composition wherein the first composition ranges from about 0.01 to 0.50 weight percent of the material composition;

Coating the material composition on a battery electrode; And

Removing excess components to form an electrode for the battery; after removal of the excess component, the battery material composition exceeds about 0.80 weight fraction of the blended composition;

.

Concept 10: The method of concept 9, wherein said polymeric binder is polyethylene. Is selected from the group consisting of polypropylene, polyamide, polyurethane, polyvinyl chloride, polyvinylidene fluoride, thermoplastic polyester resins, and mixtures thereof, and is less than about 10% by weight of the total material composition.

Concept 11: The method of concept 9 or 10 wherein said battery material composition is selected from the group consisting of lithium, oxygen, phosphorous, nitrogen, nickel, cobalt, manganese, vanadium, silicon, carbon, graphite, aluminum, niobium, titanium, zirconium, Selected from the group consisting of

Concept 12: The method of concept 9, 10 or 11, wherein the carbonaceous material of the three-dimensional network is selected from the group consisting of at least two different diameter carbon nanotubes, wherein the combined weight of the two diameters of CNTs The weight fraction of the smaller diameter CNT (A) ranges from about 0.50 to 0.95.

Concept 13: The method of concept 12, wherein the carbonaceous material of the three-dimensional network additionally contains graphene, wherein the weight ratio of graphene to the combined weight of two diameters of CNT is about 0.05 to 0.5 weight fraction.

Concept 14: The method of concept 13, wherein the carbonaceous material of the three-dimensional network additionally contains carbon black, wherein the combined weight is about 70% 10% of two diameters of CNT, about 20% 5% Graphene, and about 10% 5% carbon black.

Concept 15: The method of any of the concepts 9-14, wherein the dispersant is selected from the group consisting of poly (vinylpyrrolidone; PVP), poly (styrenesulfonate; PSS), poly (phenylacetylene; PAA) Polypyrrole (PPy), poly (p-phenylene benzobisoxazole, PBO), natural polymer, amphiphile in aqueous solution, anionic aliphatic surfactant, sodium dodecyl sulfate (SDS) (SDS), n-methylpyrrolidone, polyoxyethylene surfactant (polyvinyl alcohol), polyvinyl alcohol, polyvinyl alcohol, polyvinylpyrrolidone, polyvinylpyrrolidone, The active agent is selected from the group consisting of polyvinylidene fluoride (PVDF), carboxymethylcellulose (CMC), hydroxylethylcellulose (HEC), polyacrylic acid (PAA), polyvinyl chloride (PVC) , The dispersant Is stable at a voltage of about 4.4 volts.

1: large (large) and small (small) cathode particles
2: CNT (A)
3: Binder
4: Aluminum film
5: CNT (B)

Claims (15)

A material composition for a conductive layer on a battery electrode,
At least two carbonaceous materials of a three-dimensional network selected from the group consisting of first diameter carbon nanotubes (CNT (A)), second diameter carbon nanotubes (CNT (B)), graphene and carbon black A conductive additive comprising;
Electrode material;
Dispersing agent; And
Polymer binder;
/ RTI >
Wherein the weight fraction of the components in the material composition is from about 0.01 to 0.05 for a polymeric binder, from about 0.30 to 0.90 for an electrode material, from about 0.005 to 0.10 for a carbonaceous material, and from about 0.001 to 0.005 for a dispersant. The material composition of claim 1, wherein the bulk resistivity of the material composition is from about 0.01 to 10 ohm-cm. The method of claim 1, wherein the dispersing agent is selected from the group consisting of polyvinylpyrrolidone and Hypermer KD-1,
Wherein the dispersant is stable at a voltage of about 4.4 volts. The material composition according to claim 1, wherein the polymeric binder is PVDF. The method according to claim 1, wherein the electrode material is selected from the group consisting of Li cobalt oxide, Li iron phosphate, Li nickel oxide, Li manganese oxide, Li nickel-cobalt-manganese complex oxide, Li-S, Li nickel-cobalt- ≪ / RTI > The method of claim 1, wherein the carbonaceous material of the three-dimensional network comprises a first portion of a small (small) diameter carbon nanotube (CNT (A)) and a first portion of a large (large) Lt; RTI ID = 0.0 > a &
Characterized in that the weight ratio of the first portion (CNT (A)) to the combined weight of the first portion (CNT (A)) and the second portion (CNT (B)) ranges from about 0.50 to 0.95 Composition. The method of claim 1, wherein the carbonaceous material of the three-dimensional network further comprises graphene,
And the weight ratio of graphene to CNT (A + B) is about 0.05 to 0.5. 8. The method of claim 7, wherein the carbonaceous material of the three-dimensional network further comprises carbon black,
Here, the carbonaceous content (by weight) of the conductive additive includes about 70% 10% CNT (A + B), about 20% 5% graphene, and about 10% 5% carbon black ≪ / RTI > A method of making a material composition for a conductive layer on a battery electrode,
Forming a first composition comprising a carbonaceous material, a dispersant and a polymeric binder in a three-dimensional network;
Dispersing the three-dimensional network in the first composition into a liquid vehicle;
Mixing the first composition and the liquid vehicle with a battery material composition to produce a material composition, wherein the first composition is in the range of about 0.01 to 0.50 weight percent of the material composition;
Coating the material composition on a battery electrode; And
Removing excess components to form an electrode for the battery; after removal of the excess component, the battery material composition exceeds about 0.80 weight fraction of the blended composition;
≪ / RTI > The polymeric binder according to claim 9, wherein the polymeric binder is polyethylene. Polypropylene, polyamide, polyurethane, polyvinyl chloride, polyvinylidene fluoride, thermoplastic polyester resin, and mixtures thereof,
Lt; RTI ID = 0.0 > 10% < / RTI > by weight of the total material composition. The battery material composition according to claim 9, wherein the battery material composition is selected from the group consisting of lithium, oxygen, phosphorus, sulfur, nitrogen, nickel, cobalt, manganese, vanadium, silicon, carbon, graphite, aluminum, niobium, titanium, zirconium, ≪ / RTI > 10. The method of claim 9, wherein the carbonaceous material of the three-dimensional network is selected from the group consisting of at least two different diameter carbon nanotubes,
Wherein the weight fraction of CNT (A) of smaller diameter to the combined weight of two diameters of CNTs is in the range of about 0.50 to 0.95. 13. The method of claim 12, wherein the carbonaceous material of the three-dimensional network additionally contains graphene, wherein the weight ratio of graphene to the combined weight of two diameters of CNTs is from about 0.05 to 0.5 parts by weight ≪ / RTI > 14. The method of claim 13, wherein the carbonaceous material of the three-dimensional network additionally contains carbon black and the combined weight is about 70% 10% of two diameters of CNT, about 20% 5% graphene, Lt; RTI ID = 0.0 >% < / RTI > 5% carbon black. The method of claim 9, wherein the dispersant is selected from the group consisting of poly (vinylpyrrolidone), poly (styrene sulfonate), poly (phenylacetylene), poly (meta-phenylenevinylene) PPy), poly (p-phenylenebenzobisoxazole; PBO), a natural polymer, an amphiphilic substance in an aqueous solution, an anionic aliphatic surfactant, sodium dodecyl sulfate (SDS), cyclic lipopeptide livelihood surfactant, , Water-soluble polymers, carboxymethylcellulose, hydroxylethylcellulose, poly (vinyl alcohol), sodium dodecyl sulfate (SDS), n-methylpyrrolidone, polyoxyethylene surfactants, poly (vinylidene fluoride; PVDF), carboxymethylcellulose (CMC), hydroxylethylcellulose (HEC), polyacrylic acid (PAA), polyvinyl chloride (PVC), and combinations thereof,
Wherein the dispersant is stable at a voltage of about 4.4 volts.

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