KR20190047717A - A method of coating an electrically conductive substrate, and a related electrodepositable composition comprising graphene carbon particles - Google Patents

Abstract

A method is disclosed in which an electrically conductive substrate is impregnated with an electrodepositable composition comprising graphene carbon particles wherein the substrate acts as an electrode in an electrical circuit comprising an electrode impregnated with the composition and a counter electrode, A coating is applied over or on at least a portion of the substrate. The electrodepositable composition comprises an aqueous medium, an ionic resin, and solid particles comprising graphenic carbon particles. In addition, the solid particles include lithium-containing particles.

Description

A method of coating an electrically conductive substrate, and a related electrodepositable composition comprising graphene carbon particles

Cross-reference to related application

This application is a continuation-in-part of US patent application Ser. No. 14 / 867,307, filed September 28, 2015, filed on November 27, 2012, Continued application. The present application is also related to U.S. Patent No. 14 / 831,047, filed by U.S. Patent No. 9,150,736, and U.S. Patent Application No. 13 / 686,003 filed on November 27, 2012, filed on August 20, ). This application is a continuation-in-part of U.S. Patent Application No. 13 / 249,315 filed on September 30, 2011 (now U.S. Patent No. 8,486,363, issued July 16, 2013) 13 / 309,894 (filed on December 2, 2011) (now part of U.S. Patent No. 8,486,364 issued on July 16, 2013, part of 13 / 249,315) U.S. Patent Application No. 14 / 348,280 filed on Mar. 28, 2014 (filed on September 28, 2012), filed on March 28, 2014 (now U.S. Patent No. 9,221,688, : December 29, 2015), which is a continuation-in-part of U.S. Patent Application Serial No. 14 / 530,007 filed on October 31, 2014. These patent applications and patents are all incorporated herein by reference.

Technical field

The present invention relates to the coating of an electrically conductive substrate by electrodeposition of a composition comprising graphene carbon particles and a resin.

Electrodeposition as a coating application process entails depositing a composition on an electrically conductive substrate under the influence of an applied potential. The coating is deposited as the substrate is impregnated into the composition, wherein the substrate acts as an electrode in an electrical circuit comprising an electrode impregnated with the composition and a counter electrode, and the coating is applied to the substrate as current passes between the electrodes.

Often, the composition used in the electrodeposition process comprises a resinous phase dispersed in an aqueous medium. The composition for impregnating the substrate may comprise pigments, other fillers and additives that provide color, and because of the electrodeposition of mainly continuous resinous films, electrodeposited coatings have historically pursued properties, such as good corrosion resistance. Thus, the resin content of the composition impregnating the substrate is relatively high relative to the amount of pigment and other filler. For example, such compositions generally comprise from 0.02 to 1 part by weight of pigment relative to 1 part by weight of resin phase.

Lithium ion batteries consist of a cathode, an anode, a separator and an electrolyte. The negative electrode is a lithium deposited on top - a metal (often aluminum) foil (foil) substrate having a containing the active substance, e.g., LiFePO _4. The lithium-containing active material can be removed from a slurry containing a lithium-containing active material, a conductive carbon and a binder (e.g., polyvinylidene difluoride) in an organic solvent (e.g., n- slot die coater or roll coater. In such a slurry, the sum of the amounts of lithium-containing active material and conductive carbon is higher than the amount of binder, typically at least 9 parts by weight to 1 part by weight. However, the use of such solvent-based slurries is not environmentally desirable.

As a result, there is a need for alternative methods and compositions for depositing lithium-containing compositions on metal foil. The present invention has been made in view of the foregoing.

An aspect of the invention provides a method comprising impregnating an electrically conductive substrate with an electrodepositable composition wherein the substrate acts as an electrode in an electrical circuit comprising an electrode impregnated with the composition and a counter electrode, A coating is applied over or on at least a portion of the substrate as it passes between the electrodes, wherein the electrodepositable composition comprises: (a) an aqueous medium; (b) an ionic resin; And (c) solid particles comprising graphene carbon particles, wherein the composition has a weight ratio of solid particles to ionic resin of at least 4: 1.

Yet another aspect of the present invention is a process for the preparation of (a) an aqueous medium; (b) an ionic resin; And (c) solid particles comprising (i) graphene carbon particles and (ii) lithium-containing particles, wherein the composition comprises a weight ratio of solid particles to ionic resin of at least 4: 1 .

A further aspect of the invention provides an electrodeposited lithium ion battery electrode coating on a substrate, wherein the electrodeposited coating comprises: (a) a cured ionic resin; And (b) solid particles comprising (i) graphene carbon particles and (ii) lithium-containing particles, wherein the composition has a weight ratio of solid particles to a cured ionic resin of at least 4: 1.

For purposes of this specification, the present invention is capable of estimating various alternative parameters and sequential steps. It is also to be understood that all values expressing quantities of ingredients used in the specification and claims are to be modified in all instances by the term " about " unless otherwise indicated in the operating examples or otherwise indicated. Accordingly, unless otherwise stated, the numerical values set forth in the following specification and attached claims are subject to variation depending upon the intended characteristics to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical value should at least be understood by applying ordinary rounding techniques in light of the number of significant digits reported.

Numerical ranges and variables representing a broad scope of the invention are approximations, but numerical values used in specific embodiments are recorded as precisely as possible. However, any numerical value herein includes certain errors necessarily resulting from the standard deviation found in these individual test measurements.

It is also to be understood that any numerical range recited herein is intended to include all sub-ranges subsumed therein. For example, a range of " 1 to 10 " means that all sub-ranges with a minimum value of 1 and a maximum value of 10 (and including them), i.e., a minimum value of 1 or more and a maximum value of 10 or less, Are intended to be included.

In this application, the use of the singular includes the plural unless otherwise stated. Also, in this application, the use of " or " means " and / or " unless " and / or "

As indicated, certain embodiments of the present invention are directed to a method comprising impregnating an electroconductive substrate with an electrodepositable composition. An electrically conductive substrate suitable for use in the methods described herein includes a metal substrate and an electrically conductive composite material, such as a polymeric material containing a sufficient amount of a conductive filler such as conductive carbon particles, carbon nanotubes, carbon fibers, fullerenes, ≪ / RTI > Suitable metal substrates include, but are not limited to, iron and non-ferrous metals. Suitable ferrous metals include iron, steel and alloys thereof. Non-limiting examples of useful steel materials include cold rolled steel, galvanized (zinc coated) steel, electrogalvanized steel, stainless steel, pickled steel, GALVANNEAL, GALVALUME), galvanized (GALVAN) zinc-aluminum alloys coated on steel, and combinations thereof. Useful non-ferrous metals include aluminum, copper, manganese, nickel, zinc, magnesium and alloys thereof. In addition, a combination or composite of iron and non-ferrous metals may be used.

In certain embodiments, the substrate is embodied in the form of a sheet, coil, or foil. The term " foil " as used herein refers to a thin and flexible metal sheet. The foil may be a continuous sheet or may have a pore, a net-like structure, or a screen-like structure. Such foils may be composed of, for example, aluminum, iron, copper, manganese, nickel, combinations thereof and / or alloys thereof. In certain embodiments, the thickness of the foil (e.g., foil comprising aluminum) is less than or equal to 8 mils (203.2 m), such as less than 4 mils (101.6 m), less than 2 mils (50.8 m) or less, or 0.1 mil (2.54 μm) or greater, such as 0.2 mil (5.08 μm) or greater, 0.4 mil (10.2 μm) or greater, or 0.5 mil (12.7 μm) or greater.

The method includes impregnating an electrically conductive substrate with an electrodepositable composition, wherein the substrate acts as an electrode in an electrical circuit comprising an electrode impregnated with the composition and a counter electrode, wherein when the electrical current passes between the electrodes A coating is applied over or onto at least a portion of the substrate. As used herein, the term " on or on, " the coating may be applied directly onto at least a portion of the substrate surface, or the coating may be applied over any coating or pretreatment material previously applied to at least a portion of the substrate surface .

The term " electrodepositable composition " as used herein refers to a composition comprising an electrodepositable component. The term " electrodepositable " as used herein means that it can be deposited on an electrically conductive substrate under the influence of an applied potential.

The electrodepositable composition used in the process of the present invention comprises an aqueous medium. The term " aqueous medium " as used herein refers to a medium comprising mostly water in combination with an inert organic co-solvent alone or with water. In certain embodiments, the organic co-solvent is at least partially insoluble in water. Examples of such solvents include oxygen-containing organic solvents, such as monoalkyl ethers of ethylene glycol, diethylene glycol, propylene glycol and dipropylene glycol containing from 1 to 10 carbon atoms in the alkyl group, such as monoethyl and monobutyl Ether. Examples of other solvents which are at least partially water-miscible include alcohols such as ethanol, isopropanol, butanol and diacetone alcohol. Other solvents that are at least partially water-miscible may include coalescing solvents such as triethyl phosphate, triacetin, dipropylene diacetate, and the like. When used, the organic co-solvent is used in an amount of less than 25 wt%, less than 20 wt%, or in some cases less than 10 wt%, such as less than 5 wt%, based on the total weight of water of the composition in certain embodiments.

In certain embodiments, the aqueous medium is present in an amount of at least 75 wt%, at least 90 wt%, or at least 95 wt%, such as from 75 to 99.5 wt%, from 90 to 99 wt%, or in some cases from 95 to 99 wt% By weight of the composition of the present invention. In other words, the composition used in the process of the present invention may have a relatively low total solids content, as further described below.

The electrodepositable composition used in the method of the present invention comprises an ionic resin. The term " ionic resin " as used herein refers to any resin having a charge comprising a resin having a negatively charged ion and a resin having a positively charged ion. Thus, suitable ionic resins include anionic resins and cationic resins.

In certain embodiments of the present invention, the ionic resin comprises an anionic salt group-containing resin. Suitable anionic resins include resins that contain at least partially neutralized anionic groups, such as acid groups, such as carboxylic acid groups, that provide negative charge. Thus, non-limiting examples of suitable anionic resins include base-neutralized carboxylic acid group-containing resins.

In certain embodiments, the anionic resin comprises a water soluble anionic resin. The term " water-soluble resin " as used herein means a resin that is essentially non-uniformly blended and / or dispersible molecularly or ionically in water to form a true solution. [R. Lewis, Sr., Hawley's Condensed Chemical Dictionary, (12th Ed., 1993) at page 586. In certain embodiments, the water-soluble anionic resin comprises a cellulose derivative, such as carboxymethylcellulose and its salts. CMC is a cellulose ether in which a part of the hydroxy groups on the anhydroglucose ring are substituted with carboxymethyl groups. The carboxymethyl substitution degree may range from 0.4 to 3. Because CMC is a long chain polymer, its viscosity in an aqueous solution depends on its molecular weight, which can vary from 50,000 to 2,000,000 based on the weight average. In certain embodiments, carboxymethylcellulose has a weight average molecular weight of 50,000 or more, such as 100,000 or more, or in some cases, 200,000 or more, such as 50,000 to 1,000,000, 100,000 to 500,000 or 200,000 to 300,000. Both the degree of substitution and the viscosity of the aqueous solution can be determined through ASTM D 1439-03. The molecular weight is typically estimated from the viscosity of a standard CMC solution. According to one method, the molecular weight of CMC is determined according to the method described in Kulicke, Polymer Vol. 37 No. 13, pp. 2723-2731, 1996, which is hereby incorporated by reference in its entirety: < RTI ID = 0.0 >

[Equation 1]

In the above equation,? Is viscosity, c is concentration of CMC, _and Mw is molecular weight.

In certain embodiments of the invention, the water-soluble anionic resin, such as a cellulose derivative, such as carboxymethylcellulose, is present in an amount of at least 50 wt%, such as at least 60 wt%, at least 70 wt% %, Or in some cases, 90 wt% or more. In certain embodiments, a water soluble anionic resin, such as a cellulose derivative, such as carboxymethylcellulose, is present in an amount of up to 20% by weight, up to 15% by weight, up to 10% by weight, up to 5% by weight, To 20% by weight, 1 to 15% by weight, 5 to 15% by weight, or in some cases 1 to 3% by weight. As used herein, the term " total weight of solids " refers to the total nonvolatile content of the composition, i. E., The amount of material in the composition that is not volatilized upon heating and excludes water and organic solvents.

In certain embodiments, in addition to the water-soluble anionic resin, the composition may also include a water-dispersible anionic resin. &Quot; Water-dispersible resin " as used herein means a resin that can be distributed throughout water as finely divided particles. See Hawley's at page 435.

Examples of water-dispersible anionic resins suitable for use in the compositions described herein in combination with a water-soluble anionic resin include reaction products or adducts of a dry oil or semi-dry fatty acid ester with a dicarboxylic acid or anhydride; And reaction products of fatty acid esters, unsaturated acids or anhydrides, and any further unsaturated modified materials which further react with the polyol. Also suitable are copolymers of hydroxy-alkyl esters of unsaturated carboxylic acids, unsaturated carboxylic acids and one or more other ethylenically unsaturated monomers.

Other suitable water-dispersible anionic resins include mixtures of alkyd resins and amine-aldehyde resins, mixed esters of resinous polyols, phosphate polyepoxides or phosphate acrylic resins, such as those described in EP 0469491 B1, 56, US Patent Application Publication Nos. 2009-0045071 and [0015], and U.S. Patent Application No. 13 / 232,093 [0014] to [0040] (the disclosures of which are incorporated herein by reference). Also suitable are resins comprising at least one pendant carbamate functionality, such as those described in U.S. Patent No. 6,165,338.

In certain embodiments, the composition comprises an anionic resin composition comprising a water-soluble anionic resin, such as a cellulose derivative, such as carboxymethylcellulose, and a water-dispersible anionic resin different from the cellulose derivative, wherein the water- The anionic resin is present in the composition in an amount of less than 50% by weight, such as less than 40% by weight, less than 30% by weight, less than 20% by weight, or in some cases less than 10% by weight, based on the total weight of the anionic resin of the composition. do.

As will be appreciated, in adjusting the anionic resin to solubilize or disperse the aqueous medium, it is often at least partially neutralized with a base. Suitable bases include both organic and inorganic bases. Illustrative examples of suitable bases include ammonia, monoalkylamines, dialkylamines or trialkylamines such as ethylamine, propylenamine, dimethylamine, dibutylamine and cyclohexylamine; Monoalkanolamines, dialkanolamines or trialkanolamines such as ethanolamine, diethanolamine, triethanolamine, propanolamine, isopropanolamine, diisopropanolamine, dimethylethanolamine and diethylethanolamine; Morpholine, for example N-methylmorpholine or N-ethylmorpholine. Examples of suitable inorganic bases include hydroxides, carbonates, bicarbonates and acetate bases of alkali metals, and specific examples thereof include potassium hydroxide, lithium hydroxide and sodium hydroxide. Consequently, in certain embodiments, the composition comprises an alkali salt of a cellulose derivative, such as sodium carboxymethylcellulose, potassium carboxymethylcellulose, and / or lithium carboxymethylcellulose. In certain embodiments, the resin is at least partially neutralized, for example, 20 to 200%, 40 to 150%, such as 60 to 120%.

In certain embodiments, the water-dispersible anionic resin described above comprises an active hydrogen-containing, anionic salt group-containing resin, and the composition further comprises a curing agent comprising a reactive group reactive with active hydrogen groups. The term " active hydrogen-containing, anionic salt group-containing resin " as used herein refers to a resin comprising an active hydrogen functional group and an at least partially neutralized anionic group. The term " active hydrogen functionality ", as used herein, is defined in JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, Vol. 49, page 3181 (1927), and includes, for example, a hydroxy group, a primary or secondary amine group, and a thiol group. The term " isocyanate-reactive group " In certain embodiments, the active hydrogen functionality is a hydroxy group, a primary amine group, and / or a secondary amine group.

Suitable curing agents for use in the electrodepositable compositions comprising active hydrogen-containing, anionic salt group-containing resins include, but are not limited to, aminoplast resins and phenolic plast resins. Suitable aminoplast resins are the condensation products of aldehydes (e.g., formaldehyde, acetaldehyde, crotonaldehyde, and benzaldehyde) with amino or amido group-containing materials such as urea, melamine and benzoguanamine. The products obtained from the reaction of alcohols and formaldehyde with melamine, urea and benzoguanamine are often used. Non-limiting illustrative examples of useful aminoplast resins are available from Cytec Industries under the trademark CYMEL and from Solutia Inc. under RESIMENE < RTI ID = 0.0 > Is available. Specific examples are Cymel 1130 and 1156 and Regimens 750 and 753.

In another embodiment of the present invention, the ionic resin comprises a cationic salt group-containing resin. Suitable cationic salt group-containing resins include resins containing at least partially neutralized cationic groups, such as sulfonium groups and amine groups, that provide a positive charge.

In certain embodiments, the cationic resin comprises a water-soluble cationic resin. In certain embodiments, the water-soluble cationic resin comprises poly (C _2-4 ) -alkyleneimine, which may be linear or branched, and specific examples thereof include polyethyleneimine (PEI). As will be appreciated, PEI is produced by ring opening polymerization of ethyleneamine. Other suitable water-soluble cationic resins include poly (allylamine hydrochloride), poly (acrylamide-co-diallyl dimethylammonium chloride) and poly (2-methacryloxyethyltrimethylammonium chloride). In certain embodiments, the water-soluble cationic resin (such as those described above) has a weight average molecular weight of greater than or equal to 5,000, such as greater than or equal to 10,000, or in some cases, from 5,000 to 50,000, or in some cases, from 10,000 to 25,000.

In certain embodiments, the water-soluble cationic resin, such as PEI, is present in an amount of at least 50 wt%, such as at least 60 wt%, at least 70 wt%, at least 80 wt%, or in some cases at least 90 wt% Or more. In certain embodiments, the water-soluble cationic resin, such as PEI, is present in the composition in an amount of 20 wt% or less, 15 wt% or less, 10 wt% or less, 5 wt% or less, such as 1 to 20 wt% By weight to 15% by weight, 5 to 15% by weight, or in some cases 1 to 3% by weight.

In certain embodiments, in addition to the water-soluble cationic resin, the composition also includes a water-dispersible cationic resin. Examples of water-dispersible cationic resins suitable for use in the compositions described herein are active hydrogen-containing, cationic salt group-containing resins. The term " active hydrogen-containing, cationic salt group-containing resin " as used herein refers to a resin comprising an active hydrogen functional group and an at least partially neutralized cationic group. Examples of suitable resins for the active hydrogen-containing, cationic salt group-containing resin of the present invention include, but are not limited to, alkyd resins, acrylic resins, polyepoxides, polyamides, polyurethanes, polyureas, polyethers, and poly Ester.

More specific examples of suitable active hydrogen-containing, cationic salt group-containing resins include polyepoxide-amine adducts such as the polyglycidylether of polyphenols (such as bisphenol A) and the addition of primary and / or secondary amines Water, such as U.S. Pat. No. 4,031,050 at line 3, line 27 to line 5, line 50, US Pat. No. 4,452,963 at line 5, line 58 through line 6, and line 6 at point 6, line 26, Part of which is incorporated herein by reference). In certain embodiments, some of the amines that react with the polyepoxide are ketamine of the polyamines described in U.S. Patent No. 4,104,147 at line 6, line 23 to line 7, line 23, the disclosure of which is incorporated herein by reference. Also, non-gelled polyepoxide-polyoxyalkylene polyamine resins are suitable and are described, for example, in U.S. Patent No. 4,432,850 at line 2, line 60 to line 5, line 58, the disclosures of which are incorporated herein by reference. Also, cationic acrylic resins, such as those disclosed in U.S. Patent No. 3,455,806 at line 2, line 18 to line 3, line 61, and US Pat. No. 3,928,157 at line 2, line 29 to line 3, line 21, both of which are incorporated herein by reference May be used.

In addition to the amine salt group-containing resin, a quaternary ammonium salt group-containing resin may also be used as the cationic salt group-containing resin in the compositions described herein. Examples of these resins are formed from the reaction of an organic polyepoxide with a tertiary amine acid salt. These resins are described in U.S. Patent No. 3,962,165 at line 2, line 3 to line 11, line 7 at US Patent No. 3,975,346 at line 1, line 62 to line 17, and line US Patent No. 4,001,156 at line 1, line 37 to line 7, Are incorporated herein by reference). Examples of other suitable cationic resins include ternary sulfonium salt group-containing resins, such as those described in US Pat. No. 3,793,278 at line 1, line 32 to line 5, line 20, the disclosure of which is incorporated herein by reference. It is also possible to use cationic resins which cure through an ester exchange reaction mechanism, such as those described in European Patent Application No. 12463 B1, page 2, line 1 to page 6, line 25 (this part is incorporated herein by reference).

Other suitable cationic salt group-containing resins include those capable of forming a photodegradation resistant electrodepositable coating composition. Such a resin may be a resin comprising a cationic amine salt group derived from the pendant and / or terminal amino groups described in U.S. Patent Application Publication Nos. 2003/0054193 Al [0064] to [0088] (this part is incorporated herein by reference) . Also suitable are active hydrogen-containing, cationic salt group-containing resins derived from polyglycidyl ethers of polyhydric phenols essentially free of aliphatic carbon atoms to which more than one aromatic group is attached, as disclosed in US 2003/0054193 A1 [00961 to < RTI ID = 0.0 > (0121) < / RTI >

In certain embodiments, the composition comprises a cationic resin composition comprising a water-soluble cationic resin, such as PEI, and a water-dispersible cationic resin different from PEI, wherein the water-dispersible cationic resin is a cationic resin Is present in an amount of less than 50 wt%, such as less than 40 wt%, less than 30 wt%, less than 20 wt%, or in some cases less than 10 wt%, based on the total weight of the composition.

As will be appreciated, in adjusting the cationic resin to solubilize or disperse the aqueous medium, the resin is neutralized at least partially by treatment with, for example, an acid. Non-limiting examples of suitable acids are inorganic acids such as phosphoric and sulfamic acids, as well as organic acids such as acetic acid and lactic acid. In addition to acids, salts such as dimethylhydroxyethylammonium dihydrogenphosphate and ammonium dihydrogenphosphate may be used. In certain embodiments, the cationic resin is neutralized to at least 50%, or in some cases at least 70%, of the total theoretical neutralization equivalents. The step of solubilization or dispersion can be achieved by combining the neutralized or partially neutralized resin with water.

In certain embodiments, the composition further comprises a curing agent that reacts with the active hydrogen groups of the cationic salt group-containing resin described above. Non-limiting examples of suitable hardeners are polyisocyanates, aminoplast resins and phenolic resins, such as phenol formaldehyde condensates (including allyl ether derivatives thereof), which include at least partially blocked polyisocyanates.

In certain embodiments, the composition may comprise a catalyst that catalyzes the reaction between the curing agent and the active hydrogen-containing resin. Suitable curing catalysts include, but are not limited to, organotin compounds (e.g., dibutyltin oxide and dioctyltin oxide) and salts thereof (e.g., dibutyltin diacetate); Other metal oxides (e.g., oxides of cerium, zirconium and bismuth) and salts thereof (e.g., bismuth sulfamate and bismuth lactate). In certain embodiments, the curing catalyst comprises a cyclic guanidine as described in U.S. Patent No. 7,842,762 at line 1, line 53 to line 4, line 18, and line 16 at line 62 to line 19 at line 8, the disclosures of which are incorporated herein by reference . In some embodiments, the composition does not include an organotin compound.

The composition used in the process of the present invention further comprises solid particles. The term " solid particles " as used herein refers to solids in the form of discrete three dimensional structures that are chemically distinct from ionic resins. The shape (or morphology) of the particles may be different. For example, the sheet or plate-like graphene carbon particles described below can be used. Also, solid particles (e.g., solid beads, microbeads or hollow spheres) generally having spherical morphology, and particles that are cubic or sidewall (stretched or fibrous) may be used. When plate-like particles are used, they can be planar or at least partially bent, curled, wrinkled or distorted. Further, in certain embodiments, the additional particles may be hollow, porous, void free, or any combination thereof (e.g., a hollow center with a wall that is porous or solid). For additional information on suitable particle characteristics, see [H. Katz et al. (Ed.), Handbook of Fillers and Plastics (1987) at pages 9-10.

In certain embodiments, the solid particles comprise graphene carbon particles. The grafted carbon particles may be provided in the electrodepositable composition in any suitable amount. For example, the weight ratio of graphene carbon particles to ionic resin can typically range from 0.05: 1 to 5: 1. In certain embodiments, the weight ratio of graphene carbon particles to ionic resin may range from 0.1: 1 to 2: 1 or from 0.1: 1 to 1: 1.

As used herein, the term " graphene carbon particles " refers to carbon particles having a structure comprising at least one layer of a 1-atom-thick flat sheet of sp ² -bonded carbon atoms densely packed in a honeycomb crystal lattice it means. The average number of laminated layers may be less than 100, for example less than 50. In certain embodiments, the average number of laminated layers is 30 or less, such as 20 or less, 10 or less, or in some cases 5 or less. The graphene carbon particles may be substantially flat, but at least a portion of the flat sheet may be substantially bent, curled, wrinkled, or squashed. Particles typically have an elliptical or equiaxed morphology.

In certain embodiments, the graphene carbon particles have a thickness of less than or equal to 10 nm, less than or equal to 5 nm, or less than or equal to 4 nm, less than or equal to 3 nm, less than or equal to 2 nm, or less than or equal to 1 nm, For example, 3.6 nm or less. In certain embodiments, the graphene carbon particles can be 1-atom layer-thickness to 3-, 6-, 9-, 12-, 20- or 30-atom layer-thickness or more. In certain embodiments, the graphene carbon particles have a width greater than 50 nm, such as greater than 100 nm, in some cases greater than 100 nm and less than 500 nm, or greater than 100 nm and less than 200 nm, measured in a direction parallel to the carbon atom layer And a length. The graphene carbon particles have a very thin flake, platelet or sheet having a relatively high aspect ratio (defined as the ratio of the longest dimension of the particles to the shortest dimension of the particles) of greater than 3: 1, such as greater than 10: As shown in FIG.

In certain embodiments, graphene carbon particles have a relatively low oxygen content. For example, the graphene carbon particles have an oxygen content of not more than 2 atomic%, for example 1.5 or 1 atomic% or less, or 0.6 atomic% or less, for example about 0.5 atomic% Respectively. The oxygen content of the graphene carbon particles can be determined using X-ray photoelectron spectroscopy, for example as described in [D. R. Dreyer et al., Chem. Soc. Rev. 39, 228-240 (2010).

In certain embodiments, the graphene carbon particles have a BET specific surface area of greater than 50 m ² / g, such as from 70 to 1000 m ² / g, or in some cases from 200 to 1000 m ² / g or from 200 to 400 m ² / g . As used herein, the term " BET specific surface area " is based on the Brunauer-Emmett-Teller method described in the journal " The Journal of the American Chemical Society ", 60, 309 Quot; refers to the specific surface area determined by nitrogen adsorption according to the ASTM D 3663-78 standard.

In certain embodiments, the graphene carbon particles have a Raman spectroscopy 2D / G peak ratio of greater than 1: 1, for example greater than 1.2: 1, or 1.3: 1. As used herein, the term "2D / G peak ratio" refers to the ratio of the intensity of a 2D peak at 2692 cm ^-1 to the intensity of a G peak at 1,580 cm ^-1 .

In certain embodiments, graphene carbon particles have a relatively low bulk density. For example, the graphene carbon particles are characterized by having a bulk density (working density) of less than 0.2 g / cm ³ , for example less than 0.1 g / cm ³ . For the purposes of the present invention, the bulk density of graphene carbon particles is measured by placing 0.4 g of graphene carbon particles in a glass metering cylinder with a readable scale. The cylinder was lifted about 1 inch, the base of the cylinder hit the hard surface and patted 100 times to precipitate graphene carbon particles into the cylinder. The volume of the particles is then measured, and 0.4 g is divided by the measured volume to calculate the bulk density, where the bulk density is expressed in g / cm ³ .

In certain embodiments, graphene carbon particles have a compact density and a percent densification, which is a function of the density of the graphite powder and the specific density of substantially flat graphene carbon particles (e.g., formed from the peeled graphite) And the densification rate. It is presently believed that lower and / or lower densification rates contribute to better dispersion and / or rheological properties than grappling carbon particles, respectively, exhibiting higher compacted densities and higher densification rates. In certain embodiments, the compressed density of the graphene carbon particles is less than 0.9, such as less than 0.8, less than 0.7, such as 0.6 to 0.7. In certain embodiments, the densification rate of graphene carbon particles is less than 40%, such as less than 30%, such as 25-30%.

For purposes of the present invention, the compressed density of the graphene carbon particles is calculated from the measured thickness of the particles of a given mass after compression. Specifically, the measured thickness is determined by cooling 0.1 g of graphene carbon particles under a force of 15,000 Lb for 45 minutes in a 1.3 cm die, with a contact pressure of 500 MPa. The compressed density of the graphene carbon particles is then calculated from the thickness measured according to the following equation:

&Quot; (2) "

The densification rate of the graphene carbon particles is then determined as the ratio of the calculated compacted density of graphitic carbon particles to the density of graphite (2.2 g / cm ³ ) as determined above.

In certain embodiments, the graphene carbon particles have a bulk liquid conductivity of greater than or equal to 100 μS, eg, greater than or equal to 120 μS, eg, greater than or equal to 140 μS, measured at and immediately after mixing, eg, at 10, 20, 30, . For purposes of the present invention, the bulk liquid conductivity of graphene carbon particles is determined as follows. First, a sample containing 0.5% solution of graphene carbon particles in butyl cellosolve is sonicated for 30 minutes using a bath ultrasonic generator. Immediately after sonication, the sample is placed in a standard calibrated electrolyte conductivity cell (K = 1). A conductivity of the sample is measured by introducing a Fisher Scientific AB30 conductivity meter into the sample. Plot the conductivity for about 40 minutes.

According to certain embodiments, percolation, defined as long-distance interconnectivity, occurs between conductive graphene carbon particles. Such percation may reduce the resistance of the coating composition. Conductive graphene particles can occupy a minimum volume in the coating to form a continuous or nearly continuous network of particles. In such a case, the aspect ratio of the graphene carbon particles may affect the minimum volume required for the purgation.

In certain embodiments, at least a portion of the graphene carbon particles may be produced by a thermal process. According to embodiments of the present invention, thermally produced graphene carbon particles are prepared from a carbon-containing precursor material heated to a high temperature in a thermal zone, e.g., a plasma. As described more fully below, the carbon-containing precursor material is heated to a sufficiently high temperature, for example, above 3,500 DEG C to produce graphene carbon particles having the characteristics described above. Carbon-containing precursors, such as hydrocarbons provided in gas or liquid form, are heated in the thermal zone to produce graphene carbon particles in the thermal zone or downstream thereof. For example, thermally produced graphene carbon particles can be prepared by the systems and methods disclosed in U.S. Patent Nos. 8,486,363 and 8,486,364.

In certain embodiments, the thermally produced graphene carbon particles are prepared by a process comprising the steps of: (i) combining a 2-carbon fractional species, such as n-propanol, ethane, ethylene, acetylene, vinyl chloride, 1,2- dichloroethane, (Ii) introducing into the thermal zone (e.g., a plasma) one or more hydrocarbon precursor materials capable of forming carbon nanotubes (e.g., aldehydes and / or vinyl bromide) Can be produced by using the apparatuses and methods described in [8], [48], [S], 486, 363, and [0048] In another embodiment, the thermally produced graphene carbon particles are prepared by a process comprising: (i) providing a methane precursor material (e.g., greater than 95% or greater than 50% methane having a purity of greater than 99%, or, in some cases, ) And apparatuses and methods described in U.S. Patent Nos. 8,486,364 [0015] to [0042], wherein the methane precursor is introduced into a thermal zone (e.g., a plasma) . ≪ / RTI > In this way, grappling carbon particles having at least some, or in some cases all of the features described above, can be produced.

During the production of the graphene carbon particles by the thermal production method described above, the carbon-containing precursor is provided as a feed material capable of contacting the inert carrier gas. The carbon-containing precursor material may be heated in a thermal zone, for example, by a plasma system. In certain embodiments, the precursor material is heated to a temperature of at least 3,500 DEG C, for example, at or above 3,500 DEG C or above 4,000 DEG C to 10,000 DEG C or 20,000 DEG C. It is to be understood that although the thermal zones are generated by the plasma system, any other suitable heating system, e.g., various types of furnace (electrically heated tube furnace, etc.), may be used to generate thermal bands.

The gas stream may contact one or more quench streams injected into the plasma chamber through one or more quench stream injection ports. The quench stream can cool the gas stream to facilitate the formation of graphene carbon particles or to control its particle size or morphology. In certain embodiments of the present invention, after contacting the gaseous product stream with the quench stream, the ultrafine particles may be passed through the converging member. After the graphene carbon particles have exited the plasma system, they can be collected. Any suitable means (e.g., bag filter, cyclone separator, or deposition on a substrate) can be used to separate graphene carbon particles from the gas flow rate.

In certain embodiments, at least some of the graphene carbon particles can be obtained from commercial sources, such as Angstron, XG Sciences and other commercial sources. In such embodiments, commercially available graphene carbon particles may comprise exfoliated graphite and may have different characteristics compared to thermally produced graphene carbon particles, such as different size distributions, thicknesses, aspect ratios, structural morphologies, oxygen content And chemical bases at the base plane / edge.

In certain embodiments, graphene carbon particles are functionalized. As used herein, " functionalized " when referring to graphene carbon particles means a covalent bond of any non-carbon atom or organic group to graphene carbon particles. Graphene carbon particles are formed by the formation of covalent bonds between the carbon atoms of the particles and other chemical moieties such as carboxylic acid groups, sulfonic acid groups, hydroxy groups, halogen atoms, nitro groups, amine groups, aliphatic hydrocarbon groups, Lt; / RTI > For example, functionalization by a carbon-containing material may cause formation of a carboxylic acid group on the graphene carbon particles. Further, the graphene carbon particles can be functionalized by other reactions such as a Diels-Alder addition reaction, a 1,3-dipolar addition cyclization reaction, a free radical addition reaction or a diazonium addition reaction. In certain embodiments, the hydrocarbon and phenyl groups may be further functionalized. If the grafted carbon particles already have some hydroxy functional groups, the functional groups can be modified and extended by the reaction of these functional groups with, for example, organic isocyanates.

In certain embodiments, different types of grappling carbon particles may be used in the electrodepositable composition. For example, when thermally produced graphene carbon particles are combined with commercially available graphene carbon particles according to embodiments of the present invention, graphene carbon particle characteristics such as bimodal distribution, tri-modal distribution, etc., are achieved . The grafted carbon particles contained in the composition may have a multimodal particle size distribution, aspect ratio distribution, structural morphology, corrugatedness difference, oxygen content, and the like.

In embodiments of the present invention in which both thermally produced graphene carbon particles and commercially available graphene carbon particles (formed from exfoliated graphite) are used to produce a bimodal graphene particle size distribution, The relative amount of graphene carbon particles of the coating is adjusted to produce the desired conductive properties of the coating. For example, thermally prepared graphene particles based on the total weight of the graphene carbon particles may comprise from 1 to 50 wt%, and commercially available graphene carbon particles may comprise from 50 to 99 wt% . In certain embodiments, the thermally produced graphene carbon particles may comprise 2 or 4 to 40 weight percent, or 6 or 8 to 35 weight percent, or 10 to 30 weight percent. When such a co-dispersion of the present invention having relatively high amounts of thermally produced graphene carbon particles and commercially available graphene carbon particles is incorporated into a coating, ink or other material, Can exhibit significantly increased electrical conductivity compared to similar materials containing similar proportions. For example, the co-dispersion may increase the electrical conductivity by 10 or 20% or more as compared to the mixture. In certain embodiments, the electrical conductivity may be increased by at least 50, 70 or 90% or more.

In certain embodiments of the present invention, in addition to the graphene carbon particles, the solid particles may also be mixed with a lithium-containing particle, such as Li, and at least one element selected from Ni, Co, Fe, Mn, Metal oxides. For example, lithium-containing particles itdoe can include _{LiCoO 2, LiNiO 2, LiFePO 4} , LiCoPO 4, LiMnO 2, LiMn 2 O 4, Li (NiMnCo) O 2 and / or Li (NiCoAl) O _2, The relative amount of transition metal may vary as needed. For example, Ni, Mn and Co are not always present in relative atomic ratios of 1: 1: 1, and in some embodiments may contain additional nickel in a ratio of 5: 3: 2 or 8: 2: 2. In certain embodiments, such lithium-containing particles have a particle size of less than or equal to 10 μm, less than or equal to 5 μm, less than or equal to 3 μm, less than or equal to 1 μm, such as less than or equal to 10 nm and less than or equal to 1,000 nm, nm. < / RTI >

In certain embodiments, such lithium-containing solid particles are present in the composition in an amount of at least 50 wt%, at least 60 wt%, at least 70 wt%, at least 80 wt%, such as at least 85 wt% In an amount of 90, 93 or 96 wt% or more. In accordance with certain embodiments in which the solid particles comprise lithium-containing particles and graphene carbon particles, their relative weight percent based on the total combined weight of the lithium-containing particles and the graphene carbon particles is typically 85 to 99.5 wt% By weight of lithium-containing particles and from 0.5 to 15% by weight of graphene carbon particles, for example from 90 to 99% by weight of lithium-containing particles and from 1 to 10% by weight of graphene carbon particles, or from 92 to 98% Particles and 2 to 8 wt% graphenic carbon particles.

In certain embodiments, wherein the solid particles comprise the above-described embodiment wherein the solid particles comprise graphene carbon particles and lithium-containing particles, the composition may comprise additional electroconductive particles, such as electrically conductive carbon particles. Suitable electrically conductive particles include electrically conductive carbon black, acetylene black, carbon nanotubes, carbon fibers, fullerenes, and the like. Examples of commercially available electrically conductive carbon blacks suitable for use herein include, but are not limited to, Cabot Monarch (TM) 1300, Cabot XC-72R, Cabot LiTX 50, Cabot LiTX 200, LiTX 300, Denka Black HS-100L, Black Pearls 2000 and Vulcan XC 72 (sold by Cabot Corporation); Acheson Electrodag 230 (sold by Acheson Colloids Co., Columbian Raven 3500, sold by Columbian Carbon Co.); And Printex (trade mark) XE 2, Printex 200, Printex L and Printex L6 (sold by DeGussa Corporation, Pigments Group), and Super P (registered trademark) And C-Nergy Super C45 and C-Nergy Super C65 (sold by TIMCAL Ltd.). In certain embodiments, The electrically conductive carbon black used in the compositions described herein has an average primary particle size of less than 300 nm, such as 1 to 200 nm, 10 to 100 nm, or in some cases 30 to 50 nm before incorporation into the composition.

Other electrically conductive particles suitable for use in the present invention include, but are not limited to, electrically conductive silicas such as AEROSIL 200 (sold by Japan Aerosil Co., Ltd.); Silloid TM 364 and Silylide TM 978 all available from Fuji Davison Inc. under the trade designation SYLOID® 161, Siloid® 244, Siloid® 308, Siloid® 404 and Siloid® 978 Co., Ltd.); Metal powders such as aluminum, copper or special steels, molybdenum disulfide, iron oxide (e.g., black iron oxide), antimony-doped titanium dioxide, and nickel-doped titanium dioxide. Also suitable are particles coated with metals such as cobalt, copper, nickel, iron, tin, zinc and combinations thereof. Suitable particles that can be coated with the above-described metals include alumina, aluminum, aromatic polyesters, boron nitride, chromium, graphite, iron, molybdenum, neodymium / iron / boron, samarium cobalt, silicon carbide, stainless steel, titanium diboride, tungsten , Tungsten carbide, and zirconia particles. These metal-coated particles are commercially available from Advanced Ceramics Corp. Other metal-coated particles that may be used include ceramic microballoons, cut glass fibers, graphite powders and flakes, boron nitride, mica flakes, copper coated with carbon, copper, nickel, palladium, Powders and flakes, nickel powders and flakes, aluminum. These particles are typically metal-coated using fluid bed chemical vapor deposition techniques. These metal-coated particles are commercially available from Powdermet, Inc. Mixtures of different electrically conductive particles may be used.

In certain embodiments, the electrically conductive particles have a relative weight ratio of lithium-containing particles to graphene carbon particles or other electrically conductive particles in the composition of at least 3: 1, at least 4: 1, at least 5: 1, at least 8: : 1 or more, or in some cases 15: 1 or more, 30: 1 or more, 45: 1 or more, or 60: 1 or more. In certain embodiments, such electrically conductive particles are present in an amount of 20 wt% or less, 10 wt% or less, such as 1 to 10 wt% or 1 to 5 wt%, based on the total weight of the solids of the composition.

In addition to the graphene carbon particles described above, other types of solid particles may be included in the electrodepositable material. These solid particles may be polymeric and / or non-polymeric inorganic materials, polymeric and / or non-polymeric organic materials, composite materials, as well as any mixture of the foregoing. The term " polymer " as used herein is meant to encompass oligomers and includes, but is not limited to, homopolymers and copolymers.

The term " polymeric inorganic material " as used herein means a polymeric material having a main chain repeat unit based on an element other than carbon. The term " polymeric organic material " as used herein also means synthetic polymeric materials, semisynthetic polymeric materials and natural polymeric materials having carbon backbone repeat units.

The term " organic material " as used herein means a carbon-containing compound in which carbon is typically bonded to itself and to hydrogen, and often also to other elements, and binary compounds such as carbon oxides, carbides, ; Ternary compounds such as metal cyanide, metal carbonyl, phosgene, carbonyl sulfide and the like; Carbon-containing ionic compounds such as metal carbonates such as calcium carbonate and sodium carbonate are excluded. The term " inorganic material " as used herein means any material that is not an organic material.

The term " composite material " as used herein means a combination of two or more different materials. The particles formed from the composite material may have different surface hardness from the hardness of the inner portion of the particles below the surface of the composite material. More specifically, the surface of the particles can be modified in any manner known in the art, including chemically or physically altering the surface characteristics thereof using techniques known in the art.

For example, the particles may be coated with one or more secondary materials, or formed from a coated or encapsulated primary material to form composite particles having a softer surface. In certain embodiments, the particles formed from the composite material may be coated with a different type of primary material or formed from a capped or encapsulated primary material.

As indicated, the solid particles may comprise any of a variety of inorganic materials, such as ceramic materials, metallic materials, and mixtures of the foregoing. Non-limiting examples of such ceramic materials may include metal oxides, mixed metal oxides, metal nitrides, metal carbides, metal sulfides, metal silicates, metal borides, metal carbonates, and mixtures of the foregoing. Specific non-limiting examples of metal nitrides are boron nitride; A specific non-limiting example of the metal oxide is zinc oxide; Non-limiting examples of suitable mixed metal oxides are aluminum silicate and magnesium silicate; Non-limiting examples of suitable metal sulfides are molybdenum disulfide, tantalum disulfide, tungsten disulfide, and zinc sulfide; Non-limiting examples of metal silicates are aluminum silicate and magnesium silicate, such as vermiculite.

In certain embodiments of the present invention, the solid particles are selected from the group consisting of aluminum, barium, bismuth, boron, cadmium, calcium, cerium, cobalt, copper, iron, lanthanum, magnesium, manganese, molybdenum, phosphorus, selenium, Tin, titanium, tungsten, vanadium, yttrium, zinc and zirconium (including oxides thereof, nitrides thereof, phosphides thereof, phosphates thereof, selenides thereof, sulfides thereof, sulfates thereof and mixtures thereof ). ≪ / RTI > Suitable non-limiting examples of the aforementioned inorganic particles include alumina, silica, titania, cera, zirconia, bismuth oxide, magnesium oxide, iron oxide, aluminum silicate, boron carbide, nitrogen-doped titania and cadmium selenide.

In certain embodiments, the solid particles used in the present invention have a lamellar structure. Particles having a lamellar structure are composed of sheets or plates of atoms or particles of hexagonal arrangement. A non-limiting example of a lamellar structure is a hexagonal crystal structure. Inorganic solid particles having a lamellar fullerene buckyball structure are also useful.

Non-limiting examples of suitable materials having a lamellar structure include, but are not limited to, boron nitride, graphite, metaldicarcogenide, mica, tale, gypsum, kaolinite, calcite, cadmium iodide, . Suitable metal decahcogenides include molybdenum disulfide, molybdenum selenide, tantalum disulfide, tantalum selenide, tungsten disulfide, tungsten selenide, and mixtures thereof.

The solid particles can be formed from non-polymeric organic materials. Non-limiting examples of non-polymeric organic materials useful in the present invention include, but are not limited to, stearates (such as zinc stearate and aluminum stearate), diamonds, carbon black, and stearamides.

In certain embodiments, the solid particles comprise an organic pigment such as an azo compound (monoazo, di-azo, naphthol, naphthol AS, azo pigment lake, benzimidazolone, Isoindolinone, isoindoline, and isoindoline), and polycyclic (such as phthalocyanine, quinacridone, perylene, perinone, diketopyrrolopyrrole, thioindigo, anthraquinone, indanthrone, anthrapyrimidine, Trinone, anthanthrone, dioxazine, triarylcarbonium, quinophthalone) pigments, and mixtures of any of the foregoing.

In certain embodiments, the above-described additional solid particles have an average particle size of less than 100 [mu] m prior to incorporation into the composition, e.g., less than 50 [mu] m before incorporation into the composition. In certain embodiments, the solid particles have an average particle size of from 1 to 10,000 nm before incorporation into the composition, from 1 to 1000 nm before incorporation into the composition, or from 1 to 100 nm before incorporation into the composition.

In embodiments where the average particle size of the solid particles is at least about 1 [mu] m, the average particle size can be measured according to known laser dispersion techniques. For example, the average particle size of such particles is measured using a Horiba model LA 900 laser diffraction particle size instrument using a helium-neon laser at a wavelength of 633 nm to measure the size of the particles, (I. E., &Quot; particle size " refers to the smallest sphere that completely encloses the particle).

In embodiments where the average particle size of the solid particles is less than or equal to 1 占 퐉, the average particle size is determined by visually inspecting an electron micrograph of a transmission electron microscope (TEM) image, measuring the diameter of the particles in the image, Can be determined by calculating the particle size. Those skilled in the art will understand how to prepare such a TEM image. The diameter of the particle refers to the smallest diameter sphere that completely encloses the particle.

In certain embodiments, the composition includes other typical components such as corrosion inhibitors, antioxidants, flow control agents, surfactants, and the like.

The above-described electrodepositable composition may be prepared by any desired method including the method described in the examples. For example, in some embodiments, it may be desirable to incorporate solid particles with the aid of a composition wherein the solid particles are mixed with a water-soluble ionic resin pre-solubilized in an aqueous medium. Exemplary ionic resins suitable for this purpose include the water-soluble resins described above. The solids content of such a composition may be relatively high, for example, it may be at least 2, 3 or 4 times the total solids content of the composition of the process of the present invention. The composition may be mixed, for example, by sonication to provide a homogeneous dispersion. Such ultrasonic treatment can take 15 to 30 minutes or more. The resulting composition may then be combined with a liquid carrier (i.e., water and optionally an organic solvent) to provide a final composition for use in the methods of the present invention.

In an embodiment of the method of the present invention, the substrate is at least 4: 1, such as at least 5: 1, at least 6: 1, at least 7: 1, at least 8: Of the solid particles to the ionic resin of at least 12: 1, at least 13: 1, at least 14: 1, at least 15: 1, at least 16: 1, at least 17: 1. The solid particles may comprise from 0.05 to 100% by weight, for example from 0.1 to 10% by weight, or from 0.1 to 5% by weight of graphene carbon particles.

In addition, in certain embodiments of the method of the present invention, the substrate comprises a composition having a total solids content of from 0.5 to 25% by weight, such as from 1 to 10% by weight, or in some cases from 1 to 5% . In fact, it has been found that such compositions can provide stable dispersions of solid particles and ionic resins in an aqueous medium without the use of thickeners. The term " stable dispersion ", as used herein, refers to a dispersion that is not gelled, does not agglomerate and does not precipitate when held at a temperature of 25 DEG C for at least 60 days, or that when the precipitate is slightly precipitated, Quot;

In addition, when the composition is used in the method of the present invention, even when the weight ratio of solid particles to ionic resin in the bath is within the aforementioned range, a firm uniform coating of suitable film thickness and acceptable porosity can be provided, It has been found that the above-described method makes it particularly suitable for producing a coated substrate which can be used as a cathode for a lithium ion battery.

In the method of the present invention, the coating is applied over or onto at least a portion of the substrate through an electrodeposition process. In such a process, an electrically conductive substrate (such as any of the ones described above) that acts as an electrode (e.g., an anode in anionic electrodeposition) in an electrical circuit comprising an electrode and a counter electrode (e.g., a negative electrode in anionic electrodeposition) The composition is impregnated. Current causes deposition of a coating on the substrate across the electrodes. The applied voltage may be variable and may be, for example, as low as 1 V, or as high as V through thousands of volts, but often between 50 and 500 volts. The current density is often 0.5 to 15 A per ft ² . In certain embodiments, the residence time of the substrate in the composition is from 30 to 180 seconds.

After electrocoating, the substrate is removed from the bath and, in certain embodiments, can be baked in an oven according to the details of the composition and the end user's preference. For example, the coated substrate may be baked for 10 to 60 minutes at a temperature of 225 ℉ or less, such as 200 ℉ or less. In other cases, after the electrocoating and after removal of the substrate from the bath (and again according to the details of the composition and the preferences of the end user), the coated substrate may simply be dried under ambient conditions. As used herein, " ambient conditions " means a temperature of 10 to 100% relative humidity and a temperature in the range of -10 to 120 캜, such as 5 to 80 캜, in some cases 10 to 60 캜, Quot;

As will be appreciated from the foregoing description, in some aspects, the present invention relates to a method comprising impregnating an electroconductive substrate with an electrodepositable composition, wherein the substrate comprises an electrode and a counter electrode impregnated in the composition Wherein a coating is applied on or on at least a portion of the substrate when an electric current passes between the electrodes, the electrodepositable composition comprising: (a) an aqueous medium; (b) an ionic resin; And (c) solid particles comprising graphene carbon particles, wherein the composition has a weight ratio of solid particles to ionic resin of at least 4: 1. The present invention also relates to any method as set forth in the present paragraph wherein the substrate is a foil comprising aluminum, iron, copper, manganese, nickel, combinations thereof and / or alloys thereof, For example less than or equal to 8 mils (203.2 m), such as less than 4 mils (101.6 m), less than 2 mils (50.8 m), or in some cases less than or equal to 1 mil (25.4 m) (5.08 μm) or greater, 0.4 mil (10.2 μm) or greater, or 0.5 mil (12.7 μm) or greater. The present invention also relates to any method as set forth in this paragraph, wherein the aqueous medium comprises water alone or an inert organic co-solvent such as an organic co-solvent that is at least partially water soluble, such as an oxygen- Monoalkyl ethers of ethylene glycol, diethylene glycol, propylene glycol or dipropylene glycol containing from 1 to 10 carbon atoms such as monoethyl or monobutyl (meth) acrylates of these glycols or alcohols (such as ethanol, isopropanol, butanol and diacetone alcohol) Ether) in combination with water. The present invention also relates to any of the methods described herein wherein the organic co-solvent is less than 25%, less than 20%, or in some cases less than 10% by weight, based on the total weight of water of the electrodepositable composition, And is present in an amount of less than 5% by weight. The present invention also relates to any method as set forth in the present paragraph wherein the aqueous medium comprises at least 75 wt%, at least 90 wt%, or at least 95 wt%, such as from 75 to 99.5 wt%, 90 wt% To 99% by weight, or in some cases 95 to 99% by weight, based on the total weight of the composition. The present invention also relates to any method as set forth in this paragraph, wherein the ionic resin comprises an anionic resin, such as a base-neutralized carboxylic acid group-containing resin, wherein the ionic resin comprises a base- Containing resin is water-soluble, for example, the water-soluble resin is a cellulose derivative such as carboxymethylcellulose (e.g., carboxymethyl cellulose having a weight average molecular weight of 50,000 or more, 100,000 or more, 200,000 or more, such as 50,000 to 1,000,000, 100,000 to 500,000 or 200,000 to 300,000 ). ≪ / RTI > The present invention also relates to any method as set forth in the present paragraph wherein the water soluble resin is present in the composition in an amount of at least 50 wt%, such as at least 60 wt%, at least 70 wt%, at least 80 wt%, or at least 90 wt% Wt%, based on the total weight of the resin of the composition. The present invention also relates to any method as set forth in the present paragraph wherein the water soluble resin comprises up to 20 wt%, such as up to 15 wt%, up to 10 wt%, up to 5 wt%, such as from 1 to 20 wt% % By weight, 5 to 15% by weight, or 1 to 3% by weight, based on the total weight of the solids of the composition. The present invention also relates to any method as set forth in the present paragraph wherein the solid particles are mixed with a lithium-containing particle, such as Li, and at least one element selected from Ni, Co, Fe, Mn, And lithium-containing particles containing a metal oxide. For example, lithium-containing particles itdoe can include _{LiCoO 2, LiMO 2, LiFePO 4} , LiCoPO 4, LiMnO 2, LiMn 2 O 4, Li (NiMnCo) O 2 and / or Li (NiCoAl) O _2, The relative amount of transition metal may vary as needed. For example, Ni, Mn and Co are not always present in relative atomic ratios of 1: 1: 1 and may contain additional nickel in 5: 3: 2 or 8: 2: 2. The present invention also relates to any of the methods set forth herein, wherein the lithium-containing particles are present in an amount of at least 50 wt%, at least 60 wt%, at least 70 wt%, at least 80 wt% , 85 wt% or more, or 90 wt% or more. The present invention also relates to any of the methods described herein, wherein the solid particles are selected from the group consisting of electrically conductive particles such as graphene carbon particles, or graphene carbon particles in combination with other electrically conductive carbon particles (e.g., electrically conductive carbon black) . The present invention also relates to any method as set forth in this paragraph, wherein the relative weight ratio of lithium-containing particles to electrically conductive graphene carbon particles in the composition is at least 3: 1, at least 4: 1, at least 5: : 1 or more, 10: 1 or more, 15: 1 or more, 30: 1 or more, 45: 1 or more, or 60: The present invention also relates to any method as set forth in the present paragraph wherein the electrically conductive graphene carbon particles are present in an amount of 20 wt% or less, 10 wt% or less, such as 1 to 10 wt% 1 to 5% by weight. The present invention also relates to any method as set forth in this paragraph, wherein the electrodepositable composition comprises at least 5: 1, at least 6: 1, at least 7: 1, at least 8: 1, at least 9: , At least 11: 1, at least 12: 1, at least 13: 1, at least 14: 1, at least 15: 1, at least 16: 1 or at least 17: For example, the weight ratio of solid particles to ionic resin may be greater than 45: 1 or greater than 60: 1. The present invention also relates to any method as set forth in the present paragraph wherein the electrodepositable composition comprises from 0.5 to 25% by weight, such as from 1 to 10% by weight, such as from 1 to 5% by weight, based on the total weight of the composition, .

Also, as will be appreciated by the foregoing description, in some aspects, the present invention provides a method of making an aqueous dispersion comprising (a) an aqueous medium; (b) an ionic resin; And (c) solid particles comprising (i) graphene carbon particles, and (ii) lithium-containing particles, wherein said composition comprises at least 4: 1 solid particles versus ionic resin Weight ratio. The present invention also relates to any of the electrodepositable compositions disclosed herein wherein the composition has a ratio of at least 4: 1, at least 5: 1, at least 6: 1, at least 7: 1, at least 8: At least 10: 1, at least 11: 1, at least 12: 1, at least 13: 1, at least 14: 1, at least 15: 1, at least 16: 1, at least 17: 1, at least 45: Weight ratio of solid particles to ionic resin. The present invention also relates to any of the electrodepositable compositions described herein wherein the aqueous medium comprises water alone or an inert organic co-solvent such as an organic co-solvent that is at least partially water soluble, such as an oxygen- Monoalkyl ethers of ethylene glycol, diethylene glycol, propylene glycol or dipropylene glycol containing from 1 to 10 carbon atoms in the alkyl group, such as monoethyl of these glycols or alcohols (such as ethanol, isopropanol, butanol and diacetone alcohol) ≪ / RTI > monobutyl ether). Other at least partially water-miscible solvents may include coalescing solvents such as triethyl phosphate, triacetin, di-propylene diacetate, and the like. The present invention also relates to any of the electrodepositable compositions provided herein wherein the organic co-solvent is less than 25% by weight, less than 20% by weight, or in some cases less than 10% by weight based on the total weight of water of the electrodepositable composition , Such as less than 5% by weight. The present invention also relates to any of the electrodepositable compositions presented herein wherein the aqueous medium comprises at least 75 wt%, at least 90 wt%, or at least 95 wt%, such as from 75 to 99.5 wt%, based on the total weight of the composition, , 90 to 99 wt%, or in some cases 95 to 99 wt%, based on the total weight of the composition. The present invention also relates to any of the electrodepositable compositions presented in this paragraph, wherein the ionic resin comprises an anionic resin, such as a base-neutralized carboxylic acid group-containing resin, such as a base-neutralized carboxylic acid The gas-containing resin is water-soluble, for example, the water-soluble resin is a cellulose derivative such as carboxymethylcellulose (for example, carboxy methyl cellulose having a weight average molecular weight of 50,000 or more, 100,000 or more, 200,000 or more, such as 50,000 to 1,000,000, 100,000 to 500,000 or 200,000 to 300,000 Methylcellulose). ≪ / RTI > The present invention also relates to any of the electrodepositable compositions disclosed herein wherein the water soluble resin is present in an amount of at least 50 wt%, such as at least 60 wt%, at least 70 wt%, at least 80 wt%, or at least 90 wt% By wt., Based on the total weight of the resin of the composition. The present invention also relates to any of the electrodepositable compositions provided herein, wherein the water soluble resin comprises up to 20% by weight, up to 15% by weight, up to 10% by weight, up to 5% by weight, such as from 1 to 20% To 15% by weight, 5 to 15% by weight or 1 to 3% by weight, based on the total weight of the solids of the composition. The present invention also relates to any of the electrodepositable compositions presented in this paragraph wherein the lithium-containing particles comprise Li and a mixed metal oxide comprising at least one element selected from Ni, Co, Fe, Mn, Al and P . For example, lithium-containing particles itdoe can include _{LiCoO 2, LiNiO 2, LiFePO 4} , LiCoPO 4, LiMnO 2, LiMn 2 O 4, Li (NiMnCo) O 2 and / or Li (NiCoAl) O _2, The relative amount of transition metal may vary as needed. For example, Ni, Mn and Co are not always present in a ratio of 1: 1: 1 or 3: 3: 3 and may contain additional nickel in a ratio of 5: 3: 2 or 8: 2: 2. The present invention also relates to any of the electrodepositable compositions described herein wherein the lithium-containing particles are present in an amount of at least 50 wt%, at least 60 wt%, at least 70 wt%, at least 80 wt% % Or more, 85 wt% or more, or 90 wt% or more. The present invention also relates to any of the electrodepositable compositions described herein wherein the relative weight ratio of lithium-containing particles to graftable carbon particles in the composition is at least 3: 1, at least 4: 1, at least 5: 1, at least 8: : 1 or more, 10: 1 or more, 15: 1 or more, 30: 1 or more, 45: 1 or more, or 60: The present invention also relates to any of the electrodepositable compositions described herein wherein the graphene carbon particles are present in an amount of up to 20 wt%, such as 10 wt%, such as 1 to 10 wt% or 1 By weight to 5% by weight. The present invention also relates to any of the electrodepositable compositions disclosed herein wherein the electrodepositable composition comprises from 0.5 to 25% by weight, such as from 1 to 10% by weight, such as from 1 to 5% by weight, based on the total weight of the composition Have a total solids content.

Further, as will be understood from the foregoing description, the present invention also relates to a lithium ion battery electrode coating deposited on a substrate, wherein the electrodeposited coating comprises: (a) a cured ionic resin; And (b) solid particles comprising (i) graphene carbon particles and (ii) lithium-containing particles, wherein the coating has a weight ratio of solid particles to a cured ionic resin of at least 4: 1.

The present invention also relates to any of the electrodepositable coatings described herein wherein said coating has a thickness of at least 4: 1, at least 5: 1, at least 6: 1, at least 7: 1, at least 8: Or more, 10: 1 or more, 11: 1 or more, 12: 1 or more, 13: 1 or more, 14: 1 or more, 15: 1 or more, 16: 1 or more, 17: By weight of the solid particles to the ionic resin.

The present invention also relates to any of the electrodepositable coatings described herein, wherein the water soluble resin comprises up to 20 wt%, up to 15 wt%, up to 10 wt%, up to 5 wt%, such as from 1 to 20 wt% To 15% by weight, 5 to 15% by weight or 1 to 3% by weight, based on the total weight of the solids of the coating. The present invention also relates to any of the electrodepositable coatings described herein, wherein the lithium-containing particles comprise Li and a mixed metal oxide comprising at least one element selected from Ni, Co, Fe, Mn, . For example, lithium-containing particles itdoe can include _{LiCoO 2, LiNiO 2, LiFePO 4} , LiCoPO 4, LiMnO 2, LiMn 2 O 4, Li (NiMnCo) O 2 and / or Li (NiCoAl) O _2, The relative amount of transition metal may vary as needed. For example, Ni, Mn and Co, for example, are not always present in a ratio of 1: 1: 1 or 3: 3: 3 and may contain additional nickel in a ratio of 5: 3: 2 or 8: 2: 2 have. The present invention also relates to any of the electrodepositable coatings described herein wherein the lithium-containing particles are present in an amount of at least 50 wt%, at least 60 wt%, at least 70 wt%, at least 80 wt% % Or more, 85 wt% or more, or 90 wt% or more.

The present invention also relates to any of the electrodepositable coatings described herein wherein the relative weight ratio of lithium-containing particles to graftable carbon particles in the coating is at least 3: 1, at least 4: 1, at least 5: 1, at least 8: : 1 or more, 10: 1 or more, 15: 1 or more, 30: 1 or more, 45: 1 or more, or 60: The present invention also relates to any of the electrodepositable coatings described herein wherein the graphene carbon particles are present in an amount of up to 20% by weight, up to 10% by weight, such as from 1 to 10% by weight, based on the total weight of the solids of the coating, 1 to 5% by weight. The present invention also relates to any of the electrodepositable coatings described herein, wherein the electrodepositable coating comprises from 0.5 to 25% by weight, such as from 1 to 10% by weight, such as from 1 to 5% by weight, based on the total weight of the coating Have a total solids content.

The following examples illustrate the invention, but are not to be construed as limiting the invention to its details.

Example  One

Sodium carboxymethylcellulose (SCMC, commercially available from Sigma-Aldrich Co. LLC) (1.0 g) was dissolved in deionized water (180 g). According to the supplier's analytical certificate, the material had a degree of substitution of 0.86 and a viscosity of 470 cps was measured using a 2 wt% solution of CMC in water. According to the supplier's product data sheet, the viscosity was measured by a Brookfield model LVF viscometer using the following parameters: Spindle: # 3; Speed: 60 rpm; Temperature: 25 占 폚; Container: 120 ml poly bottle; Is ^{1 -} 20. The shear rate calculated from these parameters is 12.6 sec: and a multiplication factor. The viscosity estimate was measured by the supplier without shear lean, and a viscosity of 470 cps at a concentration of 2 wt% estimated the calculated molecular weight of 267,500 using the above equation. Subsequently, after adding thermally prepared graphene (TPG) carbon particles (4.2 g) produced in the thermal zone of the plasma reactor using methane as the precursor material according to the method described in U.S. Patent No. 8,486,364, the mixture was mixed with 25 Min. Subsequently, LiPePO ₄ (Life Power, R. P2, commercially available from Phostech Lithium Inc.) (14.75 g) was added to each of four equivalent fractions , And sonicated for 5 minutes. Finally, an additional 10 minutes of sonication was performed to ensure a homogeneous dispersion. This was then diluted with deionized water (600 g) to produce a 2.5% solid electroplating bath having a weight ratio of 18 solid particles (TPG + LFP) to ionic resin (SCMC). To carry out the coating by electrodeposition, the aluminum foil was wired as an electrode and placed in a stirred 90 ° F bath containing a thermocouple and a heating / cooling coil (which also served as a counter electrode), then the voltage was turned on at 150 V A current of 1.5 A was set. After the voltage was turned off after 180 seconds, the coated sample was removed from the bath and allowed to dry. The resulting coating had a thickness of 16 [mu] m.

Example  2

The coating was prepared according to the same procedure as in Example 1, except that thermally prepared graphene carbon particles were functionalized by the following procedure. Maleic anhydride (1.5 g) was dissolved in Aromatic 150 solvent (423 g) and TPG (7.5 g) produced by plasma was added. The mixture was sonicated for 1 hour and then heated to 180 < 0 > C with stirring under nitrogen and held for 4 hours. The mixture was cooled and filtered, and the product was washed thoroughly with acetone and dried. The product was screened through a 100 mesh screen. Then Jeffamine M-2005 (14 g) was dissolved in toluene (300 g) and the TPG product (7 g) was added with stirring, and the mixture was sonicated for 1 hour. The mixture was transferred to a reaction flask with additional toluene (300 g) and heated to 100 < 0 > C with stirring under nitrogen and held for 2 hours. After cooling, the mixture was filtered and washed with toluene, washed with acetone and redispersed in acetone, then filtered, washed with acetone and dried. The product was screened through a 100 mesh screen. The functionalized graphene carbon particles were then combined with the lithium-containing particles and the ionic resin and electrodeposited in a similar manner to that described in Example 1. [ The coating had a thickness of 35 [mu] m.

Those skilled in the art will readily appreciate that the invention can be modified without departing from the concepts disclosed in the foregoing description. Such variations are considered to be within the scope of the following claims, unless the claims are explicitly stated otherwise by their language. Accordingly, the specific embodiments described in detail herein are illustrative only and are not intended to limit the scope of the invention, which is given by the full scope of the appended claims and their equivalents.

Claims (20)

A method comprising impregnating an electroconductive substrate with an electrodepositable composition,
Said substrate acting as an electrode in an electric circuit comprising an electrode impregnated with said composition and a counter electrode,
A coating is applied over or on at least a portion of the substrate as current passes between the electrodes,
The electrodepositable composition
(a) an aqueous medium;
(b) an ionic resin; And
(c) solid particles comprising graphene carbon particles
, ≪ / RTI &
Wherein the composition has a weight ratio of solid particles to ionic resin of at least 4: 1. The method according to claim 1,
Wherein graphene carbon particles comprise thermally produced graphene carbon particles. 3. The method of claim 2,
Wherein the thermally produced graphene carbon particles are prepared in a thermal zone at a temperature in excess of 3,500 DEG C and have an average aspect ratio of greater than 3: 1. 3. The method of claim 2,
Wherein the thermally produced graphene carbon particles have a BET specific surface area of greater than 70 m ² / g. 3. The method of claim 2,
Wherein at least a portion of the thermally produced graphene carbon particles comprises a curved, curled, wrinkled, or distorted sheet. The method according to claim 1,
Wherein the composition has a weight ratio of graftable carbon particles to ionic resin of from 0.1: 1 to 2: 1. The method according to claim 1,
Wherein the ionic resin comprises an anionic resin. 8. The method of claim 7,
Wherein the anionic resin comprises a water-soluble base-neutralized carboxylic acid group-containing resin. 9. The method of claim 8,
Wherein the water-soluble resin comprises a cellulose derivative comprising an alkali salt of carboxymethylcellulose. The method according to claim 1,
Wherein the solid particles further comprise lithium-containing particles. 11. The method of claim 10,
Wherein the lithium-containing particle comprises Li, and a mixed metal oxide comprising at least one element selected from Ni, Co, Fe, Mn, Al and P. 11. The method of claim 10,
Wherein the lithium-containing particles are present in an amount of at least 50 wt% based on the total weight of the solids of the composition. 11. The method of claim 10,
Wherein the relative weight ratio of lithium-containing particles to graphene carbon particles of the composition is at least 3: 1. The method according to claim 1,
Wherein the composition has a weight ratio of solid particles to ionic resin of at least 8: 1. The method according to claim 1,
Wherein the composition has a total solids content of from 1 to 5% by weight based on the total weight of the composition. (a) an aqueous medium;
(b) an ionic resin; And
(c) (i) graphene carbon particles, and
(ii) lithium-containing particles
≪ / RTI >
Wherein the electrodepositable composition comprises:
A composition having a weight ratio of solid particles to ionic resin of at least 4: 1. 17. The method of claim 16,
An electrodepositable composition comprising graphene carbon particles thermally produced graphene carbon particles. 17. The method of claim 16,
Wherein the weight ratio of the graphene carbon particles to the ionic resin is from 0.1: 1 to 2: 1. (a) a cured ionic resin; And
(b) (i) graphene carbon particles, and
(ii) lithium-containing particles
≪ / RTI >
A lithium ion battery electrode coating electrodeposited on a substrate,
A lithium ion battery electrode coating having a weight ratio of solid particles to a cured ionic resin of at least 4: 1. 20. The method of claim 19,
Wherein the graphene carbon particles account for less than 10 weight percent of the total weight of the solid particles.