CN109689943A - The method of coating electroconductive substrates and the relevant electrodepositable composition comprising graphene carbon particle - Google Patents

The method of coating electroconductive substrates and the relevant electrodepositable composition comprising graphene carbon particle Download PDF

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Publication number
CN109689943A
CN109689943A CN201780055172.0A CN201780055172A CN109689943A CN 109689943 A CN109689943 A CN 109689943A CN 201780055172 A CN201780055172 A CN 201780055172A CN 109689943 A CN109689943 A CN 109689943A
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China
Prior art keywords
particle
weight
composition
graphene carbon
carbon particle
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CN201780055172.0A
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Chinese (zh)
Inventor
R·E·道翰保格
N·R·范尼尔
S·D·赫尔灵
洪正宏
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PPG Industries Ohio Inc
PPG Industries Inc
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PPG Industries Inc
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Priority claimed from US15/259,092 external-priority patent/US10763490B2/en
Application filed by PPG Industries Inc filed Critical PPG Industries Inc
Publication of CN109689943A publication Critical patent/CN109689943A/en
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/12—Electrophoretic coating characterised by the process characterised by the article coated
    • C25D13/16—Wires; Strips; Foils
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
    • C25D15/02—Combined electrolytic and electrophoretic processes with charged materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
    • C09D5/448—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications characterised by the additives used
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
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    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
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    • H01M4/045—Electrochemical coating; Electrochemical impregnation
    • H01M4/0452—Electrochemical coating; Electrochemical impregnation from solutions
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    • H01M4/045—Electrochemical coating; Electrochemical impregnation
    • H01M4/0457—Electrochemical coating; Electrochemical impregnation from dispersions or suspensions; Electrophoresis
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
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    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

Disclose such method, wherein conductive base is immersed in the electrodepositable composition including graphene carbon particle, the substrate is used as electrode in impregnating circuit in the composition, the circuit includes the electrode and counterelectrode, when electric current flows through between the electrode, coating is applied to above at least part of substrate.The electrodepositable composition includes aqueous medium, ion exchange resin and the solid particle including graphene carbon particle.The solid particle can further include the particle containing lithium.

Description

The method of coating electroconductive substrates and the relevant electrodepositable comprising graphene carbon particle Composition
Cross reference to related applications
The application is that Shen is continued in the part for the U.S. Patent Application Serial Number 14/867,307 that September in 2015 is submitted on the 28th Please, this application is the U.S. Patent Application Serial Number No.13/686 submitted on November 27th, 2012,003, existing United States Patent (USP) The continuation application of No.9,150,736.The U.S. Patent Application Serial Number 14/831 that this application or August in 2015 are submitted on the 20th, 047 part continuation application, this application are the United States serial No.13/686 submitted on November 27th, 2012,003, the existing U.S. The part continuation application of patent No.9,150,736.The application or the U.S. Patent Application Serial submitted on October 31st, 2014 Number 14/530,007 part continuation application, this application are the U.S. Patent Application Serial Number 14/ submitted on March 28th, 2014 It 348,280, is now the United States Patent (USP) No.9 that on December 29th, 2015 promulgates, 221,688 part continuation application, the United States Patent (USP) The thenational phase of the PCT International Patent Application sequence number PCT/US2012/057811 submitted on September 28th, 2012, the world Apply for the U.S. Patent Application Serial Number 13/249,315 submitted for 30th for September in 2011, be now what on July 16th, 2013 promulgated United States Patent (USP) No.8,486,363 part continuation application, and the international application or the U.S. submitted on December 2nd, 2011 Patent application serial number 13/309,894 is now the part continuation of the U.S. Patent number 8,486,364 of the July in 2013 of version cloth on the 16th Application, the part continuation application which is 13/249,315.All these applications and patentss are all incorporated by reference into this Text.
Invention field
The present invention relates to the compositions by electro-deposition comprising graphene carbon particle and resin come coating electroconductive substrates.
Background of invention
Electro-deposition is related under the influence of applying current potential in deposition composition to conductive base as coating method of application. The depositing coating when the substrate is impregnated in the composition, the substrate serve as the electrode and counterelectrode being impregnated in the composition Electrode in circuit, when electric current flows through between the electrode, coating is applied to the substrate.
In general, the composition used in electro-deposition method includes the resin phase being scattered in aqueous medium.Although the base It may include pigment to provide color and other fillers and additive that material, which is impregnated in composition therein, but in the past by electro-deposition The characteristic (such as significant corrosion resistance) that coating is sought is primarily due to the deposition of continuous resin film and generates.Therefore, the substrate It is relatively high that the resin content of composition therein, which is impregnated in, relative to the amount of pigment and other fillers.For example, such group It closes object and usually contains 0.02 to 1 parts by weight pigment relative to 1 parts by weight resin phase.
Lithium ion battery is made of cathode, anode, partition and electrolyte.The cathode (is compared with the active material containing lithium Such as LiFePO4) metal (usual aluminium) paper tinsel base material deposited thereon.The active material containing lithium is by (comparing contained in organic solvent Such as N- methyl -2- Pyrrolizidine ketone) in contain active material, conductive carbon and the adhesive (such as polyvinylidene fluoride) containing lithium Slurries be deposited on the substrate via slot die coating machine or roll coater.In these slurries, the active material containing lithium And the total amount of conductive carbon relative to the amount of adhesive be it is high, typically at least 9 parts by weight are relative to 1 parts by weight.However, using this The solvent type slurries of sample be in terms of environment not it is desirable that.
Therefore, it is necessary to for depositing alternative and composition on the composition to metal foil containing lithium.In view of aforementioned interior Appearance has made the present invention.
Summary of the invention
An aspect of of the present present invention provides method comprising: conductive base is impregnated into electrodepositable composition, it should Substrate is used as electrode in impregnating circuit in the composition, which includes the electrode and counterelectrode, when electric current flows through institute When stating between electrode, coating is applied to above at least part of substrate, which includes: (a) aqueous medium；(b) ion exchange resin；(c) comprising the solid particle of graphene carbon particle, wherein the composition has at least The solid particle of 4:1 and the weight ratio of ion exchange resin.
Another aspect provides electrodepositable composition, it includes: (a) aqueous medium；(b) ion tree Rouge；(c) solid particle, which includes: (i) graphene carbon particle；The particle of (ii) containing lithium, wherein the composition Weight ratio at least solid particle of 4:1 and ion exchange resin.
Further aspect of the invention provides electro-deposition lithium ion cell electrode coating on base material, the electro-deposition Coating includes: (a) cured ion exchange resin；(b) solid particle, which includes: (i) graphene carbon particle；With (ii) containing the particle of lithium, wherein the weight ratio of the solid particle of the coating and cured ion exchange resin is at least 4:1.
The detailed description of invention embodiment
For the purpose of this detailed description, it should be understood that various alternate variations and sequence of steps can be used in the present invention, in addition to it In clearly have except opposite regulation.In addition, in addition in any operation embodiment, or in which in addition explanation, all expression, example The number of the amount of the ingredient as used in description and claims, it should be understood that repaired in all cases by term " about " Decorations.Therefore, unless the contrary indication, the digital parameters stated in following description and appended claims are approximations, Can according to the present invention expected performance to be obtained and change.At least, and doctrine of equivalents is not intended to limit for claim The application of range, each digital parameters should be at least according to the digits for the effective digital reported and by using four common houses five Enter method to explain.
Although stating the digital scope of broad range of the present invention and parameter being approximation, speak approvingly of in a particular embodiment Numerical value is reported as accurately as possible.It is found however, any numerical value is necessarily inherently included in each test method Standard deviation certainty caused by certain error.
Also, it is to be understood, that any numberical range cited herein is intended to include and is entirely included in son therein Range.For example, the range of " 1 to 10 " is intended to include between the minimum value 1 and the maximum value 10 (and including end Value) whole subranges, that is to say, that there is the minimum value equal to or more than 1, and the maximum value equal to or less than 10.
In this application, singular use includes that plural number and plural number cover odd number, unless otherwise specified.In addition, In the application, the use of "or" indicates "and/or", unless otherwise specified, even if can clearly use in certain situations "and/or".
As noted, certain embodiments of the invention are related to including that conductive base is impregnated into electrodepositable combination Method in object.Conductive base suitable for method described herein includes metal base and conducing composite material, for example is contained There are the polymer profiles of enough conductive fillers, such as conductive carbon particle, carbon nanotube, carbon fiber, fullerene, graphene etc. Material.Suitable metal base includes, but are not limited to black and non-ferrous metal.Suitable ferrous metal includes iron, steel and its conjunction Gold.The non-limiting example of useful Steel material includes cold-rolled steel, zinc-plated (coating zinc) steel, electrolytic zinc-coated steel sheet, stainless steel, pickling The steel and their combination that steel, GALVANNEAL, GALVALUME and GALVAN Zn-Al alloy coat.Useful non-ferrous metal packet Include aluminium, copper, manganese, nickel, zinc, magnesium and its alloy.Combination or the composite material of black and non-ferrous metal can also be used.
In some embodiments, substrate is embodied in the form of sheet material, coiled material or foil.As used herein, term " foil " is Refer to thin and flexible metal sheet.The foil can be continuous sheet material, or can be perforation, netted, sieve-like etc..This The foil of sample can be made of such as aluminium, iron, copper, manganese, nickel, a combination thereof and/or its alloy.In some embodiments, foil (for example wraps Include the foil of aluminium) thickness be no more than 8 mils (203.2 μm), such as be no more than 4 mils (101.6 μm), be no more than 2 mils (50.8 μm) or in some cases no more than 1 mil (25.4 μm) and/or at least 0.1 mil (2.54 μm), such as at least 0.2 mil (5.08 μm), at least 0.4 mil (10.2 μm) or at least 0.5 mil (12.7 μm).
The method of the present invention includes conductive base to be immersed in electrodepositable composition, which is being immersed in the group It closes in the circuit in object and is used as electrode, which includes the electrode and counterelectrode, when electric current flows through between the electrode, coating It is applied to above at least part of substrate.As used in this article, phrase " to ... it is upper or to ... top " refer to, Coating can be directly applied on at least part of substrate surface or coating can be applied to and be applied at least one before Above any coating or material previously treated of the partial substrate surface.
As used in this article, term " electrodepositable composition " refers to the composition including electrodepositable component.Such as this Used herein, term " electrodepositable " means to deposit to conductive base under the influence of applying current potential.
Electrodepositable composition for method of the invention includes aqueous medium.As used in this article, term is " aqueous Medium ", which refers to, to be only made of water, or refers to that main includes water and the medium for combining one or more inertia organic cosolvents.? In certain embodiments, organic cosolvent is at least partly water-soluble.The example of such solvent includes oxygen containing organic solvent, Such as ethylene glycol, diethylene glycol (DEG), propylene glycol and dipropylene glycol monoalky lether, they in alkyl contain 1 to 10 carbon atom, than Such as the single ethylether and single-butyl ether of these glycol.The example of other at least partly miscible solvents of water includes alcohols, such as Ethyl alcohol, isopropanol, butanol and diacetone alcohol.At least partly the miscible solvent of water may include agglomerated solvent, such as phosphoric acid for other Triethyl, triacetin, dipropylene glycol diacetate esters (dipropylene diacetate) etc..As used, organic co-solvent The dosage of agent in some embodiments is to be less than 20 weight % less than 25 weight %, or be less than 10 weights in some cases % is measured, for example is less than 5 weight %, the total weight based on water in the composition.
In some embodiments, which is at least 75 weight percents of the total weight based on the composition Than, at least 90 weight percent or at least 95 weight percent (such as 75 to 99.5 weight percent, 90 to 99 weight percent Or 95 to 99 weight percent in some cases) amount be present in the composition for the method for the present invention.In other words, such as It is discussed further below, can have relatively low total solids content for the composition in the method for the present invention.
The electrodepositable composition for method of the invention includes ion exchange resin.As used in this article, term " ion exchange resin " refers to any resin for carrying charge, including carrying the resin of negative ion and carrying the resin of carbonium. Therefore, suitable ion exchange resin includes resin anion (R.A.) and resin cation.
In some embodiments of the present invention, ion exchange resin includes the resin containing anionic salt groups.Suitable yin Ion exchange resin includes the resin containing the anionic group being at least partly neutralized, for example assigns the acid groups of negative electrical charge, than Such as carboxylic acid group.Therefore, the non-limiting example of suitable resin anion (R.A.) includes the resin of the carboxy-containing acid group of alkali neutralization.
In some embodiments, resin anion (R.A.) includes water soluble anion resin.As used in this article, term " water-soluble resin " is to refer to essentially homogeneously be blended and/or be dispersed in water with molecule or ionic means very molten to be formed The resin of liquid.Referring to R.Lewis, Sr., Hawley ' s Condensed Chemical Dictionary, (1993 the 12nd editions) Page 586.In some embodiments, water soluble anion resin include cellulose derivative, such as carboxymethyl cellulose and The case where its salt (CMC).CMC is cellulose ether, and wherein the hydroxyl group of a part in dewatered grape saccharide ring is by carboxymethyl base Group replaces.Carboxymethyl replaces degree can be with range in 0.4-3.Since CMC is a kind of long-chain polymer, in aqueous solution Viscosity depend on its molecular weight, the molecular weight by weight in terms of can change between 50,000 and 2,000,000.In certain implementations In mode, the weight average molecular weight of carboxymethyl cellulose is at least 50,000, such as at least 100,000, or in some cases, until Lack 200,000, such as 50,000 to 1,000,000,100,000 to 500,000 or 200,000 to 300,000.Substitution degree It can be measured by ASTM D 1439-03 with the viscosity of aqueous solution.Molecular weight is typically by the viscosity of standard CMC solution To estimate.According to a kind of method, the molecular weight of CMC can be estimated in the following way using viscosity:
η [Pa S]=8.91x10-4+1.30x10-5cMW 0.9+5.33x10-8c2MW 1.8+4.60x10-15c4.34MW 3.91
Wherein η is viscosity, and c is CMC concentration, MWFor molecular weight, such as the Polymer Vol.37 No.13 of Kulicke, Pp.2723-2731, described in 1996.
In some embodiments of the present invention, water soluble anion resin, such as cellulose derivative, such as carboxymethyl Cellulose, existing amount are at least 50 weight %, such as at least 60 weight %, at least 70 weight %, at least 80 weight %, or At least 90 weight %, the total weight based on resin solid in the composition in some cases.In some embodiments, water-soluble Resin anion (R.A.), such as cellulose derivative, such as carboxymethyl cellulose, existing amount are to be no more than no more than 20 weight % 15 weight % are no more than 10 weight %, are no more than 5 weight %, such as 1 to 20 weight %, 1 to 15 weight %, 5 to 15 weights Measure %, or 1 to 3 weight % in some cases, the total weight based on solid in the composition.As used in this article, term " total weight of solid " refers to the content of total nonvolatile matter of the composition, i.e., will not volatilize when heated in the composition Material content, and not aqueous and organic solvent.
In some embodiments, other than water soluble anion resin, the composition can be also comprising water dispersible yin Ion exchange resin.As used in this article, " water-dispersed resin " is the tree for referring to be distributed in water as finely divided particle Rouge.Referring to Hawley page 435.
Suitable for composition as described herein and the water-dispersible anionic resin of water soluble anion resin combination Example includes the reaction product or adduct of dry oil or partial desiccation aliphatic ester and dicarboxylic acids or acid anhydrides；With aliphatic ester, no The reaction product of saturated acid or acid anhydrides and any other unsaturated modified material, they and polyalcohol carry out single step reaction.Also The suitably hydroxyalkyl acrylate of unsaturated carboxylic acid, unsaturated carboxylic acid and other at least one ethylenically unsaturated monomers it is interpolymerized Object.
Other suitable water-dispersible anionic resins are the mixture of alkyd resin and amine-aldehyde resins, resinous polyol Mixed ester and phosphatization polyepoxide or phosphatization acrylic resin, for example EP0469491B1 row of page 2 the 56th is to The row of page 3 the 56th, U.S. Patent Application Publication No.2009-0045071 [0004]-[0015] section and U.S. Patent Application Serial Disclosed in number 13/232,093 [0014]-[0040] section those, reference portion is incorporated herein by reference.It is also suitable It is those of carbamate-functional group resin to be flanked comprising one or more, for example be described in United States Patent (USP) No.6,165, Those of 338.
In some embodiments, the composition includes resin anion (R.A.) composition, it includes water soluble anion resin, Such as cellulose derivative, such as carboxymethyl cellulose and water-dispersible anionic resin, it is different from cellulose derivative, wherein The amount of water-dispersible anionic resin in the composition be less than 50 weight %, such as be less than 40 weight %, be less than 30 weight %, be less than 20 weight %, or in some cases be less than 10 weight %, based in the composition resin anion (R.A.) it is total Weight.
It should be understood that make resin anion (R.A.) adaptation be dissolved or dispersed in aqueous medium when, through common alkali by it extremely Partially neutralize.Suitable alkali includes organic and inorganic base.The example of exemplary suitable alkali is ammonia, monoalkylamine, dioxane Base amine or trialkylamine, such as ethamine, propylamine, dimethylamine, dibutyl amine and cyclohexylamine；Monoalkanolamine, dialkanol amine or three alkanols Amine, such as ethanol amine, diethanol amine, triethanolamine, Propanolamine, isopropanolamine, diisopropanolamine (DIPA), dimethylethanolamine and diethyl Ethylethanolamine；Morpholine, such as N-methylmorpholine or N-ethylmorpholine.The example of suitable inorganic base includes alkali metal or alkaline earth gold The hydroxide of category, carbonate, bicarbonate and acetic acid are saline and alkaline, and specific example includes potassium hydroxide, lithium hydroxide and hydrogen Sodium oxide molybdena.Therefore, in some embodiments, the composition includes the alkali metal salt (alkali salt) of cellulose derivative, Such as sodium carboxymethylcellulose, potassium carboxymethylcellulose and/or carboxymethyl cellulose lithium.In some embodiments, resin (one Kind is a variety of) it neutralizes with 20 to 200%, 40 to 150%, such as 60 to 120% and is at least partly neutralized.
In some embodiments, above-mentioned water-dispersible anionic resin includes containing reactive hydrogen, contains anion alkali The resin of group, and the composition further includes curing agent, and the curing agent is reactive anti-comprising having with the active hydrogen group Answering property group.As used in this article, term " containing reactive hydrogen, containing the resin of anionic salt groups " refers to comprising reactive hydrogen The resin of functional group and the anionic group being at least partly neutralized.As used in this article, term " reactive hydrogen functional group Group ", which refers to, has those reactive groups with isocyanates by Zerewitnoff test determination, is such as described in JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, Vol.49, page 3181 (1927), and including, for example, Hydroxyl group, primary or secondary amine groups and thiol group.In some embodiments, reactive hydrogen functional group is hydroxyl group, primary Amine groups and/or secondary amine group.
For electrodepositable composition (including containing reactive hydrogen, contain the resin of anionic salt groups) it is suitable solid Agent includes, but is not necessarily limited to, amino resin and bakelite resin.Suitable amino resin is aldehyde (such as first Aldehyde, acetaldehyde, crotonaldehyde and benzaldehyde) and the substance (such as urea, melamine and phenyl guanamines) containing amino or amide groups Condensation product.Usually using the product reacted by pure and mild formaldehyde with melamine, urea and phenyl guanamines.Useful ammonia The example of base plastic resin but unrestricted example be can be obtained from trade mark CYMEL Cytec Industries and with RESIMENE is obtained from those of Solutia Inc..Specific example is 750 He of CYMEL 1130 and 1156 and RESIMENE 753。
In other embodiments of the invention, ion exchange resin includes the resin of cation salt groups.Suitable fellatio The resin of ionic salt group includes containing the cation group (such as sulfonium base and the amine that being at least partially neutralized for assigning positive charge Base) resin.
In some embodiments, resin cation includes water-soluble cationic resins.In some embodiments, water-soluble Property resin cation include can be linear chain or branched chain poly- (C2-4) alkylene imine, specific example includes polyethyleneimine (PEI).It will be appreciated that PEI is as made from the ring-opening polymerisation of ethylene amines.Other suitable water-soluble cationic resins include Poly- (allylamine hydrochloride), poly- (acrylamide-co-diallyldimethylammonium chloride) and poly- (2- methacryloxypropyl Base ethyl-trimethyl salmiac).In some embodiments, water-soluble cationic resins (such as those mentioned above) have Have at least 5,000, such as at least 10,000, or in some cases 5,000 to 50,000, or in some cases 10,000 to 25,000 weight average molecular weight.
In some embodiments, water-soluble cationic resins, such as PEI are based on resin in the composition Total weight at least 50 weight percent, such as at least 60 weight percent, at least 70 weight percent, at least 80 weight percents Than or the amounts of at least 90 weight percent in some cases exist.In some embodiments, water-soluble cationic resins, For example PEI is to be no more than 20 weight percent based on total solids meter in the composition, be no more than 15 weight percents Than, be no more than 10 weight percent, be no more than 5 weight percent, such as 1 to 20 weight percent, 1 to 15 weight percent, 5 The amount of 1 to 3 weight percent exists to 15 weight percent or in some cases.
In some embodiments, other than water-soluble cationic resins, the composition also include water dispersible sun from Subtree rouge.The example of water dispersible cationic resin suitable for composition as described herein is the cation salt containing reactive hydrogen The resin of group.As used in this article, term " resins of the cation salt groups containing reactive hydrogen " refers to including reactive hydrogen The resin of functional group and the cation group being at least partially neutralized.Be suitable as in the present invention the fellatio containing reactive hydrogen from The examples of resins of the resin of alite group includes but is not limited to alkyd resin, acrylic compounds, polyepoxide, polyamide, poly- ammonia Ester, polyureas, polyethers and polyester etc..
The more specific examples of the suitably resin of the cation salt groups containing reactive hydrogen include polyepoxide-amine adduction Object, such as the polyglycidyl ether adduct and primary amine and/or secondary amine adduct of polyphenol, such as bisphenol-A, such as in United States Patent (USP) 4th, 031, No. 050 the 27th row of the 3rd column is to the 50th row of the 5th column, 4,452, No. 963 the 5th column the 58th rows to the 6th column of U.S. Patent No. 66th row and U.S. Patent No. 6, described in 017, No. 432 the 66th row to the 26th row of the 6th column of the 2nd column, these patents these Part is incorporated herein by reference.In some embodiments, a part of the amine reacted with polyepoxide is more The ketamine of amine, such as described in 4,104, No. 147 the 23rd rows to the 23rd row of the 7th column of the 6th column of U.S. Patent No., cited in Part be incorporated herein by reference.Equally suitable is polyepoxide-polyoxy alkylidene polyamines tree of non-gel Rouge, such as described in 4,432, No. 850 the 60th rows to the 58th row of the 5th column of the 2nd column of U.S. Patent No., cited in part It is incorporated herein by reference.In addition, cationic acrylic resins can be used, such as in U.S. Patent No. 3,455, No. 806 the 18th rows of the 2nd column are to No. 3,928,157 the 29th rows of the 2nd column of the 61st row of the 3rd column and U.S. Patent No. to the 21st row of the 3rd column Those of described in, these parts of two patents are incorporated herein by reference.
In addition to the resin containing amine salt group, the resin containing quaternary ammonium salt group can also be used and be used as in composition as described herein In cation salt groups resin.The example of these resins is by organic polyepoxide and tertiary amine acid reactant salt institute shape Those of at.It is special to the 7th row of the 11st column, the U.S. that such resin is described in No. 3,962,165 the 3rd rows of the 2nd column of U.S. Patent No. Sharp No. 3,975,346 the 62nd row of the 1st column to No. 4,001,156 the 37th rows of the 1st column of the 25th row of the 17th column and U.S. Patent No. extremely In the 7th row of 16th column, these parts of these patents are incorporated herein by reference.Other suitable resin cations Example includes the resin of the group containing ternary sulfonium salts, for example is described in 3,793, No. 278 the 32nd rows of the 1st column of U.S. Patent No. to the 5th This part of those of the 20th row of column, these patents is incorporated herein by reference.Equally, it can also be used via transesterification The cured resin cation of mechanism, such as in No. 12463B1 the 1st row of page 2 institute into the 25th row of page 6 of European Patent Application No. Description, this of this application is partly incorporated herein by reference.
The resin of other suitable cation salt groups includes the electrodepositable coating composition that can form photodegradation Those of.Such resin includes comprising the resin derived from side chain and/or the cationic amine salt group of terminal amino group, they are public It opens in 2003/0054193 A1 [0064] section of U.S. Patent Application Publication into [0088] section, this part of the disclosure is to draw Mode is incorporated herein.Equally suitable is the cation containing reactive hydrogen of the polyglycidyl ether derived from polyphenol The resin of salt groups, substantially free of the aliphatic carbon atom for being bonded to more than one aromatic group, they are described the polyphenol In patent application publication US 2003/0054193 A1 [0096] Duan Zhi [0123] section, this part of the disclosure with The mode of reference is incorporated herein.
In some embodiments, the composition includes cation resin composition, which includes Water-soluble cationic resins, such as PEI and water dispersible cationic resin different from PEI, the wherein water dispersible cationic Resin is lower than 50 weight percent, for example to be lower than 40 weight based on the total weight of resin cation in the composition Percentage is deposited lower than 30 weight percent, lower than 20 weight percent or in some cases lower than the amount of 10 weight percent It is in the composition.
It will be appreciated that the resin is for example, by with acid to make resin cation be suitable for being dissolved or dispersed in aqueous medium It handles and is at least partially neutralized.The non-limiting example of suitable acid is inorganic acid, such as phosphoric acid and sulfamic acid, and Organic acid, such as acetic acid and lactic acid etc..Besides acids, such as dimethyl hydroxyethyl ammonium dihydrogen phosphate and biphosphate can be used The salt of ammonium.In some embodiments, resin cation is at least 50 percentages of neutralization equivalent to be discussed with premier or in some feelings The degree of at least 70 percentages is neutralized in condition.Dissolution or dispersion steps can be by will being neutralized or partly being neutralized Resin is with hydration and to complete.
In some embodiments, the composition further includes curing agent with the resin with above-mentioned cation salt groups Active hydrogen group reaction.The non-limiting example of suitable curing agent is polyisocyanates, more including what is at least partly blocked Isocyanates, amino resin and phenolic resin, such as phenolformaldehyde condensate, including its allyl ether derivative.
In some embodiments, the composition may include catalyst with catalytic curing agent and containing the resin of reactive hydrogen Reaction between (one or more).Suitable curing catalysts include but is not limited to organo-tin compound (such as dibutyl oxygen Change tin and dioctyl tin oxide) and its salt (such as dibutyltin diacetate)；Other metal oxides (such as cerium, zirconium and bismuth Oxide) and its salt (such as sulfamic acid bismuth and bismuth lactate).In some embodiments, curing catalysts include cyclic guanidine, United States Patent (USP) No.7,842,762 is such as described in the 53rd row of the 1st column to the 18th row of the 4th column and the 16th column the 62nd row to the 19th column Eighth row, reference portion are incorporated herein by reference.In some embodiments, the composition does not include organo-tin compound.
Composition for method of the invention further includes solid particle.As used in this article, term " solid The solid that grain " refers to discrete 3D shape, is chemically different from ion exchange resin (one or more).Particle shape (or Form) it can be varied.For example, the graphene carbon particle of sheet or plate as described below can be used.In addition, tool can be used There are the solid particle and cube or needle-shaped (elongated or fiber of form generally spherical in shape (such as solid pearl, microballon or hollow sphere) Shape) particle.When using plate-like particles, they can be plane, or at least part can be curved, curling, fold Or warpage (buckled).In addition, in some embodiments, particle in addition can have internal structure, it is Empty, porous or non-porous or any combination above-mentioned, such as hollow center and porous or solid wall.For suitable The more information of grain characteristic, referring to H.Katz et al. (editor), Handbook of Fillers and Plastics (1987) The 9-10 pages.
In some embodiments, solid particle includes graphene carbon particle.Graphene carbon particle can be any suitable Amount is provided in the electrodepositable composition.For example, the weight ratio of graphene carbon particle and ion exchange resin can in the composition Typically in the range of 0.05:1 to 5:1.In some embodiments, the weight ratio of graphene carbon particle and ion exchange resin can range In 0.1:1 to 2:1 or 0.1:1 to 1:1.
As used in this article, term " graphene carbon particle " means the carbon particle having a structure in which, the structure packet Containing one layer or more with the sp of honeycomb lattice Close stack2The plane lamina of one atom thick of the carbon atom of bonding.Stack layer Par is smaller than 100 layers, is, for example, less than 50 layers.In some embodiments, the par of stack layer is 30 layers or more It is few, such as 20 layers or less, 10 layers or less or 5 layers or less in some cases.Graphene carbon particle can be substantially flat Flat, however, at least part of plane lamina can be substantially bending, curling, gauffer or warpage.The particle does not have usually There are near-spherical or isometric form.
In some embodiments, the thickness of graphene carbon particle measured on the direction perpendicular to carbon atomic layer is little It is received in 10 nanometers, no more than 5 nanometers or in some embodiments no more than 4 or 3 or 2 or 1 nanometers, such as no more than 3.6 Rice.In some embodiments, graphene carbon particle can be 1 atomic layer to 3,6,9,12,20 or 30 or more atomic layers It is thick.In some embodiments, the width of graphene carbon particle measured on the direction for be parallel to carbon atomic layer and length are At least 50 nanometers, 100 nanometers are greater than, be greater than 100 nanometers to 500 nanometers in some cases or is greater than 100 nanometers extremely 200 nanometers.Graphene carbon particle can have the relatively high aspect ratio higher than 3:1, for example higher than 10:1, and (aspect ratio is definition For the ratio of the shortest dimension of the longest dimension and particle of particle) superthin section, small pieces or thin slice form provide.
In some embodiments, graphene carbon particle has relatively low oxygen content.For example, even if being no more than having 5 nanometers or when thickness no more than 2 nanometers, graphene carbon particle can have no more than 2 atomic wts %, for example no more than 1.5 Atomic wts % or 1 atomic wts % or the oxygen content for being no more than 0.6 atomic wts % (for example, about 0.5 atomic wts %).Stone The usable x-ray photoelectron spectroscopy method of the oxygen content of black olefinic carbon particle (such as be described in D.R.Dreyer et al., In Chem.Soc.Rev.39,228-240 (2010)) it measures.
In some embodiments, graphene carbon particle has at least 50 meters squared per grams, such as 70 meters squared per grams extremely 1000 meters squared per grams or in some cases 200 meters squared per grams are to 1000 meters squared per grams or 200 meters squared per grams to 400 flat Square rice/gram B.E.T. specific surface area.As used herein, term " B.E.T. specific surface area " refers to based on periodical " The Journal of the American Chemical Society ", Brunauer- described in 60,309 (1938) The specific surface area that Emmett-Teller method is measured according to ASTMD 3663-78 standard by N2 adsorption.
In some embodiments, graphene carbon particle has the Raman light of at least 1:1, for example, at least 1.2:1 or 1.3:1 Compose 2D/G peak ratio.As used herein, term " 2D/G peak ratio " refers to 2692cm-1The 2D peak intensity and 1,580cm at place-1Place G peak intensity ratio.
In some embodiments, graphene carbon particle has relatively low heap density.For example, the spy of graphene carbon particle Sign, which is to have, is less than 0.2g/cm3, for example no more than 0.1g/cm3Heap density (tap density).For purposes of the present invention, The heap density of graphene carbon particle be by by 0.4 gram of graphene carbon particle be placed in the glass cylinder with readable scale come Measurement.Make graduated cylinder increase about 1 inch and by make graduated cylinder bottom strike on hard surface come jolt ramming 100 times so that graphite Olefinic carbon particle settles in graduated cylinder.Then the volume of particle is measured, and close by calculating heap divided by measured volume for 0.4 gram Degree, wherein heap density is with g/cm3It indicates.
In some embodiments, the pressed density of graphene carbon particle and densification percentage are less than powdered graphite and certain The pressure of the essentially flat graphene carbon particle those of (such as formed by exfoliated (exfoliated) graphite) of a little types Contracting density and densification percentage.It is presently believed that lower pressed density and low densification percentage respectively promote than show compared with High compression density and preferably disperse compared with the graphene carbon particle of high densification percentage and/or the rheological equationm of state.In certain implementations In mode, the pressed density of graphene carbon particle is 0.9 or smaller, is, for example, less than 0.8, less than 0.7, such as 0.6 to 0.7.? In certain embodiments, the densification percentage of graphene carbon particle be less than 40%, be, for example, less than 30%, such as 25% to 30%.
For purposes of the present invention, the pressed density of graphene carbon particle is by giving the institute of the particle of quality upon compression Measure THICKNESS CALCULATION.Specifically, measured thickness be by making 0.1 gram of graphene carbon particle in 1.3 centimetres of punch dies 15, Cold pressing is subjected under 000 pound of power 45 minutes to measure, wherein contact pressure is 500MPa.Then it is surveyed according to following equation by the institute The pressed density of the THICKNESS CALCULATION graphene carbon particle of amount:
Then, the densification percentage test of graphene carbon particle is the pressure of the calculating of the graphene carbon particle as above measured Contracting density and 2.2g/cm3The ratio of (it is the density of graphite).
In some embodiments, graphene carbon particle, after blending at once with the time point after mixing, such as 10 Minute or 20 minutes or 30 minutes or 40 minutes, there are at least 100 micro-Siemens, for example, at least 120 micro-Siemens, such as The body fluid bulk conductivity (bulk liquid conductivity) of at least 140 micro-Siemens measured.For mesh of the invention , the body fluid bulk conductivity of graphene carbon particle is to measure as follows.Firstly, will be comprising graphene carbon particle in butyl cellosolve 0.5% solution sample using bath supersonic generator ultrasonication 30 minutes.Immediately will after ultrasonication Sample is placed in the electrolytic conductance pond (K=1) through reference substance calibration.30 conductivity gauge of Fisher Scientific AB is introduced The conductivity of sample is measured into sample.It is plotted in the conductivity during about 40 minutes.
According to certain embodiments, there is the infiltration for being defined as long-range interconnectivity between electric conductivity graphene carbon particle (percolation).It is such to permeate the resistivity that may be decreased coating composition.Conductive graphene particle may occupy coating Interior minimum volume, so that the particle forms continuous or nearly singular integral network.In such circumstances, graphene carbon The aspect ratio of grain may influence to permeate required minimum volume.
In some embodiments, at least part of graphene carbon particle can be prepared by thermal method.It is according to the present invention Embodiment, the graphene carbon particle of thermal method preparation are the carbonaceous precursors by being heated to high temperature in the hot-zone of such as plasma Material is made.As described more fully below, carbonaceous precursor materials are heated to sufficiently high temperature, for example, higher than 3,500 DEG C with Generate graphene carbon particle as characterized above.By carbonaceous precursor, such as the hydrocarbon provided with gas or liquid form is in hot-zone Middle heating to generate graphene carbon particle in the hot-zone or downstream.For example, the graphene carbon particle of thermal method preparation can pass through System and method disclosed in U.S. Patent number 8,486,363 and 8,486,364 are made.
In some embodiments, the graphene carbon particle of thermal method preparation can be by using U.S. Patent number 8,486,363 The device and method described in [0022] to [0048] are made, wherein (i) by one or more two carbochain sections of being capable of forming The hydrocarbon precursor material of substance, for example, normal propyl alcohol, ethane, ethylene, acetylene, vinyl chloride, 1,2- dichloroethanes, allyl alcohol, propionic aldehyde and/ Or vinyl bromide is introduced in such as plasma of hot-zone, and (ii) heats the hydrocarbon in the hot-zone to form graphene carbon Grain.In other embodiments, the graphene carbon particle of thermal method preparation can exist by using in U.S. Patent number 8,486,364 [0015] it is made to device and method described in [0042], wherein (i) by methane precursor material for example comprising at least 50% first The material of alkane, or at least 95% or 99% purity or higher gas or liquid methane are introduced to hot-zone example in some cases In plasma, and (ii) heats methane precursor in hot-zone to form graphene carbon particle.Such method can produce With at least some, all features described above in some cases graphene carbon particles.
During producing graphene carbon particle by above-mentioned hot production method, carbonaceous precursor is as can be with inert carrier gas The supplying material of body contact provides.Carbonaceous precursor materials can heat in hot-zone for example, by plasma system.In certain realities It applies in mode, precursor material is heated at least 3,500 DEG C of temperature, such as from being higher than 3,500 DEG C or 4,000 DEG C to 10,000 DEG C or 20,000 DEG C of temperature.Although hot-zone can be generated by plasma system, it should be appreciated that can be used any other suitable Heating systems to generate hot-zone, such as various types of furnaces, including electric heating tube furnace etc..
Gas stream can inject the quenching stream in plasma chamber by least one quenching streamer loophole with one or more Contact.Quenching stream can cool down the gas stream by promote the formation of graphene carbon particle or control its granularity or in the form of.In the present invention Certain embodiments in, gaseous product flow with quenching stream contact after, ultra-fine grain may pass through convergence component.Graphene carbon After particle leaves plasma system, they can be collected.Any proper method can be used to separate graphite from air-flow Olefinic carbon particle, such as bag filter, cyclone separator or be deposited on substrate.
In some embodiments, at least part of graphene carbon particle is available from commercial source, such as obtained from Angstron, XG Sciences and other commercial sources.In such an embodiment, commercially available graphene carbon particle can wrap It compares containing exfoliated graphite and with the graphene carbon particle of thermal method preparation with different characteristic, such as different size distributions, Thickness, aspect ratio, structural form, oxygen content and in bottom surface/edge chemical functional group.
In some embodiments, graphene carbon particle is functionalized.As employed herein, " functionalization " is when being related to stone When black olefinic carbon particle, indicate that any non-carbon or any organic group are covalently bound on graphene carbon particle.The graphite Olefinic carbon particle can pass through the carbon atom and other chemical parts such as carboxylic acid group in particle, sulfonic acid group, hydroxyl, halogen original It is functionalized to form covalent bond between phenyl etc. for son, nitro, amido, aliphatic alkyl.Such as it can with carbonaceous material functionalization Cause to form carboxylic acid group on graphene carbon particle.The graphene carbon particle can also react such as Diels- by other Alder addition reaction, 1,3- Dipolar Cycloaddition, Radical Addition and diazonium compound addition reaction are functionalized. In some embodiments, hydrocarbon and phenyl can be further functionalized.If graphene carbon particle has had some hydroxyl officials It can roll into a ball, then the functional group can be reacted by these groups with such as organic isocyanate to be modified and extend (extended).
In some embodiments, different types of graphene carbon particle can be used in the electrodepositable composition.Example It such as, can when the graphene carbon particle embodiment according to the present invention of thermal method preparation is combined with commercially available graphene carbon particle Realize the graphene carbon particle characteristics of bimodal, tri-modal distribution etc..Graphene carbon particle contained in the composition can have multimodal Size distribution, distribution of aspect ratios, structural form, edge functional group difference, oxygen content etc..
In the graphene carbon particle of wherein thermal method preparation and commercially available graphene carbon particle (for example, coming from exfoliated graphite) The two is used to generate in the embodiment of the present invention of bimodal graphene size distribution, controls different types of graphene carbon particle Relative quantity is to generate the expectation Effective Conductivity of coating.For example, the graphene particles of thermal method preparation can account for 1 weight % to 50 weights % is measured, and the commercially available graphene carbon particle can account for 50 weight % to 99 weight %, the total weight based on graphene carbon particle. In some embodiments, the graphene carbon particle of thermal method preparation can account for 2 weight % or 4 weight % to 40 weight % or 6 weights Measure % or 8 weight % to 35 weight % or 10 weight % to 30 weight %.When the stone of the thermal method preparation with such relative quantity When black olefinic carbon particle and commercially available graphene carbon particle of the invention is divided into granular media and is introduced into coating, ink or other materials, Such material can be opened up compared with the analog material of the mixture for the graphene carbon particle for containing such type with similar ratio Reveal the conductivity dramatically increased.For example, this is divided into granular media can make conductivity increase at least 10% or 20% compared with mixture. In some embodiments, conductivity can increase at least 50%, 70% or 90% or more.
In some embodiments of the present invention, other than graphene carbon particle, which also includes containing lithium Particle, for example, the mixed metal oxide of at least one element comprising Li and selected from Ni, Co, Fe, Mn, Al and P.For example, Particle containing lithium may include LiCoO2, LiNiO2, LiFePO4, LiCoPO4, LiMnO2, LiMn2O4, Li (NiMnCo) O2And/or Li (NiCoAl)O2, wherein the relative quantity of transition metal can be varied as desired.For example, Ni, Mn and Co can not be always at 1:1:1 Relative atom ratio, and more nickel, such as 5:3:2 or 8:2:2 in some embodiments can be contained.In certain embodiment party In formula, before mixing the composition, the average particle size of such particle containing lithium is no more than 10 microns, is no more than 5 microns, does not surpass Cross 3 microns, be no more than 1 micron, such as 10 nanometers to 1,000 nanometer, or 500 nanometers to 1 in some cases, 000 nanometer or 600 nanometers to 800 nanometers.
In some embodiments, the amount of such solid particle containing lithium is at least 50 weight %, at least 60 weights Measure %, at least 70 weight %, at least 80 weight %, such as at least 85 weight %, or at least 90,93 or 96 weights in some cases Measure %, the total weight based on solid in the composition.It include particle and graphene carbon particle containing lithium according to wherein solid particle Certain embodiments, the sum total poidometer of particle and graphene carbon particle based on this containing lithium, their relative weight % allusion quotation Type range in 85 to 99.5 weight % containing the particle of lithium and 0.5 to 15 weight % graphene carbon particle, such as 90 to 99 weights % is measured containing the particle of lithium and 1 to 10 weight % graphene carbon particle or 92 to 98 weight % containing the particle of lithium and 2 to 8 weight % Graphene carbon particle.
In some embodiments, including those described above, wherein solid particle includes graphene carbon particle and containing the particle of lithium Embodiment, the composition may include other conductive particle, such as conductive carbon particle.Suitable conductive particle includes conduction Carbon black, acetylene black, carbon nanotube, carbon fiber, fullerene etc..Example suitable for commercially available conductive black here includes, but not It is limited to, the Cabot Monarch that Cabot Corporation is soldTM1300, Cabot XC-72R, Cabot LiTX 50, Cabot LiTX 200, Cabot LiTX 300, Denka Black HS-100L, Black Pearls 2000 and Vulcan XC 72；The Acheson Electrodag that Acheson Colloids Co. is soldTM230；Columbian Carbon Co. The Columbian Raven of saleTM3500；It is sold with DeGussa Corporation, Pigments Group PrintexTMThe Super that XE 2, Printex 200, Printex L and Printex L6 and TIMCAL Ltd. are sold And SuperLi, C-NergyTMSuper C45 and C-NergyTMSuper C65.In some embodiments, for this Average primary particle size of the conductive black of composition described in text before mixing the composition be less than 300 nanometers, such as 1 to 200 nanometers, 10 to 100 nanometers, or 30 to 50 nanometers in some cases.
It is suitable for the invention other conductive particles and includes, but are not limited to conductive silicon oxide, such as Japan 200 He of AEROSIL that Aerosil Co., Ltd. sells161,244,308,404 Hes978, all available from Fuji Davison Co., Ltd.；Metal powder, such as aluminium, copper Or special steel, molybdenum disulfide, iron oxide, such as black iron oxide, stibium doped titanium dioxide and nickel are titania-doped.It is also suitable Have the particle for being coated with the such as metal of cobalt, copper, nickel, iron, tin, zinc and combinations thereof.It is suitable to be coated with above-mentioned metal Particle includes aluminium oxide, aluminium, aromatic polyester, boron nitride, chromium, graphite, iron, molybdenum, neodymium/iron/boron, SmCo, silicon carbide, stainless Steel, titanium diboride, tungsten, tungsten carbide and zirconia particles.The particle of such metal coating is available commercially from Advanced Ceramics Corp.The particle of available other metals coating includes ceramic microsphere, short glass fiber, graphite powder and piece, boron nitride, mica Piece, copper powder and piece, nickel powder and piece are coated with the aluminium of the such as metal of carbon, copper, nickel, palladium, silicon, silver and titanium coating.These particles are typical Ground carries out metal coating using fluidized bed chemical vacuum deposition technology.The particle of such metal coating available commercially from Powdermet, Inc.The mixture of different conductive particles can be used.
In some embodiments, the amount that conductive particle is present in the composition makes the particle in the composition containing lithium It is at least 3:1, at least 4:1, at least 5:1, at least 8:1 with the relative weight of graphene carbon particle or other conductive particles ratio, until Few 10:1, or at least 15:1 in some cases, or at least 30:1, or at least 45:1, or at least 60:1.In certain embodiments In, the amount of such conductive particle is to be no more than 10 weight %, such as 1 to 10 weight % or 1 no more than 20 weight % To 5 weight %, the total weight based on solid in the composition.
Other than above-mentioned graphene carbon particle, other kinds of solid particle also may be included in the electrodepositable material In.Such solid particle can be polymer-type and/or non-polymeric inorganic material, polymer-type and/or non-polymer The mixture of type organic material, composite material and any aforementioned substances.As used in this article, term " polymer " " means to contain Lid oligomer, and including and be not limited to homopolymer and copolymer.
As used in this article, term " polymer " type inorganic material ", which refers to, to be had based on one or more members in addition to carbon The polymer-based material of the backbone repeating units of element.In addition, as used in this article, term " polymer " type organic material " refer to Synthetic polymer profile material, semi synthetic polymer profile material and natural polymer profile material, they all have the skeleton based on carbon Repetitive unit.
As used in this article, term " organic material " means carbon compound, and wherein carbon is typically keyed to itself, Be keyed to hydrogen, and be also often keyed to other elements, and exclude binary compound, such as oxycarbide, carbide, carbon Disulphide etc.；Ternary compound, such as metal cyanides, metal carbonyl, phosgene, carbonyl sulfide etc.；With it is carbon containing from Sub- compound, such as metal carbonate, such as calcium carbonate and sodium carbonate.As used in this article, term " inorganic material " refers to It is not any material of organic material.
As used in this article, term " composite material " refers to two or more combinations of different materials.By composite wood Expect that hardness of the particle formed on its surface may be different from the hardness inside its lower face particle.More specifically, particle Surface can be modified in any manner known in the art, including but not limited to using techniques known in the art to change Mode or physics mode change its surface characteristics.
For example, particle can be formed by main material, the main material coats with one or more auxiliary materials, coat or Encapsulating, to form the composite particles having compared with pressure release surface.In some embodiments, the particle formed by composite material can be by leading Material is wanted to be formed, the different form of main material main material is coated, coated or encapsulates.
As noted, solid particle may include any various inorganic material, such as ceramic material, metal material and any The mixture of aforementioned substances.The non-limiting example of this ceramic material may include the metal oxidation of metal oxide, mixing Object, metal nitride, metal carbides, metal sulfide, metal silicate, metal boride, metal carbonate and it is any before State the mixture of substance.The specific non-limiting example of metal nitride is boron nitride；Metal oxide it is specific non-limiting Example is zinc oxide；The non-limiting example of the metal oxide suitably mixed is alumina silicate and magnesium silicate；Suitable metal The non-limiting example of sulfide is molybdenum disulfide, tantalum disulfide, tungsten disulfide and zinc sulphide；Metal silicate it is non-limiting Example is alumina silicate and magnesium silicate, such as vermiculite.
In some embodiments of the present invention, solid particle include inorganic material, the inorganic material be selected from aluminium, barium, Bismuth, boron, cadmium, calcium, cerium, cobalt, copper, iron, lanthanum, magnesium, manganese, molybdenum, phosphorus, selenium, silicon, silver, sulphur, tin, titanium, tungsten, vanadium, yttrium, zinc and zirconium, including Its oxide, its nitride, its phosphide；Its phosphate, its selenides；Its sulfide；Its sulfate；And their mixing Object.The non-limiting example of suitable aforementioned inorganic particle includes aluminium oxide, silica, titanium dioxide, ceria (cera), zirconium oxide, bismuth oxide, magnesia, iron oxide, alumina silicate, boron carbide, nitrogen-doped titanium dioxide and cadmium selenide.
In some embodiments, there is layer structure for solid particle of the invention.Particle with layer structure It is made of the atom of hexagonal array or the piece or plate of particle.The non-limiting example of layer structure is hexagonal crystal structure. Inorganic solid particles with stratiform fullerene (bucky-ball) structure are also available.
The non-limiting example of suitable material with layer structure include boron nitride, graphite, metal dithionite category compound, Mica, talcum, gypsum, kaolinite, calcite, cadmium iodide, silver sulfide and its mixture.Suitable metal dithionite category compound includes Molybdenum disulfide, two selenizing molybdenums, tantalum disulfide, two selenizing tantalums, tungsten disulfide, two tungsten selenides and its mixture.
Solid particle can be formed by non-polymeric organic material.Non-polymeric organic material for use in the present invention Non-limiting example include, but are not limited to stearate (such as zinc stearate and aluminum stearate), diamond, carbon black and hard Acyl amine.
In some embodiments, solid particle includes organic pigment, such as example, azo-compound (monoazo, two idols Nitrogen, betanaphthol, naphthols AS, azo pigments color lake, benzimidazolone, two azo condensation products, metal complex, isoindolinone, Isoindoline) and it is polycyclic (phthalocyanine, quinacridone, perylene, purple cyclic ketones (perinone), diketopyrrolo-pyrrole, thioindigo, Anthraquinone, indanthrone, anthracene pyrimidine, flavanthrone, pyranthrone, anthanthrene diketone, dioxazines, triaryl carbon, quinophthalone) pigment, With the mixture of any aforementioned substances.
In some embodiments, average particle size of the above-mentioned other solid particle before mixing the composition be less than 100 microns, for example 50 microns are less than before mixing the composition.In some embodiments, which is mixing the group Mean particle size range before closing object is 1 to 1000 nanometer before mixing the composition at 1 to 10,000 nanometer, or is somebody's turn to do in incorporation It is 1 to 100 nanometer before composition.
In the embodiment that the average particle size of those solid particles is at least about 1 micron, average particle size can be according to The laser scattering technology measurement known.Such as the average particle size of this particle can be used 900 laser of Horiba Model LA and spread out Particle size instrument is penetrated, which measures the size of particle using the helium-neon laser that wavelength is 633nm, and assumes that particle has There is spherical shape, that is, " granularity " refers to the smallest sphere for surrounding particle completely.
Those solid particles average particle size less than or equal in 1 micron of embodiment, average particle size can by with Under type determines: visually inspecting the electron micrograph of transmission electron microscope (" TEM ") image, measures particle in image Diameter and amplification factor based on TEM image calculates average particle size.Those skilled in the art will appreciate that how to prepare in this way TEM image.The diameter of particle refers to the smallest diameter sphere for surrounding particle completely.
In some embodiments, the composition may include other typical ingredients, such as corrosion inhibitor, anti-oxidant Agent, flow control agent, surfactant etc..
Above-mentioned electrodepositable composition can be made in any desired manner, be included in method described in embodiment.Example Such as, in some embodiments, it may be desirable that passing through solid particle and water soluble ion tree of the predissolve in aqueous medium Rouge is mixed in composition therein to introduce the solid particle.Example ion exchange resin suitable for this purpose includes above-mentioned water-soluble tree Rouge.The solid content of such composition can be relatively high, for example 2 times, 3 times or 4 times or more in present invention side The total solids content of the composition in method.The composition can such as be mixed by ultrasonication evenly dispersed to provide Body.The ultrasonication can carry out 15 to 30 minutes or longer.Resulting composition then can with other liquid-carriers, i.e., water and appoint The organic solvent of choosing merges to provide for the final composition in the method for the present invention.
In the certain embodiments of method of the invention, in the composition by substrate dipping, the composition has at least The solid particle of 4:1 and the weight ratio of ion exchange resin, such as at least 5:1, at least 6:1, at least 7:1, at least 8:1, at least 9:1, 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, or more It is high.Solid particle may include 0.05 to 100 weight % graphene carbon particle, such as 0.1 to the 10 weight weight of % or 0.1 to 5 Measure %.
In addition, the substrate, which is impregnated in, to be had based on the total of the composition in the certain embodiments of method of the invention 0.5 to 25 weight percent of poidometer, such as 1 to 10 weight percent or 1 to 5 weight percent in some cases are total solid In the composition of body content.Really, it was found that though be not used thickener, such composition can also provide solid particle with The stable dispersion of ion exchange resin in an aqueous medium.As used in this article, term " stable dispersion " refers in this way Dispersion, not gelation, flocculation or precipitating when maintaining temperature at least 60 days of 25 DEG C, if or there are some precipitatings, Sediment can also redisperse after agitation.
It has moreover been found that when such composition is in method of the invention, even if when the solid particle in bath When with the weight ratio of ion exchange resin within the above range, the solid with suitable film thickness and acceptable porosity can be also provided Uniform coating, this can make the above method especially suitable for manufacturing the coated base that can be used as the cathode for lithium ion battery Material.
In the methods of the invention, coating is applied to above at least part of the substrate via electro-deposition method. In such method, will serve as in circuit electrode (such as anode in anionic electrodeposition) conductive base (such as It is any those of previously described) be impregnated in the composition of the above-mentioned type, the circuit include the electrode and counterelectrode (such as yin from Cathode in sub- electro-deposition).Make electric current by between electrode so that coating is deposited on the substrate.The voltage of application it is changeable and Can be for for example down to 1 volt up to several thousand volts, but it is usually between 50 and 500 volts.Current density usually exists Between 0.5 ampere/square feet and 15 amperes/square feet.In some embodiments, the stop of substrate in the composition Time is 30 to 180 seconds.
After electrocoat, which is taken out from bath, and in some embodiments, the spy depending on composition The preference of point and end user, can toast in an oven.For example, the coated substrate can at 225 °F or lower, such as 200 °F or the baking of lower temperature 10 to 60 minutes.In other cases, it (is gone back after being taken out in bath in electro-deposition and by substrate The preference of the characteristics of being depending on bath composition and end user), can simply by coated substrate at ambient conditions It is dry.As used in this article, " environmental condition " refers to relative humidity 10 to 100% and temperature range -10 to 120 DEG C, Such as 5 to 80 DEG C, 10 to 60 DEG C in some cases, and 15 to 40 DEG C of the atmospheric air in other situations again.
As understood from the foregoing description, in some respects, the present invention relates to methods comprising: conductive base is impregnated Into electrodepositable composition, which is used as electrode in impregnating circuit in the composition, which includes the electricity Pole and counterelectrode, when electric current flows through between the electrode, coating is applied to above at least part of substrate, should Electrodepositable composition includes: (a) aqueous medium；(b) ion exchange resin；(c) include graphene carbon particle solid particle, Wherein the composition has the weight ratio of at least solid particle of 4:1 and ion exchange resin.The invention further relates to what is provided in this section Any method, wherein the substrate is foil, and the foil includes aluminium, iron, copper, manganese, nickel, their combination and/or its alloy, wherein appointing The thickness what these foil can have is no more than 8 mils (203.2 μm), for example is no more than 4 mils (101.6 μm), is no more than 2 mils (50.8 μm), or it is no more than 1 mil (25.4 μm) and/or at least 0.1 mil (2.54 μm) in some cases, such as at least 0.2 mil (5.08 μm), at least 0.4 mil (10.2 μm), or at least 0.5 mil (12.7 μm).The invention further relates in this section Any method provided, wherein the aqueous medium is only made of water, or is mainly included water and combined one or more inertia and have Co-solvent content, for example be at least partially soluble in the organic cosolvent of water, such as oxygen containing organic solvent, for example, it is ethylene glycol, two sweet The monoalky lether of alcohol, propylene glycol and dipropylene glycol, they contain 1 to 10 carbon atom, such as the list of these glycol in alkyl Ethylether and single-butyl ether and alcohols, such as ethyl alcohol, isopropanol, butanol and diacetone alcohol.The invention further relates to give in this section Any method out, wherein the amount of organic cosolvent is to be less than 20 weight %, or in some cases less than 25 weight % Less than 10 weight %, for example it is less than 5 weight %, the total weight based on water in the electrodepositable composition.The invention further relates to Any method provided in this section, the amount that wherein aqueous medium is present in the electrodepositable composition are at least 75 weights %, at least 90 weight %, or at least 95 weight %, such as 75 to 99.5 weight %, 90 to 99 weight % are measured, or in some cases In 95 to 99 weight %, the total weight based on the composition.The invention further relates to any methods provided in this section, wherein should be from Subtree rouge includes resin anion (R.A.), for example, alkali neutralization carboxy-containing acid group resin, such as the wherein carboxy-containing acid group of alkali neutralization Resin be water-soluble, such as when water-soluble resin includes cellulose derivative, such as the alkali metal salt of carboxymethyl cellulose When, for example the weight average molecular weight that carboxymethyl cellulose has is at least 50,000, at least 100,000, at least 200,000, such as 50,000 to 1,000,000,100,000 to 500,000 or 200,000 to 300,000.The invention further relates to what is provided in this section Any method, the amount that wherein water-soluble resin is present in the composition are at least 50 weight %, such as at least 60 weight %, until Few 70 weight %, at least 80 weight %, or at least 90 weight %, weight % are the total weights based on resin in the composition. The invention further relates to any methods provided in this section, and wherein water-soluble resin is present in the amount in the composition no more than 20 weights % is measured, for example is no more than 15 weight %, is no more than 10 weight %, is no more than 5 weight %, such as 1 to 20 weight %, 1 to 15 weight % is measured, 5 to 15 weight the weight % of % or 1 to 3, weight % are the total weights based on solid in the composition.The present invention also relates to And any method provided in this section, wherein the solid particle includes the particle containing lithium, such as such particle containing lithium, packet Mixed metal oxide containing at least one element containing Li and selected from Ni, Co, Fe, Mn, Al and P.For example, this contains of lithium Grain may include LiCoO2, LiMO2, LiFePO4, LiCoPO4, LiMnO2, LiMn2O4, Li (NiMnCo) O2And/or Li (NiCoAl) O2, wherein the relative quantity of transition metal can be varied as desired.For example, Ni, Mn and Co can not be always at the relatively former of 1:1:1 Sub- ratio, and more nickel, such as 5:3:2 or 8:2:2 can be contained.The invention further relates to any method provided in this section, In the amount of the particle containing lithium be at least 50 weight %, at least 60 weight %, at least 70 weight %, at least 80 weight %, until Few 85 weight %, or at least 90 weight %, the total weight based on solid in the composition.The invention further relates to what is provided in this section Any method, wherein the solid particle includes conductive particle, such as graphene carbon particle or graphene carbon particle and other conductions The combination of carbon particle such as conductive black.The invention further relates to any methods provided in this section, and lithium is wherein contained in the composition Particle and the relative weight ratio of conductive graphene carbon particle be at least 3:1, at least 4:1, at least 5:1, at least 8:1, at least 10: 1, or at least 15:1, or at least 30:1, or at least 45:1, or at least 60:1.The invention further relates to any sides provided in this section Method, wherein the amount of conductive graphene carbon particle is to be no more than 10 weight %, such as 1 to 10 weight no more than 20 weight % Measure the weight of % or 1 to 5 %, the total weight based on solid in the composition.The invention further relates to any method provided in this section, Wherein the solid particle of the electrodepositable composition and the weight ratio of ion exchange resin are at least 5:1, at least 6:1, at least 7:1, At least 8:1, at least 9:1, 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, or at least 17:1.For example, the weight ratio of solid particle and ion exchange resin can be at least 45:1, or at least 60:1.The present invention is also It is related to any method provided in this section, wherein the total solids content of the electrodepositable composition is 0.5 to 25 weight %, than Such as 1 to 10 weight %, such as 1 to 5 weight %, the total weight based on the composition.
If also can appreciate the fact that from the foregoing description, in some respects, the invention further relates to electrodepositable composition, packets Contain: (a) aqueous medium；(b) ion exchange resin；(c) solid particle, which includes: (i) graphene carbon particle and (ii) Particle containing lithium, wherein the composition has the weight ratio of at least solid particle of 4:1 and ion exchange resin.The invention further relates to this Any electrodepositable composition provided in section, wherein the composition is at least solid particle of 4:1 and ion exchange resin Weight ratio, at least 5:1, at least 6:1, at least 7:1, at least 8:1, at least 9:1, at least 10:1, at least 11:1, at least 12:1, until Few 13:1, at least 14:1, at least 15:1, at least 16:1, or at least 17:1, or at least 45:1, or at least 60:1.The present invention also relates to And any electrodepositable composition provided in this section, wherein the aqueous medium is only made of water, or is mainly included water and tied One or more inertia organic cosolvents have been closed, for example have been at least partially soluble in the organic cosolvent of water, such as is oxygen containing organic Solvent, for example, ethylene glycol, diethylene glycol (DEG), propylene glycol and dipropylene glycol monoalky lether, they in alkyl contain 1 to 10 carbon original Son, such as the single ethylether and single-butyl ether and alcohols of these glycol, such as ethyl alcohol, isopropanol, butanol and diacetone alcohol. At least partly the miscible solvent of water may include agglomerated solvent, such as triethyl phosphate, triacetin, dipropylene glycol for other Diacetate esters etc..The invention further relates to any electrodepositable composition provided in this section, the wherein presence of organic cosolvent Amount is to be less than 20 weight % less than 25 weight %, or be less than 10 weight % in some cases, for example be less than 5 weight %, is based on The total weight of water in the electrodepositable composition.The invention further relates to any electrodepositable composition provided in this section, The amount that wherein aqueous medium is present in the electrodepositable composition is at least 75 weight %, at least 90 weight %, or extremely Few 95 weight %, such as 75 to 99.5 weight %, 90 to 99 weight %, or 95 to 99 weight % in some cases, being based on should The total weight of composition.The invention further relates to any electrodepositable composition provided in this section, the wherein ion exchange resin packet Containing resin anion (R.A.), for example, alkali neutralization carboxy-containing acid group resin, for example wherein the resin of the carboxy-containing acid group of alkali neutralization is It is water-soluble, such as when water-soluble resin includes cellulose derivative, for example, carboxymethyl cellulose alkali metal salt when, such as carboxylic The weight average molecular weight of methylcellulose is at least 50,000, at least 100,000, at least 200,000, such as 50,000 to 1,000, 000,100,000 to 500,000 or 200,000 to 300,000.It is any electrodepositable the invention further relates to what is provided in this section Composition, the amount that wherein water-soluble resin is present in the composition are at least 50 weight %, such as at least 60 weight %, at least 70 weight %, at least 80 weight %, or at least 90 weight %, weight % are the total weights based on resin in the composition.This Invention further relates to any electrodepositable composition provided in this section, and wherein water-soluble resin is present in the amount in the composition No more than 20 weight %, have and be no more than 15 weight %, be no more than 10 weight %, is no more than 5 weight %, such as 1 to 20 weight % is measured, 1 to 15 weight %, 5 to 15 weight the weight % of % or 1 to 3, weight % are the gross weights based on solid in the composition Amount.The invention further relates to any electrodepositable compositions provided in this section, and wherein the particle for containing lithium includes containing Li and choosing From the mixed metal oxide of at least one element of Ni, Co, Fe, Mn, Al and P.For example, the particle for containing lithium may include LiCoO2, LiNiO2, LiFePO4, LiCoPO4, LiMnO2, LiMn2O4, Li (NiMnCo) O2And/or Li (NiCoAl) O2, wherein The relative quantity of transition metal can be varied as desired.For example, Ni, Mn and Co can not be always at the ratio of 1:1:1 or 3:3:3, and And more nickel, such as 5:3:2 or up to 8:2:2 can be contained.It is any electrodepositable the invention further relates to what is provided in this section Composition, wherein the amount of the particle containing lithium is at least 50 weight %, at least 60 weight %, at least 70 weight %, at least 80 Weight %, at least 85 weight %, or at least 90 weight %, the total weight based on solid in the composition.The invention further relates to this Any electrodepositable composition provided in section, wherein the particle containing lithium is opposite with graphene carbon particle in the composition Weight ratio is at least 3:1, at least 4:1, at least 5:1, at least 8:1, at least 10:1, or at least 15:1, or at least 30:1, or at least 45:1, or at least 60:1.The invention further relates to any electrodepositable composition provided in this section, the wherein graphene carbon The amount of grain is to be no more than 10 weight %, such as 1 to the 10 weight weight % of % or 1 to 5 no more than 20 weight %, and being based on should The total weight of solid in composition.The invention further relates to any electrodepositable compositions provided in this section, and wherein this can electricity The total solids content of the composition of deposition is 0.5 to 25 weight %, such as 1 to 10 weight %, such as 1 to 5 weight %, and being based on should The total weight of composition.
As also can appreciate the fact that from the foregoing description, in some respects, the invention further relates to electro-deposition lithium on base material from The coating of sub- battery electrode coating, the electro-deposition includes: (a) cured ion exchange resin；(b) solid particle, the solid particle Include: (i) graphene carbon particle；The particle of (ii) containing lithium, the wherein solid particle of the coating and cured ion exchange resin Weight ratio is at least 4:1.
The invention further relates to any electrodepositable coating provided in this section, and wherein the coating has consolidating at least 4:1 The weight ratio of body particle and ion exchange resin, at least 5:1, at least 6:1, at least 7:1, at least 8:1, at least 9:1, at least 10:1, until Few 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 17:1, or at least 45:1, or At least 60:1.
The invention further relates to any electrodepositable coating provided in this section, and wherein water-soluble resin is present in coating Amount be to have and be no more than 15 weight % no more than 20 weight %, be no more than 10 weight %, be no more than 5 weight %, for example, 1 to 20 weight %, 1 to 15 weight %, 5 to 15 weight the weight % of % or 1 to 3, weight % are the gross weights based on solid in coating Amount.The invention further relates to any electrodepositable coating provided in this section, and wherein the particle for containing lithium includes containing Li and to be selected from The mixed metal oxide of at least one element of Ni, Co, Fe, Mn, Al and P.For example, the particle for containing lithium may include LiCoO2, LiNiO2, LiFePO4, LiCoPO4, LiMnO2, LiMn2O4, Li (NiMnCo) O2And/or Li (NiCoAl) O2, wherein The relative quantity of transition metal can be varied as desired.For example, Ni, Mn and Co can not be always at the ratio of 1:1:1 or 3:3:3, and And more nickel, such as 5:3:2 or up to 8:2:2 can be contained.It is any electrodepositable the invention further relates to what is provided in this section Coating, wherein the amount of the particle containing lithium is at least 50 weight %, at least 60 weight %, at least 70 weight %, at least 80 weights Measure %, at least 85 weight %, or at least 90 weight %, the total weight based on solid in coating.
The invention further relates to any electrodepositable coating provided in this section, wherein the particle and stone containing lithium in coating The relative weight ratio of black olefinic carbon particle is at least 3:1, at least 4:1, at least 5:1, at least 8:1, at least 10:1, or at least 15:1, Or at least 30:1, or at least 45:1, or at least 60:1.The invention further relates to any electrodepositable coating provided in this section, Wherein the amount of the graphene carbon particle is to be no more than 10 weight %, such as 1 to 10 weight % or 1 no more than 20 weight % To 5 weight %, the total weight based on solid in coating.The invention further relates to any electrodepositable coating provided in this section, Wherein the total solids content of the electrodepositable coating is 0.5 to 25 weight %, such as 1 to 10 weight %, such as 1 to 5 weight Measure %, the total weight based on coating.
Following example illustrate the present invention, however, these embodiments should not be construed to limit the invention to theirs Details.
Embodiment 1
1.0g sodium carboxymethylcellulose (" SCMC " is available commercially from Sigma-Aldrich Co.LLC) is dissolved in 180g deionization Water.According to the certificate of analysis of supplier, the degree of substitution of the material is 0.86, and is surveyed using the solution of 2 weight %CMC in water Obtained the viscosity of 470cps.According to the product data sheet of supplier, viscosity Brookfield LVF type viscosimeter uses following Parameter measurement: rotor (spindle): #3；Speed: 60rpm；Temperature: 25 DEG C；Container: 120ml polymerization bottle (polybottle)； And amplification factor: 20.It is 12.6sec by the shear rate that these parameters calculate-1.Assuming that viscosity is dilute in no shearing by supplier It is measured in the case where change, the viscosity of 470cps estimates 267,500 calculating molecule using above equation under 2 weight % concentration Amount.Then, be added the preparation of 4.2 grams of thermal methods graphene (TPG) carbon particle (carbon particle is according to United States Patent (USP) No.8 486, Method described in 364 uses methane to prepare in the hot-zone of plasma reactor as precursor material), then by mixture Ultrasonic treatment 25 minutes.Then, by 14.75g LiFePO4(" LFP ", LifeP2 is available commercially from Phostech Lithium Inc.) with the addition of 4 equal portions, it carries out being ultrasonically treated for 5 minutes after being added every time.Finally, carrying out other 10 minutes super Sonication is evenly dispersed to ensure.Then it is diluted with 600g deionized water to prepare 2.5% solid electrodeposition bath, solid particle It (TPG+LFP) is 18 with the weight ratio of ion exchange resin (SCMC).In order to be coated by electro-deposition, using aluminium foil as electrode cloth Line (wired) is placed in 90 ° containing thermocouple and the coil pipe heating/cooling (coil) for also acting as counterelectrode effect in stirring In F bath, then voltage is opened to 150 volts and electric current is set as 1.5 peaces.Voltage is closed after 180 seconds, then by the sample of coating It takes out, and is air-dried from bath.Gained coating with a thickness of 16 microns.
Embodiment 2
According to process prepares coating same as Example 1, the difference is that the graphene carbon particle of thermal method preparation It is functionalized by following process.Maleic anhydride (1.5g) is dissolved in 150 solvent of Aromatic (423g), and is added etc. from The TPG (7.5g) of son manufacture.Mixture is subjected to ultrasonic treatment 1 hour, 180 DEG C is then heated with stirring under a nitrogen and keeps 4 hours.Mixture is cooling, filtering, with the abundant washed product of acetone and drying.Product is led to and sieves with 100 mesh sieve screening.Then, Jeffamine M-2005 (14g) is dissolved in 300g toluene, and 7g TPG product is added under stiring, and will be at mixture ultrasound Reason 1 hour.Mixture is transferred in the reaction flask with 300g other toluene, is heated under stiring under a nitrogen 100 DEG C and holding 2 hours.After cooling, mixture is filtered, is washed then with toluene with acetone washing, is redispersed in acetone, so Filtering and with acetone washing and drying afterwards.Product is led to and sieves with 100 mesh sieve screening.Then with the side similar with described in embodiment 1 Formula by functionalized graphene carbon particle with containing lithium particle and ion exchange resin merge, and carry out electro-deposition.Coating is 35 microns It is thick.
The person skilled in the art will easily understand can make the specification institute public affairs changed without departing from front to the present invention The theory opened.During such change is to be considered as included in the following claims, unless the language that the claim passes through them Separately explicitly indicate that.Therefore, the specific embodiment being described in detail herein is only exemplary and does not limit of the invention Range gives the full width of appended claims and its any and whole equivalents to the scope of the present invention.

Claims (20)

1. method, comprising:
Conductive base is impregnated into electrodepositable composition, which is used as electricity in impregnating circuit in the composition Pole, the circuit include the electrode and counterelectrode, and when electric current flows through between the electrode, coating is applied at least part of Above the substrate,
The electrodepositable composition includes:
(a) aqueous medium；
(b) ion exchange resin；With
(c) include graphene carbon particle solid particle,
Wherein the composition has the weight ratio of at least solid particle of 4:1 and ion exchange resin.
2. method described in claim 1, wherein the graphene carbon particle includes the graphene carbon particle of thermal method preparation.
3. method as claimed in claim 2, wherein the graphene carbon particle of thermal method preparation is to be higher than 3,500 DEG C of heat in temperature It is being prepared in area and have greater than 3:1 average aspect ratio.
4. method as claimed in claim 2, wherein the graphene carbon particle of thermal method preparation has greater than 70 m2/gs B.E.T. specific surface area.
5. method as claimed in claim 2, the graphene carbon particle of wherein at least a part of thermal method preparation include it is curved, Curling, fold or warpage piece.
6. method described in claim 1, wherein the composition has the graphene carbon particle and ion exchange resin of 0.1:1 to 2:1 Weight ratio.
7. method described in claim 1, wherein the ion exchange resin includes resin anion (R.A.).
8. method of claim 7, wherein the resin anion (R.A.) includes the resin for the carboxy-containing acid group that water-soluble alkali neutralizes.
9. method according to any one of claims 8, wherein the water-soluble resin includes cellulose derivative, which includes The alkali metal salt of carboxymethyl cellulose.
10. method described in claim 1, wherein the solid particle further includes the particle containing lithium.
11. method described in any one of claim 10, wherein the particle for containing lithium includes mixed metal oxide, and it includes Li and choosing From at least one element of Ni, Co, Fe, Mn, Al and P.
12. method described in any one of claim 10, wherein the amount of the particle for containing lithium is at least 50 weight %, it is based on the combination The total weight of solid in object.
13. method described in any one of claim 10, the wherein relative weight of the particle in the composition containing lithium and graphene carbon particle Than being at least 3:1.
14. method described in claim 1, wherein the composition has the weight of at least solid particle of 8:1 and ion exchange resin Than.
15. method described in claim 1, wherein the composition has the total solids content of 1 to 5 weight %, it is based on the combination The total weight of object.
16. electrodepositable composition, it includes:
(a) aqueous medium；
(b) ion exchange resin；With
(c) solid particle, it includes:
(i) graphene carbon particle；With
(ii) containing the particle of lithium,
Wherein the composition has the weight ratio of at least solid particle of 4:1 and ion exchange resin.
17. electrodepositable composition described in claim 16, wherein the graphene carbon particle includes the graphite of thermal method preparation Olefinic carbon particle.
18. electrodepositable composition described in claim 16, wherein the composition has the graphene carbon of 0.1:1 to 2:1 The weight ratio of particle and ion exchange resin.
19. electro-deposition lithium ion cell electrode coating on base material, the coating of the electro-deposition includes:
(a) cured ion exchange resin；With
(b) solid particle, it includes:
(i) graphene carbon particle；With
(ii) containing the particle of lithium,
Wherein the coating has the weight ratio of at least solid particle of 4:1 and cured ion exchange resin.
20. lithium ion cell electrode coating described in claim 19, wherein the graphene carbon particle accounts for the total of the solid particle 10 weight % of weight or less.
CN201780055172.0A 2016-09-08 2017-09-08 The method of coating electroconductive substrates and the relevant electrodepositable composition comprising graphene carbon particle Pending CN109689943A (en)

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