Classifications

• • 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
  • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
  • H01M4/621—Binders
  • H01M4/622—Binders being polymers
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  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
  • H01G11/22—Electrodes
  • H01G11/30—Electrodes characterised by their material
  • H01G11/32—Carbon-based
  • H01G11/38—Carbon pastes or blends; Binders or additives therein
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  • C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
  • C09D125/02—Homopolymers or copolymers of hydrocarbons
  • C09D125/04—Homopolymers or copolymers of styrene
  • C09D125/08—Copolymers of styrene
  • C09D125/14—Copolymers of styrene with unsaturated esters
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  • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
  • C09D133/04—Homopolymers or copolymers of esters
  • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C09D133/062—Copolymers with monomers not covered by C09D133/06
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  • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
  • C09D133/04—Homopolymers or copolymers of esters
  • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C09D133/062—Copolymers with monomers not covered by C09D133/06
  • C09D133/064—Copolymers with monomers not covered by C09D133/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
• • C—CHEMISTRY; METALLURGY
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  • 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
  • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
  • C09D133/04—Homopolymers or copolymers of esters
  • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C09D133/062—Copolymers with monomers not covered by C09D133/06
  • C09D133/066—Copolymers with monomers not covered by C09D133/06 containing -OH groups
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  • 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
  • C09D5/24—Electrically-conducting paints
• • C—CHEMISTRY; METALLURGY
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  • 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
• • H—ELECTRICITY
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  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
  • H01G11/22—Electrodes
  • H01G11/30—Electrodes characterised by their material
  • H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
• • 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
  • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• • 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
  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
• • 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
  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
  • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
• • 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
  • H01M4/362—Composites
  • H01M4/364—Composites as mixtures
• • 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
  • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
• • 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
  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
  • H01M4/386—Silicon or alloys based on silicon
• • 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
  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
  • H01M4/387—Tin or alloys based on tin
• • 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
  • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
  • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
• • 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
  • H01M4/48—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
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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
  • H01M4/36—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
  • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
  • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
  • H01G11/22—Electrodes
  • H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
  • H01G11/28—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features arranged or disposed on a current collector; Layers or phases between electrodes and current collectors, e.g. adhesives
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
  • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
  • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
• • 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
  • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
  • H01M2004/027—Negative electrodes
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M2300/00—Electrolytes
  • H01M2300/0017—Non-aqueous electrolytes
  • H01M2300/0025—Organic electrolyte
• • 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

Definitions

• the invention relates to binder compositions useful for negative electrodes of non- aqueous secondary batteries.
• Lithium-ion batteries have been used widely as the power source for many devices, such as consumer electronics, electric vehicles, and power tools. Recently, the growing popularity of zero-emission electric vehicles, particularly long-range electric vehicles, has increased demand for LIB technology with further improved energy density.
• LIB Lithium-ion batteries
• the negative electrode may have potential to boost battery energy density if improved binders are used for the anode.
• US 2013/0330622 discloses a negative electrode for a secondary battery, including a negative electrode active material, a binder, and a water-soluble polymer.
• the water-soluble polymer may be a copolymer containing 15 wt % to 50 wt % of an ethyl enically unsaturated carboxylic acid monomer unit, 30 wt % to 70 wt % of a (meth)acrylic acid ester monomer unit, and 0.5 wt % to 10 wt % of a fluorine-containing (meth)acrylic acid ester monomer unit.
• US Pat. 9,461,308 discloses an electrode for a lithium ion secondary battery.
• the electrode includes an electrode active material and a water-soluble polymer that is a copolymer including 1 to 30wt% of an aromatic vinyl monomer unit, 20 to 60wt% of an unsaturated carboxylic acid monomer unit, and 0.1 to 5wt% of a crosslinkable monomer unit.
• the aromatic vinyl monomer is a sodium styrene sulfate monomer.
• US Pat. 10,224,549 discloses a high acid-containing water-soluble acrylic polymer used in combination with traditional binder as the binder solution for the active material.
• the binder composition includes a particulate binder such as styrene butadiene rubber (SBR) and a small amount ( ⁇ 5%) of the high acid-containing water-soluble polymer.
• SBR styrene butadiene rubber
• ⁇ 5% small amount of the high acid-containing water-soluble polymer.
• the high acid- containing water-soluble polymer does not contain other functional monomers.
• US 2020/0203707 discloses an electrodepositable coating composition including a binder having a pH-dependent rheology modifier that includes the residue of a crosslinking monomer and/or a monoethylenically unsaturated alkylated alkoxylate monomer; an electrochemically active material and/or an electrically conductive agent; and an aqueous medium.
• US 2020/0203704 discloses an electrodepositable coating composition including a fluoropolymer; an electrochemically active material and/or an electrically conductive agent; a pH-dependent rheology modifier; and an aqueous medium including water.
• Electrodes are often preferred over solvent-based slurries in fabrication of the electrodes of such secondary batteries due to environmental concerns.
• these electrodes are manufactured by dispersing the electrode-forming ingredients in water, casting the slurry or paste on the current collector as a thin film and then allowing the film to dry to form the electrode.
• the function of the polymeric binder is to bind the electrode-forming particulates together onto the current collector.
• the electrode-forming particulates of the negative electrode (anode) for these secondary lithium ion batteries typically includes an active material (e.g.
• the carbonaceous material that can reversibly absorb and release or host (intercalate) lithium ions to create reaction sites for lithium ion electrochemical reactions (battery charging/discharging), a conductive additive, a rheology modifier and a polymeric binder.
• the anode active material is a substance that is capable of donates or accepts electrons during the charging/discharging cycle.
• the conductive additive is typically used to improve the conductivity of the negative electrode (anode), which reduces the battery’s internal resistance, and consequently boosts power output of the battery.
• a rheology modifier is typically present in the anode slurry formulation to adjust the slurry rheology for the electrode manufacturing casting process.
• rheology modifiers used in negative electrode formulations include carboxymethylcellulose (CMC) and polyacrylic acid (PAA).
• CMC carboxymethylcellulose
• PAA polyacrylic acid
• SBR Styrene-butadiene rubber latex generally is the dominant anode binder.
• amorphous silicon can be oxidized and generate 3 ⁇ 4 gas during aqueous slurry preparation for lithium ion battery application.
• Si amorphous silicon
• the use of Si in secondary batteries is important because it may have the possibility to increase the energy density of Li ion battery anodes.
• 3 ⁇ 4 generation imposes a safety concern during large-scale battery fabrication.
• One objective of the invention is to provide a new composition including a polymeric binder for the negative electrode of an electrochemical electrical energy storage device.
• the disclosed polymers which include certain functional groups may be used as the anode binder in negative electrode formulations to provide a negative electrode with low resistivity, good adhesion to the current collector substrate, and low VOC content.
• the resulting anode binders and the resulting negative electrodes for secondary batteries have good adhesion to the current collector as well as providing functional benefits to the anode and thus the battery.
• binders of this invention also may prevent generation of 3 ⁇ 4 gas during preparation of amorphous Si-containing water-borne slurries. This is an advantage for anode production.
• compositions for use as a negative electrode on a current collector within an electrical energy storage device containing a non-aqueous electrolyte comprise, consist essentially of, or consist of: a) at least one particulate electrode-forming material; b) a polymeric binder; and c) from 0 - 40% by weight of the polymeric binder of at least one crosslinking agent capable of reacting with the polymeric binder b).
• the polymeric binder b comprises, consists of, or consists essentially of the following as polymerized monomers: i) 0.1 - 50% by weight of the polymeric binder of at least one ethylenically unsaturated ionic monomer comprising at least one functional group selected from carboxylate, sulfonate, sulfate, phosphate, phosphonate.
• these functional groups may be present in acid form, and/or present as salts, and/or present as anhydrides, ii) 10 - 99% by weight of the polymeric binder of at least one non-ionic monoethylenically unsaturated monomer, iii) 0 - 5% by weight of the polymeric binder of at least one ethylenically unsaturated monomer comprising at least one functional groups that may promote post-polymerization crosslink reactions, the at least one functional group may comprise, consist of or consist essentially of N-methylol amide, N-alkylol amide, hydroxyl group, epoxy, silane, keto or combinations thereof, iv) 0 - 5% by weight of the polymeric binder of at least one monomer comprising, consisting of or consisting essentially of at least two ethylenic unsaturations v) 0 - 30 % by weight of the polymeric binder of at least one ethylenically unsaturated monomer comprising,
• R represents a group comprising, consisting of, or consisting essentially of at least one polymerizable olefmic unsaturation, preferably a group chosen from acrylate, methacrylate, acrylurethane, methacrylurethane, vinyl, allyl, methallyl, isoprenyl, an unsaturated urethane group, in particular acrylurethane, methacrylurethane, a-a'-dimethyl -isopropenyl- benzylurethane, allylurethane, more preferably a group chosen from acrylate, methacrylate, acrylurethane, methacrylurethane, vinyl, allyl, methallyl and isoprenyl, esters of maleic acid, esters of itaconic acid, esters of crotonic acid, even more preferably a methacrylate group, and mixtures thereof, and R' represents a hydrogen or aryl chain with 5 to 60 carbon atoms or alkyl chain
• the polymeric binder b) has a Tg of 55 °C or less and/or a minimum film forming temperature of 25 °C or less.
• the composition may also include the following optional components: c) from 0 - 40% by weight of the polymeric binder of at least one crosslinking agent capable of reacting with the polymeric binder b); d) from 0 -10% by weight of the polymeric binder of one or more wetting agents, e) from 0 - 10% by weight of the polymeric binder of one or more dispersing agents, f) from 0 - 10% by weight of the polymeric binder of one or more volatile organic compounds (VOC), and/or adhesion promoters, and/or coalescent agents, g) from 0 - 200% by weight of the polymeric binder of one or more rheology modifier additives, h) from 0 - 10% by weight of the polymeric binder of one or more additives comprising, consisting of or consisting essentially of anti-setting agents, surfactants, and mixtures thereof.
• VOC volatile organic compounds
• composition for use as an electrode as disclosed herein is typically prepared as a slurry, although it may be in the form of a solution, a dispersion, or a paste.
• Forming the electrode may be done by applying a layer of the electrode forming slurry composition to the current collector. The conductive layer is then dried, to form the layer of electrode material, i.e. the active material layer, which is adhered to the current collector.
• the binder(s) of the invention provide a matrix for the particulate electrode-forming materials, which typically include an active material and a conductive material.
• electrode refers to the dried layer of the electrode-forming slurry composition that is cast onto the current collector.
• electrodes are manufactured by casting the slurry or paste of dispersed electrode-forming ingredients and binder(s) as a thin fdm and then allowing the fdm to dry to form an electrode. This dried fdm is referred to as the electrode.
• the term “electrode assembly” is the combination of the current collector and the dried electrode that is dried thereon.
• the slurry or paste of dispersed electrode-forming ingredients and binder(s) can be cast onto current collector such as an aluminum, copper or nickel foil to form the electrode assembly.
• the electrode assembly can be further coated with a separator-forming slurry such as alumina and binder dispersed in water.
• the separator slurry can be cast simultaneously with the electrode slurry in a one-step process using a dual or a multi-die in a wet-on-wet process. Alternatively, after the electrode is dried, the separator slurry may be cast onto the electrode, or a free standing separator can be adhered onto the electrode surface.
• the electrode assembly therefore includes the current collector, the dried electrode fdm, and optionally a separator fdm on the top surface of the electrode.
• slurry means a free-flowing or flowable and/or pumpable suspension including fine solid materials and binder in water.
• fine solids may include, inter alia, polymeric binder particles, in addition to the solid particles that are usually the electrochemically active material(s) and conductive materials(s) necessary to form the electrode for a secondary battery.
• Additives may also be dissolved in the water such as dispersing agents used to improve the quality dispersion, of the fine solid material.
• composition for use as an electrode can be deposited by any method known in the art.
• application methods include spraying, rolling, draw bar application, bird bar application, gravure, slot coating, or other coil coating methods.
• the composition is dried optionally with heat.
• the coating of the composition may be optionally calendered before or after the drying step, to remove water and any other volatile materials. The drying times, temperatures, and vacuum used can be adjusted to achieve the desired drying.
• the current collector may be in the structural form of a mesh, a foam, a foil, a rod, or other morphology that does not interfere with current collector function.
• Current collector materials vary depending on whether an electrode is a positive electrode or a negative electrode.
• the most common current collectors for a negative electrode are sheets or foils of aluminum (Al°), copper (Cu°) or nickel (Ni°) metal.
• Al° aluminum
• Cu° copper
• Ni° nickel
• the electrode material is applied to and must adhere to the surface of the current collector of the lithium ion battery.
• crosslinking functionalities and/or reactive functionalities may be incorporated into the polymeric binders b) of the invention to balance mechanical properties and enhance film formation when applied to a current collector substrate.
• the in-situ crosslink functionalities crosslink the polymeric binder b) during polymerization.
• the post polymerization crosslink functionalities crosslink the polymeric binder b) during and after negative electrode film formation when the composition including the polymeric binder b) is applied to the current collector substrate to form the electrode.
• compositions for use as an electrode on a current collector within an energy storage device containing a non-aqueous electrolyte comprises, consists of or consists essentially of a) at least one particulate electrode-forming material, b) a polymeric binder, and optionally, from 0 to 40% by weight of the polymeric binder, of c) one or more optional crosslinking agents capable of reacting with the polymeric binder b).
• the crosslinking agent c) used depends on the type of post-crosslink monomer included in the binder b). Certain post-crosslink functionalities included in the binder b) do not require an external crosslinking agent c).
• the particulate electrode forming material a) includes particulate active materials and conductive particles that are held together (physically and/or chemically) by the polymeric binder b).
• the active materials are materials that are capable of intercalating lithium ions, /. ⁇ ?., are able to absorb/release lithium ions. Such active materials are known in the art.
• Conductive particles are also known in the art and are materials capable of conducting electrons. Certain materials are capable of performing both functions in an electrode.
• the particulate electrode-forming materials a) may include but are not limited to a conductive carbon additive, carbon nanotubes (CNTs), synthetic graphite, natural graphite, hard carbon, activated carbon, carbon black, graphene, mesoporous carbon, amorphous silicon, semi crystalline silicon, silicon oxides, silicon nanowires, tin, tin oxides, germanium, lithium titanate, mixtures or composites of the aforementioned materials, and/or other materials known in the art or described herein as suitable for use as the anode in a lithium ion battery.
• These particulates may include active materials, i.e ., materials capable of intercalating (accepting) lithium ions, and conductive materials.
• the electrode film of a lithium ion capacitor and/or a lithium ion battery can include about 80 weight percent, preferably up to 90, or 94, and more preferably up to 98 weight percent of the particulate anode-forming materials a), after drying.
• These electrode forming materials a) are typically in the form of solid powders.
• Conductive carbon materials such as carbon black and graphite powders are widely used in positive and negative electrodes to decrease the inner electrical resistance of an electrochemical system.
• Non-limiting examples of conductive carbon may include furnace black, acetylene black, CNT, fine graphite powder, vapor deposited graphite fibers, and Ketjen carbon black.
• the typical loading level of the conductive carbon relative to the active material in the electrode forming materials a) is usually within the range of 0.1% by weight to 20% by weight, and more preferably within the range of 0.5% by weight to 10% by weight of the total amount of the particulate electrode-forming materials a).
• the amount of the particulate electrode-forming materials a) (including both the active material and the conductive carbon) present in the electrode forming composition may be from 50 wt% to 99 wt% of the total dried weight of the composition, preferably from 80 to 98 and most preferably from 94 to 98wt% of the total dried weight of the composition.
• the anode in the present invention further includes a polymeric binder.
• the binder is present in the electrode.
• One function of the binder is to bind together particulate anode forming materials to form the electrode.
• the polymeric binder also may serve to adhere the electrode to the current collector.
• the polymeric binder b) may be in the form of polymerized particles. These particles may be provided in the form of an emulsion or latex.
• the Tg of the disclosed polymeric binder b) should be within a certain range.
• the Tg is the temperature below which the physical properties of polymers changes from thermoplastic (e.g. flexible, soft, stretchable) to those of the glassy state which limits flexibility and elongation of the polymeric binder b).
• the Tg of the polymeric binder b) may be at about or preferably below room temperature, i.e. below 55 °C, below 45 °C, below 35 °C, below 25 °C, below 20 °C, or below 10°C, according to certain embodiments.
• the minimum film formation temperature (MFFT) of the polymeric binder b) latex particles is the minimum temperature where the coalescence of the polymeric particles occurs as the water evaporates to form continuous films.
• the MFFT is the minimum temperature at which the polymeric binder b) particles coalesce to form a continuous film.
• the polymeric binder b) advantageously has an MFFT near or below room temperature, i.e., below 55 °C, below 50 °C, below 45 °C, below 35 °C, below 25 °C, or below 20 °C, according to certain embodiments.
• the electrode forming composition has a VOC content of from 0 to less than 5 wt%, in another embodiment from 0 to less than 1 wt %, and in still another embodiment from 0 to less than 0.1 wt%.
• the polymeric binder b) includes, as polymerized monomers, a number of monomers. The selection of polymerization method for the disclosed polymeric binder b) is not particularly limited. Any polymerization method can be used to synthesize the disclosed binder.
• Non-limiting methods may include solution polymerization, emulsion polymerization, bulk polymerization, and suspension polymerization, free radical polymerization, controlled polymerization, and ionic polymerization.
• polymeric binder b) is prepared through free radical polymerization via emulsion polymerization.
• the number average molecular weight of the disclosed binder is preferably 1000 g/mol or more, and more preferably 5000 g/mol or more, and even more preferably 10,000 g mol or more.
• number average molecular weights are determined by gel permeation chromatography, using polystyrene standards.
• the polymeric binder b) may have a volume average particle size of from 30 to 500 nm, or can be a mixture of various particle sizes from 30 to 500 nm.
• the particle size is preferably within the range of 30 - 400 nm, and more preferably within the range of 40 - 350 nm, and even more preferably within the range of 50 - 300 nm.
• volume average particle sizes are determined by dynamic light scattering (DLS).
• the loading of the polymeric binder b) in the composition relative to the electrode forming materials a) is preferably 1% by weight or more binder, more preferably 2% by weight or more, and preferably 30% by weight or less, and more preferably 20% by weight or less.
• the loading of the polymeric binder b) is within the aforementioned range, it can provide good binding performance.
• the polymeric binder b) contains a certain weight percentage of monoethylenically unsaturated monomer i) comprising, consisting of, or consisting essentially of at least one functional group selected from carboxylate, sulfonate, sulfate, phosphate, phosphonate, in acid, and/or salt, and/or anhydride form.
• the disclosed polymeric binder b) containing a certain percentage of functional group containing monomers i) may have increased viscosity upon neutralization treatment in aqueous solution.
• the disclosed polymeric binder b) may function as a self-thickening binder in an anode slurry.
• the self-thickening binder can be used with or without a traditional rheology modifier, e.g. carboxymethylcellulose (CMC), in the composition disclosed herein.
• CMC carboxymethylcellulose
• the neutralization step may be important for providing a functional self-thickening binder.
• the completely or partially neutralized binder should have sufficient solubility to swell in aqueous solution to increase the solution viscosity.
• Some polymeric binder b) examples containing acid functional groups as monomer i) may have tunable aqueous solution viscosity upon pH adjustment.
• the tunable solution rheology of the polymeric binder b) may enable them to function as a self-thickening binder in an anode slurry with or without traditional rheology modifiers.
• the weight percentage of the monoethylenically unsaturated ionic monomer i) included in the disclosed polymeric binder b) is preferably within the range of 0.1 - 50 wt% by weight, and more preferably within the range of 1 - 45 wt% by weight, and particularly preferably within the range of 5 - 45 wt% by weight of the polymeric binder b).
• the selection of the monoethylenically unsaturated ionic monomer i) is not particularly limited.
• Non-limiting examples may include (meth) acrylic acid, 2-carboxyethyl acrylate, 2-polycarboxy ethyl acrylate, mono-ester of itaconic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, 2-acrylamide- 2-methylpropane sulfonic acid, 4-styrenesulfonic acid, vinylsulfonic acid, 2-sulfoethyl methacrylate, phosphate esters of polyalkylene glycol mono(meth)acrylate, polyalkylene glycol allyl ether phosphate, vinylphosphonic acid, 2-(methacryloyloxy)ethyl phosphonic acid, and mixtures thereof.
• acid forms, and or salt forms and/or anhydride forms, (if chemically possible) of any of these monomers Preferred are 0.1-50 wt%, more preferred are 1- 45 wt%, and most preferred are 5-45 wt%.
• the polymeric binder b) may further comprise, consist of or consist essentially of one or more non-ionic monoethylenically unsaturated monomers ii).
• the selection of the non-ionic monoethylenically unsaturated monomer ii) is not particularly limited.
• Non-limiting examples may include acrylic and methacrylic acid esters, such as Cl to C 12 alkyl (meth)acrylates, styrene and derivatives thereof, vinyl acetate, vinyl versatate, (meth)acrylamide, (meth)acrylonitrile and derivatives thereof, diisobutylene, vinylpyrrolidone, vinylcaprolactam and mixtures thereof.
• Non-ionic monomers ii) that provide corresponding low Tg polymers are preferred for the disclosed polymeric binder b).
• ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate are preferred to lower the Tg of the disclosed polymeric binder a).
• the weight percentage of the non-ionic monoethylenically unsaturated monomer ii) in the disclosed polymeric binder b) is preferably within the range of 10 to 99 wt% by weight, and more preferably within the range of 20 to 95 wt% by weight, and particularly preferably within the range of 30 to 90 wt% by weight of the polymeric binder b).
• the disclosed polymeric binder b) may further comprise, consist of or consist essentially of one or more crosslinkable monomers iii) that include functional groups that may enable post polymerization crosslink reactions. If more than one functional group is present, the functional groups may be the same or different. Suitable functional groups that can enable post polymerization crosslink reactions may be selected from at least one of N-methylol amide, N- alkylol amide, hydroxyl group, epoxy, silane, and keto groups. The selection of the crosslinkable ethylenically unsaturated monomer iii) is not particularly limited.
• Non-limiting examples of the post-polymerization crosslinkable ethylenically unsaturated monomer iii) may comprise, consist of or consist essentially of N-methylol(meth)acrylamide, vinyl glycidyl ether, allyl glycidyl ether, glycidyl (meth)acrylate, diacetone acrylamide, acetoaetoxyethyl methacrylate, (meth)acryloxyalkyltrialkoxysilanes, vinyltrialkoxysilanes and mixtures thereof.
• the weight percentage of the crosslinkable ethylenically unsaturated monomer iii) in the disclosed polymeric binder b) is preferably within the range of 0 - 5 wt% by weight of the polymeric binder b), more preferably from 0.1 to 3 wt% and most preferably from 0.2 to 2 wt% of the polymeric binder b).
• the polymeric binder b) may also comprise, consist of or consist essentially of at least one monomer comprising at least two ethylenic unsaturations iv). These monomers comprising at least two ethylenic unsaturations iv) are capable of in-situ crosslinking of the polymeric binder, meaning the binder b) is crosslinked during polymerization.
• Non-limiting examples of these monomers iv) are allylic ethers obtained from polyols; preferably allylic ethers obtained from polyols and selected from pentaerythritol, sorbitol, or sucrose; acrylic or methacrylic esters obtained from polyols, preferably acrylic or methacrylic esters obtained from polyols and selected from pentaerythritol, sorbitol, or sucrose; divinyl naphthalene, trivinylbenzene, 1,2,4- trivinylcyclohexane, triallyl pentaerythritol, diallyl pentaerythritol, diallyl sucrose, trimethyl olpropane diallyl ether, 1,6-hexanediol di(meth)acrylate, allyl (meth)acrylate, diallyl itaconate, diallyl fumarate, diallyl maleate, butanediol dim
• More preferred monomers iv) are 1,6-hexanediol di(meth)acrylate, allyl (meth)acrylate, ethylene di(meth)acrylate, poly(ethylene glycol) di(meth)acrylate, trimethylolpropane tri(meth)acrylate, diallyl phthalate, divinylbenzene and mixtures thereof.
• Most preferred monomers iv) are 1,6-hexanediol di(meth)acrylate, allyl (meth)acrylate, polyethylene glycol) di(meth)acrylate, diallyl phthalate, divinylbenzene.
• These monomers iv) may be present in the polymeric binder b) at from 0 - 5% wt%, preferably in the range of from 0.01 - 3 wt% and more preferably within the range of 0.05 - 2 wt%, and particularly preferably within the range of 0.1 - 1 wt% by weight of the polymeric binder b).
• the inventive polymeric binder b) may further comprise, consist of or consist essentially of one or more ethylenically unsaturated monomers v) that include functional groups that may improve the interaction between the binder and the electrode active materials. These functional groups may also improve the interaction between the binder and the electrode conductive materials.
• the functional groups in the monomer v) may be comprise, consist of or consist essentially of at least one of silane, ureido, amine, hydroxyl group, and combinations thereof.
• the selection of monomers v) is not particularly limited.
• the monomers v) may be ethylenically unsaturated monomers with functional groups comprising, consisting of or consisting essentially of at least one of silane, ureido, amine and hydroxyl group.
• functional groups comprising, consisting of or consisting essentially of at least one of silane, ureido, amine and hydroxyl group.
• monomers containing these functional groups comprise
• monomers v) are selected from at least one of (meth)acryloxyalkyltrialkoxysilanes, vinyltrialkoxysilanes, (meth)acrylate ester of substituted urea, (meth)acryl amide of substituted urea, allyl ether of substituted urea, aminoalkyl (meth)acrylate, hydroxyalkyl (meth)acrylate, and mixtures thereof.
• monomers v) are selected from at least one of (meth)acryloxyalkyltrialkoxysilanes, vinyltrialkoxysilanes, aminoalkyl (meth)acrylate, hydroxyalkyl (meth)acrylate, and mixtures thereof.
• the weight percentage of the ethyl enically unsaturated functional monomers v) is preferably within the range of 0- 30 wt%, preferably the range of 0.01 - 10 wt%, and more preferably within the range of 0.05 - 7.5 wt%, and even more preferably within the range of 0.1 - 5 wt% by weight of the polymeric binder b).
• the monomers v) may include silane or hydroxyl groups, as may some of the monomers iii).
• monomers v) and iii) both include one or more of silane and hydroxyl groups there may be up to 35 wt% of a monomer including a silane or hydroxyl group or epoxy group in the polymerizable binder b), by weight of the polymeric binder b).
• the disclosed polymeric binder b) may further comprise, consist of or consist essentially of an oxyalkylated monomer or monomers with ethylenic unsaturation and terminated by a hydrogen or aryl chain with 5 to 60 carbon atoms or alkyl chain with 1 to 60 carbon atoms, having the following formula: wherein: m and p represent a number of alkyl ene oxide units of between 0 and 150, n represents a number of ethylene oxide units of between 5 and 150, q represents a whole number at least equal to 1 and such that 5£(m+n+p)q£150, and preferentially such that 15 £ (m+n+p)q£120,
• Ri and R2 represent methyl or ethyl
• R represents a group comprising, consisting of, or consisting essentially of at least one polymerizable olefmic unsaturation, preferably a group chosen from acrylate, methacrylate, acrylurethane, methacrylurethane, vinyl, allyl, methallyl, isoprenyl, an unsaturated urethane group, in particular acrylurethane, methacrylurethane, a-a'-dimethyl -isopropenyl- benzylurethane, allylurethane, more preferably a group chosen from acrylate, methacrylate, acrylurethane, methacrylurethane, vinyl, allyl, methallyl and isoprenyl, esters of maleic acid, esters of itaconic acid, esters of crotonic acid, even more preferably a methacrylate group, and mixtures thereof, and
• R' represents a hydrogen or aryl chain with 5 to 60 carbon atoms or alkyl chain end with 1 to 60 carbon atoms.
• the weight percentage of the oxyalkylated monomer vi) in the disclosed polymeric binder b) is preferably within the range of 0 - 30 wt%, and more preferably within the range of 0 - 20 wt%, and particularly preferably within the range of 0.1 - 20 wt% by weight of the polymeric binder b).
• the disclosed composition may also comprise, consist of or consist essentially of an optional crosslinking agent c).
• the crosslinking agent c) may react with functional groups of the disclosed polymeric binder b).
• the post-crosslinkable functionalities in monomer iii) may be crosslinked with or without external agents. That means some of the post- crosslinkable functionalities may react with themselves to crosslink. However, some of the post- crosslinkable functionalities in iii) may require external agents to react with to effect crosslinking.
• the crosslinking agents c) referred herein is a component separate from the polymeric binder b) which is capable of reacting with some of the post-crosslinkable functionalities in monomer iii).
• the crosslinking agent c) may be added to the polymeric binder b) during binder preparation.
• the crosslinking agent c) may also or instead be added to the negative electrode slurry during electrode manufacturing as a two pack binder composition.
• the selection of the crosslinking agent c) is not particularly limited. Any crosslinking agent that comprises two or more functional groups that can react with the disclosed polymeric binder b) or the materials present in the negative electrode may be used as the crosslinking agent c).
• Non limiting examples of the reactive functional groups within the crosslinking agent c) comprise silane, epoxy, amine, alcohol, blocked isocyanate, aziridine, and carbodiimide.
• Suitable crosslinking agents c) include but are not limited to at least one of alkoxysilanes, alkoxysilanes derivatives, dihydrazides, polyfunctional hydrazides, diamines, polyfunctional amines, diepoxies, polyfunctional epoxies, diols, polyols, polyfunctional blocked isocyanate, polyfunctional aziridine, polyfunctional carbodiimide, and mixtures thereof.
• crosslinkers c) may be selected from at least one of g- glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, trimethoxypropyl silane, adipic acid dihydrazide, sebacic acid dihydrazide, valine dihydrazide, isophthalic dihydrazide, hexamethylenediamine, polyvinylalcohol, bisphenol A diglycidyl ether, 1,4-butanediol diglycidyl ether, blocked polyisocyanates (e.g.
• Desmodur ® BL 3175 SN from Covestro pentaerythritol tris(3-(l-aziridinyl)propionate), polycarbodiimide crosslinker (e g. CARBODILITETM V-02, CARBODILITETM V-02-L2, CARBODILITETM SV-02, CARBODILITETM V-10, CARBODILITETM SW-12G, CARBODILITETM E-02, CARBODILITETM E-03A, CARBODILITETM E-05, CARBODILITETM E-07s from Nisshinbo), and combinations thereof.
• polycarbodiimide crosslinker e g. CARBODILITETM V-02, CARBODILITETM V-02-L2, CARBODILITETM SV-02, CARBODILITETM V-10, CARBODILITETM SW-12G, CARBODILITETM E-02, CARBODILITETM E-03A, CARBOD
• preferred crosslinkers c) may be selected from at least one of g -glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, adipic acid dihydrazide, hexamethylenediamine, polyvinylalcohol, bisphenol A diglycidyl ether, 1,4- butanediol diglycidyl ether, blocked polyisocyanates (e.g. Desmodur ® BL 3175 SN from Covestro), pentaerythritol tris(3-(l-aziridinyl)propionate), polycarbodiimide crosslinker (e.g.
• more preferred crosslinkers c) are g - glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, adipic acid dihydrazide, hexamethylenediamine, polyvinylalcohol, polycarbodiimide crosslinker (e g.
• the weight percentage of the crosslinking agent c) relative to the polymeric binder b) included in the composition for use as an electrode on a current collector within an electrical energy storage device containing a non-aqueous electrolyte is preferably within the range of 0 - 40 wt% by weight, and more preferably within the range of 0.01 - 20 wt% by weight, and even more preferably within 0.05 - 10 wt% by weight of the polymeric binder b).
• Optional Components/Additives is preferably within the range of 0 - 40 wt% by weight, and more preferably within the range of 0.01 - 20 wt% by weight, and even more preferably within 0.05 - 10 wt% by weight of the polymeric binder b).
• the composition may also include the following optional components: d) from 0 -10% by weight of the polymeric binder of one or more wetting agents, e) from 0 - 10% by weight of the polymeric binder of one or more dispersing agents, f) from 0 - 10% by weight of the polymeric binder of one or more volatile organic compounds (VOC), and/or adhesion promoters, and/or coalescent agents, g) from 0 - 200% by weight of the polymeric binder of one or more rheology modifier additives, h) from 0 - 10% by weight of the polymeric binder of one or more additives comprising, consisting of or consisting essentially of anti-setting agents, surfactants, and mixtures thereof.
• VOC volatile organic compounds
• Surfactants and/or anti-settling agents may be added to the binder slurry composition at 0 to 10 parts, preferably from 0.1 to 10 parts, and more preferably 0.5 to 5 parts per 100 parts of water. These anti-settling agents or surfactants are added to the binder dispersion post polymerization, generally to improve the shelf stability, and provide additional stabilization during slurry preparation. Some surfactant/anti-settling agent is also present in the composition remaining from the polymerization process.
• Useful anti-settling agents include, but are not limited to, ionic surfactants such as salts of alkyl sulfates, sulfonates, phosphates, phophonates (such as sodium lauryl sulfate and ammonium lauryl sulfate) and salts of partially fluorinated alkyl sulfates, carboxylates, phosphates, phosphonates (such as those sold under the CAPSTONE brandname by DuPont), and non-ionic surfactants such as the TRITON X series (from Dow) and PLURONIC series (from BASF). In one embodiment, only anionic surfactants are used. It is preferred that no fluorinated surfactants are present in the composition, either residual surfactant from the polymerization process, or added post-polymerization in forming or concentrating an aqueous dispersion.
• ionic surfactants such as salts of alkyl sulfates, sulfonates, phosphat
• Wetting agents may be incorporated into the composition at from 0 to 5 parts, and preferably from 0 to 3 parts per 100 parts of water.
• Surfactants can serve as wetting agents, but wetting agents may also include non-surfactants.
• the wetting agent can be an organic solvent. The presence of optional wetting agents permits uniform dispersion of powdery inorganic material(s) into aqueous dispersion of vinylidene fluoride polymer.
• Useful wetting agents include, but are not limited to, ionic and non-ionic surfactants such as the TRITON series (from Dow) and the PLURONIC series (from BASF), and organic liquids that are compatible with the aqueous dispersion, including but not limited to NMP, DMSO, and acetone.
• ionic and non-ionic surfactants such as the TRITON series (from Dow) and the PLURONIC series (from BASF)
• organic liquids that are compatible with the aqueous dispersion, including but not limited to NMP, DMSO, and acetone.
• Thickeners and rheology modifiers may be present in the fluoropolymer separator composition at from 0 to 10 parts, preferably from 0 to 5 parts per 100 parts of water.
• the addition of water-soluble thickener or rheology modifier to the above dispersion prevents or slows down the settling of inorganic powdery materials while providing appropriate slurry viscosity for a coating process.
• Useful thickeners include, but are not limited to the ACRYSOL series (from Dow Chemical);Rheotech series(from Coatex ), Viscoatex series (from Coatex) partially neutralized poly (acrylic acid) or poly (methacrylic acid) such as CARBOPOL from Lubrizol or Viscodis 100N from Coatex; and carboxylated alkyl cellulose, such as carboxylated methyl cellulose (CMC). Adjustment of the formulation pH can improve the effectiveness of some of the thickeners. In addition to organic rheology modifiers, inorganic rheology modifiers can also be used alone or in combination.
• Useful inorganic rheology modifiers include, but are not limited to, inorganic rheology modifiers including but not limited to natural clays such as montmorillonite and bentonite, manmade clays such as laponite, and others such as silica, and talc.
• fugitive adhesion promoter helps to produce the interconnectivity needed in coatings formed from the composition of the invention.
• fugitive adhesion promoter an agent that increases the interconnectivity of the composition after coating. The fugitive adhesion promoter is then capable of being removed from the formed substrate generally by evaporation (for a chemical) or by dissipation (for added energy).
• the fugitive adhesion promoter can be a chemical material, an energy source combined with pressure, or a combination, used at an effective amount to cause interconnectivity of the components of the aqueous composition during formation of the electrode.
• the composition contains 0 to 150 parts, preferably 0 to 100 parts, and more preferably from 0 to 30 parts, of one or more fugitive adhesion promoters per 100 parts of water.
• this is an organic liquid, that is soluble or miscible in water. This organic liquid acts as a plasticizer or coalescent agent acrylic particles, making them tacky and capable of acting as discrete adhesion points during the drying step.
• a useful organic solvent or coalescent agents include, but are not limited to those in the table below.
• useful energy sources include, but are not limited to, heat, IR radiation, and radio frequency (RF).
• RF radio frequency
• the temperature during the processing of the electrode should be about 20 to 50oC above the glass transition point of the acrylic binder.
• pressure - such as a calendering step
• the inventive composition for an electrode is suitable for use on a current collector within an electrical energy storage device containing a non-aqueous electrolyte, such as a secondary battery device.
• a non-aqueous electrolyte such as a secondary battery device.
• Such devices include an anode, a cathode, a separator between the anode and the cathode, and electrolyte.
• An electrode, such as an anode including the composition, in dried form, for use as an electrode on a substrate (i.e., current collector) within an electrical energy storage device disclosed herein is provided.
• Such an electrode is preferably used as anode and therefore most preferably the composition disclosed for use as an electrode disclosed herein is applied to an electroconductive substrate current collector made from copper.
• an electrical energy storage device selected from a non-aqueous-type battery, a capacitor, and a membrane electrode assembly that incorporates electrode comprising an electroconductive substrate coated on at least one surface with the composition for use as an electrode as disclosed herein, in dried form.
• Kits The composition for use as an electrode on a current collector within an electrical energy storage device containing a non-aqueous electrolyte may be provided in the form of a kit.
• the at least one crosslinking agent c) may be combined with the polymeric binder b) to form a first component of the kit; and the at least one particulate electrode-forming material a) may be a second component of the kit.
• Another embodiment of a kit is also provided.
• the at least one particulate electrode-forming material a) may be the a first component of the kit; the polymeric binder b) may be a second component of the kit; and the at least one crosslinking agent c) may be a third component of the kit.
• Electrodes were calendared at very high pressure at room temperature to arrive at desired porosity. Porosity of the electrodes were back calculated from its expected (weight contribution of each component) and apparent densities where the apparent densities was obtained by measuring weight and volume of the electrode using micrometer and 5 decimal point balance.
• Volume average particle size was measured by dynamic light scattering using a Nanotrac UPAl 50 from Microtrac.
• the monomer pre-emulsion was feed into the reactor over 4 stages. 293.4 g of the monomer pre-emulsion was feed into the reactor over 45 mins, followed by a 15 mins feed pause. Then the rest of the monomer pre-emulsion was feed into the reactor following the same feeding profile over three stages. After the completion of the delayed initiator feed over 260 mins, the contents in reactor was cooked for 30 mins before allowing the medium to cool to 70 °C. During the 30 mins cook, a post oxidizer solution containing 2.60 g of 70% t-butyl hydroperoxide and 18.64 g of deionized water was prepared in a glass beaker.
• a post reducer solution containing 1.80 g of Bruggolite® FF6M and 36.00 g of deionized water was also prepared in a glass beaker. The post oxidizer and post reducer solution were then feed into the reactor over 75 mins after the 30 mins cook. The medium was allowed to cool, and filtered.
• Example 2 Production of Binder
• the binder was produced in a similar manner as in Example 1 except that monomers selection and ratio were different. The weight percentage of each monomer used is listed in Table 1.
• Example 3 Production of Binder
• the binder was produced in a similar manner as Example 1 except that monomers selection and ratio were different.
• the weight percentage of each monomer used is listed in Table 1.
• Example 4 Production of Binder The binder was produced in a similar manner as compared to Example 1 except that monomers selection and ratio were different. The weight percentage of each monomer used is listed in Table 1.
• the binder was produced in a similar manner as Example 1 except that monomers selection and ratio were different.
• the weight percentage of each monomer used is listed in Table 1.
• the monomer pre-emulsion was feed into the reactor over 4 stages. 313.34 g of the monomer pre-emulsion was feed into the reactor over 45 mins, followed by a 15 mins feed pause. Then the rest of the monomer pre-emulsion was feed into the reactor following the same feeding profile over three stages. After the completion of the delayed initiator feed over 260 mins, the contents in reactor was cooked for 30 mins before allowing the medium to cool to 70 °C. During the 30 mins cook, a post oxidizer solution containing 2.83 g of 70% t-butyl hydroperoxide and 18.64 g of deionized water was prepared in a glass beaker.
• a post reducer solution containing 1.96 g of Bruggolite® FF6M and 36.00 g of deionized water was also prepared in a glass beaker. The post oxidizer and post reducer solution were then feed into the reactor over 75 mins after the 30 mins cook. The medium was allowed to cool, and filtered.
• the monomer pre-emulsion was feed into the reactor over 4 stages. 306.90 g of the monomer pre emulsion was feed into the reactor over 45 mins, followed by a 15 mins feed pause. Then the rest of the monomer pre-emulsion was feed into the reactor following the same feeding profile over three stages. After the completion of the delayed initiator feed over 260 mins, the contents in reactor was cooked for 30 mins before allowing the medium to cool to 70 °C. During the 30 mins cook, a post oxidizer solution containing 3.25 g of 70% t-butyl hydroperoxide and 23.30 g of deionized water was prepared in a glass beaker.
• a post reducer solution containing 2.25 g of Bruggolite® FF6M and 45.00 g of deionized water was also prepared in a glass beaker. The post oxidizer and post reducer solution were then feed into the reactor over 75 mins after the 30 mins cook. The medium was allowed to cool, and filtered.
• the binder was produced in a similar manner as Example 7 except that monomers selection and ratio were different.
• the weight percentage of each monomer used is listed in Table 1.
• a post reducer solution containing 2.70 g of Bruggolite® FF6M and 45.00 g of deionized water was also prepared in a glass beaker. The post oxidizer and post reducer solution were then feed into the reactor over 75 mins after the 30 mins cook. The medium was allowed to cool, and filtered.
• PAM600, 3.65 g of diacetone acrylamide, 4.06 g of AMPS® 2405 were weighed out in a second glass beaker and mixed with 1.22 of Rhodacal® A-246 MBA and 91.25 g of deionized water to prepare monomer pre-emulsion 2.
• 1.98 g of ammonium persulfate was weighed in a third glass beaker, dissolved in 15.00 g of deionized water to prepare initial initiator.
• 0.90 g of ammonium persulfate was dissolved in 40.00 g water in a fourth beaker to prepare delayed initiator.
• the contents of the reactor were heated to a temperature of 83 ⁇ 2 °C. 60.46 g of the monomer pre-emulsion 1 and the initial initiator were first introduced into the reactor. After the peak of the reaction exotherm, the remaining of the monomer pre-emulsion 1, the third stream base feed and the delayed initiator were feed into the reactor while keeping the reactor temperature 90 ⁇ 2°C. The third stream based feed and the delayed initiator solution were feed into the reactor over 260 mins. The monomer pre-emulsion 1 was feed into the reactor over 3 stages. 280.80 g of the monomer pre-emulsion 1 was feed into the reactor over 45 mins, followed by a 15 mins feed pause.
• a post reducer solution containing 3.20 g of Bruggolite® FF6M and 40.00 g of deionized water was also prepared in a glass beaker.
• the post oxidizer and post reducer solution were then feed into the reactor over 75 mins after the 30 mins cook.
• the medium was allowed to cool to room temperature.
• mixture of 4.00 g of ammonium hydroxide and 4.00 g of deionized water was added to the medium.
• the latex was then filtered.
• the third stream base feed and the delayed initiator were feed into the reactor while keeping the reactor temperature 90 ⁇ 2°C.
• the delayed initiator solution and the third stream base solution were feed into the reactor over 260 mins.
• the monomer pre-emulsion was feed into the reactor over 4 stages. 280.8 g of the monomer pre-emulsion was feed into the reactor over 45 mins, followed by a 15 mins feed pause. Then the rest of the monomer pre-emulsion was feed into the reactor following the same feeding profile over three stages.
• the contents in reactor was cooked for 30 mins before allowing the medium to cool to 70 °C.
• a post oxidizer solution containing 4.60 g of 70% t-butyl hydroperoxide and 25.00 g of deionized water was prepared in a glass beaker.
• a post reducer solution containing 3.20 g of Bruggolite® FF6M and 40.00 g of deionized water was also prepared in a glass beaker. The post oxidizer and post reducer solution were then feed into the reactor over 75 mins after the 30 mins cook. The medium was allowed to cool, and filtered.
• the monomer pre emulsion and the initial initiator were first introduced into the reactor. After the peak of the reaction exotherm, the remaining of the monomer pre-emulsion, the third stream base feed and the delayed initiator were feed into the reactor while keeping the reactor temperature 90 ⁇ 2°C. The delayed initiator solution and the third stream base were feed into the reactor over 260 mins.
• the monomer pre-emulsion was feed into the reactor over 4 stages. 317.48 g of the monomer pre-emulsion was feed into the reactor over 45 mins, followed by a 15 mins feed pause. Then the rest of the monomer pre-emulsion was feed into the reactor following the same feeding profile over three stages.
• the contents in reactor was cooked for 30 mins before allowing the medium to cool to 70 °C.
• a post oxidizer solution containing 2.60 g of 70% t-butyl hydroperoxide and 23.30 g of deionized water was prepared in a glass beaker.
• the post oxidizer and post reducer solution were then feed into the reactor over 75 mins after the 30 mins cook.
• the medium was allowed to cool, and filtered.
• the slurries prepared above were cast on to copper foil with a wet thickness of about 110 pm and placed in to a convection oven for 30 min at 120°C. Then, the electrode was calendared to reach porosity of about 30 % by volume. Adhesion measurements were performed with an Instron using 180 degree peel at 50 mm/min crosshead speed using 1 inch wide electrode specimens according to ASTM-D903 (2017).
• AAEM acetoacetoxyethyl methacrylate iii)
• ACN acrylonitrile ii)
• DAAM diacetone acrylamide iii)
• HEA 2-hydroxyethyl acrylate iii)
• MMA methyl methacrylate ii)
• PAA polyacrylic acid
• SBR styrene butadiene rubber
• SSS sodium 4-vinylbenzenesulfonate i)
• Sty styrene ii)
• Peel adhesion is a measure of binder’s binding ability in electrode. High peel adhesion is preferred for electrode processing and battery cycling. 10 N/m or larger is generally preferred for electrode processing. It can be seen that peel adhesion of all inventive Examples are larger than 10 N/m. Peel adhesion for Comparative Example 1 is not available due to unstable slurry.

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