# US 12,015,156 B2 · Solvents and slurries comprising a poly(carboxylic acid) binder for silicon electrode manufacture > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 12,015,156 B2 - Document ID: US12015156B2 - Status: Granted - Kind: B2 - Application number: 17/987,605 - Filed: 2022-11-15 - Published: 2023-03-23 - Granted: 2024-06-18 - Earliest claimed: 2020-05-29 - Assignees: Uchicago Argonne, LLC - Applicants: Uchicago Argonne, LLC - Inventors: Lu Zhang; Zhangxing Shi; Andrew Jansen; Stephen Trask - Web page: https://patentgrep.com/patent/US12015156B2 ## CPC - H01M 4/622: {being polymers} - C08K 3/02: Elements - C08K 3/04: Carbon - C08L 33/02: Homopolymers or copolymers of acids; Metal or ammonium salts thereof - C09D 1/00: Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances - C09D 7/20: Diluents or solvents - C09D 7/61: inorganic - C09D 7/62: modified by treatment with other compounds - C09D 7/67: {Particle size smaller than 100 nm} - C09D 7/68: {Particle size between 100-1000 nm} - H01B 1/22: the conductive material comprising metals or alloys - H01M 4/0404: {by coating on electrode collectors} - H01M 4/0471: {involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis} - H01M 4/133: Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx - H01M 4/134: Electrodes based on metals, Si or alloys - H01M 4/1395: of electrodes based on metals, Si or alloys - H01M 4/364: {as mixtures} - H01M 4/386: {Silicon or alloys based on silicon} - H01M 4/587: for inserting or intercalating light metals - H01M 10/0525: Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries - C08K 2003/023: {Silicon} - C08K 2201/005: Additives being defined by their particle size in general - C08K 2201/011: Nanostructured additives - H01M 2004/027: {Negative electrodes} - H01M 2220/20: Batteries in motive systems, e.g. vehicle, ship, plane - Y02E 60/10: Energy storage using batteries - H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY - C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09) - C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06) - 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 (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D) - H01B: CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES (selection for magnetic properties H01F1/00; waveguides H01P {; printed circuits H05K}) - Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION ## Abstract An silicon-containing electrode is formed by coating a silicon-containing slurry onto a conductive current collector. The slurry comprises a binder solution comprising a poly(carboxylic acid) binder dissolved in a mixed solvent system comprising an amide solvent of Formula I, as described herein, and a second solvent which can be water and/or an organic solvent. The binder preferably comprises poly(acrylic acid). The mixed solvent system comprises about 10 to about 99 vol % of the amide solvent of Formula I. The binder solution is utilized as a solvent for a slurry of silicon-containing particles for preparing the silicon-containing electrode. The slurries comprising the mixed solvent system have higher viscosity and are more stable than slurries containing the same concentrations of silicon particles, carbon particles, and binder in water as the sole solvent. ## Claims ### Claim 1 A silicon-containing electrode formed by coating a silicon-containing slurry onto a conductive current collector, and drying the resulting coating; wherein the slurry comprises: a poly(carboxylic acid) binder and a particulate anode active material in a mixed solvent system comprising a first solvent and a second solvent that is miscible with the first solvent; wherein first solvent is an amide of Formula I: R1, R2, and R3 each independently is H, alkyl, alkoxy, or a polyether group; the second solvent is selected from the group consisting of water, and organic solvent, and a combination thereof; the first solvent and the second solvent are present in the mixed solvent system in a respective volume ratio of about 99:1 to about 1:9; the organic solvent comprises one or more material selected from the group consisting of an alcohol, an ether, a nitrile, and an amide that is different from the amide of the first solvent; and the particulate anode active material comprises silicon-containing particles, or a combination of silicon-containing particles and carbon particles; wherein the poly(carboxylic acid) binder comprises at least one material selected from the group consisting of poly(aspartic acid), poly(glutamic acid), poly(methacrylic acid), and poly(4-vinylbenzoic acid). ### Claim 2 (depends on 1) The electrode of claim 1, wherein the slurry comprises about 50 to about 90 percent by weight (wt %) of the anode active material and about 10 to about 50 wt % of the poly(carboxylic acid) binder based on the combined weight of the anode active material and the binder present in the slurry. ### Claim 3 (depends on 1) The electrode of claim 1, wherein the silicon-containing particles comprise at least one material selected from the group consisting of silicon nanoparticles, carbon coated silicon nanoparticles, and silicon/silicon oxide nanocomposite particles. ### Claim 4 (depends on 1) The electrode of claim 1, wherein the silicon-containing particles comprise silicon nanoparticles. ### Claim 5 (depends on 4) The electrode of claim 4, wherein the silicon nanoparticles have a particle size in the range of about 10 to about 200 nm as determined by transmission electron microscopy. ### Claim 6 (depends on 1) The electrode of claim 1, wherein the slurry comprises about 10 to about 90 wt % of the silicon-containing particles. ### Claim 7 (depends on 1) The electrode of claim 1, wherein the slurry comprises about 5 to about 85 wt % of the carbon particles. ### Claim 8 (depends on 7) The electrode of claim 7, wherein the carbon particles comprise at least one material selected from the group consisting of graphite, carbon black, carbon nanotubes, carbon nanofibers, hard carbon, and graphene. ### Claim 9 (depends on 7) The electrode of claim 7, wherein the carbon particles comprise graphite. ### Claim 10 (depends on 1) The electrode of claim 1, wherein the anode active material comprises a mixture of the silicon-containing particles and the carbon particles in a respective weight ratio of about 1:9 to about 9:1. ### Claim 11 (depends on 1) The electrode of claim 1, wherein the mixed solvent comprises about 10 to about 90 vol % N-methylacetamide in water. ### Claim 12 (depends on 1) The electrode of claim 1, wherein the coating is performed on a reverse comma roll coating apparatus. ### Claim 13 (depends on 1) A lithium electrochemical cell comprising an anode, a cathode, a lithium ion-conducting separator between the anode and the cathode, and a lithium ion-containing electrolyte contacting the anode, the cathode, and the separator; wherein the anode is the electrode of claim 1. ### Claim 14 (depends on 13) A battery comprising a plurality of electrochemical cells of claim 13 electrically connected together in series, in parallel, or in both series and parallel. ### Claim 15 A silicon-containing electrode formed by coating a silicon-containing slurry onto a conductive current collector, and drying the resulting coating; wherein the slurry comprises: a poly(carboxylic acid) binder and a particulate anode active material in a solvent comprising about 10 to about 90 vol % N-methylacetamide in water; wherein the particulate anode active material comprises silicon nanoparticles, or a combination of silicon nanoparticles and carbon particles; the slurry comprises 50 to about 90 wt % of the anode active material and about 10 to about 50 wt % of the binder based on the combined weight of the anode active material and binder present in the slurry, and the carbon particles comprise one or more materials selected from the group consisting of graphite, carbon black, carbon nanotubes, carbon nanofibers, hard carbon, and graphene; and wherein the coating is performed on a reverse comma roll coating apparatus; wherein the poly(carboxylic acid) binder comprises at least one material selected from the group consisting of poly(aspartic acid), poly(glutamic acid), poly(methacrylic acid), and poly(4-vinylbenzoic acid). ### Claim 16 (depends on 15) The electrode of claim 15, wherein the anode active material comprises a mixture of the silicon nanoparticles and the graphite particles in a respective weight ratio of about 1:9 to about 9:1. ### Claim 17 (depends on 15) A lithium electrochemical cell comprising an anode, a cathode, a lithium ion-conducting separator between the anode and the cathode, and a lithium ion-containing electrolyte contacting the anode, the cathode, and the separator; wherein the anode is the electrode of claim 15. ### Claim 18 (depends on 17) A battery comprising a plurality of electrochemical cells of claim 17 electrically connected together in series, in parallel, or in both series and parallel.