# US 12,009,505 B2 · Conducting polymer network/graphene-protected negative electrode for a lithium-ion battery > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 12,009,505 B2 - Document ID: US12009505B2 - Status: Granted - Kind: B2 - Application number: 15/930,179 - Filed: 2020-05-12 - Published: 2021-11-18 - Granted: 2024-06-11 - Earliest claimed: 2020-05-12 - Assignees: Honeycomb Battery Company - Applicants: Global Graphene Group, Inc. - Inventors: Sheng-Yi Lu; Aruna Zhamu; Bor Z. Jang - Web page: https://patentgrep.com/patent/US12009505B2 ## CPC - H01M 4/364: {as mixtures} - H01M 4/366: {as layered products} - 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 4/137: Electrodes based on electro-active polymers - H01M 4/1393: of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx - H01M 4/1395: of electrodes based on metals, Si or alloys - H01M 4/1399: of electrodes based on electro-active polymers - H01M 4/38: of elements or alloys - H01M 4/602: {Polymers} - H01M 4/62: Selection of inactive substances as ingredients for active masses, e.g. binders, fillers - H01M 4/624: {Electric conductive fillers} - H01M 4/625: {Carbon or graphite} - H01M 10/052: Li-accumulators - H01M 10/0525: Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries - H01M 2004/021: {Physical characteristics, e.g. porosity, surface area} - H01M 2004/027: {Negative electrodes} - Y02E 60/10: Energy storage using batteries - H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY - Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION ## Abstract Provided is a composite layer of graphene sheets and anode particles being dispersed in a conducting polymer network for a lithium battery anode (negative electrode), the layer comprising a mixture of a conducting polymer network, multiple graphene sheets, and multiple particles of an anode active material, wherein the anode particles have a diameter or thickness from 0.5 nm to 20 μm and occupy from 30% to 98% by weight, the graphene sheets occupy from 0.01% to 25% by weight, and the conducting polymer network occupies from 1% to 30% by weight based on the total mixture weight and wherein the graphene sheets and the conducting polymer network together form dual conducting pathways for both electrons and lithium ions. ## Claims ### Claim 1 A layer of conducting polymer network/graphene-protected anode particles for a lithium battery anode, said layer comprising a mixture of multiple graphene sheets and multiple primary particles of an anode active material that are dispersed in or bonded by a conducting polymer network, wherein the primary particles have a diameter or thickness from 0.5 nm to 20 m and occupy from 30% to 98% by weight, the graphene sheets occupy from 0.01% to 25% by weight, and the conducting polymer network occupies from 1% to 30% by weight based on the total mixture weight and wherein the graphene sheets and the conducting polymer network together form dual conducting pathways for both electrons and lithium ions, wherein said conducting polymer network comprises a polyaniline hydrogel, polypyrrole hydrogel, or polythiophene hydrogel. ### Claim 2 (depends on 1) The layer of claim 1, wherein the multiple graphene sheets contain single-layer or few-layer graphene, wherein said few-layer graphene sheets have 2-10 layers of stacked graphene planes having an inter-plane spacing d002 from 0.3354 nm to 0.7 nm as measured by X-ray diffraction and said single-layer or few-layer graphene sheets contain a pristine graphene material having essentially zero % of non-carbon elements, or a non-pristine graphene material having 0.001% to 50% by weight of non-carbon elements. ### Claim 3 (depends on 2) The layer of claim 2, wherein said non-pristine graphene is selected from graphene oxide, reduced graphene oxide, graphene fluoride, graphene chloride, graphene bromide, graphene iodide, hydrogenated graphene, doped graphene, chemically functionalized graphene, or a combination thereof. ### Claim 4 (depends on 1) The layer of claim 1, wherein said multiple graphene sheets exceed percolation threshold that form a 3D network of electron-conducting pathways. ### Claim 5 (depends on 1) The layer of claim 1, wherein said anode active material primary particles contain particles pre-coated with a film of a conductive material selected from a carbon, pitch, carbonized resin, non-crosslinked conductive polymer, conductive organic material, metal coating, metal oxide shell, graphene, or a combination thereof. ### Claim 6 (depends on 1) The layer of claim 1, wherein said anode active material primary particles are selected from the group consisting of: (A) lithiated and un-lithiated silicon (Si), germanium (Ge), tin (Sn), lead (Pb), phosphorus (P), antimony (Sb), bismuth (Bi), zinc (Zn), aluminum (Al), titanium (Ti), nickel (Ni), cobalt (Co), niobium (Nb), and cadmium (Cd); (B) lithiated and un-lithiated alloys or intermetallic compounds of Si, Ge, Sn, Pb, P, Sb, Bi, Zn, Al, Ti, Ni, Co, Nb, or Cd with other elements; (C) lithiated and un-lithiated oxides, carbides, nitrides, sulfides, phosphides, selenides, and tellurides of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Fe, Ni, Co, or Cd, and their mixtures, composites, or lithium-containing composites; (D) lithiated and un-lithiated salts and hydroxides of Sn; (E) lithium aluminate, lithium transition metal oxide; and combinations thereof. ### Claim 7 (depends on 1) The layer of claim 1, wherein said anode active material particles are porous having surface pores, internal pores, or both surface and internal pores. ### Claim 8 (depends on 1) The layer of claim 1, wherein said layer has pores dispersed therein. ### Claim 9 (depends on 1) The layer of claim 1, wherein said anode active material particles include nano-scaled particles, flakes, beads, pellets, spheres, wires, fibers, filaments, discs, ribbons, tubes, or rods, having a diameter or thickness from 2 nm to 100 nm. ### Claim 10 (depends on 1) The layer of claim 1, further comprising an electron-conducting material selected from carbon nanotubes, carbon nano-fibers, carbon fibers, graphite fibers, expanded graphite flakes, coke, carbon particles, or a combination thereof. ### Claim 11 (depends on 1) The layer of claim 1, further comprising a lithium ion-conducing polymer that is blended with the conducting polymer network wherein the lithium ion-conducting polymer is selected from poly(ethylene oxide), polypropylene oxide, poly(ethylene glycol), poly(acrylonitrile), poly(methyl methacrylate), poly(vinylidene fluoride), poly(bis((methoxyethoxy)ethoxy)-phosphazene, polyvinyl chloride, polydimethylsiloxane, poly(vinylidene fluoride)-hexafluoropropylene, cyanoethyl poly(vinyl alcohol), a pentaerythritol tetraacrylate-based polymer, an aliphatic polycarbonate, a single Li-ion conducting solid polymer electrolyte with a carboxylate anion, a sulfonylimide anion, or sulfonate anion, a crosslinked electrolyte of poly(ethylene glycol) diacrylate or poly(ethylene glycol) methyl ether acrylate, a sulfonated derivative thereof, or a combination thereof. ### Claim 12 (depends on 1) The layer of claim 1, further comprising a lithium ion-conducing material dispersed therein wherein the lithium ion-conducting material is selected from Li2CO3, Li2O, Li2C2O4, LiOH, LiX, ROCO2Li, HCOLi, ROLi, (ROCO2Li)2, (CH2OCO2Li)2, Li2S, LixSOy, wherein X=F, Cl, I, or Br, R=a hydrocarbon group, 0