# US 9,437,344 B2 · Graphite or carbon particulates for the lithium ion battery anode > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 9,437,344 B2 - Document ID: US9437344B2 - Status: Granted - Kind: B2 - Application number: 12/804,413 - Filed: 2010-07-22 - Published: 2012-01-26 - Granted: 2016-09-06 - Earliest claimed: 2010-07-22 - Assignees: Nanotek Instruments, Inc. - Applicants: Aruna Zhamu; Jinjun Shi; Guorong Chen; Qing Fang; Bor Z. Jang; Ming C. Wang - Inventors: Aruna Zhamu; Jinjun Shi; Guorong Chen; Qing Fang; Bor Z. Jang; Ming C. Wang - Web page: https://patentgrep.com/patent/US9437344B2 ## CPC - H01B 1/122: {Ionic conductors} - C01B 32/21: After-treatment - H01M 4/133: Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx - 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 - Y02E 60/10: Energy storage using batteries - Y02T 10/70: Energy storage systems for electromobility, e.g. batteries - Y10T 428/30: Self-sustaining carbon mass or layer with impregnant or other layer - 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}) - C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C} - 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 - Y02T: CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION - Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION ## Abstract This invention provides a graphite or graphite-carbon particulate for use as a lithium secondary battery anode material having a high-rate capability. The particulate is formed of a core carbon or graphite particle and a plurality of satellite carbon or graphite particles that are each separately bonded to the core particle wherein the core particle is spherical in shape, slightly elongate in shape with a major axis-to-minor axis ratio less than 2, or fibril in shape, and wherein the satellite particles are disc-, platelet-, or flake-like particles each containing a graphite crystallite with a crystallographic c-axis dimension Lc and a lateral dimension. Preferably, Lc is less than 100 nm and the flake/platelet lateral dimension is less than 1 μm. The core particle may be selected from natural graphite, artificial graphite, spherical graphite, graphitic coke, meso-carbon micro-bead, soft carbon, hard carbon, graphitic fibril, carbon nano-fiber, carbon fiber, or graphite fiber. Preferably, the flat-shaped particles are randomly oriented with respect to one another. ## Claims ### Claim 1 A graphite or combined graphite-carbon particulate for forming a lithium secondary battery anode material, said particulate consists of an orientation-controlling core particle of carbon or graphite and a plurality of satellite carbon or graphite particles that are each separately bonded or attached to said core particle at a surface of said core particle, wherein the core particle is spherical or ellipsoidal in shape with a major axis-to-minor axis ratio less than 2, or a fibril shape having a diameter from 200 nm to 5 μm, wherein said satellite particles are flat-shaped, disc-, platelet-, or flake-like particles having a thickness less than 100 nm and a lateral dimension less than 1 μm that are selected from nano graphene platelets, graphite oxide, or graphite fluoride each consisting of a graphite crystallite having a preferred orientation defined by a crystallographic c-axis, wherein said satellite particles are single-crystal structures that are randomly oriented with respect to one another for the purpose of increasing power capability of said particulate, and wherein said satellite particles are bonded to said core particle using a conductive binder selected from an amorphous carbon, a polymeric carbon, a pitch, petroleum pitch, coal tar pitch, meso-phase pitch, coke, a conductive organic or polymer, or a combination thereof. ### Claim 2 (depends on 1) The graphite or combined graphite-carbon particulate of claim 1, wherein said core particle is selected from natural graphite, artificial graphite, spherical graphite or graphite globule, graphitic coke, meso-carbon micro-bead, soft carbon, hard carbon, graphitic fibril, carbon nano-fiber, carbon fiber, or graphite fiber. ### Claim 3 (depends on 1) The graphite or combined graphite-carbon particulate of claim 1, wherein said core particle is a graphitic fibril obtained by splitting a micron-diameter carbon or graphite fiber wherein said fibril has a diameter or thickness less than 5 μm. ### Claim 4 (depends on 1) The graphite or combined graphite-carbon particulate of claim 1, wherein said core particle is a graphitic fibril obtained by carbonizing and graphitizing an electron-spun polymer, organic, or pitch fiber. ### Claim 5 (depends on 1) The graphite or combined graphite-carbon particulate of claim 1, wherein said core particle is a spherical or spheroidal graphite. ### Claim 6 (depends on 1) The graphite or combined graphite-carbon particulate of claim 1, wherein said core particle is a meso-carbon micro-bead or a carbon or graphite particle obtained by hydrothermal synthesis. ### Claim 7 (depends on 1) The graphite or combined graphite-carbon particulate of claim 1, wherein at least one of said satellite carbon or graphite particles is an expanded graphite particle or nano graphene platelet coated with a carbon layer. ### Claim 8 (depends on 1) The graphite or combined graphite-carbon particulate of claim 1, which is a non-porous solid particulate. ### Claim 9 (depends on 1) The graphite or combined graphite-carbon particulate of claim 1, wherein at least one of said satellite carbon or graphite particles has a lateral dimension less than 1 μm. ### Claim 10 (depends on 1) The graphite or combined graphite-carbon particulate of claim 1, which provides a tap density of at least 1.1 g/cm3. ### Claim 11 (depends on 1) The graphite or combined graphite-carbon particulate of claim 1, which provides a tap density of at least 1.2 g/cm3. ### Claim 12 (depends on 1) The graphite or combined graphite-carbon particulate of claim 1, wherein at least one of said satellite carbon or graphite particles has a graphite crystal having a crystallographic c-axis dimension Lc less than 100 nm. ### Claim 13 (depends on 1) The graphite or combined graphite-carbon particulate of claim 1, wherein at least one of said satellite carbon or graphite particles has a graphite crystal having a crystallographic c-axis dimension Lc less than 80 nm. ### Claim 14 (depends on 1) The graphite or combined graphite-carbon particulate of claim 1, wherein at least one of said satellite particles is bonded to said core particle using an electrically conductive binder material. ### Claim 15 (depends on 1) The graphite or combined graphite-carbon particulate of claim 1, wherein at least one of said satellite particles is bonded to said core particle using an electrically conductive binder material selected from coal tar pitch, petroleum pitch, meso-phase pitch, coke, a conjugate chain polymer, or an amorphous carbon obtained from chemical vapor deposition or pyrolyzation of an organic precursor. ### Claim 16 (depends on 1) The graphite or combined graphite-carbon particulate of claim 1, wherein at least one of said satellite particles or core particle is coated with a non-graphitic carbon. ### Claim 17 (depends on 1) The graphite or combined graphite-carbon particulate of claim 1, wherein a degree of orientation as defined by the ratio I(110)/I(004) is greater than 0.2, wherein I(110) is the X-ray diffraction peak intensity of (110) planes and I(004) is the X-ray diffraction peak intensity of (004) planes of a graphite crystal. ### Claim 18 (depends on 1) The graphite or combined graphite-carbon particulate of claim 1, wherein a degree of orientation as defined by the ratio I(110)/I(004) is greater than 0.5, wherein I(110) is the X-ray diffraction peak intensity of (110) planes and I(004) is the X-ray diffraction peak intensity of (004) planes of a graphite crystal. ### Claim 19 (depends on 1) The graphite or combined graphite-carbon particulate of claim 1, wherein at least said core particle or satellite particles has a graphite crystal structure having an inter-planar spacing d002 of at least 0.336 nm derived from a (002) reflection peak in powder X-ray diffraction. ### Claim 20 (depends on 1) The graphite or combined graphite-carbon particulate of claim 1, which provides a lithium storage specific capacity of at least 350 mAh/g. ### Claim 21 (depends on 1) The graphite or combined graphite-carbon particulate of claim 1, which provides a lithium storage specific capacity of at least 355 mAh/g. ### Claim 22 (depends on 1) The graphite or combined graphite-carbon particulate of claim 1, which provides a lithium storage specific capacity of at least 330 mAh/g, which decreases by less than 15% when the charge or discharge rate is increased by 20 times. ### Claim 23 (depends on 1) The graphite or combined graphite-carbon particulate of claim 1, which provides a lithium storage specific capacity of at least 330 mAh/g, which decreases by less than 10% when the charge or discharge rate is increased by 20 times. ### Claim 24 (depends on 1) The graphite or combined graphite-carbon particulate of claim 1, which provides a lithium storage specific capacity of at least 355 mAh/g, which decreases by less than 15% when the charge or discharge rate is increased by 20 times. ### Claim 25 (depends on 1) The graphite or combined graphite-carbon particulate of claim 1, which provides an anode volumetric capacity density greater than 350 mAh/cm3. ### Claim 26 (depends on 1) The graphite or combined graphite-carbon particulate of claim 1, which provides an anode volumetric capacity density greater than 400 mAh/cm3. ### Claim 27 (depends on 1) A graphite or carbon paste containing a graphite or combined graphite-carbon particulate of claim 1 and a liquid medium as a precursor to an anode. ### Claim 28 (depends on 1) A lithium ion battery negative electrode comprising a graphite or combined graphite-carbon particulate of claim 1. ### Claim 29 (depends on 1) A lithium ion battery comprising a negative electrode which comprises a graphite or combined graphite-carbon particulate of claim 1. ### Claim 30 A graphite or combined graphite-carbon particulate for forming a lithium secondary battery anode material, said particulate is non-porous and is formed of an orientation-controlling core particle or portion of graphite or carbon that is spherical, spheroidal, or ellipsoidal in shape, and a plurality of flat-shaped satellite or perimeter portions of graphite that are integral with said core particle or portion, wherein said satellite or perimeter portions of graphite are single-crystal structures, and wherein the particulate is spherical in shape or ellipsoidal in shape with a major axis-to-minor axis ratio less than 2, or a fibril shape having a diameter from 200 nm to 5 μm, and said flat-shaped satellite portion consists of nano graphene platelets, graphite oxide, or graphite fluoride having a preferred orientation defined by a crystallographic c-axis thereof and wherein said plurality of flat-shaped satellite or perimeter portions of graphite are randomly oriented with respect to one another for the purpose of increasing power capability of said particulate, and said flat-shaped satellite portion consists of nano graphene platelets, graphite oxide, or graphite fluoride having a thickness less than 100 nm and a lateral dimension less than 1 μm.