Patent
US 11,973,211 B2PROCESS FOR PRODUCING METAL NANOWIRES AND NANOWIRE-GRAPHENE HYBRID PARTICULATES
Bor Z. Jang
Honeycomb Battery Company, Dayton, OH (US)·Apr. 30, 2024·US
Copyright © 2026 Matter42. All rights reserved.
Patent
Atlas literature
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US 11,973,211 B2Patent drawings and their descriptions. Click a drawing to enlarge it.
FIG. 1(B) A flow chart showing another preferred route to preparing metal nanowires from particles of the same metal material, having a diameter from 50 nm to …
FIG. 2 Phase diagram of the Ag—Cu system, having a 5 eutectic point: 778.1° C. and 28.1% Cu.
FIG. 3 Phase diagram of the Ti—Ni system, having a Eutectic point: 942° C., 28% Ni.
FIG. 4(A) SEM image of Si nanowires grown from Si particles without the presence of graphene sheets or graphite 10 flakes.
FIG. 5(B) SEM image of Cu nanowires, grown in the 15 presence of graphene sheets.
FIG. 6(B) SEM image of Ag nanowires grown in the presence of graphene sheets.
FIG. 7 Schematic drawing to illustrate the process for 20 producing exfoliated graphite, expanded graphite flakes, and graphene sheets.
FIG. 8(A) SEM images of exfoliated graphite worms imaged at a low magnification;
FIG. 9 The effect of nanowire diameter on the rate capability of an anode active material in a lithium-ion battery.
FIG. 10 The charge/discharge cycling behaviors of two 30 lithium-ion cells, one featuring Zn nanowires grown in situ inside graphene sheet-encapsulated …
Claims define the patent's legal scope. Independent claims stand alone; dependent claims (nested) narrow them. Click a claim to expand its dependents.
A process for producing graphene/metal nanowire hybrid material composition, said process comprising: (A) preparing a catalyst metal-coated mixture mass, which includes (i) mixing exfoliated graphite flakes, having a flake thickness from 100 nm to 1 µm, or graphene sheets, having a thickness from 0.34 nm to 100 nm, with source metal particles, having a particle diameter from 50 nm to 50 µm, to form a mixture and (ii) depositing a catalytic metal, in the form of nan-oparticles having a size from 1 nm to 100 nm or a coating having a thickness from 1 nm to 100 nm, onto surfaces of said exfoliated graphite flakes or graphene sheets and/or surfaces of said source metal particles, wherein said source metal material is a transition metal selected from Mn, Ag, Pd, Zn, Cd, Mo, Nb, Zr, an alloy thereof, or a combination thereof, Be, Ca, an alloy thereof, a compound thereof, or a combination thereof; and (B) exposing said catalyst metal-coated mixture mass to a high temperature environment, from 100° C. to 2,500° C., for a period of time sufficient to enable a catalytic metal-assisted growth of multiple metal nanowires, having a diameter or thickness from 2 nm to 100 nm, from said source metal particles to form said graphene-metal nanowire hybrid material composition.
The process of claim 1, wherein said catalytic metal is selected from Cu, Ni, Co, Mn, Fe, Ti, Al, Ag, Au, Pt, Pd, Pb, Bi, Sb, Zn, Cd, Ga, In, Zr, Te, P, Sn, Ge, Si, As, Te, Se, or a combination thereof.
The process of claim 1, wherein said graphene sheets are selected from a single- layer sheet or few-layer platelet of pristine graphene, graphene oxide, reduced graphene oxide, graphene fluoride, graphene bromide, graphene iodide, boron-doped graphene, nitrogen-doped graphene, chemically functionalized graphene, or a combination thereof, wherein few layer is defined as less than 10 layers of graphene planes.
The process of claim 1, wherein said graphene sheets or exfoliated graphite flakes and said metal particles are mixed to form a mixture in a particulate form of multiple secondary particles having a size from 1 µm to 30 µm.
The process of claim 1, wherein said step (A) comprises mixing said graphene sheets or exfoliated graphite flakes and said source metal particles to form a mixture in such a manner that one or a plurality of said source metal particles are wrapped around by graphene sheets or exfoliated graph-ite flakes.
The process of claim 1, wherein said graphene sheets or exfoliated graphite flakes and said source metal particles are mixed to form a mixture and an optional conductive additive is added to this mixture to increase the conductivity of the mixture, wherein the conductive additive is selected from natural graphite, artificial graphite, mesophase carbon, mesophase pitch, mesocarbon microbead, soft carbon, hard carbon, coke, carbon fiber, carbon nanofiber, carbon nanotube, carbon black, or a combination thereof.
The process of claim 1, wherein said step of depositing a catalytic metal includes (a) dissolving or dispersing a catalytic metal precursor in a liquid to form a precursor solution, (b) bringing said precursor solution in contact with surfaces of said graphene sheets or exfoliated graphite flakes and/or surfaces of said source metal particles, (c) removing said liquid; and (d) chemically or thermally converting said catalytic metal precursor to said catalytic metal coating or nanoparticles.
The process of claim 1, wherein said step of depos-iting a catalytic metal is conducted by a procedure of physical vapor deposition, chemical vapor deposition, sput-tering, plasma deposition, laser ablation, plasma spraying, ultrasonic spraying, printing, electrochemical deposition, electrode plating, electrodeless plating, chemical plating, ball milling, or a combination thereof.
The process of claim 1, wherein said procedure of exposing said catalyst metal-coated metal material to a high temperature environment is conducted in a protective atmo-sphere of an inert gas, nitrogen gas, hydrogen gas, a mixture thereof, or in a vacuum.
The process of claim 1, wherein said source metal material and said catalytic metal form an eutectic point and said procedure of exposing said catalyst metal-coated source metal material to a high temperature environment includes exposing said material to a temperature equal to or higher than said eutectic point for a desired period of time and then bringing said material to a temperature below said eutectic point.
The process of claim 1, wherein said step of mixing the source metal particles and graphene sheets is conducted by liquid solution mixing, homogenizer mixing, high shear-ing mixing, wet milling, air milling, or ball-milling.
The process of claim 1, wherein said mixing of said graphene sheets with source metal particles is conducted after surfaces of said graphene sheets and/or said source metal particles are deposited with said catalytic metal.
The process of claim 1, wherein said mixing of graphene sheets with source metal particles is conducted in such a manner that the resulting mixture is in a form of porous secondary particles having a diameter from 1 µm to 20 µm and having sub-micron pores therein from 2 nm to 1 5 µm in size.
The process of claim 1, further comprising a proce-dure of separating said graphene sheets from said metal nanowires.
The process of claim 1, further comprising a proce-dure of removing said catalytic metal from said graphene-metal nanowire hybrid material composition.
The process of claim 1, further comprising a proce-dure of mixing said graphene/metal nanowire hybrid com-position with a carbonaceous or graphitic material as a conductive additive and an optional binder material to form an electrode layer, wherein said carbonaceous or graphitic B₂ material is selected from a chemical vapor deposition car-bon, physical vapor deposition carbon, amorphous carbon, chemical vapor infiltration carbon, polymeric carbon or carbonized resin, pitch-derived carbon, natural graphite, artificial graphite, mesophase carbon, mesophase pitch, mesocarbon microbead, soft carbon, hard carbon, coke, carbon fiber, carbon nanofiber, carbon nanotube, carbon black, or a combination thereof.
A graphene-metal nanowire hybrid material compo-sition produced by the process of claim 1.
A battery electrode containing a graphene-metal nanowire hybrid material composition produced by the process of claim 1.
A lithium battery containing graphene-metal nanowire hybrid material composition produced by the process of claim 1 as an anode active material. ∗ ∗ ∗ ∗ ∗
Layer stacks claimed or described, ordered top of device to substrate.
battery electrode
lithium battery
Materials described outside the worked examples.
graphene sheets/exfoliated graphite flakes
source metal particles
Additional fabrication and treatment steps described in the patent.
Measurements and analyses referenced in the patent, with their drawing references.
FIG. 4(A) SEM image of Si nanowires grown from Si particles without the presence of graphene sheets or graphite 10 flakes.
Performance values and ranges asserted in the specification or claims.
| Property | Value | Material |
|---|---|---|
Thickness | 12–18 nm | — |
Thickness | 23–46 nm |
Patents and literature cited by this patent (applicant and examiner references).
Cited patents · 4
Cited non-patent literature · 1
Related documents with shared materials, methods, properties, or citations.
Patent
Atlas literature
Patent
US 11,973,211 B2Patent drawings and their descriptions. Click a drawing to enlarge it.
FIG. 1(B) A flow chart showing another preferred route to preparing metal nanowires from particles of the same metal material, having a diameter from 50 nm to …
FIG. 2 Phase diagram of the Ag—Cu system, having a 5 eutectic point: 778.1° C. and 28.1% Cu.
FIG. 3 Phase diagram of the Ti—Ni system, having a Eutectic point: 942° C., 28% Ni.
FIG. 4(A) SEM image of Si nanowires grown from Si particles without the presence of graphene sheets or graphite 10 flakes.
FIG. 5(B) SEM image of Cu nanowires, grown in the 15 presence of graphene sheets.
FIG. 6(B) SEM image of Ag nanowires grown in the presence of graphene sheets.
FIG. 7 Schematic drawing to illustrate the process for 20 producing exfoliated graphite, expanded graphite flakes, and graphene sheets.
FIG. 8(A) SEM images of exfoliated graphite worms imaged at a low magnification;
FIG. 9 The effect of nanowire diameter on the rate capability of an anode active material in a lithium-ion battery.
FIG. 10 The charge/discharge cycling behaviors of two 30 lithium-ion cells, one featuring Zn nanowires grown in situ inside graphene sheet-encapsulated …
Claims define the patent's legal scope. Independent claims stand alone; dependent claims (nested) narrow them. Click a claim to expand its dependents.
A process for producing graphene/metal nanowire hybrid material composition, said process comprising: (A) preparing a catalyst metal-coated mixture mass, which includes (i) mixing exfoliated graphite flakes, having a flake thickness from 100 nm to 1 µm, or graphene sheets, having a thickness from 0.34 nm to 100 nm, with source metal particles, having a particle diameter from 50 nm to 50 µm, to form a mixture and (ii) depositing a catalytic metal, in the form of nan-oparticles having a size from 1 nm to 100 nm or a coating having a thickness from 1 nm to 100 nm, onto surfaces of said exfoliated graphite flakes or graphene sheets and/or surfaces of said source metal particles, wherein said source metal material is a transition metal selected from Mn, Ag, Pd, Zn, Cd, Mo, Nb, Zr, an alloy thereof, or a combination thereof, Be, Ca, an alloy thereof, a compound thereof, or a combination thereof; and (B) exposing said catalyst metal-coated mixture mass to a high temperature environment, from 100° C. to 2,500° C., for a period of time sufficient to enable a catalytic metal-assisted growth of multiple metal nanowires, having a diameter or thickness from 2 nm to 100 nm, from said source metal particles to form said graphene-metal nanowire hybrid material composition.
The process of claim 1, wherein said catalytic metal is selected from Cu, Ni, Co, Mn, Fe, Ti, Al, Ag, Au, Pt, Pd, Pb, Bi, Sb, Zn, Cd, Ga, In, Zr, Te, P, Sn, Ge, Si, As, Te, Se, or a combination thereof.
The process of claim 1, wherein said graphene sheets are selected from a single- layer sheet or few-layer platelet of pristine graphene, graphene oxide, reduced graphene oxide, graphene fluoride, graphene bromide, graphene iodide, boron-doped graphene, nitrogen-doped graphene, chemically functionalized graphene, or a combination thereof, wherein few layer is defined as less than 10 layers of graphene planes.
The process of claim 1, wherein said graphene sheets or exfoliated graphite flakes and said metal particles are mixed to form a mixture in a particulate form of multiple secondary particles having a size from 1 µm to 30 µm.
The process of claim 1, wherein said step (A) comprises mixing said graphene sheets or exfoliated graphite flakes and said source metal particles to form a mixture in such a manner that one or a plurality of said source metal particles are wrapped around by graphene sheets or exfoliated graph-ite flakes.
The process of claim 1, wherein said graphene sheets or exfoliated graphite flakes and said source metal particles are mixed to form a mixture and an optional conductive additive is added to this mixture to increase the conductivity of the mixture, wherein the conductive additive is selected from natural graphite, artificial graphite, mesophase carbon, mesophase pitch, mesocarbon microbead, soft carbon, hard carbon, coke, carbon fiber, carbon nanofiber, carbon nanotube, carbon black, or a combination thereof.
The process of claim 1, wherein said step of depositing a catalytic metal includes (a) dissolving or dispersing a catalytic metal precursor in a liquid to form a precursor solution, (b) bringing said precursor solution in contact with surfaces of said graphene sheets or exfoliated graphite flakes and/or surfaces of said source metal particles, (c) removing said liquid; and (d) chemically or thermally converting said catalytic metal precursor to said catalytic metal coating or nanoparticles.
The process of claim 1, wherein said step of depos-iting a catalytic metal is conducted by a procedure of physical vapor deposition, chemical vapor deposition, sput-tering, plasma deposition, laser ablation, plasma spraying, ultrasonic spraying, printing, electrochemical deposition, electrode plating, electrodeless plating, chemical plating, ball milling, or a combination thereof.
The process of claim 1, wherein said procedure of exposing said catalyst metal-coated metal material to a high temperature environment is conducted in a protective atmo-sphere of an inert gas, nitrogen gas, hydrogen gas, a mixture thereof, or in a vacuum.
The process of claim 1, wherein said source metal material and said catalytic metal form an eutectic point and said procedure of exposing said catalyst metal-coated source metal material to a high temperature environment includes exposing said material to a temperature equal to or higher than said eutectic point for a desired period of time and then bringing said material to a temperature below said eutectic point.
The process of claim 1, wherein said step of mixing the source metal particles and graphene sheets is conducted by liquid solution mixing, homogenizer mixing, high shear-ing mixing, wet milling, air milling, or ball-milling.
The process of claim 1, wherein said mixing of said graphene sheets with source metal particles is conducted after surfaces of said graphene sheets and/or said source metal particles are deposited with said catalytic metal.
The process of claim 1, wherein said mixing of graphene sheets with source metal particles is conducted in such a manner that the resulting mixture is in a form of porous secondary particles having a diameter from 1 µm to 20 µm and having sub-micron pores therein from 2 nm to 1 5 µm in size.
The process of claim 1, further comprising a proce-dure of separating said graphene sheets from said metal nanowires.
The process of claim 1, further comprising a proce-dure of removing said catalytic metal from said graphene-metal nanowire hybrid material composition.
The process of claim 1, further comprising a proce-dure of mixing said graphene/metal nanowire hybrid com-position with a carbonaceous or graphitic material as a conductive additive and an optional binder material to form an electrode layer, wherein said carbonaceous or graphitic B₂ material is selected from a chemical vapor deposition car-bon, physical vapor deposition carbon, amorphous carbon, chemical vapor infiltration carbon, polymeric carbon or carbonized resin, pitch-derived carbon, natural graphite, artificial graphite, mesophase carbon, mesophase pitch, mesocarbon microbead, soft carbon, hard carbon, coke, carbon fiber, carbon nanofiber, carbon nanotube, carbon black, or a combination thereof.
A graphene-metal nanowire hybrid material compo-sition produced by the process of claim 1.
A battery electrode containing a graphene-metal nanowire hybrid material composition produced by the process of claim 1.
A lithium battery containing graphene-metal nanowire hybrid material composition produced by the process of claim 1 as an anode active material. ∗ ∗ ∗ ∗ ∗
Layer stacks claimed or described, ordered top of device to substrate.
battery electrode
lithium battery
Materials described outside the worked examples.
graphene sheets/exfoliated graphite flakes
source metal particles
Additional fabrication and treatment steps described in the patent.
Measurements and analyses referenced in the patent, with their drawing references.
FIG. 4(A) SEM image of Si nanowires grown from Si particles without the presence of graphene sheets or graphite 10 flakes.
Performance values and ranges asserted in the specification or claims.
| Property | Value | Material |
|---|---|---|
Thickness | 12–18 nm | — |
Thickness | 23–46 nm |
Patents and literature cited by this patent (applicant and examiner references).
Cited patents · 4
Cited non-patent literature · 1
Related documents with shared materials, methods, properties, or citations.
Patent
Atlas literature
Patent
US 11,973,211 B2Patent drawings and their descriptions. Click a drawing to enlarge it.
FIG. 1(B) A flow chart showing another preferred route to preparing metal nanowires from particles of the same metal material, having a diameter from 50 nm to …
FIG. 2 Phase diagram of the Ag—Cu system, having a 5 eutectic point: 778.1° C. and 28.1% Cu.
FIG. 3 Phase diagram of the Ti—Ni system, having a Eutectic point: 942° C., 28% Ni.
FIG. 4(A) SEM image of Si nanowires grown from Si particles without the presence of graphene sheets or graphite 10 flakes.
FIG. 5(B) SEM image of Cu nanowires, grown in the 15 presence of graphene sheets.
FIG. 6(B) SEM image of Ag nanowires grown in the presence of graphene sheets.
FIG. 7 Schematic drawing to illustrate the process for 20 producing exfoliated graphite, expanded graphite flakes, and graphene sheets.
FIG. 8(A) SEM images of exfoliated graphite worms imaged at a low magnification;
FIG. 9 The effect of nanowire diameter on the rate capability of an anode active material in a lithium-ion battery.
FIG. 10 The charge/discharge cycling behaviors of two 30 lithium-ion cells, one featuring Zn nanowires grown in situ inside graphene sheet-encapsulated …
Claims define the patent's legal scope. Independent claims stand alone; dependent claims (nested) narrow them. Click a claim to expand its dependents.
A process for producing graphene/metal nanowire hybrid material composition, said process comprising: (A) preparing a catalyst metal-coated mixture mass, which includes (i) mixing exfoliated graphite flakes, having a flake thickness from 100 nm to 1 µm, or graphene sheets, having a thickness from 0.34 nm to 100 nm, with source metal particles, having a particle diameter from 50 nm to 50 µm, to form a mixture and (ii) depositing a catalytic metal, in the form of nan-oparticles having a size from 1 nm to 100 nm or a coating having a thickness from 1 nm to 100 nm, onto surfaces of said exfoliated graphite flakes or graphene sheets and/or surfaces of said source metal particles, wherein said source metal material is a transition metal selected from Mn, Ag, Pd, Zn, Cd, Mo, Nb, Zr, an alloy thereof, or a combination thereof, Be, Ca, an alloy thereof, a compound thereof, or a combination thereof; and (B) exposing said catalyst metal-coated mixture mass to a high temperature environment, from 100° C. to 2,500° C., for a period of time sufficient to enable a catalytic metal-assisted growth of multiple metal nanowires, having a diameter or thickness from 2 nm to 100 nm, from said source metal particles to form said graphene-metal nanowire hybrid material composition.
The process of claim 1, wherein said catalytic metal is selected from Cu, Ni, Co, Mn, Fe, Ti, Al, Ag, Au, Pt, Pd, Pb, Bi, Sb, Zn, Cd, Ga, In, Zr, Te, P, Sn, Ge, Si, As, Te, Se, or a combination thereof.
The process of claim 1, wherein said graphene sheets are selected from a single- layer sheet or few-layer platelet of pristine graphene, graphene oxide, reduced graphene oxide, graphene fluoride, graphene bromide, graphene iodide, boron-doped graphene, nitrogen-doped graphene, chemically functionalized graphene, or a combination thereof, wherein few layer is defined as less than 10 layers of graphene planes.
The process of claim 1, wherein said graphene sheets or exfoliated graphite flakes and said metal particles are mixed to form a mixture in a particulate form of multiple secondary particles having a size from 1 µm to 30 µm.
The process of claim 1, wherein said step (A) comprises mixing said graphene sheets or exfoliated graphite flakes and said source metal particles to form a mixture in such a manner that one or a plurality of said source metal particles are wrapped around by graphene sheets or exfoliated graph-ite flakes.
The process of claim 1, wherein said graphene sheets or exfoliated graphite flakes and said source metal particles are mixed to form a mixture and an optional conductive additive is added to this mixture to increase the conductivity of the mixture, wherein the conductive additive is selected from natural graphite, artificial graphite, mesophase carbon, mesophase pitch, mesocarbon microbead, soft carbon, hard carbon, coke, carbon fiber, carbon nanofiber, carbon nanotube, carbon black, or a combination thereof.
The process of claim 1, wherein said step of depositing a catalytic metal includes (a) dissolving or dispersing a catalytic metal precursor in a liquid to form a precursor solution, (b) bringing said precursor solution in contact with surfaces of said graphene sheets or exfoliated graphite flakes and/or surfaces of said source metal particles, (c) removing said liquid; and (d) chemically or thermally converting said catalytic metal precursor to said catalytic metal coating or nanoparticles.
The process of claim 1, wherein said step of depos-iting a catalytic metal is conducted by a procedure of physical vapor deposition, chemical vapor deposition, sput-tering, plasma deposition, laser ablation, plasma spraying, ultrasonic spraying, printing, electrochemical deposition, electrode plating, electrodeless plating, chemical plating, ball milling, or a combination thereof.
The process of claim 1, wherein said procedure of exposing said catalyst metal-coated metal material to a high temperature environment is conducted in a protective atmo-sphere of an inert gas, nitrogen gas, hydrogen gas, a mixture thereof, or in a vacuum.
The process of claim 1, wherein said source metal material and said catalytic metal form an eutectic point and said procedure of exposing said catalyst metal-coated source metal material to a high temperature environment includes exposing said material to a temperature equal to or higher than said eutectic point for a desired period of time and then bringing said material to a temperature below said eutectic point.
The process of claim 1, wherein said step of mixing the source metal particles and graphene sheets is conducted by liquid solution mixing, homogenizer mixing, high shear-ing mixing, wet milling, air milling, or ball-milling.
The process of claim 1, wherein said mixing of said graphene sheets with source metal particles is conducted after surfaces of said graphene sheets and/or said source metal particles are deposited with said catalytic metal.
The process of claim 1, wherein said mixing of graphene sheets with source metal particles is conducted in such a manner that the resulting mixture is in a form of porous secondary particles having a diameter from 1 µm to 20 µm and having sub-micron pores therein from 2 nm to 1 5 µm in size.
The process of claim 1, further comprising a proce-dure of separating said graphene sheets from said metal nanowires.
The process of claim 1, further comprising a proce-dure of removing said catalytic metal from said graphene-metal nanowire hybrid material composition.
The process of claim 1, further comprising a proce-dure of mixing said graphene/metal nanowire hybrid com-position with a carbonaceous or graphitic material as a conductive additive and an optional binder material to form an electrode layer, wherein said carbonaceous or graphitic B₂ material is selected from a chemical vapor deposition car-bon, physical vapor deposition carbon, amorphous carbon, chemical vapor infiltration carbon, polymeric carbon or carbonized resin, pitch-derived carbon, natural graphite, artificial graphite, mesophase carbon, mesophase pitch, mesocarbon microbead, soft carbon, hard carbon, coke, carbon fiber, carbon nanofiber, carbon nanotube, carbon black, or a combination thereof.
A graphene-metal nanowire hybrid material compo-sition produced by the process of claim 1.
A battery electrode containing a graphene-metal nanowire hybrid material composition produced by the process of claim 1.
A lithium battery containing graphene-metal nanowire hybrid material composition produced by the process of claim 1 as an anode active material. ∗ ∗ ∗ ∗ ∗
Layer stacks claimed or described, ordered top of device to substrate.
battery electrode
lithium battery
Materials described outside the worked examples.
graphene sheets/exfoliated graphite flakes
source metal particles
Additional fabrication and treatment steps described in the patent.
Measurements and analyses referenced in the patent, with their drawing references.
FIG. 4(A) SEM image of Si nanowires grown from Si particles without the presence of graphene sheets or graphite 10 flakes.
Performance values and ranges asserted in the specification or claims.
| Property | Value | Material |
|---|---|---|
Thickness | 12–18 nm | — |
Thickness | 23–46 nm |
Patents and literature cited by this patent (applicant and examiner references).
Cited patents · 4
Cited non-patent literature · 1
Related documents with shared materials, methods, properties, or citations.
Patent
Atlas literature
Patent
US 11,973,211 B2Patent drawings and their descriptions. Click a drawing to enlarge it.
FIG. 1(B) A flow chart showing another preferred route to preparing metal nanowires from particles of the same metal material, having a diameter from 50 nm to …
FIG. 2 Phase diagram of the Ag—Cu system, having a 5 eutectic point: 778.1° C. and 28.1% Cu.
FIG. 3 Phase diagram of the Ti—Ni system, having a Eutectic point: 942° C., 28% Ni.
FIG. 4(A) SEM image of Si nanowires grown from Si particles without the presence of graphene sheets or graphite 10 flakes.
FIG. 5(B) SEM image of Cu nanowires, grown in the 15 presence of graphene sheets.
FIG. 6(B) SEM image of Ag nanowires grown in the presence of graphene sheets.
FIG. 7 Schematic drawing to illustrate the process for 20 producing exfoliated graphite, expanded graphite flakes, and graphene sheets.
FIG. 8(A) SEM images of exfoliated graphite worms imaged at a low magnification;
FIG. 9 The effect of nanowire diameter on the rate capability of an anode active material in a lithium-ion battery.
FIG. 10 The charge/discharge cycling behaviors of two 30 lithium-ion cells, one featuring Zn nanowires grown in situ inside graphene sheet-encapsulated …
Claims define the patent's legal scope. Independent claims stand alone; dependent claims (nested) narrow them. Click a claim to expand its dependents.
A process for producing graphene/metal nanowire hybrid material composition, said process comprising: (A) preparing a catalyst metal-coated mixture mass, which includes (i) mixing exfoliated graphite flakes, having a flake thickness from 100 nm to 1 µm, or graphene sheets, having a thickness from 0.34 nm to 100 nm, with source metal particles, having a particle diameter from 50 nm to 50 µm, to form a mixture and (ii) depositing a catalytic metal, in the form of nan-oparticles having a size from 1 nm to 100 nm or a coating having a thickness from 1 nm to 100 nm, onto surfaces of said exfoliated graphite flakes or graphene sheets and/or surfaces of said source metal particles, wherein said source metal material is a transition metal selected from Mn, Ag, Pd, Zn, Cd, Mo, Nb, Zr, an alloy thereof, or a combination thereof, Be, Ca, an alloy thereof, a compound thereof, or a combination thereof; and (B) exposing said catalyst metal-coated mixture mass to a high temperature environment, from 100° C. to 2,500° C., for a period of time sufficient to enable a catalytic metal-assisted growth of multiple metal nanowires, having a diameter or thickness from 2 nm to 100 nm, from said source metal particles to form said graphene-metal nanowire hybrid material composition.
The process of claim 1, wherein said catalytic metal is selected from Cu, Ni, Co, Mn, Fe, Ti, Al, Ag, Au, Pt, Pd, Pb, Bi, Sb, Zn, Cd, Ga, In, Zr, Te, P, Sn, Ge, Si, As, Te, Se, or a combination thereof.
The process of claim 1, wherein said graphene sheets are selected from a single- layer sheet or few-layer platelet of pristine graphene, graphene oxide, reduced graphene oxide, graphene fluoride, graphene bromide, graphene iodide, boron-doped graphene, nitrogen-doped graphene, chemically functionalized graphene, or a combination thereof, wherein few layer is defined as less than 10 layers of graphene planes.
The process of claim 1, wherein said graphene sheets or exfoliated graphite flakes and said metal particles are mixed to form a mixture in a particulate form of multiple secondary particles having a size from 1 µm to 30 µm.
The process of claim 1, wherein said step (A) comprises mixing said graphene sheets or exfoliated graphite flakes and said source metal particles to form a mixture in such a manner that one or a plurality of said source metal particles are wrapped around by graphene sheets or exfoliated graph-ite flakes.
The process of claim 1, wherein said graphene sheets or exfoliated graphite flakes and said source metal particles are mixed to form a mixture and an optional conductive additive is added to this mixture to increase the conductivity of the mixture, wherein the conductive additive is selected from natural graphite, artificial graphite, mesophase carbon, mesophase pitch, mesocarbon microbead, soft carbon, hard carbon, coke, carbon fiber, carbon nanofiber, carbon nanotube, carbon black, or a combination thereof.
The process of claim 1, wherein said step of depositing a catalytic metal includes (a) dissolving or dispersing a catalytic metal precursor in a liquid to form a precursor solution, (b) bringing said precursor solution in contact with surfaces of said graphene sheets or exfoliated graphite flakes and/or surfaces of said source metal particles, (c) removing said liquid; and (d) chemically or thermally converting said catalytic metal precursor to said catalytic metal coating or nanoparticles.
The process of claim 1, wherein said step of depos-iting a catalytic metal is conducted by a procedure of physical vapor deposition, chemical vapor deposition, sput-tering, plasma deposition, laser ablation, plasma spraying, ultrasonic spraying, printing, electrochemical deposition, electrode plating, electrodeless plating, chemical plating, ball milling, or a combination thereof.
The process of claim 1, wherein said procedure of exposing said catalyst metal-coated metal material to a high temperature environment is conducted in a protective atmo-sphere of an inert gas, nitrogen gas, hydrogen gas, a mixture thereof, or in a vacuum.
The process of claim 1, wherein said source metal material and said catalytic metal form an eutectic point and said procedure of exposing said catalyst metal-coated source metal material to a high temperature environment includes exposing said material to a temperature equal to or higher than said eutectic point for a desired period of time and then bringing said material to a temperature below said eutectic point.
The process of claim 1, wherein said step of mixing the source metal particles and graphene sheets is conducted by liquid solution mixing, homogenizer mixing, high shear-ing mixing, wet milling, air milling, or ball-milling.
The process of claim 1, wherein said mixing of said graphene sheets with source metal particles is conducted after surfaces of said graphene sheets and/or said source metal particles are deposited with said catalytic metal.
The process of claim 1, wherein said mixing of graphene sheets with source metal particles is conducted in such a manner that the resulting mixture is in a form of porous secondary particles having a diameter from 1 µm to 20 µm and having sub-micron pores therein from 2 nm to 1 5 µm in size.
The process of claim 1, further comprising a proce-dure of separating said graphene sheets from said metal nanowires.
The process of claim 1, further comprising a proce-dure of removing said catalytic metal from said graphene-metal nanowire hybrid material composition.
The process of claim 1, further comprising a proce-dure of mixing said graphene/metal nanowire hybrid com-position with a carbonaceous or graphitic material as a conductive additive and an optional binder material to form an electrode layer, wherein said carbonaceous or graphitic B₂ material is selected from a chemical vapor deposition car-bon, physical vapor deposition carbon, amorphous carbon, chemical vapor infiltration carbon, polymeric carbon or carbonized resin, pitch-derived carbon, natural graphite, artificial graphite, mesophase carbon, mesophase pitch, mesocarbon microbead, soft carbon, hard carbon, coke, carbon fiber, carbon nanofiber, carbon nanotube, carbon black, or a combination thereof.
A graphene-metal nanowire hybrid material compo-sition produced by the process of claim 1.
A battery electrode containing a graphene-metal nanowire hybrid material composition produced by the process of claim 1.
A lithium battery containing graphene-metal nanowire hybrid material composition produced by the process of claim 1 as an anode active material. ∗ ∗ ∗ ∗ ∗
Layer stacks claimed or described, ordered top of device to substrate.
battery electrode
lithium battery
Materials described outside the worked examples.
graphene sheets/exfoliated graphite flakes
source metal particles
Additional fabrication and treatment steps described in the patent.
Measurements and analyses referenced in the patent, with their drawing references.
FIG. 4(A) SEM image of Si nanowires grown from Si particles without the presence of graphene sheets or graphite 10 flakes.
Performance values and ranges asserted in the specification or claims.
| Property | Value | Material |
|---|---|---|
Thickness | 12–18 nm | — |
Thickness | 23–46 nm |
Patents and literature cited by this patent (applicant and examiner references).
Cited patents · 4
Cited non-patent literature · 1
Related documents with shared materials, methods, properties, or citations.
catalytic metal
metal nanowires
carbonaceous/graphitic conductive additive
graphene-metal nanowire hybrid material composition
FIG. 5(B) SEM image of Cu nanowires, grown in the 15 presence of graphene sheets.
FIG. 6(B) SEM image of Ag nanowires grown in the presence of graphene sheets.
FIG. 8(A) SEM images of exfoliated graphite worms imaged at a low magnification;
| — |
Thickness | 10–21 nm | — |
Duration | 900–7200 s | — |
Thickness | 2–20 nm | — |
Thickness | 22–35 nm | — |
Duration | 24–96 hours | — |
Thickness | 100–20000 nm | — |
Duration | 48–72 hours | — |
Thickness | 10–500 µm | — |
Thickness | 15–25 nm | — |
Temperature | 300–600 °C | — |
Duration | 48–96 hours | — |
Duration | 10–100 minutes | — |
Thickness | 7–18 nm | — |
Thickness | 3–15 µm | — |
Thickness | 35–100 nm | — |
Thickness | 1.3–3.7 nm | — |
Thickness | 27–66 nm | — |
Thickness | 8–15 nm | — |
Thickness | 13–25 nm | — |
Thickness | 33–56 nm | — |
Thickness | ≥ 35 nm | — |
Thickness | 100–1000 nm | — |
Thickness | 0.34–100 nm | — |
Thickness | 50–50000 nm | — |
Thickness | 1–100 nm | — |
Temperature | 100–2500 °C | — |
Thickness | 2–100 nm | — |
Thickness | 50–100000 nm | — |
Thickness | 20–100 nm | — |
Temperature | 200–1500 °C | — |
Temperature | 300–1200 °C | — |
Thickness | 100–10000 nm | — |
Temperature | 778–930 °C | — |
Duration | 60–10800 s | — |
Temperature | 950–1450 °C | — |
Thickness | 1–20 µm | — |
Thickness | 2–1000 nm | — |
Duration | 30–120 s | — |
Thickness | 0.3–10 µm | — |
Thickness | 2–35 nm | — |
Thickness | 35–90 nm | — |
Duration | 0.5–96 hours | — |
Thickness | 2–5 µm | — |
Thickness | 1–1000 µm | — |
Thickness | 10–30 µm | — |
Duration | 1–180 minutes | — |
Temperature | 450–650 °C | — |
Temperature | 500–1500 °C | — |
Temperature | 350–1500 °C | — |
Temperature | 800–1050 °C | — |
Thickness | 0.6–1.1 nm | — |
Thickness | ≤ 10 nm | — |
Thickness | ≤ 1 nm | — |
Thickness | ≤ 50 nm | — |
Thickness | ≤ 20 nm | — |
Thickness | ≤ 3 µm | — |
Thickness | ≤ 7 nm | — |
Thickness | ≥ 3 µm | — |
Thickness | ≥ 50 nm | — |
Thickness | ≥ 60 nm | — |
Thickness | ≥ 1 nm | — |
Thickness | 1–30 µm | — |
Thickness | 0.2–50 µm | — |
Thickness | 0.5–5 µm | — |
Temperature | 100–1000 °C | — |
Temperature | 300–2500 °C | — |
Thickness | 1–100 µm | — |
Thickness | 2–50 µm | — |
Thickness | 5–20 µm | — |
catalytic metal
metal nanowires
carbonaceous/graphitic conductive additive
graphene-metal nanowire hybrid material composition
FIG. 5(B) SEM image of Cu nanowires, grown in the 15 presence of graphene sheets.
FIG. 6(B) SEM image of Ag nanowires grown in the presence of graphene sheets.
FIG. 8(A) SEM images of exfoliated graphite worms imaged at a low magnification;
| — |
Thickness | 10–21 nm | — |
Duration | 900–7200 s | — |
Thickness | 2–20 nm | — |
Thickness | 22–35 nm | — |
Duration | 24–96 hours | — |
Thickness | 100–20000 nm | — |
Duration | 48–72 hours | — |
Thickness | 10–500 µm | — |
Thickness | 15–25 nm | — |
Temperature | 300–600 °C | — |
Duration | 48–96 hours | — |
Duration | 10–100 minutes | — |
Thickness | 7–18 nm | — |
Thickness | 3–15 µm | — |
Thickness | 35–100 nm | — |
Thickness | 1.3–3.7 nm | — |
Thickness | 27–66 nm | — |
Thickness | 8–15 nm | — |
Thickness | 13–25 nm | — |
Thickness | 33–56 nm | — |
Thickness | ≥ 35 nm | — |
Thickness | 100–1000 nm | — |
Thickness | 0.34–100 nm | — |
Thickness | 50–50000 nm | — |
Thickness | 1–100 nm | — |
Temperature | 100–2500 °C | — |
Thickness | 2–100 nm | — |
Thickness | 50–100000 nm | — |
Thickness | 20–100 nm | — |
Temperature | 200–1500 °C | — |
Temperature | 300–1200 °C | — |
Thickness | 100–10000 nm | — |
Temperature | 778–930 °C | — |
Duration | 60–10800 s | — |
Temperature | 950–1450 °C | — |
Thickness | 1–20 µm | — |
Thickness | 2–1000 nm | — |
Duration | 30–120 s | — |
Thickness | 0.3–10 µm | — |
Thickness | 2–35 nm | — |
Thickness | 35–90 nm | — |
Duration | 0.5–96 hours | — |
Thickness | 2–5 µm | — |
Thickness | 1–1000 µm | — |
Thickness | 10–30 µm | — |
Duration | 1–180 minutes | — |
Temperature | 450–650 °C | — |
Temperature | 500–1500 °C | — |
Temperature | 350–1500 °C | — |
Temperature | 800–1050 °C | — |
Thickness | 0.6–1.1 nm | — |
Thickness | ≤ 10 nm | — |
Thickness | ≤ 1 nm | — |
Thickness | ≤ 50 nm | — |
Thickness | ≤ 20 nm | — |
Thickness | ≤ 3 µm | — |
Thickness | ≤ 7 nm | — |
Thickness | ≥ 3 µm | — |
Thickness | ≥ 50 nm | — |
Thickness | ≥ 60 nm | — |
Thickness | ≥ 1 nm | — |
Thickness | 1–30 µm | — |
Thickness | 0.2–50 µm | — |
Thickness | 0.5–5 µm | — |
Temperature | 100–1000 °C | — |
Temperature | 300–2500 °C | — |
Thickness | 1–100 µm | — |
Thickness | 2–50 µm | — |
Thickness | 5–20 µm | — |
catalytic metal
metal nanowires
carbonaceous/graphitic conductive additive
graphene-metal nanowire hybrid material composition
FIG. 5(B) SEM image of Cu nanowires, grown in the 15 presence of graphene sheets.
FIG. 6(B) SEM image of Ag nanowires grown in the presence of graphene sheets.
FIG. 8(A) SEM images of exfoliated graphite worms imaged at a low magnification;
| — |
Thickness | 10–21 nm | — |
Duration | 900–7200 s | — |
Thickness | 2–20 nm | — |
Thickness | 22–35 nm | — |
Duration | 24–96 hours | — |
Thickness | 100–20000 nm | — |
Duration | 48–72 hours | — |
Thickness | 10–500 µm | — |
Thickness | 15–25 nm | — |
Temperature | 300–600 °C | — |
Duration | 48–96 hours | — |
Duration | 10–100 minutes | — |
Thickness | 7–18 nm | — |
Thickness | 3–15 µm | — |
Thickness | 35–100 nm | — |
Thickness | 1.3–3.7 nm | — |
Thickness | 27–66 nm | — |
Thickness | 8–15 nm | — |
Thickness | 13–25 nm | — |
Thickness | 33–56 nm | — |
Thickness | ≥ 35 nm | — |
Thickness | 100–1000 nm | — |
Thickness | 0.34–100 nm | — |
Thickness | 50–50000 nm | — |
Thickness | 1–100 nm | — |
Temperature | 100–2500 °C | — |
Thickness | 2–100 nm | — |
Thickness | 50–100000 nm | — |
Thickness | 20–100 nm | — |
Temperature | 200–1500 °C | — |
Temperature | 300–1200 °C | — |
Thickness | 100–10000 nm | — |
Temperature | 778–930 °C | — |
Duration | 60–10800 s | — |
Temperature | 950–1450 °C | — |
Thickness | 1–20 µm | — |
Thickness | 2–1000 nm | — |
Duration | 30–120 s | — |
Thickness | 0.3–10 µm | — |
Thickness | 2–35 nm | — |
Thickness | 35–90 nm | — |
Duration | 0.5–96 hours | — |
Thickness | 2–5 µm | — |
Thickness | 1–1000 µm | — |
Thickness | 10–30 µm | — |
Duration | 1–180 minutes | — |
Temperature | 450–650 °C | — |
Temperature | 500–1500 °C | — |
Temperature | 350–1500 °C | — |
Temperature | 800–1050 °C | — |
Thickness | 0.6–1.1 nm | — |
Thickness | ≤ 10 nm | — |
Thickness | ≤ 1 nm | — |
Thickness | ≤ 50 nm | — |
Thickness | ≤ 20 nm | — |
Thickness | ≤ 3 µm | — |
Thickness | ≤ 7 nm | — |
Thickness | ≥ 3 µm | — |
Thickness | ≥ 50 nm | — |
Thickness | ≥ 60 nm | — |
Thickness | ≥ 1 nm | — |
Thickness | 1–30 µm | — |
Thickness | 0.2–50 µm | — |
Thickness | 0.5–5 µm | — |
Temperature | 100–1000 °C | — |
Temperature | 300–2500 °C | — |
Thickness | 1–100 µm | — |
Thickness | 2–50 µm | — |
Thickness | 5–20 µm | — |
catalytic metal
metal nanowires
carbonaceous/graphitic conductive additive
graphene-metal nanowire hybrid material composition
FIG. 5(B) SEM image of Cu nanowires, grown in the 15 presence of graphene sheets.
FIG. 6(B) SEM image of Ag nanowires grown in the presence of graphene sheets.
FIG. 8(A) SEM images of exfoliated graphite worms imaged at a low magnification;
| — |
Thickness | 10–21 nm | — |
Duration | 900–7200 s | — |
Thickness | 2–20 nm | — |
Thickness | 22–35 nm | — |
Duration | 24–96 hours | — |
Thickness | 100–20000 nm | — |
Duration | 48–72 hours | — |
Thickness | 10–500 µm | — |
Thickness | 15–25 nm | — |
Temperature | 300–600 °C | — |
Duration | 48–96 hours | — |
Duration | 10–100 minutes | — |
Thickness | 7–18 nm | — |
Thickness | 3–15 µm | — |
Thickness | 35–100 nm | — |
Thickness | 1.3–3.7 nm | — |
Thickness | 27–66 nm | — |
Thickness | 8–15 nm | — |
Thickness | 13–25 nm | — |
Thickness | 33–56 nm | — |
Thickness | ≥ 35 nm | — |
Thickness | 100–1000 nm | — |
Thickness | 0.34–100 nm | — |
Thickness | 50–50000 nm | — |
Thickness | 1–100 nm | — |
Temperature | 100–2500 °C | — |
Thickness | 2–100 nm | — |
Thickness | 50–100000 nm | — |
Thickness | 20–100 nm | — |
Temperature | 200–1500 °C | — |
Temperature | 300–1200 °C | — |
Thickness | 100–10000 nm | — |
Temperature | 778–930 °C | — |
Duration | 60–10800 s | — |
Temperature | 950–1450 °C | — |
Thickness | 1–20 µm | — |
Thickness | 2–1000 nm | — |
Duration | 30–120 s | — |
Thickness | 0.3–10 µm | — |
Thickness | 2–35 nm | — |
Thickness | 35–90 nm | — |
Duration | 0.5–96 hours | — |
Thickness | 2–5 µm | — |
Thickness | 1–1000 µm | — |
Thickness | 10–30 µm | — |
Duration | 1–180 minutes | — |
Temperature | 450–650 °C | — |
Temperature | 500–1500 °C | — |
Temperature | 350–1500 °C | — |
Temperature | 800–1050 °C | — |
Thickness | 0.6–1.1 nm | — |
Thickness | ≤ 10 nm | — |
Thickness | ≤ 1 nm | — |
Thickness | ≤ 50 nm | — |
Thickness | ≤ 20 nm | — |
Thickness | ≤ 3 µm | — |
Thickness | ≤ 7 nm | — |
Thickness | ≥ 3 µm | — |
Thickness | ≥ 50 nm | — |
Thickness | ≥ 60 nm | — |
Thickness | ≥ 1 nm | — |
Thickness | 1–30 µm | — |
Thickness | 0.2–50 µm | — |
Thickness | 0.5–5 µm | — |
Temperature | 100–1000 °C | — |
Temperature | 300–2500 °C | — |
Thickness | 1–100 µm | — |
Thickness | 2–50 µm | — |
Thickness | 5–20 µm | — |