Patent
US 10,008,723Chemical-Free Production of Graphene-Wrapped Electrode Active Material Particles for Battery Applications
Aruna Zhamu
US
Copyright © 2026 Matter42. All rights reserved.
Patent drawings and their descriptions. Click a drawing to enlarge it.
FIG. 1 A flow chart showing the most commonly used prior art process of producing highly oxidized graphene sheets (or nano graphene platelets, NGPs) that …
FIG. 2 A diagram showing the presently invented process for producing graphene-embraced or encapsulated electrode active material particles via an energy …
FIG. 3 A diagram showing the presently invented process for producing graphene-embraced electrode active material particles via a continuous ball mill.
FIG. 4 Charge-discharge cycling behaviors of 3 lithium cells featuring Co 3 0 4 particle-based anodes: a) containing un-protected Co 3 0 4 particles, b) …
FIG. 5 Charge-discharge cycling behaviors of 2 lithium cells featuring Sn O 2 particle-based anodes: one containing un-protected Sn O 2 particles and the other …
FIG. 6 Charge-discharge cycling behaviors of 3 lithium cells featuring micron-scaled (3 pm) Si particle-based anodes: a) one cell containing un-protected Si …
FIG. 7 Charge-discharge cycling behaviors of 2 lithium cells featuring lithium iron phosphate (LFP) particle-based cathodes: one containing un-protected LFO …
FIG. 8 Charge-discharge cycling behaviors of 3 lithium cells featuring LiV 2 05 nanorod-based cathodes: a) containing protected LiV 2 0 5 nanorods (mixed with …
Claims define the patent's legal scope. Independent claims stand alone; dependent claims (nested) narrow them. Click a claim to expand its dependents.
An impact-transfer method of producing a graphene-embraced or graphene-encapsulated electrode active material directly from a graphitic material, said method comprising: a) mixing multiple particles of a graphitic material, multiple particles of a solid electrode active material, and non-polymeric particles of ball-milling media to form a mixture in an impacting chamber of an energy impacting apparatus, wherein said graphitic material has never been previously intercalated, oxidized, or exfoliated and said impacting chamber contains therein no previously produced isolated graphene sheets; b) operating said energy impacting apparatus with a frequency and an intensity for a length of time sufficient for peeling off graphene sheets from said particles of graphitic material and transferring said peeled graphene sheets to surfaces of said solid electrode active material particles and fully embrace or encapsulate said particles to produce particles of graphene- embraced or graphene-encapsulated electrode active material inside said impacting chamber; and c) recovering said particles of graphene-embraced or graphene-encapsulated electrode active material from said impacting chamber and separating said nonpolymeric particles of ball- milling media from said particles of graphene-embraced or graphene-encapsulated electrode active material.
The method of claim 1, wherein said non-polymeric particles of ball-milling media contain milling balls selected from ceramic particles, including ZrO 2 and non-ZrO 2 metal oxide particles, metal particles, glass particles, or a combination thereof.
The method of claim 1, further comprising a step of incorporating said graphene-embraced electrode active material into a battery electrode.
The method of claim 1, wherein an amount of residual graphitic material remains after said step b) and said method further comprises a step of incorporating said graphene-embraced electrode active material and said residual graphitic material into a battery electrode wherein said residual graphitic material is used as a conductive additive in said battery electrode.
The method of claim 1, wherein an amount of residual graphitic material remains after said step b), and said step c) includes a step of partially or completely separating said residual amount of said graphitic material from said graphene-embraced electrode active material.
The method of claim 1, wherein said particles of solid electrode active material contain prelithiated or pre-sodiated particles having 0.1 % to 54.7 % by weight of lithium or sodium ions preloaded into said particles prior to step (a) of mixing.
The method of claim 1, wherein said particles of solid electrode active material contain particles pre-coated with a layer of conductive material selected from a carbon, pitch, carbonized resin, conductive polymer, conductive organic material, metal coating, metal oxide shell, or a combination thereof.
The method of claim 1, wherein said particles of solid electrode active material contain particles pre-coated with a carbon precursor material prior to step (a), wherein said carbon precursor material is selected from a coal tar pitch, petroleum pitch, mesophase pitch, polymer, organic material, or a combination thereof so that said carbon precursor material resides between surfaces of said particles of solid electrode active material and said graphene sheets, and said method further contains a step of heat-treating said graphene-embraced electrode active material to convert said carbon precursor material to a carbon material and pores, wherein said pores form empty spaces between surfaces of said particles of solid electrode active material and said graphene sheets and said carbon material is coated on said surfaces of solid electrode active material particles and/or chemically bonds said graphene sheets together.
The method of claim 1, wherein said particles of solid electrode active material contain particles pre-coated with a sacrificial material selected from a metal, pitch, polymer, organic material, or a combination thereof so that said sacrificial material resides between surfaces of said particles of solid electrode active material and said graphene sheets, and said method further contains a step of partially or completely removing said sacrificial material to form empty spaces between surfaces of said solid electrode active material particles and said graphene sheets.
The method of claim 1, further comprising a step of exposing said graphene-embraced electrode active material to a liquid or vapor of a conductive material that is conductive to electrons and/or ions of lithium, sodium, magnesium, aluminum, or zinc.
The method of claim 1, wherein said particles of electrode active material are an anode active material selected from the group consisting of: (A) lithiated and un-lithiated silicon (Si), germanium (Ge), tin (S n), lead (Pb), antimony (Sb), bismuth (Bi), zin c (Zn), aluminum (Al), titanium (Ti), nickel (Ni), cobalt (C o), and cadmium (Cd); (B) lithiated and un-lithiated alloys or intermetallic compounds of Si, Ge, S n, Pb, Sb, Bi, Zn, Al, Ti, Ni, C o, or Cd with other elements; (C) lithiated and un-lithiated oxides, carbides, nitrides, sul f ides, phosphides, selenides, and tellurides of Si, Ge, S n, Pb, Sb, Bi, Zn, Al, Ti, Fe, Ni, C o, or Cd, and their mixtures, composites, or lithium-containing composites; (D) lithiated and un-lithiated salts and hydroxides of S n; (E) lithium titanate, lithium manganate, lithium aluminate, lithium-containing titanium oxide, lithium transition metal oxide; and combinations thereof.
The method of claim 1, wherein said electrode active material is a cathode active material selected from an inorganic material, an organic or polymeric material, a metal oxide/phosphate/sulfide, or a combination thereof.
The method of claim 1, wherein said electrode active material is a cathode active material selected from sulfur, sulfur compound, sulfur-carbon composite, sulfur-polymer composite, lithium polysulfide, transition metal dichalcogenide, a transition metal trichalcogenide, or a combination thereof.
The method of claim 1, wherein said electrode active material is a cathode active material containing a mixture of an organic material and an inorganic material or a metal oxide/phosphate/sulfide.
The method of claim 1, wherein said electrode active material particles include powder, flakes, beads, pellets, spheres, wires, fibers, filaments, discs, ribbons, or rods, having a diameter or thickness from 10 nm to 20 pm.
The method of claim 1, wherein said graphitic material is selected from natural graphite, synthetic graphite, highly oriented pyrolytic graphite, graphite fiber, graphitic nanofiber, graphite fluoride, chemically modified graphite, mesocarbon micro-bead, partially crystalline graphite, or a combination thereof.
The method of claim 1, wherein the energy impacting apparatus is a vibratory ball mill, planetary ball mill, high energy mill, basket mill, agitator ball mill, cryogenic ball mill, micro ball mill, tumbler ball mill, continuous ball mill, stirred ball mill, pressurized ball mill, plasma-assisted ball mill, freezer mill, vibratory sieve, bead mill, nano bead mill, ultrasonic homogenizer mill, centrifugal planetary mixer, vacuum ball mill, or resonant acoustic mixer.
The method of claim 1 wherein said graphene sheets contain single-layer graphene sheets.
The method of claim 1 wherein said graphene sheets contain at least 80 % single-layer graphene or at least 80 % few-layer graphene having no greater than 10 graphene planes.
The method of claim 1, wherein said procedure of operating said energy impacting apparatus is conducted in a continuous manner using a continuous energy impacting device.
A mass of graphene-embraced particles of solid active material produced by the method of claim 1, wherein a graphene proportion is from 0.01 % to 2 0% by weight based on the total weight of graphene and solid active material particles combined.
A battery electrode containing said graphene-embraced or graphene-encapsulated electrode active material produced in claim 1.
A battery electrode containing said graphene-embraced or graphene-encapsulated electrode active material produced in claim 1 as an electrode active material, wherein said battery is a lithium-ion battery, lithium metal secondary battery, lithium-sulfur battery, lithium-air battery, lithium-selenium battery, sodium-ion battery, sodium metal secondary battery, sodium-sulfur battery, sodium-air battery, magnesium-ion battery, magnesium metal battery, aluminum-ion battery, aluminum metal secondary battery, zinc-ion battery, zin c metal battery, or zinc-air battery.
Layer stacks claimed or described, ordered top of device to substrate.
battery electrode
battery
Materials described outside the worked examples.
graphene sheets
solid electrode active material
graphitic material
ball-milling media (non-polymeric)
conductive coating material
carbon precursor material
anode active material
cathode active material
metal oxide/phosphate/sulfide cathode material
sulfur-based cathode material
inorganic cathode material (TiS2, TaS2, MoS2, NbSe3, MnO2, CoO2, iron oxide, vanadium oxide)
vanadium oxide cathode material
lithium transition metal oxide/phosphate/borate cathode material
inorganic cathode material (bismuth selenide/telluride, transition metal dichalcogenide/trichalcogenide, boron nitride)
organic/polymeric cathode active material
phthalocyanine compound
Additional fabrication and treatment steps described in the patent.
Performance values and ranges asserted in the specification or claims.
| Property | Value | Material |
|---|---|---|
Duration | 600–3600 s | — |
Thickness | 20–200 nm | — |
Duration | 0.5–4 hours | — |
Duration | 5–120 hours | — |
Temperature | 800–1100 °C | — |
Temperature | 950–1050 °C | — |
Duration | 0.5–2 hours | — |
Thickness | 30–55 nm | — |
Duration | ≤ 1 hour | — |
Duration | ≤ 2 hours | — |
Thickness | ≤ 200 nm | — |
Related documents with shared materials, methods, properties, or citations.
METHOD OF PRODUCING GRAPHENE-CARBON HYBRID FOAM-PROTECTED ANODE ACTIVE MATERIAL COATING FOR LITHIUM-ION BATTERIES
ANODE MATERIAL OF NANO-SILICON HAVING MULTILAYER-GRAPHENE AS CARRIER AND COATED WITH SILICON SUBOXIDE AND WITH AMORPHOUS CARBON LAYER AND METHOD FOR FABRICATING THE SAME
Chemical-free production of graphene materials
Patent drawings and their descriptions. Click a drawing to enlarge it.
FIG. 1 A flow chart showing the most commonly used prior art process of producing highly oxidized graphene sheets (or nano graphene platelets, NGPs) that …
FIG. 2 A diagram showing the presently invented process for producing graphene-embraced or encapsulated electrode active material particles via an energy …
FIG. 3 A diagram showing the presently invented process for producing graphene-embraced electrode active material particles via a continuous ball mill.
FIG. 4 Charge-discharge cycling behaviors of 3 lithium cells featuring Co 3 0 4 particle-based anodes: a) containing un-protected Co 3 0 4 particles, b) …
FIG. 5 Charge-discharge cycling behaviors of 2 lithium cells featuring Sn O 2 particle-based anodes: one containing un-protected Sn O 2 particles and the other …
FIG. 6 Charge-discharge cycling behaviors of 3 lithium cells featuring micron-scaled (3 pm) Si particle-based anodes: a) one cell containing un-protected Si …
FIG. 7 Charge-discharge cycling behaviors of 2 lithium cells featuring lithium iron phosphate (LFP) particle-based cathodes: one containing un-protected LFO …
FIG. 8 Charge-discharge cycling behaviors of 3 lithium cells featuring LiV 2 05 nanorod-based cathodes: a) containing protected LiV 2 0 5 nanorods (mixed with …
Claims define the patent's legal scope. Independent claims stand alone; dependent claims (nested) narrow them. Click a claim to expand its dependents.
An impact-transfer method of producing a graphene-embraced or graphene-encapsulated electrode active material directly from a graphitic material, said method comprising: a) mixing multiple particles of a graphitic material, multiple particles of a solid electrode active material, and non-polymeric particles of ball-milling media to form a mixture in an impacting chamber of an energy impacting apparatus, wherein said graphitic material has never been previously intercalated, oxidized, or exfoliated and said impacting chamber contains therein no previously produced isolated graphene sheets; b) operating said energy impacting apparatus with a frequency and an intensity for a length of time sufficient for peeling off graphene sheets from said particles of graphitic material and transferring said peeled graphene sheets to surfaces of said solid electrode active material particles and fully embrace or encapsulate said particles to produce particles of graphene- embraced or graphene-encapsulated electrode active material inside said impacting chamber; and c) recovering said particles of graphene-embraced or graphene-encapsulated electrode active material from said impacting chamber and separating said nonpolymeric particles of ball- milling media from said particles of graphene-embraced or graphene-encapsulated electrode active material.
The method of claim 1, wherein said non-polymeric particles of ball-milling media contain milling balls selected from ceramic particles, including ZrO 2 and non-ZrO 2 metal oxide particles, metal particles, glass particles, or a combination thereof.
The method of claim 1, further comprising a step of incorporating said graphene-embraced electrode active material into a battery electrode.
The method of claim 1, wherein an amount of residual graphitic material remains after said step b) and said method further comprises a step of incorporating said graphene-embraced electrode active material and said residual graphitic material into a battery electrode wherein said residual graphitic material is used as a conductive additive in said battery electrode.
The method of claim 1, wherein an amount of residual graphitic material remains after said step b), and said step c) includes a step of partially or completely separating said residual amount of said graphitic material from said graphene-embraced electrode active material.
The method of claim 1, wherein said particles of solid electrode active material contain prelithiated or pre-sodiated particles having 0.1 % to 54.7 % by weight of lithium or sodium ions preloaded into said particles prior to step (a) of mixing.
The method of claim 1, wherein said particles of solid electrode active material contain particles pre-coated with a layer of conductive material selected from a carbon, pitch, carbonized resin, conductive polymer, conductive organic material, metal coating, metal oxide shell, or a combination thereof.
The method of claim 1, wherein said particles of solid electrode active material contain particles pre-coated with a carbon precursor material prior to step (a), wherein said carbon precursor material is selected from a coal tar pitch, petroleum pitch, mesophase pitch, polymer, organic material, or a combination thereof so that said carbon precursor material resides between surfaces of said particles of solid electrode active material and said graphene sheets, and said method further contains a step of heat-treating said graphene-embraced electrode active material to convert said carbon precursor material to a carbon material and pores, wherein said pores form empty spaces between surfaces of said particles of solid electrode active material and said graphene sheets and said carbon material is coated on said surfaces of solid electrode active material particles and/or chemically bonds said graphene sheets together.
The method of claim 1, wherein said particles of solid electrode active material contain particles pre-coated with a sacrificial material selected from a metal, pitch, polymer, organic material, or a combination thereof so that said sacrificial material resides between surfaces of said particles of solid electrode active material and said graphene sheets, and said method further contains a step of partially or completely removing said sacrificial material to form empty spaces between surfaces of said solid electrode active material particles and said graphene sheets.
The method of claim 1, further comprising a step of exposing said graphene-embraced electrode active material to a liquid or vapor of a conductive material that is conductive to electrons and/or ions of lithium, sodium, magnesium, aluminum, or zinc.
The method of claim 1, wherein said particles of electrode active material are an anode active material selected from the group consisting of: (A) lithiated and un-lithiated silicon (Si), germanium (Ge), tin (S n), lead (Pb), antimony (Sb), bismuth (Bi), zin c (Zn), aluminum (Al), titanium (Ti), nickel (Ni), cobalt (C o), and cadmium (Cd); (B) lithiated and un-lithiated alloys or intermetallic compounds of Si, Ge, S n, Pb, Sb, Bi, Zn, Al, Ti, Ni, C o, or Cd with other elements; (C) lithiated and un-lithiated oxides, carbides, nitrides, sul f ides, phosphides, selenides, and tellurides of Si, Ge, S n, Pb, Sb, Bi, Zn, Al, Ti, Fe, Ni, C o, or Cd, and their mixtures, composites, or lithium-containing composites; (D) lithiated and un-lithiated salts and hydroxides of S n; (E) lithium titanate, lithium manganate, lithium aluminate, lithium-containing titanium oxide, lithium transition metal oxide; and combinations thereof.
The method of claim 1, wherein said electrode active material is a cathode active material selected from an inorganic material, an organic or polymeric material, a metal oxide/phosphate/sulfide, or a combination thereof.
The method of claim 1, wherein said electrode active material is a cathode active material selected from sulfur, sulfur compound, sulfur-carbon composite, sulfur-polymer composite, lithium polysulfide, transition metal dichalcogenide, a transition metal trichalcogenide, or a combination thereof.
The method of claim 1, wherein said electrode active material is a cathode active material containing a mixture of an organic material and an inorganic material or a metal oxide/phosphate/sulfide.
The method of claim 1, wherein said electrode active material particles include powder, flakes, beads, pellets, spheres, wires, fibers, filaments, discs, ribbons, or rods, having a diameter or thickness from 10 nm to 20 pm.
The method of claim 1, wherein said graphitic material is selected from natural graphite, synthetic graphite, highly oriented pyrolytic graphite, graphite fiber, graphitic nanofiber, graphite fluoride, chemically modified graphite, mesocarbon micro-bead, partially crystalline graphite, or a combination thereof.
The method of claim 1, wherein the energy impacting apparatus is a vibratory ball mill, planetary ball mill, high energy mill, basket mill, agitator ball mill, cryogenic ball mill, micro ball mill, tumbler ball mill, continuous ball mill, stirred ball mill, pressurized ball mill, plasma-assisted ball mill, freezer mill, vibratory sieve, bead mill, nano bead mill, ultrasonic homogenizer mill, centrifugal planetary mixer, vacuum ball mill, or resonant acoustic mixer.
The method of claim 1 wherein said graphene sheets contain single-layer graphene sheets.
The method of claim 1 wherein said graphene sheets contain at least 80 % single-layer graphene or at least 80 % few-layer graphene having no greater than 10 graphene planes.
The method of claim 1, wherein said procedure of operating said energy impacting apparatus is conducted in a continuous manner using a continuous energy impacting device.
A mass of graphene-embraced particles of solid active material produced by the method of claim 1, wherein a graphene proportion is from 0.01 % to 2 0% by weight based on the total weight of graphene and solid active material particles combined.
A battery electrode containing said graphene-embraced or graphene-encapsulated electrode active material produced in claim 1.
A battery electrode containing said graphene-embraced or graphene-encapsulated electrode active material produced in claim 1 as an electrode active material, wherein said battery is a lithium-ion battery, lithium metal secondary battery, lithium-sulfur battery, lithium-air battery, lithium-selenium battery, sodium-ion battery, sodium metal secondary battery, sodium-sulfur battery, sodium-air battery, magnesium-ion battery, magnesium metal battery, aluminum-ion battery, aluminum metal secondary battery, zinc-ion battery, zin c metal battery, or zinc-air battery.
Layer stacks claimed or described, ordered top of device to substrate.
battery electrode
battery
Materials described outside the worked examples.
graphene sheets
solid electrode active material
graphitic material
ball-milling media (non-polymeric)
conductive coating material
carbon precursor material
anode active material
cathode active material
metal oxide/phosphate/sulfide cathode material
sulfur-based cathode material
inorganic cathode material (TiS2, TaS2, MoS2, NbSe3, MnO2, CoO2, iron oxide, vanadium oxide)
vanadium oxide cathode material
lithium transition metal oxide/phosphate/borate cathode material
inorganic cathode material (bismuth selenide/telluride, transition metal dichalcogenide/trichalcogenide, boron nitride)
organic/polymeric cathode active material
phthalocyanine compound
Additional fabrication and treatment steps described in the patent.
Performance values and ranges asserted in the specification or claims.
| Property | Value | Material |
|---|---|---|
Duration | 600–3600 s | — |
Thickness | 20–200 nm | — |
Duration | 0.5–4 hours | — |
Duration | 5–120 hours | — |
Temperature | 800–1100 °C | — |
Temperature | 950–1050 °C | — |
Duration | 0.5–2 hours | — |
Thickness | 30–55 nm | — |
Duration | ≤ 1 hour | — |
Duration | ≤ 2 hours | — |
Thickness | ≤ 200 nm | — |
Related documents with shared materials, methods, properties, or citations.
METHOD OF PRODUCING GRAPHENE-CARBON HYBRID FOAM-PROTECTED ANODE ACTIVE MATERIAL COATING FOR LITHIUM-ION BATTERIES
ANODE MATERIAL OF NANO-SILICON HAVING MULTILAYER-GRAPHENE AS CARRIER AND COATED WITH SILICON SUBOXIDE AND WITH AMORPHOUS CARBON LAYER AND METHOD FOR FABRICATING THE SAME
Chemical-free production of graphene materials
Patent drawings and their descriptions. Click a drawing to enlarge it.
FIG. 1 A flow chart showing the most commonly used prior art process of producing highly oxidized graphene sheets (or nano graphene platelets, NGPs) that …
FIG. 2 A diagram showing the presently invented process for producing graphene-embraced or encapsulated electrode active material particles via an energy …
FIG. 3 A diagram showing the presently invented process for producing graphene-embraced electrode active material particles via a continuous ball mill.
FIG. 4 Charge-discharge cycling behaviors of 3 lithium cells featuring Co 3 0 4 particle-based anodes: a) containing un-protected Co 3 0 4 particles, b) …
FIG. 5 Charge-discharge cycling behaviors of 2 lithium cells featuring Sn O 2 particle-based anodes: one containing un-protected Sn O 2 particles and the other …
FIG. 6 Charge-discharge cycling behaviors of 3 lithium cells featuring micron-scaled (3 pm) Si particle-based anodes: a) one cell containing un-protected Si …
FIG. 7 Charge-discharge cycling behaviors of 2 lithium cells featuring lithium iron phosphate (LFP) particle-based cathodes: one containing un-protected LFO …
FIG. 8 Charge-discharge cycling behaviors of 3 lithium cells featuring LiV 2 05 nanorod-based cathodes: a) containing protected LiV 2 0 5 nanorods (mixed with …
Claims define the patent's legal scope. Independent claims stand alone; dependent claims (nested) narrow them. Click a claim to expand its dependents.
An impact-transfer method of producing a graphene-embraced or graphene-encapsulated electrode active material directly from a graphitic material, said method comprising: a) mixing multiple particles of a graphitic material, multiple particles of a solid electrode active material, and non-polymeric particles of ball-milling media to form a mixture in an impacting chamber of an energy impacting apparatus, wherein said graphitic material has never been previously intercalated, oxidized, or exfoliated and said impacting chamber contains therein no previously produced isolated graphene sheets; b) operating said energy impacting apparatus with a frequency and an intensity for a length of time sufficient for peeling off graphene sheets from said particles of graphitic material and transferring said peeled graphene sheets to surfaces of said solid electrode active material particles and fully embrace or encapsulate said particles to produce particles of graphene- embraced or graphene-encapsulated electrode active material inside said impacting chamber; and c) recovering said particles of graphene-embraced or graphene-encapsulated electrode active material from said impacting chamber and separating said nonpolymeric particles of ball- milling media from said particles of graphene-embraced or graphene-encapsulated electrode active material.
The method of claim 1, wherein said non-polymeric particles of ball-milling media contain milling balls selected from ceramic particles, including ZrO 2 and non-ZrO 2 metal oxide particles, metal particles, glass particles, or a combination thereof.
The method of claim 1, further comprising a step of incorporating said graphene-embraced electrode active material into a battery electrode.
The method of claim 1, wherein an amount of residual graphitic material remains after said step b) and said method further comprises a step of incorporating said graphene-embraced electrode active material and said residual graphitic material into a battery electrode wherein said residual graphitic material is used as a conductive additive in said battery electrode.
The method of claim 1, wherein an amount of residual graphitic material remains after said step b), and said step c) includes a step of partially or completely separating said residual amount of said graphitic material from said graphene-embraced electrode active material.
The method of claim 1, wherein said particles of solid electrode active material contain prelithiated or pre-sodiated particles having 0.1 % to 54.7 % by weight of lithium or sodium ions preloaded into said particles prior to step (a) of mixing.
The method of claim 1, wherein said particles of solid electrode active material contain particles pre-coated with a layer of conductive material selected from a carbon, pitch, carbonized resin, conductive polymer, conductive organic material, metal coating, metal oxide shell, or a combination thereof.
The method of claim 1, wherein said particles of solid electrode active material contain particles pre-coated with a carbon precursor material prior to step (a), wherein said carbon precursor material is selected from a coal tar pitch, petroleum pitch, mesophase pitch, polymer, organic material, or a combination thereof so that said carbon precursor material resides between surfaces of said particles of solid electrode active material and said graphene sheets, and said method further contains a step of heat-treating said graphene-embraced electrode active material to convert said carbon precursor material to a carbon material and pores, wherein said pores form empty spaces between surfaces of said particles of solid electrode active material and said graphene sheets and said carbon material is coated on said surfaces of solid electrode active material particles and/or chemically bonds said graphene sheets together.
The method of claim 1, wherein said particles of solid electrode active material contain particles pre-coated with a sacrificial material selected from a metal, pitch, polymer, organic material, or a combination thereof so that said sacrificial material resides between surfaces of said particles of solid electrode active material and said graphene sheets, and said method further contains a step of partially or completely removing said sacrificial material to form empty spaces between surfaces of said solid electrode active material particles and said graphene sheets.
The method of claim 1, further comprising a step of exposing said graphene-embraced electrode active material to a liquid or vapor of a conductive material that is conductive to electrons and/or ions of lithium, sodium, magnesium, aluminum, or zinc.
The method of claim 1, wherein said particles of electrode active material are an anode active material selected from the group consisting of: (A) lithiated and un-lithiated silicon (Si), germanium (Ge), tin (S n), lead (Pb), antimony (Sb), bismuth (Bi), zin c (Zn), aluminum (Al), titanium (Ti), nickel (Ni), cobalt (C o), and cadmium (Cd); (B) lithiated and un-lithiated alloys or intermetallic compounds of Si, Ge, S n, Pb, Sb, Bi, Zn, Al, Ti, Ni, C o, or Cd with other elements; (C) lithiated and un-lithiated oxides, carbides, nitrides, sul f ides, phosphides, selenides, and tellurides of Si, Ge, S n, Pb, Sb, Bi, Zn, Al, Ti, Fe, Ni, C o, or Cd, and their mixtures, composites, or lithium-containing composites; (D) lithiated and un-lithiated salts and hydroxides of S n; (E) lithium titanate, lithium manganate, lithium aluminate, lithium-containing titanium oxide, lithium transition metal oxide; and combinations thereof.
The method of claim 1, wherein said electrode active material is a cathode active material selected from an inorganic material, an organic or polymeric material, a metal oxide/phosphate/sulfide, or a combination thereof.
The method of claim 1, wherein said electrode active material is a cathode active material selected from sulfur, sulfur compound, sulfur-carbon composite, sulfur-polymer composite, lithium polysulfide, transition metal dichalcogenide, a transition metal trichalcogenide, or a combination thereof.
The method of claim 1, wherein said electrode active material is a cathode active material containing a mixture of an organic material and an inorganic material or a metal oxide/phosphate/sulfide.
The method of claim 1, wherein said electrode active material particles include powder, flakes, beads, pellets, spheres, wires, fibers, filaments, discs, ribbons, or rods, having a diameter or thickness from 10 nm to 20 pm.
The method of claim 1, wherein said graphitic material is selected from natural graphite, synthetic graphite, highly oriented pyrolytic graphite, graphite fiber, graphitic nanofiber, graphite fluoride, chemically modified graphite, mesocarbon micro-bead, partially crystalline graphite, or a combination thereof.
The method of claim 1, wherein the energy impacting apparatus is a vibratory ball mill, planetary ball mill, high energy mill, basket mill, agitator ball mill, cryogenic ball mill, micro ball mill, tumbler ball mill, continuous ball mill, stirred ball mill, pressurized ball mill, plasma-assisted ball mill, freezer mill, vibratory sieve, bead mill, nano bead mill, ultrasonic homogenizer mill, centrifugal planetary mixer, vacuum ball mill, or resonant acoustic mixer.
The method of claim 1 wherein said graphene sheets contain single-layer graphene sheets.
The method of claim 1 wherein said graphene sheets contain at least 80 % single-layer graphene or at least 80 % few-layer graphene having no greater than 10 graphene planes.
The method of claim 1, wherein said procedure of operating said energy impacting apparatus is conducted in a continuous manner using a continuous energy impacting device.
A mass of graphene-embraced particles of solid active material produced by the method of claim 1, wherein a graphene proportion is from 0.01 % to 2 0% by weight based on the total weight of graphene and solid active material particles combined.
A battery electrode containing said graphene-embraced or graphene-encapsulated electrode active material produced in claim 1.
A battery electrode containing said graphene-embraced or graphene-encapsulated electrode active material produced in claim 1 as an electrode active material, wherein said battery is a lithium-ion battery, lithium metal secondary battery, lithium-sulfur battery, lithium-air battery, lithium-selenium battery, sodium-ion battery, sodium metal secondary battery, sodium-sulfur battery, sodium-air battery, magnesium-ion battery, magnesium metal battery, aluminum-ion battery, aluminum metal secondary battery, zinc-ion battery, zin c metal battery, or zinc-air battery.
Layer stacks claimed or described, ordered top of device to substrate.
battery electrode
battery
Materials described outside the worked examples.
graphene sheets
solid electrode active material
graphitic material
ball-milling media (non-polymeric)
conductive coating material
carbon precursor material
anode active material
cathode active material
metal oxide/phosphate/sulfide cathode material
sulfur-based cathode material
inorganic cathode material (TiS2, TaS2, MoS2, NbSe3, MnO2, CoO2, iron oxide, vanadium oxide)
vanadium oxide cathode material
lithium transition metal oxide/phosphate/borate cathode material
inorganic cathode material (bismuth selenide/telluride, transition metal dichalcogenide/trichalcogenide, boron nitride)
organic/polymeric cathode active material
phthalocyanine compound
Additional fabrication and treatment steps described in the patent.
Performance values and ranges asserted in the specification or claims.
| Property | Value | Material |
|---|---|---|
Duration | 600–3600 s | — |
Thickness | 20–200 nm | — |
Duration | 0.5–4 hours | — |
Duration | 5–120 hours | — |
Temperature | 800–1100 °C | — |
Temperature | 950–1050 °C | — |
Duration | 0.5–2 hours | — |
Thickness | 30–55 nm | — |
Duration | ≤ 1 hour | — |
Duration | ≤ 2 hours | — |
Thickness | ≤ 200 nm | — |
Related documents with shared materials, methods, properties, or citations.
METHOD OF PRODUCING GRAPHENE-CARBON HYBRID FOAM-PROTECTED ANODE ACTIVE MATERIAL COATING FOR LITHIUM-ION BATTERIES
ANODE MATERIAL OF NANO-SILICON HAVING MULTILAYER-GRAPHENE AS CARRIER AND COATED WITH SILICON SUBOXIDE AND WITH AMORPHOUS CARBON LAYER AND METHOD FOR FABRICATING THE SAME
Chemical-free production of graphene materials
Patent drawings and their descriptions. Click a drawing to enlarge it.
FIG. 1 A flow chart showing the most commonly used prior art process of producing highly oxidized graphene sheets (or nano graphene platelets, NGPs) that …
FIG. 2 A diagram showing the presently invented process for producing graphene-embraced or encapsulated electrode active material particles via an energy …
FIG. 3 A diagram showing the presently invented process for producing graphene-embraced electrode active material particles via a continuous ball mill.
FIG. 4 Charge-discharge cycling behaviors of 3 lithium cells featuring Co 3 0 4 particle-based anodes: a) containing un-protected Co 3 0 4 particles, b) …
FIG. 5 Charge-discharge cycling behaviors of 2 lithium cells featuring Sn O 2 particle-based anodes: one containing un-protected Sn O 2 particles and the other …
FIG. 6 Charge-discharge cycling behaviors of 3 lithium cells featuring micron-scaled (3 pm) Si particle-based anodes: a) one cell containing un-protected Si …
FIG. 7 Charge-discharge cycling behaviors of 2 lithium cells featuring lithium iron phosphate (LFP) particle-based cathodes: one containing un-protected LFO …
FIG. 8 Charge-discharge cycling behaviors of 3 lithium cells featuring LiV 2 05 nanorod-based cathodes: a) containing protected LiV 2 0 5 nanorods (mixed with …
Claims define the patent's legal scope. Independent claims stand alone; dependent claims (nested) narrow them. Click a claim to expand its dependents.
An impact-transfer method of producing a graphene-embraced or graphene-encapsulated electrode active material directly from a graphitic material, said method comprising: a) mixing multiple particles of a graphitic material, multiple particles of a solid electrode active material, and non-polymeric particles of ball-milling media to form a mixture in an impacting chamber of an energy impacting apparatus, wherein said graphitic material has never been previously intercalated, oxidized, or exfoliated and said impacting chamber contains therein no previously produced isolated graphene sheets; b) operating said energy impacting apparatus with a frequency and an intensity for a length of time sufficient for peeling off graphene sheets from said particles of graphitic material and transferring said peeled graphene sheets to surfaces of said solid electrode active material particles and fully embrace or encapsulate said particles to produce particles of graphene- embraced or graphene-encapsulated electrode active material inside said impacting chamber; and c) recovering said particles of graphene-embraced or graphene-encapsulated electrode active material from said impacting chamber and separating said nonpolymeric particles of ball- milling media from said particles of graphene-embraced or graphene-encapsulated electrode active material.
The method of claim 1, wherein said non-polymeric particles of ball-milling media contain milling balls selected from ceramic particles, including ZrO 2 and non-ZrO 2 metal oxide particles, metal particles, glass particles, or a combination thereof.
The method of claim 1, further comprising a step of incorporating said graphene-embraced electrode active material into a battery electrode.
The method of claim 1, wherein an amount of residual graphitic material remains after said step b) and said method further comprises a step of incorporating said graphene-embraced electrode active material and said residual graphitic material into a battery electrode wherein said residual graphitic material is used as a conductive additive in said battery electrode.
The method of claim 1, wherein an amount of residual graphitic material remains after said step b), and said step c) includes a step of partially or completely separating said residual amount of said graphitic material from said graphene-embraced electrode active material.
The method of claim 1, wherein said particles of solid electrode active material contain prelithiated or pre-sodiated particles having 0.1 % to 54.7 % by weight of lithium or sodium ions preloaded into said particles prior to step (a) of mixing.
The method of claim 1, wherein said particles of solid electrode active material contain particles pre-coated with a layer of conductive material selected from a carbon, pitch, carbonized resin, conductive polymer, conductive organic material, metal coating, metal oxide shell, or a combination thereof.
The method of claim 1, wherein said particles of solid electrode active material contain particles pre-coated with a carbon precursor material prior to step (a), wherein said carbon precursor material is selected from a coal tar pitch, petroleum pitch, mesophase pitch, polymer, organic material, or a combination thereof so that said carbon precursor material resides between surfaces of said particles of solid electrode active material and said graphene sheets, and said method further contains a step of heat-treating said graphene-embraced electrode active material to convert said carbon precursor material to a carbon material and pores, wherein said pores form empty spaces between surfaces of said particles of solid electrode active material and said graphene sheets and said carbon material is coated on said surfaces of solid electrode active material particles and/or chemically bonds said graphene sheets together.
The method of claim 1, wherein said particles of solid electrode active material contain particles pre-coated with a sacrificial material selected from a metal, pitch, polymer, organic material, or a combination thereof so that said sacrificial material resides between surfaces of said particles of solid electrode active material and said graphene sheets, and said method further contains a step of partially or completely removing said sacrificial material to form empty spaces between surfaces of said solid electrode active material particles and said graphene sheets.
The method of claim 1, further comprising a step of exposing said graphene-embraced electrode active material to a liquid or vapor of a conductive material that is conductive to electrons and/or ions of lithium, sodium, magnesium, aluminum, or zinc.
The method of claim 1, wherein said particles of electrode active material are an anode active material selected from the group consisting of: (A) lithiated and un-lithiated silicon (Si), germanium (Ge), tin (S n), lead (Pb), antimony (Sb), bismuth (Bi), zin c (Zn), aluminum (Al), titanium (Ti), nickel (Ni), cobalt (C o), and cadmium (Cd); (B) lithiated and un-lithiated alloys or intermetallic compounds of Si, Ge, S n, Pb, Sb, Bi, Zn, Al, Ti, Ni, C o, or Cd with other elements; (C) lithiated and un-lithiated oxides, carbides, nitrides, sul f ides, phosphides, selenides, and tellurides of Si, Ge, S n, Pb, Sb, Bi, Zn, Al, Ti, Fe, Ni, C o, or Cd, and their mixtures, composites, or lithium-containing composites; (D) lithiated and un-lithiated salts and hydroxides of S n; (E) lithium titanate, lithium manganate, lithium aluminate, lithium-containing titanium oxide, lithium transition metal oxide; and combinations thereof.
The method of claim 1, wherein said electrode active material is a cathode active material selected from an inorganic material, an organic or polymeric material, a metal oxide/phosphate/sulfide, or a combination thereof.
The method of claim 1, wherein said electrode active material is a cathode active material selected from sulfur, sulfur compound, sulfur-carbon composite, sulfur-polymer composite, lithium polysulfide, transition metal dichalcogenide, a transition metal trichalcogenide, or a combination thereof.
The method of claim 1, wherein said electrode active material is a cathode active material containing a mixture of an organic material and an inorganic material or a metal oxide/phosphate/sulfide.
The method of claim 1, wherein said electrode active material particles include powder, flakes, beads, pellets, spheres, wires, fibers, filaments, discs, ribbons, or rods, having a diameter or thickness from 10 nm to 20 pm.
The method of claim 1, wherein said graphitic material is selected from natural graphite, synthetic graphite, highly oriented pyrolytic graphite, graphite fiber, graphitic nanofiber, graphite fluoride, chemically modified graphite, mesocarbon micro-bead, partially crystalline graphite, or a combination thereof.
The method of claim 1, wherein the energy impacting apparatus is a vibratory ball mill, planetary ball mill, high energy mill, basket mill, agitator ball mill, cryogenic ball mill, micro ball mill, tumbler ball mill, continuous ball mill, stirred ball mill, pressurized ball mill, plasma-assisted ball mill, freezer mill, vibratory sieve, bead mill, nano bead mill, ultrasonic homogenizer mill, centrifugal planetary mixer, vacuum ball mill, or resonant acoustic mixer.
The method of claim 1 wherein said graphene sheets contain single-layer graphene sheets.
The method of claim 1 wherein said graphene sheets contain at least 80 % single-layer graphene or at least 80 % few-layer graphene having no greater than 10 graphene planes.
The method of claim 1, wherein said procedure of operating said energy impacting apparatus is conducted in a continuous manner using a continuous energy impacting device.
A mass of graphene-embraced particles of solid active material produced by the method of claim 1, wherein a graphene proportion is from 0.01 % to 2 0% by weight based on the total weight of graphene and solid active material particles combined.
A battery electrode containing said graphene-embraced or graphene-encapsulated electrode active material produced in claim 1.
A battery electrode containing said graphene-embraced or graphene-encapsulated electrode active material produced in claim 1 as an electrode active material, wherein said battery is a lithium-ion battery, lithium metal secondary battery, lithium-sulfur battery, lithium-air battery, lithium-selenium battery, sodium-ion battery, sodium metal secondary battery, sodium-sulfur battery, sodium-air battery, magnesium-ion battery, magnesium metal battery, aluminum-ion battery, aluminum metal secondary battery, zinc-ion battery, zin c metal battery, or zinc-air battery.
Layer stacks claimed or described, ordered top of device to substrate.
battery electrode
battery
Materials described outside the worked examples.
graphene sheets
solid electrode active material
graphitic material
ball-milling media (non-polymeric)
conductive coating material
carbon precursor material
anode active material
cathode active material
metal oxide/phosphate/sulfide cathode material
sulfur-based cathode material
inorganic cathode material (TiS2, TaS2, MoS2, NbSe3, MnO2, CoO2, iron oxide, vanadium oxide)
vanadium oxide cathode material
lithium transition metal oxide/phosphate/borate cathode material
inorganic cathode material (bismuth selenide/telluride, transition metal dichalcogenide/trichalcogenide, boron nitride)
organic/polymeric cathode active material
phthalocyanine compound
Additional fabrication and treatment steps described in the patent.
Performance values and ranges asserted in the specification or claims.
| Property | Value | Material |
|---|---|---|
Duration | 600–3600 s | — |
Thickness | 20–200 nm | — |
Duration | 0.5–4 hours | — |
Duration | 5–120 hours | — |
Temperature | 800–1100 °C | — |
Temperature | 950–1050 °C | — |
Duration | 0.5–2 hours | — |
Thickness | 30–55 nm | — |
Duration | ≤ 1 hour | — |
Duration | ≤ 2 hours | — |
Thickness | ≤ 200 nm | — |
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