Patent
US 11,289,698CHEMICAL-FREE PRODUCTION OF GRAPHENE-PROTECTED POROUS ANODE PARTICLES FOR LITHIUM BATTERIES
Bor Z. Jang
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) Schematic illustrating the notion that expansion of Si particles, upon lithium intercalation during charging of a prior art lithium-ion battery, can …
FIG. 3(B) Schematic of the presently invented encapsulated single primary particle of an anode active material (prelithiated or unlithiated). The primary …
FIG. 4 A diagram showing the presently invented process for producing graphene-embraced, polymer-coated electrode active material particles via a continuous …
FIG. 5 The charge-discharge cycling behaviors of 2 lithium cells featuring Co 3 0 4 particle-based anodes: one cell containing graphene-embraced Co 3 0 4 …
FIG. 6 The specific capacity values of 3 lithium-ion cells having Sn₀ 2 particles as the an anode active material: one cell featuring graphene-encapsulated Sn O …
FIG. 7 The specific capacity values of 2 lithium-ion cells each featuring micron-scaled (3 p m) Si particle-based anodes: one cell containing graphene-embraced …
FIG. 8 Specific capacities of 2 lithium-ion cells having a core of Si nanowires (SiNW) embedded in an expanded graphite flake-reinforced carbon foam matrix …
FIG. 9 Cycle life of a lithium-ion cell containing graphene-encapsulated carbon foam matrix- protected porous Si particles, plotted as a function of the total …
FIG. 10 Cycle life of a lithium-ion cell containing graphene-encapsulated porous Sn particles, plotted as a function of the total pore-to-solid ratio in the …
Claims define the patent's legal scope. Independent claims stand alone; dependent claims (nested) narrow them. Click a claim to expand its dependents.
An anode particulate for a lithium battery, said anode particulate comprising a core and a thin encapsulating layer that encapsulates or embraces said core, wherein said core comprises a single or a plurality of porous primary particles of an anode active material, having a pore volume Vpp and solid volume Va, dispersed or embedded in a porous carbon matrix or carbon foam, wherein said porous carbon matrix or carbon foam contains pores having a pore volume Vp, and said thin encapsulating layer comprises graphene sheets and has a thickness from 1 nm to 10 p m, an electric conductivity from 10 -6 S/cm to 20,000 S/cm and a lithium ion conductivity from 10-8 S/cm to 5 x 10-2 S/cm and wherein the volume ratio Vp/Va is from 1.0/1.0 to 10/1.0 or the total pore volume ratio (Vp+Vpp)/Va is from 1.3/1.0 to 20/1.0, and the porous carbon matrix or carbon foam electronically and/or ionically connects the encapsulating layer to the primary particles of the anode active material, wherein said porous primary particles contain at least one particle that is porous having a free space, in a form of surface pores and/or internal pores, to expand into when said battery is charged. Currently amended
The anode particulate of claim 1, wherein said graphene sheets are selected from pristine graphene, graphene fluoride, graphene chloride, graphene bromide, graphene iodide, nitrogenated graphene, hydrogenated graphene, doped graphene, chemically functionalized graphene, a combination thereof, or a combination thereof with graphene oxide or reduced graphene oxide. Original
The anode particulate of claim 1, wherein said graphene sheets are selected from CVD graphene, graphene oxide (GO), or reduced graphene oxide (RGO). Original
The anode particulate of claim 1, wherein said graphene sheets in said encapsulating layer are chemically bonded with a carbon material. Original
The anode particulate of claim 1, wherein said porous carbon matrix or carbon foam is reinforced with a high-strength material selected from carbon nanotubes, carbon nanofibers, carbon or graphite fibers, graphene sheets, expanded graphite flakes, polymer fibrils, glass fibers, ceramic fibers, metal filaments or metal nanowires, whiskers, or a combination thereof. Original
The anode particulate of claim 1, wherein said anode active material is selected from the group consisting of: (a) silicon (Si), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), bismuth (Bi), zinc (Zn), aluminum (Al), titanium (Ti), nickel (Ni), cobalt (Co), and cadmium (Cd); (b) alloys or intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Ni, Co, or Cd with other elements; (c) oxides, carbides, nitrides, sulfides, phosphides, selenides, and tellurides of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Fe, Ni, Co, V, or Cd, and their mixtures, composites, or lithium-containing composites; (d) salts and hydroxides of Sn; (e) lithium titanate, lithium manganate, lithium aluminate, lithium-containing titanium oxide, lithium transition metal oxide; (f) prelithiated versions thereof; (g) particles of Li, Li alloy, or surface-stabilized Li having at least 60% by weight of lithium element therein; and (h) combinations thereof. Original
The anode particulate of claim 1, wherein said anode active material contains a prelithiated Si, prelithiated Ge, prelithiated Sn, prelithiated SnO x, prelithiated SiO x, prelithiated iron oxide, prelithiated V O 2, prelithiated C 030 4, prelithiated Ni 3 0 4, lithium titanate, or a combination thereof, wherein x = 1 to 2. Original
The anode particulate of claim 1, wherein said anode active material is in a form of nano particle, nano wire, nano fiber, nano tube, nano sheet, nano belt, nano ribbon, nano disc, nano platelet, or nano horn having a thickness or diameter from 0.5 nm to 100 nm. Original
The anode particulate of claim 1, wherein at least one of said primary anode active material particles is coated with a layer of carbon, graphite, or graphene disposed between said prima r y particle and said porous carbon foam. Original
The anode particulate of claim 1, wherein said anode particulate further comprises from 0.1% to 40% by weight of a lithium ion-conducting additive dispersed in said thin encapsulating layer or in ionic contact with said anode active material particles encapsulated therein. Currently amended
A mass of anode particulates containing the anode particulate of claim 1. Original
A battery anode containing said anode particulate of claim 1. Currently amended
An anode particulate for a lithium battery, said anode particulate comprising a core and a thin encapsulating layer that encapsulates or embraces said core, wherein said core comprises a single or a plurality of porous primary particles of an anode active material, having a pore volume Vpp and solid volume Va, wherein thin encapsulating layer comprises graphene sheets and has a thickness from 1 nm to 10 p m and an electric conductivity from 10-6 S/cm to 20,000 S/cm and wherein the volume ratio Vpp/Va is from 0.1/1.0 to 10/1.0 and said porous primary particles contain at least one particle that is porous having a free space, in a form of surface pores and/or internal pores, to expand into when said battery is charged. Currently amended
The anode particulate of claim 2, wherein said graphene sheets are selected from pristine graphene, graphene fluoride, graphene chloride, graphene bromide, graphene iodide, nitrogenated graphene, hydrogenated graphene, doped graphene, chemically functionalized graphene, or a combination thereof and wherein said graphene sheets do not include CVD graphene, graphene oxide (GO), and reduced graphene oxide (RGO) Original
The anode particulate of claim 2, wherein said anode active material is selected from the group consisting of: (a) silicon (Si), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), bismuth (Bi), zinc (Zn), aluminum (Al), titanium (Ti), nickel (Ni), cobalt (Co), and cadmium (Cd); (b) alloys or intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Ni, Co, or Cd with other elements; (c) oxides, carbides, nitrides, sulfides, phosphides, selenides, and tellurides of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Fe, Ni, Co, V, or Cd, and their mixtures, composites, or lithium-containing composites; (d) salts and hydroxides of Sn; (e) lithium titanate, lithium manganate, lithium aluminate, lithium-containing titanium oxide, lithium transition metal oxide; (f) prelithiated versions thereof; (g) particles of Li, Li alloy, or surface-stabilized Li having at least 60% by weight of lithium element therein; and (h) combinations thereof. Original
The anode particulate of claim 2, wherein said anode active material contains a prelithiated Si, prelithiated Ge, prelithiated Sn, prelithiated SnO x, prelithiated SiO x, prelithiated iron oxide, prelithiated V O 2, prelithiated C 030 4, prelithiated Ni 3 0 4, lithium titanate, or a combination thereof, wherein x = 1 to 2. Original
The anode particulate of claim 2, wherein said anode active material is in a form of nano particle, nano wire, nano fiber, nano tube, nano sheet, nano belt, nano ribbon, nano disc, nano platelet, or nano horn having a thickness or diameter from 0.5 nm to 100 nm. Original
The anode particulate of claim 2, wherein at least one of said porous primary anode active material particles is coated with a layer of carbon, graphene, or graphite disposed between said primary particle and said encapsulating layer. Original
The anode particulate of claim 2, wherein said anode particulate further comprises from 0.1% to 40% by weight of a lithium ion-conducting additive dispersed in said thin encapsulating layer or in ionic contact with said anode active material particles encapsulated therein Currently amended
A mass of anode particulates containing the anode particulate of claim 2. Original
A battery anode containing said anode particulate of claim 2. Currently amended
Layer stacks claimed or described, ordered top of device to substrate.
anode particulate for lithium battery
battery anode
lithium battery (lithium-ion, lithium metal, lithium-sulfur, lithium-air, or lithium-selenium)
No layer stack recorded.
Materials described outside the worked examples.
anode active material (porous primary particles)
graphene sheets (encapsulating layer)
porous carbon matrix or carbon foam
pristine graphene, graphene fluoride, graphene chloride, graphene bromide, graphene iodide, nitrogenated graphene, hydrogenated graphene, doped graphene, chemically functionalized graphene
graphene oxide (GO) or reduced graphene oxide (RGO)
carbon nanotubes, carbon nanofibers, carbon or graphite fibers, expanded graphite flakes, polymer fibrils, glass fibers, ceramic fibers, metal filaments or metal nanowires, whiskers
anode active material: Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Ni, Co, Cd; alloys; oxides, carbides, nitrides, sulfides, phosphides, selenides, tellurides; lithium titanate, lithium manganate, lithium aluminate; Li, Li alloy
Li alloy containing Zn, Ag, Au, Mg, Ni, Ti, Fe, Co, or V
prelithiated Si, prelithiated Ge, prelithiated Sn, prelithiated SnOx, prelithiated SiOx, prelithiated iron oxide, prelithiated VO2, prelithiated Co₃O4, prelithiated Ni₃O4, lithium titanate
lithium ion-conducting additive (Li₂CO3, Li₂O, Li₂C₂O4, LiOH, LiX, ROCO₂Li, HCOLi, ROLi, (ROCO₂Li)2)
lithium salt (LiClO4, LiPF6, LiBF4, LiAsF6, LiCF₃SO3, LiN(CF₃SO₂)2, LiBOB, LiBF₂C₂O4, LiNO3, LiPF₃(CF₂CF₃)3, LiBETI, LiTFSI, ionic liquid-based lithium salt)
Performance values and ranges asserted in the specification or claims.
| Property | Value | Material |
|---|---|---|
thin encapsulating layer thickness | 1–10000 nm | graphene sheets (encapsulating layer) |
encapsulating layer electric conductivity | 0.000001–20000 S/cm | graphene sheets (encapsulating layer) |
encapsulating layer lithium ion conductivity | 1e-8–0.05 S/cm | graphene sheets (encapsulating layer) |
Thickness | 1–100 nm | — |
Duration | 600–3600 s | — |
Thickness | 5–100 nm | — |
Thickness | 10–100 nm | — |
Temperature | 130–230 °C | — |
Duration | 3–8 hours | — |
Duration | 0.5–3 hours | — |
Duration | 5–120 hours | — |
Temperature | 800–1100 °C | — |
Temperature | 950–1050 °C | — |
Duration | 30–60 minutes | — |
Pressure | 1–50000 mPa | — |
Temperature | 500–1200 °C | — |
Temperature | 700–1500 °C | — |
Thickness | ≤ 1 nm | — |
Thickness | ≤ 10 nm | — |
Duration | ≤ 1 hour | — |
Duration | ≤ 2 hours | — |
Thickness | 0.5–100 nm | — |
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) Schematic illustrating the notion that expansion of Si particles, upon lithium intercalation during charging of a prior art lithium-ion battery, can …
FIG. 3(B) Schematic of the presently invented encapsulated single primary particle of an anode active material (prelithiated or unlithiated). The primary …
FIG. 4 A diagram showing the presently invented process for producing graphene-embraced, polymer-coated electrode active material particles via a continuous …
FIG. 5 The charge-discharge cycling behaviors of 2 lithium cells featuring Co 3 0 4 particle-based anodes: one cell containing graphene-embraced Co 3 0 4 …
FIG. 6 The specific capacity values of 3 lithium-ion cells having Sn₀ 2 particles as the an anode active material: one cell featuring graphene-encapsulated Sn O …
FIG. 7 The specific capacity values of 2 lithium-ion cells each featuring micron-scaled (3 p m) Si particle-based anodes: one cell containing graphene-embraced …
FIG. 8 Specific capacities of 2 lithium-ion cells having a core of Si nanowires (SiNW) embedded in an expanded graphite flake-reinforced carbon foam matrix …
FIG. 9 Cycle life of a lithium-ion cell containing graphene-encapsulated carbon foam matrix- protected porous Si particles, plotted as a function of the total …
FIG. 10 Cycle life of a lithium-ion cell containing graphene-encapsulated porous Sn particles, plotted as a function of the total pore-to-solid ratio in the …
Claims define the patent's legal scope. Independent claims stand alone; dependent claims (nested) narrow them. Click a claim to expand its dependents.
An anode particulate for a lithium battery, said anode particulate comprising a core and a thin encapsulating layer that encapsulates or embraces said core, wherein said core comprises a single or a plurality of porous primary particles of an anode active material, having a pore volume Vpp and solid volume Va, dispersed or embedded in a porous carbon matrix or carbon foam, wherein said porous carbon matrix or carbon foam contains pores having a pore volume Vp, and said thin encapsulating layer comprises graphene sheets and has a thickness from 1 nm to 10 p m, an electric conductivity from 10 -6 S/cm to 20,000 S/cm and a lithium ion conductivity from 10-8 S/cm to 5 x 10-2 S/cm and wherein the volume ratio Vp/Va is from 1.0/1.0 to 10/1.0 or the total pore volume ratio (Vp+Vpp)/Va is from 1.3/1.0 to 20/1.0, and the porous carbon matrix or carbon foam electronically and/or ionically connects the encapsulating layer to the primary particles of the anode active material, wherein said porous primary particles contain at least one particle that is porous having a free space, in a form of surface pores and/or internal pores, to expand into when said battery is charged. Currently amended
The anode particulate of claim 1, wherein said graphene sheets are selected from pristine graphene, graphene fluoride, graphene chloride, graphene bromide, graphene iodide, nitrogenated graphene, hydrogenated graphene, doped graphene, chemically functionalized graphene, a combination thereof, or a combination thereof with graphene oxide or reduced graphene oxide. Original
The anode particulate of claim 1, wherein said graphene sheets are selected from CVD graphene, graphene oxide (GO), or reduced graphene oxide (RGO). Original
The anode particulate of claim 1, wherein said graphene sheets in said encapsulating layer are chemically bonded with a carbon material. Original
The anode particulate of claim 1, wherein said porous carbon matrix or carbon foam is reinforced with a high-strength material selected from carbon nanotubes, carbon nanofibers, carbon or graphite fibers, graphene sheets, expanded graphite flakes, polymer fibrils, glass fibers, ceramic fibers, metal filaments or metal nanowires, whiskers, or a combination thereof. Original
The anode particulate of claim 1, wherein said anode active material is selected from the group consisting of: (a) silicon (Si), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), bismuth (Bi), zinc (Zn), aluminum (Al), titanium (Ti), nickel (Ni), cobalt (Co), and cadmium (Cd); (b) alloys or intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Ni, Co, or Cd with other elements; (c) oxides, carbides, nitrides, sulfides, phosphides, selenides, and tellurides of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Fe, Ni, Co, V, or Cd, and their mixtures, composites, or lithium-containing composites; (d) salts and hydroxides of Sn; (e) lithium titanate, lithium manganate, lithium aluminate, lithium-containing titanium oxide, lithium transition metal oxide; (f) prelithiated versions thereof; (g) particles of Li, Li alloy, or surface-stabilized Li having at least 60% by weight of lithium element therein; and (h) combinations thereof. Original
The anode particulate of claim 1, wherein said anode active material contains a prelithiated Si, prelithiated Ge, prelithiated Sn, prelithiated SnO x, prelithiated SiO x, prelithiated iron oxide, prelithiated V O 2, prelithiated C 030 4, prelithiated Ni 3 0 4, lithium titanate, or a combination thereof, wherein x = 1 to 2. Original
The anode particulate of claim 1, wherein said anode active material is in a form of nano particle, nano wire, nano fiber, nano tube, nano sheet, nano belt, nano ribbon, nano disc, nano platelet, or nano horn having a thickness or diameter from 0.5 nm to 100 nm. Original
The anode particulate of claim 1, wherein at least one of said primary anode active material particles is coated with a layer of carbon, graphite, or graphene disposed between said prima r y particle and said porous carbon foam. Original
The anode particulate of claim 1, wherein said anode particulate further comprises from 0.1% to 40% by weight of a lithium ion-conducting additive dispersed in said thin encapsulating layer or in ionic contact with said anode active material particles encapsulated therein. Currently amended
A mass of anode particulates containing the anode particulate of claim 1. Original
A battery anode containing said anode particulate of claim 1. Currently amended
An anode particulate for a lithium battery, said anode particulate comprising a core and a thin encapsulating layer that encapsulates or embraces said core, wherein said core comprises a single or a plurality of porous primary particles of an anode active material, having a pore volume Vpp and solid volume Va, wherein thin encapsulating layer comprises graphene sheets and has a thickness from 1 nm to 10 p m and an electric conductivity from 10-6 S/cm to 20,000 S/cm and wherein the volume ratio Vpp/Va is from 0.1/1.0 to 10/1.0 and said porous primary particles contain at least one particle that is porous having a free space, in a form of surface pores and/or internal pores, to expand into when said battery is charged. Currently amended
The anode particulate of claim 2, wherein said graphene sheets are selected from pristine graphene, graphene fluoride, graphene chloride, graphene bromide, graphene iodide, nitrogenated graphene, hydrogenated graphene, doped graphene, chemically functionalized graphene, or a combination thereof and wherein said graphene sheets do not include CVD graphene, graphene oxide (GO), and reduced graphene oxide (RGO) Original
The anode particulate of claim 2, wherein said anode active material is selected from the group consisting of: (a) silicon (Si), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), bismuth (Bi), zinc (Zn), aluminum (Al), titanium (Ti), nickel (Ni), cobalt (Co), and cadmium (Cd); (b) alloys or intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Ni, Co, or Cd with other elements; (c) oxides, carbides, nitrides, sulfides, phosphides, selenides, and tellurides of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Fe, Ni, Co, V, or Cd, and their mixtures, composites, or lithium-containing composites; (d) salts and hydroxides of Sn; (e) lithium titanate, lithium manganate, lithium aluminate, lithium-containing titanium oxide, lithium transition metal oxide; (f) prelithiated versions thereof; (g) particles of Li, Li alloy, or surface-stabilized Li having at least 60% by weight of lithium element therein; and (h) combinations thereof. Original
The anode particulate of claim 2, wherein said anode active material contains a prelithiated Si, prelithiated Ge, prelithiated Sn, prelithiated SnO x, prelithiated SiO x, prelithiated iron oxide, prelithiated V O 2, prelithiated C 030 4, prelithiated Ni 3 0 4, lithium titanate, or a combination thereof, wherein x = 1 to 2. Original
The anode particulate of claim 2, wherein said anode active material is in a form of nano particle, nano wire, nano fiber, nano tube, nano sheet, nano belt, nano ribbon, nano disc, nano platelet, or nano horn having a thickness or diameter from 0.5 nm to 100 nm. Original
The anode particulate of claim 2, wherein at least one of said porous primary anode active material particles is coated with a layer of carbon, graphene, or graphite disposed between said primary particle and said encapsulating layer. Original
The anode particulate of claim 2, wherein said anode particulate further comprises from 0.1% to 40% by weight of a lithium ion-conducting additive dispersed in said thin encapsulating layer or in ionic contact with said anode active material particles encapsulated therein Currently amended
A mass of anode particulates containing the anode particulate of claim 2. Original
A battery anode containing said anode particulate of claim 2. Currently amended
Layer stacks claimed or described, ordered top of device to substrate.
anode particulate for lithium battery
battery anode
lithium battery (lithium-ion, lithium metal, lithium-sulfur, lithium-air, or lithium-selenium)
No layer stack recorded.
Materials described outside the worked examples.
anode active material (porous primary particles)
graphene sheets (encapsulating layer)
porous carbon matrix or carbon foam
pristine graphene, graphene fluoride, graphene chloride, graphene bromide, graphene iodide, nitrogenated graphene, hydrogenated graphene, doped graphene, chemically functionalized graphene
graphene oxide (GO) or reduced graphene oxide (RGO)
carbon nanotubes, carbon nanofibers, carbon or graphite fibers, expanded graphite flakes, polymer fibrils, glass fibers, ceramic fibers, metal filaments or metal nanowires, whiskers
anode active material: Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Ni, Co, Cd; alloys; oxides, carbides, nitrides, sulfides, phosphides, selenides, tellurides; lithium titanate, lithium manganate, lithium aluminate; Li, Li alloy
Li alloy containing Zn, Ag, Au, Mg, Ni, Ti, Fe, Co, or V
prelithiated Si, prelithiated Ge, prelithiated Sn, prelithiated SnOx, prelithiated SiOx, prelithiated iron oxide, prelithiated VO2, prelithiated Co₃O4, prelithiated Ni₃O4, lithium titanate
lithium ion-conducting additive (Li₂CO3, Li₂O, Li₂C₂O4, LiOH, LiX, ROCO₂Li, HCOLi, ROLi, (ROCO₂Li)2)
lithium salt (LiClO4, LiPF6, LiBF4, LiAsF6, LiCF₃SO3, LiN(CF₃SO₂)2, LiBOB, LiBF₂C₂O4, LiNO3, LiPF₃(CF₂CF₃)3, LiBETI, LiTFSI, ionic liquid-based lithium salt)
Performance values and ranges asserted in the specification or claims.
| Property | Value | Material |
|---|---|---|
thin encapsulating layer thickness | 1–10000 nm | graphene sheets (encapsulating layer) |
encapsulating layer electric conductivity | 0.000001–20000 S/cm | graphene sheets (encapsulating layer) |
encapsulating layer lithium ion conductivity | 1e-8–0.05 S/cm | graphene sheets (encapsulating layer) |
Thickness | 1–100 nm | — |
Duration | 600–3600 s | — |
Thickness | 5–100 nm | — |
Thickness | 10–100 nm | — |
Temperature | 130–230 °C | — |
Duration | 3–8 hours | — |
Duration | 0.5–3 hours | — |
Duration | 5–120 hours | — |
Temperature | 800–1100 °C | — |
Temperature | 950–1050 °C | — |
Duration | 30–60 minutes | — |
Pressure | 1–50000 mPa | — |
Temperature | 500–1200 °C | — |
Temperature | 700–1500 °C | — |
Thickness | ≤ 1 nm | — |
Thickness | ≤ 10 nm | — |
Duration | ≤ 1 hour | — |
Duration | ≤ 2 hours | — |
Thickness | 0.5–100 nm | — |
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) Schematic illustrating the notion that expansion of Si particles, upon lithium intercalation during charging of a prior art lithium-ion battery, can …
FIG. 3(B) Schematic of the presently invented encapsulated single primary particle of an anode active material (prelithiated or unlithiated). The primary …
FIG. 4 A diagram showing the presently invented process for producing graphene-embraced, polymer-coated electrode active material particles via a continuous …
FIG. 5 The charge-discharge cycling behaviors of 2 lithium cells featuring Co 3 0 4 particle-based anodes: one cell containing graphene-embraced Co 3 0 4 …
FIG. 6 The specific capacity values of 3 lithium-ion cells having Sn₀ 2 particles as the an anode active material: one cell featuring graphene-encapsulated Sn O …
FIG. 7 The specific capacity values of 2 lithium-ion cells each featuring micron-scaled (3 p m) Si particle-based anodes: one cell containing graphene-embraced …
FIG. 8 Specific capacities of 2 lithium-ion cells having a core of Si nanowires (SiNW) embedded in an expanded graphite flake-reinforced carbon foam matrix …
FIG. 9 Cycle life of a lithium-ion cell containing graphene-encapsulated carbon foam matrix- protected porous Si particles, plotted as a function of the total …
FIG. 10 Cycle life of a lithium-ion cell containing graphene-encapsulated porous Sn particles, plotted as a function of the total pore-to-solid ratio in the …
Claims define the patent's legal scope. Independent claims stand alone; dependent claims (nested) narrow them. Click a claim to expand its dependents.
An anode particulate for a lithium battery, said anode particulate comprising a core and a thin encapsulating layer that encapsulates or embraces said core, wherein said core comprises a single or a plurality of porous primary particles of an anode active material, having a pore volume Vpp and solid volume Va, dispersed or embedded in a porous carbon matrix or carbon foam, wherein said porous carbon matrix or carbon foam contains pores having a pore volume Vp, and said thin encapsulating layer comprises graphene sheets and has a thickness from 1 nm to 10 p m, an electric conductivity from 10 -6 S/cm to 20,000 S/cm and a lithium ion conductivity from 10-8 S/cm to 5 x 10-2 S/cm and wherein the volume ratio Vp/Va is from 1.0/1.0 to 10/1.0 or the total pore volume ratio (Vp+Vpp)/Va is from 1.3/1.0 to 20/1.0, and the porous carbon matrix or carbon foam electronically and/or ionically connects the encapsulating layer to the primary particles of the anode active material, wherein said porous primary particles contain at least one particle that is porous having a free space, in a form of surface pores and/or internal pores, to expand into when said battery is charged. Currently amended
The anode particulate of claim 1, wherein said graphene sheets are selected from pristine graphene, graphene fluoride, graphene chloride, graphene bromide, graphene iodide, nitrogenated graphene, hydrogenated graphene, doped graphene, chemically functionalized graphene, a combination thereof, or a combination thereof with graphene oxide or reduced graphene oxide. Original
The anode particulate of claim 1, wherein said graphene sheets are selected from CVD graphene, graphene oxide (GO), or reduced graphene oxide (RGO). Original
The anode particulate of claim 1, wherein said graphene sheets in said encapsulating layer are chemically bonded with a carbon material. Original
The anode particulate of claim 1, wherein said porous carbon matrix or carbon foam is reinforced with a high-strength material selected from carbon nanotubes, carbon nanofibers, carbon or graphite fibers, graphene sheets, expanded graphite flakes, polymer fibrils, glass fibers, ceramic fibers, metal filaments or metal nanowires, whiskers, or a combination thereof. Original
The anode particulate of claim 1, wherein said anode active material is selected from the group consisting of: (a) silicon (Si), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), bismuth (Bi), zinc (Zn), aluminum (Al), titanium (Ti), nickel (Ni), cobalt (Co), and cadmium (Cd); (b) alloys or intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Ni, Co, or Cd with other elements; (c) oxides, carbides, nitrides, sulfides, phosphides, selenides, and tellurides of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Fe, Ni, Co, V, or Cd, and their mixtures, composites, or lithium-containing composites; (d) salts and hydroxides of Sn; (e) lithium titanate, lithium manganate, lithium aluminate, lithium-containing titanium oxide, lithium transition metal oxide; (f) prelithiated versions thereof; (g) particles of Li, Li alloy, or surface-stabilized Li having at least 60% by weight of lithium element therein; and (h) combinations thereof. Original
The anode particulate of claim 1, wherein said anode active material contains a prelithiated Si, prelithiated Ge, prelithiated Sn, prelithiated SnO x, prelithiated SiO x, prelithiated iron oxide, prelithiated V O 2, prelithiated C 030 4, prelithiated Ni 3 0 4, lithium titanate, or a combination thereof, wherein x = 1 to 2. Original
The anode particulate of claim 1, wherein said anode active material is in a form of nano particle, nano wire, nano fiber, nano tube, nano sheet, nano belt, nano ribbon, nano disc, nano platelet, or nano horn having a thickness or diameter from 0.5 nm to 100 nm. Original
The anode particulate of claim 1, wherein at least one of said primary anode active material particles is coated with a layer of carbon, graphite, or graphene disposed between said prima r y particle and said porous carbon foam. Original
The anode particulate of claim 1, wherein said anode particulate further comprises from 0.1% to 40% by weight of a lithium ion-conducting additive dispersed in said thin encapsulating layer or in ionic contact with said anode active material particles encapsulated therein. Currently amended
A mass of anode particulates containing the anode particulate of claim 1. Original
A battery anode containing said anode particulate of claim 1. Currently amended
An anode particulate for a lithium battery, said anode particulate comprising a core and a thin encapsulating layer that encapsulates or embraces said core, wherein said core comprises a single or a plurality of porous primary particles of an anode active material, having a pore volume Vpp and solid volume Va, wherein thin encapsulating layer comprises graphene sheets and has a thickness from 1 nm to 10 p m and an electric conductivity from 10-6 S/cm to 20,000 S/cm and wherein the volume ratio Vpp/Va is from 0.1/1.0 to 10/1.0 and said porous primary particles contain at least one particle that is porous having a free space, in a form of surface pores and/or internal pores, to expand into when said battery is charged. Currently amended
The anode particulate of claim 2, wherein said graphene sheets are selected from pristine graphene, graphene fluoride, graphene chloride, graphene bromide, graphene iodide, nitrogenated graphene, hydrogenated graphene, doped graphene, chemically functionalized graphene, or a combination thereof and wherein said graphene sheets do not include CVD graphene, graphene oxide (GO), and reduced graphene oxide (RGO) Original
The anode particulate of claim 2, wherein said anode active material is selected from the group consisting of: (a) silicon (Si), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), bismuth (Bi), zinc (Zn), aluminum (Al), titanium (Ti), nickel (Ni), cobalt (Co), and cadmium (Cd); (b) alloys or intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Ni, Co, or Cd with other elements; (c) oxides, carbides, nitrides, sulfides, phosphides, selenides, and tellurides of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Fe, Ni, Co, V, or Cd, and their mixtures, composites, or lithium-containing composites; (d) salts and hydroxides of Sn; (e) lithium titanate, lithium manganate, lithium aluminate, lithium-containing titanium oxide, lithium transition metal oxide; (f) prelithiated versions thereof; (g) particles of Li, Li alloy, or surface-stabilized Li having at least 60% by weight of lithium element therein; and (h) combinations thereof. Original
The anode particulate of claim 2, wherein said anode active material contains a prelithiated Si, prelithiated Ge, prelithiated Sn, prelithiated SnO x, prelithiated SiO x, prelithiated iron oxide, prelithiated V O 2, prelithiated C 030 4, prelithiated Ni 3 0 4, lithium titanate, or a combination thereof, wherein x = 1 to 2. Original
The anode particulate of claim 2, wherein said anode active material is in a form of nano particle, nano wire, nano fiber, nano tube, nano sheet, nano belt, nano ribbon, nano disc, nano platelet, or nano horn having a thickness or diameter from 0.5 nm to 100 nm. Original
The anode particulate of claim 2, wherein at least one of said porous primary anode active material particles is coated with a layer of carbon, graphene, or graphite disposed between said primary particle and said encapsulating layer. Original
The anode particulate of claim 2, wherein said anode particulate further comprises from 0.1% to 40% by weight of a lithium ion-conducting additive dispersed in said thin encapsulating layer or in ionic contact with said anode active material particles encapsulated therein Currently amended
A mass of anode particulates containing the anode particulate of claim 2. Original
A battery anode containing said anode particulate of claim 2. Currently amended
Layer stacks claimed or described, ordered top of device to substrate.
anode particulate for lithium battery
battery anode
lithium battery (lithium-ion, lithium metal, lithium-sulfur, lithium-air, or lithium-selenium)
No layer stack recorded.
Materials described outside the worked examples.
anode active material (porous primary particles)
graphene sheets (encapsulating layer)
porous carbon matrix or carbon foam
pristine graphene, graphene fluoride, graphene chloride, graphene bromide, graphene iodide, nitrogenated graphene, hydrogenated graphene, doped graphene, chemically functionalized graphene
graphene oxide (GO) or reduced graphene oxide (RGO)
carbon nanotubes, carbon nanofibers, carbon or graphite fibers, expanded graphite flakes, polymer fibrils, glass fibers, ceramic fibers, metal filaments or metal nanowires, whiskers
anode active material: Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Ni, Co, Cd; alloys; oxides, carbides, nitrides, sulfides, phosphides, selenides, tellurides; lithium titanate, lithium manganate, lithium aluminate; Li, Li alloy
Li alloy containing Zn, Ag, Au, Mg, Ni, Ti, Fe, Co, or V
prelithiated Si, prelithiated Ge, prelithiated Sn, prelithiated SnOx, prelithiated SiOx, prelithiated iron oxide, prelithiated VO2, prelithiated Co₃O4, prelithiated Ni₃O4, lithium titanate
lithium ion-conducting additive (Li₂CO3, Li₂O, Li₂C₂O4, LiOH, LiX, ROCO₂Li, HCOLi, ROLi, (ROCO₂Li)2)
lithium salt (LiClO4, LiPF6, LiBF4, LiAsF6, LiCF₃SO3, LiN(CF₃SO₂)2, LiBOB, LiBF₂C₂O4, LiNO3, LiPF₃(CF₂CF₃)3, LiBETI, LiTFSI, ionic liquid-based lithium salt)
Performance values and ranges asserted in the specification or claims.
| Property | Value | Material |
|---|---|---|
thin encapsulating layer thickness | 1–10000 nm | graphene sheets (encapsulating layer) |
encapsulating layer electric conductivity | 0.000001–20000 S/cm | graphene sheets (encapsulating layer) |
encapsulating layer lithium ion conductivity | 1e-8–0.05 S/cm | graphene sheets (encapsulating layer) |
Thickness | 1–100 nm | — |
Duration | 600–3600 s | — |
Thickness | 5–100 nm | — |
Thickness | 10–100 nm | — |
Temperature | 130–230 °C | — |
Duration | 3–8 hours | — |
Duration | 0.5–3 hours | — |
Duration | 5–120 hours | — |
Temperature | 800–1100 °C | — |
Temperature | 950–1050 °C | — |
Duration | 30–60 minutes | — |
Pressure | 1–50000 mPa | — |
Temperature | 500–1200 °C | — |
Temperature | 700–1500 °C | — |
Thickness | ≤ 1 nm | — |
Thickness | ≤ 10 nm | — |
Duration | ≤ 1 hour | — |
Duration | ≤ 2 hours | — |
Thickness | 0.5–100 nm | — |
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) Schematic illustrating the notion that expansion of Si particles, upon lithium intercalation during charging of a prior art lithium-ion battery, can …
FIG. 3(B) Schematic of the presently invented encapsulated single primary particle of an anode active material (prelithiated or unlithiated). The primary …
FIG. 4 A diagram showing the presently invented process for producing graphene-embraced, polymer-coated electrode active material particles via a continuous …
FIG. 5 The charge-discharge cycling behaviors of 2 lithium cells featuring Co 3 0 4 particle-based anodes: one cell containing graphene-embraced Co 3 0 4 …
FIG. 6 The specific capacity values of 3 lithium-ion cells having Sn₀ 2 particles as the an anode active material: one cell featuring graphene-encapsulated Sn O …
FIG. 7 The specific capacity values of 2 lithium-ion cells each featuring micron-scaled (3 p m) Si particle-based anodes: one cell containing graphene-embraced …
FIG. 8 Specific capacities of 2 lithium-ion cells having a core of Si nanowires (SiNW) embedded in an expanded graphite flake-reinforced carbon foam matrix …
FIG. 9 Cycle life of a lithium-ion cell containing graphene-encapsulated carbon foam matrix- protected porous Si particles, plotted as a function of the total …
FIG. 10 Cycle life of a lithium-ion cell containing graphene-encapsulated porous Sn particles, plotted as a function of the total pore-to-solid ratio in the …
Claims define the patent's legal scope. Independent claims stand alone; dependent claims (nested) narrow them. Click a claim to expand its dependents.
An anode particulate for a lithium battery, said anode particulate comprising a core and a thin encapsulating layer that encapsulates or embraces said core, wherein said core comprises a single or a plurality of porous primary particles of an anode active material, having a pore volume Vpp and solid volume Va, dispersed or embedded in a porous carbon matrix or carbon foam, wherein said porous carbon matrix or carbon foam contains pores having a pore volume Vp, and said thin encapsulating layer comprises graphene sheets and has a thickness from 1 nm to 10 p m, an electric conductivity from 10 -6 S/cm to 20,000 S/cm and a lithium ion conductivity from 10-8 S/cm to 5 x 10-2 S/cm and wherein the volume ratio Vp/Va is from 1.0/1.0 to 10/1.0 or the total pore volume ratio (Vp+Vpp)/Va is from 1.3/1.0 to 20/1.0, and the porous carbon matrix or carbon foam electronically and/or ionically connects the encapsulating layer to the primary particles of the anode active material, wherein said porous primary particles contain at least one particle that is porous having a free space, in a form of surface pores and/or internal pores, to expand into when said battery is charged. Currently amended
The anode particulate of claim 1, wherein said graphene sheets are selected from pristine graphene, graphene fluoride, graphene chloride, graphene bromide, graphene iodide, nitrogenated graphene, hydrogenated graphene, doped graphene, chemically functionalized graphene, a combination thereof, or a combination thereof with graphene oxide or reduced graphene oxide. Original
The anode particulate of claim 1, wherein said graphene sheets are selected from CVD graphene, graphene oxide (GO), or reduced graphene oxide (RGO). Original
The anode particulate of claim 1, wherein said graphene sheets in said encapsulating layer are chemically bonded with a carbon material. Original
The anode particulate of claim 1, wherein said porous carbon matrix or carbon foam is reinforced with a high-strength material selected from carbon nanotubes, carbon nanofibers, carbon or graphite fibers, graphene sheets, expanded graphite flakes, polymer fibrils, glass fibers, ceramic fibers, metal filaments or metal nanowires, whiskers, or a combination thereof. Original
The anode particulate of claim 1, wherein said anode active material is selected from the group consisting of: (a) silicon (Si), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), bismuth (Bi), zinc (Zn), aluminum (Al), titanium (Ti), nickel (Ni), cobalt (Co), and cadmium (Cd); (b) alloys or intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Ni, Co, or Cd with other elements; (c) oxides, carbides, nitrides, sulfides, phosphides, selenides, and tellurides of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Fe, Ni, Co, V, or Cd, and their mixtures, composites, or lithium-containing composites; (d) salts and hydroxides of Sn; (e) lithium titanate, lithium manganate, lithium aluminate, lithium-containing titanium oxide, lithium transition metal oxide; (f) prelithiated versions thereof; (g) particles of Li, Li alloy, or surface-stabilized Li having at least 60% by weight of lithium element therein; and (h) combinations thereof. Original
The anode particulate of claim 1, wherein said anode active material contains a prelithiated Si, prelithiated Ge, prelithiated Sn, prelithiated SnO x, prelithiated SiO x, prelithiated iron oxide, prelithiated V O 2, prelithiated C 030 4, prelithiated Ni 3 0 4, lithium titanate, or a combination thereof, wherein x = 1 to 2. Original
The anode particulate of claim 1, wherein said anode active material is in a form of nano particle, nano wire, nano fiber, nano tube, nano sheet, nano belt, nano ribbon, nano disc, nano platelet, or nano horn having a thickness or diameter from 0.5 nm to 100 nm. Original
The anode particulate of claim 1, wherein at least one of said primary anode active material particles is coated with a layer of carbon, graphite, or graphene disposed between said prima r y particle and said porous carbon foam. Original
The anode particulate of claim 1, wherein said anode particulate further comprises from 0.1% to 40% by weight of a lithium ion-conducting additive dispersed in said thin encapsulating layer or in ionic contact with said anode active material particles encapsulated therein. Currently amended
A mass of anode particulates containing the anode particulate of claim 1. Original
A battery anode containing said anode particulate of claim 1. Currently amended
An anode particulate for a lithium battery, said anode particulate comprising a core and a thin encapsulating layer that encapsulates or embraces said core, wherein said core comprises a single or a plurality of porous primary particles of an anode active material, having a pore volume Vpp and solid volume Va, wherein thin encapsulating layer comprises graphene sheets and has a thickness from 1 nm to 10 p m and an electric conductivity from 10-6 S/cm to 20,000 S/cm and wherein the volume ratio Vpp/Va is from 0.1/1.0 to 10/1.0 and said porous primary particles contain at least one particle that is porous having a free space, in a form of surface pores and/or internal pores, to expand into when said battery is charged. Currently amended
The anode particulate of claim 2, wherein said graphene sheets are selected from pristine graphene, graphene fluoride, graphene chloride, graphene bromide, graphene iodide, nitrogenated graphene, hydrogenated graphene, doped graphene, chemically functionalized graphene, or a combination thereof and wherein said graphene sheets do not include CVD graphene, graphene oxide (GO), and reduced graphene oxide (RGO) Original
The anode particulate of claim 2, wherein said anode active material is selected from the group consisting of: (a) silicon (Si), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), bismuth (Bi), zinc (Zn), aluminum (Al), titanium (Ti), nickel (Ni), cobalt (Co), and cadmium (Cd); (b) alloys or intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Ni, Co, or Cd with other elements; (c) oxides, carbides, nitrides, sulfides, phosphides, selenides, and tellurides of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Fe, Ni, Co, V, or Cd, and their mixtures, composites, or lithium-containing composites; (d) salts and hydroxides of Sn; (e) lithium titanate, lithium manganate, lithium aluminate, lithium-containing titanium oxide, lithium transition metal oxide; (f) prelithiated versions thereof; (g) particles of Li, Li alloy, or surface-stabilized Li having at least 60% by weight of lithium element therein; and (h) combinations thereof. Original
The anode particulate of claim 2, wherein said anode active material contains a prelithiated Si, prelithiated Ge, prelithiated Sn, prelithiated SnO x, prelithiated SiO x, prelithiated iron oxide, prelithiated V O 2, prelithiated C 030 4, prelithiated Ni 3 0 4, lithium titanate, or a combination thereof, wherein x = 1 to 2. Original
The anode particulate of claim 2, wherein said anode active material is in a form of nano particle, nano wire, nano fiber, nano tube, nano sheet, nano belt, nano ribbon, nano disc, nano platelet, or nano horn having a thickness or diameter from 0.5 nm to 100 nm. Original
The anode particulate of claim 2, wherein at least one of said porous primary anode active material particles is coated with a layer of carbon, graphene, or graphite disposed between said primary particle and said encapsulating layer. Original
The anode particulate of claim 2, wherein said anode particulate further comprises from 0.1% to 40% by weight of a lithium ion-conducting additive dispersed in said thin encapsulating layer or in ionic contact with said anode active material particles encapsulated therein Currently amended
A mass of anode particulates containing the anode particulate of claim 2. Original
A battery anode containing said anode particulate of claim 2. Currently amended
Layer stacks claimed or described, ordered top of device to substrate.
anode particulate for lithium battery
battery anode
lithium battery (lithium-ion, lithium metal, lithium-sulfur, lithium-air, or lithium-selenium)
No layer stack recorded.
Materials described outside the worked examples.
anode active material (porous primary particles)
graphene sheets (encapsulating layer)
porous carbon matrix or carbon foam
pristine graphene, graphene fluoride, graphene chloride, graphene bromide, graphene iodide, nitrogenated graphene, hydrogenated graphene, doped graphene, chemically functionalized graphene
graphene oxide (GO) or reduced graphene oxide (RGO)
carbon nanotubes, carbon nanofibers, carbon or graphite fibers, expanded graphite flakes, polymer fibrils, glass fibers, ceramic fibers, metal filaments or metal nanowires, whiskers
anode active material: Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Ni, Co, Cd; alloys; oxides, carbides, nitrides, sulfides, phosphides, selenides, tellurides; lithium titanate, lithium manganate, lithium aluminate; Li, Li alloy
Li alloy containing Zn, Ag, Au, Mg, Ni, Ti, Fe, Co, or V
prelithiated Si, prelithiated Ge, prelithiated Sn, prelithiated SnOx, prelithiated SiOx, prelithiated iron oxide, prelithiated VO2, prelithiated Co₃O4, prelithiated Ni₃O4, lithium titanate
lithium ion-conducting additive (Li₂CO3, Li₂O, Li₂C₂O4, LiOH, LiX, ROCO₂Li, HCOLi, ROLi, (ROCO₂Li)2)
lithium salt (LiClO4, LiPF6, LiBF4, LiAsF6, LiCF₃SO3, LiN(CF₃SO₂)2, LiBOB, LiBF₂C₂O4, LiNO3, LiPF₃(CF₂CF₃)3, LiBETI, LiTFSI, ionic liquid-based lithium salt)
Performance values and ranges asserted in the specification or claims.
| Property | Value | Material |
|---|---|---|
thin encapsulating layer thickness | 1–10000 nm | graphene sheets (encapsulating layer) |
encapsulating layer electric conductivity | 0.000001–20000 S/cm | graphene sheets (encapsulating layer) |
encapsulating layer lithium ion conductivity | 1e-8–0.05 S/cm | graphene sheets (encapsulating layer) |
Thickness | 1–100 nm | — |
Duration | 600–3600 s | — |
Thickness | 5–100 nm | — |
Thickness | 10–100 nm | — |
Temperature | 130–230 °C | — |
Duration | 3–8 hours | — |
Duration | 0.5–3 hours | — |
Duration | 5–120 hours | — |
Temperature | 800–1100 °C | — |
Temperature | 950–1050 °C | — |
Duration | 30–60 minutes | — |
Pressure | 1–50000 mPa | — |
Temperature | 500–1200 °C | — |
Temperature | 700–1500 °C | — |
Thickness | ≤ 1 nm | — |
Thickness | ≤ 10 nm | — |
Duration | ≤ 1 hour | — |
Duration | ≤ 2 hours | — |
Thickness | 0.5–100 nm | — |