Processes for the preparation of expanded graphite and exfoliated graphene oxide

Patent metadata

Field	Value
Publication number	US-12552672-B2
Application number	US-202118026167-A
Country	US
Kind code	B2
Filing date	Sep 20, 2021
Priority date	Sep 18, 2020
Publication date	Feb 17, 2026
Grant date	Feb 17, 2026

Abstract

The present application relates to expanded graphite and exfoliated graphene oxide. More specifically, the present application relates to process for their preparation and uses thereof. The present application includes a process for preparing expanded graphite comprising: mixing graphite with H2SO4/H3PO4 to form a first mixture; adding KMnO4 to the first mixture to form a second and mixture; adding at least one Fe(III) salt to the second mixture under conditions to form a solid graphite-intercalated compound; separating the solid graphite-intercalated compound from the second mixture; and heating the solid graphite-intercalated compound under conditions to provide the expanded graphite. The present application also includes a process for preparing exfoliated graphene oxide comprising: compressing expanded graphite to form a flexible graphite foil; immersing the flexible graphite foil in a solution comprising at least one alkali metal hydroxide and optionally at least one oxidizing agent, and applying voltage under conditions to electrochemically exfoliate the flexible graphite foil to provide the exfoliated graphene oxide.

First claim

The invention claimed is:

1 . A process for preparing expanded graphite comprising:
a) mixing graphite with H 2 SO 4 /H 3 PO 4 to form a first mixture; b) adding KMnO 4 to the first mixture to form a second mixture; c) adding at least one Fe(III) salt to the second mixture under conditions to form a solid graphite-intercalated compound; d) separating the solid graphite-intercalated compound from the second mixture; and e) heating the solid graphite-intercalated compound under conditions to provide the expanded graphite.

2 . The process of claim 1 , wherein a) and/or b) and/or c) is carried out at a temperature from about 0° C. to about 40° C.

3 . The process of claim 1 , wherein the H 2 SO 4 /H 3 PO 4 is present in a ratio of at least 10:1 mL:grams of graphite.

4 . The process of claim 1 , wherein the H 2 SO 4 /H 3 PO 4 is present in a volume ratio of H 2 SO 4 :H 3 PO 4 of 10-x:x, where x is equal to 0.1 to 4.

5 . The process of claim 1 , wherein the KMnO 4 is present in a ratio (w/w) of about 1:1 to about 4:1 KMnO 4 :graphite.

6 . The process of claim 1 , wherein the at least one Fe(III) salt is selected from the group consisting of FeCl 3 , Fe(NO 3 ) 3 and Fe 2 (SO 4 ) 3 and their hydrates.

7 . The process of claim 1 , wherein the at least one Fe(III) salt is in a ratio (w/w) of about 0.25:1 to about 2:1, Fe(III) salt:graphite.

8 . The process of claim 1 , wherein the graphite is graphite powder.

9 . The process of claim 1 , further comprising rinsing and/or drying the graphite-intercalated compound prior to e).

10 . The process of claim 1 , wherein e) is carried out at a temperature of about 350° C. to about 800° C.

11 . The process of claim 1 , wherein the expanded graphite is prepared in the absence of binder.

12 . The process of claim 1 , wherein the expanded graphite has an about 20 to about 100 times volume expansion from the graphite.

13 . A process for preparing exfoliated graphene oxide comprising:
a) compressing expanded graphite to form a flexible graphite foil; b) immersing the flexible graphite foil in a solution comprising at least one alkali metal hydroxide and optionally at least one oxidizing agent, and applying a first voltage; c) removing at least a portion of the flexible graphite foil from the solution; d) re-immersing the flexible graphite foil in the solution and applying a second voltage under conditions to electrochemically exfoliate the flexible graphite foil to provide the exfoliated graphene oxide.

14 . The process of claim 13 , wherein the at least one alkali metal hydroxide is selected from NaOH, LiOH, KOH, or mixtures thereof.

15 . The process of claim 13 , wherein the at least one oxidizing agent, when present, is H 2 O 2 .

16 . The process of claim 13 , wherein the first voltage is about +0.1 to about +3 V.

17 . The process of claim 16 , wherein the second voltage is greater than +3 V.

18 . The process of claim 13 , wherein the exfoliated graphene oxide has an oxygen content of about 15% to about 30%.

19 . The process of claim 16 , wherein at least step d) is carried out by an automated system.

20 . The process of claim 16 , wherein steps b), c) and d) are carried out by an automated system.

21 . A process for preparing exfoliated graphene oxide comprising:
a) mixing graphite with H 2 SO 4 /H 3 PO 4 to form a first mixture; b) adding KMnO 4 to the first mixture to form a second mixture; c) adding at least one Fe(III) salt to the second mixture under conditions to form a solid graphite-intercalated compound; d) separating the solid graphite-intercalated compound from the second mixture; e) heating the solid graphite-intercalated compound under conditions to provide expanded graphite; f) compressing the expanded graphite to form a flexible graphite foil; g) immersing the flexible graphite foil in a solution comprising at least one alkali metal hydroxide and optionally at least one oxidizing agent, and applying a first voltage; h) removing at least a portion of the flexible graphite foil from the solution; i) re-immersing the flexible graphite foil in the solution and applying a second voltage under conditions to electrochemically exfoliate the flexible graphite foil to provide the exfoliated graphene oxide.

Assignees

• Univ Guelph
• Zen Graphene Solutions Ltd

Inventors

• Chen Aicheng
• Salverda Michael
• Thiruppathi Antony Raj
• Sidhureddy Boopathi
• Rahmati Farnood

Classifications

• C01B32/225

  Expansion; Exfoliation · CPC title

• C01B32/19

  by exfoliation · CPC title

• Y02E60/10

  Energy storage using batteries · CPC title

• C30B7/12

  by electrolysis · CPC title

• C01B32/198 Primary

  Graphene oxide · CPC title