Method for preparing biomass graphene by using cellulose as raw material

• US 10,494,263 B2
• Filed: 01/21/2016
• Issued: 12/03/2019
• Est. Priority Date: 03/04/2015
• Status: Active Grant

• Current Assignee: Heilongjiang University, Jinan Shengquan Group Share-Holding Company Limited
• Original Assignee: Heilongjiang University
• Inventors: Fu, Honggang, Wang, Lei, Tang, Yilin, Zhang, Jinzhu, Zheng, Yingfu, Jiang, Baojiang
• Primary Examiner(s): McCracken, Daniel C.
• Application Number:
  US15/555,289
• Publication Number:
  US 20180037460A1
• Time in Patent Office: 1,412 Days
• CPC Class Codes: B01J 27/043 with iron group metals or platinum group metals
• CPC Class Codes: B01J 27/128 with iron group metals or platinum group metals
• CPC Class Codes: B01J 27/26 Cyanides
• CPC Class Codes: C01B 32/184 Preparation
• CPC Class Codes: C08B 15/08 Fractionation of cellulose, e.g. separation of cellulose crystallites
• CPC Class Codes: G01N 21/65 Raman scattering

Abstract

A method for preparing biomass graphene by using cellulose as a raw material includes preparing a catalyst solution, carrying out ionic coordination and high-temperature deoxidization on cellulose and a catalyst so as to obtain a precursor, carrying out thermal treatment and pre-carbonization, and carrying out acid treatment and drying to obtain the graphene. The graphene is uniform in morphology with a single-layer or multi-layer two-dimensional layered structure having a dimension of 0.5 μm to 2 μm, and an electric conductivity of 25000 S/m to 45000 S/m. The graphene can be applied to electrode materials of super capacitors and lithium ion batteries, and can also be added to resin and rubber as an additive so as to improve physical properties of the resin and the rubber.

Claims

1. A method for preparing biomass graphene using cellulose as a raw material, comprising:

preparing a catalyst solution, wherein a catalyst is added to distilled water to form a first mixture, the first mixture is stirred for 10 to 30 min to form a catalyst solution, in which the ratio of catalyst to solvent is within 2;

100 to 35;

100;

preparation a precursor, wherein a biomass cellulose is added to the catalyst solution to form a second mixture, the second mixture is stirred for 1 to 4 hours then deoxidized at a high temperature and dried to obtain a precursor, in which the mass ratio of cellulose to solvent is within 3;

100 to 40;

100;

heat-treating the precursor including a pre-carbonization step and a secondary carbonization step, wherein the pre-carbonization step includes heating the precursor to within 220 to 650°

C. at 10 to 20°

C./min for 1 to 6 hours in an atmosphere including at least one of nitrogen gas, argon gas, and hydrogen gas to obtain a pre-carbonized precursor, and the secondary carbonization step includes heating the pre-carbonized precursor to within 900 to 1650°

C. at 5 to 16°

C./min for 4 to 15 hours to obtain a heat-treated product; and

obtaining graphene, wherein the heat-treated product is acid-treated, centrifuged, washed with distilled water to neutral, and dried at 80-110°

C. to obtain graphene.

2. The method of claim 1, wherein the biomass cellulose is at least one of cellulose extracted from corncobs, corn stalks, sorghum stalks, soybean stalks, stems or leaves of cattail, coconut shells, and palm shells.

3. The method of claim 1, wherein the catalyst is at least one of FeCl₂, FeCl₃, K₃[Fe(CN)₆], and K₄[Fe(CN)₆].

4. The method of claim 1, wherein the first mixture is stirred for 13 to 25 minutes, and the ratio of catalyst to solvent being within 3:

100 to 25;

100.

5. The method of claim 4, wherein the first mixture is stirred for 15 to 20 minutes, and the ratio of catalyst to solvent being within 4:

100 to 15;

100.

6. The method of claim 1, wherein the second mixture is stirred for 2 to 3 hours, and the deoxidation is conducted at one of 110 to 205°

C. for 6 to 16 hours and 110 to 170°

C. for 5 minutes to 2 hours at 3-9 kW in microwave strength.

7. The method of claim 6, wherein the deoxidation is conducted at one of 120 to 180°

C. for 8 to 12 hours and 130 to 160°

C. for 20 minutes to 1.5 hours at 4 to 7 kW in microwave strength.

8. The method of claim 1, wherein the pre-carbonization step includes heating the precursor to within 300 to 450°

C. at 11 to 16°

C./min for 2 to 5 hours, and the secondary carbonization step includes heating the pre-carbonized precursor to within 1000 to 1550°

C. at 5 to 12°

C./min for 5 to 10 hours.

9. The method of claim 8, wherein the pre-carbonization step includes heating the precursor to within 330 to 420°

C. at 12 to 16°

C./min for 2 to 4 hours, and the secondary carbonization step includes heating the pre-carbonized precursor to within 1050 to 1450°

C. at 6 to 12°

C./min for 5 to 8 hours.

10. The method of claim 1, wherein acid-treating is performed with acid comprising at least sulfuric acid, perchloric acid, and nitric acid, and drying is performed between 90 to 105°

C.