Fluorinated graphene and preparation method thereof
The present invention relates to a preparation method of fluorinated graphene. The method for preparing fluorinated graphene, including the following steps: S1), under the protection of inert gas, the graphene undergoes a fluorination reaction with a first fluorinating agent, the reaction temperature is 150-550° C., the reaction time is 2-20 h, and a fluorinated graphene crude product is obtained. The graphene is graphene powder, or a graphene film; the first fluorinating agent includes fluorine gas; S2), under the protection of inert gas, the fluorinated graphene crude product undergoes a fluorination reaction with a second fluorinating agent, the reaction temperature is 150-400° C., the reaction time is 2-10 h, and a fluorinated graphene is obtained. The second fluorinating agent is gas-phase fluoride. By using the method, fluorinated graphene having a high fluorine content can be prepared, the fluorine content is close to the theoretical level, and the defect density is low.
1. A preparation method of fluorinated graphene, comprising:
S1), under the protection of an inert gas, performing a first fluorination reaction between a graphene and a first fluorinating agent, wherein a reaction temperature is 150-550° C., a reaction time is 2-20 h, and a fluorinated graphene crude product is obtained; and wherein the graphene is graphene powder, or a graphene film; and the first fluorinating agent comprises a fluorine gas; and next
S2), under the protection of an inert gas, performing a second fluorination reaction between the fluorinated graphene crude product and a second fluorinating agent, wherein the reaction temperature is 150-400° C., the reaction time is 2-10 h, and a fluorinated graphene is obtained; and wherein the second fluorinating agent is a gas-phase fluoride.
2. The preparation method according to claim 1 , wherein the step S1) is specifically as follows:
under the protection of the inert gas, mixed gas of the fluorine gas and the inert gas is introduced into a surface of the graphene continuously to perform the first fluorination reaction; and a volume ratio of the fluorine gas to the mixed gas is (1-30):100.
3. The preparation method according to claim 2 , wherein the step S2) is specifically as follows:
under the protection of the inert gas, mixed gas of the gas-phase fluoride and the inert gas is introduced to a surface of the fluorinated graphene crude product to perform the second fluorination reaction; and a volume ratio of the gas-phase fluoride to the mixed gas is (20-80):100.
4. The preparation method according to claim 3 , wherein the gas-phase fluoride is one or more selected from the group consisting of phosphorus trifluoride, bromine trifluoride, iodine trifluoride, sulfur tetrafluoride, anhydrous hydrogen fluoride, boron trifluoride, nitrogen trifluoride, sulfuryl fluoride-trimethylamine, sulfuryl fluoride-dimethylamine, sulfuryl fluoride-monomethylamine, sulfuryl fluoride-ammonia, sulfuryl fluoride, thionyl fluoride-trimethylamine, thionyl fluoride-dimethylamine, thionyl fluoride-monomethylamine, thionyl fluoride-ammonia, thionyl fluoride, and antimony pentafluoride.
5. The preparation method according to claim 1 , wherein before step S1), the preparation method further comprises:
S0), heating the graphene at a temperature of 200-300° C. for 2-4 h under an inert gas atmosphere.
6. The preparation method according to claim 1 , wherein after step S2), the preparation method further comprises: performing water-washing, alcohol-washing and drying on the fluorinated graphene sequentially.
7. The preparation method according to claim 1 , wherein in the step S1), the first fluorinating agent further comprises fluorination catalyst gas;
the fluorination catalyst gas comprises one or more selected from the group consisting of phosphorus trifluoride, bromine trifluoride, iodine trifluoride, sulfur tetrafluoride, anhydrous hydrogen fluoride, boron trifluoride, nitrogen trifluoride, sulfuryl fluoride-trimethylamine, sulfuryl fluoride-dimethylamine, sulfuryl fluoride-monomethylamine, sulfuryl fluoride-ammonia, sulfuryl fluoride, thionyl fluoride-trimethylamine, thionyl fluoride-dimethylamine, thionyl fluoride-monomethylamine, thionyl fluoride-ammonia, thionyl fluoride, and antimony pentafluoride; and a volume ratio of the fluorination catalyst gas to first fluorination agent gas is (20-80):100.
8. The preparation method according to claim 7 , wherein in the step S1), the reaction temperature is 150-400° C.
9. The preparation method according to claim 2 , wherein in the step S1), the first fluorinating agent further comprises fluorination catalyst gas;
the fluorination catalyst gas comprises one or more selected from the group consisting of phosphorus trifluoride, bromine trifluoride, iodine trifluoride, sulfur tetrafluoride, anhydrous hydrogen fluoride, boron trifluoride, nitrogen trifluoride, sulfuryl fluoride-trimethylamine, sulfuryl fluoride-dimethylamine, sulfuryl fluoride-monomethylamine, sulfuryl fluoride-ammonia, sulfuryl fluoride, thionyl fluoride-trimethylamine, thionyl fluoride-dimethylamine, thionyl fluoride-monomethylamine, thionyl fluoride-ammonia, thionyl fluoride, and antimony pentafluoride; and a volume ratio of the fluorination catalyst gas to first fluorination agent gas is (20-80):100.
10. The preparation method according to claim 3 , wherein in the step S1), the first fluorinating agent further comprises fluorination catalyst gas;
the fluorination catalyst gas comprises one or more selected from the group consisting of phosphorus trifluoride, bromine trifluoride, iodine trifluoride, sulfur tetrafluoride, anhydrous hydrogen fluoride, boron trifluoride, nitrogen trifluoride, sulfuryl fluoride-trimethylamine, sulfuryl fluoride-dimethylamine, sulfuryl fluoride-monomethylamine, sulfuryl fluoride-ammonia, sulfuryl fluoride, thionyl fluoride-trimethylamine, thionyl fluoride-dimethylamine, thionyl fluoride-monomethylamine, thionyl fluoride-ammonia, thionyl fluoride, and antimony pentafluoride; and a volume ratio of the fluorination catalyst gas to first fluorination agent gas is (20-80):100.
11. The preparation method according to claim 4 , wherein in the step S1), the first fluorinating agent further comprises fluorination catalyst gas;
the fluorination catalyst gas comprises one or more selected from the group consisting of phosphorus trifluoride, bromine trifluoride, iodine trifluoride, sulfur tetrafluoride, anhydrous hydrogen fluoride, boron trifluoride, nitrogen trifluoride, sulfuryl fluoride-trimethylamine, sulfuryl fluoride-dimethylamine, sulfuryl fluoride-monomethylamine, sulfuryl fluoride-ammonia, sulfuryl fluoride, thionyl fluoride-trimethylamine, thionyl fluoride-dimethylamine, thionyl fluoride-monomethylamine, thionyl fluoride-ammonia, thionyl fluoride, and antimony pentafluoride; and a volume ratio of the fluorination catalyst gas to first fluorination agent gas is (20-80):100.
12. The preparation method according to claim 5 , wherein in the step S1), the first fluorinating agent further comprises fluorination catalyst gas;
the fluorination catalyst gas comprises one or more selected from the group consisting of phosphorus trifluoride, bromine trifluoride, iodine trifluoride, sulfur tetrafluoride, anhydrous hydrogen fluoride, boron trifluoride, nitrogen trifluoride, sulfuryl fluoride-trimethylamine, sulfuryl fluoride-dimethylamine, sulfuryl fluoride-monomethylamine, sulfuryl fluoride-ammonia, sulfuryl fluoride, thionyl fluoride-trimethylamine, thionyl fluoride-dimethylamine, thionyl fluoride-monomethylamine, thionyl fluoride-ammonia, thionyl fluoride, and antimony pentafluoride; and a volume ratio of the fluorination catalyst gas to first fluorination agent gas is (20-80):100.
13. The preparation method according to claim 6 , wherein in the step S1), the first fluorinating agent further comprises fluorination catalyst gas;
the fluorination catalyst gas comprises one or more selected from the group consisting of phosphorus trifluoride, bromine trifluoride, iodine trifluoride, sulfur tetrafluoride, anhydrous hydrogen fluoride, boron trifluoride, nitrogen trifluoride, sulfuryl fluoride-trimethylamine, sulfuryl fluoride-dimethylamine, sulfuryl fluoride-monomethylamine, sulfuryl fluoride-ammonia, sulfuryl fluoride, thionyl fluoride-trimethylamine, thionyl fluoride-dimethylamine, thionyl fluoride-monomethylamine, thionyl fluoride-ammonia, thionyl fluoride, and antimony pentafluoride; and a volume ratio of the fluorination catalyst gas to first fluorination agent gas is (20-80):100.
14. The preparation method according to claim 9 , wherein in the step S1), the reaction temperature is 150-400° C.
15. The preparation method according to claim 10 , wherein in the step S1), the reaction temperature is 150-400° C.
16. The preparation method according to claim 11 , wherein in the step S1), the reaction temperature is 150-400° C.
17. The preparation method according to claim 12 , wherein in the step S1), the reaction temperature is 150-400° C.
18. The preparation method according to claim 13 , wherein in the step S1), the reaction temperature is 150-400° C.