Graphene-based composite material as well as preparation method and application thereof

Abstract

The invention relates to the field of graphene-based materials, and discloses a graphene-based composite material as well as a preparation method and application thereof, the composite material comprises a structural unit A from a polymaleimide compound as shown in a formula I, a structural unit B from a graphene-based substance and a structural unit D from furan resin, the structural unit B and the structural unit D are respectively connected with the structural unit A through the structural unit C shown in the formula II; in the formula (I), R is selected from alkylene of C1-C4, alkenylene of C2-C4, alkynylene of C2-C4, substituted or unsubstituted aryl of C6-C18, substituted or unsubstituted aromatic ether of C6-C18, or-(CH2CH2O) x-; in the formula (I), R is selected from alkyl of C1-C4, alkenylene of C2-C4, alkynylene of C2-C4, substituted or unsubstituted aryl of C6-C18, or-(CH2CH2O) x-; wherein R1 is an alkylene group with 1 to 4 carbon atoms; ar is a residue after a polyethyleneimine reaction; x is an integer of 1-8. According to the graphene-based composite material, the polymaleimide compound, the graphene-based substance and the furan resin are combined, and the obtained composite material is high in graphene-based substance content and high in conductivity.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of graphene-based materials, and particularly relates to a graphene-based composite material and a preparation method and application thereof. BACKGROUND

[0002] Graphene is the basic structural unit of graphene, carbon nanotubes, carbon fibers, fullerenes and graphite. Graphene is a single-layer graphite, in which carbon atoms are connected by sp2 hybrid orbitals to form a hexagonal honeycomb-like planar structure, and at the same time, a π bond is generated by contributing one electron of a p orbital, and the π electron can move freely. The unique 2D structure of graphene, excellent mechanical, electrical, optical, thermal, and magnetic properties, often combined with organic polymers to produce new materials with unique functions and excellent performance, and in many fields such as supercapacitors, lithium-ion batteries, fuel cells, proton exchange membrane fuel cells, and solar cells, optoelectronic devices, sensors, energy conversion and storage materials, heterogeneous catalytic materials, high-performance composite materials, environmental functional materials, medical and biological materials, etc., all show unique advantages and excellent application prospects.

[0003] However, due to the inorganic properties of graphene and its regular hexagonal honeycomb-like planar structure, when it is physically mixed with organic polymers, the compatibility is poor, and graphene is easy to aggregate, which not only causes difficulties in processing, but also seriously affects the performance of the material. Especially in the case of high content of graphene in the polymer, the problem caused by poor compatibility is particularly obvious. In order to solve this problem, many research groups modify the surface of graphene, and then composite with organic polymers, which helps to form chemical bonds between graphene-based and polymer.

[0004] CN113270606A discloses a high-strength graphite bipolar plate and a preparation method thereof, by selecting appropriate formula and proportion of each component of the bipolar plate material, such as selecting rubber and silane coupling agent as toughening agent, the resistivity and air permeability of the bipolar plate are reduced, and the mechanical strength is improved, but in the actual use of fuel cells, the chemical bond of silane coupling is unstable and easily hydrolyzed, causing silicon to be detached.

[0005] CN108102290A discloses a graphene grafted modified phenolic resin material and a preparation method thereof, an azido-phenolic resin is prepared by using chloromethylated phenolic resin and azide compound, and then the azido-phenolic resin is grafted onto graphene, thereby obtaining a graphene grafted modified phenolic resin material, which solves the problems of easy aggregation of graphene and interface between graphene and phenolic resin, and the obtained material has excellent mechanical properties and thermal stability. However, chloromethylation of phenolic resin is required, and the compatibility of graphene and phenolic resin is poor, and the prepared polymer has low breaking strength.

[0006] CN108102289A discloses a phenolic resin grafted carbon nanotube composite material and a preparation method thereof. The composite material comprises 100 parts by weight of phenolic resin and 0.1-5 parts by weight of carbon nanotubes. The preparation method of the composite material comprises mixing azidated phenolic resin and carbon nanotubes in a solvent, and separating the product after the reaction is completed. The phenolic resin is grafted onto the carbon nanotubes by a chemical grafting method to solve the problems of easy aggregation of carbon nanotubes and interface between carbon nanotubes and phenolic resin. These technologies, because of chloromethylation and then azidation on the phenolic resin, have less active sites that can react with graphene, and the content of graphene in the product is low.

[0007] Therefore, it is necessary to develop a composite material that can effectively improve the compatibility of graphene-based substances with high molecular materials. SUMMARY

[0008] The purpose of the present application is to overcome the problems of poor compatibility of graphene-based substances with high molecular materials and low content of graphene-based substances in the combined product in the prior art, and to provide a graphene-based composite material, a preparation method and application thereof. The graphene-based composite material combines a polymaleimide compound, a graphene-based substance and a furan resin, and the obtained composite material has high content of graphene-based substances and strong conductivity.

[0009] To achieve the above-mentioned purpose, the first aspect of the present application provides a graphene-based composite material, wherein the composite material comprises a structural unit A from a polymaleimide compound shown in formula I, a structural unit B from a graphene-based substance and a structural unit D from a furan resin.

[0010] The structural unit B and the structural unit D are connected to the structural unit A through a structural unit C shown in formula II, respectively.

[0011]

[0012] wherein R is selected from C1-C4 alkylene, C2-C4 alkenylene, C2-C4 alkynylene, substituted or unsubstituted C6-C18 aromatic group, substituted or unsubstituted C6-C18 aromatic ether group, or -(CH2CH2O) x -;

[0013] wherein R1 is C1-C4 alkylene; Ar is the residue after polyethyleneimine reaction; x is an integer from 1 to 8.

[0014] The second aspect of the present application provides a preparation method of a graphene-based composite material, wherein the method comprises the following steps:

[0015] (1) mixing a multi-maleimide compound with a graphene-based substance under anaerobic conditions to obtain a mixture, performing a first Diels-Alder reaction to obtain the graphene-based copolymer;

[0016] (2) mixing the graphene-based copolymer with a furan resin, performing a second Diels-Alder reaction to obtain the graphene-based composite material;

[0017] The multi-maleimide compound has a structure shown in Formula I;

[0018]

[0019] wherein R is selected from C1-C4 alkylene, C2-C4 alkenylene, C2-C4 alkynylene, substituted or unsubstituted C6-C18 aromatic group, substituted or unsubstituted C6-C18 aromatic ether group, or -(CH2CH2O) x -;

[0020] wherein R1 is C1-C4 alkylene; Ar is a residue after polyethyleneimine reaction; x is an integer from 1 to 8.

[0021] The third aspect of the present application provides a graphene-based composite material prepared by the preparation method of the second aspect.

[0022] The fourth aspect of the present application provides an application of the graphene-based composite material of the first aspect or the third aspect in at least one of the fields of batteries, functional materials and catalytic materials.

[0023] Through the above technical solution, the following beneficial effects are obtained:

[0024] The graphene-based composite material provided by the present application, wherein the multi-maleimide compound is connected to the graphene-based substance and the furan resin by chemical bonds respectively, effectively improves the compatibility of the graphene-based substance with the organic polymer material, the content of the graphene-based substance in the composite material is adjustable, and the product has high electrical conductivity and excellent air tightness. DETAILED DESCRIPTION

[0025] The endpoints of the ranges and any values disclosed herein are not limited to the precise values recited as the exact dimensions are not considered critical for the present application. The endpoints of the ranges and any values are only approximations as the ranges and values are understood to include values approximating the value in and around the ranges, values between the endpoints, values within the range, and values within the single points. Any numerical value can be expressed as a range or value using a term such as "about," "substantially," or "approximately."

[0026] The first aspect of the present application provides a graphene-based composite material, wherein the composite material comprises structural unit A from a polymaleimide compound shown in Formula I, structural unit B from a graphene-based substance, and structural unit D from a furan resin.

[0027] Structural unit B and structural unit D are connected with structural unit A through structural unit C shown in Formula II, respectively.

[0028]

[0029] wherein R is selected from C1-C4 alkylene, C2-C4 alkenylene, C2-C4 alkynylene, substituted or unsubstituted C6-C18 aromatic group, substituted or unsubstituted C6-C18 aromatic ether group, or -(CH2CH2O) x -.

[0030] wherein R1 is C1-C4 alkylene; Ar is a residue after polyethyleneimine reaction; x is an integer from 1 to 8.

[0031] In the present application, structural unit C shown in Formula II is a six-membered ring stereoscopic structure part formed by Diels-Alder reaction. Structural unit A from the polymaleimide compound and structural unit B from the graphene-based substance are connected through structural unit C to form a high molecular copolymer, which is further combined with the furan resin to obtain the graphene-based composite material. The graphene-based substance content in the composite material is high, and the chemical bonds generated overcome the incompatibility of the graphene-based substance and the organic high polymer material. The graphene-based composite material has strong conductive function and good material air tightness.

[0032] According to the present application, preferably, in the composite material, the content of structural unit B from the graphene-based substance is 30-90 wt%, preferably 40-85 wt%; the content of structural unit A from the polymaleimide compound is 5-30 wt%, preferably 5-20 wt%; and the content of structural unit D from the furan resin is 5-60 wt%, preferably 5-40 wt%. In the present application, the content of structural unit A, structural unit B and structural unit D meets the above range, which can improve the conductive capacity and air tightness of the graphene-based composite material. If the addition amount of the furan resin is too much, the conductivity of the composite material will decrease, and if the addition amount of the furan resin is too little, the mechanical properties of the composite material will decrease.

[0033] In the present application, the graphene-based unit refers to a structural unit from a graphene-based substance in the graphene-based composite material. In the present application, the content of the structural unit of each component in the composite material is obtained by back calculation from the nitrogen content. The N element content in the graphene-based composite material is analyzed by elemental analysis method. Since the N in the composite material is from the polymaleimide compound, the content of the maleimide group in the structural unit A of the graphene-based composite material can be back calculated. The content of the structural unit B from the graphene-based substance in the graphene-based copolymer is calculated by normalization method. The content of each component in the graphene-based composite material is further calculated.

[0034] In the present application, preferably, the nitrogen content in the composite material is 1-4 wt%, preferably 1.2-3 wt%.

[0035] In the present application, the C1-C4 alkylene group can be a linear alkylene group or a branched alkylene group, and specifically can be methylene, ethylene, propylene or butylene, wherein butylene and propylene are preferred.

[0036] In the present application, the C2-C4 alkenylene group can be a linear alkenylene group or a branched alkenylene group, and specifically can be vinylene, propenylene or butenylene, wherein butenylene and propenylene are preferred.

[0037] In the present application, the C2-C4 alkynylene group can be a linear alkynylene group or a branched alkynylene group, and specifically can be ethynylene, propynylene or butynylene, wherein butynylene and propynylene are preferred.

[0038] In the present application, the substituted or unsubstituted C6-C18 aromatic group or the substituted or unsubstituted C6-C18 aromatic ether group has at least one substituent selected from alkyl, alkenyl, alkoxy, ester, ether and hydroxyl.

[0039] In the present application, the substituted or unsubstituted C6-C18 aromatic ether group has a general structure of Ar'-O-Ar" or Ar'-O-R2, wherein Ar' and Ar" are aromatic groups, and R2 is a C1-C4 alkyl group.

[0040] According to the present application, the polymaleimide compound is a compound containing at least two maleimide groups in the art.

[0041] According to the present application, preferably, R is selected from C1-C4 alkylene group, substituted or unsubstituted C6-C18 aromatic group, substituted or unsubstituted C6-C18 aromatic ether group,

[0042] wherein R1 is a C1-C4 alkylene group; and Ar is a residue after reaction of polyethyleneimine.

[0043] In the present application, preferably, R is selected from butylene, propylene, substituted or unsubstituted C6-C18 aromatic ether group,

[0044] wherein, R1 is methylene; Ar is the residue after reaction of polyethylene imine.

[0045] More preferably, the poly-maleimide compound is selected from at least one of N,N'-4,4'-diphenylalkylalkane bismaleimide, N,N'-4,4'-diphenyl ether bismaleimide, N,N',N"-(1,3,5-triazine-2,4,6-triyl) trimaleimide, and maleimide polyethylene imine.

[0046] In the present application, the source of the maleimide polyethylene imine is not particularly limited, which can be commercially available or prepared by existing methods. The content of polyethylene imine is 1-30 wt% based on the total weight of the maleimide polyethylene imine.

[0047] According to the present application, preferably, the graphene-based substance is selected from at least one of graphene, expanded graphite, and carbon nanotube. In the present application, the type and source of the graphene-based substance are not particularly limited, as long as the technical effects of the present application can be achieved.

[0048] In the present application, the type and source of the graphene are not particularly limited, which can be commercially available or prepared by existing methods.

[0049] In the present application, the expanded graphite has the conventional interpretation in the art, and the expansion ratio of the expanded graphite is limited in a wide range, as long as the effects of the present application can be achieved. The expansion ratio of the expanded graphite can be adjusted by those skilled in the art, preferably, the expansion ratio of the expanded graphite is 150-400 times.

[0050] In the present application, the carbon nanotube is a conventional carbon nanotube material in the art. The diameter and length of the carbon nanotube are not particularly limited, preferably, the average tube diameter of the carbon nanotube is 5-50 nm, and the average length is 10-200 μm.

[0051] According to the present application, the furan resin is a conventional furan resin product in the art, and the type and source of the furan resin are not particularly limited, which can be commercially available or prepared by existing technologies. Preferably, the furan resin is selected from at least one of furfuryl alcohol resin, furfural resin, furfuryl ketone resin, and furfuryl urea resin.

[0052] According to the present application, preferably, the furan resin has an apparent viscosity of 10-80 mPa·s at 20℃, preferably 15-55 mPa·s. In the present application, the viscosity of the furan resin satisfies the above range, and the furan resin reacts more thoroughly and compatibly with the polymaleimide compound and the graphene-based substance, and the obtained composite material has a high content of graphene-based units. The viscosity is measured by a rotary viscometer.

[0053] According to the present application, preferably, the graphene-based composite material has an electrical conductivity of greater than or equal to 200 S / cm, preferably 300-600 S / cm.

[0054] The present application provides a preparation method of a graphene-based composite material.

[0055] (1) mixing a polymaleimide compound and a graphene-based substance under an oxygen-free condition to obtain a mixture, performing a first Diels-Alder reaction to obtain the graphene-based copolymer;

[0056] (2) mixing the graphene-based copolymer and a furan resin to perform a second Diels-Alder reaction to obtain the graphene-based composite material;

[0057] The polymaleimide compound has a structure shown in Formula I;

[0058]

[0059] wherein R is selected from C1-C4 alkylene, C2-C4 alkenylene, C2-C4 alkynylene, substituted or unsubstituted C6-C18 aromatic group, substituted or unsubstituted C6-C18 aromatic ether group, or -(CH2CH2O) x -;

[0060] wherein R1 is C1-C4 alkylene; Ar is a residue after polyethyleneimine reaction; x is an integer of 1-8.

[0061] In the present application, preferably, the preparation method is simple, the graphene-based copolymer is obtained through the first Diels-Alder reaction, and the copolymer is combined with the furan resin through the second Diels-Alder reaction to obtain the graphene-based composite material, which simplifies the reaction process, the reaction conditions are controllable, and the graphene-based composite material after curing has the characteristics of high electrical conductivity and good air tightness.

[0062] In the present application, the Diels-Alder reaction has the conventional interpretation in the art, which refers to the 1,4 addition reaction of a conjugated diene with a dienophile under certain conditions. In the present application, the structural unit A and the structural unit B are connected through the structural unit C shown in formula II to form a six-membered ring structure, forming a chemical bond between the graphene-based substance and the polymaleimide compound instead of simple physical mixing, eliminating the physical interface between the two, forming an integrated material, thereby achieving the effect of improving the air tightness and bending strength. Compared with single maleimide, the polymaleimide can introduce multiple graphene-based substances into the polymer, increasing the content of graphene-based substances and improving the electrical conductivity. The structural unit A and the structural unit D are connected through the structural unit C, and the furan resin forms a chemical bond with the polymaleimide compound through a chemical reaction, further improving the compatibility of the graphene-based substance and the organic high polymer material.

[0063] According to the present application, preferably, the mass ratio of the maleimide group in the polymaleimide compound to the furan resin is 0.08-6:1, for example, 0.08:1, 0.1:1, 0.12:1, 0.15:1, 0.18:1, 0.2:1, 0.25:1, 0.5:1, 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1, 5.5:1, 6:1, or any range between any two of them, preferably 0.18-2.5:1.

[0064] According to the present application, preferably, the mass ratio of the maleimide group in the polymaleimide compound to the graphene-based substance is 0.06-1:1, for example, 0.06:1, 0.08:1, 0.1:1, 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.8:1, 1:1, or any range between any two of them, preferably 0.08-0.5:1.

[0065] According to the present application, preferably, the graphene-based substance is selected from at least one of graphene, expanded graphite, and carbon nanotubes.

[0066] According to the present application, preferably, the furan resin is selected from at least one of furfuryl alcohol resin, furfural resin, furfuryl ketone resin, and furfuryl urea resin.

[0067] In the present application, preferably, R is selected from C1-C4 alkylene, substituted or unsubstituted C6-C18 aromatic group, substituted or unsubstituted C6-C18 aromatic ether group,

[0068] wherein R1 is C1-C4 alkylene; Ar is the residue after polyethyleneimine reaction.

[0069] More preferably, the poly-maleimide compound is selected from at least one of N,N'-4,4'-diphenylalkane bismaleimide, N,N'-4,4'-diphenyl ether bismaleimide, N,N',N"-(1,3,5-triazine-2,4,6-triyl)trimaleimide, and maleimide-modified polyethyleneimine.

[0070] In the present application, the types and sources of the graphene-based substance, the furan resin, and the poly-maleimide compound are described in the foregoing description, and will not be repeated here.

[0071] In the present application, the oxygen-free condition refers to a condition without oxygen. Preferably, the Diels-Alder reaction is carried out under a protective atmosphere, which is preferably selected from at least one of nitrogen, helium, and argon.

[0072] According to the present application, preferably, the poly-maleimide compound is mixed with the graphene-based substance to obtain a mixture, and the mixing time and conditions are not particularly limited, as long as the mixture is uniform. Preferably, the mixing conditions include that the mixing time is 0.5-6h, preferably 2-4h.

[0073] In the present application, preferably, the mixing is carried out under ultrasonic assistance. The ultrasonic assistance can make the graphene-based substance and the poly-maleimide compound mix more uniformly.

[0074] According to the present application, the conditions of the ultrasonic assistance are not particularly limited, and preferably, the conditions of the ultrasonic assistance include that the ultrasonic time is 0.5-6h, preferably 1-3h; and the ultrasonic power is 500-900W, preferably 600-800W.

[0075] In the present application, preferably, the mixture of the graphene-based substance and the poly-maleimide compound further comprises a dispersion liquid, which is a conventional organic solvent and / or inorganic solvent in the art, and is preferably selected from at least one of acetone, ethanol, and dioxane.

[0076] In the present application, the amount of the dispersion liquid added is not particularly limited, and those skilled in the art can adjust the amount of the dispersion liquid added adaptively according to the mixing condition of the mixture, and preferably, the amount of the dispersion liquid added is 2-50mL, preferably 5-20mL, based on 1g of the poly-maleimide compound.

[0077] According to a preferred embodiment of the present application, the mixing includes dispersing the poly-maleimide compound in a dispersion liquid, adding the graphene-based substance, and carrying out ultrasonic mixing. Here, "dispersion" is a process of mixing a solid or liquid substance with a liquid to obtain a uniform or multi-phase mixture. The liquid can play a dissolving role, or a dispersion role of isolating solid or liquid molecules.

[0078] According to the present application, preferably, the conditions of the first Diels-Alder reaction include: reaction time is 0.1-20h, preferably 0.5-12h; reaction temperature is 0-100℃, preferably 15-90℃.

[0079] In the present application, preferably, the first Diels-Alder reaction is carried out in the presence of a first catalyst. The first catalyst can be added or not added, as long as the Diels-Alder reaction can be carried out to obtain the copolymer, which can be selected adaptively by those skilled in the art according to the reaction condition.

[0080] In the present application, preferably, the mass ratio of the first catalyst to the maleimide group in the poly-maleimide compound is 0-1:1, preferably 0.01-0.5:1.

[0081] According to the present application, preferably, the second Diels-Alder reaction is carried out in the presence of a second catalyst.

[0082] According to the present application, preferably, the conditions of the second Diels-Alder reaction include: under oxygen-free conditions, reaction temperature is 0-99℃, preferably 15-90℃; reaction time is 0.1-20h, preferably 1-8h.

[0083] According to the present application, preferably, the mass ratio of the second catalyst to the furan resin is 0.005-0.5:1, for example 0.005:1, 0.008:1, 0.01:1, 0.02:1, 0.03:1, 0.05:1, 0.08:1, 0.1:1, 0.2:1, 0.3:1, 0.4:1, 0.5:1, or any range between any two of them, preferably 0.01-0.1:1.

[0084] According to the present application, preferably, the first catalyst and the second catalyst are Lewis acid catalysts, each independently selected from at least one of ferric chloride, aluminum chloride, zinc chloride, magnesium chloride, antimony chloride, boron trifluoride, zinc tetrafluoroborate, and copper nitrate.

[0085] In the present application, the first catalyst and the second catalyst can be added directly or in the form of a catalyst solution. When added by solution, the mass concentration of the catalyst solution is not particularly limited, preferably 5-20wt%.

[0086] In the present application, preferably, the first Diels-Alder reaction and the second Diels-Alder reaction are carried out with the assistance of ball milling and / or plasticizing.

[0087] In the present application, preferably, the ball-milling conditions include: ball-milling time of 1-6h, preferably 2-5h; ball-milling speed of 150-800rpm, preferably 300-600rpm. The ball-milling equipment is not particularly limited, as long as it can make the Diels-Alder reaction proceed uniformly, preferably, the ball-milling is carried out in a ball mill.

[0088] In the present application, preferably, the plasticating conditions include: plasticating time of 1-6h, preferably 2-5h; plasticating speed of 40-200rpm, preferably 80-150rpm. The plasticating equipment is not particularly limited, as long as it can make the Diels-Alder reaction proceed uniformly, preferably, the plasticating is carried out in an internal mixer.

[0089] In the present application, the equipment for carrying out the Diels-Alder reaction is not particularly limited, when the ball-milling and / or plasticating is not carried out, the Diels-Alder reaction is carried out in a closed kettle.

[0090] In the present application, preferably, after the first Diels-Alder reaction, the process of post-treatment of the reaction product is further included. The post-treatment process includes: removing the dispersion liquid in the reaction product to obtain a coagulum. The removal method of the dispersion liquid is not particularly limited, and those skilled in the art can select a suitable method to remove the dispersion liquid in the reaction product, preferably vacuum drying. The conditions and equipment of the vacuum drying are not particularly limited, specifically, the temperature of the vacuum drying is 40-100℃.

[0091] In the present application, preferably, after the first Diels-Alder reaction, the process of optional purification of the reaction product is further included, and the purification method is not particularly limited, according to a preferred embodiment of the present application, the reaction product is washed with deionized water.

[0092] In the present application, preferably, after the second Diels-Alder reaction, the reaction product is subjected to solid-liquid separation and washing to obtain a graphene-based composite material. The solid-liquid separation and washing method is not particularly limited. According to a preferred embodiment of the present application, the second Diels-Alder reaction product is filtered and then washed with deionized water.

[0093] The third aspect of the present application provides a graphene-based composite material prepared by the preparation method of the second aspect.

[0094] According to the present application, preferably, in the composite material, the content of the structural unit B from the graphene-based substance is 30-90wt%, preferably 40-85wt%; the content of the structural unit A from the polymaleimide compound is 5-30wt%, preferably 7-20wt%; and the content of the structural unit D from the furan resin is 5-60wt%, preferably 8-40wt%.

[0095] In the present application, preferably, before the testing, the graphene-based composite material is further subjected to a curing process. The curing conditions are not particularly limited, and preferably, the curing conditions include: in the presence of a curing agent, the curing temperature is 20-60℃, and the curing time is 0.5-6h.

[0096] In the present application, the curing agent is a conventional furan resin curing agent in the art, which can be commercially available or prepared by using the existing method. The amount of addition is not particularly limited, and those skilled in the art can adaptively adjust the type and amount of the curing agent according to the curing condition. Preferably, the curing agent is selected from at least one of benzenesulfonyl chloride, p-toluenesulfonyl chloride, p-toluenesulfonic acid, ethyl sulfate and petroleum sulfonic acid. The mass ratio of the structural unit D from the furan resin to the curing agent in the graphene-based composite material is 1:0.001-0.3, preferably 1:0.01-0.2.

[0097] In the present application, preferably, the electrical conductivity of the graphene-based composite material is greater than or equal to 200S / cm, preferably 300-600S / cm.

[0098] In the present application, preferably, the hydrogen permeability of the graphene-based composite material is 1×10 -9 cm 3 ·cm -2 ·s -1 to 5×10 -7 cm 3 ·cm -2 ·s -1 , preferably 2×10 -9 cm 3 ·cm -2 ·s -1 to 2×10 -7 cm 3 ·cm -2 ·s -1 .

[0099] In the present application, the electrical conductivity and hydrogen permeability of the graphene-based composite material are tested by GB / T20042.6-2011 “Proton Exchange Membrane Fuel Cell Part 6: Test Method for Bipolar Plate Properties”.

[0100] The fourth aspect of the present application provides application of the graphene-based composite material of the first aspect or the third aspect in at least one of the fields of batteries, functional materials and catalytic materials.

[0101] In the present application, the graphene-based composite material has high electrical conductivity and high bending strength and low hydrogen permeability, and the graphene-based composite material is used in the field of batteries, thereby reducing hydrogen permeation and prolonging the service life of phenolic resin.

[0102] The present application will be described in detail below through examples. In the following examples and comparative examples, unless otherwise specified, the reagents used in the present application are commercially available.

[0103] Example 1

[0104] (1) Under the protection of helium atmosphere, 3.2 grams of N,N',N"-(1,3,5-triazine-2,4,6-triyl) trimaleimide were dispersed in 200 mL of dioxane, 25 grams of graphene (the mass ratio of maleimide groups to structural unit B was 1:10) were added, and they were mixed uniformly under the assistance of ultrasonic stirring at a power of 750 W, and then transferred into a sealed kettle, and a first Diels-Alder reaction was carried out at 90℃ for 4 hours, and then vacuum drying was performed at 50℃ to remove dioxane, thereby obtaining 26.6 grams of graphene-based copolymer, which was washed and purified by deionized water, and through element analysis, it was found that the nitrogen content was 2.6wt%, and thus it was calculated that the content of graphene-based units in the graphene-based copolymer was 88.7wt%.

[0105] (2) Under the protection of helium atmosphere, 28 grams of commercially available FL-105 type furan resin (Jinan Shengquan Group Co., Ltd., apparent viscosity 29 mPa.s at 20℃, nitrogen content 0, same below) and 25 grams of the graphene-based copolymer described above were fully stirred and mixed at room temperature for 4 hours, 2.8 grams of 10wt% iron trichloride solution was added, and the temperature was raised to 90℃, and a second Diels-Alder reaction was carried out for 1 hour, and then filtration was performed, and the graphene-based composite material was washed with deionized water for three times, and then vacuum drying was performed, thereby obtaining 46 grams of graphene-based composite material. It was found that the nitrogen content therein was 1.23wt%.

[0106] The above-mentioned composite material 20 grams was added with 0.53 grams of commercially available p-toluenesulfonic acid curing agent with a brand of XY-GS-02 (Suzhou Xingye Material Technology Co., Ltd.), and curing was performed at 20℃ for 1 hour, thereby obtaining product 1A.

[0107] Example 2

[0108] (1) The graphene-based copolymer was prepared according to the method of Example 1;

[0109] (2) Take 1.5 grams of commercially available furan resin of type XY-90-00 (Suzhou Xingye Material Science and Technology Co., Ltd., apparent viscosity 17 mPa.s at 20°C, nitrogen content 0) and 25 grams of the above graphene-based copolymer, mix thoroughly, add 1.5 grams of 10 wt% iron trichloride solution under stirring, heat to 30°C, and carry out the second Diels-Alder reaction for 8 hours. Filter and wash with deionized water three times to obtain 23 grams of the product graphene-based composite material. The nitrogen content therein is measured to be 2.45 wt%.

[0110] Take 20 grams of the above composite material, add 0.53 grams of commercially available p-toluenesulfonic acid curing agent of grade XY-GS-02, and cure at 20°C for 1 hour to obtain product 2A.

[0111] Example 3

[0112] (1) Prepare the graphene-based copolymer according to the method of Example 1;

[0113] (2) Take 1.5 grams of commercially available furan resin of type XY-90-00 (Suzhou Xingye Material Science and Technology Co., Ltd.) and 25 grams of the above graphene-based copolymer, mix thoroughly, add 0.1 grams of 10 wt% iron trichloride solution under stirring, heat to 60°C, and carry out the second Diels-Alder reaction for 4 hours. Filter and wash with deionized water three times to obtain 21 grams of the product graphene-based composite material. The nitrogen content therein is measured to be 2.45 wt%.

[0114] Take 20 grams of the above composite material, add 0.53 grams of commercially available p-toluenesulfonic acid curing agent of grade XY-GS-02, and cure at 20°C for 1 hour to obtain product 3A.

[0115] Example 4

[0116] (1) Under a nitrogen atmosphere, take 10 grams of commercially available N,N'(4,4'-diphenylmethane) bismaleimide (maleimide group content 53.6 wt%) and disperse in 100 mL of acetone to obtain a mixed solution. Mix 26.8 grams of carbon nanotubes with an average tube diameter of 40 nm, an average length of 15 μm, and a specific surface area of 40 m 2 / gram (mass ratio of maleimide group to structural unit B 1:5) with the mixed solution under ultrasonic assistance at a power of 750 W, and then ball mill in a ball mill at 50°C for 2 hours at a ball milling rate of 300 rpm. Remove the acetone under vacuum drying at 50°C, and purify by washing with deionized water to obtain 34 grams of graphene-based copolymer. The nitrogen content is 2.12 wt% by elemental analysis, and the content of graphene-based units is 72.8 wt%.

[0117] (2) Under the protection of nitrogen, 28 grams of commercially available furan resin (FL-105, produced by Jinan Shengquan Group Co., Ltd.) and 10.39 grams of the graphene-based copolymer described above were thoroughly mixed, 2.8 grams of 10 wt% ferric chloride solution was added under stirring, and the temperature was raised to 90°C. After the second Diels-Alder reaction was performed for 1 hour, the product, graphene-based composite material, 35 grams, was obtained by filtration and washing with deionized water three times. The nitrogen content in the product was 1.22 wt%.

[0118] The above composite material, 20 grams, was added with 0.53 grams of commercially available p-toluenesulfonic acid curing agent with the trade name of XY-GS-02 (Suzhou Xingye Material Science and Technology Co., Ltd.), and cured at 20°C for 1 hour to obtain product 4A.

[0119] Example 5

[0120] (1) The graphene-based copolymer was prepared according to the method of Example 1;

[0121] (2) Under the protection of helium, 35 grams of commercially available furan resin (FL-105, produced by Jinan Shengquan Group Co., Ltd.) and 25 grams of the graphene-based copolymer described above were thoroughly mixed, 1 gram of 10 wt% ferric chloride solution was added under stirring, and the temperature was raised to 90°C. After the reaction was performed for 1 hour, the product, graphene-based composite material, 56 grams, was obtained by filtration and washing with deionized water three times. The nitrogen content in the product was 1.09 wt%.

[0122] The above composite material, 20 grams, was added with 0.53 grams of commercially available p-toluenesulfonic acid curing agent with the trade name of XY-GS-02 (Suzhou Xingye Material Science and Technology Co., Ltd.), and cured at 20°C for 1 hour to obtain product 5A.

[0123] Example 6

[0124] The composite material was prepared according to the method of Example 1, except that the amount of N,N',N"-(1,3,5-triazine-2,4,6-triyl)trimaleimide was changed to 2.4 grams, and other conditions were the same as in Example 1. The graphene-based copolymer, 25.3 grams, was obtained, and the nitrogen content thereof was 2.56 wt%. It was calculated that the content of graphene-based unit in the graphene-based copolymer was 88.9 wt%.

[0125] (2) Under helium atmosphere, take 28 grams of commercially available furan resin FL-105 (Jinan Shengquan Group Co., Ltd., apparent viscosity 29 mPa.s at 20℃, nitrogen content 0, same below) and 25 grams of the graphene-based copolymer above, mix at room temperature for 4 hours, add 2.8 grams of 10wt% ferric chloride solution, heat to 90℃, and conduct the second Diels-Alder reaction for 1 hour. Filter, wash with deionized water three times, and vacuum dry to obtain 44 grams of graphene-based composite material. Measure the nitrogen content to be 1.15wt%.

[0126] Take 20 grams of the composite material above, add 0.53 grams of commercially available p-toluenesulfonic acid curing agent XY-GS-02 (Suzhou Xingye Material Technology Co., Ltd.), and cure at 20℃ for 1 hour to obtain product 6A.

[0127] Comparative Example 1

[0128] (1) Prepare the graphene-based copolymer according to the method of Example 1;

[0129] (2) Take 25 grams of commercially available furan resin FL-105 (Jinan Shengquan Group Co., Ltd.) and 25 grams of the graphene-based copolymer above, mix at room temperature for 0.5 hours to obtain 50 grams of material. Measure the nitrogen content to be 1.23wt%.

[0130] Take 20 grams of the material above, add 0.53 grams of commercially available p-toluenesulfonic acid curing agent XY-GS-02, and cure at 20℃ for 1 hour to obtain cured product 1B.

[0131] Comparative Example 2

[0132] (1) Prepare the graphene-based copolymer according to the method of Example 1;

[0133] (2) Take 1.5 grams of commercially available furan resin XY-90-00 (Suzhou Xingye Material Technology Co., Ltd.) and 25 grams of the graphene-based copolymer above, mix at room temperature for 0.5 hours to obtain 26.5 grams of material. Measure the nitrogen content to be 2.45wt%.

[0134] Take 20 grams of the material above, add 0.53 grams of commercially available p-toluenesulfonic acid curing agent XY-GS-02, and cure at 20℃ for 1 hour to obtain cured product 2B.

[0135] Comparative Example 3

[0136] (1) Prepare the graphene-based copolymer according to the method of Example 1;

[0137] (2) Take 28 grams of commercially available furan resin of type FL-105 (Jinan Shengquan Group Co., Ltd.) and 25 grams of the above graphene-based copolymer, mix at room temperature for 4 hours, heat to 90°C, keep for 1 hour, and then obtain 53 grams of product. The nitrogen content is 1.23 wt%.

[0138] Take 20 grams of the above product, add 0.53 grams of commercially available p-toluenesulfonic acid curing agent with trade name XY-GS-02 (Suzhou Xingye Material Science and Technology Co., Ltd.), and cure at 20°C for 1 hour to obtain the cured product 3B.

[0139] Comparative Example 4

[0140] Under helium atmosphere, disperse 3.2 grams of N,N',N"-(1,3,5-triazine-2,4,6-triyl) trimaleimide in 200 mL dioxane, add 28 grams of FL-105 type furan resin and 2.8 grams of 10 wt% ferric chloride solution, heat to 90°C in a sealed kettle, keep for 1 hour, then cool to room temperature, add 25 grams of graphene, and mix uniformly under ultrasonic assistance with a power of 750 W. Heat to 90°C in a sealed kettle, and react for 4 hours. Remove dioxane by vacuum drying at 50°C, then purify by washing with deionized water, and dry to obtain 43 grams of graphene-based copolymer. The nitrogen content is 1.24 wt%.

[0141] Take 20 grams of the above composite material, add 0.53 grams of commercially available p-toluenesulfonic acid curing agent with trade name XY-GS-02 (Suzhou Xingye Material Science and Technology Co., Ltd.), and cure at 20°C for 1 hour to obtain product 4B.

[0142] Comparative Example 5

[0143] (1) Prepare the graphene-based copolymer according to the method of Example 1, except that use 2.5 grams of maleimide instead of N,N',N"-(1,3,5-triazine-2,4,6-triyl) trimaleimide, and other conditions are the same as in Example 1, to obtain 25.8 grams of graphene-based copolymer, and the nitrogen content is 1.54 wt%. The content of graphene-based units is 89.3 wt%.

[0144] (2) Under helium atmosphere, take 28 grams of commercially available furan resin of type FL-105 (Jinan Shengquan Group Co., Ltd.) and 24.8 grams of the above graphene-based copolymer, mix at room temperature for 4 hours, add 2.8 grams of 10 wt% ferric chloride solution, heat to 90°C, and perform the second Diels-Alder reaction for 1 hour. Filter, wash with deionized water three times, and obtain 44.4 grams of graphene-based composite material. The nitrogen content is 0.78 wt%.

[0145] Cure under the same conditions as in Example 1 to obtain product 5B.

[0146] The composition and performance of the cured graphene-based composite material are shown in Table 1.

[0147] Table 1

[0148]

[0149] Note: The graphene-based unit content in Comparative Examples 1-3 in Table 1 is the graphene-based unit content in the cured product.

[0150] As can be seen from the results in Table 1, the graphene-based composite material prepared in the present application has high electrical conductivity and low hydrogen permeability, and has high electrical conductivity and high airtightness.

[0151] The above describes the preferred embodiments of the present application, but the present application is not limited thereto. Within the technical concept of the present application, various simple modifications can be made to the technical solutions of the present application, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be considered as disclosed by the present application, and all fall within the protection scope of the present application.

Claims

1. A graphene-based composite material, characterized by, The composite material comprises structural unit A from a multi-maleimide compound shown in formula I, structural unit B from a graphene-based substance, and structural unit D from a furan resin; Structural unit B and structural unit D are connected with structural unit A through structural unit C shown in formula II respectively; wherein R is selected from C1-C4 alkylene, C2-C4 alkenylene, C2-C4 alkynylene, substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted C6-C18 aryl ether, or -(CH2CH2O) x -; wherein R1 is C1-C4 alkylene; Ar is a residue after reaction of polyethylene imine; x is an integer from 1 to 8.

2. The composite material of claim 1, wherein, In the composite material, the content of structural unit B from the graphene-based substance is 30-90wt%, preferably 40-85wt%; The content of structural unit A from the multi-maleimide compound is 5-30wt%, preferably 5-20wt%; the content of structural unit D from the furan resin is 5-60wt%, preferably 5-50wt%.

3. The composite material of claim 1 or 2, wherein, R is selected from C1-C4 alkylene, substituted or unsubstituted C6-C18 aromatic group, substituted or unsubstituted C6-C18 aromatic ether group, wherein R1 is C1-C4 alkylene; Ar is a residue after reaction of polyethylene imine; Preferably, the multi-maleimide compound is selected from at least one of N,N'-4,4'-diphenylalkylalkane bismaleimide, N,N'-4,4'-diphenyl ether bismaleimide, N,N',N"-(1,3,5-triazine-2,4,6-triyl) trimaleimide, and maleimide polyethylene imine; Preferably, the graphene-based substance is selected from at least one of graphene, expanded graphite, and carbon nanotube; Preferably, the furan resin is selected from at least one of furfuryl alcohol resin, furfural resin, furfuryl ketone resin, and furfuryl urea resin; Preferably, the furan resin has an apparent viscosity of 10-80mPa·s at 20℃, preferably 15-55mPa·s.

4. The composite material according to any one of claims 1 to 3, wherein, The graphene-based composite material has an electrical conductivity greater than or equal to 200S / cm, preferably 300-600S / cm.

5. A method of preparing a graphene-based composite material, characterized by, The method comprises the following steps: (1) mixing a multi-maleimide compound with a graphene-based substance under anaerobic conditions to obtain a mixture, performing a first Diels-Alder reaction to obtain the graphene-based copolymer; (2) mixing the graphene-based copolymer with a furan resin, performing a second Diels-Alder reaction to obtain the graphene-based composite material; The multi-maleimide compound has a structure shown in formula I; wherein R is selected from C1-C4 alkylene, C2-C4 alkenylene, C2-C4 alkynylene, substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted C6-C18 aryl ether, or -(CH2CH2O) x -; wherein R1 is C1-C4 alkylene; Ar is a residue after reaction of polyethylene imine; x is an integer from 1 to 8.

6. The production method according to claim 5, wherein The graphene-based substance is selected from at least one of graphene, expanded graphite, and carbon nanotube; Preferably, the furan resin is selected from at least one of furfuryl alcohol resin, furfural resin, furfuryl ketone resin, and furfuryl urea resin; Preferably, the multi-maleimide compound is selected from at least one of N,N'-4,4'-diphenylalkylalkane bismaleimide, N,N'-4,4'-diphenyl ether bismaleimide, N,N',N"-(1,3,5-triazine-2,4,6-triyl) trimaleimide, and maleimide polyethylene imine.

7. The production method according to claim 5 or 6, wherein The mass ratio of the maleimide groups in the multi-maleimide compound to the furan resin is 0.08-6:1, preferably 0.18-2.5:1; Preferably, the mass ratio of the maleimide groups in the multi-maleimide compound to the graphene-based substance is 0.06-1:1, preferably 0.08-0.5:

1.

8. The method of making according to any one of claims 5-7, wherein, The conditions of the first Diels-Alder reaction include: the reaction time is 0.1-20h, preferably 0.5-12h; the reaction temperature is 0-100℃, preferably 15-90℃; Preferably, the first Diels-Alder reaction is carried out in the presence of a first catalyst; Preferably, the second Diels-Alder reaction is carried out in the presence of a second catalyst; Preferably, the conditions of the second Diels-Alder reaction include: under oxygen-free conditions, the reaction temperature is 0-99℃, preferably 15-90℃; the reaction time is 0.1-20h, preferably 1-8h.

9. The production method according to claim 8, wherein The mass ratio of the second catalyst to the furan resin is 0.005-0.5:1, preferably 0.01-0.1:1; Preferably, the first catalyst and the second catalyst are each independently selected from at least one of ferric trichloride, aluminum chloride, zinc chloride, magnesium chloride, antimony chloride, boron trifluoride, zinc tetrafluoroborate, and copper nitrate.

10. A graphene-based composite material prepared by the preparation method of any one of claims 5-9.

11. Use of the graphene-based composite material of any one of claims 1-4, 10 in at least one of the fields of batteries, functional materials, and catalytic materials.

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