CN114591127A - Metastable composite material and preparation method thereof - Google Patents

Metastable composite material and preparation method thereof Download PDF

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CN114591127A
CN114591127A CN202210179774.XA CN202210179774A CN114591127A CN 114591127 A CN114591127 A CN 114591127A CN 202210179774 A CN202210179774 A CN 202210179774A CN 114591127 A CN114591127 A CN 114591127A
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composite material
metastable
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graphene
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CN114591127B (en
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沈强
易卓然
孙一
邓皓源
覃梅
罗国强
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Wuhan University of Technology WUT
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    • C—CHEMISTRY; METALLURGY
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    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
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Abstract

The invention discloses a metastable composite material and a preparation method thereof. The metastable state composite material has a core-shell structure, wherein the core is aluminum particles coated by fluorine-containing polymer, and the shell layer is a sulfonated graphene coating layer or a reduced graphene oxide coating layer. The preparation method comprises the following steps: 1) adding the aluminum particle dispersion liquid into a fluorine-containing polymer solution, mixing, and separating to obtain fluorine-containing polymer coated aluminum particles; 2) dispersing sulfonated graphene or reduced graphene oxide in a solvent to prepare a dispersion liquid; 3) adding the fluoropolymer-coated aluminum particles into the dispersion liquid obtained in the step 2), mixing, and separating to obtain the metastable composite material. The metastable composite material not only has a uniform and compact coating structure with good interface combination, but also has the advantages of high utilization rate of active aluminum, good heat transfer efficiency, fast energy release, good heat resistance and stability and the like, and the preparation process is simple and controllable, has low cost and is suitable for large-area application.

Description

Metastable composite material and preparation method thereof
Technical Field
The invention relates to the field of composite material preparation, in particular to a metastable composite material and a preparation method thereof.
Background
Metastable composites (MICs), which are generally composed of a metal fuel and an oxidant, are two-component or multi-component energetic composites with a fine structure. MICs has attracted considerable attention for its high energy density and excellent combustion properties and has been used in the research fields of propellants, explosives and pyrotechnics. In a metastable composite aluminum particle system, aluminum particles with high energy density, wide sources and rapid reaction are commonly used as metal fuels, an oxidant generally comprises metal oxides and fluorine-containing polymers, and the fluorine-containing polymers are commonly used for solving the problem of energy release resistance of the aluminum particles and improving the utilization rate of active aluminum due to the advantages of excellent weather resistance, aluminum-based reactivity improvement and the like at normal temperature.
However, the thermal conductivity of the fluoropolymer itself is usually very low, so that the effective heat transfer performance of the aluminum particle fuel-fluoropolymer oxidant in the fluoropolymer/aluminum particle metastable composite system is greatly hindered, which is reflected in that the heat transfer efficiency and the energy release rate of the composite powder in the combustion process are limited.
Therefore, there is a need to research a metastable composite material with high utilization rate of active aluminum, good heat transfer efficiency, fast energy release, good heat resistance and good stability.
Disclosure of Invention
In order to overcome the problems of the prior art, it is an object of the present invention to provide a metastable composite material.
The second purpose of the invention is to provide a preparation method of the metastable composite material.
The technical scheme adopted by the invention is as follows:
in a first aspect, the present invention provides a metastable state composite material having a core-shell structure, wherein the core is an aluminum particle coated with a fluoropolymer, and the shell is a sulfonated graphene coating layer or a reduced graphene oxide coating layer.
Preferably, the fluoropolymer content in the fluoropolymer-coated aluminum particles is 5 to 15% by mass.
More preferably, the fluoropolymer content in the fluoropolymer-coated aluminum particles is 6 to 10% by mass.
Preferably, the average particle diameter of the aluminum particles in the fluoropolymer-coated aluminum particles is 1 to 10 μm.
More preferably, the average particle diameter of the aluminum particles in the fluoropolymer-coated aluminum particles is 3 to 6 μm.
Preferably, the fluorine-containing polymer is at least one of polyvinylidene fluoride, polytetrafluoroethylene, fluorinated ethylene propylene copolymer and fluoroolefin-vinyl ether copolymer.
More preferably, the fluoropolymer is polyvinylidene fluoride.
Preferably, the mass percentage content of the shell layer in the metastable state composite material is 0.5-8%.
Further preferably, the mass percentage of the shell layer in the metastable state composite material is 1-5%.
Preferably, the sulfonated graphene is in a sheet shape.
Preferably, the sulfonated graphene is a graphene containing sulfonic acid groups.
Preferably, the graphene containing sulfonic acid groups is prepared from sulfonated polyether ether ketone and graphene oxide serving as raw materials.
Specifically, sulfonated graphene (sulfonic group-containing graphene) is prepared by grafting sulfonic groups on graphene oxide by utilizing the non-covalent interaction between flaky graphene oxide and a sulfonated polyether ether ketone SPEEK which is a macromolecular polymer, and then performing reduction treatment to obtain fluffy graphene (SPG) containing the sulfonic groups.
Preferably, the reduced graphene oxide is in a sheet shape.
Preferably, the enthalpy of the metastable composite material at the temperature range of 750-1300 ℃ is 12200J/g-16710J/g.
In a second aspect, the present invention provides a method of preparing the metastable composite material of the first aspect, comprising the steps of:
1) adding the aluminum particle dispersion liquid into a fluorine-containing polymer solution, mixing, and separating a solid product to obtain fluorine-containing polymer coated aluminum particles;
2) dispersing sulfonated graphene or reduced graphene oxide in a solvent to prepare a dispersion liquid;
3) adding the fluoropolymer-coated aluminum particles into the dispersion liquid obtained in the step 2), mixing, and separating a solid product to obtain the metastable-state composite material.
Preferably, there is a temperature difference of 15 ℃ to 50 ℃ between the aluminum particle dispersion of step 1) and the fluoropolymer solution.
Preferably, the mass ratio of the aluminum particles and the fluoropolymer in the step 1) is 1: 0.05-1: 0.10.
Preferably, the preparation process of the sulfonated graphene in the step 2) is as follows: firstly, sulfonated polyether ether ketone is adopted to treat the graphene oxide, and then a reducing agent is used for reduction.
Further preferably, the preparation process of the sulfonated graphene in step 2) is as follows: adding graphene oxide into sulfonated polyether ether ketone dispersion liquid, performing ultrasonic dispersion at 50-80 ℃, adding a reducing agent, reacting for 6-20 h at 80-120 ℃, and performing vacuum freeze drying to obtain the sulfonated graphene.
Preferably, the reducing agent is at least one of hydrazine hydrate, sodium borohydride and ascorbic acid.
Preferably, the vacuum freeze-drying is carried out at a temperature of-30 ℃ to-50 ℃ and a vacuum degree of 10Pa to 20 Pa.
According to the preparation method, Sulfonated Graphene is adopted, and aims to construct sulfonic acid groups on the surface of Graphene Oxide (GO) and remove oxygen-containing groups by a chemical reduction method, so that Sulfonated Graphene (SPG) with higher heat resistance is obtained. Due to SO present in SPG3H group dipole with-CF2Strong dipole interaction between dipoles enables the sulfonated graphene coating to be more compact, and better interface bonding can be realized between the sulfonated graphene (SPG) and PVDF on the surface of aluminum particles (such as polyvinylidene fluoride coated aluminum particle material, namely PVDF @ Al composite powder) of the fluoropolymer coating, so that the active aluminum has high utilization rate, good heat transfer efficiency and energy releaseThe metastable state composite material (namely SPG @ PVDF @ Al composite powder) has the advantages of high release speed, good heat resistance and good stability.
Preferably, the solvent in step 2) is alcohol and/or water.
Further preferably, the alcohol is at least one of a monohydric alcohol, a dihydric alcohol and a trihydric alcohol.
Preferably, the concentration of the sulfonated graphene or the reduced graphene oxide in the dispersion liquid in the step 2) is 0.1 g/L-0.10 g/L.
Further preferably, the concentration of the sulfonated graphene or the reduced graphene oxide in the dispersion liquid in the step 2) is 0.2 g/L-0.6 g/L.
Preferably, step 2) further comprises ultrasonic treatment, and the ultrasonic treatment is performed by using a cell disrupter.
Preferably, the amount of the aluminum particles added in the fluoropolymer coating layer in step 3) is 0.8 to 1.2g by mass.
More preferably, the amount of the aluminum particles added to the fluoropolymer coating layer in step 3) is 0.9 to 1.1 g.
Preferably, the process of re-separating the solid product in step 1) and step 3) specifically comprises: and (5) carrying out suction filtration, washing and drying.
Preferably, the drying is vacuum drying.
Preferably, the drying temperature is 50 ℃ to 65 ℃.
Preferably, the drying time is 10h to 16 h.
The invention has the beneficial effects that: the metastable composite material not only has a double-coating structure with uniformity, compactness and good interface combination, but also has the advantages of high utilization rate of active aluminum, good heat transfer efficiency, quick energy release, good heat resistance and stability and the like, and the preparation process is simple and controllable, has low cost and is suitable for large-area application. The method specifically comprises the following steps:
1) according to the invention, high-thermal-conductivity graphene (sulfonated graphene or reduced graphene oxide) is introduced into aluminum particles with fluorine-containing polymer coating layers, the interface bonding strength of the high-thermal-conductivity graphene-polymer is improved through the interaction of the high-thermal-conductivity graphene and fluorine-containing compounds, the heat transfer path of the reduced graphene-polymer interface or sulfonated graphene-polymer interface is enhanced, and the thermal resistance of the high-thermal-conductivity graphene-polymer interface can be effectively reduced;
2) the metastable state composite material is coated and modified by sulfonated graphene or reduced graphene oxide, so that the heat resistance of a metastable state composite material system is further improved, the existence time of the metastable state composite material in the powder application heat transfer process is prolonged, the obstruction of heat transfer in the metastable state composite system application is further reduced, and the utilization rate and the energy release of active aluminum particles are further improved;
3) after the metastable state composite material is subjected to thermal weight gain, the mass can be increased to 70.31 percent, and the enthalpy measured at the temperature range of 750-1300 ℃ can reach 16710J/g;
4) the preparation method of the metastable state composite material is simple and controllable, the component can be accurately controlled, the metastable state composite material with good interface combination can be obtained, and the metastable state composite material has the characteristics of low cost and good comprehensive thermodynamic performance.
Drawings
Fig. 1 is a TG diagram of sulfonated graphene SPG, graphene oxide GO, and thermally reduced graphene RGO.
FIG. 2 is an SEM image of the metastable composite material of example 1 and example 2.
Fig. 3 is an infrared spectrum of sulfonated polyether ether ketone SPEEK, sulfonated graphene SPG, graphene oxide GO, and thermally reduced graphene RGO.
FIG. 4 is a graph of the infrared spectra of the metastable composites of example 1 and comparative example 1.
FIG. 5 is a graph of the results of a thermal lock-in analysis test of the metastable composite materials of example 1, example 2 and comparative example 1.
FIG. 6 is a graph of the results of the thermal weight gain test for the metastable composites of example 1, example 2 and comparative example 1.
FIG. 7 is a graph of the results of enthalpy of fusion tests for the metastable composites of example 1, example 2 and comparative example 1.
Detailed Description
The invention will be further explained and illustrated with reference to specific examples.
Example 1
A metastable composite material, the preparation method comprising the following steps:
1) preparing a graphene oxide dispersion liquid: selecting graphene oxide with the particle size of 0.5-3 microns, and ultrasonically and uniformly dispersing the graphene oxide in distilled water through a cell disruptor to obtain 2mg/mL graphene oxide dispersion liquid;
2) preparing sulfonated graphene by adopting a solution blending modification method: adding 1g of sulfonated polyether ether ketone into 50mL of distilled water, stirring at 60 ℃ for dissolving, and adding the graphene oxide dispersion liquid obtained in the step 1) for continuous ultrasonic dispersion to obtain a mixed dispersion liquid;
adding 0.1mL of 85% hydrazine hydrate into the mixed dispersion liquid, carrying out reduction reaction by using a condensation reflux device (the reaction temperature is 100 ℃, the reaction time is 12 hours), and carrying out vacuum freeze drying for 48 hours (the temperature is minus 40 ℃, and the vacuum degree is 10 a-20 Pa) to obtain fluffy sulfonated graphene (marked as SPG);
3) preparing SPG @ PVDF @ Al composite powder by adopting a blending method: weighing 20mg of sulfonated graphene, uniformly dispersing the sulfonated graphene in an ethanol solution by using a cell disruptor (water: alcohol: 40mL:4 mL: 10:1), adding PVDF @ Al composite powder (the PVDF @ Al composite powder is added according to the mass of the sulfonated graphene), stirring until no powder floats on the surface of the dispersion, after the reaction is finished, carrying out suction filtration, washing and vacuum drying at 60 ℃ for 12h to obtain a metastable state composite material (marked as SPG @ PVDF @ Al composite powder, wherein the mass fraction of the sulfonated graphene is 2%).
The sulfonated polyether ether ketone (SPEEK) in example 1 is prepared as follows:
1) 6g of polyetheretherketone (particle size 50 μm) are weighed out and added slowly to 200mL of concentrated H2SO4(95-97 wt.%) and stirring vigorously to obtain a sulfonation reaction solution (solution concentration of polyetheretherketone is 0.03 g/mL);
2) after the sulfonation reaction solution is placed at room temperature for reaction for 48 hours, slowly adding 10 times of ice-cold distilled water at 0-5 ℃ into the violently stirred reaction solution to terminate the reaction;
3) soaking the reaction vessel for terminating the reaction in the step 2) in water, cooling for 12h, filtering, washing the precipitate with a large amount of distilled water until the pH value is 6-7, and drying the precipitate in a vacuum oven at 70 ℃ for 12h to obtain sulfonated polyether ether ketone (SPEEK).
The preparation method of the PVDF @ Al composite powder in example 1 of the present invention (see example 1 in patent publication No. CN 113683471A) specifically comprises the following steps:
1) weighing 1g of aluminum particles with the average particle size of 5 mu m, adding the aluminum particles into a solution with the volume ratio of water to ethanol of 1:1 (the actual dosage of the water and the ethanol is 20mL), and carrying out ultrasonic treatment for 30min by a cell disruption instrument at the power of 150W to obtain an aluminum particle suspension;
2) weighing 0.08g of polyvinylidene fluoride (PVDF), adding into 20mL of N, N-dimethylformamide solution, and stirring for 15min at 40 ℃ in a water bath kettle at the stirring speed of 800rpm to obtain a completely dissolved PVDF solution;
3) dripping a PVDF solution into an aluminum particle suspension under stirring at the speed of 2mL/min, performing suction filtration and washing after dripping is finished, and performing vacuum drying at 60 ℃ for 12 hours to obtain PVDF @ Al composite powder (namely polyvinylidene fluoride coated micron aluminum composite powder);
wherein, the purity of the Al powder is 99.9 percent, and the grain diameter is 4.5 to 5.5 mu m; the purity of the polyvinylidene fluoride is more than 99.9%, and the relative molecular mass is about 476000 (average).
Example 2
A metastable composite material, the preparation method comprising the following steps:
preparing RGO @ PVDF @ Al composite powder by a blending method: weighing 20mg of commercial thermal Reduction Graphene (RGO), uniformly dispersing in an ethanol solution by using a cell disruptor (water: alcohol: 40mL:4 mL: 10:1) in an ultrasonic manner, adding PVDF @ Al composite powder, stirring until no powder floats on the surface in the dispersion liquid, after the reaction is finished, carrying out suction filtration and washing, and carrying out vacuum drying at 60 ℃ for 12h to obtain a metastable state composite material (marked as RGO @ PVDF @ Al composite powder, wherein the mass fraction of the commercial thermal reduction Graphene is 2%).
Example 3
A metastable composite material, the preparation method comprising the steps of:
1) preparing a graphene oxide dispersion liquid: selecting graphene oxide with the particle size of 0.5-3 microns, and uniformly dispersing the graphene oxide in distilled water by using a cell disruptor to obtain 1mg/mL graphene oxide dispersion liquid;
2) preparing sulfonated graphene by adopting a solution blending modification method: adding 1g of sulfonated polyether ether ketone into 50mL of distilled water, stirring at 60 ℃ for dissolving, and adding the graphene oxide dispersion liquid obtained in the step 1) for continuous ultrasonic dispersion to obtain a mixed dispersion liquid;
adding 0.1mL of 85% hydrazine hydrate into the mixed dispersion liquid, carrying out reduction reaction by using a condensation reflux device (the reaction temperature is 100 ℃, the reaction time is 6 hours), and carrying out vacuum freeze drying for 48 hours to obtain fluffy sulfonated graphene (marked as SPG);
3) preparing SPG @ PVDF @ Al composite powder by adopting a blending method: weighing 10mg of sulfonated graphene, uniformly dispersing the sulfonated graphene in 40mL of distilled water by using a cell disruptor through ultrasonic waves, adding PVDF @ Al composite powder, stirring until no powder floats on the surface in a dispersion liquid, performing suction filtration and washing after the reaction is finished, and performing vacuum drying for 12h at the temperature of 60 ℃ to obtain a metastable state composite material (marked as SPG @ PVDF @ Al composite powder, wherein the mass fraction of the sulfonated graphene is 1%).
Example 4
A metastable composite material, the preparation method comprising the following steps:
preparing RGO @ PVDF @ Al composite powder by adopting a blending method: weighing 10mg of commercial thermal Reduction Graphene (RGO), uniformly dispersing in 40mL of distilled water by using a cell disruptor through ultrasound, adding PVDF @ Al composite powder, stirring until no powder floats on the surface in the dispersion liquid, and after the reaction is finished, carrying out suction filtration, washing and vacuum drying to obtain the metastable state composite material (marked as RGO @ PVDF @ Al composite powder, wherein the mass fraction of the commercial thermal reduction graphene is 1%).
Example 5
A metastable composite material, the preparation method comprising the following steps:
1) preparing a graphene oxide dispersion liquid: selecting graphene oxide with the particle size of 0.5-3 microns, and ultrasonically and uniformly dispersing the graphene oxide in distilled water through a cell disruptor to obtain 2mg/mL graphene oxide dispersion liquid;
2) preparing sulfonated graphene by adopting a solution blending modification method: adding 1g of sulfonated polyether ether ketone into 50mL of distilled water, stirring at 60 ℃ for dissolving, and adding the graphene oxide dispersion liquid obtained in the step 1) for continuous ultrasonic dispersion to obtain a mixed dispersion liquid;
adding 0.07mL of 85% hydrazine hydrate into the mixed dispersion liquid, carrying out reduction reaction by using a condensation reflux device (the reaction temperature is 100 ℃, the reaction time is 18 hours), and carrying out vacuum freeze drying for 48 hours to obtain fluffy sulfonated graphene (marked as SPG);
3) preparing SPG @ PVDF @ Al composite powder by adopting a blending method: weighing 30mg of sulfonated graphene, uniformly dispersing the sulfonated graphene in 60mL of ethanol by using a cell disruptor through ultrasound, adding the PVDF @ Al composite powder, stirring until no powder in the dispersion liquid floats on the surface, after the reaction is finished, carrying out suction filtration, washing and vacuum drying at 60 ℃ for 12h to obtain the metastable state composite material (marked as SPG @ PVDF @ Al composite powder, wherein the mass fraction of the sulfonated graphene is 3%).
Example 6
A metastable composite material, the preparation method comprising the following steps:
preparing RGO @ PVDF @ Al composite powder by adopting a blending method: weighing 30mg of commercial thermal Reduction Graphene (RGO), uniformly dispersing in 60mL of ethanol by using a cell disruptor by using ultrasound, adding PVDF @ Al composite powder, stirring until no powder floats on the surface in the dispersion liquid, after the reaction is finished, performing suction filtration, washing, and performing vacuum drying at 60 ℃ for 12h to obtain a metastable state composite material (marked as RGO @ PVDF @ Al composite powder, wherein the mass fraction of the commercial thermal reduction graphene is 3%).
Example 7
A metastable composite material, the preparation method comprising the following steps:
1) preparing a graphene oxide dispersion liquid: selecting graphene oxide with the particle size of 0.5-3 microns, and ultrasonically and uniformly dispersing the graphene oxide in distilled water through a cell disruptor to obtain 2mg/mL graphene oxide dispersion liquid;
2) preparing sulfonated graphene by adopting a solution blending modification method: adding 1g of sulfonated polyether ether ketone into 50mL of distilled water, stirring at 60 ℃ for dissolving, and adding the graphene oxide dispersion liquid obtained in the step 1) for continuous ultrasonic dispersion to obtain a mixed dispersion liquid;
adding 0.08mL of 85% hydrazine hydrate into the mixed dispersion liquid, carrying out reduction reaction by using a condensation reflux device (the reaction temperature is 100 ℃, the reaction time is 14h), and carrying out vacuum freeze drying for 48h to obtain fluffy sulfonated graphene (marked as SPG);
3) preparing SPG @ PVDF @ Al composite powder by a blending method: weighing 40mg of sulfonated graphene, uniformly dispersing the sulfonated graphene in an ethanol solution (water: ethanol is 80mL:40mL is 2:1), adding PVDF @ Al composite powder, stirring until no powder floats on the surface in the dispersion liquid, performing suction filtration, washing and vacuum drying at 60 ℃ for 12 hours after the reaction is finished, and obtaining the metastable state composite material (namely the SPG coated PVDF @ Al composite powder is marked as SPG @ PVDF @ Al composite powder, wherein the mass fraction of the sulfonated graphene is 4%).
Example 8
A metastable composite material, the preparation method comprising the following steps:
preparing RGO @ PVDF @ Al composite powder by adopting a blending method: weighing 40mg of commercial thermal Reduction Graphene (RGO), uniformly dispersing in an ethanol solution (water: ethanol 80mL:40 mL: 2:1) by using a cell disruptor by using ultrasound, adding PVDF @ Al composite powder, stirring until no powder floats on the surface of the dispersion, after the reaction is finished, carrying out suction filtration, washing, and vacuum drying at 60 ℃ for 12h to obtain the metastable state composite material (marked as RGO @ PVDF @ Al composite powder, wherein the mass fraction of the commercial thermal reduction graphene is 4%).
Comparative example 1
The present comparative example provides a PVDF @ Al composite powder, and a method for preparing the PVDF @ Al composite powder (see example 1 of patent document with patent publication No. CN 113683471A), specifically including the following steps:
1) weighing 1g of aluminum particles with the average particle size of 5 mu m, adding the aluminum particles into a solution with the volume ratio of water to ethanol of 1:1 (the actual dosage of the water and the ethanol is 20mL), and carrying out ultrasonic treatment for 30min by a cell disruption instrument at the power of 150W to obtain an aluminum particle suspension;
2) weighing 0.08g of polyvinylidene fluoride (PVDF), adding into 20mL of N, N-dimethylformamide solution, and stirring for 15min at 40 ℃ in a water bath kettle at the stirring speed of 800rpm to obtain a completely dissolved PVDF solution;
3) dropwise adding the PVDF solution into the aluminum particle suspension in a stirring state at the speed of 2mL/min, carrying out suction filtration and washing after dropwise adding is finished, and carrying out vacuum drying at 60 ℃ for 12h to obtain PVDF @ Al composite powder (namely polyvinylidene fluoride coated micron aluminum composite powder).
The PVDF @ Al composite powder is a PVDF-coated Al composite material, the RGO @ PVDF @ Al composite powder is an RGO-coated PVDF @ Al composite powder, and the RGO @ PVDF @ Al composite powder is an SPG-coated PVDF @ Al composite powder. The PVDF @ Al composite powders in examples 2 to 7 and comparative example 1 were all the same as in example 1, and the sulfonated polyether ether ketone in examples 3, 5, and 7 were all the same as in example 1. The commercial thermally reduced graphene of example 2, example 4, example 6 and example 8 was obtained from Nanjing Ginko Nykuk nanotechnology Co., Ltd (particle size 0.5 μm to 10 μm, thickness 1nm, carbon content 80 wt%, oxygen content 10 wt%).
And (3) performance testing:
the metastable state composite materials prepared in the embodiment 1 and the embodiment 2 are respectively used as representatives of the SPG @ PVDF @ Al composite powder and the RGO @ PVDF @ Al composite powder to carry out related characterization and performance tests.
1) Thermal analysis tests were performed on sulfonated graphene SPG, graphene oxide GO, and thermally reduced graphene RGO used in examples 1 to 8 (test conditions: air atmosphere, test temperature interval of 40 ℃ to 800 ℃), and Thermogravimetric (TG) results are shown in fig. 1.
As can be seen from fig. 1: in an air atmosphere, the quality of the sulfonated graphene SPG is slowly reduced along with the increase of the temperature, the sulfonated graphene SPG is not completely decomposed until 700 ℃, the residual quality of the sample approaches to 0, the graphene oxide GO is completely decomposed at 500 ℃, the thermally reduced graphene RGO is completely decomposed at 600 ℃, and obviously, the sulfonated graphene SPG has stronger heat resistance.
2) Scanning Electron Microscopy (SEM) images of the metastable composite material of example 1 and example 2 are shown in fig. 2. Wherein, a and b are SEM images of the SPG @ PVDF @ Al composite powder (the mass percentage of SPG is 2%) in example 1 under different magnifications, and c and d are SEM images of RGO @ PVDF @ Al composite powder (the mass percentage of RGO is 2%).
As can be seen from fig. 2: it can be seen from a and b that the SPG @ PVDF @ Al composite powder in example 1 is in a core-shell structure, and the sheet-shaped sulfonated graphene SPG can be effectively, uniformly, dispersedly and tightly coated on the surface of the PVDF @ Al composite powder, and thus is in a single-layer coating structure. It can be seen from c and d that the RGO @ PVDF @ Al composite powder prepared in example 2 also has a core-shell structure, and the lamellar thermally reduced graphene RGO can be effectively, uniformly, dispersedly and tightly coated on the surface of the PVDF @ Al composite powder, but a multi-layer coated structure can be observed on the surface of the RGO @ PVDF @ Al composite powder. The surface coating morphology of the metastable composite material in the example 1 and the example 2 is similar, but the SPG in the example 1 is coated by a single layer and is coated more tightly.
3) Infrared spectra of sulfonated polyetheretherketone SPEEK, sulfonated graphene SPG, graphene oxide GO, and thermally reduced graphene RGO prepared or used in the examples are shown in fig. 3. The IR spectra of the metastable composite material (SPG @ PVDF @ Al composite powder) of example 1 and the metastable composite material (PVDF @ Al composite powder) of comparative example 1 are shown in FIG. 4.
As can be seen from fig. 3: for graphene oxide GO, the characteristic peaks appear: 3193cm-1(iii) a-OH stretching vibration peak at 1728cm-1Carboxylic acid C ═ O stretching vibration peak at 1616cm-1Sp of (A)2Hybrid C ═ C vibration peak, 1362cm-1-1055cm-1And C-OH, -COO-and C-O-C vibration peaks, and during the preparation of the sulfonated graphene SPG by carrying out surface modification and chemical reduction on GO, the characteristic peak of GO disappears or the strength is obviously reduced.
The sulfonated graphene SPG prepared by the example method has an O ═ S ═ O symmetric stretching vibration peak (1080 cm)-1) And S ═ O stretching vibration peak (1022 cm)-1) And S-O stretching vibration peak (708 cm)-1) Three characteristic peaks, which verify sulfo SO3The presence of H. Meanwhile, compared with GO and SPEEK, the three characteristic peaks are shifted up on the sulfonated graphene SPG, which shows that the non-covalent interaction exists between the flaky oxidized graphene used as the raw material in the sulfonated graphene SPG and the sulfonated polyether ether ketone SPEEK which is a macromolecular polymer. The thermally reduced graphene RGO used in the examples also had a lower content of oxygen-containing groups, and was also subjected to reduction treatment, except that the surface was free of sulfonic acid groups, compared to the sulfonated graphene SPG used in the examples.
As can be seen from fig. 4: there are essentially no characteristic peaks for (aluminum material) Al. 532cm for pure PVDF powder-1、616cm-1、764cm-1、795cm-1、978cm-1Etc. the characteristic peaks shown correspond to the polycrystalline structure of PVDF. In the SPG @ PVDF @ Al composite powder, the polycrystalline peak of pure PVDF powder disappears or weakens, and the method specifically comprises the following steps: 503cm-1、840cm-1、1243cm-1、1274cm-1A series of weak characteristic peaks appear at the position, and belong to the polycrystalline structure of PVDF; 840cm-1、1274cm-1The appearance of characteristic peaks indicates that the beta phase in the material is retained; and a gamma phase (1243 cm)-1). The beta phase and the gamma phase exist in the SPG @ PVDF @ Al composite powder at the same time, and the transformation of the crystallinity is an important factor influencing the thermal resistance of the graphene-polymer interface, which indicates that the thermal resistance of the SPG @ PVDF @ Al composite powder can be changed. However, no SPG characteristic peak is observed in the SPG @ PVDF @ Al composite powder, which indicates that the SPG has a small content in the composite material and is uniformly distributed in the coating layer, and interaction possibly exists between the SPG and the core PVDF @ Al composite powder; and phase-CF in SPG @ PVDF @ Al composite powder2The bending vibration peak of-is shifted to a high position and shifted to a higher 881cm-1(PVDF @ Al composite powder-CF2The peak of bending vibration of-appears at 879cm-1Of) is due to SO present in SPG3H group dipole with-CF2Strong dipole interactions between dipoles.
4) A graph of the thermal sync analysis of the metastable composite materials of example 1, example 2 and comparative example 1 is shown in fig. 5. The thermal synchronous analysis atmosphere is air, the heating rate is 10 ℃/min, and the heating range is 40-1300 ℃. Wherein a is a TG diagram of the SPG @ PVDF @ Al composite powder in the example 1 and the PVDF @ Al composite powder in the comparative example 1, b is a DSC diagram of the SPG @ PVDF @ Al composite powder in the example 1 and the PVDF @ Al composite powder in the comparative example 1, c is a TG diagram of the GRO @ PVDF @ Al composite powder in the example 2 and the PVDF @ Al composite powder in the comparative example 1, and d is a DSC diagram of the GRO @ PVDF @ Al composite powder in the example 2 and the PVDF @ Al composite powder in the comparative example 1.
As can be seen from fig. 5: FIG. 5 (a) shows that the SPG @ PVDF @ Al composite powder of example 1 has a decreased thermal weight gain slope at 1300 ℃ indicating that the oxidation process tends to be gradual, while FIG. 5 (c) shows that the RGO @ PVDF @ Al composite of example 2 has no decrease in thermal weight gain slope at 1300 ℃ and still has an increasing trend due to incomplete utilization of active aluminum.
Referring to fig. 5 (b), the PVDF @ Al composite material in comparative example 1 has a bimodal effect (referring to a bimodal state at about 200 ℃), which is caused by the reaction of PVDF and Al, and the addition of both SPG and RGO does not change the bimodal effect, which indicates that the graphene material (referring to SPG and RGO) does not participate in any reaction in the system, and only plays a role in promoting heat transfer. Meanwhile, the surface oxidation of the SPG @ PVDF @ Al composite powder at 600 ℃ has a more obvious promoting effect, and the peak area and the strength of double peaks (which means double peaks at about 600 ℃) are higher, which is caused by the fact that the SPG is more resistant to high temperature. See (d) in FIG. 5, the effect of RGO on the composite system in example 2 is similar to that of SPG, and likewise does not participate in any reaction in the system, but it does not produce a surface oxidized bimodal after 600 ℃. Compared with the PVDF @ Al composite powder in the comparative example 1, the SPG and the RGO obviously improve the overall heat gain and enthalpy of the metastable composite materials in the examples 1 and 2.
Although the heat resistance of RGO is lower than that of SPG, the heat weight gain and the enthalpy of the system are improved less by SPG, the improvement of the interface bonding strength by the sulfonic acid group in the SPG @ PVDF @ Al composite powder is also shown to enable the energy release of the system to be more excellent, and the RGO is a more preferable technical scheme.
5) The heat gain and enthalpy comparison graphs of the SPG @ PVDF @ Al composite powder in example 1, the RGO @ PVDF @ Al composite powder prepared in example 2, the PVDF @ Al composite powder prepared in comparative example 1, and the raw material Al powder are shown in FIG. 6 and FIG. 7, respectively. The test results of thermal weight gain are based on data from the temperature range of 40 ℃ to 1300 ℃, while the enthalpy comparison analysis is based on data from the temperature range of 750 ℃ to 1300 ℃, and the related test results of synchronous thermal analysis are shown in table 1.
As can be seen from fig. 6, fig. 7 and table 1: compared with PVDF @ Al composite powder, the SPG @ PVDF @ Al composite powder and the RGO @ PVDF @ Al composite powder can effectively improve the energy release of a system, and show that the composite powder can better utilize active Al and has good heat resistance and heat transfer performance, and the analysis results of the test correspond to those in FIG. 5. The SPG @ PVDF @ Al composite powder is improved more remarkably, the weight gain can reach 70.31% after a thermal analysis test, and the enthalpy reaches 16710J/g.
TABLE 1 Simultaneous thermal analysis test results
Figure BDA0003520020720000101
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (10)

1. A metastable state composite material is characterized by having a core-shell structure, wherein the core is an aluminum particle coated by a fluorine-containing polymer, and the shell layer is a sulfonated graphene coating layer or a reduced graphene oxide coating layer.
2. The metastable composite material according to claim 1, characterized in that the fluoropolymer-coated aluminum particles have a fluoropolymer content of 5 to 15% by mass.
3. Metastable composite material according to claim 1 or 2, characterized in that the average particle size of the aluminum particles of said fluoropolymer-coated aluminum particles is between 1 μm and 10 μm.
4. Metastable composite material according to claim 3, characterized in that said fluoropolymer is at least one of polyvinylidene fluoride, polytetrafluoroethylene, fluorinated ethylene propylene copolymer, fluoroolefin-vinyl ether copolymer.
5. The metastable composite material according to claim 4, characterized in that: the mass percentage content of the shell layer in the metastable state composite material is 0.5-8%.
6. A method for preparing a metastable composite material according to any of claims 1 to 5, characterized by comprising the following steps:
1) adding the aluminum particle dispersion liquid into a fluorine-containing polymer solution, mixing, and separating a solid product to obtain fluorine-containing polymer coated aluminum particles;
2) dispersing sulfonated graphene or reduced graphene oxide in a solvent to prepare a dispersion liquid;
3) adding the fluoropolymer-coated aluminum particles into the dispersion liquid obtained in the step 2), mixing, and separating a solid product to obtain the metastable-state composite material.
7. The method for preparing the metastable composite material according to claim 6, wherein the step 2) of preparing the sulfonated graphene comprises the following steps: firstly, sulfonated polyether ether ketone is adopted to treat the graphene oxide, and then a reducing agent is used for reduction.
8. The method for preparing the metastable composite material according to claim 7, wherein the step 2) of preparing the sulfonated graphene comprises the following steps: adding graphene oxide into sulfonated polyether ether ketone dispersion liquid, performing ultrasonic dispersion at 50-80 ℃, adding a reducing agent, reacting for 6-20 h at 80-120 ℃, and performing vacuum freeze drying to obtain the sulfonated graphene.
9. The method of preparing a metastable composite material according to claim 8, characterized in that the reducing agent is at least one of hydrazine hydrate, sodium borohydride and ascorbic acid.
10. The method for the preparation of a metastable composite material according to claim 8 or 9, characterized in that the vacuum freeze-drying is carried out at a temperature of-30 ℃ to-50 ℃ and a vacuum degree of 10Pa to 20 Pa.
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