CN109148169B - Preparation method and application of graphene composite material - Google Patents
Preparation method and application of graphene composite material Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 113
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- 239000002131 composite material Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
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- 238000005406 washing Methods 0.000 claims abstract description 12
- 230000001681 protective effect Effects 0.000 claims abstract description 9
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- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims abstract description 7
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- 239000010935 stainless steel Substances 0.000 claims abstract description 7
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- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims abstract description 7
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- 238000000576 coating method Methods 0.000 claims description 13
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- 238000007254 oxidation reaction Methods 0.000 claims description 13
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- 239000000843 powder Substances 0.000 claims description 11
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- 239000010949 copper Substances 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
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- 239000012286 potassium permanganate Substances 0.000 claims description 9
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- 238000003828 vacuum filtration Methods 0.000 claims description 8
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- 239000004570 mortar (masonry) Substances 0.000 claims description 7
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 7
- 229910000831 Steel Inorganic materials 0.000 claims description 5
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- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 150000004706 metal oxides Chemical class 0.000 claims description 5
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- 238000012360 testing method Methods 0.000 description 8
- 229910001416 lithium ion Inorganic materials 0.000 description 6
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- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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Abstract
The invention provides a preparation method and application of a graphene composite material, wherein the method comprises the following steps: step 1, placing graphite oxide in a container, adding distilled water, performing ultrasonic treatment to obtain a graphene oxide suspension, and adding fully dissolved SnCl into the graphene oxide suspension4·5H2O, the graphite oxide and the SnCl4·5H2Performing ultrasonic dispersion for 20-25 min to obtain a prepared solution, wherein the mass ratio of O is 1.3: 1-1.5: 1; step 2, transferring the prepared solution into a polytetrafluoroethylene tank, placing the polytetrafluoroethylene tank into a stainless steel high-pressure reaction kettle, sealing, reacting at a constant temperature for 16-18 hours, and naturally cooling to room temperature; step 3, repeatedly washing the product obtained in the step 3-5 times by using distilled water, and performing suction filtration until the solution is neutral; step 4, drying at the constant temperature of 80 ℃, fully grinding, putting into an atmosphere tube furnace, and introducing protective gas N2And heating to 680-700 ℃, preserving the temperature for l-1.5 h, and cooling to room temperature to obtain the graphene composite material. The invention can solve the problem of poor electrical property.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a preparation method and application of a graphene composite material.
Background
With the increasing and obvious greenhouse effect, the ecological environment is more and more emphasized by people. Energy crisis and environmental protection are now the core of sustainable development in human society. The development of new energy sources is imminent. Among them, chemical power sources represented by lithium ion batteries and supercapacitors are used as novel clean energy sources, have the advantages of cleanness, no pollution, high energy utilization rate and low cost, and are more and more popular with people.
Whether a super capacitor or a lithium ion battery, the core affecting the performance is the electrode material. The traditional electrode material is difficult to meet the requirements of people on energy storage systems. The development of electrode materials with high capacity, high rate capability and long service life is urgently needed. The graphene composite material is expected to be used as a motor material for preparing a super capacitor or a lithium ion battery, but the existing graphene composite material has poor electrical properties, for example, the first charge and discharge capacity is not high, so that the energy density of the prepared super capacitor or the lithium ion battery is low.
Disclosure of Invention
In view of the above situation, an aspect of the present invention provides a method for preparing a graphene composite material, which solves the problem of poor electrical properties.
A preparation method of a graphene composite material comprises the following steps:
According to the preparation method of the graphene composite material provided by the invention, graphene and SnO are finally prepared2Wherein SnO2Energy is stored through an oxidation-reduction process, and graphene is stored through Li+Is embedded inOr the graphene is used as a conductive medium, so that the electron transfer in the lithium desorption and insertion process can be effectively promoted, and the SnO can be effectively improved2In addition, since graphene is coated on SnO2Can effectively inhibit SnO in the charge-discharge process2Prevents SnO2Thus SnO2The composition with the graphene is favorable for improving SnO2The final charge and discharge tests show that the prepared graphene composite material has advantages in first charge and discharge capacity compared with the graphene composite material in the prior art.
In addition, the preparation method of the graphene composite material according to the present invention may further have the following additional technical features:
further, before the step of placing the graphite oxide in the container, the method further comprises the step of preparing the graphite oxide, specifically comprising:
step 11, pre-oxidizing graphite:
adding concentrated H to the vessel2SO4Then the mixture is put into an oil bath pot for mechanical stirring, and natural graphite, potassium persulfate and P are sequentially added2O5After uniformly stirring, reacting for 3 hours at 70-80 ℃, cooling to room temperature, slowly adding distilled water into the container, and controlling the temperature in the container to be not more than 80 ℃; carrying out vacuum filtration on the mixed solution, placing the obtained filter cake in a clean beaker, adding distilled water again for dilution, carrying out vacuum filtration again until the filtrate is neutral, and finally placing the filter cake in an air-blast drying oven at 80 ℃ for drying for 10-12 h to obtain a pre-oxidation product;
step 12, oxidation of graphite:
step 121, add concentrated H to beaker under ice bath condition2SO4Grinding the pre-oxidized product obtained in the previous step, adding the ground pre-oxidized product into a beaker, uniformly stirring, and slowly adding the ground KMnO4Powder is fully reacted for 4 hours;
step 122, transferring the beaker into an oil bath kettle preheated to 35 ℃, mechanically stirring, reacting for 2 hours, slowly adding distilled water into a titration flask after the reaction is finished, and keeping the temperature in the beaker not to exceed 80 ℃, wherein the solution is dark brown;
step 123, raising the temperature of the oil bath to 95 ℃, mechanically stirring and reacting for 30min to obtain a yellowish solution, and adding H into the beaker2O2Changing the solution from light yellow to bright yellow, then adding 10% hydrochloric acid solution to remove unreacted metal oxide, repeatedly washing the product with distilled water until the solution is neutral, and finally freeze-drying the slurry-like product;
step 13, grinding:
and fully grinding the product freeze-dried in the last step by using an agate mortar to obtain the graphite oxide.
Further, in the step 1, the ultrasonic treatment is carried out for 4-6 hours after the distilled water is added.
Further, in the step 2, the temperature of the isothermal reaction is 160-175 ℃.
Further, in the step 4, protective gas N is introduced2Then heating to 700 ℃ at a speed of 15 ℃/min and then preserving heat for lh.
Further, in the step 11, the natural graphite, the potassium persulfate and the P are sequentially added in a mass ratio of 2:1:12O5。
Further, in the step 121, the KMnO4The mass of the powder is 4-5 times of that of the natural graphite.
Further, in the step 13, after fully grinding with an agate mortar, the graphite oxide is obtained by sieving with a 100-mesh sieve.
The invention also provides an application of the graphene composite material prepared by the method, and the prepared graphene composite material is used for an electric double layer super capacitor, and the assembling method of the electric double layer super capacitor comprises the following steps:
step 21, size mixing:
according to the mass percentage of 80: 10: 10 respectively weighing the graphene composite material, polytetrafluoroethylene emulsion with solid content of 60% and conductive carbon black, adding a proper amount of dispersant, uniformly stirring, heating to 60 ℃, and continuously stirring until absolute ethyl alcohol is completely volatilized to obtain a plasticine-shaped mixture;
step 22, coating:
coating the mixture on foamed nickel, flattening, putting into a vacuum drying oven, and drying under 0.08Mpa for 48h to obtain a coated electrode;
step 13, assembling:
punching the coated electrodes into a plurality of circular electrode plates, taking the two electrodes as a group with the same or close weight, and filling N2In the glove box according to: and assembling a copper cap, a copper sheet, the coated electrode, a diaphragm, the coated electrode, a steel ingot and a nut into a double electric layer super capacitor in sequence.
Compared with the prior art, the energy density of the finally prepared electric double layer super capacitor has advantages.
Further, in the step 22, the temperature in the vacuum drying oven is controlled to be 50-55 ℃.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
Fig. 1 is a flowchart of a method for preparing a graphene composite material according to an embodiment of the present invention.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Several embodiments of the invention are presented in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
Referring to fig. 1, an embodiment of the present invention provides a method for preparing a graphene composite material, including:
According to the preparation method of the graphene composite material provided by the embodiment of the invention, graphene and SnO are finally prepared2Wherein SnO2Energy is stored through an oxidation-reduction process, and graphene is stored through Li+The graphene is used as a conductive medium, so that the electron transfer in the lithium desorption process can be effectively promoted, and the SnO can be effectively improved2In addition, since graphene is coated on SnO2Can effectively inhibit SnO in the charge-discharge process2Prevents SnO2Thus SnO2The composition with the graphene is favorable for improving SnO2The final charge and discharge tests show that the prepared graphene composite material has the first charge and discharge capacity which is the same as that of the graphene in the prior artCompared with the composite material, the composite material has the advantages.
The following examples are intended to illustrate the invention in more detail. The embodiments of the present invention are not limited to the following specific examples. The present invention can be modified and implemented as appropriate within the scope of the main claim.
Example one
A preparation method of a graphene composite material comprises the following steps:
step 101, pre-oxidation of graphite:
adding concentrated H to the vessel2SO4Then placing the mixture into an oil bath pan for mechanical stirring, and sequentially adding natural graphite, potassium persulfate and P in a mass ratio of 2:1:12O5After being stirred uniformly, the mixture reacts for 3 hours at 70 ℃, distilled water is slowly added into a container after the mixture is cooled to room temperature, and the temperature in the container is controlled not to exceed 80 ℃; carrying out vacuum filtration on the mixed solution, placing the obtained filter cake in a clean beaker, adding distilled water again for dilution, carrying out vacuum filtration again until the filtrate is neutral, and finally placing the filter cake in an air-blast drying oven at 80 ℃ for drying for 10-12 h to obtain a pre-oxidation product;
step 102, oxidation of graphite:
step 1021, adding concentrated H to the beaker under ice bath conditions2SO4Grinding the pre-oxidized product obtained in the previous step, adding the ground pre-oxidized product into a beaker, uniformly stirring, and slowly adding the ground KMnO4Powder of said KMnO4The mass of the powder is 4 times of that of the natural graphite, and the reaction is fully carried out for 4 hours;
step 122, transferring the beaker into an oil bath kettle preheated to 35 ℃, mechanically stirring, reacting for 2 hours, slowly adding distilled water into a titration flask after the reaction is finished, and keeping the temperature in the beaker not to exceed 80 ℃, wherein the solution is dark brown;
step 123, raising the temperature of the oil bath to 95 ℃, mechanically stirring and reacting for 30min to obtain a yellowish solution, and adding H into the beaker2O2Changing the solution from light yellow to bright yellow, adding 10% (v/v) hydrochloric acid solution to remove unreacted metal oxide, and repeatedly washing the product with distilled water until the product is completely washedThe solution is neutral, and finally the slurry-like product is frozen and dried;
step 103, grinding:
fully grinding the product freeze-dried in the last step by using an agate mortar, and then sieving the product by using a 100-mesh sieve to obtain graphite oxide;
104, placing the graphite oxide in a container, adding distilled water, performing ultrasonic treatment for 4 hours to obtain a graphene oxide suspension, and adding fully dissolved SnCl into the graphene oxide suspension4·5H2O, the graphite oxide and the SnCl4·5H2Performing ultrasonic dispersion for 20min to obtain a prepared solution, wherein the mass ratio of O is 1.3: 1;
105, transferring the prepared solution into a polytetrafluoroethylene tank, placing the polytetrafluoroethylene tank into a stainless steel high-pressure reaction kettle, sealing, carrying out constant-temperature reaction 16, and then naturally cooling to room temperature, wherein the constant-temperature reaction temperature is 160 ℃;
step 106, repeatedly washing the product obtained in the step 3-5 times by using distilled water, and performing suction filtration until the solution is neutral;
107, drying at the constant temperature of 80 ℃, fully grinding, putting into an atmosphere tube furnace, and introducing protective gas N2And heating to 700 ℃ at a speed of 15 ℃/min, then preserving heat for lh, and cooling to room temperature to obtain the graphene composite material.
Through electrical property tests, the first charge and discharge capacities of the graphene composite material prepared in the embodiment are 842.2mAh g-1974.6mAh g-1。
The embodiment also provides an application of the graphene composite material prepared in the above, and the prepared graphene composite material is used for an electric double layer supercapacitor, and an assembly method of the electric double layer supercapacitor includes:
step 201, size mixing:
according to the mass percentage of 80: 10: 10 respectively weighing the graphene composite material, polytetrafluoroethylene emulsion with solid content of 60% and conductive carbon black, adding a proper amount of dispersant (alcohol), uniformly stirring, heating to 60 ℃, and continuously stirring until absolute ethyl alcohol is completely volatilized to obtain a plasticine-like mixture;
step 202, coating:
coating the mixture on foamed nickel, flattening, and putting into a vacuum drying oven, wherein the temperature in the vacuum drying oven is controlled at 50 ℃, and the drying is carried out for 48 hours under 0.08Mpa, so as to obtain the electrode with a good coating film;
step 13, assembling:
punching the coated electrodes into a plurality of circular electrode plates, taking the two electrodes as a group with the same or close weight, and filling N2In the glove box according to: and assembling a copper cap, a copper sheet, the coated electrode, a diaphragm, the coated electrode, a steel ingot and a nut into a double electric layer super capacitor in sequence.
Through electrical tests, the energy density of the finally prepared electric double layer super capacitor is 168.5 Wh/kg.
Example two
A preparation method of a graphene composite material comprises the following steps:
step 101, pre-oxidation of graphite:
adding concentrated H to the vessel2SO4Then placing the mixture into an oil bath pan for mechanical stirring, and sequentially adding natural graphite, potassium persulfate and P in a mass ratio of 2:1:12O5After being stirred uniformly, the mixture reacts for 3 hours at 75 ℃, distilled water is slowly added into the container after the mixture is cooled to room temperature, and the temperature in the container is controlled not to exceed 80 ℃; carrying out vacuum filtration on the mixed solution, placing the obtained filter cake in a clean beaker, adding distilled water again for dilution, carrying out vacuum filtration again until the filtrate is neutral, and finally placing the filter cake in an air-blast drying oven at 80 ℃ for drying for 10-12 h to obtain a pre-oxidation product;
step 102, oxidation of graphite:
step 1021, adding concentrated H to the beaker under ice bath conditions2SO4Grinding the pre-oxidized product obtained in the previous step, adding the ground pre-oxidized product into a beaker, uniformly stirring, and slowly adding the ground KMnO4Powder of said KMnO4The mass of the powder is 4.5 times of that of the natural graphite, and the reaction is fully carried out for 4 hours;
step 122, transferring the beaker into an oil bath kettle preheated to 35 ℃, mechanically stirring, reacting for 2 hours, slowly adding distilled water into a titration flask after the reaction is finished, and keeping the temperature in the beaker not to exceed 80 ℃, wherein the solution is dark brown;
step 123, raising the temperature of the oil bath to 95 ℃, mechanically stirring and reacting for 30min to obtain a yellowish solution, and adding H into the beaker2O2Changing the solution from light yellow to bright yellow, then adding 10% (v/v) hydrochloric acid solution to remove unreacted metal oxide, repeatedly washing the product with distilled water until the solution is neutral, and finally freeze-drying the slurry-like product;
step 103, grinding:
fully grinding the product freeze-dried in the last step by using an agate mortar, and then sieving the product by using a 100-mesh sieve to obtain graphite oxide;
104, placing the graphite oxide in a container, adding distilled water, performing ultrasonic treatment for 5 hours to obtain a graphene oxide suspension, and adding fully dissolved SnCl into the graphene oxide suspension4·5H2O, the graphite oxide and the SnCl4·5H2Performing ultrasonic dispersion for 22min to obtain a prepared solution, wherein the mass ratio of O is 1.4: 1;
105, transferring the prepared solution to a polytetrafluoroethylene tank, placing the polytetrafluoroethylene tank in a stainless steel high-pressure reaction kettle, sealing, reacting at a constant temperature for 17 hours, and naturally cooling to room temperature, wherein the temperature of the constant-temperature reaction is 170 ℃;
step 106, repeatedly washing the product obtained in the step 3-5 times by using distilled water, and performing suction filtration until the solution is neutral;
107, drying at the constant temperature of 80 ℃, fully grinding, putting into an atmosphere tube furnace, and introducing protective gas N2And heating to 680 ℃ at the speed of 15 ℃/min, preserving the heat for l.5h, and cooling to room temperature to obtain the graphene composite material.
Through electrical property tests, the first charge and discharge capacities of the graphene composite material prepared in the embodiment are 837.4mAh g-1953.2mAh g-1。
The embodiment also provides an application of the graphene composite material prepared in the above, and the prepared graphene composite material is used for an electric double layer supercapacitor, and an assembly method of the electric double layer supercapacitor includes:
step 201, size mixing:
according to the mass percentage of 80: 10: 10 respectively weighing the graphene composite material, polytetrafluoroethylene emulsion with solid content of 60% and conductive carbon black, adding a proper amount of dispersant (alcohol), uniformly stirring, heating to 60 ℃, and continuously stirring until absolute ethyl alcohol is completely volatilized to obtain a plasticine-like mixture;
step 202, coating:
coating the mixture on foamed nickel, flattening, and putting into a vacuum drying oven, wherein the temperature in the vacuum drying oven is controlled at 53 ℃, and the drying is carried out for 48 hours under 0.08Mpa, so as to obtain the electrode with a good coating film;
step 13, assembling:
punching the coated electrodes into a plurality of circular electrode plates, taking the two electrodes as a group with the same or close weight, and filling N2In the glove box according to: and assembling a copper cap, a copper sheet, the coated electrode, a diaphragm, the coated electrode, a steel ingot and a nut into a double electric layer super capacitor in sequence.
Through electrical property tests, the energy density of the finally prepared electric double layer super capacitor is 159.7 Wh/kg.
EXAMPLE III
A preparation method of a graphene composite material comprises the following steps:
step 101, pre-oxidation of graphite:
adding concentrated H to the vessel2SO4Then placing the mixture into an oil bath pan for mechanical stirring, and sequentially adding natural graphite, potassium persulfate and P in a mass ratio of 2:1:12O5After being stirred uniformly, the mixture reacts for 3 hours at the temperature of 80 ℃, distilled water is slowly added into a container after the mixture is cooled to the room temperature, and the temperature in the container is controlled not to exceed 80 ℃; vacuum filtering the mixed solution to obtain filter cake, diluting with distilled water, filtering until the filtrate is neutral, and filteringDrying the cake in a forced air drying oven at 80 ℃ for 10-12 h to obtain a pre-oxidation product;
step 102, oxidation of graphite:
step 1021, adding concentrated H to the beaker under ice bath conditions2SO4Grinding the pre-oxidized product obtained in the previous step, adding the ground pre-oxidized product into a beaker, uniformly stirring, and slowly adding the ground KMnO4Powder of said KMnO4The mass of the powder is 5 times of that of the natural graphite, and the powder is fully reacted for 4 hours;
step 122, transferring the beaker into an oil bath kettle preheated to 35 ℃, mechanically stirring, reacting for 2 hours, slowly adding distilled water into a titration flask after the reaction is finished, and keeping the temperature in the beaker not to exceed 80 ℃, wherein the solution is dark brown;
step 123, raising the temperature of the oil bath to 95 ℃, mechanically stirring and reacting for 30min to obtain a yellowish solution, and adding H into the beaker2O2Changing the solution from light yellow to bright yellow, then adding 10% (v/v) hydrochloric acid solution to remove unreacted metal oxide, repeatedly washing the product with distilled water until the solution is neutral, and finally freeze-drying the slurry-like product;
step 103, grinding:
fully grinding the product freeze-dried in the last step by using an agate mortar, and then sieving the product by using a 100-mesh sieve to obtain graphite oxide;
104, placing the graphite oxide in a container, adding distilled water, performing ultrasonic treatment for 6 hours to obtain a graphene oxide suspension, and adding fully dissolved SnCl into the graphene oxide suspension4·5H2O, the graphite oxide and the SnCl4·5H2Performing ultrasonic dispersion for 25min to obtain a prepared solution, wherein the mass ratio of O is 1.5: 1;
105, transferring the prepared solution to a polytetrafluoroethylene tank, placing the polytetrafluoroethylene tank in a stainless steel high-pressure reaction kettle, sealing, reacting at a constant temperature for 18 hours, and naturally cooling to room temperature, wherein the constant temperature reaction temperature is 175 ℃;
step 106, repeatedly washing the product obtained in the step 3-5 times by using distilled water, and performing suction filtration until the solution is neutral;
107, drying at the constant temperature of 80 ℃, fully grinding, putting into an atmosphere tube furnace, and introducing protective gas N2And heating to 690 ℃ at a speed of 15 ℃/min, preserving the heat for l.3h, and cooling to room temperature to obtain the graphene composite material.
Through electrical property tests, the first charge and discharge capacities of the graphene composite material prepared in the embodiment are 843.9mAh g-1947.1mAh g-1。
The embodiment also provides an application of the graphene composite material prepared in the above, and the prepared graphene composite material is used for an electric double layer supercapacitor, and an assembly method of the electric double layer supercapacitor includes:
step 201, size mixing:
according to the mass percentage of 80: 10: 10 respectively weighing the graphene composite material, polytetrafluoroethylene emulsion with solid content of 60% and conductive carbon black, adding a proper amount of dispersant (alcohol), uniformly stirring, heating to 60 ℃, and continuously stirring until absolute ethyl alcohol is completely volatilized to obtain a plasticine-like mixture;
step 202, coating:
coating the mixture on foamed nickel, flattening, and putting into a vacuum drying oven, wherein the temperature in the vacuum drying oven is controlled at 55 ℃, and drying is carried out for 48 hours under 0.08Mpa, so as to obtain an electrode with a good coating film;
step 13, assembling:
punching the coated electrodes into a plurality of circular electrode plates, taking the two electrodes as a group with the same or close weight, and filling N2In the glove box according to: and assembling a copper cap, a copper sheet, the coated electrode, a diaphragm, the coated electrode, a steel ingot and a nut into a double electric layer super capacitor in sequence.
Through electrical property tests, the energy density of the finally prepared electric double layer super capacitor is 155.8 Wh/kg.
The table compares the first charge and discharge capacity of the graphene composite material prepared by the three embodiments and the method in the prior art and the energy density of the electric double layer supercapacitor, and it is obvious from the table that the first charge and discharge capacity of the graphene composite material finally prepared by the method in the three embodiments of the invention and the energy density of the electric double layer supercapacitor are superior to those in the prior art, and the method has obvious advantages.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (8)
1. A preparation method of a graphene composite material is characterized by comprising the following steps:
step 1, placing graphite oxide in a container, adding distilled water, performing ultrasonic treatment to obtain a graphene oxide suspension, and adding fully dissolved SnCl into the graphene oxide suspension4·5H2O, the graphite oxide and the SnCl4·5H2Performing ultrasonic dispersion for 20-25 min to obtain a prepared solution, wherein the mass ratio of O is 1.3: 1-1.5: 1;
step 2, transferring the prepared solution into a polytetrafluoroethylene tank, placing the polytetrafluoroethylene tank into a stainless steel high-pressure reaction kettle, sealing, reacting at a constant temperature for 16-18 hours, and naturally cooling to room temperature;
step 3, repeatedly washing the product obtained in the step 3-5 times by using distilled water, and performing suction filtration until the solution is neutral;
step 4, drying at the constant temperature of 80 ℃, fully grinding, putting into an atmosphere tube furnace, and introducing protective gas N2Heating to 680-700 ℃, preserving heat for l-1.5 h, and cooling to room temperature to obtain the graphene composite materialWherein a protective gas N is introduced2Then heating to 700 ℃ at a speed of 15 ℃/min and then preserving heat for lh;
before the step of placing the graphite oxide in the container, the method further comprises the step of preparing the graphite oxide, and specifically comprises the following steps:
step 11, pre-oxidizing graphite:
adding concentrated H to the vessel2SO4Then the mixture is put into an oil bath pot for mechanical stirring, and natural graphite, potassium persulfate and P are sequentially added2O5After uniformly stirring, reacting for 3 hours at 70-80 ℃, cooling to room temperature, slowly adding distilled water into the container, and controlling the temperature in the container to be not more than 80 ℃; carrying out vacuum filtration on the mixed solution, placing the obtained filter cake in a clean beaker, adding distilled water again for dilution, carrying out vacuum filtration again until the filtrate is neutral, and finally placing the filter cake in an air-blast drying oven at 80 ℃ for drying for 10-12 h to obtain a pre-oxidation product;
step 12, oxidation of graphite:
step 121, add concentrated H to beaker under ice bath condition2SO4Grinding the pre-oxidized product obtained in the previous step, adding the ground pre-oxidized product into a beaker, uniformly stirring, and slowly adding the ground KMnO4Powder is fully reacted for 4 hours;
step 122, transferring the beaker into an oil bath kettle preheated to 35 ℃, mechanically stirring, reacting for 2 hours, slowly adding distilled water into a titration flask after the reaction is finished, and keeping the temperature in the beaker not to exceed 80 ℃, wherein the solution is dark brown;
step 123, raising the temperature of the oil bath to 95 ℃, mechanically stirring and reacting for 30min to obtain a yellowish solution, and adding H into the beaker2O2Changing the solution from light yellow to bright yellow, then adding 10% hydrochloric acid solution to remove unreacted metal oxide, repeatedly washing the product with distilled water until the solution is neutral, and finally freeze-drying the slurry-like product;
step 13, grinding:
and fully grinding the product freeze-dried in the last step by using an agate mortar to obtain the graphite oxide.
2. The preparation method of the graphene composite material according to claim 1, wherein in the step 1, the ultrasonic treatment is performed for 4-6 hours after the distilled water is added.
3. The preparation method of the graphene composite material according to claim 1, wherein in the step 2, the temperature of the isothermal reaction is 160-175 ℃.
4. The method for preparing the graphene composite material according to claim 2, wherein in the step 11, the natural graphite, the potassium persulfate and the P are sequentially added in a mass ratio of 2:1:12O5。
5. The method for preparing the graphene composite material according to claim 2, wherein in the step 121, the KMnO is used4The mass of the powder is 4-5 times of that of the natural graphite.
6. The method for preparing the graphene composite material according to claim 2, wherein in the step 13, the graphite oxide is obtained by fully grinding with an agate mortar and then sieving with a 100-mesh sieve.
7. Use of the graphene composite material prepared according to claim 1, wherein the prepared graphene composite material is used in an electric double layer supercapacitor, and the method for assembling the electric double layer supercapacitor comprises:
step 21, size mixing:
according to the mass percentage of 80: 10: 10 respectively weighing the graphene composite material, polytetrafluoroethylene emulsion with solid content of 60% and conductive carbon black, adding a proper amount of dispersant, uniformly stirring, heating to 60 ℃, and continuously stirring until absolute ethyl alcohol is completely volatilized to obtain a plasticine-shaped mixture;
step 22, coating:
coating the mixture on foamed nickel, flattening, putting into a vacuum drying oven, and drying under 0.08Mpa for 48h to obtain a coated electrode;
step 13, assembling:
punching the coated electrodes into a plurality of circular electrode plates, taking the two electrodes as a group with the same or close weight, and filling N2In the glove box according to: and assembling a copper cap, a copper sheet, the coated electrode, a diaphragm, the coated electrode, a steel ingot and a nut into a double electric layer super capacitor in sequence.
8. The application of the graphene composite material according to claim 7, wherein in the step 22, the temperature in the vacuum drying oven is controlled to be 50-55 ℃.
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Denomination of invention: Preparation Method and Application of Graphene Composite Materials Effective date of registration: 20230808 Granted publication date: 20201117 Pledgee: Yunongshang Financial Leasing Co.,Ltd. Pledgor: NANCHANG INSTITUTE OF TECHNOLOGY Registration number: Y2023980051441 |