CN109148169A - The preparation method and application of graphene composite material - Google Patents
The preparation method and application of graphene composite material Download PDFInfo
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- CN109148169A CN109148169A CN201810838173.9A CN201810838173A CN109148169A CN 109148169 A CN109148169 A CN 109148169A CN 201810838173 A CN201810838173 A CN 201810838173A CN 109148169 A CN109148169 A CN 109148169A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 79
- 239000002131 composite material Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 38
- 239000010439 graphite Substances 0.000 claims abstract description 38
- 239000012153 distilled water Substances 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000000725 suspension Substances 0.000 claims abstract description 12
- 230000001681 protective effect Effects 0.000 claims abstract description 9
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims abstract description 7
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 7
- 239000010935 stainless steel Substances 0.000 claims abstract description 7
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims abstract description 7
- 238000010792 warming Methods 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 43
- 239000000047 product Substances 0.000 claims description 32
- 230000003647 oxidation Effects 0.000 claims description 20
- 238000007254 oxidation reaction Methods 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 10
- 239000012065 filter cake Substances 0.000 claims description 10
- 238000010907 mechanical stirring Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 10
- -1 after mixing evenly Chemical compound 0.000 claims description 9
- 229910021382 natural graphite Inorganic materials 0.000 claims description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 239000004570 mortar (masonry) Substances 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 6
- 235000019394 potassium persulphate Nutrition 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 241000238370 Sepia Species 0.000 claims description 5
- 229910000831 Steel Inorganic materials 0.000 claims description 5
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 5
- 239000012895 dilution Substances 0.000 claims description 5
- 238000010790 dilution Methods 0.000 claims description 5
- 239000002270 dispersing agent Substances 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 239000006260 foam Substances 0.000 claims description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 239000012286 potassium permanganate Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000010959 steel Substances 0.000 claims description 5
- 238000004448 titration Methods 0.000 claims description 5
- 238000000527 sonication Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims 1
- 239000000839 emulsion Substances 0.000 claims 1
- 238000000227 grinding Methods 0.000 claims 1
- 229910044991 metal oxide Inorganic materials 0.000 claims 1
- 150000004706 metal oxides Chemical class 0.000 claims 1
- 239000002023 wood Substances 0.000 claims 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 16
- 239000004810 polytetrafluoroethylene Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 239000006210 lotion Substances 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 230000005611 electricity Effects 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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Abstract
The present invention provides a kind of preparation method and applications of graphene composite material, the described method includes: step 1, graphite oxide is placed in container, it is ultrasonically treated after distilled water is added, graphene oxide suspension is obtained, the SnCl sufficiently dissolved is added into graphene oxide suspension4·5H2O, the graphite oxide and the SnCl4·5H2Mass ratio 1.3:1~1.5:1 of O, 20~25min of ultrasonic disperse obtain configured solution；Step 2, the prepared solution is transferred in polytetrafluoroethyltank tank, is placed in the autoclave of stainless steel, sealed, cooled to room temperature after 16~18h of isothermal reaction；Step 3, product obtained in above-mentioned steps is washed 3~5 times repeatedly with distilled water, is filtered, until solution is in neutrality；Step 4, it after 80 DEG C of freeze-day with constant temperature, is fully ground, is put into atmosphere tube type furnace, be passed through protective gas N2, l~1.5h is kept the temperature after being warming up to 680~700 DEG C, is cooled to room temperature to get the graphene composite material is arrived.The present invention can solve electric property difference problem.
Description
Technical field
The present invention relates to technical field of composite materials, a kind of preparation method more particularly to graphene composite material and answer
With.
Background technique
Further obvious with greenhouse effects, ecological environment is more and more valued by people.Energy crisis and environment are protected
The core of human social is had become before eye protection.The Development of Novel energy is extremely urgent.Wherein, with lithium-ion electric
Pond and supercapacitor are the electrochmical power source of representative as novel clean energy resource, have cleanliness without any pollution, high-energy utilization rate
With low cost advantage, increasingly by the pro-gaze of people.
Either supercapacitor or lithium ion battery, the core for influencing its performance is all electrode material.Traditional electricity
Pole material has been difficult the requirement for meeting people to energy-storage system.Urgent need exploitation has high capacity, high rate capability, longevity
The electrode material of life.Graphene composite material is expected to prepare the system of supercapacitor or lithium ion battery as motor material
It is standby, but that there is also electric properties is poor for existing graphene composite material, for example, the capacity of charge and discharge for the first time is not high, causes to make
The energy density of standby supercapacitor or lithium ion battery out is lower.
Summary of the invention
In view of the above situation, an aspect of of the present present invention provides a kind of preparation method of graphene composite material, solves electricity
Performance difference problem.
A kind of preparation method of graphene composite material, comprising:
Step 1, graphite oxide is placed in container, is ultrasonically treated after distilled water is added, it is outstanding to obtain graphene oxide
The SnCl sufficiently dissolved is added into graphene oxide suspension for supernatant liquid4·5H2O, the graphite oxide with it is described
SnCl4·5H2Mass ratio 1.3:1~1.5:1 of O, 20~25min of ultrasonic disperse obtain configured solution；
Step 2, the prepared solution is transferred in polytetrafluoroethyltank tank, is placed in the autoclave of stainless steel
In, it seals, cooled to room temperature after 16~18h of isothermal reaction；
Step 3, product obtained in above-mentioned steps is washed 3~5 times repeatedly with distilled water, is filtered, until solution is in neutrality
Until；
Step 4, it after 80 DEG C of freeze-day with constant temperature, is fully ground, is put into atmosphere tube type furnace, be passed through protective gas N2, heating
L~1.5h is kept the temperature after to 680~700 DEG C, is cooled to room temperature to get the graphene composite material is arrived.
The preparation method of the graphene composite material provided according to the present invention, finally prepares graphene and SnO2It is compound
Material, wherein SnO2It is by oxidation-reduction process energy storage, graphene is to pass through Li+Insertion or adsorption energy-storing, graphene make
For a kind of conducting medium, the electron transmission during removal lithium embedded can have been effectively facilitated, can also effectively improve SnO2Capacity characteristic,
Further, since graphene coated is in SnO2Nano particle around, can effectively inhibit SnO in charge and discharge process2Huge body
Product expansion, prevents SnO2Nano particle reunion, therefore SnO2It is compound with graphene, be conducive to improve SnO2Appearance
Measure utilization rate, final charge-discharge test shows the stone of the graphene composite material of preparation charge and discharge capacity and the prior art for the first time
Black alkene composite material is compared, and has advantage.
In addition, the preparation method of above-mentioned graphene composite material according to the present invention, can also have following additional skill
Art feature:
Further, it is described graphite oxide is placed in the step in container before, the method also includes graphite oxides
Preparation, specifically includes:
Step 11, the pre-oxidation of graphite:
Dense H is added into container2SO4, it is then placed in mechanical stirring in oil bath pan, sequentially adds natural graphite, persulfuric acid
Potassium, P2O5, after mixing evenly, distilled water is slowly added in 70~80 DEG C of reaction 3h into container after being cooled to room temperature, control is held
Temperature in device is no more than 80 DEG C；Mixed solution is filtered by vacuum, obtained filter cake is placed in clean beaker, again plus
Enter distilled water dilution, then filters, until filtrate is in neutrality, filter cake is finally put into 80 DEG C of air dry ovens dry 10~
12h obtains pre-oxidation product；
Step 12, the oxidation of graphite:
Step 121, dense H is added into beaker under condition of ice bath2SO4, the pre-oxidation product that upper step is obtained grinds
After be added in beaker, stir evenly, finely ground KMnO be slowly added4Powder, sufficiently reaction 4h；
Step 122, beaker is transferred to and is previously heated in 35 DEG C of oil bath pans, mechanical stirring reacts 2h, and reaction is completed
Afterwards, distilled water is slowly added with titration bottle, the temperature in beaker is kept to be no more than 80 DEG C, solution is in sepia at this time；
Step 123, oil bath temperature is risen to 95 DEG C, mechanic whirl-nett reaction 30min, solution is in faint yellow, into beaker
H is added2O2, solution becomes glassy yellow by faint yellow, and 10% hydrochloric acid solution is then added, removes the complete metal oxygen of unreacted
Compound, then product is washed to solution repeatedly with distilled water and is in neutrality, finally slimy product is freeze-dried；
Step 13, it grinds:
After the product being freeze-dried in previous step is fully ground with agate mortar, the graphite oxide is obtained.
Further, in the step 1, sonication treatment time is carried out as 4~6h after distilled water is added.
Further, in the step 2, the temperature of isothermal reaction is 160~175 DEG C.
Further, in the step 4, it is passed through protective gas N2Lh is kept the temperature after being warming up to 700 DEG C afterwards with 15 DEG C/min.
Further, in the step 11, the natural graphite, potassium peroxydisulfate, the P of mass ratio 2:1:1 are sequentially added2O5。
Further, in the step 121, the KMnO4The quality of powder is 4~5 times of the natural graphite quality.
Further, it in the step 13, after agate mortar is fully ground, sieves with 100 mesh sieve, obtains the graphite oxide.
Another aspect of the present invention also provides a kind of application of the graphene composite material of above method preparation, will be obtained
The graphene composite material is used for double electric layers supercapacitor, and the assemble method of the double electric layers supercapacitor includes:
Step 21, it sizes mixing:
80:10:10 weighs the polytetrafluoroethylene (PTFE) of the graphene composite material, solid content 60% respectively by mass percentage
Lotion and conductive black are added suitable dispersing agent, stir evenly, and are heated to 60 DEG C, are stirred continuously to dehydrated alcohol and are evaporated completely
Entirely, the mixture of rubber pureed is obtained；
Step 22, film:
It is coated in described in nickel foam, flattens, be put into vacuum oven, dry 48h, obtains film at 0.08Mpa
Good electrode；
Step 13, it assembles:
The good electrode of the film is washed into several circular electric pole pieces, take two electrode weights identical or it is close be one
Group is being full of N2Glove box according to the good electrode-membrane-film of copper cap-copper sheet-film good electrode-rust
Steel ingot-nut sequence is assembled into double electric layers supercapacitor.
The energy density of the double electric layers supercapacitor finally prepared compared with prior art, has advantage.
Further, in the step 22, the temperature in the vacuum oven is controlled at 50~55 DEG C.
Additional aspect and advantage of the invention will be set forth in part in the description, and will partially become from the following description
Obviously, or practice through the invention is recognized.
Detailed description of the invention
Fig. 1 is the flow chart of the preparation method of the graphene composite material of embodiment of the present invention.
Specific embodiment
To facilitate the understanding of the present invention, a more comprehensive description of the invention is given in the following sections with reference to the relevant attached drawings.In attached drawing
Give several embodiments of the invention.But the invention can be realized in many different forms, however it is not limited to this paper institute
The embodiment of description.On the contrary, purpose of providing these embodiments is make it is more thorough and comprehensive to the disclosure.
Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention
The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool
The purpose of the embodiment of body, it is not intended that in the limitation present invention.Term " and or " used herein includes one or more phases
Any and all combinations of the listed item of pass.
Referring to Fig. 1, embodiments of the present invention provide a kind of preparation method of graphene composite material, comprising:
Step 1, graphite oxide is placed in container, is ultrasonically treated after distilled water is added, it is outstanding to obtain graphene oxide
The SnCl sufficiently dissolved is added into graphene oxide suspension for supernatant liquid4·5H2O, the graphite oxide with it is described
SnCl4·5H2Mass ratio 1.3:1~1.5:1 of O, 20~25min of ultrasonic disperse obtain configured solution；
Step 2, the prepared solution is transferred in polytetrafluoroethyltank tank, is placed in the autoclave of stainless steel
In, it seals, cooled to room temperature after 16~18h of isothermal reaction；
Step 3, product obtained in above-mentioned steps is washed 3~5 times repeatedly with distilled water, is filtered, until solution is in neutrality
Until；
Step 4, it after 80 DEG C of freeze-day with constant temperature, is fully ground, is put into atmosphere tube type furnace, be passed through protective gas N2, heating
L~1.5h is kept the temperature after to 680~700 DEG C, is cooled to room temperature to get the graphene composite material is arrived.
According to the present invention embodiment provide graphene composite material preparation method, finally prepare graphene and
SnO2Composite material, wherein SnO2It is by oxidation-reduction process energy storage, graphene is to pass through Li+Insertion or absorption storage
Can, graphene can effectively facilitate the electron transmission during removal lithium embedded as a kind of conducting medium, can also effectively improve SnO2
Capacity characteristic, further, since graphene coated is in SnO2Nano particle around, can effectively inhibit in charge and discharge process
SnO2Enormousness expansion, prevent SnO2Nano particle reunion, therefore SnO2It is compound with graphene, be conducive to
Improve SnO2Capacity utilization, final charge-discharge test shows the graphene composite material of preparation charge and discharge capacity for the first time
Compared with the graphene composite material of the prior art, there is advantage.
Divide multiple embodiments that the embodiment of the present invention is further detailed below.The embodiment of the present invention be not limited to
Under specific embodiment.Within the scope of the unchanged main rights, implementation can appropriate be changed.
Embodiment one
A kind of preparation method of graphene composite material, comprising:
Step 101, the pre-oxidation of graphite:
Dense H is added into container2SO4, it is then placed in mechanical stirring in oil bath pan, sequentially adds the natural of mass ratio 2:1:1
Graphite, potassium peroxydisulfate, P2O5, after mixing evenly, distilled water is slowly added into container after being cooled to room temperature by 70 DEG C of reaction 3h,
The temperature controlled in container is no more than 80 DEG C；Mixed solution is filtered by vacuum, obtained filter cake is placed in clean beaker,
Distilled water dilution is added again, then filters, until filtrate is in neutrality, finally filter cake is put into 80 DEG C of air dry ovens and is done
Dry 10~12h obtains pre-oxidation product；
Step 102, the oxidation of graphite:
Step 1021, dense H is added into beaker under condition of ice bath2SO4, the pre-oxidation product that upper step is obtained grinds
It is added in beaker, stirs evenly after mill, finely ground KMnO is slowly added4Powder, the KMnO4The quality of powder is described
4 times of natural graphite quality, sufficiently reaction 4h；
Step 122, beaker is transferred to and is previously heated in 35 DEG C of oil bath pans, mechanical stirring reacts 2h, and reaction is completed
Afterwards, distilled water is slowly added with titration bottle, the temperature in beaker is kept to be no more than 80 DEG C, solution is in sepia at this time；
Step 123, oil bath temperature is risen to 95 DEG C, mechanic whirl-nett reaction 30min, solution is in faint yellow, into beaker
H is added2O2, solution becomes glassy yellow by faint yellow, and the hydrochloric acid solution of 10% (v/v) is then added, and removal unreacted is completely golden
Belong to oxide, then product is washed to solution repeatedly with distilled water and is in neutrality, is finally freeze-dried slimy product；
Step 103, it grinds:
It after the product being freeze-dried in previous step is fully ground with agate mortar, sieves with 100 mesh sieve, obtains graphite oxide；
Step 104, the graphite oxide is placed in container, carries out ultrasonic treatment 4h after distilled water is added, is aoxidized
The SnCl sufficiently dissolved is added into graphene oxide suspension for graphene suspension4·5H2O, the graphite oxide with
The SnCl4·5H2The mass ratio 1.3:1 of O, ultrasonic disperse 20min obtain configured solution；
Step 105, the prepared solution is transferred in polytetrafluoroethyltank tank, is placed in the autoclave of stainless steel
In, sealing, cooled to room temperature after isothermal reaction 16, wherein the temperature of isothermal reaction is 160 DEG C；
Step 106, product obtained in above-mentioned steps is washed 3~5 times repeatedly with distilled water, is filtered, until during solution is in
Until property；
Step 107, it after 80 DEG C of freeze-day with constant temperature, is fully ground, is put into atmosphere tube type furnace, be passed through protective gas N2, with
15 DEG C/min keeps the temperature lh after being warming up to 700 DEG C, is cooled to room temperature to get the graphene composite material is arrived.
By electrical testing, the capacity of charge and discharge for the first time for the graphene composite material that the present embodiment is prepared is respectively
842.2mAh·g-1And 974.6mAhg-1。
The present embodiment also proposes the application of the above-mentioned graphene composite material prepared, and the graphene obtained is compound
Material is used for double electric layers supercapacitor, and the assemble method of the double electric layers supercapacitor includes:
Step 201, it sizes mixing:
80:10:10 weighs the polytetrafluoroethylene (PTFE) of the graphene composite material, solid content 60% respectively by mass percentage
Lotion and conductive black are added suitable dispersing agent (alcohol), stir evenly, and are heated to 60 DEG C, are stirred continuously to dehydrated alcohol
Volatilization completely, obtains the mixture of rubber pureed；
Step 202, film:
It is coated in described in nickel foam, flattens, be put into vacuum oven, the temperature control in the vacuum oven exists
50 DEG C, dry 48h, obtains the good electrode of film at 0.08Mpa；
Step 13, it assembles:
The good electrode of the film is washed into several circular electric pole pieces, take two electrode weights identical or it is close be one
Group is being full of N2Glove box according to the good electrode-membrane-film of copper cap-copper sheet-film good electrode-rust
Steel ingot-nut sequence is assembled into double electric layers supercapacitor.
By electrical testing, the energy density for the double electric layers supercapacitor finally prepared is 168.5Wh/kg.
Embodiment two
A kind of preparation method of graphene composite material, comprising:
Step 101, the pre-oxidation of graphite:
Dense H is added into container2SO4, it is then placed in mechanical stirring in oil bath pan, sequentially adds the natural of mass ratio 2:1:1
Graphite, potassium peroxydisulfate, P2O5, after mixing evenly, distilled water is slowly added into container after being cooled to room temperature by 75 DEG C of reaction 3h,
The temperature controlled in container is no more than 80 DEG C；Mixed solution is filtered by vacuum, obtained filter cake is placed in clean beaker,
Distilled water dilution is added again, then filters, until filtrate is in neutrality, finally filter cake is put into 80 DEG C of air dry ovens and is done
Dry 10~12h obtains pre-oxidation product；
Step 102, the oxidation of graphite:
Step 1021, dense H is added into beaker under condition of ice bath2SO4, the pre-oxidation product that upper step is obtained grinds
It is added in beaker, stirs evenly after mill, finely ground KMnO is slowly added4Powder, the KMnO4The quality of powder is described
4.5 times of natural graphite quality, sufficiently reaction 4h；
Step 122, beaker is transferred to and is previously heated in 35 DEG C of oil bath pans, mechanical stirring reacts 2h, and reaction is completed
Afterwards, distilled water is slowly added with titration bottle, the temperature in beaker is kept to be no more than 80 DEG C, solution is in sepia at this time；
Step 123, oil bath temperature is risen to 95 DEG C, mechanic whirl-nett reaction 30min, solution is in faint yellow, into beaker
H is added2O2, solution becomes glassy yellow by faint yellow, and the hydrochloric acid solution of 10% (v/v) is then added, and removal unreacted is completely golden
Belong to oxide, then product is washed to solution repeatedly with distilled water and is in neutrality, is finally freeze-dried slimy product；
Step 103, it grinds:
It after the product being freeze-dried in previous step is fully ground with agate mortar, sieves with 100 mesh sieve, obtains graphite oxide；
Step 104, the graphite oxide is placed in container, carries out ultrasonic treatment 5h after distilled water is added, is aoxidized
The SnCl sufficiently dissolved is added into graphene oxide suspension for graphene suspension4·5H2O, the graphite oxide with
The SnCl4·5H2The mass ratio 1.4:1 of O, ultrasonic disperse 22min obtain configured solution；
Step 105, the prepared solution is transferred in polytetrafluoroethyltank tank, is placed in the autoclave of stainless steel
In, it seals, cooled to room temperature after isothermal reaction 17h, wherein the temperature of isothermal reaction is 170 DEG C；
Step 106, product obtained in above-mentioned steps is washed 3~5 times repeatedly with distilled water, is filtered, until during solution is in
Until property；
Step 107, it after 80 DEG C of freeze-day with constant temperature, is fully ground, is put into atmosphere tube type furnace, be passed through protective gas N2, with
L.5h 15 DEG C/min is kept the temperature after being warming up to 680 DEG C, be cooled to room temperature to get the graphene composite material is arrived.
By electrical testing, the capacity of charge and discharge for the first time for the graphene composite material that the present embodiment is prepared is respectively
837.4mAh·g-1And 953.2mAhg-1。
The present embodiment also proposes the application of the above-mentioned graphene composite material prepared, and the graphene obtained is compound
Material is used for double electric layers supercapacitor, and the assemble method of the double electric layers supercapacitor includes:
Step 201, it sizes mixing:
80:10:10 weighs the polytetrafluoroethylene (PTFE) of the graphene composite material, solid content 60% respectively by mass percentage
Lotion and conductive black are added suitable dispersing agent (alcohol), stir evenly, and are heated to 60 DEG C, are stirred continuously to dehydrated alcohol
Volatilization completely, obtains the mixture of rubber pureed；
Step 202, film:
It is coated in described in nickel foam, flattens, be put into vacuum oven, the temperature control in the vacuum oven exists
53 DEG C, dry 48h, obtains the good electrode of film at 0.08Mpa；
Step 13, it assembles:
The good electrode of the film is washed into several circular electric pole pieces, take two electrode weights identical or it is close be one
Group is being full of N2Glove box according to the good electrode-membrane-film of copper cap-copper sheet-film good electrode-rust
Steel ingot-nut sequence is assembled into double electric layers supercapacitor.
By electrical testing, the energy density for the double electric layers supercapacitor finally prepared is 159.7Wh/kg.
Embodiment three
A kind of preparation method of graphene composite material, comprising:
Step 101, the pre-oxidation of graphite:
Dense H is added into container2SO4, it is then placed in mechanical stirring in oil bath pan, sequentially adds the natural of mass ratio 2:1:1
Graphite, potassium peroxydisulfate, P2O5, after mixing evenly, distilled water is slowly added into container after being cooled to room temperature by 80 DEG C of reaction 3h,
The temperature controlled in container is no more than 80 DEG C；Mixed solution is filtered by vacuum, obtained filter cake is placed in clean beaker,
Distilled water dilution is added again, then filters, until filtrate is in neutrality, finally filter cake is put into 80 DEG C of air dry ovens and is done
Dry 10~12h obtains pre-oxidation product；
Step 102, the oxidation of graphite:
Step 1021, dense H is added into beaker under condition of ice bath2SO4, the pre-oxidation product that upper step is obtained grinds
It is added in beaker, stirs evenly after mill, finely ground KMnO is slowly added4Powder, the KMnO4The quality of powder is described
5 times of natural graphite quality, sufficiently reaction 4h；
Step 122, beaker is transferred to and is previously heated in 35 DEG C of oil bath pans, mechanical stirring reacts 2h, and reaction is completed
Afterwards, distilled water is slowly added with titration bottle, the temperature in beaker is kept to be no more than 80 DEG C, solution is in sepia at this time；
Step 123, oil bath temperature is risen to 95 DEG C, mechanic whirl-nett reaction 30min, solution is in faint yellow, into beaker
H is added2O2, solution becomes glassy yellow by faint yellow, and the hydrochloric acid solution of 10% (v/v) is then added, and removal unreacted is completely golden
Belong to oxide, then product is washed to solution repeatedly with distilled water and is in neutrality, is finally freeze-dried slimy product；
Step 103, it grinds:
It after the product being freeze-dried in previous step is fully ground with agate mortar, sieves with 100 mesh sieve, obtains graphite oxide；
Step 104, the graphite oxide is placed in container, carries out ultrasonic treatment 6h after distilled water is added, is aoxidized
The SnCl sufficiently dissolved is added into graphene oxide suspension for graphene suspension4·5H2O, the graphite oxide with
The SnCl4·5H2The mass ratio 1.5:1 of O, ultrasonic disperse 25min obtain configured solution；
Step 105, the prepared solution is transferred in polytetrafluoroethyltank tank, is placed in the autoclave of stainless steel
In, it seals, cooled to room temperature after isothermal reaction 18h, wherein the temperature of isothermal reaction is 175 DEG C；
Step 106, product obtained in above-mentioned steps is washed 3~5 times repeatedly with distilled water, is filtered, until during solution is in
Until property；
Step 107, it after 80 DEG C of freeze-day with constant temperature, is fully ground, is put into atmosphere tube type furnace, be passed through protective gas N2, with
L.3h 15 DEG C/min is kept the temperature after being warming up to 690 DEG C, be cooled to room temperature to get the graphene composite material is arrived.
By electrical testing, the capacity of charge and discharge for the first time for the graphene composite material that the present embodiment is prepared is respectively
843.9mAh·g-1And 947.1mAhg-1。
The present embodiment also proposes the application of the above-mentioned graphene composite material prepared, and the graphene obtained is compound
Material is used for double electric layers supercapacitor, and the assemble method of the double electric layers supercapacitor includes:
Step 201, it sizes mixing:
80:10:10 weighs the polytetrafluoroethylene (PTFE) of the graphene composite material, solid content 60% respectively by mass percentage
Lotion and conductive black are added suitable dispersing agent (alcohol), stir evenly, and are heated to 60 DEG C, are stirred continuously to dehydrated alcohol
Volatilization completely, obtains the mixture of rubber pureed；
Step 202, film:
It is coated in described in nickel foam, flattens, be put into vacuum oven, the temperature control in the vacuum oven exists
55 DEG C, dry 48h, obtains the good electrode of film at 0.08Mpa；
Step 13, it assembles:
The good electrode of the film is washed into several circular electric pole pieces, take two electrode weights identical or it is close be one
Group is being full of N2Glove box according to the good electrode-membrane-film of copper cap-copper sheet-film good electrode-rust
Steel ingot-nut sequence is assembled into double electric layers supercapacitor.
By electrical testing, the energy density for the double electric layers supercapacitor finally prepared is 155.8Wh/kg.
Upper table compared the graphene composite material prepared using the method for above three embodiments and the prior art
The energy density of charge and discharge capacity and double electric layers supercapacitor for the first time, from table, it is apparent that using the present invention three
The capacity of charge and discharge for the first time for the graphene composite material that the method for embodiment is finally prepared and the super electricity of electric double layer prepared
The energy density of container is superior to the prior art, has a clear superiority.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
Limitations on the scope of the patent of the present invention therefore cannot be interpreted as.It should be pointed out that for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to guarantor of the invention
Protect range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (10)
1. a kind of preparation method of graphene composite material characterized by comprising
Step 1, graphite oxide is placed in container, is ultrasonically treated after distilled water is added, obtains graphene oxide suspension,
The SnCl sufficiently dissolved is added into graphene oxide suspension4·5H2O, the graphite oxide and the SnCl4·
5H2Mass ratio 1.3:1~1.5:1 of O, 20~25min of ultrasonic disperse obtain configured solution；
Step 2, the prepared solution is transferred in polytetrafluoroethyltank tank, is placed in the autoclave of stainless steel, it is close
It seals, cooled to room temperature after 16~18h of isothermal reaction；
Step 3, product obtained in above-mentioned steps is washed 3~5 times repeatedly with distilled water, is filtered, until solution is in neutrality；
Step 4, it after 80 DEG C of freeze-day with constant temperature, is fully ground, is put into atmosphere tube type furnace, be passed through protective gas N2, it is warming up to 680
L~1.5h is kept the temperature after~700 DEG C, is cooled to room temperature to get the graphene composite material is arrived.
2. the preparation method of graphene composite material according to claim 1, which is characterized in that described to set graphite oxide
Before step in container, the method also includes the preparations of graphite oxide, specifically include:
Step 11, the pre-oxidation of graphite:
Dense H is added into container2SO4, be then placed in mechanical stirring in oil bath pan, sequentially add natural graphite, potassium peroxydisulfate,
P2O5, after mixing evenly, distilled water is slowly added in 70~80 DEG C of reaction 3h into container after being cooled to room temperature, and controls in container
Temperature be no more than 80 DEG C；Mixed solution is filtered by vacuum, obtained filter cake is placed in clean beaker, is added steams again
Distilled water dilution, then filter, until filtrate is in neutrality, filter cake is finally put into 80 DEG C of air dry ovens dry 10~12h,
Obtain pre-oxidation product；
Step 12, the oxidation of graphite:
Step 121, dense H is added into beaker under condition of ice bath2SO4, add after the pre-oxidation product grinding that upper step is obtained
Enter into beaker, stir evenly, finely ground KMnO is slowly added4Powder, sufficiently reaction 4h；
Step 122, beaker is transferred to and is previously heated in 35 DEG C of oil bath pans, mechanical stirring reacts 2h, after the reaction was completed, uses
Distilled water is slowly added in titration bottle, and the temperature in beaker is kept to be no more than 80 DEG C, and solution is in sepia at this time；
Step 123, oil bath temperature is risen to 95 DEG C, mechanic whirl-nett reaction 30min, solution is added in faint yellow into beaker
H2O2, solution becomes glassy yellow by faint yellow, and 10% hydrochloric acid solution is then added, removes the complete metal oxide of unreacted,
Product is washed to solution with distilled water repeatedly again and is in neutrality, is finally freeze-dried slimy product；
Step 13, it grinds:
After the product being freeze-dried in previous step is fully ground with agate mortar, the graphite oxide is obtained.
3. the preparation method of graphene composite material according to claim 1, which is characterized in that in the step 1, be added
It is 4~6h that sonication treatment time is carried out after distilled water.
4. the preparation method of graphene composite material according to claim 1, which is characterized in that in the step 2, constant temperature
The temperature of reaction is 160~175 DEG C.
5. the preparation method of graphene composite material according to claim 1, which is characterized in that in the step 4, be passed through
Protective gas N2Lh is kept the temperature after being warming up to 700 DEG C afterwards with 15 DEG C/min.
6. the preparation method of graphene composite material according to claim 2, which is characterized in that in the step 11, according to
The secondary natural graphite, potassium peroxydisulfate, the P that mass ratio 2:1:1 is added2O5。
7. the preparation method of graphene composite material according to claim 2, which is characterized in that in the step 121, institute
State KMnO4The quality of powder is 4~5 times of the natural graphite quality.
8. the preparation method of graphene composite material according to claim 2, which is characterized in that in the step 13, Ma
It after Nao mortar is fully ground, sieves with 100 mesh sieve, obtains the graphite oxide.
9. the application of graphene composite material prepared by claim 1, which is characterized in that by the graphene composite wood obtained
Material is used for double electric layers supercapacitor, and the assemble method of the double electric layers supercapacitor includes:
Step 21, it sizes mixing:
80:10:10 weighs the ptfe emulsion of the graphene composite material, solid content 60% respectively by mass percentage
And conductive black, suitable dispersing agent is added, stirs evenly, is heated to 60 DEG C, is stirred continuously to dehydrated alcohol volatilization completely, obtain
To the mixture of rubber pureed；
Step 22, film:
It is coated in described in nickel foam, flattens, be put into vacuum oven, dry 48h, it is good to obtain film at 0.08Mpa
Electrode；
Step 13, it assembles:
The good electrode of the film is washed into several circular electric pole pieces, take two electrode weights identical or it is close be one group,
It is being full of N2Glove box according to the good electrode-membrane-film of copper cap-copper sheet-film good electrode-rust steel
Ingot-nut sequence is assembled into double electric layers supercapacitor.
10. the application of graphene composite material according to claim 9, which is characterized in that described true in the step 22
Temperature in empty drying box is controlled at 50~55 DEG C.
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| CN112758976A (en) * | 2020-12-23 | 2021-05-07 | 陕西科技大学 | SnO (stannic oxide)2rGO composite material, preparation method thereof and ethanol sensor based on composite material |
| CN113436908A (en) * | 2021-06-10 | 2021-09-24 | 同济大学 | Structural super capacitor and preparation method thereof |
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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 |