CN107359053B - Graphene/carbon nano-cellulose complex carbon material and its preparation method and application - Google Patents
Graphene/carbon nano-cellulose complex carbon material and its preparation method and application Download PDFInfo
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- CN107359053B CN107359053B CN201710474525.2A CN201710474525A CN107359053B CN 107359053 B CN107359053 B CN 107359053B CN 201710474525 A CN201710474525 A CN 201710474525A CN 107359053 B CN107359053 B CN 107359053B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 229920002678 cellulose Polymers 0.000 title claims abstract description 61
- 239000001913 cellulose Substances 0.000 title claims abstract description 60
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 51
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 23
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000007864 aqueous solution Substances 0.000 claims abstract description 23
- 239000002131 composite material Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 239000011261 inert gas Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 60
- 229910052759 nickel Inorganic materials 0.000 claims description 30
- 239000006260 foam Substances 0.000 claims description 18
- 239000000017 hydrogel Substances 0.000 claims description 13
- 238000002604 ultrasonography Methods 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 8
- 229920000515 polycarbonate Polymers 0.000 claims description 7
- 239000004417 polycarbonate Substances 0.000 claims description 7
- 239000006230 acetylene black Substances 0.000 claims description 5
- 239000003792 electrolyte Substances 0.000 claims description 5
- 238000002386 leaching Methods 0.000 claims description 5
- 238000010907 mechanical stirring Methods 0.000 claims description 5
- 239000002033 PVDF binder Substances 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- 239000004020 conductor Substances 0.000 claims description 3
- 239000002134 carbon nanofiber Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000003763 carbonization Methods 0.000 abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- 238000001291 vacuum drying Methods 0.000 description 11
- 238000001035 drying Methods 0.000 description 9
- 239000007772 electrode material Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 6
- 238000010000 carbonizing Methods 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000002484 cyclic voltammetry Methods 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 235000010980 cellulose Nutrition 0.000 description 4
- 238000001453 impedance spectrum Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002023 wood Substances 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- 239000012620 biological material Substances 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 3
- 238000010892 electric spark Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- -1 graphite alkene Chemical class 0.000 description 2
- 238000005087 graphitization Methods 0.000 description 2
- 239000006210 lotion Substances 0.000 description 2
- 239000002121 nanofiber Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 150000004651 carbonic acid esters Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The present invention relates to a kind of graphene/carbon nano-cellulose complex carbon materials and its preparation method and application, specific preparation step are as follows: (1) graphene oxide is mixed into nano-cellulose aqueous solution, obtains pretreated compound through mixing, water removal, preheating；(2) pretreated compound is carried out to microwave treatment under inert gas protection to get graphene/carbon nano-cellulose composite material is arrived.Compared with prior art, graphene oxide is mixed into nano-cellulose aqueous solution by the present invention, after being pre-processed, using microwave heating, the high temperature that microwave generates part is absorbed, the carbonization of nano-cellulose is caused, nano-cellulose conductivity after carbonization is promoted, microwave can be further absorbed, continues to be carbonized to cause the nano-cellulose not being carbonized, to complete the process of whole low-temperature carbonizations, whole process only needs 2-5s, high temperature time-consuming process is avoided, cost is reduced, there are industrialized potentiality.
Description
Technical field
The present invention relates to complex carbon material technical fields, and in particular to graphene/carbon nano-cellulose complex carbon material
And its preparation method and application.
Background technique
Supercapacitor is the new type of energy storage device between traditional capacitor and secondary cell.It is close with high power
Degree, high-energy density, the advantages that having extended cycle life have in fields such as mobile communication, information technology, consumer electronics, aerospaces
Have broad application prospects, and causes the extensive concern of countries in the world.Carbon material physics, chemical property are more stable, have larger
Specific surface area and preferable conductivity, have important utilization in energy storage field, be the ideal material for preparing electrode of super capacitor.
But existing carbon materials preparation method for material is complicated, energy consumption and at high cost, and can produce to environment and endanger to a certain degree, limits it
Industrial applications as electrode material for super capacitor.
Cellulose forms because abundance, green are renewable, low in cost to prepare porous carbon materials by biomaterial
Important presoma.Cellulose it is higher can to obtain carbon content by the method for high temperature cabonization except non-carbon elements such as deoxidations and hydrogen
Carbon material make carbon atom arrangement ordering then using graphitization processing, obtain high performance carbon material, but to obtain
The carbon material of high conductivity (100S/m) needs 1700 DEG C of high temperature graphitization processing.Therefore a kind of conveniently low temperature is needed
Carbonization method improves the cost performance of carbonized celulose.
Summary of the invention
The purpose of the present invention is to solve the above-mentioned problems and provides a kind of graphene/carbon nanofiber of low energy consumption
Plain complex carbon material and its preparation method and application.
The purpose of the present invention is achieved through the following technical solutions:
A kind of preparation method of graphene/carbon nano-cellulose complex carbon material, specifically includes the following steps:
(1) graphene oxide is mixed into nano-cellulose aqueous solution, is obtained through mixing, water removal, preheating pretreated multiple
Close object；
(2) pretreated compound is carried out to microwave treatment under inert gas protection to get graphene/carbon nanometer is arrived
Cellulose composite material.
Further, the concentration of nano-cellulose in aqueous solution described in step (1) is 1-10mg/ml, the oxygen
The mass ratio of graphite alkene and nano-cellulose is 1:5-20.
Further, graphene oxide is dispersed in nano-cellulose water using ultrasound and mechanical stirring by step (1)
In solution.
Further, it is filtered when step (1) removes water using polycarbonate leaching film, obtains the dark brown hydrogel of pie, then will
Hydrogel dry 10-12h at a temperature of 40-60 DEG C, the product after drying is preheated, and preheating temperature is 100-300 degree.It adopts
It is heated in nitrogen atmosphere with tube furnace, heating rate is 2 DEG C/min, keeps the temperature 1h, then natural cooling.
Further, inert gas described in step (2) is nitrogen or argon gas.
Further, step (2) microwave treatment is carried out using micro-wave oven, power 500-1000W, time 2-10s.
The graphene/carbon nano-cellulose composite material is used to prepare supercapacitor.Method particularly includes: by stone
Black alkene/carbonization nano-cellulose composite material is pulverized, viscous using PVDF (Kynoar) or PTFE (polytetrafluoroethylene (PTFE))
Knot agent, acetylene black conductor are mixed evenly, and coated in nickel sheet or cover in nickel foam, and electrode is made in dry out solvent,
Use filter paper as diaphragm, with KOH or K2SO4As electrolyte, button supercapacitor is packaged into using button cell shell.
Preparing carbon material in inert gas high temperature carbonization by biological materials such as celluloses is one widely used
Method, but the inert gas that the process needs that the tube furnace of high temperature can be provided and largely flows is used as protection gas, to devices call
It is higher, it wastes inert gas and takes a long time, limit the large-scale application of high temperature cabonization.Preparation method of the present invention will aoxidize
Graphene is mixed into nano-cellulose aqueous solution, after being pre-processed, the high temperature that microwave generates part can be absorbed, as miniature
Heating source causes the carbonization of nano-cellulose, and the nano-cellulose conductivity after carbonization is promoted, and can further absorb microwave, thus
Cause the nano-cellulose not being carbonized to continue to be carbonized, to complete the process of whole low-temperature carbonizations, whole process only needs 2-5s,
Microwave carbonisation can be completed using easy micro-wave oven, and inert gas only needs to avoid traditional method full of container
The high temperature time-consuming process of middle carbonization biological material, reduces costs, has industrialized potentiality.Microwave can quick, low energy consumption
Conductive material is heated to very high temperature by ground, can absorb microwave as heating source initiation nano-cellulose by the way that graphene is added
Carbonization, to quickly and efficiently obtain better carbonized product, obtains the carbon material of high conductivity.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of supercapacitor；
Fig. 2 is the cyclic voltammetry curve of the supercapacitor prepared using this method；
Fig. 3 is the constant current charge-discharge curve of the supercapacitor prepared using this method；
Fig. 4 is the Nyquist curve of the supercapacitor prepared using this method.
Specific embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
Step 1, nano-cellulose is configured to the aqueous solution of 2mg/ml, is put it into small beaker, rotor is added with 300
Rev/min revolving speed stirring, graphene oxide water solution (0.5mg/ml) is added while stirring.It will be obtained after mixing
Mixed solution in the Ultrasound Instrument of tip ultrasound 30 minutes to get to both mixed aqueous solution (graphene oxide: nano-cellulose
=1:5).
Step 2, the obtained mixed solution polycarbonate leaching film of 200nm is filtered by vacuum, obtains the dark brown water of pie
Gel.Hydrogel and filter membrane are put into togerther in vacuum drying oven, vacuum drying 12 hours is in 50 DEG C to get to one layer of composite wood
Expect film.Film color is uniform, it was demonstrated that its mixed effect is ideal.
Step 3, the product after drying is heated in nitrogen atmosphere with tube furnace, heating rate is 2 DEG C/min, heating
To 300 DEG C, 1 hour is kept the temperature, then natural cooling.
Step 4, the composite material after heat treatment is put into vial, changes the gas in vial into argon gas, then
It is put into micro-wave oven, microwave radiation 2 seconds for being 1000w with power, obtains the nano-cellulose composite wood of graphene auxiliary carbonization
Material, obtained carbonized product become silver gray.
Step 5, obtained composite material is weighed, is put into the vial of 50ml, vial is put into the mistake of glove box
It crosses and changes inert gas in storehouse into, lid is tightened, the junction of bottle cap and body is sealed with parafilm, then takes out, makes
The mixture in argon atmosphere is acted on 2 seconds with the power of 1000w, it can be seen that the mixture in bottle generates electric spark, then
Bottle is put into draught cupboard, bottleneck is opened, allows to cool to room temperature, obtains compound carbonizing product.
Step 6, it is carried out in draught cupboard, compound carbonizing product obtained in step 2 is put into agate mortar, liquid relief is used
Rifle drops evenly NMP (N-Methyl pyrrolidone) solution of PVDF (Kynoar), and the quality of PVDF accounts for the 5% of gross mass,
The acetylene black for adding 5% is ground into sticky liquid after doing appropriate dilution with NMP.
Step 7,50 microns of thick nickel sheet are cut into the sequin that diameter is 1.2cm, the nickel sheet that will be cut using slicer
It is put into acetone and is cleaned by ultrasonic 30 minutes, then nickel sheet is taken out, be put into ethyl alcohol and be cleaned by ultrasonic 30 minutes, by cleaned nickel sheet
With being dried with nitrogen, as collector.It will weigh per a piece of nickel sheet, then be uniformly coated on the slurry in step 6 with key
In the one side of nickel sheet, coated nickel sheet is put into vacuum drying oven, 120 DEG C at a temperature of vacuum drying 12 hours.It will dry
The nickel sheet weighing of carrying electrode materials after dry, calculates the quality of poor quality as electrode material.
Step 8, mold, spring leaf is 30 minutes ultrasonic in ethanol, it is dried for standby.By qualitative filter paper be cut into diameter and
The same disk of battery case diameter, the diaphragm as supercapacitor.Use qualitative filter paper as diaphragm, then with mold and step 7
In nickel sheet be assembled into supercapacitor, 6M potassium hydroxide is added dropwise as electrolyte, is then packaged with battery sealing machine, such as
Shown in Fig. 1.
Step 9, it by the device prepared static 30 minutes, is then tested using electrochemical workstation, cyclic voltammetry
Sweep speed is 10mV/s and 100mV/s, and the current density of constant current charge-discharge test is 2A/g, 1A/g, 0.1A/g, 0.05A/
G, the range of impedance spectrum test are 0.01Hz-100kHz, and Fig. 2 is the cyclic voltammetry curve of example 1, are not aoxidized significantly in figure
Reduction peak.
Embodiment 2
Step 1, nano-cellulose is configured to the aqueous solution of 1-10mg/ml, is put it into small beaker, be added rotor with
300 revs/min of revolving speed stirring, is added dropwise graphene oxide water solution (2mg/ml) while stirring.It will be obtained after mixing
Mixed solution in the Ultrasound Instrument of tip ultrasound 30 minutes to get to both mixed aqueous solution (graphene oxide: nanofiber
Element=1:20).
Step 2, the obtained mixed solution polycarbonate leaching film of 200nm is filtered by vacuum, obtains the dark brown water of pie
Gel.Hydrogel and filter membrane are put into togerther in vacuum drying oven, vacuum drying 12 hours is in 50 DEG C to get to one layer of composite wood
Expect film.Film color is uniform, it was demonstrated that its mixed effect is ideal.
Step 3, the mixture of the nano-cellulose after draining and graphene oxide is put into baking oven the vacuum at 50 DEG C
Drying 12 hours.Product after draining is heated in nitrogen atmosphere with tube furnace, heating rate is 2 DEG C/min, is heated to
300 DEG C, 1 hour is kept the temperature, then natural cooling.
Step 4, the composite material after heat treatment is put into vial, changes the gas in vial into argon gas, then
It is put into micro-wave oven, microwave radiation 2 seconds for being 1000w with power, obtains the nano-cellulose composite wood of graphene auxiliary carbonization
Material, obtained carbonized product become silver gray.
Step 5, obtained composite material is weighed, is put into the vial of 50ml, vial is put into the mistake of glove box
It crosses and changes inert gas in storehouse into, lid is tightened, the junction of bottle cap and body is sealed with parafilm, then takes out, makes
The mixture in argon atmosphere is acted on 2 seconds with the power of 1000w, it can be seen that the mixture in bottle generates electric spark, then
Bottle is put into draught cupboard, bottleneck is opened, allows to cool to room temperature, obtains compound carbonizing product.
Step 6, compound carbonizing product obtained in step 5 is put into agate mortar, drops evenly PTFE with liquid-transfering gun
Lotion, PTFE account for the 5% of gross mass, add 5% acetylene black, are ground into sticky liquid.
Step 7,50 microns of thick nickel foams are cut into the sequin that diameter is 1.2cm, the bubble that will be cut using slicer
Foam nickel, which is put into acetone, to be cleaned by ultrasonic 30 minutes, is taken out, is put into ethyl alcohol and is cleaned by ultrasonic 30 minutes.Cleaned nickel foam is used
It is dried with nitrogen, as collector.It will weigh per a piece of nickel foam, then be uniformly coated on the slurry in step 6 with key
In the one side of nickel foam, coated nickel foam is compressed, is put into vacuum drying oven, it is small in 100 DEG C of at a temperature of vacuum drying 4
When.The nickel foam of carrying electrode materials after drying is weighed, the quality of poor quality as electrode material is calculated.
Step 8, mold, spring leaf is 30 minutes ultrasonic in ethanol, it is dried for standby.By qualitative filter paper be cut into diameter and
The same disk of battery case diameter, the diaphragm as supercapacitor.It is assembled into supercapacitor with the nickel foam in step 7,
6M potassium hydroxide is added dropwise as electrolyte, is then packaged with battery sealing machine.
Step 9, it by the device prepared static 30 minutes, is then tested using electrochemical workstation, cyclic voltammetry
Sweep speed is 10mV/s and 100mV/s, and the current density of constant current charge-discharge test is 2A/g, 1A/g, 0.1A/g, 0.05A/
G, the range of impedance spectrum test are 0.01Hz-100kHz, and Fig. 3 is the constant current charge-discharge curve of the present embodiment, charge and discharge in figure
Curve is almost symmetrical, illustrates that the device charge and discharge have invertibity.
Embodiment 3
Step 1, nano-cellulose is configured to the aqueous solution of 1-10mg/ml, is put it into small beaker, be added rotor with
300 revs/min of revolving speed stirring, is added dropwise graphene oxide water solution (5mg/ml) while stirring.It will be obtained after mixing
Mixed solution in the Ultrasound Instrument of tip ultrasound 30 minutes to get to both mixed aqueous solution (graphene oxide: nanofiber
Element=1:5).
Step 2, the graphene oxide solution polycarbonate leaching film of 200nm is filtered by vacuum, obtains the dark brown water of pie
Gel.Hydrogel and filter membrane are put into togerther in vacuum drying oven, vacuum drying 12 hours is in 50 DEG C to get arriving graphene oxide
Film.Product after draining is heated in nitrogen atmosphere with tube furnace, heating rate is 2 DEG C/min, is heated to 300 DEG C, is protected
Temperature 1 hour, then natural cooling.
Step 3, obtained composite material is weighed, is put into the vial of 50ml, vial is put into the mistake of glove box
It crosses and changes inert gas in storehouse into, lid is tightened, the junction of bottle cap and body is sealed with parafilm, then takes out, makes
The mixture in argon atmosphere is acted on 2 seconds with the power of 1000w, it can be seen that the mixture in bottle generates electric spark, then
Bottle is put into draught cupboard, bottleneck is opened, allows to cool to room temperature, obtains compound carbonizing product.
Step 4, compound carbonizing product obtained in step 2 is put into agate mortar, drops evenly PTFE with liquid-transfering gun
Lotion, PTFE account for the 5% of gross mass, add 5% acetylene black, are ground into sticky liquid.
Step 5,500 microns of thick nickel foams are cut into the sequin that diameter is 1.2cm, the nickel that will be cut using slicer
Piece, which is put into acetone, to be cleaned by ultrasonic 30 minutes, then nickel foam is taken out, and is put into ethyl alcohol and is cleaned by ultrasonic 30 minutes, will be cleaned
Nickel foam is with being dried with nitrogen, as collector.It will weigh per a piece of nickel foam, it is then that the slurry key in step 6 is uniform
Ground is coated in the one side of nickel foam, and coated nickel foam is compressed, is put into vacuum drying oven, 100 DEG C at a temperature of it is true
Sky drying 4 hours.The nickel foam of carrying electrode materials after drying is weighed, the quality of poor quality as electrode material is calculated.
Step 6, mold, spring leaf is 30 minutes ultrasonic in ethanol, it is dried for standby.By qualitative filter paper be cut into diameter and
The same disk of battery case diameter, the diaphragm as supercapacitor.It is assembled into supercapacitor with the nickel foam in step 7,
6M potassium hydroxide is added dropwise as electrolyte, is then packaged with battery sealing machine.
Step 7, it by the device prepared static 30 minutes, is then tested using electrochemical workstation, cyclic voltammetry
Sweep speed is 10mV/s and 100mV/s, and the current density of constant current charge-discharge test is 2A/g, 1A/g, 0.1A/g, 0.05A/
The range of g, impedance spectrum test are 0.01Hz-100kHz.Fig. 4 is the impedance spectrum of example 3, contact resistance very little in figure, and explanation is
Electrode material in the case where no addition conductive black is set also to have good conductivity；Impedance semicircle radius is smaller, illustrate from
Son transmission is easier to.
Embodiment 4
A kind of preparation method of graphene/carbon nano-cellulose complex carbon material, specific steps:
(1) graphene oxide is mixed into nano-cellulose aqueous solution, is obtained through mixing, water removal, preheating pretreated multiple
Close object, wherein the concentration of nano-cellulose in aqueous solution is 1mg/ml, and the mass ratio of graphene oxide and nano-cellulose is
Graphene oxide is dispersed in nano-cellulose aqueous solution using ultrasound and mechanical stirring, is filtered using polycarbonate by 1:5
Film filters, and obtains the dark brown hydrogel of pie, then hydrogel is dried 12h at a temperature of 40 DEG C, the product after drying is carried out
Preheating, preheating temperature are 100 degree, are heated in nitrogen atmosphere using tube furnace, and heating rate is 2 DEG C/min, keeps the temperature 1h, so
Natural cooling afterwards.
(2) pretreated compound is subjected to microwave treatment under nitrogen or argon, is carried out using micro-wave oven, power
500W, the time be 10s to get arrive graphene/carbon nano-cellulose composite material.
Embodiment 5
A kind of preparation method of graphene/carbon nano-cellulose complex carbon material, specific steps:
(1) graphene oxide is mixed into nano-cellulose aqueous solution, is obtained through mixing, water removal, preheating pretreated multiple
Close object, wherein the concentration of nano-cellulose in aqueous solution is 5mg/ml, and the mass ratio of graphene oxide and nano-cellulose is
Graphene oxide is dispersed in nano-cellulose aqueous solution, using polycarbonate by 1:10 using ultrasound and mechanical stirring
Filter membrane filters, and obtains the dark brown hydrogel of pie, then hydrogel is dried 11h at 50 °C, by the product after drying into
Row preheating, preheating temperature are 200 degree, are heated in nitrogen atmosphere using tube furnace, and heating rate is 2 DEG C/min, heat preservation
1.5h, then natural cooling.
(2) pretreated compound is subjected to microwave treatment under nitrogen or argon, is carried out using micro-wave oven, power
800W, the time be 5s to get arrive graphene/carbon nano-cellulose composite material.
Embodiment 6
A kind of preparation method of graphene/carbon nano-cellulose complex carbon material, specific steps:
(1) graphene oxide is mixed into nano-cellulose aqueous solution, is obtained through mixing, water removal, preheating pretreated multiple
Close object, wherein the concentration of nano-cellulose in aqueous solution is 10mg/ml, the mass ratio of graphene oxide and nano-cellulose
For 1:20, graphene oxide is dispersed in nano-cellulose aqueous solution using ultrasound and mechanical stirring, using poly- carbonic acid
Ester filter membrane filters, and the dark brown hydrogel of pie is obtained, then hydrogel is dried 10h at a temperature of 60 DEG C, by the product after drying
It is preheated, preheating temperature is 300 degree, is heated in nitrogen atmosphere using tube furnace, and heating rate is 2 DEG C/min, heat preservation
1.5h, then natural cooling.
(2) pretreated compound is subjected to microwave treatment under nitrogen or argon, is carried out using micro-wave oven, power
1000W, the time be 2s to get arrive graphene/carbon nano-cellulose composite material.
Claims (5)
1. a kind of preparation method of graphene/carbon nano-cellulose complex carbon material, which is characterized in that specifically include following step
It is rapid:
(1) graphene oxide is mixed into nano-cellulose aqueous solution, obtains pretreated compound through mixing, water removal, preheating；
(2) pretreated compound is carried out to microwave treatment under inert gas protection to get graphene/carbon nanofiber is arrived
Plain composite material,
Wherein, the concentration of nano-cellulose in aqueous solution described in step (1) is 1-10mg/ml, the graphene oxide
Mass ratio with nano-cellulose is 1:5-20,
Graphene oxide is dispersed in nano-cellulose aqueous solution by step (1) using ultrasound and mechanical stirring,
Step (1) preheating temperature is 100-300 degree, is heated in nitrogen atmosphere using tube furnace, and heating rate is 2 DEG C/min,
1h is kept the temperature, then natural cooling,
Step (2) microwave treatment is carried out using micro-wave oven, power 500-1000W, time 2-10s.
2. a kind of preparation method of graphene/carbon nano-cellulose complex carbon material according to claim 1, feature
It is, step (1) specifically uses polycarbonate leaching film to filter when removing water, and obtains the dark brown hydrogel of pie, then hydrogel is existed
Dry 10-12h at a temperature of 40-60 DEG C.
3. graphene/carbon nano-cellulose composite material prepared by preparation method as claimed in claim 1 or 2.
4. graphene/carbon nano-cellulose composite material as claimed in claim 3 is used to prepare supercapacitor.
5. graphene/carbon nano-cellulose composite material according to claim 4 is used to prepare supercapacitor, special
Sign is, method particularly includes: graphene/carbon nano-cellulose composite material is pulverized, PVDF or PTFE bonding is used
Agent, acetylene black conductor are mixed evenly, and coated in nickel sheet or cover in nickel foam, and electrode is made in dry out solvent, use
Filter paper is as diaphragm, with KOH or K2SO4As electrolyte, button supercapacitor is packaged into using button cell shell.
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| CN108751178A (en) * | 2018-07-09 | 2018-11-06 | 合肥艾飞新材料有限公司 | A kind of carbonized graphite alkene and preparation method thereof |
| CN109433191B (en) * | 2018-11-09 | 2021-10-22 | 济南大学 | Method for bonding powder catalyst |
| CN112366316B (en) * | 2020-09-27 | 2022-03-01 | 泰山学院 | Preparation method and application of nitrogen and phosphorus co-doped graphene |
| CN112366094A (en) * | 2020-10-30 | 2021-02-12 | 南京理工大学 | Preparation method of flexible carbon-based membrane electrode material based on plant fibers |
| CN112911919A (en) * | 2021-02-04 | 2021-06-04 | 四川大学 | Carbonized loofah sponge/nano nickel/rGO electromagnetic shielding material and preparation method thereof |
| CN113415800B (en) * | 2021-06-23 | 2022-12-27 | 桂林理工大学 | Carbon foam material and preparation method and application thereof |
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