CN107359053A - 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
- Publication number
- CN107359053A CN107359053A CN201710474525.2A CN201710474525A CN107359053A CN 107359053 A CN107359053 A CN 107359053A CN 201710474525 A CN201710474525 A CN 201710474525A CN 107359053 A CN107359053 A CN 107359053A
- Authority
- CN
- China
- Prior art keywords
- cellulose
- graphene
- nano
- preparation
- carbon nano
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 229920002678 cellulose Polymers 0.000 title claims abstract description 66
- 239000001913 cellulose Substances 0.000 title claims abstract description 65
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 56
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 28
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000002131 composite material Substances 0.000 claims abstract description 21
- 239000007864 aqueous solution Substances 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011261 inert gas Substances 0.000 claims abstract description 12
- -1 blended Substances 0.000 claims abstract description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 60
- 229910052759 nickel Inorganic materials 0.000 claims description 30
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
- 239000006260 foam Substances 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 13
- 239000000017 hydrogel Substances 0.000 claims description 13
- 238000002604 ultrasonography Methods 0.000 claims description 11
- 229910052786 argon Inorganic materials 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 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
- 230000004888 barrier function Effects 0.000 claims description 6
- 239000006230 acetylene black Substances 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 5
- 239000003792 electrolyte Substances 0.000 claims description 5
- 238000002386 leaching Methods 0.000 claims description 5
- 239000004417 polycarbonate Substances 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
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 238000003763 carbonization Methods 0.000 abstract description 14
- 230000008569 process Effects 0.000 abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- 239000007772 electrode material Substances 0.000 description 8
- 239000000203 mixture Substances 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
- 238000010000 carbonizing Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- 238000002484 cyclic voltammetry Methods 0.000 description 5
- 238000001035 drying 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
- 239000003517 fume Substances 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000012620 biological material Substances 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 3
- 230000008859 change Effects 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
- 238000002156 mixing Methods 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
- 239000004425 Makrolon Substances 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005087 graphitization Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000002121 nanofiber Substances 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
- 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
- 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
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 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
- 230000009467 reduction Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001960 triggered effect Effects 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 material and its preparation method and application, specific preparation process is：(1) graphene oxide is mixed into the nano-cellulose aqueous solution, blended, water removal, the compound pre-processed；(2) compound of pretreatment is subjected to microwave treatment under inert gas shielding, that is, obtains graphene/carbon nano-cellulose composite.Compared with prior art, graphene oxide is mixed into the nano-cellulose aqueous solution by the present invention, after being pre-processed, heated using microwave, absorb microwave and produce local high temperature, trigger the carbonization of nano-cellulose, nano-cellulose electrical conductivity lifting after carbonization, microwave can be further absorbed, so as to trigger the nano-cellulose not being carbonized to continue to be carbonized, so as to complete the process of whole low-temperature carbonizations, whole process only needs 2 5s, high temperature time-consuming process is avoided, reduces cost, there are industrialized potentiality.
Description
Technical field
The present invention relates to complex carbon material technical field, and in particular to graphene/carbon nano-cellulose complex carbon material
And its preparation method and application.
Background technology
Ultracapacitor 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, Aero-Space
Have broad application prospects, and cause the extensive concern of countries in the world.Carbon material physics, chemical property are relatively stable, and tool is larger
Specific surface area and preferable electrical 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 cost are high, and environment can be generated and endangered to a certain degree, limit it
Industrial applications as electrode material for super capacitor.
Cellulose is formed to prepare porous carbon materials by biomaterial because abundance, green are renewable, cost is cheap
Important presoma.Cellulose it is higher can to obtain carbon content by the method for high temperature cabonization except non-carbon elements such as deoxidation and hydrogen
Carbon material, then pass through graphitization processing again, make carbon atom arrangement ordering, 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.
The content of the invention
The purpose of the present invention is exactly to provide a kind of graphene/carbon nanofiber of low energy consumption to solve the above problems
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 following steps：
(1) graphene oxide is mixed into the nano-cellulose aqueous solution, blended, water removal, answering of being pre-processed
Compound；
(2) compound of pretreatment is subjected to microwave treatment under inert gas shielding, that is, obtains graphene/carbon nanometer
Cellulose composite material.
Further, the concentration of the nano-cellulose described in step (1) in aqueous is 1-10mg/ml, described oxygen
The mass ratio of graphite alkene and nano-cellulose is 1：5-20.
Further, graphene oxide is dispersed in nano-cellulose water by step (1) using ultrasound and mechanical agitation
In solution.
Further, filtered when step (1) removes water using polycarbonate leaching film, obtain the dark brown hydrogel of pie, then will
Hydrogel dries 10-12h at a temperature of 40-60 DEG C, dried product is preheated, preheating temperature is 100-300 degree.Adopt
Heated with tube furnace in nitrogen atmosphere, heating rate is 2 DEG C/min, is incubated 1h, then natural cooling.
Further, the 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.
Described graphene/carbon nano-cellulose composite is used to prepare ultracapacitor.Specific method is：By stone
Black alkene/carbonization nano-cellulose composite 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,
By the use of filter paper as barrier film, with KOH or K2SO4As electrolyte, button ultracapacitor is packaged into using button cell shell.
It is one widely used to prepare carbon material in inert gas high temperature carbonization by biological materials such as celluloses
Method, but the inert gas that the process needs to provide the tube furnace of high temperature and largely flow is used as protection gas, to devices call
It is higher, inert gas and time-consuming longer is wasted, limits the large-scale application of high temperature cabonization.Preparation method of the present invention, it will aoxidize
Graphene is mixed into the nano-cellulose aqueous solution, after being pre-processed, can be absorbed microwave and be produced local high temperature, as miniature
Heating source triggers the carbonization of nano-cellulose, the nano-cellulose electrical conductivity lifting after carbonization, can further absorb microwave, so as to
The nano-cellulose not being carbonized is triggered to continue to be carbonized, so as 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 be full of container, avoids traditional method
The high temperature time-consuming process of middle carbonization biological material, reduces cost, has industrialized potentiality.Microwave can quickly, low energy consumption
Conductive material is heated to very high temperature by ground, can be used as heating source initiation nano-cellulose by adding graphene absorption microwave
Carbonization, so as to quickly and efficiently obtain more preferable carbonized product, obtain the carbon material of high conductivity.
Brief description of the drawings
Fig. 1 is the structural representation of ultracapacitor；
Fig. 2 is the cyclic voltammetry curve of the ultracapacitor prepared using this method；
Fig. 3 is the constant current charge-discharge curve of the ultracapacitor prepared using this method；
Fig. 4 is the Nyquist curves of the ultracapacitor prepared using this method.
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 2mg/ml aqueous solution, put it into small beaker, adds rotor with 300
Rev/min rotating speed stirring, graphene oxide water solution (0.5mg/ml) is added while stirring.It will be obtained after mixing
Mixed solution ultrasound 30 minutes in sophisticated Ultrasound Instrument, that is, obtain the mixed aqueous solution (graphene oxide of the two：Nano-cellulose
=1：5).
Step 2, obtained mixed solution is filtered by vacuum with 200nm polycarbonate leaching film, obtains the dark brown water of pie
Gel.Hydrogel and filter membrane are put into vacuum drying oven together, vacuum drying 12 hours in 50 DEG C, that is, obtain one layer of composite wood
Expect film.Film color is uniform, it was demonstrated that its mixed effect is preferable.
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 incubated, then natural cooling.
Step 4, the composite after heat treatment is put into vial, changes the gas in vial into argon gas, then
It is put into micro-wave oven, the 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 is weighed, be put into 50ml vial, vial is put into the mistake of glove box
Cross and change 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 gas atmosphere is acted on 2 seconds with 1000w power, it can be seen that the mixture in bottle produces electric spark, then
Bottle is put into fume hood, bottleneck is opened, allows to cool to room temperature, obtains compound carbonizing product.
Step 6, carried out in fume hood, the compound carbonizing product obtained in step 2 is put into agate mortar, uses liquid relief
NMP (1-METHYLPYRROLIDONE) solution of PVDF (Kynoar) is uniformly added dropwise in rifle, and PVDF quality accounts for the 5% of gross mass,
5% acetylene black is added, after doing appropriate dilution with NMP, is ground into sticky liquid.
Step 7,50 microns of thick nickel sheet are cut into using slicer a diameter of 1.2cm sequin, the nickel sheet that will be cut
It is put into acetone and is cleaned by ultrasonic 30 minutes, then nickel sheet is taken out, is put into ethanol and is cleaned by ultrasonic 30 minutes, by cleaned nickel sheet
Dried up 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, vacuum drying 12 hours at a temperature of 120 DEG C.It will dry
The nickel sheet of carrying electrode materials after dry is weighed, and calculates the quality of poor quality as electrode material.
Step 8, it is mould, spring leaf is ultrasonic 30 minutes in ethanol, it is dried for standby.By qualitative filter paper be cut into diameter and
The same disk of battery case diameter, the barrier film as ultracapacitor.By the use of qualitative filter paper as barrier film, then with mould and step 7
In nickel sheet be assembled into ultracapacitor, 6M potassium hydroxide is added dropwise as electrolyte, is then packaged with battery sealing machine, such as
Shown in Fig. 1.
Step 9, by static 30 minutes of the device prepared, 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 scope of impedance spectrum test is 0.01Hz-100kHz, and Fig. 2 is the cyclic voltammetry curve of example 1, is not aoxidized significantly in figure
Reduction peak.
Embodiment 2
Step 1, nano-cellulose is configured to the 1-10mg/ml aqueous solution, put it into small beaker, add rotor with
300 revs/min of rotating speed stirring, graphene oxide water solution (2mg/ml) is added dropwise while stirring.It will be obtained after mixing
Mixed solution in sophisticated Ultrasound Instrument ultrasound 30 minutes, that is, obtain the mixed aqueous solution (graphene oxide of the two：Nanofiber
Element=1：20).
Step 2, obtained mixed solution is filtered by vacuum with 200nm polycarbonate leaching film, obtains the dark brown water of pie
Gel.Hydrogel and filter membrane are put into vacuum drying oven together, vacuum drying 12 hours in 50 DEG C, that is, obtain one layer of composite wood
Expect film.Film color is uniform, it was demonstrated that its mixed effect is preferable.
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 incubated, then natural cooling.
Step 4, the composite after heat treatment is put into vial, changes the gas in vial into argon gas, then
It is put into micro-wave oven, the 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 is weighed, be put into 50ml vial, vial is put into the mistake of glove box
Cross and change 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 gas atmosphere is acted on 2 seconds with 1000w power, it can be seen that the mixture in bottle produces electric spark, then
Bottle is put into fume hood, bottleneck is opened, allows to cool to room temperature, obtains compound carbonizing product.
Step 6, the compound carbonizing product obtained in step 5 is put into agate mortar, PTFE is uniformly added dropwise with liquid-transfering gun
Emulsion, 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 using slicer a diameter of 1.2cm sequin, the bubble that will be cut
Foam nickel, which is put into acetone, to be cleaned by ultrasonic 30 minutes, is taken out, is put into ethanol and is cleaned by ultrasonic 30 minutes.Cleaned nickel foam is used
Nitrogen dries up, 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, vacuum drying 4 is small at a temperature of 100 DEG C
When.The nickel foam of carrying electrode materials after drying is weighed, calculates the quality of poor quality as electrode material.
Step 8, it is mould, spring leaf is ultrasonic 30 minutes in ethanol, it is dried for standby.By qualitative filter paper be cut into diameter and
The same disk of battery case diameter, the barrier film as ultracapacitor.Ultracapacitor is assembled into the nickel foam in step 7,
6M potassium hydroxide is added dropwise as electrolyte, is then packaged with battery sealing machine.
Step 9, by static 30 minutes of the device prepared, 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 scope of impedance spectrum test is 0.01Hz-100kHz, and Fig. 3 is the constant current charge-discharge curve of the present embodiment, discharge and recharge in figure
Curve is almost symmetrical, illustrates that the device discharge and recharge has invertibity.
Embodiment 3
Step 1, nano-cellulose is configured to the 1-10mg/ml aqueous solution, put it into small beaker, add rotor with
300 revs/min of rotating speed stirring, graphene oxide water solution (5mg/ml) is added dropwise while stirring.It will be obtained after mixing
Mixed solution in sophisticated Ultrasound Instrument ultrasound 30 minutes, that is, obtain the mixed aqueous solution (graphene oxide of the two：Nanofiber
Element=1：5).
Step 2, graphene oxide solution is filtered by vacuum with 200nm polycarbonate leaching film, obtains the dark brown water of pie
Gel.Hydrogel and filter membrane are put into vacuum drying oven together, vacuum drying 12 hours, that is, obtain graphene oxide in 50 DEG C
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 is weighed, be put into 50ml vial, vial is put into the mistake of glove box
Cross and change 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 gas atmosphere is acted on 2 seconds with 1000w power, it can be seen that the mixture in bottle produces electric spark, then
Bottle is put into fume hood, bottleneck is opened, allows to cool to room temperature, obtains compound carbonizing product.
Step 4, the compound carbonizing product obtained in step 2 is put into agate mortar, PTFE is uniformly added dropwise with liquid-transfering gun
Emulsion, 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 using slicer a diameter of 1.2cm sequin, the nickel that will be cut
Piece, which is put into acetone, to be cleaned by ultrasonic 30 minutes, then nickel foam is taken out, and is put into ethanol and is cleaned by ultrasonic 30 minutes, will be cleaned
Nickel foam is dried up with nitrogen, as collector.It will be weighed per a piece of nickel foam, it is then that the slurry key in step 6 is uniform
In one side of the ground coated in nickel foam, coated nickel foam is compressed, is put into vacuum drying oven, it is true at a temperature of 100 DEG C
Sky drying 4 hours.The nickel foam of carrying electrode materials after drying is weighed, calculates the quality of poor quality as electrode material.
Step 6, it is mould, spring leaf is ultrasonic 30 minutes in ethanol, it is dried for standby.By qualitative filter paper be cut into diameter and
The same disk of battery case diameter, the barrier film as ultracapacitor.Ultracapacitor is assembled into the nickel foam in step 7,
6M potassium hydroxide is added dropwise as electrolyte, is then packaged with battery sealing machine.
Step 7, by static 30 minutes of the device prepared, 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 scope of impedance spectrum test is 0.01Hz-100kHz.Fig. 4 is the impedance spectrum of example 3, contact resistance very little in figure, and explanation is
The electrode material in the case of no addition conductive black is set also to have good electrical 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 the nano-cellulose aqueous solution, blended, water removal, answering of being pre-processed
Compound, wherein, the concentration of nano-cellulose in aqueous is 1mg/ml, and the mass ratio of graphene oxide and nano-cellulose is
1：5, graphene oxide is dispersed in the nano-cellulose aqueous solution using ultrasound and mechanical agitation, filtered using makrolon
Film is filtered, and obtains the dark brown hydrogel of pie, then hydrogel is dried into 12h at a temperature of 40 DEG C, and dried product is carried out
Preheating, preheating temperature are 100 degree, are heated using tube furnace in nitrogen atmosphere, and heating rate is 2 DEG C/min, are incubated 1h, so
Natural cooling afterwards.
(2) compound of pretreatment is subjected to microwave treatment under nitrogen or argon, carried out using micro-wave oven, power
500W, time 10s, that is, obtain graphene/carbon nano-cellulose composite.
Embodiment 5
A kind of preparation method of graphene/carbon nano-cellulose complex carbon material, specific steps：
(1) graphene oxide is mixed into the nano-cellulose aqueous solution, blended, water removal, answering of being pre-processed
Compound, wherein, the concentration of nano-cellulose in aqueous is 5mg/ml, and the mass ratio of graphene oxide and nano-cellulose is
1：10, graphene oxide is dispersed in the nano-cellulose aqueous solution using ultrasound and mechanical agitation, using makrolon
Filter membrane is filtered, and obtains the dark brown hydrogel of pie, then hydrogel is dried into 11h at a temperature of 50 DEG C, and dried product is entered
Row preheating, preheating temperature are 200 degree, are heated using tube furnace in nitrogen atmosphere, and heating rate is 2 DEG C/min, insulation
1.5h, then natural cooling.
(2) compound of pretreatment is subjected to microwave treatment under nitrogen or argon, carried out using micro-wave oven, power
800W, time 5s, that is, obtain graphene/carbon nano-cellulose composite.
Embodiment 6
A kind of preparation method of graphene/carbon nano-cellulose complex carbon material, specific steps：
(1) graphene oxide is mixed into the nano-cellulose aqueous solution, blended, water removal, answering of being pre-processed
Compound, wherein, the concentration of nano-cellulose in aqueous is 10mg/ml, graphene oxide and nano-cellulose mass ratio
For 1：20, graphene oxide is dispersed in the nano-cellulose aqueous solution using ultrasound and mechanical agitation, using poly- carbonic acid
Ester filter membrane is filtered, and obtains the dark brown hydrogel of pie, then hydrogel is dried into 10h at a temperature of 60 DEG C, by dried product
Preheated, preheating temperature is 300 degree, is heated using tube furnace in nitrogen atmosphere, and heating rate is 2 DEG C/min, insulation
1.5h, then natural cooling.
(2) compound of pretreatment is subjected to microwave treatment under nitrogen or argon, carried out using micro-wave oven, power
1000W, time 2s, that is, obtain graphene/carbon nano-cellulose composite.
Claims (10)
1. a kind of preparation method of graphene/carbon nano-cellulose complex carbon material, it is characterised in that specifically include following step
Suddenly：
(1) graphene oxide is mixed into the nano-cellulose aqueous solution, blended, water removal, the compound pre-processed；
(2) compound of pretreatment is subjected to microwave treatment under inert gas shielding, that is, obtains graphene/carbon nanofiber
Plain composite.
2. a kind of preparation method of graphene/carbon nano-cellulose complex carbon material according to claim 1, its feature
It is, the concentration of the nano-cellulose described in step (1) in aqueous is 1-10mg/ml, and described graphene oxide is with receiving
The mass ratio of rice cellulose is 1：5-20.
3. a kind of preparation method of graphene/carbon nano-cellulose complex carbon material according to claim 1, its feature
It is, graphene oxide is dispersed in the nano-cellulose aqueous solution by step (1) using ultrasound and mechanical agitation.
4. a kind of preparation method of graphene/carbon nano-cellulose complex carbon material according to claim 1, its feature
It is, is specifically filtered when step (1) removes water using polycarbonate leaching film, obtain the dark brown hydrogel of pie, then hydrogel is existed
10-12h is dried at a temperature of 40-60 DEG C.
5. a kind of preparation method of graphene/carbon nano-cellulose complex carbon material according to claim 4, its feature
It is, dried product is preheated, preheating temperature is 100-300 degree.
6. a kind of preparation method of graphene/carbon nano-cellulose complex carbon material according to claim 5, its feature
It is, heated using tube furnace in nitrogen atmosphere, heating rate is 2 DEG C/min, is incubated 1h, then natural cooling.
7. a kind of preparation method of graphene/carbon nano-cellulose complex carbon material according to claim 1, its feature
It is, the inert gas described in step (2) is nitrogen or argon gas, and microwave treatment is carried out using micro-wave oven, power 500-1000W,
Time is 2-10s.
8. the graphene/carbon nano-cellulose composite prepared by the preparation method as described in claim 1-7 is any.
9. graphene/carbon nano-cellulose composite as claimed in claim 8 is used to prepare ultracapacitor.
10. graphene/carbon nano-cellulose composite according to claim 9 is used to prepare ultracapacitor, its
It is characterised by, specific method is：Graphene/carbon nano-cellulose composite is pulverized, glued using PVDF or 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,
By the use of filter paper as barrier film, with KOH or K2SO4As electrolyte, button ultracapacitor is packaged into using button cell shell.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710474525.2A CN107359053B (en) | 2017-06-21 | 2017-06-21 | Graphene/carbon nano-cellulose complex carbon material and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710474525.2A CN107359053B (en) | 2017-06-21 | 2017-06-21 | Graphene/carbon nano-cellulose complex carbon material and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107359053A true CN107359053A (en) | 2017-11-17 |
| CN107359053B CN107359053B (en) | 2019-10-01 |
Family
ID=60273539
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710474525.2A Active CN107359053B (en) | 2017-06-21 | 2017-06-21 | Graphene/carbon nano-cellulose complex carbon material and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107359053B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108493400A (en) * | 2018-04-26 | 2018-09-04 | 广东永邦新能源股份有限公司 | A kind of high-voltage anode piece and preparation method thereof |
| 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 |
| CN109433191A (en) * | 2018-11-09 | 2019-03-08 | 济南大学 | A method of cohering powder catalyst |
| CN112366316A (en) * | 2020-09-27 | 2021-02-12 | 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 |
| CN113415800A (en) * | 2021-06-23 | 2021-09-21 | 桂林理工大学 | Carbon foam material and preparation method and application thereof |
| CN115376839A (en) * | 2022-09-22 | 2022-11-22 | 闽江学院 | Method for preparing supercapacitor by packaging flexible nano cellulose membrane |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105566659A (en) * | 2015-12-25 | 2016-05-11 | 郑州轻工业学院 | Graphene oxide/nano cellulose aerogel and preparation method and application thereof |
| CN106024413A (en) * | 2016-07-20 | 2016-10-12 | 扬州大学 | Super capacitor device made of graphitized nitrogen doped porous nanometer sheet carbon material |
| CN106057495A (en) * | 2016-05-18 | 2016-10-26 | 哈尔滨万鑫石墨谷科技有限公司 | Super capacitor flexible electrode, preparation method and super capacitor |
| CN106158426A (en) * | 2016-08-19 | 2016-11-23 | 南京林业大学 | A kind of method preparing flexible super capacitor wire electrode |
| CN106276888A (en) * | 2016-07-20 | 2017-01-04 | 扬州大学 | A kind of ultracapacitor device of foxtail millet scytoblastema porous active Carbon Materials |
| CN106517157A (en) * | 2016-10-28 | 2017-03-22 | 华北电力大学 | Nitrogen-doped carbon nanofiber/graphene aerogel preparation method and application |
-
2017
- 2017-06-21 CN CN201710474525.2A patent/CN107359053B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105566659A (en) * | 2015-12-25 | 2016-05-11 | 郑州轻工业学院 | Graphene oxide/nano cellulose aerogel and preparation method and application thereof |
| CN106057495A (en) * | 2016-05-18 | 2016-10-26 | 哈尔滨万鑫石墨谷科技有限公司 | Super capacitor flexible electrode, preparation method and super capacitor |
| CN106024413A (en) * | 2016-07-20 | 2016-10-12 | 扬州大学 | Super capacitor device made of graphitized nitrogen doped porous nanometer sheet carbon material |
| CN106276888A (en) * | 2016-07-20 | 2017-01-04 | 扬州大学 | A kind of ultracapacitor device of foxtail millet scytoblastema porous active Carbon Materials |
| CN106158426A (en) * | 2016-08-19 | 2016-11-23 | 南京林业大学 | A kind of method preparing flexible super capacitor wire electrode |
| CN106517157A (en) * | 2016-10-28 | 2017-03-22 | 华北电力大学 | Nitrogen-doped carbon nanofiber/graphene aerogel preparation method and application |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108493400A (en) * | 2018-04-26 | 2018-09-04 | 广东永邦新能源股份有限公司 | A kind of high-voltage anode piece and preparation method thereof |
| CN108493400B (en) * | 2018-04-26 | 2020-07-24 | 广东永邦新能源股份有限公司 | High-voltage positive plate and preparation method thereof |
| 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 |
| CN109433191A (en) * | 2018-11-09 | 2019-03-08 | 济南大学 | A method of cohering powder catalyst |
| CN112366316A (en) * | 2020-09-27 | 2021-02-12 | 泰山学院 | Preparation method and application of nitrogen and phosphorus co-doped graphene |
| 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 |
| CN113415800A (en) * | 2021-06-23 | 2021-09-21 | 桂林理工大学 | Carbon foam material and preparation method and application thereof |
| CN113415800B (en) * | 2021-06-23 | 2022-12-27 | 桂林理工大学 | Carbon foam material and preparation method and application thereof |
| CN115376839A (en) * | 2022-09-22 | 2022-11-22 | 闽江学院 | Method for preparing supercapacitor by packaging flexible nano cellulose membrane |
| CN115376839B (en) * | 2022-09-22 | 2024-01-12 | 闽江学院 | Method for preparing super capacitor by packaging flexible nanocellulose film |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107359053B (en) | 2019-10-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107359053B (en) | Graphene/carbon nano-cellulose complex carbon material and its preparation method and application | |
| Yang et al. | Hierarchical NiS2 modified with bifunctional carbon for enhanced potassium‐ion storage | |
| Genovese et al. | Ultrathin all-solid-state supercapacitor devices based on chitosan activated carbon electrodes and polymer electrolytes | |
| CN105811007B (en) | Electrolyte Gel, lithium-sulfur cell and preparation method | |
| CN103236560B (en) | A kind of sulfur/carbon composite anode material of lithium-sulfur cell and its preparation method and application | |
| CN105633372A (en) | Nickel sulfide nanoparticle/nitrogen-doped fiber-based carbon aerogel composite material and preparation method therefor | |
| Hu et al. | A Stable Biomass‐Derived Hard Carbon Anode for High‐Performance Sodium‐Ion Full Battery | |
| Xia et al. | Nitrogen and oxygen dual-doped hierarchical porous carbon derived from rapeseed meal for high performance lithium–sulfur batteries | |
| CN106024408B (en) | A kind of ruthenium-oxide-vulcanization carbon/carbon-copper composite material, using and a kind of electrode slice of ultracapacitor | |
| CN103074007B (en) | The preparation method of lithium ion battery silicium cathode use tackiness agent and silicium cathode | |
| CN102820456B (en) | Porous carbon/sulfur composite material, its preparation method and application | |
| CN104701541A (en) | Lithium-ion battery with WS2 serving as positive electrode and preparation method of lithium-ion battery | |
| Ortiz-Olivares et al. | Production of nanoarchitectonics corncob activated carbon as electrode material for enhanced supercapacitor performance | |
| CN108807808A (en) | A kind of biomass carbon aeroge is modified lithium-sulfur cell dedicated diaphragm and preparation method thereof and lithium-sulfur cell | |
| CN105977491A (en) | Nitrogen-doped hierarchical porous carbon electrode material and application thereof | |
| WO2023104141A1 (en) | N/o co-doped molybdenum sulfide@porous carbon composite electrode material and preparation method therefor, negative electrode material and preparation method therefor, and use thereof | |
| CN111082047A (en) | Preparation method and application of two-dimensional carbide crystal base Zif-67 derived cobalt oxide material | |
| CN106816576A (en) | A kind of preparation method of anode material of lithium-ion battery and products thereof and application | |
| CN106298260B (en) | A kind of preparation method of fluorinated carbon material super-capacitor pole piece | |
| CN108198691A (en) | Nitrogenize the preparation method and dye-sensitized solar cells of carbon derivative and redox graphene compound | |
| CN103078088B (en) | Lithium ion battery cathode material | |
| Tu et al. | Biomass-based porous carbon for high-performance supercapacitor electrode materials prepared from Canada goldenrod | |
| CN103606680A (en) | Preparation method of natural graphite composite N-doped carbon nanofibers webs cathode material | |
| CN109148829A (en) | A kind of biomass derived Nano Carbon nickel oxide electrode and its application | |
| CN108666152A (en) | A kind of self-heating micro super capacitor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |