CN104576077A - Graphene/ lignin-based activated carbon preparation method and application in supercapacitors - Google Patents
Graphene/ lignin-based activated carbon preparation method and application in supercapacitors Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 266
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 67
- 229920005610 lignin Polymers 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 31
- 239000010439 graphite Substances 0.000 claims abstract description 31
- 239000002131 composite material Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 8
- 230000009467 reduction Effects 0.000 claims abstract description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 60
- 239000003990 capacitor Substances 0.000 claims description 26
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000003792 electrolyte Substances 0.000 claims description 16
- -1 polytetrafluoroethylene Polymers 0.000 claims description 11
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 229910021538 borax Inorganic materials 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 239000004328 sodium tetraborate Substances 0.000 claims description 9
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 6
- 239000003431 cross linking reagent Substances 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 3
- 230000004888 barrier function Effects 0.000 claims description 3
- 239000005486 organic electrolyte Substances 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 2
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims 1
- 239000007772 electrode material Substances 0.000 abstract description 9
- 238000012546 transfer Methods 0.000 abstract description 6
- 230000004913 activation Effects 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 238000000197 pyrolysis Methods 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 description 13
- 238000001816 cooling Methods 0.000 description 12
- 239000006185 dispersion Substances 0.000 description 12
- 239000010410 layer Substances 0.000 description 12
- 238000000967 suction filtration Methods 0.000 description 12
- 239000003643 water by type Substances 0.000 description 12
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 10
- 150000005207 1,3-dihydroxybenzenes Chemical class 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000012300 argon atmosphere Substances 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000004146 energy storage Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000006260 foam Substances 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 239000002127 nanobelt Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000004964 aerogel Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical group Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 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
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
-
- 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
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- Carbon And Carbon Compounds (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention belongs to the field of chemistry, provides a graphene/lignin-based activated carbon preparation method and application in supercapacitors. The method includes the steps that 1, lignin-based activated carbon is prepared; 2, graphite oxide and the activated carbon are mixed, and a graphite oxide/lignin-based activated carbon compound is obtained; 3, pyrolysis reduction is conducted on the compound obtained after alkaline activation is conducted, and graphene/ lignin-based activated carbon composite material is prepared; 4, electrode plates are prepared. Compared with the prior art, the obtained graphene/lignin-based activated carbon has a larger specific surface, lower mass transfer resistance and more excellent electric conductivity. Furthermore, the composite graphene/lignin-based activated carbon is applied to electrode material of the supercapacitors, and the cost and performance are greatly superior to those of existing activated carbon material.
Description
Technical field
The invention belongs to chemical field, particularly a kind of preparation method of Graphene/Lignin-Based Activated Carbon and the application in ultracapacitor.
Background technology
Ultracapacitor is a kind of novel energy storage device grown up the 1970s and 1980s in last century, it is a kind of power supply between traditional capacitor and battery with property, main dependence electric double layer and redox fake capacitance store electrical energy, be thus different from traditional chemical power source.The outstanding advantages of ultracapacitor is that power density is high, the discharge and recharge time is short, have extended cycle life and operating temperature range wide, in fields such as national defence, railway, electric automobile electronics, communication, Aero-Space, there is wide application prospect.According to the difference of energy storage mechnism, ultracapacitor can be divided three classes: based on the double electric layer capacitor of porous carbon electrode/electrolyte interface electric double layer energy storage, based on the pseudocapacitor of metal oxide or the energy storage of conductive polymer surfaces Quick Oxidation reduction reaction, and two electrodes are respectively with the mixed capacitor that electric double layer and pseudo-capacitance are energy storage mechanism, also claim asymmetric capacitor.Current, the main flow of commercialization ultracapacitor is double electric layer capacitor (comprising inorganic electrolyte liquid system and organic electrolyte system two kinds).Wherein double electric layer capacitor utilizes electronics and ion or dipole to align produced electric double layer to store electric charge in electrode/solution surface, Faradic pseudo-capacitor is then, by electroactive substance, the electric capacity that chemisorbed, desorption or redox reaction cause occurs in the accurate two-dimensional space of electrode surface or body phase, can be divided into absorption fake capacitance and redox fake capacitance.Therefore, the performance of electrode material directly determines the energy storage quality of capacitor.
At present, the material being applied to ultracapacitor mainly contains carbon-based material (active carbon, carbon nano-tube, charcoal-aero gel, Graphene), transition metal oxide or hydroxide and conducting polymer (polyaniline).And material with carbon element because of physicochemical properties stablize, cost is low, various informative, easy processing, the features such as aperture structure controllability is good and (Arunabha Ghosh, the Young Hee Lee that is widely used, ChemSusChem 2012,5 (3), 480-499).Wherein active carbon is because have the advantages such as specific area is large, pore structure is adjustable, electrochemical stability is high, it is simple, cheap to prepare, abundant raw material, environmental protection, has important application and Development volue in electrode material for super capacitor.After Ruoff equals reported first in 2008 capacitive property of Graphene, this there is two-dimensional nanostructure, the novel charcoal material of high conductivity receives publicity rapidly in the application in ultracapacitor field, become a focus (the Stoller M D of current research, Park S, Zhu Y, An J, Ruoff R S, Nano Lett 2008,8,3498-3502).Graphene is a kind of New Type of Carbon material of carbon atom tightly packed one-tenth individual layer bi-dimensional cellular shape lattice structure, it has the pore structure of sheet and good electronic conductivity, in electric double layer charge and discharge process, these characteristics are conducive to the fast transfer of ion and electronics, therefore it has the distinguishing features such as the high and charge-discharge of electrochemical stability, conductivity is fast, is desirable electrode material.
But although the active carbon specific area being applied to ultracapacitor is at present large, its conductivity reduces with the increase of its specific area, thus the extreme influence charge-discharge performance of electric double layer capacitance.There is strong Van der Waals force in graphene film interlayer, they are easy to reunite, even come back to non-graphitic state, this will bring the specific surface of grapheme material and conductivity significantly to reduce, cause Graphene super capacitor ratio capacitance to reduce rapidly, this seriously constrains the extensive use of Graphene in ultracapacitor.In addition, Graphene preparation technology is not mature enough, and cost is too high, hinders its industrial applications.Therefore, a kind of active carbon/graphene composite material is built and synergy has great practical value both effectively realizing.
Summary of the invention
, Graphene lower for active carbon conductivity of the prior art is reunited serious and that cost is higher problem, the invention provides the preparation method of a kind of Graphene and absorbent charcoal composite material.The method has effectively prepared the high-performance combination electrode material that a kind of Stability Analysis of Structures, conductivity are high, ratio capacitance is comparatively large and specific area is excellent, and method is simple, green economy.
For solving the problems of the technologies described above, the technical solution used in the present invention is:
Graphene/the preparation method of Lignin-Based Activated Carbon composite material and the application in ultracapacitor, comprise the following steps:
1) one or both person's mixture in NaOH, potassium hydroxide and lignin are dissolved in deionized water in the ratio of 1:1 ~ 6:1, stir successively, after evaporate to dryness in atmosphere of inert gases with 500 ~ 900 DEG C of Pintsch process 1 ~ 4 hour, obtained Lignin-Based Activated Carbon;
2) by Lignin-Based Activated Carbon prepared in step 1) and graphite oxide in the ratio ultrasonic disperse of 10:1 ~ 5:1 in deionized water, add one or more in glutaraldehyde, resorcinol, borax in deionized water as crosslinking agent, react dry after 1 ~ 5 hour under 25 DEG C of room temperatures, obtain graphite oxide/Lignin-Based Activated Carbon compound;
3) by step 2) graphite oxide/Lignin-Based Activated Carbon compound of preparing and potassium hydroxide is scattered in deionized water by the mass ratio of 1:1 ~ 1:6, stir successively, filter, after oven dry in be mixed with 1% ~ 20% inert gas reducibility gas in Pintsch process reduction, obtain Graphene/Lignin-Based Activated Carbon composite material, described Pintsch process temperature and time is respectively 550 ~ 950 DEG C and 1 ~ 5 hour;
Further, described inert gas is one or more in nitrogen, argon gas, helium.
Further, the technique utilizing the Graphene/lignin-base active composite material taking above technique to prepare to prepare ultracapacitor is: mixed with polytetrafluoroethylene by Graphene/lignin-base active composite material and to mix with the mass ratio of 1:0.15 ~ 1:0.05 and to stir, be applied to Pao Droplets nickel surface, be assembled into the electrode slice of ultracapacitor.
Further, the barrier film of described assembling super capacitor can select polypropylene material to make, and the electrolyte of described assembling super capacitor is the organic electrolyte that tetraethylammonium tetrafluoroborate and acetonitrile or propene carbonate are prepared.
The preferred embodiment of a kind of Graphene/preparation method of Lignin-Based Activated Carbon composite material of the present invention and the application in ultracapacitor comprises the following steps:
1) preparation of Lignin-Based Activated Carbon: take 2 ~ 5 g lignin, 2 ~ 30 g potassium hydroxide, mixing is dissolved in 50 ~ 100 mL deionized waters, stir 1 ~ 4 hour in 40 ~ 90 DEG C of waters bath with thermostatic control, slow solvent evaporated, is placed in tube furnace, 500 ~ 900 DEG C of constant temperature 1 ~ 4 hour is warmed up to 5 ~ 10 DEG C/min in nitrogen atmosphere, cooling is taken out, and is washed to neutrality, suction filtration, vacuumize at 60 ~ 90 DEG C, obtains Lignin-Based Activated Carbon;
2) preparation of graphite oxide/Lignin-Based Activated Carbon compound: take 0.2 ~ 0.8 g graphite oxide ultrasonic disperse and form stable graphene oxide dispersion in deionized water, add 1 ~ 8 g Lignin-Based Activated Carbon, add 15 ~ 25 mM glutaraldehydes, 9 ~ 12 mM resorcinols, 0.05 ~ 0.07 mM borax, ultrasonic reaction 1 ~ 5 hour, filter, dry at 50 ~ 70 DEG C of temperature, obtain graphite oxide/Lignin-Based Activated Carbon compound;
3) preparation of Graphene Lignin-Based Activated Carbon composite material: take 2.8 ~ 5.6 g graphite oxide/Lignin-Based Activated Carbon compounds, 8.4 ~ 33.6 g potassium hydroxide, ultrasonic disperse is in deionized water, stir 1 ~ 5 hour at 60 ~ 80 DEG C, filtering drying, be placed in tube furnace, 550 ~ 950 DEG C are warmed up to and constant temperature 1 ~ 5 hour with 5 ~ 10 DEG C/min speed in containing the argon atmosphere of 3% ~ 6% hydrogen, cooling is taken out, be washed to neutrality, suction filtration, vacuumize at 60 ~ 90 DEG C, obtains Graphene/Lignin-Based Activated Carbon composite material.
4) electrode preparation: weigh 30 mg Graphenes/Lignin-Based Activated Carbon composite material grinding, add the binding agent PTFE15% that proportion is 15%, with absolute ethyl alcohol ultrasonic disperse 30 min, be coated in nickel foam surface after dispersion, at 60 ~ 105 DEG C, vacuumize obtained required electrode slice after 6 ~ 12 hours.
In the preferred embodiment, lignin high temperature direct carbonization after activation of potassium hydroxide obtains Lignin-Based Activated Carbon; Graphene oxide is evenly coated on activated carbon surface and forms stable graphite oxide/Lignin-Based Activated Carbon compound by the chemical bonding effect of glutaraldehyde, resorcinol, borax etc.; Graphite oxide/Lignin-Based Activated Carbon compound is mixed with potassium hydroxide, prepares Graphene/Lignin-Based Activated Carbon composite material through Pintsch process reduction.Research shows, the Graphene obtained/Lignin-Based Activated Carbon composite material conductivity under pressure 20 Mpa is 25 more than S/cm, and it can be used as the electrode material of ultracapacitor, specific capacitance is at 130 F g
-1above, after circulation charge-discharge 1000 times, its capacity can also keep more than 96%.
Each preferred version of the present invention can combinationally use mutually.
Compared with prior art, the present invention has following significant advantage:
(1) the present invention adopts organic crosslinking agent to prepare the Graphene/Lignin-Based Activated Carbon composite material of Stability Analysis of Structures, excellent electric conductivity.By the chemical bonding effect of crosslinking agent by graphene coated in activated carbon surface, effectively prevent the reunion of Graphene.The superior electrical conductivity of Graphene itself and huge specific area, add the specific area of electron transmission between activated carbon particles and active carbon, the electric double layer capacitance amount part of super capacitor obviously increased.In addition, prepare the exsertile active carbon of electrochemistry with lignin and itself also widened the range of application of lignin, while increase active carbon source, effectively improve the recycling of crops rubbish, environmental protection.
(2) for super capacitor, the mass transfer problem between electroactive composition and electrolyte is the key factor of determining electrode material property quality.Only have the electroactive composition that can touch electrolyte just may play a role in the charge and discharge process of super capacitor, which is buried can not touch electrolyte electroactive composition in electrode interior to the charge-discharge capacity of super capacitor without any contribution.Active carbon involved in the present invention has abundant pore structure, it carries out electrochemical reaction and provides flourishing mass transfer channel network for power on active component and electrolyte of electrode on interface, make electrolyte can be deep into inside fully to contact with the basic structural unit-nanobelt of electrode material, can there is electrochemical reaction with electrolyte in the electroactive composition on nanobelt surface, its mass transfer rate is apparently higher than prior art on interface.In addition, active carbon macromolecular structure prevents the reunion of graphene nanobelt, and Graphene superior electrical conductivity makes electro transfer also obvious faster than prior art, thus causes the electric double layer capacitance amount part of super capacitor obviously to increase.
(3) Graphene in the present invention/Lignin-Based Activated Carbon composite material is not only electrode interior and provides electron transmission passage fast between electrode and collector, and its abundant open opening structure is more convenient for carrying out ion-exchange between electrode active material and electrolyte, thus the charge-discharge power characteristic that to have caused super capacitor to possess more excellent, can still keep higher specific capacitance in discharge and recharge under high current density.Ultracapacitor obtained by the present invention can also reach 90 more than F/g at 20 A/g discharge capacity, is obviously better than prior art.
Embodiment
Further illustrate the present invention by embodiment below, but the present invention is not limited.The experimental technique of unreceipted actual conditions in the following example, usually conveniently condition, or according to the condition that manufacturer advises." room temperature ", " normal pressure " described in the present invention refers to temperature between regular job and air pressure, is generally 25 DEG C, an atmospheric pressure.
In following embodiment, the work electrode that the electro-chemical test of electric capacity is used scribbles composite material Pao Droplets nickel sheet (10 mm × 1, mm × 10 mm), be platinum plate electrode (10 mm × 1, mm × 10 mm) to electrode, reference electrode is saturated calomel electrode electrode.Electro-chemical test adopts time-measuring electric potential, and operating voltage-1.2 ~ 1.3 V, constant current charge-discharge current density is 1.0 A/g.
embodiment 1
3 g lignin, 9 g potassium hydroxide mixing are dissolved in 50 mL deionized waters, stir 2 hours in 70 DEG C of waters bath with thermostatic control, slow solvent evaporated, be placed in tube furnace, in nitrogen atmosphere, be warmed up to 850 DEG C of constant temperature 1 hour with 5 DEG C/min, cooling is taken out, be washed to neutrality, suction filtration, vacuumize at 70 DEG C, obtains Lignin-Based Activated Carbon.Take 0.25 g graphite oxide ultrasonic disperse and form stable graphene oxide dispersion in deionized water, add 2.25 g Lignin-Based Activated Carbons, add 24 mM glutaraldehydes, 12 mM resorcinols, 0.08 mM borax, ultrasonic reaction 2 hours, filter, 60 DEG C of oven dry, obtain graphite oxide/Lignin-Based Activated Carbon compound.Take 3 g graphite oxide/Lignin-Based Activated Carbon compounds, 9 g potassium hydroxide, ultrasonic disperse is in deionized water, stir 3 hours at 60 DEG C, filtering drying, is placed in tube furnace, 850 DEG C are warmed up to and constant temperature 1 hour with 5 DEG C/min in containing the argon atmosphere of 5% hydrogen, cooling is taken out, and is washed to neutrality, suction filtration, vacuumize at 70 DEG C, obtains Graphene/Lignin-Based Activated Carbon composite material.Weigh 30 mg Graphenes/Lignin-Based Activated Carbon composite material grinding, add a little binding agent PTFE(15%), with a small amount of absolute ethyl alcohol ultrasonic disperse 30 min, be coated in nickel foam surface after dispersion, at 60 DEG C, vacuumize obtained required electrode slice after 12 hours.Using obtained Graphene/Lignin-Based Activated Carbon electrode as work electrode with to electrode, 1 mol/L tetraethylammonium tetrafluoroborate/propene carbonate is electrolyte assembling super capacitor, its capacitance is 142 F/g, and after discharge and recharge 1000 times, capacitance keeps 97.5 %.
embodiment 2
3 g lignin, 12 g potassium hydroxide mixing are dissolved in 50 mL deionized waters, stir 2 hours in 70 DEG C of waters bath with thermostatic control, slow solvent evaporated, be placed in tube furnace, in nitrogen atmosphere, be warmed up to 750 DEG C of constant temperature 2 hours with 5 DEG C/min, cooling is taken out, be washed to neutrality, suction filtration, vacuumize at 70 DEG C, obtains Lignin-Based Activated Carbon.Take 0.25 g graphite oxide ultrasonic disperse and form stable graphene oxide dispersion in deionized water, add 2.5 g Lignin-Based Activated Carbons, add 24 mM glutaraldehydes, 12 mM resorcinols, 0.08 mM borax, ultrasonic reaction 2 hours, filter, 60 DEG C of oven dry, obtain graphite oxide/Lignin-Based Activated Carbon compound.Take 3 g graphite oxide/Lignin-Based Activated Carbon compounds, 12 g potassium hydroxide, ultrasonic disperse is in deionized water, stir 2 hours at 60 DEG C, filtering drying, is placed in tube furnace, 850 DEG C are warmed up to and constant temperature 2 hours with 5 DEG C/min in containing the argon atmosphere of 5% hydrogen, cooling is taken out, and is washed to neutrality, suction filtration, vacuumize at 70 DEG C, obtains Graphene/Lignin-Based Activated Carbon composite material.Weigh 30 mg Graphenes/Lignin-Based Activated Carbon composite material grinding, add a little binding agent PTFE(15%), with a small amount of absolute ethyl alcohol ultrasonic disperse 30 min, be coated in nickel foam surface after dispersion, at 60 DEG C, vacuumize obtained required electrode slice after 12 hours.Using obtained Graphene/Lignin-Based Activated Carbon electrode as work electrode with to electrode, 1 mol/L tetraethylammonium tetrafluoroborate/propene carbonate is electrolyte assembling super capacitor, its capacitance is 150 F/g, and after discharge and recharge 1000 times, capacitance keeps 98.3%.
embodiment 3
3 g lignin, 15 g potassium hydroxide mixing are dissolved in 50 mL deionized waters, stir 2 hours in 70 DEG C of waters bath with thermostatic control, slow solvent evaporated, be placed in tube furnace, in nitrogen atmosphere, be warmed up to 650 DEG C of constant temperature 3 hours with 5 DEG C/min, cooling is taken out, be washed to neutrality, suction filtration, vacuumize at 70 DEG C, obtains Lignin-Based Activated Carbon.Take 0.25 g graphite oxide ultrasonic disperse and form stable graphene oxide dispersion in deionized water, add 2 g Lignin-Based Activated Carbons, add 24 mM glutaraldehydes, 12 mM resorcinols, 0.08 mM borax, ultrasonic reaction 3 hours, filter, 60 DEG C of oven dry, obtain graphite oxide/Lignin-Based Activated Carbon compound.Take 3 g graphite oxide/Lignin-Based Activated Carbon compounds, 15 g potassium hydroxide, ultrasonic disperse is in deionized water, stir 4 hours at 60 DEG C, filtering drying, is placed in tube furnace, 850 DEG C are warmed up to and constant temperature 3 hours with 5 DEG C/min in containing the argon atmosphere of 5% hydrogen, cooling is taken out, and is washed to neutrality, suction filtration, vacuumize at 70 DEG C, obtains Graphene/Lignin-Based Activated Carbon composite material.Weigh 30 mg Graphenes/Lignin-Based Activated Carbon composite material grinding, add a little binding agent PTFE(15%), with a small amount of absolute ethyl alcohol ultrasonic disperse 30 min, be coated in nickel foam surface after dispersion, at 60 DEG C, vacuumize obtained required electrode slice after 12 hours.Using obtained Graphene/Lignin-Based Activated Carbon electrode as work electrode with to electrode, 1 mol/L tetraethylammonium tetrafluoroborate/propene carbonate is electrolyte assembling super capacitor, its capacitance is 140 F/g, and after discharge and recharge 1000 times, capacitance keeps 98.2%.
embodiment 4
3 g lignin, 18 g potassium hydroxide mixing are dissolved in 50 mL deionized waters, stir 1 hour in 70 DEG C of waters bath with thermostatic control, slow solvent evaporated, be placed in tube furnace, in nitrogen atmosphere, be warmed up to 750 DEG C of constant temperature 1 hour with 5 DEG C/min, cooling is taken out, be washed to neutrality, suction filtration, vacuumize at 70 DEG C, obtains Lignin-Based Activated Carbon.Take 0.25 g graphite oxide ultrasonic disperse and form stable graphene oxide dispersion in deionized water, add 1.5 g Lignin-Based Activated Carbons, add 24 mM glutaraldehydes, 12 mM resorcinols, 0.08 mM borax, ultrasonic reaction 3 hours, filter, 60 DEG C of oven dry, obtain graphite oxide/Lignin-Based Activated Carbon compound.Take 3 g graphite oxide/Lignin-Based Activated Carbon compounds, 18 g potassium hydroxide, ultrasonic disperse is in deionized water, stir 3 hours at 60 DEG C, filtering drying, is placed in tube furnace, 750 DEG C are warmed up to and constant temperature 3 hours with 5 DEG C/min in containing the argon atmosphere of 5% hydrogen, cooling is taken out, and is washed to neutrality, suction filtration, vacuumize at 70 DEG C, obtains Graphene/Lignin-Based Activated Carbon composite material.Weigh 30mg Graphene/Lignin-Based Activated Carbon composite material grinding, add a little binding agent PTFE(15%), with a small amount of absolute ethyl alcohol ultrasonic disperse 30 min, be coated in nickel foam surface after dispersion, at 60 DEG C, vacuumize obtained required electrode slice after 12 hours.Using obtained Graphene/Lignin-Based Activated Carbon electrode as work electrode with to electrode, 1 mol/L tetraethylammonium tetrafluoroborate/propene carbonate is electrolyte assembling super capacitor, its capacitance is 135 F/g, and after discharge and recharge 1000 times, capacitance keeps 97.9%.
embodiment 5
3 g lignin, 15 g potassium hydroxide mixing are dissolved in 50 mL deionized waters, stir 2 hours in 70 DEG C of waters bath with thermostatic control, slow solvent evaporated, be placed in tube furnace, in nitrogen atmosphere, be warmed up to 850 DEG C of constant temperature 1 hour with 5 DEG C/min, cooling is taken out, be washed to neutrality, suction filtration, vacuumize at 70 DEG C, obtains Lignin-Based Activated Carbon.Take 0.25 g graphite oxide ultrasonic disperse and form stable graphene oxide dispersion in deionized water, add 1.25 g Lignin-Based Activated Carbons, add 24 mM glutaraldehydes, 12 mM resorcinols, 0.08 mM borax, ultrasonic reaction 5 hours, filter, 60 DEG C of oven dry, obtain graphite oxide/Lignin-Based Activated Carbon compound.Take 3 g graphite oxide/Lignin-Based Activated Carbon compounds, 10 g potassium hydroxide, ultrasonic disperse is in deionized water, stir 3 hours at 60 DEG C, filtering drying, is placed in tube furnace, 950 DEG C are warmed up to and constant temperature 1 hour with 5 DEG C/min in containing the argon atmosphere of 5% hydrogen, cooling is taken out, and is washed to neutrality, suction filtration, vacuumize at 70 DEG C, obtains Graphene/Lignin-Based Activated Carbon composite material.Weigh 30 mg Graphenes/Lignin-Based Activated Carbon composite material grinding, add a little binding agent PTFE(15%), with a small amount of absolute ethyl alcohol ultrasonic disperse 30 min, be coated in nickel foam surface after dispersion, at 60 DEG C, vacuumize obtained required electrode slice after 12 hours.Using obtained Graphene/Lignin-Based Activated Carbon electrode as work electrode with to electrode, 1 mol/L tetraethylammonium tetrafluoroborate/propene carbonate is electrolyte assembling super capacitor, its capacitance is 132 F/g, and after discharge and recharge 1000 times, capacitance keeps 97.4%.
Claims (8)
1. a preparation method for Graphene/Lignin-Based Activated Carbon, is characterized in that, comprises the following steps:
1) lignin and alkaline matter are dissolved in deionized water, stir, evaporate to dryness, inert atmosphere Pintsch process, obtained Lignin-Based Activated Carbon;
2) by 1) prepared Lignin Activated Carbon mixes with graphite oxide, and ultrasonic disperse, adds crosslinking agent, reacts under room temperature, and drying, obtains graphite oxide/Lignin-Based Activated Carbon compound;
3) by 2) graphite oxide/Lignin-Based Activated Carbon compound of preparing and potassium hydroxide is scattered in deionized water, successively through stirring, filter, after oven dry, Pintsch process reduction in the inert atmosphere being mixed with reducibility gas, obtains Graphene/Lignin-Based Activated Carbon composite material.
2. the preparation method of a kind of Graphene/Lignin-Based Activated Carbon according to claim 1, is characterized in that, described alkaline material is NaOH or potassium hydroxide, or the mixture of NaOH and potassium hydroxide.
3. the preparation method of a kind of Graphene/Lignin-Based Activated Carbon according to claim 1, it is characterized in that, in described step 1), the mass ratio of lignin and alkaline matter is 1:1 ~ 1:6, and described Pintsch process temperature and time is respectively 500 ~ 900 DEG C and 1 ~ 4 hour.
4. the preparation method of a kind of Graphene/Lignin-Based Activated Carbon according to claim 1, is characterized in that, described step 2) in Lignin-Based Activated Carbon and the mass ratio of graphite oxide be 10:1 ~ 5:1.
5. the preparation method of a kind of Graphene/Lignin-Based Activated Carbon according to claim 1, it is characterized in that, described step 2) in crosslinking agent be one or more in glutaraldehyde, resorcinol and borax, described room temperature is 25 DEG C, and the room temperature lower reaction time is 1 ~ 5 hour.
6. the preparation method of a kind of Graphene/Lignin-Based Activated Carbon according to claim 1, it is characterized in that, the mass ratio of graphite oxide in described step 3)/Lignin-Based Activated Carbon compound and potassium hydroxide is 1:1 ~ 1:6, and Pintsch process temperature and time is respectively 550 ~ 950 DEG C and 1 ~ 5 hour.
7. Graphene/the Lignin-Based Activated Carbon utilizing the preparation method of a kind of Graphene/Lignin-Based Activated Carbon according to claim 1 to prepare is in the application of ultracapacitor, it is characterized in that, Graphene/lignin-base active composite material and polytetrafluoroethylene is the steps include: to mix according to the mass ratio of 1:0.15 ~ 1:0.05, stir, be applied to Pao Droplets nickel surface, be prepared into super capacitor electrode slice.
8. Graphene/Lignin-Based Activated Carbon according to claim 7 is in the application of ultracapacitor, it is characterized in that, the barrier film of described assembling super capacitor is selected from the barrier film that polypropylene material makes, and the electrolyte of described assembling super capacitor is the organic electrolyte that tetraethylammonium tetrafluoroborate and acetonitrile or propene carbonate are prepared.
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