CN106683910A - Flaky carbonyl functionalized carbon material, preparation method thereof and application thereof in preparation of supercapacitor - Google Patents
Flaky carbonyl functionalized carbon material, preparation method thereof and application thereof in preparation of supercapacitor Download PDFInfo
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 53
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000000203 mixture Substances 0.000 claims abstract description 26
- 239000002243 precursor Substances 0.000 claims abstract description 26
- 239000011347 resin Substances 0.000 claims abstract description 19
- 229920005989 resin Polymers 0.000 claims abstract description 19
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims abstract description 12
- 239000000347 magnesium hydroxide Substances 0.000 claims abstract description 12
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims abstract description 12
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 8
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 8
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 7
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 6
- 238000005470 impregnation Methods 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 229910052799 carbon Inorganic materials 0.000 claims description 16
- 238000007306 functionalization reaction Methods 0.000 claims description 14
- 238000007711 solidification Methods 0.000 claims description 5
- 230000008023 solidification Effects 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 3
- LUBNKNNXRUCCRO-UHFFFAOYSA-N phenol 1,3,5-trimethylbenzene Chemical compound C1(=CC(=CC(=C1)C)C)C.C1(=CC=CC=C1)O LUBNKNNXRUCCRO-UHFFFAOYSA-N 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- 238000010828 elution Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims 2
- 239000007772 electrode material Substances 0.000 abstract description 9
- 238000004146 energy storage Methods 0.000 abstract description 8
- 239000003792 electrolyte Substances 0.000 abstract description 4
- 238000005406 washing Methods 0.000 abstract description 3
- 239000003513 alkali Substances 0.000 abstract 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract 2
- 238000003763 carbonization Methods 0.000 abstract 1
- 230000006698 induction Effects 0.000 abstract 1
- 238000005554 pickling Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 8
- 230000005540 biological transmission Effects 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 238000010276 construction Methods 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 239000003990 capacitor Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000012983 electrochemical energy storage Methods 0.000 description 4
- 239000011267 electrode slurry Substances 0.000 description 4
- 239000000395 magnesium oxide Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 150000005206 1,2-dihydroxybenzenes Chemical class 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- DBQBWZSDXNFYJI-UHFFFAOYSA-N [B].[N].[P] Chemical compound [B].[N].[P] DBQBWZSDXNFYJI-UHFFFAOYSA-N 0.000 description 1
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- RFXSFVVPCLGHAU-UHFFFAOYSA-N benzene;phenol Chemical group C1=CC=CC=C1.OC1=CC=CC=C1.OC1=CC=CC=C1 RFXSFVVPCLGHAU-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical compound [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010998 test method 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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
-
- 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)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
Abstract
The invention provides a preparation method of a flaky carbonyl functionalized carbon material. The preparation method comprises the following steps: mixing 0.5-2 mol/L soluble phenolic precursor solution with formaldehyde in accordance with a molar ratio of 1:3, impregnating the mixture onto magnesium hydroxide or calcium hydroxide by using an initial wet impregnation method, forming a mixture of resin/solid alkali by using the surface alkaline induction of solid alkali, and performing further thermosetting, high temperature carbonization, pickling, filtering, washing and drying on the obtained mixture of resin/solid alkali to obtain the flaky carbonyl functionalized carbon material. The flaky carbonyl functionalized carbon material prepared by the method and applied to supercapacitor energy storage as an electrode material has high specific capacity and excellent cycle stability, and the capacitance in 1.0M sulfuric acid electrolyte is up to 622F/g.
Description
Technical field：
Synthesis and electrochemical energy storage application field the invention belongs to functionalized carbon based nano-material, are related to a kind of utilization to urge
The method synthesis of the property changed template-mediated has the carbon material of the carbonyl functionalization of platelet morphology and its is preparing electric chemical super
The application of capacitor.
Background technology：
Ultracapacitor is a kind of novel energy storage apparatus between traditional capacitor and rechargeable battery, and it has power
Density is high, long service life, temperature in use wide ranges, and the characteristics of charging rate is fast, it is right worldwide to cause in recent years
The research boom of ultracapacitor, and come into wide application field.
Carbon-based electrode material is one of conventional electrode material for super capacitor, and its is conductive good, and heat endurance is good,
Long service life, it is easy to synthesize, abundance, environment-friendly overall characteristic, it is used for ultracapacitor as electrode material
Energy storage has a good application prospect.Even so, carbon-based electrode material is applied to electrochemical energy storage there are problems that.Carbon
It is low capacity that sill is applied to electrochemical energy storage and is particularly applied to one of problem present in ultracapacitor energy storage, because
The contribution of capacity mostlys come from limited electrochemical double layer capacitance contribution.For this problem, way widely used at present
One of be that functionalization is carried out to the surface of carbon material, by functionalization its surface introduce with fake capacitance performance function base
Group, such that it is able to effectively improve the capacity of its electrochemical energy storage.Patent (the application number of Gao Qiuming et al.：
200810036883.6) a kind of preparation method of nitrogen-doped porous carbon material is reported, its synthetic method is with mesopore silicon oxide powder
Body, ethylenediamine prepares order mesoporous carboritride for predecessor, and the method synthesis step is cumbersome to be unfavorable for preparing on a large scale, and
And the capacitance of the N doping meso-porous carbon material prepared using its method is relatively low, highest only has 328F/g.In fortune flower et al.
Patent (application number：201310713624.3) a kind of preparation method of ultracapacitor phosphorus doping porous carbon materials is reported,
Using carbohydrate and inorganic acid for precursor prepares phosphorus doping porous carbon materials by the method for prepolymerization and high temperature cabonization, profit
The capacitance of the phosphorus doping porous carbon materials prepared with the method is very low, only 267F/g.Qiao Jin beautiful et al. patent (application
Number：201410647456.7) a kind of preparation method of nitrogen sulphur codope mesoporous carbon electrode material is reported, using nanometer titanium dioxide
Silicon is template, and polyethyleneimine is precursor, and the capacitance highest of the doping carbon material prepared using the method only has 279F/g.
Patent (the application number of Sun Liguo et al.：201510001515.8) a kind of preparation side of the porous carbon microballon of the nitrogen that adulterates is reported
Method, the method has also used silica for template, and synthesis step is relatively cumbersome, the doping carbon material prepared using the method
Capacitance is very low, only 218F/g.Patent (the application number of Wang Jing et al.：201510458188.9) report a kind of ellipsoid
Nitrogen boron phosphorus doping mesoporous carbon preparation method and application, the method using ellipsoid mesoporous silicon oxide be hard template, have
Machine high molecular polymer is carbon source, and nitrogenous precursor is nitrogen source, and boracic presoma is boron source, and phosphorous presoma is phosphorus source.Utilize
The capacitance of the meso-porous carbon material of doping functionalization prepared by the method is 366F/g.Analysis above shows, reports at present
The capacitive property of carbon material of doping functionalization especially capacity is also poor, the actual application of distance is also differed farther out.Separately
Outward, the synthetic method of report has poor efficiency, high cost, defect not environmentally, the synthesis side of wherein most report at present
Method all relies on silicon substrate template, is analyzed with reference to more than, and the functionalized carbon with high power capacity is obtained with a kind of simple effective method
Base electrode material is still present challenge.
The content of the invention：
The invention provides the preparation method and its ultracapacitor energy storage of a kind of laminar carbonyl functional carbon material
Energy.The electrode material of this functionalization can be in 1.0M H2SO4In electrolyte, electric capacity memory capacity (up to 622F/g) high is realized
With excellent cycle life, at higher current densities, be may remain in by its capacity after the continuous discharge and recharge of 10000 times
99%.
The present invention can be achieved through the following technical solutions：
A kind of preparation method of laminar carbonyl functional carbon material, it comprises the following steps：
Step 1, by soluble phenolic precursors it is soluble in water obtain concentration for 0.5-2mol/L precursor solutions and according to phenol/
Aldehyde is 1:3 molar ratio adds 37% formalin to the mixing precursor solution being well mixed in precursor solution；
Step 2, by step 1 prepare mixed solution by impregnate method be impregnated on solid base powder react obtain
The mixture of oligomeric resin/template；
Step 3, the mixture thermosetting of the oligomeric resin/template that will be obtained in step 2 obtain the mixing of solidified resin/template
Thing；
Step 4, the mixture of the solidified resin/template that will be obtained in step 3 be calcined under high temperature argon atmosphere obtain carbon/
The mixture of template；
Step 5, the mixture of the carbon/template that will be obtained in step 4 utilize salt acid elution, filtering, drying to thin slice
The carbon material of shape carbonyl functionalization.
The preparation method of above-mentioned laminar carbonyl functional carbon material, the phenolic precursors described in step 1 are phenol, adjacent benzene
Diphenol, mesitylene phenol.
The preparation method of above-mentioned laminar carbonyl functional carbon material, the solid base described in step 2 is laminar hydrogen-oxygen
Change magnesium or laminar calcium hydroxide, dipping method is incipient wetness impregnation, and dip time is 24-72h.
The preparation method of above-mentioned laminar carbonyl functional carbon material, the solidification temperature described in step 3 is 80-120 DEG C,
Hardening time is 12-48h.
The preparation method of above-mentioned laminar carbonyl functional carbon material, the sintering temperature described in step 4 is 600-800
DEG C, roasting time is 1-4h.
Laminar carbonyl functional carbon material obtained in a kind of preparation method of above-mentioned laminar carbonyl functional carbon material.
Application of the above-mentioned laminar carbonyl functional carbon material in ultracapacitor is prepared.
A kind of ultracapacitor storage that aqueous systems electrolyte is applied to using above-mentioned laminar carbonyl functional carbon material
The method of testing of energy, it comprises the following steps：
Step 1, the laminar carbonyl functional carbon material that will be prepared, conductive black and binding agent (polytetrafluoroethylene (PTFE)) according to
80:10:10 ratio be mixed and dispersed in obtaining electrode slurry in absolute ethyl alcohol；
Step 2, the electrode slurry that step 1 is obtained is coated on stainless (steel) wire, then at drying in 80 DEG C of baking oven
Reason obtains electrode plates in 24 hours, will obtain after electrode plates are compacted under the pressure of 10Mpa, using electrochemical workstation
Carry out ultracapacitor energy storage performance test.
The laminar carbonyl functional carbon material of the method test is in 1.0M H2SO4Electric capacity memory capacity in electrolyte is high
Up to 622F/g, at higher current densities, 99% is may remain in by its capacity after the continuous discharge and recharge of 10000 times.
The beneficial effects of the present invention are：
1. it is template that this method employs cheap and inorganic base that is easily removing, greatly reduces cost, Er Qieben
Method it is simple to operate, be easy to large-scale production；
2. the method can be widely used in the synthesis of the carbon material of other element doping functionalization, such as nitrogen, phosphorus, boron
Deng the synthesis of the carbon material of doping；
3. this electrode material cost is cheap, and its energy-storage property is superior, with good prospects for commercial application.
Brief description of the drawings：
Fig. 1 is the transmission electron microscope photo of laminar carbonyl functional carbon material prepared by embodiment 1.
Fig. 2 is the high-resolution-ration transmission electric-lens photo of laminar carbonyl functional carbon material prepared by embodiment 1.
Fig. 3 is the X-ray diffractogram of laminar carbonyl functional carbon material prepared by embodiment 1.
Fig. 4 is the nitrogen adsorption isotherm of laminar carbonyl functional carbon material prepared by embodiment 1.
Fig. 5 is the infrared spectrogram of laminar carbonyl functional carbon material prepared by embodiment 1.
Fig. 6 is the transmission electron microscope photo of the laminar carbonyl functional carbon material that embodiment 2 is obtained.
Fig. 7 is the transmission electron microscope photo of the laminar carbonyl functional carbon material that embodiment 3 is obtained.
Fig. 8 is that the capacity of the super capacitor performance of laminar carbonyl functional carbon material prepared by embodiment 1 is close with electric current
The change comparison diagram of degree.
Fig. 9 is the cycle life figure of the super capacitor performance of laminar carbonyl functional carbon material prepared by embodiment 1.
Specific embodiment：
The present invention will be described in detail with following embodiment, but these embodiments be only to illustrate the invention,
And the invention is not limited in this.
Embodiment 1
0.94g phenol obtains the precursor solution that concentration is 0.5mol/L in being dissolved in 20ml water, then by 2.5ml formaldehyde
(37%) it is added in precursor solution to be well mixed and obtains mixing precursor solution.The mixing precursor solution that will be prepared is by just wet
The method of dipping is impregnated on calcium hydroxide and keeps 72h to obtain the mixture of oligomeric resin/calcium hydroxide, by oligomeric resin/
The mixture of calcium hydroxide obtains solidified resin/calcium hydroxide mixture after thermosetting 48h at 120 DEG C.The solidification tree that will be obtained
The mixture of fat/calcium hydroxide is calcined the composite construction that 4h obtains carbon/calcium oxide in 600 DEG C of argon gas atmosphere, by carbon/oxidation
The composite construction of calcium is placed in the hydrochloric acid that 100ml concentration is 0.2mol/L and performs etching removal calcium oxide, then carries out suction filtration, washes
Wash drying to the carbon material of laminar carbonyl functionalization.The pattern of product is characterized by transmission electron microscope, as shown in figure 1, producing
The crystallinity of thing is characterized as shown in Figures 2 and 3 by high power transmission electron microscope and powder x-ray diffraction, and the pore structure of product passes through
Transmission electron microscope and nitrogen adsorption isotherm characterize as shown in Figure 4.The surface carbonyl group of product passes through infrared spectrum characterization such as Fig. 5
It is shown.
Embodiment 2
1.11g catechols obtain the precursor solution that concentration is 1.0mol/L in being dissolved in 10.0ml water, then by 2.5ml first
Aldehyde (37%) is added in precursor solution to be well mixed and obtains mixing precursor solution.The mixing precursor solution that will be prepared is by just
The method of wet impregnation is impregnated on magnesium hydroxide and keeps 48h to obtain the mixture of oligomeric resin/magnesium hydroxide, by oligomeric tree
The mixture of fat/magnesium hydroxide obtains solidified resin/magnesium hydroxide mixture after thermosetting 24h at 100 DEG C.The solidification that will be obtained
The mixture of resin/magnesium hydroxide is calcined the composite construction that 2h obtains carbon/magnesia in 700 DEG C of argon gas atmosphere, by carbon/oxygen
The composite construction for changing magnesium is placed in 100ml concentration to perform etching removal magnesia in the hydrochloric acid of 0.2mol/L, then carries out suction filtration,
Washing and drying is the carbon material for obtaining laminar carbonyl functionalization, and the pattern of product is as shown in Figure 6.
Embodiment 3
1.26g mesitylene phenol obtains the precursor solution that concentration is 2.0mol/L in being dissolved in 5.0ml water, then by 2.5ml first
Aldehyde (37%) is added in precursor solution to be well mixed and obtains mixing precursor solution.The mixing precursor solution that will be prepared is by just
The method of wet impregnation is impregnated on magnesium hydroxide and keeps 24h to obtain the mixture of oligomeric resin/magnesium hydroxide, by oligomeric tree
The mixture of fat/magnesium hydroxide obtains solidified resin/magnesium hydroxide mixture after thermosetting 12h at 80 DEG C.The solidification that will be obtained
The mixture of resin/magnesium hydroxide is calcined the composite construction that 1h obtains carbon/magnesia in 800 DEG C of argon gas atmosphere, by carbon/oxygen
The composite construction for changing magnesium is placed in 100ml concentration to perform etching removal magnesia in the hydrochloric acid of 0.2mol/L, then carries out suction filtration,
Washing and drying is the carbon material for obtaining laminar carbonyl functionalization, and the pattern of product is as shown in Figure 7.
Performance of the supercapacitor test is tested using the method for three electrodes, and specific test process is by with following reality
Example is applied to be described in detail.
Performance of the supercapacitor testing example
The carbon material of the laminar carbonyl functionalization that will be prepared, conductive black and binding agent (polytetrafluoroethylene (PTFE)) are according to 80：
10：10 ratio be mixed and dispersed in obtaining electrode slurry in absolute ethyl alcohol.The electrode slurry that will be obtained is coated to stainless
On steel mesh, then dried process obtains electrode plates in 24 hours in 80 DEG C of baking oven, will obtain pressure of the electrode plates in 10Mpa
After being compacted under power, ultracapacitor energy storage performance test is carried out using electrochemical workstation.Performance of the supercapacitor is tested
Capacity and cycle life data as shown in Figure 8 and Figure 9.
Claims (7)
1. a kind of preparation method of laminar carbonyl functional carbon material, it is characterized in that it comprises the following steps：
Step 1, by the soluble phenolic precursors concentration that obtains soluble in water it is for 0.5-2mol/L precursor solutions and according to phenol/aldehyde
1:3 molar ratio adds 37% formalin to the mixing precursor solution being well mixed in precursor solution；
Step 2, by step 1 prepare mixed solution by impregnate method be impregnated on solid base powder react obtain oligomeric
The mixture of resin/template；
Step 3, the mixture thermosetting of the oligomeric resin/template that will be obtained in step 2 obtain the mixture of solidified resin/template；
Step 4, the mixture of the solidified resin/template that will be obtained in step 3 are calcined under high temperature argon atmosphere and obtain carbon/template
Mixture；
Step 5, the mixture of the carbon/template that will be obtained in step 4 utilize salt acid elution, filtering, drying to laminar carbonyl
The carbon material of base functionalization.
2. the preparation method of laminar carbonyl functional carbon material according to claim 1, it is characterized in that：Described in step 1
Phenolic precursors be phenol, catechol, mesitylene phenol.
3. the preparation method of laminar carbonyl functional carbon material according to claim 1, it is characterized in that：Described in step 2
Solid base be laminar magnesium hydroxide or laminar calcium hydroxide, dipping method is incipient wetness impregnation, and dip time is 24-72h.
4. the preparation method of laminar carbonyl functional carbon material according to claim 1, it is characterized in that：Described in step 3
Solidification temperature be 80-120 DEG C, hardening time is 12-48h.
5. the preparation method of laminar carbonyl functional carbon material according to claim 1, it is characterized in that：Described in step 4
Sintering temperature be 600-800 DEG C, roasting time is 1-4h.
6. laminar carbonyl functionalization obtained in the preparation method of laminar carbonyl functional carbon material described in a kind of claim 1
Carbon material.
7. application of the laminar carbonyl functional carbon material described in claim 6 in ultracapacitor is prepared.
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| US20090214413A1 (en) * | 2006-12-21 | 2009-08-27 | Addiego William P | Ordered mesoporous carbons and method for manufacturing same |
| CN103979529A (en) * | 2014-06-04 | 2014-08-13 | 北京化工大学 | Preparation method of porous carbon material and application of porous carbon material as electrode material |
| CN104759252A (en) * | 2015-03-23 | 2015-07-08 | 江苏大学 | A method of preparing porous carbon by adopting spherical zinc oxide as a template and applications of the porous carbon |
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| US20090214413A1 (en) * | 2006-12-21 | 2009-08-27 | Addiego William P | Ordered mesoporous carbons and method for manufacturing same |
| CN103979529A (en) * | 2014-06-04 | 2014-08-13 | 北京化工大学 | Preparation method of porous carbon material and application of porous carbon material as electrode material |
| CN104759252A (en) * | 2015-03-23 | 2015-07-08 | 江苏大学 | A method of preparing porous carbon by adopting spherical zinc oxide as a template and applications of the porous carbon |
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