CN116206907A - Highly graphitized porous activated carbon material and preparation method and application thereof - Google Patents
Highly graphitized porous activated carbon material and preparation method and application thereof Download PDFInfo
- Publication number
- CN116206907A CN116206907A CN202310231939.8A CN202310231939A CN116206907A CN 116206907 A CN116206907 A CN 116206907A CN 202310231939 A CN202310231939 A CN 202310231939A CN 116206907 A CN116206907 A CN 116206907A
- Authority
- CN
- China
- Prior art keywords
- carbon material
- activated carbon
- porous activated
- puffing
- water
- 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.)
- Pending
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 239000000463 material Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 230000004913 activation Effects 0.000 claims abstract description 24
- 230000001007 puffing effect Effects 0.000 claims abstract description 23
- 239000007772 electrode material Substances 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000007833 carbon precursor Substances 0.000 claims abstract description 9
- 238000003763 carbonization Methods 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 9
- 239000010439 graphite Substances 0.000 claims abstract description 9
- 238000004321 preservation Methods 0.000 claims abstract description 9
- 239000012298 atmosphere Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 3
- 238000005303 weighing Methods 0.000 claims abstract description 3
- 239000003575 carbonaceous material Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 15
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 claims description 12
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 10
- 230000000630 rising effect Effects 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 3
- 238000005087 graphitization Methods 0.000 abstract description 6
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 230000001276 controlling effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000012983 electrochemical energy storage Methods 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- -1 polytetrafluoroethylene Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000001237 Raman spectrum Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000011363 dried mixture Substances 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 240000007049 Juglans regia Species 0.000 description 1
- 235000009496 Juglans regia Nutrition 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000002003 electron diffraction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 125000003071 maltose group Chemical group 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 235000020234 walnut Nutrition 0.000 description 1
Images
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
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—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)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a highly graphitized porous activated carbon material, a preparation method and application thereof, wherein a carbon precursor and water are mixed in a graphite crucible, heat preservation is carried out for 2 hours at 155 ℃ under inert atmosphere, then the temperature is raised to 955 ℃ for heat preservation for 2 hours for pre-puffing carbonization treatment, and a pre-puffing intermediate is obtained; respectively weighing the pre-puffing intermediate and potassium hydroxide according to the mass ratio of 1:2, uniformly mixing in water, drying, and then placing in a nitrogen atmosphere for heat preservation at 755 ℃ for 2 hours for activation treatment; cooling to room temperature along with the furnace, taking out, washing with water to neutrality, and drying. According to the invention, the high graphitization porous activated carbon material is obtained by regulating and controlling the water content of the carbon precursor and utilizing a bubble puffing carbonization auxiliary KOH activation strategy, the number of reactive active sites of the electrode material is increased, the conductivity of the material is improved, the specific capacitance of the supercapacitor can be increased, and meanwhile, the electrochemical performance parameters such as good cycle life of the electrode material are maintained.
Description
Technical Field
The invention belongs to the technical field of nano material preparation, and particularly relates to a highly graphitized porous activated carbon material, and a preparation method and application thereof.
Background
The porous active carbon material isThe current commercialized super capacitor is the most widely applied electrode active material, and the abundant micro/mesoporous channels increase the specific surface area of the material and form abundant electrochemical active sites, so that an unblocked path can be provided for the permeation/diffusion of ions in electrolyte, and the dynamic process of ion migration is accelerated, so that the super capacitor has excellent electrochemical energy storage characteristics. At present, the method for constructing the pore structure of the activated carbon material and increasing the specific surface area of the activated carbon material mainly comprises an activation method, including gas activation, salt activation, acid/alkali activation and the like, wherein the KOH activation strategy is the most commonly used carbon material activation method. For example: shang (Nano Energy,75, (2525) 154531) et al synthesized a specific surface area of up to 3577m based on KOH activation with walnut shell as the carbon source 2 Per gram of carbon material, the constructed soft pack supercapacitor exhibits an ultra-high energy density (125 Wh kg -1 ) And power density (155 kW kg) -1 )。
However, the temperature of KOH heat treatment activation is generally low (< 755 ℃, too high a heat treatment activation temperature will cause excessive corrosion of the carbon material, resulting in low product yield), and the lower activation temperature causes low crystallinity of the carbon material, poor electrical conductivity, and seriously affects the electrochemical energy storage performance of the activated carbon-based supercapacitor. In addition, from the aspect of an activation mechanism, the KOH activation needs to have a certain basic specific surface area of the carbon material, so that the KOH is fully contacted with the carbon material, and the activation efficiency is improved.
At present, a porous active carbon material with high crystallinity and large specific surface area is prepared by using a bubble puffing carbonization pretreatment to obtain an initial carbon material with a certain basic specific surface area and high crystallinity and then performing KOH activation, which has not been reported yet.
Disclosure of Invention
The invention aims to provide a preparation method of a highly graphitized porous activated carbon material, which realizes the preparation of the porous activated carbon material with high crystallinity and large specific surface area and improves the electrochemical energy storage property of the porous activated carbon material.
The second purpose of the invention is to provide the highly graphitized porous activated carbon material prepared by the preparation method.
The invention also aims to provide application of the highly graphitized porous activated carbon material.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
in a first aspect, the invention provides a method for preparing a highly graphitized porous activated carbon material, comprising the following steps:
(1) Mixing a carbon precursor containing C element with water in a graphite crucible according to a certain proportion, uniformly stirring, placing in a tube furnace, carrying out heat preservation treatment for 2 hours at 155 ℃ under an inert atmosphere, then heating to 955 ℃ for heat preservation treatment for 2 hours, carrying out pre-puffing carbonization treatment, and finally cooling to room temperature along with the furnace to obtain a pre-puffing intermediate;
(2) Respectively weighing the pre-puffing intermediate obtained in the step (1) and potassium hydroxide according to the mass ratio of 1:2, uniformly mixing in water, drying, putting into a tube furnace again, and performing heat preservation treatment for 2h at 755 ℃ under nitrogen atmosphere to perform activation treatment;
(3) Cooling to room temperature along with the furnace, taking out, washing with water to neutrality, and drying to obtain the porous active carbon material.
Preferably, the carbon precursor containing the C element in the step (1) is maltose powder.
Preferably, the mixing ratio of the maltose powder and water in the step (1) is 1g:5.8mL, the water is too low to dissolve maltose, and the too high water is easy to cause the viscosity of the mixture to be reduced, so that the puffing porosity is reduced.
Preferably, the temperature rising rate of the first stage in the step (1) is 5 ℃/min, and the temperature rising rate of the second stage is 2 ℃/min.
Preferably, in step (2), the heating rate of the tube furnace is 3 ℃/min.
In a second aspect, the present invention provides highly graphitized porous activated carbon materials prepared by the above-described preparation method.
The porous carbon nanomaterial obtained by the pre-puffing treatment and the auxiliary KOH activation has obvious pore canal and uniform pore size distribution, thereby achieving the purpose of increasing the ion transmission rate.
The porous carbon nano material obtained by the pre-puffing treatment and the auxiliary KOH activation has high crystallinity, thereby achieving the purpose of increasing the conductivity of the material.
In a third aspect, the present invention provides the use of the highly graphitized porous activated carbon material described above as an electrode material for a supercapacitor.
Coating a high graphitization porous active carbon material, a binder polytetrafluoroethylene and conductive carbon black on foam nickel according to a mass ratio of 85:15:5, drying for 12 hours at 155 ℃ in a vacuum drying oven, and pressing under 15MPa to prepare the porous active carbon material with a load of about 1.5mg cm -2 Is provided.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the preparation method, the water content of the carbon precursor is regulated and controlled, the preparation of the intermediate which is beneficial to the entry of the activating agent is realized by utilizing a pre-puffing strategy, and then the high graphitization porous activated carbon material is finally obtained by utilizing a KOH activation method.
2. The heat treatment process for puffing and carbonizing the water bubbles has high temperature, and is beneficial to improving the graphitization degree of the activated carbon material.
3. The preparation process disclosed by the invention is simple and controllable, and has good repeatability.
4. The high graphitized porous active carbon prepared by the invention is used as an electrode material, the number of reactive sites of the electrode material is increased, the conductivity of the material is improved, the specific capacitance of the super capacitor can be increased, and meanwhile, the electrochemical performance parameters such as good cycle life of the electrode material are maintained.
Drawings
FIG. 1 (a) is a digital photograph of an initial activated carbon material prepared by pre-puffing carbonization in example 1;
FIG. 1 (b, c) is a Scanning Electron Microscope (SEM) image at various magnifications of the porous activated carbon material prepared in example 1;
FIG. 1 (d) is a Transmission Electron Microscope (TEM) image of the porous activated carbon material prepared in example 1;
FIG. 2 is an X-ray electron diffraction (XRD) pattern of the porous activated carbon material prepared in example 1;
FIG. 3 is a Raman spectrum of the porous activated carbon material prepared in example 1;
FIG. 4 (a) is an X-ray photoelectron spectrum (XPS) of the porous activated carbon material prepared in example 1;
FIG. 4 (b) is a C1s high resolution X-ray photoelectron spectrum of the porous activated carbon material prepared in example 1;
FIG. 4 (c) is an O1s high resolution X-ray photoelectron spectrum of the porous activated carbon material prepared in example 1;
FIG. 4 (d) is an N1s high resolution X-ray photoelectron spectrum of the porous activated carbon material prepared in example 1;
FIG. 5 (a) is a comparative graph of nitrogen isothermal adsorption/desorption curves of the porous activated carbon materials prepared in the comparative examples and examples 1 to 4;
FIG. 5 (b) is a graph showing pore size distribution of the porous activated carbon materials prepared in comparative examples and examples 1 to 4;
FIG. 6 (a) is a graph showing that the porous activated carbon material electrodes prepared in comparative examples and examples 1 to 4 have a sweep rate of 25mV s in a three-electrode system -1 Cyclic voltammograms at time;
FIG. 6 (b) shows the porous activated carbon material electrodes prepared in comparative examples and examples 1 to 4 having a current density of 2Ag in a three-electrode system -1 Constant current charge-discharge curve graph;
fig. 7 is a graph showing the relationship between specific capacitance and current density of the supercapacitor assembled from the electrode material prepared in example 1.
Detailed Description
The technical scheme of the invention is further described and illustrated by the following specific embodiments and the attached drawings. Unless otherwise indicated, all materials used in the examples of the present invention are those commonly used in the art, and all methods used in the examples are those commonly used in the art.
Example 1
2g of maltose powder as a carbon precursor was weighed into a graphite crucible and stirred well with 1.6mL of deionized water. At N 2 Heating to 155 ℃ at a speed of 5 ℃/min in a tube furnace under the protection of atmosphere, preserving heat for 125min, heating to 955 ℃ at a speed of 2 ℃/min, preserving heat for 125min, carrying out pre-puffing treatment, and finally cooling to room temperature along with the furnace to obtain the pre-puffing intermediate.
Pre-puffingThe intermediate and KOH are dissolved in 25mL of deionized water according to the mass ratio of 1:2, and the mixture is placed in a blast drying oven for drying after being uniformly stirred. Transferring the dried mixture into a graphite crucible, and adding N 2 Heating to 755 ℃ at a speed of 3 ℃/min in a tube furnace under atmosphere protection, preserving heat for 125min, performing KOH etching activation treatment, cooling to room temperature along with the furnace, taking out the mixture, and flushing with deionized water until the product is neutral to obtain the nitrogen-doped porous active carbon material.
The expansion carbonization heat treatment temperature is preferably 955 ℃. Too low a heat treatment temperature is disadvantageous in increasing the graphitization degree of the initial carbon material prepared by bubble expansion carbonization.
The mass ratio of the pre-puffing intermediate to the potassium hydroxide is preferably 1:2, and the mass ratio is too small to achieve the purpose of etching holes. Excessive mass ratios can cause excessive corrosion and lower product yields.
Calcination under a nitrogen atmosphere during activation both prevents loss of the carbon material and nitrogen doping of the carbon material. High graphitization nitrogen doped porous active carbon material with large specific surface area and uniform pore canal is obtained through high temperature calcination.
Example 2
The preparation procedure of this example was essentially the same as in example 1, except that: 5.8mL deionized water was added to dissolve the maltose powder.
Example 3
The preparation procedure of this example was essentially the same as in example 1, except that: 1.2mL deionized water was added to dissolve the maltose powder.
Example 4
The preparation procedure of this example was essentially the same as in example 1, except that: 2mL of deionized water was added to dissolve the maltose powder.
Comparative example
2g of maltose powder was weighed as a carbon precursor and placed in a graphite crucible in N 2 Heating to 155 ℃ at a speed of 5 ℃/min in a tube furnace under atmosphere protection, preserving heat for 125min, heating to 955 ℃ at a speed of 2 ℃/min, preserving heat for 125min, performing pre-puffing treatment, and cooling to room temperature along with the furnace to obtain the pre-puffing productAn intermediate.
Dissolving the pre-puffed intermediate and KOH in 25mL of deionized water according to the mass ratio of 1:2, uniformly stirring, and drying in a blast drying oven. Placing the dried mixture in a graphite crucible, under N 2 Heating to 755 ℃ at a speed of 3 ℃/min in a tube furnace under atmosphere protection, preserving heat for 125min, performing KOH etching activation treatment, cooling to room temperature along with the furnace, taking out the mixture, and flushing with deionized water until the product is neutral to obtain the nitrogen-doped porous active carbon material.
FIG. 1 (a) is an optical image of the pre-expanded intermediate prepared in example 1, which has been annealed at 155℃and 955℃to produce a surface-rich pore structure due to expansion of water molecules and cleavage of maltose functionalities. Fig. 1 (b-c) are SEM images of the nitrogen-doped porous activated carbon material prepared in example 1 at different magnifications. The prepared nitrogen-doped porous active carbon material is composed of nano particles, and a large number of cracks are found in the material, so that a channel is provided for permeation/diffusion of electrolyte, and full utilization of active substances is facilitated. Fig. 1 (d) is a high resolution transmission electron microscope (HTEM) image of the nitrogen-doped porous activated carbon material prepared in example 1, showing that the adjacent lattice spacing of the prepared material is about 5.341nm, responsive to the graphite (552) interplanar spacing.
Fig. 2 is an X-ray diffraction pattern (XRD) of the nitrogen-doped porous activated carbon material prepared in example 1, showing two characteristic peaks around 26 ° and 43 °, which are related to specific faces (552) and (155) of graphite.
FIG. 3 is a Raman spectrum of the nitrogen-doped porous activated carbon material prepared in example 1, wherein a "disordered" D peak (-1355 cm) appears -1 ) And a "crystallization" G peak (-1586 cm) -1 ) These peaks are shown to be associated with carbon materials. I obtained by calculation D /I G The ratio was 5.93, indicating that the prepared sample had undergone a highly graphitized transformation.
Fig. 4 (a) is an X-ray photoelectron spectroscopy (XPS) measurement scan of the nitrogen-doped porous activated carbon material prepared in example 1, which shows that the surface composition of the prepared nitrogen-doped porous activated carbon material is C, N, O, and the nitrogen element is successfully doped into the carbon material. FIGS. 4 (b) -4 (d) are high-resolution C1s, O1s and N1s XPS spectra collected from the nitrogen-doped porous activated carbon materials prepared in examples 2-4, respectively, showing that the prepared nitrogen-doped porous activated carbon materials have rich functional groups, greatly promote wettability of electrodes, and perform effective mass transfer.
Fig. 5 (a) -5 (b) are comparative graphs and pore size distribution graphs of nitrogen isothermal adsorption/desorption curves of the nitrogen-doped porous activated carbon materials prepared in comparative examples and examples 1-4, respectively. The pictures show that the specific surface area gradually increases with the increase of the water content, and the water content reaches the highest value when the water adding amount is 1.6mL, and the specific surface area is in a decreasing trend when the water content is continuously increased to 2 mL. Because excessive water reduces the viscosity of maltose, low viscosity maltose is difficult to be in H during the pre-puffing carbonization process 2 The internal/external space of the O bubbles establishes stable balance, thereby limiting the growth of pores and reducing the specific surface area;
the nitrogen-doped porous active carbon materials prepared in the comparative example and the examples 1-4 are respectively coated on foam nickel with the adhesive polytetrafluoroethylene and the conductive carbon black in the mass ratio of 85:15:5. Drying in vacuum drying oven at 155 deg.C for 12 hr, pressing under 15MPa, and making into powder with load of about 1.5mg cm -2 Is provided. The Hg/HgO is used as a reference electrode, the platinum sheet electrode is used as a counter electrode, and the 6mol/L KOH solution is used as electrolyte to form a three-electrode system, and electrochemical behavior characterization is carried out at room temperature.
FIG. 6 (a) shows that the nitrogen-doped porous activated carbon material electrodes prepared in comparative examples and examples 1 to 4 have a sweep rate of 25mV s in a three-electrode system -1 The cyclic voltammogram shows that the electrode material obtained in example 1 has the largest area specific capacitance at the same sweep rate;
FIG. 6 (b) shows the current density of 2Ag in a three-electrode system for the nitrogen-doped porous activated carbon material electrodes prepared in comparative examples and examples 1-4 -1 Constant current charge-discharge curve graph shows that the electrode material obtained in example 1 has the longest discharge time at the same current density. Sample C-1.6 obtained in example 1 is therefore the optimal electrode material.
The working electrode prepared in example 1 was combined with a KOH solution of 6mol/L electrolyte and porous polypropylene as a separator to construct a supercapacitor, and the electrochemical performance was tested at room temperature.
FIG. 7 is a graph showing the relationship between the specific capacitance and the current density of the electrode material assembly prepared in example 1, wherein the specific capacitance obtained in example 2 was 132.7F/g at a current density of 5.5A/g, and the specific capacitance was maintained at 62.3% when the current density was increased to 25A/g. The electrode material has good multiplying power performance.
Claims (7)
1. The preparation method of the highly graphitized porous activated carbon material is characterized by comprising the following steps of:
(1) Mixing a carbon precursor containing C element with water in a graphite crucible according to a certain proportion, uniformly stirring, placing in a tube furnace, carrying out heat preservation treatment for 2 hours at 155 ℃ under an inert atmosphere, then heating to 955 ℃ for heat preservation treatment for 2 hours, carrying out pre-puffing carbonization treatment, and finally cooling to room temperature along with the furnace to obtain a pre-puffing intermediate;
(2) Respectively weighing the pre-puffing intermediate obtained in the step (1) and potassium hydroxide according to the mass ratio of 1:2, uniformly mixing in water, drying, putting into a tube furnace again, and performing heat preservation treatment for 2h at 755 ℃ under nitrogen atmosphere to perform activation treatment;
(3) Cooling to room temperature along with the furnace, taking out, washing with water to neutrality, and drying to obtain the porous active carbon material.
2. The method for preparing a highly graphitized porous activated carbon material according to claim 1, wherein the carbon precursor containing C element in the step (1) is maltose powder.
3. The method for preparing highly graphitized porous activated carbon material according to claim 2, wherein the mixing ratio of the maltose powder and water in the step (1) is 1g:5.8mL.
4. The method for preparing highly graphitized porous activated carbon material according to claim 1, wherein the temperature rising rate of the first stage in the step (1) is 5 ℃/min and the temperature rising rate of the second stage is 2 ℃/min.
5. The method for preparing highly graphitized porous activated carbon material according to claim 1, wherein in the step (2), the heating rate of the tube furnace is 3 ℃/min.
6. A highly graphitized porous activated carbon material, characterized in that it is prepared by the preparation method according to any one of claims 1 to 5.
7. The use of the highly graphitized porous activated carbon material according to claim 6 as an electrode material for supercapacitors.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310231939.8A CN116206907A (en) | 2023-03-10 | 2023-03-10 | Highly graphitized porous activated carbon material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310231939.8A CN116206907A (en) | 2023-03-10 | 2023-03-10 | Highly graphitized porous activated carbon material and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116206907A true CN116206907A (en) | 2023-06-02 |
Family
ID=86519066
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310231939.8A Pending CN116206907A (en) | 2023-03-10 | 2023-03-10 | Highly graphitized porous activated carbon material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116206907A (en) |
-
2023
- 2023-03-10 CN CN202310231939.8A patent/CN116206907A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20190260012A1 (en) | Method for preparing boron-doped porous carbon sphere | |
| CN110467182B (en) | Reaction template-based hierarchical porous carbon-based material and preparation method and application thereof | |
| CN112830472B (en) | Preparation method of porous carbon, porous carbon obtained by preparation method and application of porous carbon | |
| CN112374485A (en) | Preparation method of nitrogen-phosphorus double-doped foamy carbon for zinc ion hybrid capacitor | |
| CN111153403B (en) | Alginate-based porous carbon and preparation method and application thereof | |
| CN114506838B (en) | Three-dimensional conductive network reinforced nickel-doped carbon aerogel material and preparation method and application thereof | |
| CN112786869B (en) | Preparation method of ferric oxide/spiral carbon nanofiber composite anode material | |
| CN114890403A (en) | Nitrogen-doped polymer derived carbon material and application thereof in sodium ion battery | |
| CN110504450B (en) | Preparation method of heteroatom-doped hierarchical pore carbon material and application of heteroatom-doped hierarchical pore carbon material in lithium battery negative electrode slurry | |
| CN108987732B (en) | SiO composite cathode material of lithium ion battery and preparation method thereof | |
| US20230234851A1 (en) | Boron-sulfur-codoped porous carbon material and preparation method and use thereof | |
| CN115376837B (en) | Nitrogen-fluorine co-doped honeycomb activated carbon and preparation method and application thereof | |
| CN110137494B (en) | Porous hard carbon microsphere material and preparation method thereof, button cell and preparation method thereof | |
| CN116206907A (en) | Highly graphitized porous activated carbon material and preparation method and application thereof | |
| CN114899382A (en) | N-doped porous carbon double-shell microsphere structure coated Co 3 O 4 Material, preparation method and application thereof | |
| CN115124020A (en) | Boron-nitrogen co-doped carbon material with hierarchical holes and preparation method and application thereof | |
| CN113690437A (en) | Graphite-phase carbon nitride/graphene lithium-sulfur battery positive electrode material and preparation method thereof | |
| CN111313020B (en) | Preparation method of sulfur-doped nitrogen-rich carbon material, electrode and application of sulfur-doped nitrogen-rich carbon material in sodium/potassium ion battery | |
| CN111924842A (en) | Lotus stalk-based electrode material and preparation method thereof | |
| CN117133866B (en) | Preparation method of modified three-dimensional electrode material and sodium ion battery | |
| CN115206693B (en) | Biomass high-doping high-defect carbon material and preparation method and application thereof | |
| CN116632233B (en) | High-performance sodium ion battery doped hard carbon negative electrode material and preparation method thereof | |
| CN116002659B (en) | Hard carbon anode material, preparation method and application thereof, and battery | |
| CN116443877B (en) | Coal-based three-dimensional porous carbon and preparation method and application thereof | |
| CN116947018A (en) | Porous carbon material doped with zinc monoatoms in pore confinement, preparation method of porous carbon material and application of porous carbon material as anode material of lithium ion 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 |