CN109279601A - A kind of porous carbon materials and the preparation method and application thereof with carbonization structure - Google Patents
A kind of porous carbon materials and the preparation method and application thereof with carbonization structure Download PDFInfo
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- CN109279601A CN109279601A CN201811428983.3A CN201811428983A CN109279601A CN 109279601 A CN109279601 A CN 109279601A CN 201811428983 A CN201811428983 A CN 201811428983A CN 109279601 A CN109279601 A CN 109279601A
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 60
- 238000003763 carbonization Methods 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 13
- 239000012190 activator Substances 0.000 claims abstract description 12
- 239000003513 alkali Substances 0.000 claims abstract description 11
- 239000007772 electrode material Substances 0.000 claims abstract description 11
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 8
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 30
- 239000007787 solid Substances 0.000 claims description 21
- 239000003245 coal Substances 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- 238000005554 pickling Methods 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 238000004146 energy storage Methods 0.000 claims description 7
- 239000003208 petroleum Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 2
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 27
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 8
- 150000004706 metal oxides Chemical group 0.000 abstract description 8
- 238000005087 graphitization Methods 0.000 abstract description 5
- 239000003990 capacitor Substances 0.000 abstract description 3
- 238000000227 grinding Methods 0.000 description 20
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 239000004570 mortar (masonry) Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000012299 nitrogen atmosphere Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229910003023 Mg-Al Inorganic materials 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 229910021392 nanocarbon Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 241000772415 Neovison vison Species 0.000 description 2
- ZFCRHJMORPMYON-UHFFFAOYSA-G aluminum;magnesium;iron(2+);heptahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Al+3].[Fe+2] ZFCRHJMORPMYON-UHFFFAOYSA-G 0.000 description 2
- RJZNFXWQRHAVBP-UHFFFAOYSA-I aluminum;magnesium;pentahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Al+3] RJZNFXWQRHAVBP-UHFFFAOYSA-I 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- GPKAEXVTJYXMAB-UHFFFAOYSA-G [Co+2].[OH-].[Mg+2].[Al+3].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-] Chemical compound [Co+2].[OH-].[Mg+2].[Al+3].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-] GPKAEXVTJYXMAB-UHFFFAOYSA-G 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/205—Preparation
-
- 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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/44—Raw materials therefor, e.g. resins or coal
-
- 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)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Organic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Carbon And Carbon Compounds (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention provides a kind of porous carbon materials and the preparation method and application thereof with carbonization structure, carbon source and catalyst and alkali activator is sufficiently mixed uniformly, the thermally treated porous carbon materials for obtaining having carbonization structure；Catalyst is metal oxide or metal hydroxides.The present invention uses the catalyst of metal oxide or metal hydroxides as catalyzed graphitization, carbon source can be dispersed in catalyst surface, the graphitization that carbon material is helped to realize through high temperature cabonization process promotes the electric conductivity of carbon material and the utilization rate of catalyst.Meanwhile metal oxide or metal hydroxides can promote carbon source to form porous structure during heat treatment, increase specific surface area.The prepared porous carbon materials with carbonization structure are as electrode material for super capacitor, with specific capacitance is high, multiplying power property is good, has extended cycle life.
Description
Technical field
The invention belongs to carbon material preparation and field of new energy technologies, are related to a kind of porous carbon with carbonization structure
Material and the preparation method and application thereof.
Background technique
Nano-carbon material is due to the outstanding advantages such as conductive height, stable structure, cheap, environmentally protective, in energy
The fields such as source, chemical industry, environment show broad prospect of application.Especially in the new energy device such as supercapacitor, lithium ion battery
In terms of part energy storage, nano-carbon material plays a significant role as electrode material.Common nano-carbon material is mainly with porous active
Based on charcoal, and the most commonly used a kind of electrode material of commercial applications at present.This kind of carbon material has the specific surface area of superelevation
And porosity, it can effectively reinforce absorption and desorption process of the electrolyte ion on its surface, and then promote its chemical property.
However, the porous carbon materials currently prepared exist mostly in the form of unordered or undefined structure, electronics is limited to a certain extent
Quick transmission inside it, and then affect the high rate performance of electrode material.In addition, preparing for this kind of porous carbon materials is usual
There is also Residual carbons it is low, at high cost, preparation process is time-consuming the problems such as, be unfavorable for scale application.
Summary of the invention
Aiming at the problems existing in the prior art, the present invention provide a kind of porous carbon materials with carbonization structure and its
Preparation method and application carry out catalyzed graphitization as catalyst using metal oxide or metal hydroxides, are prepared
Have many advantages, such as the porous carbon materials of carbonization structure, which has large specific surface area, electric conductivity high, is used as super capacitor
The electrode material of the energy storage devices such as device shows excellent chemical property.
The present invention is to be achieved through the following technical solutions:
A kind of preparation method of the porous carbon materials with carbonization structure, carbon source and catalyst and alkali activator are filled
Divide and is uniformly mixed, the thermally treated porous carbon materials for obtaining that there is carbonization structure；Catalyst is metal oxide or metallic hydrogen
Oxide.
Preferably, the metallic element in catalyst is the one or more of iron, cobalt, magnesium and aluminium.
Preferably, alkali activator is potassium hydroxide or sodium hydroxide.
Preferably, carbon source is the solid residue of generation during petroleum or coal chemical industry, and preparation method specifically includes following step
It is rapid:
Step 1, the solid residue generated during petroleum or coal chemical industry is crushed, grind into powder, with catalyst and alkali
Property activator is sufficiently mixed uniformly, obtains mix powder；
Step 2, the mix powder that step 1 obtains is calcined twice under an inert atmosphere, be first warming up to 120 DEG C~
250 DEG C are once calcined, then are warming up to 700 DEG C~1200 DEG C progress secondary clacinings, obtain reaction product；
Step 3, reaction product step 2 obtained is washed, drying, grinds, and is made porous with carbonization structure
Carbon material.
Further, in step 1, the mass ratio of solid residue, catalyst and alkali activator is 1:(1~10): (1~
5)。
Further, in step 2, a calcination time is 0.5~1 hour, and the secondary clacining time is 0.5~3 hour.
Further, in step 2, the heating rate calcined twice is 2~10 DEG C/min.
Further, in step 3, washing is using pickling and washing, until washing to neutrality.
The porous carbon materials with carbonization structure that the preparation method is prepared.
Application of the porous carbon materials with carbonization structure as electrode material in energy storage device.
Compared with prior art, the invention has the following beneficial technical effects:
The present invention uses the catalyst of metal oxide or metal hydroxides as catalyzed graphitization, and carbon source can be equal
It is even to be dispersed in catalyst surface, the graphitization of carbon material is helped to realize through high temperature cabonization process, promotes the electric conductivity of carbon material
With the utilization rate of catalyst.Meanwhile metal oxide or metal hydroxides can promote carbon source shape during heat treatment
At porous structure, increase specific surface area.The introducing of alkali activator can carry out in-situ activation and inorganic to prepared carbon material
Impurity removal further promotes its specific surface area, improves energy storage effect to the greatest extent.It is prepared with carbonization structure
Porous carbon materials have many advantages, such as that specific capacitance is high, multiplying power property is good, has extended cycle life as electrode material for super capacitor.
Further, petroleum or coal chemical industry process can generate the by-products such as a large amount of solid residue, these solid residues master
It to be made of, can be regarded as a kind of preferable honest and clean high carbon containing organic component, unreacted raw material and micro inorganic impurity
Valence carbon source is used to prepare porous carbon materials, but there has been no directly prepare it with carbonization structure porous carbon materials at present
Report.The solid residue that the method for the present invention is generated using petroleum or coal chemical industry process can reduce the system of porous carbon materials as raw material
Standby cost.In addition, it is the preparation method simple process, safe operation, low in cost, there is broad prospect of application.
The porous carbon materials that the present invention is prepared, show apparent carbonization structure, and specific surface area is up to
2300m2Between/g, the electrode material as energy storage device is used, and has the characteristics that specific capacitance is high, multiplying power property is good.
Detailed description of the invention
Fig. 1 is that there is embodiment 3 the low power TEM of carbonization structure porous carbon materials to scheme；
Fig. 2 is that there is embodiment 3 the high-resolution TEM of carbonization structure porous carbon materials to scheme；
Fig. 3 is nitrogen adsorption/desorption curve that embodiment 8 has carbonization structure porous carbon materials.
Fig. 4 is that embodiment 8 has cyclic voltammetry curve figure of the carbonization structure porous carbon materials at 20mV/s.
Fig. 5 is that embodiment 8 has cyclic voltammetry curve figure of the carbonization structure porous carbon materials at 100mV/s.
Specific embodiment
Below with reference to specific embodiment, the present invention is described in further detail, it is described be explanation of the invention and
It is not to limit.
Preparation method of the present invention with carbonization structure porous carbon materials, comprising the following steps:
Step 1, the solid residue generated during petroleum or coal chemical industry is crushed, is added in mortar, grind into powder；
Then, it is separately added into a certain amount of catalyst and alkali activator, is sufficiently mixed uniformly, obtains mixture.Catalyst is metal
Oxide or metal hydroxides, in catalyst metallic element be iron, cobalt, magnesium, aluminium element it is one or more；Alkali activator
For one of potassium hydroxide and sodium hydroxide.The mass ratio of solid residue and catalyst is 1:(1~10), solid residue and alkali
Property activator mass ratio be 1:(1~5).
Step 2, the resulting mixture of step 1 is transferred in inert atmosphere high temperature process furnances, is warming up to 120 DEG C~250
DEG C keep 0.5~1 hour, be then heated to 700 DEG C~1200 DEG C keep 0.5~3 hour, heating rate be 2~10 DEG C/
Min, cooled to room temperature；The inert atmosphere is one of nitrogen and argon gas.
Step 3, the obtained product in step 2 is taken out, grinding is broken, washs through pickling, deionized water to neutrality, dries
Dry, the porous carbon materials with carbonization structure are made in grinding.
The porous carbon materials that the preparation method obtains, show apparent carbonization structure, and specific surface area is up to
2300m2/ g, the electrode material that can be used as energy storage device use.
Embodiment 1
(1) solid residue that 1g coal process generates is crushed, is added in mortar, grind into powder.Then, respectively
1g magnesium hydroxide and 1g potassium hydroxide is added, is sufficiently mixed uniformly.
(2) mixture in step (1) is transferred in nitrogen atmosphere high temperature process furnances, is kept for 0.5 hour at 120 DEG C,
It is then heated to 700 DEG C to be kept for 3 hours, heating rate is 2 DEG C/min, cooled to room temperature.
(3) the obtained product in step (2) is taken out, grinding is broken, washs through pickling, deionized water to neutrality, dries
Dry, the porous carbon materials with carbonization structure are made in grinding.
Embodiment 2
(1) solid residue that 1g coal process generates is crushed, is added in mortar, grind into powder.Then, respectively
2g Mg-Al composite oxide and 1g potassium hydroxide is added, is sufficiently mixed uniformly.
(2) mixture in step (1) is transferred in nitrogen atmosphere high temperature process furnances, is kept for 0.5 hour at 120 DEG C,
It is then heated to 700 DEG C to be kept for 3 hours, heating rate is 2 DEG C/min, cooled to room temperature.
(3) the obtained product in step (2) is taken out, grinding is broken, washs through pickling, deionized water to neutrality, dries
Dry, the porous carbon materials with carbonization structure are made in grinding.
Embodiment 3
(1) solid residue that 1g coal process generates is crushed, is added in mortar, grind into powder.Then, respectively
2g magnesium aluminum hydroxide and 3g potassium hydroxide is added, is sufficiently mixed uniformly.
(2) mixture in step (1) is transferred in nitrogen atmosphere high temperature process furnances, is kept for 1 hour at 150 DEG C, with
After be heated to 800 DEG C keep 2 hours, heating rate be 5 DEG C/min, cooled to room temperature.
(3) the obtained product in step (2) is taken out, grinding is broken, washs through pickling, deionized water to neutrality, dries
Dry, the porous carbon materials with carbonization structure are made in grinding.
The TEM figure for the porous carbon materials that embodiment 3 is prepared is as depicted in figs. 1 and 2.It is characterized by the TEM of Fig. 1 and Fig. 2
As can be seen that prepared carbon material has typical porous and carbonization structure, spacing of lattice about 0.34nm.
Embodiment 4
(1) solid residue that 1g coal process generates is crushed, is added in mortar, grind into powder.Then, respectively
10g iron magnesium aluminum hydroxide and 5g potassium hydroxide is added, is sufficiently mixed uniformly.
(2) mixture in step (1) is transferred in nitrogen atmosphere high temperature process furnances, is kept for 1 hour at 200 DEG C, with
After be heated to 800 DEG C keep 1 hour, heating rate be 10 DEG C/min, cooled to room temperature.
(3) the obtained product in step (2) is taken out, grinding is broken, washs through pickling, deionized water to neutrality, dries
Dry, the porous carbon materials with carbonization structure are made in grinding.
Embodiment 5
(1) solid residue that 2g coal process generates is crushed, is added in mortar, grind into powder.Then, respectively
3g magnesium aluminum hydroxide and 6g potassium hydroxide is added, is sufficiently mixed uniformly.
(2) mixture in step (1) is transferred in nitrogen atmosphere high temperature process furnances, is kept for 1 hour at 250 DEG C, with
After be heated to 800 DEG C keep 1 hour, heating rate be 5 DEG C/min, cooled to room temperature.
(3) the obtained product in step (2) is taken out, grinding is broken, washs through pickling, deionized water to neutrality, dries
Dry, the porous carbon materials with carbonization structure are made in grinding.
Embodiment 6
(1) solid residue that 2g coal process generates is crushed, is added in mortar, grind into powder.Then, respectively
5g iron Mg-Al composite oxide and 5g potassium hydroxide is added, is sufficiently mixed uniformly.
(2) mixture in step (1) is transferred in nitrogen atmosphere high temperature process furnances, is kept for 1 hour at 150 DEG C, with
After be heated to 900 DEG C keep 1 hour, heating rate be 10 DEG C/min, cooled to room temperature.
(3) the obtained product in step (2) is taken out, grinding is broken, washs through pickling, deionized water to neutrality, dries
Dry, the porous carbon materials with carbonization structure are made in grinding.
Embodiment 7
(1) solid residue that 1g coal is generated with mink cell focus process is crushed, is added in mortar, grind into powder.
Then, it is separately added into 10g cobalt Mg-Al composite oxide and 2g sodium hydroxide, is sufficiently mixed uniformly.
(2) mixture in step (1) is transferred in nitrogen atmosphere high temperature process furnances, is kept for 0.5 hour at 200 DEG C,
It is then heated to 1200 DEG C to be kept for 0.5 hour, heating rate is 10 DEG C/min, cooled to room temperature.
(3) the obtained product in step (2) is taken out, grinding is broken, washs through pickling, deionized water to neutrality, dries
Dry, the porous carbon materials with carbonization structure are made in grinding.
Embodiment 8
(1) solid residue that 1g coal process generates is crushed, is added in mortar, grind into powder.Then, respectively
5g iron magnesium aluminum hydroxide and 5g potassium hydroxide is added, is sufficiently mixed uniformly.
(2) mixture in step (1) is transferred in nitrogen atmosphere high temperature process furnances, is kept for 1 hour at 200 DEG C, with
After be heated to 800 DEG C keep 1 hour, heating rate be 5 DEG C/min, cooled to room temperature.
(3) the obtained product in step (2) is taken out, grinding is broken, washs through pickling, deionized water to neutrality, dries
Dry, the porous carbon materials with carbonization structure are made in grinding.
Embodiment 8 prepare the porous carbon materials with carbonization structure nitrogen adsorption/desorption curve as shown in figure 3,
Its specific surface area is up to 2300m2/g.In addition, the electrode material as supercapacitor carries out electrochemical property test, knot
Fruit is as shown in Figure 4 and Figure 5, and cyclic voltammetry curve all has good rectangular shape under different scanning rates, shows excellent
Multiplying power property.
Embodiment 9
(1) solid residue that 3g coal is generated with mink cell focus process is crushed, is added in mortar, grind into powder.
Then, it is separately added into 30g cobalt magnesium aluminum hydroxide and 15g sodium hydroxide, is sufficiently mixed uniformly.
(2) mixture in step (1) is transferred in nitrogen atmosphere high temperature process furnances, is kept for 0.5 hour at 200 DEG C,
It is then heated to 800 DEG C to be kept for 1 hour, heating rate is 5 DEG C/min, cooled to room temperature.
(3) the obtained product in step (2) is taken out, grinding is broken, washs through pickling, deionized water to neutrality, dries
Dry, the porous carbon materials with carbonization structure are made in grinding.
Claims (10)
1. a kind of preparation method of the porous carbon materials with carbonization structure, which is characterized in that by carbon source and catalyst and alkali
Property activator is sufficiently mixed uniformly, the thermally treated porous carbon materials for obtaining having carbonization structure；Catalyst is metal oxidation
Object or metal hydroxides.
2. the preparation method of the porous carbon materials according to claim 1 with carbonization structure, which is characterized in that catalysis
Metallic element in agent is the one or more of iron, cobalt, magnesium and aluminium.
3. the preparation method of the porous carbon materials according to claim 1 with carbonization structure, which is characterized in that alkalinity
Activator is potassium hydroxide or sodium hydroxide.
4. the preparation method of the porous carbon materials according to claim 1 with carbonization structure, which is characterized in that carbon source
For the solid residue generated during petroleum or coal chemical industry, preparation method specifically includes the following steps:
Step 1, the solid residue generated during petroleum or coal chemical industry is crushed, grind into powder, it is living with catalyst and alkalinity
Agent is sufficiently mixed uniformly, obtains mix powder；
Step 2, the mix powder that step 1 obtains is calcined twice under an inert atmosphere, is first warming up to 120 DEG C~250
It DEG C is once calcined, then is warming up to 700 DEG C~1200 DEG C progress secondary clacinings, obtain reaction product；
Step 3, reaction product step 2 obtained is washed, drying, grinds, and the porous carbon with carbonization structure is made
Material.
5. the preparation method of the porous carbon materials according to claim 4 with carbonization structure, which is characterized in that step
In 1, the mass ratio of solid residue, catalyst and alkali activator is 1:(1~10): (1~5).
6. the preparation method of the porous carbon materials according to claim 4 with carbonization structure, which is characterized in that step
In 2, a calcination time is 0.5~1 hour, and the secondary clacining time is 0.5~3 hour.
7. the preparation method of the porous carbon materials according to claim 4 with carbonization structure, which is characterized in that step
In 2, the heating rate calcined twice is 2~10 DEG C/min.
8. the preparation method of the porous carbon materials according to claim 4 with carbonization structure, which is characterized in that step
In 3, washing is using pickling and washing, until washing to neutrality.
9. the porous carbon materials with carbonization structure that the described in any item preparation methods of claim 1-8 are prepared.
10. the porous carbon materials as claimed in claim 9 with carbonization structure answering in energy storage device as electrode material
With.
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| CN114702026A (en) * | 2022-05-17 | 2022-07-05 | 太原科技大学 | Method for preparing hollow porous graphitized carbon microspheres by mechanical grinding |
| CN114702026B (en) * | 2022-05-17 | 2023-06-16 | 太原科技大学 | Method for preparing hollow porous graphitized carbon microsphere by mechanical grinding |
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