CN109553098A - A kind of method and application preparing the foramen magnum-mesoporous carbon of high-specific surface area using salt template - Google Patents
A kind of method and application preparing the foramen magnum-mesoporous carbon of high-specific surface area using salt template Download PDFInfo
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- CN109553098A CN109553098A CN201811021947.5A CN201811021947A CN109553098A CN 109553098 A CN109553098 A CN 109553098A CN 201811021947 A CN201811021947 A CN 201811021947A CN 109553098 A CN109553098 A CN 109553098A
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
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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
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/336—Preparation characterised by gaseous activating agents
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- 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
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- 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
Abstract
The invention discloses a kind of methods for preparing the foramen magnum-mesoporous carbon material of high-specific surface area using salt template, the following steps are included: the molten hot water of biomass gelatin is formed colloidal sol, inorganic salts are added as template, it is placed in after being cooled to room temperature in 4 DEG C of insulating box and forms hydrogel, then continued placement at -20 DEG C and form frozen glue；Frozen glue is freeze-dried, aeroge is obtained and roasts to obtain black silicon carbide product for 400-1000 DEG C under argon atmosphere.It is washed, is filtered, drying obtains final products.The method of the present invention uses soluble biomass carbon source and inorganic salts for raw material, and method simplicity is at low cost, is not related to insoluble metal template, does not need pickling, not kish impurity, environmentally protective；Prepared carbon material has high-specific surface area (2872cm2 g‑1), three-dimensional continuous, macropore (50-150nm) abundant and mesoporous (2-4 nm), the features such as nitrogen atom doping.It is applied in 4V ionic liquid super capacitor, is capable of providing 92Wh kg‑1Energy density and excellent power density.
Description
Technical field
The invention belongs to carbon material technical fields, are related to a kind of preparation method of foramen magnum-mesoporous carbon material of high specific area.
Background technique
Porous carbon materials have widely in adsorbent, supercapacitor, rechargeable secondary cell and fuel cell field
Application prospect.Currently, business porous carbon materials are often obtained by strong basicity KOH activator high-temperature activation, carbon source used is mostly solid
Bulk is cleaned before high-temperature activation, is crushed, the processes such as carbonization pretreatment and ball milling mixing activator, subsequent mistake
Journey further relates to the acid pickling step of corrosion contamination, process it is loaded down with trivial details it is complicated not environmentally, it is difficult and since activator and carbon source are solids
To guarantee uniformly mixing and sufficiently activation, the porous carbon materials being prepared usually have a flourishing micropore, and mesoporous and macropore
Ratio is seldom.Micropore abundant is conducive to maintain higher specific surface area, however pore size is smaller, mesoporous and macropore missing
So that the mass transfer of gas molecule or electrolyte in duct is become slow, seriously affects it in high-performance adsorbent and energy storage material
The application in material field.Currently, possessing the porous carbon materials of high-specific surface area and foramen magnum-mesoporous both characteristics of structure simultaneously still
There is no preferable technology to be developed.
It is well known that template is manufacture macropore and mesoporous effective ways.For example, the report in 2014 such as Qian utilizes
MgO is template, CH4High temperature is vapor-deposited to obtain high-specific surface area (2411 cm2 g-1) grapheme material；2015, Huang etc.
It is template using SBA-15, the meso-porous carbon material of bigger serface can be prepared through chemical vapor deposition, be applied to
Three electrode aqueous super capacitors possess the specific capacitance of 790 F/g；In addition, some researchers in synthetic system by being added silicon
Macropore can be obtained through subsequent pickling in ball or PS ball template.Macropore and Jie is successfully prepared using hard template method in the above technology
Hole porous carbon materials, but it is related to cumbersome subsequent template treatment process simultaneously, as the removing of MgO template needs to use HCl, band
The disadvantage come is metal Mg2+, halogen Cl-Easily remain；And the removal of the mesoporous template of SBA-15, silicon ball and PS ball macropore template is then
Need to use the HF of severe toxicity.Moreover, big pore or mesoporous template need synthesis in advance at this stage, further increase behaviour
Make difficulty and cost of material.
In conclusion be prepared while having high specific area and foramen magnum-mesoporous structure carbon material it is inexpensive, succinct,
The technology of green non-pollution is urgently developed.
Summary of the invention
In order to solve the above-mentioned technical problem, the purpose of the present invention is to provide a kind of inexpensive, succinct, environmentally protective systems
The foramen magnum-mesoporous carbon material of Preparation Method acquisition high specific area.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of preparation method of foramen magnum-mesoporous carbon material of high-ratio surface, comprising the following steps:
1 g solubility carbon source is dissolved in 20 mL 60-80 DEG C hot water by step 1, forms uniform colloidal sol；
Wherein, the soluble carbon source is gelatin, agarose, polyvinyl alcohol -124, sodium carboxymethylcellulose；The soluble carbon
Source is preferably gelatin；
One or more inorganic salts, stirring and dissolving to uniform colloidal sol are added in step 2, Xiang Shangshu colloidal sol；
Wherein the inorganic salts are sodium nitrate, potassium nitrate, sodium chloride, potassium chloride, sodium sulphate；The inorganic salts are preferably nitric acid
Sodium；
Wherein, the amount that the sodium nitrate is added is 0.25-2 g；Sodium nitrate additional amount is preferably 0.75 g；
Step 3, above-mentioned mixed sols are cooled to room temperature, and 12-24 H-shaped is refrigerated in 4 DEG C of insulating boxs into hydrogel, continue-
12-24 h is placed at 20 DEG C and is dipped in liquid nitrogen 1-5 min forms frozen glue；
Step 4, by frozen glue, vacuum freeze drying 24-36 h removes water to obtain aeroge in freeze dryer；
Aeroge is placed in tube furnace by step 5, is passed through inert gas, carries out high temperature pyrolysis activation, is obtained black silicon carbide and is produced
Object；
Wherein, the inert atmosphere of high temperature pyrolysis activation is nitrogen, argon gas, and temperature is 400-1000 DEG C, heating rate 2-20
DEG C/min, pyrolysis time is 1-3 h；
Preferably, pyrolysis activation phenomenon is argon gas, and temperature is 900 DEG C, and heating rate is 5 DEG C/min, and pyrolysis time is 1 h；
Step 6 carries out cleaning 1-3 times to black silicon carbide product, filters, drying obtains porous carbon materials；
Wherein, cleaning black silicon carbide product solvent for use is ethyl alcohol, acetone, water or their mixture；Black silicon carbide is cleaned to produce
Object solvent for use is preferably water.
In the present invention, it is to solve carbon source and template activator using soluble carbon source and soluble inorganic salt template purpose
The problem of insufficient contact；
In the present invention, the gelatin solubility carbon source of use has following feature and advantage: the high score rich in amino, carboxyl and hydroxyl
Subchain has hydrogen bond crosslinks and gel complexing；
It the use of sodium nitrate is that salt template has following feature and advantage: cheap, neutral solubility inorganic salts in the present invention,
It can be used as template, can also be used as activator；It is not decomposed under lower temperature, can be used as the hard template of manufacture macropore；Higher temperatures
Lower decomposition is spent, can be used as the mesoporous sacrifice activator certainly of manufacture；
The foramen magnum-mesoporous carbon material of the high specific area that the present invention is prepared is mainly based upon following mechanism: the gelling properties of gelatin
So that sodium nitrate is highly dispersed in aeroge system, play the role of a nanometer confinement, contact is uniformly abundant.In high temperature pyrolysis mistake
Cheng Zhong can be used as macropore hard template when temperature is lower than sodium nitrate decomposition temperature, and when temperature is higher than sodium nitrate decomposition temperature,
As mesoporous activator, therefore pyrolysis is activated under preference temperature, can obtain the three-dimensional character structure of macropore and mesoporous interconnection,
In it is abundant it is mesoporous be conducive to maintain high-specific surface area.
Removing template process of the present invention be not necessarily to toxic high pollution sour treatment process, can directly be cleaned by water into
Row removal, kish impurity and halogen, succinct not environmentally friendly.
In addition to the above advantage, the porous carbon materials prepared have the feature that three-dimensional continuous foramen magnum-mesoporous the present invention
Structure, big pore size 50-200 nm, mesopore size 2-4 nm, specific surface area 600-3000 cm2 g-1, nitrogen auto-dope.
Raw material proportioning of the present invention can equal proportion amplification, be easy to amplify preparation；
Detailed description of the invention
Fig. 1 is the infrared spectrogram of gelatin in embodiment 1.
Fig. 2 is the scanning electron microscope and transmission electron microscope picture of C-25-800 sample in embodiment 1.
Fig. 3 is the scanning electron microscope (SEM) photograph of C-0.5-800 sample in embodiment 2.
Fig. 4 is the transmission electron microscope picture of C-0.5-800 sample in embodiment 2.
Fig. 5 is the scanning electron microscope (SEM) photograph and transmission electron microscope picture of C-0.75-800 sample in embodiment 3.
Fig. 6 is the transmission electron microscope picture of sample in embodiment 4.
Fig. 7 is the transmission electron microscope picture of C-0.75-400 sample in embodiment 5.
Fig. 8 is the transmission electron microscope picture of C-0.75-700 sample in embodiment 6.
Fig. 9 a, Fig. 9 b and Fig. 9 c are the transmission electron microscope pictures of C-0.75-900 sample in embodiment 7.
Fig. 9 d is the N of C-0.75-900 sample in embodiment 72Adsorption desorption curve and graph of pore diameter distribution.
Figure 13 is embodiment 1, embodiment 2, embodiment 3, embodiment 5, embodiment 6, the N of sample in embodiment 72Adsorption desorption
As a result.
Figure 14 is embodiment 1, embodiment 2, embodiment 3, embodiment 5, embodiment 6, and the sample in embodiment 7 is penetrated according to X
The constituent content that photoelectron spectra obtains.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that described herein, specific examples are only used to explain the present invention, is not used to limit
The fixed present invention.
Embodiment 1
It taking 1 g gelatin in 20 mL deionized waters, is warming up to 80 DEG C, is completely dissolved to gelatin, stirring keeps its evenly dispersed, with
After 0.25 g sodium nitrate is added, stirring and dissolving forms uniform colloidal sol, and is cooled to room temperature.
Above-mentioned colloidal sol is placed in 12 h in 4 DEG C of insulating box, forms it into hydrogel, and continues to place at -20 DEG C
Then 12 h impregnate 1-5 min in liquid nitrogen, obtain frozen glue.
Frozen glue is placed in freeze dryer, 36 h of vacuum freeze drying obtains aeroge.
Aeroge is placed in tube furnace, is passed through argon gas, rises to 800 DEG C with the rate of 5 DEG C/min, and protect at 800 DEG C
1 h is held, after naturally cool to room temperature, obtains black silicon carbide product.
Black silicon carbide product is collected, beaker is placed in, deionized water is added, 2 h of stirring and washing is filtered, washs, dried
To final products, it is labeled as C-0.25-800.
Functional group's measurement, the result is shown in Figure 1 are carried out to gelatin using infrared spectroscopy, the results showed that, there are rich for gelatin chains
Rich hydroxyl, carboxyl and amino group.C-0.25-800 is carried out with electronic scanner microscope and transmission electron microscope microcosmic
Pattern measurement uses N as a result such as Fig. 2 a and Fig. 2 b2Adsorption desorption experiment detects its specific surface area and pore structure, and the result is shown in Figure 13 should
Elemental analysis, the result is shown in Figure 14 are carried out to it with x-ray photoelectron spectroscopy, the above characterization obtains the pore structure of C-0.25-800
Ateliosis, specific surface area are 833.99 m2 g-1, 0.301 cm of Kong Rongwei3 g-1, N doping atomic percentage content is
4.62 %。
Embodiment 2
It taking 1 g gelatin in 20 mL deionized waters, is warming up to 80 DEG C, is completely dissolved to gelatin, stirring keeps its evenly dispersed, with
After 0.5 g sodium nitrate is added, stirring and dissolving forms uniform colloidal sol, and is cooled to room temperature.
Above-mentioned colloidal sol is placed in 12 h in 4 DEG C of insulating box, forms it into hydrogel, and continues to place at -20 DEG C
Then 12 h impregnate 1-5 min in liquid nitrogen, obtain frozen glue.
Frozen glue is placed in freeze dryer, 36 h of vacuum freeze drying obtains aeroge.
Aeroge is placed in tube furnace, is passed through argon gas, rises to 800 DEG C with the rate of 5 DEG C/min, and protect at 800 DEG C
1 h is held, after naturally cool to room temperature, obtains black silicon carbide product.
Black silicon carbide product is collected, beaker is placed in, deionized water is added, 2 h of stirring and washing is filtered, washs, dried
To final products, it is labeled as C-0.5-800.
Microscopic appearance observation is carried out to it with electronic scanner microscope, as a result such as Fig. 3, it can be seen that C-0.5-800 exists
Macropore abundant, but cell channels are closed, and are further three-dimensional with transmission electron microscope observation (Fig. 4) discovery C-0.5-800
Continuous foramen magnum-mesoporous structure, big pore size use N in 2-4 nm in 50-150 nm, mesopore size2Adsorption desorption experiment detects it
Specific surface area and pore structure, the result is shown in Figure 13 carry out elemental analysis, the result is shown in Figure 14 to it with x-ray photoelectron spectroscopy；More than
Characterization obtains the foramen magnum-mesoporous structure of formation of C-0.5-800, and specific surface area is 1774.09 m2 g-1, Kong Rongwei 0.944
cm3 g-1, N doping atomic percentage content is 3.90 %.
Embodiment 3
It taking 1 g gelatin in 20 mL deionized waters, is warming up to 80 DEG C, is completely dissolved to gelatin, stirring keeps its evenly dispersed, with
After 0.75 g sodium nitrate is added, stirring and dissolving forms uniform colloidal sol, and is cooled to room temperature.
Above-mentioned colloidal sol is placed in 12 h in 4 DEG C of insulating box, forms it into hydrogel, and continues to place at -20 DEG C
Then 12 h impregnate 1-5 min in liquid nitrogen, obtain frozen glue.
Frozen glue is placed in freeze dryer, 36 h of vacuum freeze drying obtains aeroge.
Aeroge is placed in tube furnace, is passed through argon gas, rises to 800 DEG C with the rate of 5 DEG C/min, and protect at 800 DEG C
1 h is held, after naturally cool to room temperature, obtains black silicon carbide product.
Black silicon carbide product is collected, beaker is placed in, deionized water is added, 2 h of stirring and washing is filtered, washs, dried
To final products, it is labeled as C-0.75-800.
Microscopic appearance observation is carried out to it with electronic scanner microscope and transmission electron microscope, as a result such as Fig. 5, test knot
Fruit shows that the duct of C-0.75-800 is sufficiently flourishing, possesses open foramen magnum-mesoporous structure, big pore size is in 50-150
Nm, mesopore size use N in 2-4 nm2Adsorption desorption experiment detects its specific surface area and pore structure, the result is shown in Figure 13, specific surface
Product is 2777.1 m2 g-1, 1.618 cm of Kong Rongwei3 g-1, elemental analysis is carried out to it with x-ray photoelectron spectroscopy, is as a result seen
Figure 14, it is 3.43 % that nitrogen, which mixes atomic percentage content,.
Embodiment 4
It taking 1 g gelatin in 20 mL deionized waters, is warming up to 80 DEG C, is completely dissolved to gelatin, stirring keeps its evenly dispersed, with
After 0.75 g sodium chloride is added, stirring and dissolving forms uniform colloidal sol, and is cooled to room temperature.
Above-mentioned colloidal sol is placed in 12 h in 4 DEG C of insulating box, forms it into hydrogel, and continues to place at -20 DEG C
Then 12 h impregnate 1-5 min in liquid nitrogen, obtain frozen glue.
Frozen glue is placed in freeze dryer, 36 h of vacuum freeze drying obtains aeroge.
Aeroge is placed in tube furnace, is passed through argon gas, rises to 800 DEG C with the rate of 5 DEG C/min, and protect at 800 DEG C
1 h is held, after naturally cool to room temperature, obtains black silicon carbide product.
Black silicon carbide product is collected, beaker is placed in, deionized water is added, 2 h of stirring and washing is filtered, washs, dried
To final products.
Microscopic appearance observation is carried out to it with electronic scanner microscope and transmission electron microscope, as a result sees Fig. 6, it is seen that should
There are continuous macroporous structures for sample, but not mesoporous.
Embodiment 5
It taking 1 g gelatin in 20 mL deionized waters, is warming up to 80 DEG C, is completely dissolved to gelatin, stirring keeps its evenly dispersed, with
After 0.75 g sodium nitrate is added, stirring and dissolving forms uniform colloidal sol, and is cooled to room temperature.
Above-mentioned colloidal sol is placed in 12 h in 4 DEG C of insulating box, forms it into hydrogel, and continues to place at -20 DEG C
Then 12 h impregnate 1-5 min in liquid nitrogen, obtain frozen glue.
Frozen glue is placed in freeze dryer, 36 h of vacuum freeze drying obtains aeroge.
Aeroge is placed in tube furnace, is passed through argon gas, rises to 400 DEG C with the rate of 5 DEG C/min, and protect at 400 DEG C
1 h is held, after naturally cool to room temperature, obtains black silicon carbide product.
Black silicon carbide product is collected, beaker is placed in, deionized water is added, 2 h of stirring and washing is filtered, washs, dried
To final products, it is labeled as C-0.75-400.
Microscopic appearance observation is carried out to it with electronic scanner microscope and transmission electron microscope, as a result such as Fig. 7, as a result table
Bright, C-0.75-400 has continuous macroporous structure, and big pore size is in 50-150 nm, but shortage is mesoporous, uses N2Adsorption desorption experiment inspection
Its specific surface area and pore structure, the result is shown in Figure 13 are surveyed, specific surface area is 671.23 m2 g-1, 0.399 cm of Kong Rongwei3 g-1,
Elemental analysis, the result is shown in Figure 14 are carried out to it with x-ray photoelectron spectroscopy, N doping atomic percentage content is 9.67 %.
Embodiment 6
It taking 1 g gelatin in 20 mL deionized waters, is warming up to 80 DEG C, is completely dissolved to gelatin, stirring keeps its evenly dispersed, with
After 0.75 g sodium nitrate is added, stirring and dissolving forms uniform colloidal sol, and is cooled to room temperature.
Above-mentioned colloidal sol is placed in 12 h in 4 DEG C of insulating box, forms it into hydrogel, and continues to place at -20 DEG C
Then 12 h impregnate 1-5 min in liquid nitrogen, obtain frozen glue.
Frozen glue is placed in freeze dryer, 36 h of vacuum freeze drying obtains aeroge.
Aeroge is placed in tube furnace, is passed through argon gas, rises to 700 DEG C with the rate of 5 DEG C/min, and protect at 700 DEG C
1 h is held, after naturally cool to room temperature, obtains black silicon carbide product.
Black silicon carbide product is collected, beaker is placed in, deionized water is added, 2 h of stirring and washing is filtered, washs, dried
To final products, it is labeled as C-0.75-700.
Microscopic appearance observation is carried out to it with electronic scanner microscope and transmission electron microscope, as a result such as Fig. 8, as a result table
Bright C-0.75-700 has a continuous foramen magnum-mesoporous structure, big pore size 50-150 nm, and there are more mesoporous, uses N2It inhales de-
Attached experiment detects its specific surface area and pore structure, the result is shown in Figure 13, and specific surface area is 2593.2 m2 g-1, Kong Rongwei 1.454
cm3 g-1, elemental analysis, the result is shown in Figure 14 are carried out to it with x-ray photoelectron spectroscopy, N doping atomic percentage content is
5.94 %。
Embodiment 7
It taking 1 g gelatin in 20 mL deionized waters, is warming up to 80 DEG C, is completely dissolved to gelatin, stirring keeps its evenly dispersed, with
After 0.75 g sodium nitrate is added, stirring and dissolving forms uniform colloidal sol, and is cooled to room temperature.
Above-mentioned colloidal sol is placed in 12 h in 4 DEG C of insulating box, forms it into hydrogel, and continues to place at -20 DEG C
Then 12 h impregnate 1-5 min in liquid nitrogen, obtain frozen glue.
Frozen glue is placed in freeze dryer, 36 h of vacuum freeze drying obtains aeroge.
Aeroge is placed in tube furnace, is passed through argon gas, rises to 900 DEG C with the rate of 5 DEG C/min, and protect at 900 DEG C
1 h is held, after naturally cool to room temperature, obtains black silicon carbide product.
Black silicon carbide product is collected, beaker is placed in, deionized water is added, 2 h of stirring and washing is filtered, washs, dried
To final products, it is labeled as C-0.75-900.
Microscopic appearance observation is carried out to it with electronic scanner microscope and transmission electron microscope, as a result such as Fig. 9 a, Fig. 9 b
With Fig. 9 c, the results showed that C-0.75-900 has the flourishing foramen magnum-mesoporous channel of three-dimensional, and big pore size 50-200 nm has
Abundant mesoporous, mesopore size 2-4 nm, specific surface area is 2872.2 m2 g-1, 1.618 cm of Kong Rongwei3 g-1, mesoporous point
Cloth is coincide in 2-4 nm with transmission electron microscope results, carries out elemental analysis to it with x-ray photoelectron spectroscopy, the result is shown in Figure 14,
It is 2.24 % that its nitrogen, which mixes atomic percentage content,.
It is super capacitance electrode material by the foramen magnum-mesoporous carbon material being prepared in embodiment 7, by following experimental procedure
Following electrochemical property test is carried out to it.
Working electrode preparation method: foramen magnum-mesoporous carbon is mixed with acetylene black and PVDF according to 8:1:1, is molten with NMP
Agent, grinding form slurry, slurry are coated to diameter phi=13mm, in thickness d=1mm foamed nickel current collector, sample is 60oUnder C after dry 24 h, in 10MPa lower sheeting.Two equal electrode slices of quality are selected, 2032 types are assembled into glove box
Button cell, septation are glass fibre element, electrolyte EMIBF4.Performance survey is carried out using EC Lab electrochemical workstation
Examination.
Cyclic voltammetry curve test is carried out at 0-4 V, and sweep speed is 5-1000 mV/s, test result such as Figure 10 institute
Show.CV curve shows typical double layer characteristic, and does not deform significantly in 1000 mV/s lower curves, illustrates to have good
Good invertibity and power characteristic.
Constant current charge-discharge test is tested under different current densities respectively, and test result is as shown in figure 11.It calculates
The specific capacitance arrived is respectively 166 under 0.5,1,2,5,10,20,30,50,75,100 A/g current density,
152, 142, 135, 127, 118, 111, 98, 84, 70 F/g。
In Figure 12, Ragone figure shows the energy density and power density of foramen magnum-mesoporous carbon.Power density is 1 kW
kg-1When, 92 Wh kg can be obtained-1Energy density, in the 200 kW kg of power density of superelevation-1Under, still it is able to maintain 39 Wh
kg-1Energy density.
Above embodiments prove, by salt template, can successfully be prepared while have high-specific surface area, macropore-
Mesoporous interconnection, the porous carbon materials of N doping characteristic, this method raw material is cheap, prepared by simple process, environmentally protective, easy amplification；
With EMIBF4In the system of electrolyte, to use foramen magnum-mesoporous carbon as electrode material, excellent energy can be exported
Density value and high power density values have great application potential in supercapacitor applications field.It adopts this method
Obtained foramen magnum-mesoporous carbon is not limited to be applied to supercapacitor, in other field, as adsorbent, electro-catalysis, lithium/sodium from
Sub- battery also has biggish application potential.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (9)
1. a kind of method for preparing the foramen magnum-mesoporous carbon material of high-specific surface area using salt template, it is characterised in that following steps: step
Rapid 1, soluble carbon source is dissolved in 60-80 DEG C of hot water, forms uniform colloidal sol；It is added in step 2, Xiang Shangshu colloidal sol a kind of or more
Kind inorganic salts, stirring and dissolving to uniform colloidal sol；Step 3, above-mentioned mixed sols are cooled to room temperature, and are placed in 4 DEG C of insulating boxs
12-24 H-shaped continues to place 12-24 h at -20 DEG C and be dipped in liquid nitrogen 1-5 min to form frozen glue at hydrogel；Step 4 is incited somebody to action
Frozen glue vacuum freeze drying 24-36 h in freeze dryer removes water to obtain aeroge；Aeroge is placed in tube furnace by step 5, is led to
Enter inert gas, carry out high temperature pyrolysis activation, obtains black silicon carbide product；Step 6 carries out cleaning 1-3 to black silicon carbide product
It is secondary, it filters, drying obtains porous carbon materials.
2. above-mentioned foramen magnum-mesoporous carbon is super capacitance electrode material that is a kind of while having high-energy density and power density, make
With 1- ethyl-3-methylimidazole tetrafluoro boric acid (EMIBF4) it is electrolyte, under the operating voltage of 4 V, power density is 1 kW
kg-1When, 92 Wh kg can be obtained-1Energy density, in the 200 kW kg of power density of superelevation-1Under, still it is able to maintain 39 Wh
kg-1Energy density.
3. preparation method according to claim 1, which is characterized in that the ratio of hot water and gelatin is (5 mL:1 g)-(30
mL:1 g)；The ratio of hot water and gelatin is preferably 20 mL:1 g.
4. preparation method according to claim 1, which is characterized in that the inorganic salts be sodium nitrate, potassium nitrate, sodium chloride,
Potassium chloride, sodium sulphate；The inorganic salts are preferably sodium nitrate.
5. preparation method according to claim 1, which is characterized in that the mass ratio of sodium nitrate and gelatin is (0.25-2): 1；
The ratio of inorganic salts and gelatin is preferably 0.75:1.
6. preparation method according to claim 1, which is characterized in that the inert atmosphere of high temperature pyrolysis activation is nitrogen, argon gas；
Being pyrolyzed activation phenomenon is preferably argon gas.
7. preparation method according to claim 1, which is characterized in that the temperature of high temperature pyrolysis activation is 400-1000 DEG C, is risen
Warm rate is 2-20 DEG C/min, and pyrolysis time is 1-3 h；Preferably, pyrolysis activation temperature is 900 DEG C, heating rate 5
DEG C/min, pyrolysis time is 1 h.
8. preparation method according to claim 1, which is characterized in that cleaning black silicon carbide product solvent for use be ethyl alcohol, third
Ketone, water or their mixture；Cleaning black silicon carbide product solvent for use is preferably water.
9. the porous carbon materials prepared according to claim 1, it is characterised in that: three-dimensional continuous foramen magnum-mesoporous structure, macropore
Size 50-200 nm, mesopore size 2-4 nm, specific surface area 600-3000 cm2 g-1, N doping atomic percentage content 2.24-
9.07 at%。
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110155980A (en) * | 2019-05-20 | 2019-08-23 | 北京化工大学 | A kind of preparation method of the three-dimensional porous carbon material of honeycomb |
| CN110357088A (en) * | 2019-08-20 | 2019-10-22 | 中国科学院长春应用化学研究所 | A kind of method and application preparing graphene oxide based on gelatin |
| CN110474060A (en) * | 2019-07-01 | 2019-11-19 | 吉林大学 | A kind of preparation method and oxygen reduction catalyst application of efficiently three-dimensional netted nitrogen auto-dope carbon aerogels |
| CN111874886A (en) * | 2020-06-18 | 2020-11-03 | 华南理工大学 | Nitrogen-doped porous carbon material and preparation method and application thereof |
| CN111977652A (en) * | 2020-08-19 | 2020-11-24 | 中国海洋大学 | Micro-explosion method for preparing bio-derived porous carbon and application of bio-derived porous carbon in super capacitor |
| CN113893867A (en) * | 2021-11-16 | 2022-01-07 | 泰州学院 | Preparation method of hydrodesulfurization catalyst with mesoporous carbon material as carrier |
| CN113893823A (en) * | 2021-11-10 | 2022-01-07 | 福州大学 | Passion fruit-based biomass charcoal material and preparation method and application thereof |
| CN113942995A (en) * | 2021-11-15 | 2022-01-18 | 中国空间技术研究院 | Heteroatom-doped porous carbon material and preparation method and application thereof |
| CN114229824A (en) * | 2021-12-14 | 2022-03-25 | 中国石油大学(华东) | Porous carbon material and preparation method thereof, lithium-sulfur battery modified diaphragm and preparation method thereof, and lithium-sulfur battery |
| CN114524433A (en) * | 2020-11-23 | 2022-05-24 | 中国科学院大连化学物理研究所 | Preparation method of graded porous hard carbon, application, negative electrode and electrode |
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110155980A (en) * | 2019-05-20 | 2019-08-23 | 北京化工大学 | A kind of preparation method of the three-dimensional porous carbon material of honeycomb |
| CN110474060A (en) * | 2019-07-01 | 2019-11-19 | 吉林大学 | A kind of preparation method and oxygen reduction catalyst application of efficiently three-dimensional netted nitrogen auto-dope carbon aerogels |
| CN110357088A (en) * | 2019-08-20 | 2019-10-22 | 中国科学院长春应用化学研究所 | A kind of method and application preparing graphene oxide based on gelatin |
| CN111874886B (en) * | 2020-06-18 | 2022-03-25 | 华南理工大学 | Nitrogen-doped porous carbon material and preparation method and application thereof |
| CN111874886A (en) * | 2020-06-18 | 2020-11-03 | 华南理工大学 | Nitrogen-doped porous carbon material and preparation method and application thereof |
| CN111977652A (en) * | 2020-08-19 | 2020-11-24 | 中国海洋大学 | Micro-explosion method for preparing bio-derived porous carbon and application of bio-derived porous carbon in super capacitor |
| CN111977652B (en) * | 2020-08-19 | 2023-08-04 | 中国海洋大学 | Preparation of bio-derived porous carbon by micro-explosion method and application of bio-derived porous carbon in super capacitor |
| CN114524433A (en) * | 2020-11-23 | 2022-05-24 | 中国科学院大连化学物理研究所 | Preparation method of graded porous hard carbon, application, negative electrode and electrode |
| CN114524433B (en) * | 2020-11-23 | 2024-01-12 | 中国科学院大连化学物理研究所 | Preparation method of graded porous hard carbon, application, negative electrode and electrode |
| CN113893823A (en) * | 2021-11-10 | 2022-01-07 | 福州大学 | Passion fruit-based biomass charcoal material and preparation method and application thereof |
| CN113942995A (en) * | 2021-11-15 | 2022-01-18 | 中国空间技术研究院 | Heteroatom-doped porous carbon material and preparation method and application thereof |
| CN113942995B (en) * | 2021-11-15 | 2023-12-08 | 中国空间技术研究院 | Heteroatom doped porous carbon material and preparation method and application thereof |
| CN113893867A (en) * | 2021-11-16 | 2022-01-07 | 泰州学院 | Preparation method of hydrodesulfurization catalyst with mesoporous carbon material as carrier |
| CN114229824A (en) * | 2021-12-14 | 2022-03-25 | 中国石油大学(华东) | Porous carbon material and preparation method thereof, lithium-sulfur battery modified diaphragm and preparation method thereof, and lithium-sulfur battery |
| CN114920237A (en) * | 2022-05-31 | 2022-08-19 | 中南大学 | Novel single-layer graphene aerogel and preparation method and application thereof |
| CN114920237B (en) * | 2022-05-31 | 2024-03-15 | 中南大学 | Single-layer graphene aerogel and preparation method and application thereof |
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