CN106976864B - A kind of micropore carbon aerogels and preparation method thereof - Google Patents
A kind of micropore carbon aerogels and preparation method thereof Download PDFInfo
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- CN106976864B CN106976864B CN201710364105.9A CN201710364105A CN106976864B CN 106976864 B CN106976864 B CN 106976864B CN 201710364105 A CN201710364105 A CN 201710364105A CN 106976864 B CN106976864 B CN 106976864B
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- C—CHEMISTRY; METALLURGY
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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Abstract
The present invention relates to a kind of micropore carbon aerogels and preparation method thereof, and LiNO is added by preparing a step in organic wet gel3、KNO3And K2SO4The mixing Eutectic molten salt of composition is prepared, and has following parameter：Specific surface area 850-1350m2/ g, pore-size distribution 1-2nm, hole hold 0.38-0.43cm3/ g, CO under normal temperature and pressure2Adsorbance be 3.2-3.8mmol/g, micropore carbon aerogels specific surface area prepared by the present invention is high, and narrow pore size distribution range, pore volume is big, stronger to the adsorption capacity of carbon dioxide.Preparation method step of the invention is simple, and easy to operate, production cost is low, process time section, environmentally friendly.
Description
Technical field
The present invention relates to a kind of micropore carbon aerogels and preparation method thereof, belong to carbon aerogels preparation field.
Background technique
Carbon aerogels are a kind of novel light porous materials, because it is good with stability, porosity is high, specific surface area
Greatly, conductivity is high and more substance and the characteristics of electron-transport duct, should make catalyst carrier, hydrogen storage material, absorption extensively
Material and supercapacitor or the electrode material of lithium ion battery etc., energy crisis and the environment for advantageously accounting for today's society are dirty
Dye problem and become research hotspot.
Carbon aerogels are because its application field is different, and to performance requirement difference, therefore preparation method is not quite similar.For
In as CO2For the carbon aerogels of adsorbent, there is certain requirement to its aperture.CN201611110955.8 is disclosed
A kind of preparation method of carbon aerogels, by the way that using resorcinol and formaldehyde as raw material, organic amine is catalyst, water is solvent,
It stirs evenly, carries out gel reaction, obtain intermediate product and then carry out aging process, obtain organic wet gel, then taken out
Vacuum and drying process obtain organic aerogel, and finally heating carbonization, cooled to room temperature obtain carbon under nitrogen protection
Aeroge uses weak base organic amine as catalyst, and being unfavorable for cost reduces and unfriendly to environment.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of superior performances, are conducive to CO2The carbon aerogels of gas absorption,
And it is simple to provide its step, preparation method easy to operate.
To solve the above problems, the technical solution adopted by the present invention is that：
Technical theme one
The present invention provides a kind of micropore carbon aerogels, key technology point is, by preparing in organic wet gel
One step adds LiNO3、KNO3And K2SO4The mixing Eutectic molten salt of composition is prepared, and has following parameter：Specific surface area 850-
1350 m2/ g, pore-size distribution 1-2nm, hole hold 0.38-0.43cm3/ g, CO under normal temperature and pressure2Adsorbance be 3.2-3.8mmol/
g。
Further, the mass percent composition of the mixing Eutectic molten salt of LiNO3, KNO3 and K2SO4 is as follows：
LiNO336~42%；
KNO346~52%；
K2SO412~18%.
Further, it is prepared especially by following steps：
Step 1：Organic wet gel preparation
It according to molar ratio is 1 by polyhydroxy benzenes and formaldehyde:2 mixing, be added deionized water be configured to mass fraction be 35~
45% reaction solution, adds LiNO3、KNO3And K2SO4The mixing Eutectic molten salt of composition, the additional amount of Eutectic molten salt are polyhydroxy
The 13~25% of base benzene and formaldehyde gross mass, reaction solution is sealed after mixing, 40 DEG C is kept the temperature sufficiently reaction 3 days, between being made
The organic wet gel of benzenediol-phloroglucinol-formaldehyde, the polyhydroxy benzenes are the mixture of phloroglucin and resorcinol；
Step 2：Freeze-drying
Organic wet gel prepared by step 1 is directly placed into freeze drying box, it is drying for one day in -70~-80 DEG C, it obtains
To organic aerogel；
Step 3：High temperature carbonization
The organic aerogel that step 2 obtains is carbonized under vacuum-pumping conditions, with 10~30mL/min in carbonization process
Rate be constantly passed through protection gas, first 280~320 DEG C are warming up to from room temperature with the rate of 1.3~1.7 DEG C/min, then with 1.8
~2.2 DEG C/min rate is kept for 2~4 hours after being warming up to 900 ± 10 DEG C, then is slowly dropped to room temperature, obtains the carbon of black
Aeroge；
Step 4：Pickling
It is impregnated, is cleaned by ultrasonic, each half an hour with hydrochloric acid solution, cleaning is three times.
Technical theme two
The present invention provides a kind of preparation method of micropore carbon aerogels as described in technical theme one, specifically includes as follows
Step：
Step 1：Organic wet gel preparation
It according to molar ratio is 1 by polyhydroxy benzenes and formaldehyde:2 mixing, be added deionized water be configured to mass fraction be 35~
45% reaction solution, adds LiNO3、KNO3And K2SO4The mixing Eutectic molten salt of composition, the additional amount of Eutectic molten salt are polyhydroxy
The 13~25% of base benzene and formaldehyde gross mass, reaction solution is sealed after mixing, keeps the temperature 40-60 DEG C sufficiently reaction 2-4 days, system
The organic wet gel of resorcinol-phloroglucinol-formaldehyde is obtained, the polyhydroxy benzenes is the mixture of phloroglucin and resorcinol；
Step 2：Freeze-drying
Organic wet gel prepared by step 1 is directly placed into freeze drying box, it is drying for one day in -70~-80 DEG C, it obtains
To organic aerogel；
Step 3：High temperature carbonization
The organic aerogel that step 2 obtains is carbonized under vacuum-pumping conditions, with 10~30mL/min in carbonization process
Rate be constantly passed through protection gas, first 280~320 DEG C are warming up to from room temperature with the rate of 1.3~1.7 DEG C/min, then with 1.8
~2.2 DEG C/min rate is kept for 2~4 hours after being warming up to 900 ± 10 DEG C, then is slowly dropped to room temperature, obtains the carbon of black
Aeroge；
Step 4：It is impregnated, is cleaned by ultrasonic, each half an hour with hydrochloric acid solution, cleaning is three times.
Further, the LiNO3、KNO3And K2SO4The mass percent composition of the mixing Eutectic molten salt of composition is as follows：
LiNO336~42%；
KNO346~52%；
K2SO412~18%.
Further, it is 6.5~7.5 that the polyhydroxy benzenes, which is molar ratio,:The mixing of 1 resorcinol and phloroglucin
Object.
Further, it is 7 that the polyhydroxy benzenes, which is molar ratio,:1 resorcinol and the mixture of phloroglucin.
Further, the condition that reaction solution is uniformly mixed by the ultrasonic wave is as follows：Temperature is 15~30 DEG C, is mixed extremely
Until solution becomes complete clear.
Further, the protection gas in the step 3 be selected from one or both of helium, neon, argon gas and nitrogen with
On combination.
Further, the hydrochloric acid solution in the step 4 is the hydrochloric acid solution of 0.05~0.15mol/L.
Further, include the following steps：
Step 1：Organic wet gel preparation
It according to molar ratio is 1 by polyhydroxy benzenes and formaldehyde:2 mixing, it is 40% that deionized water, which is added, and is configured to mass fraction
Reaction solution, add LiNO3、KNO3And K2SO4The mixing Eutectic molten salt of composition, the additional amount of Eutectic molten salt are polyhydroxy benzenes
With the 20% of formaldehyde gross mass, reaction solution is sealed after mixing, keeps the temperature 50 DEG C sufficiently reaction 3 days, resorcinol-is made
The organic wet gel of benzenetriol-formaldehyde, the polyhydroxy benzenes are that molar ratio is 7:1 phloroglucin and the mixture of resorcinol；
Step 2：Freeze-drying
Organic wet gel prepared by step 1 is directly placed into freeze drying box, it is drying for one day in -80 ± 5 DEG C, it obtains
Organic aerogel；
Step 3：High temperature carbonization
The organic aerogel that step 2 obtains is carbonized under vacuum-pumping conditions, with the speed of 20mL/min in carbonization process
Rate is constantly passed through protection gas, is first warming up to 300 DEG C from room temperature with the rate of 1.5 DEG C/min, is then warming up to 2 DEG C/min rate
3 hours are kept after 900 ± 5 DEG C, then are slowly dropped to room temperature, obtain the carbon aerogels of black；
Step 4：Pickling
It is impregnated with the hydrochloric acid solution of 0.1mol/L, ultrasonic cleaning, each half an hour, cleaning is three times.
Heretofore described normal temperature and pressure refers to 20 DEG C -30 DEG C of temperature, a standard atmospheric pressure.
Generated beneficial effect is by adopting the above technical scheme：
The present invention by being added LiNO during the preparation process3、KNO3And K2SO4The mixing Eutectic molten salt of composition, so that in charcoal
It can be decomposed into metal oxide during change, finally by certain density pickling, remove metal salt, leave hole, effectively increase
Specific surface area, ensure that the aperture of suitable size.Test proves that utilizing LiNO3、KNO3And K2SO4The mixing of composition is low
Congruent melting salt system can also effectively improve the adsorption capacity to carbon dioxide.
Raw material of the present invention is resorcinol, phloroglucin and formaldehyde, more functional group's hydroxyl be on the one hand conducive to react into
Capable is more complete, and prior one side is the crosslinking to be formed macromolecular more abundant, cooperates with LiNO3、KNO3With
K2SO4Effective filling of the mixing Eutectic molten salt system of composition, conducive to more robust carbon skeleton and finer and close is formed after pyrocarbon
3D network structure.
The present invention is carbonized again by freeze-drying, is conducive to the integrality for keeping carbon aerogels material, is avoided structure and collapse
It collapses, is conducive to molding.
Micropore carbon aerogels specific surface area prepared by the present invention is high, and narrow pore size distribution range, pore volume is big, to carbon dioxide
Adsorption capacity it is stronger.Preparation method step of the invention is simple, and easy to operate, production cost is low, process time section, to environment
It is friendly.
Detailed description of the invention
Attached drawing 1 is the adsorption isotherm of carbon aerogels prepared by embodiment 1；
Attached drawing 2 is the graph of pore diameter distribution of carbon aerogels prepared by embodiment 1；
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, invention is carried out combined with specific embodiments below
Clear, complete description.
Embodiment 1
Step 1：Organic wet gel preparation
It according to molar ratio is 1 by polyhydroxy benzenes and formaldehyde:2 mixing, it is 40% that deionized water, which is added, and is configured to mass fraction
Reaction solution, add containing 38%LiNO3, 46%KNO3And 16%K2SO4Mixing Eutectic molten salt, mix Eutectic molten salt plus
Enter 20% that amount is polyhydroxy benzenes and formaldehyde gross mass, reaction solution sealed after mixing, keeps the temperature 50 DEG C sufficiently reaction 3 days,
The organic wet gel of resorcinol-phloroglucinol-formaldehyde is made, the polyhydroxy benzenes is that molar ratio is 7:1 phloroglucin and
The mixture of benzenediol；
Step 2：Freeze-drying
Organic wet gel prepared by step 1 is directly placed into freeze drying box, it is drying for one day in -80 ± 5 DEG C, it obtains
Organic aerogel；
Step 3：High temperature carbonization
The organic aerogel that step 2 obtains is carbonized under vacuum-pumping conditions, with the speed of 20mL/min in carbonization process
Rate is constantly passed through N2, 300 DEG C first are warming up to from room temperature with the rate of 1.5 DEG C/min, is then warming up to 900 with 2 DEG C/min rate
3 hours are kept after ± 5 DEG C, then are slowly dropped to room temperature, obtain the carbon aerogels of black；
Step 4：Pickling
It is impregnated with the hydrochloric acid solution of 0.1mol/L, ultrasonic cleaning, each half an hour, cleaning is three times.
The carbon aerogels parameter being prepared is as follows：Specific surface area 1200m2/ g, pore-size distribution 1-2nm, hole hold 0.41cm3/
G, CO under normal temperature and pressure2Adsorbance be 3.5mmol/g.
Embodiment 2
Step 1：Organic wet gel preparation
It according to molar ratio is 1 by polyhydroxy benzenes and formaldehyde:2 mixing, it is 40% that deionized water, which is added, and is configured to mass fraction
Reaction solution, add containing 36%LiNO3, 52%KNO3And 12%K2SO4Mixing Eutectic molten salt, mix Eutectic molten salt plus
Enter 20% that amount is polyhydroxy benzenes and formaldehyde gross mass, reaction solution sealed after mixing, keeps the temperature 50 DEG C sufficiently reaction 3 days,
The organic wet gel of resorcinol-phloroglucinol-formaldehyde is made, the polyhydroxy benzenes is that molar ratio is 7:1 phloroglucin and
The mixture of benzenediol；
Step 2：Freeze-drying
Organic wet gel prepared by step 1 is directly placed into freeze drying box, it is drying for one day in -80 ± 5 DEG C, it obtains
Organic aerogel；
Step 3：High temperature carbonization
The organic aerogel that step 2 obtains is carbonized under vacuum-pumping conditions, with the speed of 20mL/min in carbonization process
Rate is constantly passed through N2, 300 DEG C first are warming up to from room temperature with the rate of 1.5 DEG C/min, is then warming up to 900 with 2 DEG C/min rate
3 hours are kept after ± 5 DEG C, then are slowly dropped to room temperature, obtain the carbon aerogels of black；
Step 4：Pickling
It is impregnated with the hydrochloric acid solution of 0.1mol/L, ultrasonic cleaning, each half an hour, cleaning is three times.
The carbon aerogels parameter being prepared is as follows：Specific surface area 1000m2/ g, pore-size distribution 1-1.8nm, Kong Rong
0.40cm3/ g, CO under normal temperature and pressure2Adsorbance be 3.3mmol/g.
Embodiment 3
Step 1：Organic wet gel preparation
It according to molar ratio is 1 by polyhydroxy benzenes and formaldehyde:2 mixing, it is 40% that deionized water, which is added, and is configured to mass fraction
Reaction solution, add containing 42%LiNO3, 46%KNO3And 12%K2SO4Mixing Eutectic molten salt, mix Eutectic molten salt plus
Entering amount is stupid 20% with formaldehyde gross mass of polyhydroxy, and reaction solution is sealed after mixing, keeps the temperature 50 DEG C sufficiently reaction 3 days,
The organic wet gel of resorcinol-phloroglucinol-formaldehyde is made, the polyhydroxy benzenes is that molar ratio is 7:1 phloroglucin and
The mixture of benzenediol；
Step 2：Freeze-drying
Organic wet gel prepared by step 1 is directly placed into freeze drying box, it is drying for one day in -80 ± 5 DEG C, it obtains
Organic aerogel；
Step 3：High temperature carbonization
The organic aerogel that step 2 obtains is carbonized under vacuum-pumping conditions, with the speed of 20mL/min in carbonization process
Rate is constantly passed through N2, 300 DEG C first are warming up to from room temperature with the rate of 1.5 DEG C/min, is then warming up to 900 with 2 DEG C/min rate
3 hours are kept after ± 5 DEG C, then are slowly dropped to room temperature, obtain the carbon aerogels of black；
Step 4：Pickling
It is impregnated with the hydrochloric acid solution of 0.1mol/L, ultrasonic cleaning, each half an hour, cleaning is three times.
The carbon aerogels parameter being prepared is as follows：Specific surface area 850m2/ g, pore-size distribution 1-1.5nm, hole hold 0.39
cm3/ g, CO under normal temperature and pressure2Adsorbance be 3.2mmol/g.
Embodiment 4
Step 1：Organic wet gel preparation
It according to molar ratio is 1 by polyhydroxy benzenes and formaldehyde:2 mixing, it is 40% that deionized water, which is added, and is configured to mass fraction
Reaction solution, add containing 36%LiNO3, 46%KNO3And 18%K2SO4Mixing Eutectic molten salt, mix Eutectic molten salt plus
Enter 20% that amount is polyhydroxy benzenes and formaldehyde gross mass, reaction solution sealed after mixing, keeps the temperature 50 DEG C sufficiently reaction 3 days,
The organic wet gel of resorcinol-phloroglucinol-formaldehyde is made, the polyhydroxy benzenes is that molar ratio is 7:1 phloroglucin and
The mixture of benzenediol；
Step 2：Freeze-drying
Organic wet gel prepared by step 1 is directly placed into freeze drying box, it is drying for one day in -80 ± 5 DEG C, it obtains
Organic aerogel；
Step 3：High temperature carbonization
The organic aerogel that step 2 obtains is carbonized under vacuum-pumping conditions, with the speed of 20mL/min in carbonization process
Rate is constantly passed through N2, 300 DEG C first are warming up to from room temperature with the rate of 1.5 DEG C/min, is then warming up to 900 with 2 DEG C/min rate
3 hours are kept after ± 5 DEG C, then are slowly dropped to room temperature, obtain the carbon aerogels of black；
Step 4：Pickling
It is impregnated with the hydrochloric acid solution of 0.05mol/L, ultrasonic cleaning, each half an hour, cleaning is three times.
The carbon aerogels parameter being prepared is as follows：Specific surface area 1300m2/ g, pore-size distribution 1-2nm, hole hold 0.42cm3/
G, CO under normal temperature and pressure2Adsorbance be 3.7mmol/g.
Embodiment 5
Step 1：Organic wet gel preparation
It according to molar ratio is 1 by polyhydroxy benzenes and formaldehyde:2 mixing, it is 35% that deionized water, which is added, and is configured to mass fraction
Reaction solution, add containing 38%LiNO3, 46%KNO3And 16%K2SO4Mixing Eutectic molten salt, mix Eutectic molten salt plus
Enter 25% that amount is polyhydroxy benzenes and formaldehyde gross mass, reaction solution sealed after mixing, keeps the temperature 50 DEG C sufficiently reaction 3 days,
The organic wet gel of resorcinol-phloroglucinol-formaldehyde is made, the polyhydroxy benzenes is that molar ratio is 6.5:1 phloroglucin and
The mixture of resorcinol；
Step 2：Freeze-drying
Organic wet gel prepared by step 1 is directly placed into freeze drying box, it is drying for one day in -75 ± 5 DEG C, it obtains
Organic aerogel；
Step 3：High temperature carbonization
The organic aerogel that step 2 obtains is carbonized under vacuum-pumping conditions, with the speed of 10mL/min in carbonization process
Rate is constantly passed through argon gas, is first warming up to 300 DEG C from room temperature with the rate of 1.3 DEG C/min, is then warming up to 2.2 DEG C/min rate
3 hours are kept after 900 ± 5 DEG C, then are slowly dropped to room temperature, obtain the carbon aerogels of black；
Step 4：Pickling
It is impregnated with the hydrochloric acid solution of 0.15mol/L, ultrasonic cleaning, each half an hour, cleaning is three times.
The carbon aerogels parameter being prepared is as follows：Specific surface area 1150m2/ g, pore-size distribution 1-2nm, hole hold 0.40cm3/
G, CO under normal temperature and pressure2Adsorbance be 3.4mmol/g.
Embodiment 6
Step 1：Organic wet gel preparation
It according to molar ratio is 1 by polyhydroxy benzenes and formaldehyde:2 mixing, it is 45% that deionized water, which is added, and is configured to mass fraction
Reaction solution, add containing 38%LiNO3, 46%KNO3And 16%K2SO4Mixing Eutectic molten salt, mix Eutectic molten salt plus
Entering amount is stupid 13% with formaldehyde gross mass of polyhydroxy, and reaction solution is sealed after mixing, keeps the temperature 50 DEG C sufficiently reaction 3 days,
The organic wet gel of resorcinol-phloroglucinol-formaldehyde is made, the polyhydroxy benzenes is that molar ratio is 7.5:1 phloroglucin and
The mixture of resorcinol；
Step 2：Freeze-drying
Organic wet gel prepared by step 1 is directly placed into freeze drying box, it is drying for one day in -70 ± 5 DEG C, it obtains
Organic aerogel；
Step 3：High temperature carbonization
The organic aerogel that step 2 obtains is carbonized under vacuum-pumping conditions, with the speed of 30mL/min in carbonization process
Rate is constantly passed through N2, 320 DEG C first are warming up to from room temperature with the rate of 1.7 DEG C/min, is then warming up to 1.8 DEG C/min rate
3 hours are kept after 900 ± 5 DEG C, then are slowly dropped to room temperature, obtain the carbon aerogels of black；
Step 4：Pickling
It is impregnated with the hydrochloric acid solution of 0.1mol/L, ultrasonic cleaning, each half an hour, cleaning is three times.
The carbon aerogels parameter being prepared is as follows：Specific surface area 950m2/ g, pore-size distribution 1-2nm, hole hold 0.39cm3/
G, CO under normal temperature and pressure2Adsorbance be 3.3mmol/g.
Comparative example 1
According to the preparation method of embodiment 1, difference is with containing 45%LiNO3And 55%KNO3Mixing Eutectic molten salt replace
In generation, contains 38%LiNO3, 46%KNO3And 16%K2SO4Mixing Eutectic molten salt.The carbon aerogels parameter being prepared is as follows：Than
Surface area 590m2/ g, pore-size distribution 0.8-1.3nm, hole hold 0.25cm3/ g, CO under normal temperature and pressure2Adsorbance be 1.8mmol/
g。
Comparative example 2
According to the preparation method of embodiment 1, difference is with containing 38%LiNO3, 46%KNO3It is low with the mixing of 16%KCl
Congruent melting salt substitution contains 38%LiNO3, 46%KNO3And 16%K2SO4Mixing Eutectic molten salt.The carbon aerogels parameter being prepared
It is as follows：Specific surface area 630m2/ g, pore-size distribution 0.8-1.5nm, hole hold 0.28cm3/ g, CO under normal temperature and pressure2Adsorbance be
2.0mmol/g。
Comparative example 3
According to the preparation method of embodiment 1, difference is with containing 38%LiNO3, 46%KNO3And 16%KCO3Mixing it is low
Congruent melting salt substitution contains 38%LiNO3, 46%KNO3And 16%K2SO4Mixing Eutectic molten salt.The carbon aerogels parameter being prepared
It is as follows：Specific surface area 650m2/ g, pore-size distribution 0.7-1.6nm, hole hold 0.29m3/ g, CO under normal temperature and pressure2Adsorbance be
2.1mmol/g。
Comparative example 4
According to the preparation method of embodiment 1, difference is with containing 38%LiNO3, 46%KNO3With 16%Zn NO3Mixing
Eutectic molten salt substitution contains 38%LiNO3, 46%KNO3And 16%K2SO4Mixing Eutectic molten salt.The carbon aerogels ginseng being prepared
Number is as follows：Specific surface area 530m2/ g, pore-size distribution 0.2-0.9nm, hole hold 0.23cm3/ g, CO under normal temperature and pressure2Adsorbance be
1.8mmol/g。
Test example 1
According to the preparation method of embodiment 1, to K in the mixing Eutectic molten salt of LiNO3, KNO3 and K2SO42SO4Content into
Row observational study, the performance parameter for the carbon aerogels being prepared are shown in Table 1, and the performance parameter in table in each cross battens is followed successively by
Specific surface area (m2/ g), pore-size distribution (nm), Kong Rong (cm3/ g), CO under normal temperature and pressure2Adsorbance (mmol/g).
Table 1K2SO4Content investigates test and obtained carbon aerogels performance parameter table
Test 2
According to the preparation method of embodiment 1, to LiNO in the mixing Eutectic molten salt of LiNO3, KNO3 and K2SO43And KNO3Two
The content of kind salt carries out observational study, and the first file is K2SO4Percentage composition, the first row be LiNO3Percentage composition, it is remaining
Amount is KNO3, three total 100%.The performance parameter for the carbon aerogels being prepared is shown in Table 2, the property in table in each cross battens
Energy parameter is followed successively by specific surface area (m2/ g), pore-size distribution (nm), Kong Rong (cm3/ g), CO under normal temperature and pressure2Adsorbance
(mmol/g)。
2 LiNO of table3And KNO3Content investigate test and obtained carbon aerogels performance parameter table
Finally it should be noted that：The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although
Present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that：It still may be used
To modify to technical solution documented by previous embodiment or equivalent replacement of some of the technical features；And
These are modified or replaceed, the spirit and model of technical solution of the embodiment of the present invention that it does not separate the essence of the corresponding technical solution
It encloses.
Claims (8)
1. a kind of preparation method of micropore carbon aerogels, which is characterized in that specifically comprise the following steps：
Step 1：Organic wet gel preparation
It according to molar ratio is 1 by polyhydroxy benzenes and formaldehyde:2 mixing, it is 35 ~ 45% that deionized water, which is added, and is configured to mass fraction
Reaction solution adds LiNO3、KNO3And K2SO4The mixing Eutectic molten salt of composition, the additional amount of Eutectic molten salt be polyhydroxy benzenes with
The 13 ~ 25% of formaldehyde gross mass seal reaction solution after mixing, keep the temperature 40-60 DEG C sufficiently reaction 2-4 days, isophthalic two is made
The organic wet gel of phenol-phloroglucinol-formaldehyde, the polyhydroxy benzenes are the mixture of phloroglucin and resorcinol；
Step 2：Freeze-drying
Organic wet gel prepared by step 1 is directly placed into freeze drying box, it is drying for one day in -70 ~ -80 DEG C, it obtains organic
Aeroge；
Step 3：High temperature carbonization
The organic aerogel that step 2 obtains is carbonized under vacuum-pumping conditions, with the speed of 10 ~ 30mL/min in carbonization process
Rate is constantly passed through protection gas, first 280 ~ 320 DEG C is warming up to from room temperature with the rate of 1.3 ~ 1.7 DEG C/min, then with 1.8 ~ 2.2
DEG C/min rate keeps for 2 ~ 4 hours after being warming up to 900 ± 10 DEG C, then it is slowly dropped to room temperature, obtains the carbon aerogels of black；
Step 4：Pickling
It is impregnated, is cleaned by ultrasonic, each half an hour with hydrochloric acid solution, cleaning is three times；
Obtained micropore carbon aerogels have following parameter：Specific surface area 850-1350 m2/ g, pore-size distribution 1-2nm, Kong Rong
0.38-0.43 cm3/ g, CO under normal temperature and pressure2Adsorbance be 3.2-3.8mmol/g.
2. a kind of preparation method of micropore carbon aerogels according to claim 1, which is characterized in that the LiNO3、KNO3
And K2SO4The mass percent composition of the mixing Eutectic molten salt of composition is as follows：
LiNO336~42%；
KNO346~52%；
K2SO4 12~18%。
3. a kind of preparation method of micropore carbon aerogels according to claim 1, which is characterized in that the polyhydroxy benzenes is
Molar ratio is 6.5 ~ 7.5:1 resorcinol and the mixture of phloroglucin.
4. a kind of preparation method of micropore carbon aerogels according to claim 1, which is characterized in that the polyhydroxy benzenes is
Molar ratio is 7:1 resorcinol and the mixture of phloroglucin.
5. a kind of preparation method of micropore carbon aerogels according to claim 1, which is characterized in that the reaction solution mixing
Uniform condition is as follows：Temperature is 15~30 DEG C, is mixed until solution becomes complete clear.
6. a kind of preparation method of micropore carbon aerogels according to claim 1, which is characterized in that in the step 3
Gas is protected to be selected from the combination of one or more of helium, neon, argon gas and nitrogen.
7. a kind of preparation method of micropore carbon aerogels according to claim 1, which is characterized in that the hydrochloric acid solution
For the hydrochloric acid solution of 0.05 ~ 0.15mol/L.
8. a kind of preparation method of micropore carbon aerogels according to claim 1, which is characterized in that included following step
Suddenly：
Step 1：Organic wet gel preparation
It according to molar ratio is 1 by polyhydroxy benzenes and formaldehyde:2 mixing are added deionized water and are configured to the reaction that mass fraction is 40%
Liquid adds LiNO3、KNO3And K2SO4The mixing Eutectic molten salt of composition, the additional amount of Eutectic molten salt are polyhydroxy benzenes and formaldehyde
The 20% of gross mass seals reaction solution after mixing, keeps the temperature 50 DEG C sufficiently reaction 3 days, resorcinol-phloroglucin-is made
The organic wet gel of formaldehyde, the polyhydroxy benzenes are that molar ratio is 7:1 phloroglucin and the mixture of resorcinol；
Step 2：Freeze-drying
Organic wet gel prepared by step 1 is directly placed into freeze drying box, it is drying for one day in -80 ± 5 DEG C, it obtains organic
Aeroge；
Step 3：High temperature carbonization
The organic aerogel that step 2 obtains is carbonized under vacuum-pumping conditions, in carbonization process not with the rate of 20mL/min
It is open close to enter to protect gas, 300 DEG C first are warming up to from room temperature with the rate of 1.5 DEG C/min, is then warming up to 900 with 2 DEG C/min rate
3 hours are kept after ± 5 DEG C, then are slowly dropped to room temperature, obtain the carbon aerogels of black；
Step 4：Pickling
It is impregnated with the hydrochloric acid solution of 0.1mol/L, ultrasonic cleaning, each half an hour, cleaning is three times.
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