CN109081328A - A method of preparing the three-dimensional porous carbon nanosheet ball of N doping - Google Patents
A method of preparing the three-dimensional porous carbon nanosheet ball of N doping Download PDFInfo
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- CN109081328A CN109081328A CN201811047079.8A CN201811047079A CN109081328A CN 109081328 A CN109081328 A CN 109081328A CN 201811047079 A CN201811047079 A CN 201811047079A CN 109081328 A CN109081328 A CN 109081328A
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- nacl
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- porous carbon
- doping
- presoma
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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
- C01B32/15—Nano-sized carbon materials
Abstract
The present invention relates to a kind of methods for preparing the three-dimensional porous carbon nanosheet ball of N doping, comprising: prepares presoma: selecting iron chloride (FeCl3), ammonium citrate (C6H5O7(NH4)3), sodium chloride (NaCl) and ammonium acetate (CH3COONH4) it is then in deionized water by the above material mixed dissolution raw material obtains uniform solution, then balling-up by spraying, so that presoma be made；Prepare porous carbon nanosheet ball: presoma being warming up to 700-800 DEG C under an argon atmosphere, keeps the temperature 2h, after be cooled to room temperature, obtain the calcined product containing a small amount of Fe；Cleaning removes NaCl and obtains Fe@N-3DCNSB, adds the HCl of 1mol/L, is stirred to react 6h at 50 DEG C, the three-dimensional porous carbon nanosheet ball of N doping can be obtained.
Description
Technical field
The present invention relates to it is a kind of can the cheap volume production method for preparing the three-dimensional porous carbon nanosheet ball of N doping, belong to a nanometer material
Expect preparation technical field.
Background technique
The three-dimensional porous carbon nanosheet ball of N doping has excellent physicochemical property, such as: it is big specific surface area, high
Mechanical strength, excellent electric conductivity and thermal conductivity etc., thus it can be applied in numerous areas, especially in electrochemical field,
Pore structure abundant and make the porous carbon nanosheet ball that can be applied to high-performance electric with the nitrogen-atoms adulterated in carbon nanosheet
Pole material, for example: sodium-ion battery positive and negative pole material, electrochemical capacitance, lithium-sulfur cell and fuel cell etc..
Currently, hydro-thermal, solvent heat combination mould plate technique are to prepare the common method of porous spherical carbonaceous.But hydro-thermal and molten
Agent thermal mould plate technique production cost is higher, and process is complex, and yield is lower, and unsuitable heavy industrialization prepares porous
Carbon nanosheet ball.These all seriously limit it in the practical application of electrochemical field.So the preparation of high-volume and high-purity
The three-dimensional porous carbon nanosheet ball of N doping is still the problem to be solved such as one.
Summary of the invention
In view of the deficiencies of the prior art, the technical issues of present invention intends to solve is to provide one kind and simply prepares N doping three
The method for tieing up porous carbon nanosheet ball；This method process is simple, low in cost, controllability is good, obtained porous carbon nanosheet ball
Pattern uniformity, yield are big, are suitble to large-scale industrial production.The present invention solve above-mentioned technical problem technical solution be,
A method of the three-dimensional porous carbon nanosheet ball of N doping is prepared, using following technique:
1) presoma is prepared
According to Fe3+:C:Na+The ratio between amount of substance be 1.116-20:22-27:90-110 relationship, select iron chloride
(FeCl3), ammonium citrate (C6H5O7(NH4)3), sodium chloride (NaCl) and ammonium acetate (CH3COONH4) be raw material, then will more than
Material mixed dissolution in deionized water, obtains uniform solution, then balling-up by spraying, so that presoma be made, is denoted as FeCl3@
C6H5O7(NH4)3@CH3COONH4@NaCl)；
2) porous carbon nanosheet ball is prepared
Presoma made from step 1 is warming up to 700-800 DEG C under an argon atmosphere, keeps the temperature 2h, after be cooled to room temperature, obtain
To the calcined product for containing a small amount of Fe, it is denoted as Fe@N-3DCNSB@NaCl；By the cleaned removing NaCl of Fe@N-3DCNSB@NaCl
Fe@N-3DCNSB is obtained, the HCl of 1mol/L is added, is stirred to react 6h at 50 DEG C, the three-dimensional porous of N doping can be obtained
Carbon nanosheet ball (is denoted as N-3DPCNSB).
Compared with prior art, the method for the present invention has the advantage that (1) using NaCl (recyclable to recycle) as mould
Plate uses cheap FeCl3、C6H5O7(NH4)3And CH3COONH4As raw material, cost is greatly saved；(2) more prepared by
Hole carbon nanosheet ball purity is high, yield is big, favorable repeatability, and preparation process and equipment are simple, is easy to the following large-scale industry
Change practical application.
Detailed description of the invention
Fig. 1 is presoma FeCl prepared by the present invention3@C6H5O7(NH4)3@CH3COONH4The SEM image of@NaCl；
Fig. 2 is the SEM image of the calcined product Fe@N-3DCNSB@NaCl containing a small amount of Fe prepared by the present invention；
The SEM image that Fig. 3 is the Fe@N-3DCNSB after washing removes NaCl prepared by the present invention；
Fig. 4 is the SEM image of the N-3DPCNSB obtained after overpickling prepared by the present invention；
Fig. 5 is the TEM image of the N-3DPCNSB obtained after overpickling prepared by the present invention；
Fig. 6 is the TEM image that the N-3DPCNSB obtained after overpickling prepared by the present invention is further amplified.
The present invention does not address place and is suitable for the prior art.
Specific embodiment
The specific embodiment of preparation method of the present invention is given below.Preparation that these embodiments are only used for that the present invention will be described in detail
Method is not intended to limit the protection scope of the claim of this application.
Embodiment 1
According to Fe3+:C:Na+The ratio between amount of substance be 1.18:25:100 relationship, by the FeCl of 0.548g3, 2.9g's
C6H5O7(NH4)3, the CH of 1.2g3COONH4It is dissolved in 115mL deionized water with the NaCl of 16.5g, 6h is stirred at room temperature to guarantee
C6H5O7(NH4)3It is sufficiently complexed with metal salt.Gained uniform solution is spray-dried by spray dryer.In this process
In, by burden CH3COONH4、C6H5O7(NH4)3And FeCl3NaCl be self-assembly of georama, the size of ball is at just
State distribution.Since at high temperature, the water of droplet surface volatilizees rapidly, the water of drop internal carries NaCl and migrates to surface,
It is caused to be self-assembly of georama presoma FeCl in the extremely short time3@C6H5O7(NH4)3@CH3COONH4@NaCl, wherein
CH3COONH4Play the role of being complexed and stablize NaCl, is conducive to NaCl and is self-assembled into hollow sphere.Presoma is placed in tube furnace
In, lead to argon gas first to exclude air, be then warming up to 750 DEG C with 8 DEG C/min, keep the temperature 2h, after be cooled to room temperature, obtain calcining and produce
Object Fe@[email protected] is washed with deionized three times, drying obtains sample F [email protected] will be on 0.15g
Tell that sample is put into the dilute HCl of 1mol/L that 70mL in beaker and is added, be stirred to react 6h or more at 50 DEG C, then to product spend from
Three times, drying obtains final products to sub- water washing, i.e., the uniform porous carbon nanosheet ball N-3DPCNSB of N doping.
Embodiment 2
According to Fe3+:C:Na+The ratio between amount of substance be 1.14:24:100 relationship, by the FeCl of 0.552g3, 2.9g's
C6H5O7(NH4)3, the CH of 1.31g3COONH4It is dissolved in 115mL deionized water with the NaCl of 18g, 6h is stirred at room temperature to guarantee
C6H5O7(NH4)3It is sufficiently complexed with metal salt.Gained uniform solution is spray-dried by spray dryer.In this process
In, by burden CH3COONH4、C6H5O7(NH4)3And FeCl3NaCl be self-assembly of georama, the size of ball is at just
State distribution.Since at high temperature, the water of droplet surface volatilizees rapidly, the water of drop internal carries NaCl and migrates to surface,
It is caused to be self-assembly of georama presoma FeCl in the extremely short time3@C6H5O7(NH4)3@CH3COONH4@NaCl, wherein
CH3COONH4Play the role of being complexed and stablize NaCl, is conducive to NaCl and is self-assembled into hollow sphere.Presoma is placed in tube furnace
In, lead to argon gas first to exclude air, be then warming up to 750 DEG C with 6 DEG C/min, keep the temperature 2h, after be cooled to room temperature, obtain calcining and produce
Object Fe@[email protected] is washed with deionized three times, drying obtains sample F [email protected] will be on 0.15g
It tells that sample is put into the dilute HCl of 0.5mol/L that 140mL in beaker and is added, 9h or more is stirred to react at 50 DEG C, then use product
Deionized water is washed three times, and drying obtains final products, i.e., the uniform porous carbon nanosheet ball N-3DPCNSB of N doping.
Embodiment 3
According to Fe3+:C:Na+The ratio between amount of substance be 1:21:100 relationship, by the FeCl of 0.554g3, the C of 2.9g6H5O7
(NH4)3, the CH of 1.45g3COONH4It is dissolved in 115mL deionized water with the NaCl of 20g, 6h is stirred at room temperature to guarantee C6H5O7
(NH4)3It is sufficiently complexed with metal salt.Gained uniform solution is spray-dried by spray dryer.In the process, quilt
Burden CH3COONH4、C6H5O7(NH4)3And FeCl3NaCl be self-assembly of georama, the size of ball is at normal state point
Cloth.Since at high temperature, the water of droplet surface volatilizees rapidly, the water of drop internal carries NaCl and migrates to surface, extremely short
Time in cause it to be self-assembly of georama presoma FeCl3@C6H5O7(NH4)3@CH3COONH4@NaCl, it is therein
CH3COONH4Play the role of being complexed and stablize NaCl, is conducive to NaCl and is self-assembled into hollow sphere.Presoma is placed in tube furnace,
Lead to argon gas first to exclude air, be then warming up to 750 DEG C with 5 DEG C/min, keep the temperature 2h, after be cooled to room temperature, obtain calcined product
Fe@[email protected] is washed with deionized three times, drying obtains sample F [email protected] is appealed
Sample is put into 1mol/L dilute HCl, the room temperature sonic oscillation 1h or more that 70mL in beaker and is added, then product is washed with deionized water
It washs three times, drying obtains final products, i.e., the uniform porous carbon nanosheet ball N-3DPCNSB of N doping.
Claims (1)
1. a kind of method for preparing the three-dimensional porous carbon nanosheet ball of N doping, using following technique:
1) presoma is prepared
According to Fe3+:C:Na+The ratio between amount of substance be 1.116-20:22-27:90-110 relationship, select iron chloride (FeCl3)、
Ammonium citrate (C6H5O7(NH4)3), sodium chloride (NaCl) and ammonium acetate (CH3COONH4) it is raw material, then the above material is mixed
Dissolution in deionized water, obtains uniform solution, then balling-up by spraying, so that presoma be made, is denoted as FeCl3@C6H5O7(NH4)3@
CH3COONH4@NaCl)。
2) porous carbon nanosheet ball is prepared
Presoma made from step 1 is warming up to 700-800 DEG C under an argon atmosphere, keeps the temperature 2h, after be cooled to room temperature, contained
There is the calcined product of a small amount of Fe, is denoted as Fe@N-3DCNSB@NaCl；The cleaned removing NaCl of Fe@N-3DCNSB@NaCl is obtained
Fe@N-3DCNSB, adds the HCl of 1mol/L, is stirred to react 6h at 50 DEG C, and the three-dimensional porous carbon that N doping can be obtained is received
Rice piece ball (being denoted as N-3DPCNSB).
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Cited By (4)
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| CN109817932A (en) * | 2019-01-29 | 2019-05-28 | 西安航空学院 | One-step method prepares N- and adulterates porous carbon coating SnO2-Co3O4The method and its application of composite material |
| CN110127662A (en) * | 2019-05-26 | 2019-08-16 | 天津大学 | A method of assist charing Small molecule organic solvents to prepare porous charcoal using alkali metal |
| CN110739449A (en) * | 2019-09-26 | 2020-01-31 | 天津大学 | Preparation of Embedded FeS2Method for preparing three-dimensional microspheres surrounded by nitrogen/sulfur co-doped carbon nanosheets of nanoparticles |
| CN110767885A (en) * | 2019-09-26 | 2020-02-07 | 天津大学 | Preparation of Embedded Sb @ Sb2O3Method for forming three-dimensional microspheres surrounded by nitrogen-doped carbon nanosheets of core-shell structure nanoparticles |
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| CN109817932A (en) * | 2019-01-29 | 2019-05-28 | 西安航空学院 | One-step method prepares N- and adulterates porous carbon coating SnO2-Co3O4The method and its application of composite material |
| CN110127662A (en) * | 2019-05-26 | 2019-08-16 | 天津大学 | A method of assist charing Small molecule organic solvents to prepare porous charcoal using alkali metal |
| CN110127662B (en) * | 2019-05-26 | 2022-02-01 | 天津大学 | Method for preparing porous carbon by using alkali metal-assisted carbonization small-molecule organic solvent |
| CN110739449A (en) * | 2019-09-26 | 2020-01-31 | 天津大学 | Preparation of Embedded FeS2Method for preparing three-dimensional microspheres surrounded by nitrogen/sulfur co-doped carbon nanosheets of nanoparticles |
| CN110767885A (en) * | 2019-09-26 | 2020-02-07 | 天津大学 | Preparation of Embedded Sb @ Sb2O3Method for forming three-dimensional microspheres surrounded by nitrogen-doped carbon nanosheets of core-shell structure nanoparticles |
| CN110767885B (en) * | 2019-09-26 | 2022-07-08 | 天津大学 | Preparation of Embedded Sb @ Sb2O3Method for forming three-dimensional microspheres surrounded by nitrogen-doped carbon nanosheets of core-shell structure nanoparticles |
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