CN113493196B - Boron-nitrogen co-doped porous carbon material and preparation method and application thereof - Google Patents
Boron-nitrogen co-doped porous carbon material and preparation method and application thereof Download PDFInfo
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 79
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- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000004327 boric acid Substances 0.000 claims abstract description 21
- 239000011259 mixed solution Substances 0.000 claims abstract description 19
- 238000000227 grinding Methods 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 14
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- 238000000034 method Methods 0.000 abstract description 26
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 15
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 19
- 238000003763 carbonization Methods 0.000 description 12
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- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 239000003990 capacitor Substances 0.000 description 9
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- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 7
- 229910052796 boron Inorganic materials 0.000 description 7
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
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- 239000003792 electrolyte Substances 0.000 description 4
- 238000012876 topography Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
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- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
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- 230000000694 effects Effects 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
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- 238000010521 absorption reaction Methods 0.000 description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
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- 238000005554 pickling Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- 229960001763 zinc sulfate Drugs 0.000 description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 description 2
- COIQUVGFTILYGA-UHFFFAOYSA-N (4-hydroxyphenyl)boronic acid Chemical compound OB(O)C1=CC=C(O)C=C1 COIQUVGFTILYGA-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- RRQBXRCWHNKYJY-UHFFFAOYSA-N OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.O.O.O.O Chemical compound OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N.O.O.O.O RRQBXRCWHNKYJY-UHFFFAOYSA-N 0.000 description 1
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- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
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- 239000000843 powder Substances 0.000 description 1
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- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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Abstract
The invention provides a boron-nitrogen co-doped porous carbon material and a preparation method and application thereof, wherein the preparation method of the porous material comprises the following steps: adding boric acid into organic amine, and mixing to obtain a mixed solution; and carbonizing the mixed solution in an inert atmosphere to obtain the boron-nitrogen co-doped porous carbon material. The preparation method breaks through the limitation that the organic amine is volatile and can not be directly pyrolyzed to prepare carbon, and the organic amine is stabilized by the Lewis acid-base interaction between the organic amine and boric acid so as to be directly converted into carbon in the pyrolyzing process; according to the method, boric acid and organic amine are fully mixed by a liquid phase dissolving method, the defect that solid phase grinding is difficult to uniformly disperse is overcome, the appearance and the structure of a product are more uniform, and large-scale production is facilitated.
Description
Technical Field
The invention relates to the technical field of carbon materials, in particular to a boron-nitrogen co-doped porous carbon material and a preparation method and application thereof.
Background
Carbon materials have been widely used in many fields such as conductive materials, refractory materials, corrosion-resistant materials, wear-resistant lubricating materials, and casting and molding materials because of their excellent physicochemical properties. The porous carbon has a pore channel structure with uniform distribution, so that the specific surface area of the carbon material is greatly improved, and the porous carbon has wide application in the fields of catalysis, adsorption and electrochemistry. In order to further improve the performance of the porous carbon, elements such as N, B and the like are doped into carbon in an atom doping mode, so that the internal electronic structure of the carbon material can be effectively improved, the surface reaction activity is improved, and the application field of the carbon material is further widened. Therefore, the preparation of nitrogen and boron codoped porous carbon draws great attention.
The prior art discloses a preparation method of a boron-nitrogen co-doped carbon material, which comprises the following steps: adding cyanamide into a p-hydroxyphenylboronic acid solution, and performing freeze drying to obtain white precursor powder; carbonizing the mixture in a tubular furnace to obtain a boron-nitrogen co-doped carbon material; the prior art also discloses a method for preparing a boron-nitrogen co-doped biomass carbon material by a hydrothermal method, which takes fir bark as a raw material, wherein boron and nitrogen are derived from ammonium pentaborate tetrahydrate, boron-nitrogen heteroatoms are doped by a microwave hydrothermal auxiliary method, and then porous carbon is obtained by a high-temperature carbonization method.
However, the preparation method of the boron-nitrogen co-doped carbon material is complicated in process, low in doping amount and small in specific surface area of the prepared carbon material. Based on the technical defects existing in the current preparation of boron-nitrogen co-doped carbon materials, improvement on the technical defects is needed.
Disclosure of Invention
In view of the above, the invention provides a boron-nitrogen co-doped porous carbon material, and a preparation method and an application thereof, so as to solve or partially solve technical problems in the prior art.
In a first aspect, the invention provides a preparation method of a boron-nitrogen co-doped porous carbon material, which comprises the following steps:
adding boric acid into organic amine, stirring and mixing to obtain a mixed solution;
and carbonizing the mixed solution in an inert atmosphere to obtain the boron-nitrogen co-doped porous carbon material.
Preferably, in the preparation method of the boron-nitrogen co-doped porous carbon material, the organic amine includes one or more of ethanolamine, ethylenediamine, triethylamine, aniline and the like.
Preferably, the preparation method of the boron-nitrogen co-doped porous carbon material has the carbonization temperature of 500-900 ℃ and the carbonization time of 1-2 h.
Preferably, in the preparation method of the boron-nitrogen co-doped porous carbon material, the mass volume ratio of the boric acid to the organic amine is (4-10) g (10-15) ml.
Preferably, the preparation method of the boron-nitrogen co-doped porous carbon material comprises the steps of carbonizing the mixed solution in an inert atmosphere, and then grinding, pickling, washing and drying the carbide obtained after carbonization.
Preferably, in the preparation method of the boron-nitrogen co-doped porous carbon material, the acid used for acid washing is 1-2 mol/L sulfuric acid solution, and the acid washing time is 3-5 hours.
Preferably, the preparation method of the boron-nitrogen co-doped porous carbon material comprises the steps of adding boric acid into organic amine, and stirring at 20-25 ℃ for 20-24 hours to obtain a mixed solution.
Preferably, in the preparation method of the boron-nitrogen co-doped porous carbon material, the temperature is raised to 500-900 ℃ at a speed of 4-6 ℃/min during carbonization.
In a second aspect, the invention also provides a boron-nitrogen co-doped porous carbon material prepared by the preparation method.
In a third aspect, the invention also provides application of the boron-nitrogen co-doped porous carbon material as a battery electrode material, a hydrogen storage material, an adsorption material and a catalytic material.
Compared with the prior art, the boron-nitrogen co-doped porous carbon material has the following beneficial effects:
(1) According to the preparation method of the boron-nitrogen co-doped porous carbon material, the limitation that organic amine is volatile and can not be directly pyrolyzed to prepare carbon is broken through, and the organic amine is stabilized through the Lewis acid-base interaction between the organic amine and boric acid so that the organic amine is directly converted into carbon in the pyrolyzing process; according to the method, the boric acid and the organic amine are fully mixed by a liquid phase dissolving method, so that the defect that solid phase grinding is difficult to uniformly disperse is avoided, the appearance and the structure of the product are more uniform, and the method is favorable for large-scale production; boric acid is used as a boron source, and boric acid is pyrolyzed to become boron oxide which can be used as a template, so that the specific surface area of the carbon material is greatly increased, a product is directly obtained by a one-step carbonization method, the process is simple, and large-scale industrial production is facilitated; compared with the preparation methods such as a hydrothermal method, a template method, a carbonization-activation two-step method and the like, the preparation method has the advantages of simple experimental process, low cost, easiness in operation control and good process repeatability, the prepared porous carbon material has good appearance, the material is doped with boron atoms and nitrogen atoms, the internal electronic structure of the carbon material can be effectively improved, the surface activity is improved, and the material has very wide prospects in the fields of battery electrode materials, hydrogen storage materials, adsorption, catalysis and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. It is obvious that the drawings in the following description are only some embodiments of the invention, and that for a person skilled in the art, other drawings can be derived from them without inventive effort.
Fig. 1 is an XRD pattern of the boron-nitrogen co-doped porous carbon material prepared in example 1 of the present invention;
fig. 2 is a surface topography diagram of the boron-nitrogen co-doped porous carbon material prepared in embodiment 1 of the present invention;
fig. 3 is an XPS spectrum of the boron-nitrogen co-doped porous carbon material prepared in example 1 of the present invention;
fig. 4 is a nitrogen adsorption and desorption graph of the boron-nitrogen co-doped porous carbon material prepared in embodiment 1 of the present invention;
fig. 5 is a charge-discharge curve diagram of a zinc ion hybrid capacitor assembled by using the boron-nitrogen co-doped porous carbon material prepared in example 1 as a cathode;
fig. 6 is an XRD pattern of the boron-nitrogen co-doped porous carbon material prepared in example 2 of the present invention;
fig. 7 is a surface topography of the boron-nitrogen co-doped porous carbon material prepared in embodiment 2 of the present invention;
fig. 8 is an XPS spectrum of the boron-nitrogen co-doped porous carbon material prepared in example 2 of the present invention;
fig. 9 is a nitrogen gas adsorption and desorption graph of the boron-nitrogen co-doped porous carbon material prepared in embodiment 2 of the present invention;
fig. 10 is a charge-discharge curve diagram of a zinc ion hybrid capacitor assembled by using the boron-nitrogen co-doped porous carbon material prepared in example 2 as a cathode;
Detailed Description
In the following, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The embodiment of the application provides a preparation method of a boron-nitrogen co-doped porous carbon material, which comprises the following steps:
s1, adding boric acid into organic amine, and stirring and mixing to obtain a mixed solution;
s2, carbonizing the mixed solution in an inert atmosphere to obtain the boron-nitrogen co-doped porous carbon material.
It should be noted that the inert gases used in the examples of the present application include helium, neon, argon, etc., and the carbon source and the nitrogen source are derived from organic amines (e.g., ethanolamine, ethylenediamine, triethylamine, aniline, etc.); according to the preparation method of the boron-nitrogen co-doped porous carbon material, the limitation that organic amine is volatile and can not be directly pyrolyzed to prepare carbon is broken through, and the organic amine is stabilized through the Lewis acid-base interaction between the organic amine and boric acid so that the organic amine is directly converted into carbon in the pyrolyzing process; according to the method, boric acid and organic amine are fully mixed by a liquid phase dissolving method, so that the defect that solid phase grinding is difficult to uniformly disperse is avoided, the appearance and the structure of a product are more uniform, and large-scale production is facilitated; boric acid is used as a boron source, and boric acid is pyrolyzed and changed into boron oxide which can be used as a template, so that the specific surface area of the carbon material is greatly increased, a product is directly obtained by a one-step carbonization method, the process is simple, and large-scale industrial production is facilitated; compared with preparation methods such as a hydrothermal method, a template method and a carbonization-activation two-step method, the preparation method has the advantages of simple experimental process, low cost, easiness in operation control and good process repeatability, the prepared porous carbon material has good appearance, the material is doped with boron atoms and nitrogen atoms, the internal electronic structure of the carbon material can be effectively improved, the surface activity is improved, and the material has a very wide prospect in the fields of battery electrode materials, hydrogen storage materials, adsorption, catalysis and the like.
In some embodiments, the organic amine comprises one or more of ethanolamine, ethylenediamine, triethylamine, aniline, and the like.
In some embodiments, the carbonization temperature is 500 to 900 ℃ and the carbonization time is 1 to 2 hours.
In some embodiments, the mass to volume ratio of boric acid to the organic amine is (4 to 10) g (10 to 15) ml.
In some embodiments, carbonizing the mixed solution under an inert atmosphere further comprises grinding, pickling, washing with water, and drying the carbide obtained after carbonization.
In some embodiments, the acid used for acid washing is 1 to 2mol/L sulfuric acid solution, and the acid washing time is 3 to 5 hours. In the examples of the present application, soluble impurities can be dissolved by washing with an acidic solution, and in practice, a sulfuric acid solution, a nitric acid solution, a hydrochloric acid solution, an acetic acid solution, or the like can be used.
In some embodiments, the boric acid is added to the organic amine and stirred for 20-24 hours at 20-25 ℃ to obtain a mixed solution.
In some embodiments, the temperature is increased to 500-900 ℃ at 4-6 ℃/min during carbonization. In the embodiment of the application, the temperature is raised to 500-900 ℃ at the rate of 4-6 ℃/min, and after carbonization is carried out for 1-2 h, the porous carbon material is obtained after cooling in a natural state.
Based on the same inventive concept, the invention also provides a boron-nitrogen co-doped porous carbon material prepared by the preparation method.
Based on the same inventive concept, the invention also provides application of the boron-nitrogen co-doped porous carbon material as a battery electrode material, a hydrogen storage material, an adsorption material and a catalytic material.
The following further describes a preparation method of the boron-nitrogen co-doped porous carbon material according to the present application with specific examples.
Example 1
A preparation method of a boron-nitrogen co-doped porous carbon material comprises the following steps:
s1, adding 8g of boric acid into 12ml of ethanolamine, and stirring for 14 hours at 25 ℃ to obtain a mixed solution;
s2, placing the mixed solution in a tube furnace, heating the mixed solution to 800 ℃ from room temperature at a heating rate of 5 ℃/min under the protection of helium, preserving heat for 1h, cooling to room temperature, and taking out to obtain carbide;
and S3, grinding the carbide, adding the ground carbide into a 1mol/L sulfuric acid solution, stirring for 5 hours, washing with deionized water, filtering, and drying to obtain the boron-nitrogen co-doped porous carbon material.
Example 2
A preparation method of a boron-nitrogen co-doped porous carbon material comprises the following steps:
s1, adding 8g of boric acid into 12ml of ethylenediamine, and stirring for 14 hours at 25 ℃ to obtain a mixed solution;
s2, placing the mixed solution in a tube furnace, heating the mixed solution from room temperature to 800 ℃ at a heating rate of 5 ℃/min under the protection of helium, preserving heat for 1h, cooling to room temperature, and taking out to obtain carbide;
and S3, grinding the carbide, adding the ground carbide into a 1mol/L sulfuric acid solution, stirring for 5 hours, washing with deionized water, filtering, and drying to obtain the boron-nitrogen co-doped porous carbon material.
Performance test
The XRD pattern of the boron-nitrogen co-doped porous carbon material prepared in example 1 was tested, and the result is shown in fig. 1. It can be seen from fig. 1 that the prepared boron-nitrogen co-doped porous carbon material is an amorphous carbon material.
The surface topography of the boron-nitrogen co-doped porous carbon material prepared in example 1 was tested, and the results are shown in fig. 2. From fig. 2, it can be seen that the prepared boron-nitrogen co-doped porous carbon material presents a porous morphology similar to a foam board.
The XPS spectrum of the boron-nitrogen co-doped porous carbon material prepared in example 1 was tested, and the result is shown in fig. 3. It can be seen from fig. 3 that a large amount of nitrogen and boron elements are doped into the carbon lattice.
The boron-nitrogen co-doped porous carbon material prepared in example 1 was tested for a nitrogen adsorption/desorption curve, and the results are shown in fig. 4. Wherein, the nitrogen absorption and desorption curve is tested according to the national standard GB/T19587-2004 'determination of solid matter specific surface area by gas absorption BET method'.
From fig. 4, it can be seen that the prepared boron-nitrogen co-doped porous carbon material contains a large amount of mesopores, and the function of boric acid in forming boron oxide after pyrolysis as a template is verified.
The boron-nitrogen co-doped porous carbon material prepared in the example 1 is used as a cathode to assemble a zinc ion hybrid capacitor; the capacitor comprises a positive electrode, electrolyte, a negative electrode and a diaphragm; the carbon material, a binder and conductive carbon black are mixed according to the mass ratio of 8:1:1 is coated on a current collector to form a positive electrode, a zinc sheet or a zinc foil is used as a negative electrode, a zinc sulfate solution with the concentration of 2mol/L is used as an electrolyte, and filter paper is used as a diaphragm. The charge and discharge curves were measured, and the results are shown in FIG. 5. As can be seen from FIG. 5, the maximum specific capacity of the zinc ion hybrid capacitor can reach 96mAh/g.
The XRD pattern of the boron-nitrogen co-doped porous carbon material prepared in example 2 was tested, and the result is shown in fig. 6. It can be seen from fig. 6 that the prepared boron-nitrogen co-doped porous carbon material is an amorphous carbon material.
The surface topography of the boron-nitrogen co-doped porous carbon material prepared in example 2 was tested, and the results are shown in fig. 7. From fig. 7, it can be seen that the prepared boron-nitrogen co-doped porous carbon material presents a porous morphology similar to a foam board.
The XPS spectrum of the boron-nitrogen co-doped porous carbon material prepared in example 2 was tested, and the result is shown in fig. 8. It can be seen from fig. 8 that a large amount of nitrogen and boron elements are doped into the carbon lattice.
The boron-nitrogen co-doped porous carbon material prepared in example 2 was tested for nitrogen adsorption and desorption curves, and the results are shown in fig. 9. It can be seen from fig. 9 that the prepared boron-nitrogen co-doped porous carbon material contains a large number of mesopores.
The boron-nitrogen co-doped porous carbon material prepared in example 2 was used as a cathode to assemble a zinc ion hybrid capacitor, and the charge-discharge curve of the zinc ion hybrid capacitor was tested, and the result is shown in fig. 10. The capacitor comprises a positive electrode, electrolyte, a negative electrode and a diaphragm; the carbon material, a binder and conductive carbon black are mixed according to the mass ratio of 8:1:1 is coated on a current collector to form a positive electrode, a zinc sheet or a zinc foil is used as a negative electrode, a zinc sulfate solution with the concentration of 2mol/L is used as an electrolyte, and filter paper is used as a diaphragm. As can be seen from FIG. 10, the maximum specific capacity of the zinc ion hybrid capacitor can reach 87mAh/g.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (3)
1. The preparation method of the boron-nitrogen co-doped porous carbon material is characterized by comprising the following steps of:
adding 8g of boric acid into 12ml of ethanolamine or 12ml of ethylenediamine, and stirring for 14 hours at 25 ℃ to obtain a mixed solution;
placing the mixed solution in a tube furnace, heating the mixed solution to 800 ℃ from room temperature at a heating rate of 5 ℃/min under the protection of helium, preserving heat for 1h, cooling to room temperature, and taking out to obtain carbide;
and grinding the carbide, adding the ground carbide into 1mol/L sulfuric acid solution, stirring for 5 hours, washing by using deionized water, carrying out suction filtration, and drying to obtain the boron-nitrogen co-doped porous carbon material.
2. A boron-nitrogen co-doped porous carbon material, which is prepared by the preparation method of claim 1.
3. The boron-nitrogen co-doped porous carbon material of claim 2 is applied as a battery electrode material, a hydrogen storage material, an adsorption material and a catalytic material.
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