CN111977633A - Method for preparing phosphorus/oxygen-doped nano porous carbon material by microwave method - Google Patents
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- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 45
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000011574 phosphorus Substances 0.000 title claims abstract description 44
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 35
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 27
- 239000001301 oxygen Substances 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 21
- 238000005406 washing Methods 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 15
- 239000012535 impurity Substances 0.000 claims abstract description 14
- 239000002270 dispersing agent Substances 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 230000002745 absorbent Effects 0.000 claims abstract description 6
- 239000002250 absorbent Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000002253 acid Substances 0.000 claims abstract description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 40
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical group OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims description 34
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims description 34
- 239000000467 phytic acid Substances 0.000 claims description 34
- 235000002949 phytic acid Nutrition 0.000 claims description 34
- 229940068041 phytic acid Drugs 0.000 claims description 34
- 239000001508 potassium citrate Substances 0.000 claims description 25
- 229960002635 potassium citrate Drugs 0.000 claims description 25
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical group [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 claims description 25
- 235000011082 potassium citrates Nutrition 0.000 claims description 25
- 230000035484 reaction time Effects 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 23
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 20
- 238000010438 heat treatment Methods 0.000 description 19
- 235000019441 ethanol Nutrition 0.000 description 17
- 239000000463 material Substances 0.000 description 13
- 239000010453 quartz Substances 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 10
- 239000007772 electrode material Substances 0.000 description 9
- 239000011148 porous material Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000003990 capacitor Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- SQUHHTBVTRBESD-UHFFFAOYSA-N Hexa-Ac-myo-Inositol Natural products CC(=O)OC1C(OC(C)=O)C(OC(C)=O)C(OC(C)=O)C(OC(C)=O)C1OC(C)=O SQUHHTBVTRBESD-UHFFFAOYSA-N 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- CDAISMWEOUEBRE-GPIVLXJGSA-N inositol Chemical compound O[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@H](O)[C@@H]1O CDAISMWEOUEBRE-GPIVLXJGSA-N 0.000 description 3
- 229960000367 inositol Drugs 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- CDAISMWEOUEBRE-UHFFFAOYSA-N scyllo-inosotol Natural products OC1C(O)C(O)C(O)C(O)C1O CDAISMWEOUEBRE-UHFFFAOYSA-N 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 229960004756 ethanol Drugs 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000008859 change Effects 0.000 description 1
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- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
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- 238000009792 diffusion process Methods 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229960003975 potassium Drugs 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
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- 238000001179 sorption measurement Methods 0.000 description 1
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- 230000007847 structural defect Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
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- 230000002123 temporal effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a method for preparing a phosphorus/oxygen doped nano porous carbon material by a microwave method, which comprises the following steps of (1) uniformly mixing a carbon source, a phosphorus source and a microwave absorbent according to different proportions to obtain a mixture; (2) and placing the dispersing agent and the mixture in a microwave reactor, carrying out microwave reaction in the air atmosphere, after the product is naturally cooled, carrying out acid washing and water washing on the product to remove impurities, and drying to obtain the phosphorus/oxygen doped nano porous carbon material. The product has stable physical and chemical properties, and has high specific surface area and specific capacitance.
Description
Technical Field
The invention relates to a preparation method of a nano material, in particular to a method for preparing a phosphorus/oxygen doped nano porous carbon material by a microwave method.
Background
With the excessive consumption and exhaustion of fossil fuels, the energy demand is more and more urgent, the energy crisis problem is solved to a great extent by the appearance of novel renewable energy sources such as solar energy, wind energy, hydroenergy, nuclear energy and the like, energy obtained by new energy sources is mainly stored and utilized in the form of electric energy at present, and new challenges are provided for energy storage equipment and devices. Super capacitors are an important energy storage device, and are different from conventional capacitors and combine the advantages of conventional capacitors and rechargeable batteries, including high power density, high energy density, rapid charge and discharge, long cycle time and high stability, thereby attracting interest and being widely applied to electronic devices, smart grids or hybrid and electric vehicles.
In general, high ion transport rate and achievable specific surface area, high conductivity and high electrochemical stability are required for high-performance supercapacitor electrodes, and various efforts have been made to prepare electrode materials having excellent performance and determining the performance of supercapacitors. The carbon material has the characteristics of high conductivity, large specific surface area, low cost, excellent cycling stability, environmental friendliness and the like, and plays a key role in the electrode material of the supercapacitor. The pore structure and distribution of porous carbon play a key role in the electrochemical performance of the porous carbon, the hierarchical porous carbon has great attraction to energy storage, the mesopores and the macropores are favorable for the rapid diffusion of electrolyte, and the micropores provide higher specific surface area, so the pore diameter is accurately controlled, the pore structure is optimized, and the surface of a carbon electrode can be close to electrolyte ions to obtain better electrochemical performance. Most carbon materials have high power density and excellent stability as supercapacitor electrodes, and the specific capacitance and energy density are insufficient to meet the requirements of practical application. Therefore, development of an electrode material for a supercapacitor excellent in performance has become a common expectation. Researches show that the introduction of heteroatoms such as B, N, P, S can increase the pseudocapacitance of the carbon material and improve the surface wettability and the conductivity of the material so that the good cycle performance of the material is kept. These heteroatoms can serve the dual function of increasing the carbon material capacitance and improving electron transport, thereby providing greater electrical conductivity. Doping can not only improve the conductivity of the carbon skeleton, but also introduce additional pseudo capacitance for the super capacitor. Phosphorus doping can improve the wettability and electrochemical stability of carbon, so that the electrode has excellent rate performance and cycle performance, phosphorus atoms have larger atomic radius and lower electronegativity than carbon atoms, structural defects and charge density of carbon in the phosphorus-doped carbon material can be changed, and structural distortion and charge density change are expected to improve the capacitance performance.
However, current strategies for making porous carbons typically include soft/hard moldsPlates, chemical/physical activation or organic reactions, etc., which are a complex and time-consuming task and are often accompanied by complex disassembly procedures, and thus are difficult to achieve on a large scale. Although activators such as KOH, ZnCl may be utilized2Or phosphoric acid and the like and carbon are subjected to chemical reaction at high temperature to obtain high porosity and large surface area, but the treatment process is complicated, and carbonization is carried out for 1-4h at high temperature (600-1000 ℃) under the protection of inert atmosphere, which is a necessary condition for preparing porous carbon by using various raw materials, the process has low energy utilization rate and is difficult to bear, the necessary protection of inert gas makes the manufacturing condition harsh, the manufacturing process usually has high energy consumption and partial yield, secondary pollution can be generated due to low post-treatment, and the process is not beneficial to energy conservation and environmental protection. However, due to the advantages of time and energy saving, fast temperature rise, environmental friendliness, uniform heating and the like, microwave penetrates through a sample, energy is converted by dipole rotation and ion conduction, and the energy is transmitted outwards to cause a temperature gradient from the inside to the outside of particles, so that rapid temperature rise is realized in a short time. Therefore, it has become a very popular and useful technique in chemical synthesis due to its advantages in terms of rapid, uniform volume heating and sharp contraction of synthesis time. In addition, its significant advantages in heating and reaction time over other processes have facilitated its use in chemical reactions and inorganic material synthesis.
At present, a microwave reaction method is a novel heating method, has the advantages of high temperature rise rate, high reaction degree, energy conservation, environmental protection and the like, and is tried to be researched by researchers due to the nano carbon material. The graphene oxide is reduced by adopting microwave solid phase heating, so that breakthrough progress is achieved, and graphene prepared by a Voiry research group by adopting a method of combining preheating treatment of a household microwave oven with microwave reduction (published in Science, 2016, 353 and 1413) has high carbon group content and few surface defects. Microwave heating results in a rapid increase in temperature, facilitating rapid removal of oxygen-containing groups on a time scale that is too short to compromise the stability of the sheet. However, in the pretreatment step, a long-time conventional heating method is required to pre-reduce the graphene oxide, so that the pretreatment step is shortened to improve the production efficiency of the microwave solid-phase heating process, and further research is still required.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a method for preparing a phosphorus/oxygen doped nano porous carbon material by a microwave method, which has stable physicochemical properties and higher specific surface area and specific capacitance.
The technical scheme is as follows: the invention provides a method for preparing a phosphorus/oxygen doped nano porous carbon material by a microwave method, which comprises the following steps:
(1) uniformly mixing a carbon source, a phosphorus source and a microwave absorbent according to different proportions to obtain a mixture;
(2) and placing the dispersing agent and the mixture in a microwave reactor, carrying out microwave reaction in the air atmosphere, after the product is naturally cooled, carrying out acid washing and water washing on the product to remove impurities, and drying to obtain the phosphorus/oxygen doped nano porous carbon material.
Further, the carbon source is potassium citrate; the phosphorus source is phytic acid; the microwave absorbent is phytic acid.
Further, the mass ratio of the potassium citrate to the phytic acid is 2: 0.5-1.25.
Further, the dispersing agent is one or more of distilled water, ethanol, methanol and isopropanol.
Further, the dispersant is ethanol.
Further, the mass ratio of the dispersing agent to the mixture is 1-3: 2.
Furthermore, the power of the microwave reaction is 400-600W.
Further, the microwave reaction time is 0.5-4 min.
In the above technical scheme:
the acid for washing the product is preferably hydrochloric acid, the concentration is preferably between 10 and 50 percent, and the optimal concentration is between 20 and 40 percent.
The drying temperature is preferably 50-100 ℃, and the optimal temperature is 50-70 ℃.
The phosphorus content of the material is preferably 0.2-1%. The oxygen content of the material is preferably 6% to 10%. The pore diameter of the material is preferably 0.1 to 2 μm. Thickness of nanosheet of materialPreferably 10nm to 100 nm. The specific surface area of the material is preferably 400m2g-1～1000m2g-1. The capacitance value of the material is preferably 200F g-1～350F g-1. The capacity retention rate of the material after 5000 cycles is preferably 90-97%.
Has the advantages that: according to the invention, potassium citrate is used as a carbon source, phytic acid is used as a phosphorus source and a microwave absorbent, the method is green and environment-friendly, the cost is low, and the obtained phosphorus/oxygen doped nano porous carbon material has stable physicochemical properties and higher specific surface area and specific capacitance. Meanwhile, no high-energy consumption equipment is arranged in the production process, so that the problems of high energy consumption and long time consumption in the production of the phosphorus/oxygen doped nano porous carbon material are solved.
Drawings
FIG. 1 is a scanning picture of potassium citrate, phytic acid and ethanol in a ratio of 2: 0.75: 2 at a microwave power of 500W for different reaction times: a: 0.5min, b: 1min, c: 2min, d: 3min, e: 4 min;
FIG. 2 is a scanning picture of phytic acid with different contents when the microwave power is 500W and the reaction time is 2 min: a: 0.5g, b: 0.75g, c: 1g, d: 1.25 g;
FIG. 3 is a scanning picture of potassium citrate, phytic acid, ethanol 2: 0.75: 2 in different microwave power for 2 min: a: 400W, b: 500W, c: 600W;
FIG. 4 shows CV curves and GCD curves of the material obtained in example B, wherein a is a curve obtained by using MP/O-PC500-0.75 at 10-100 mV s-1CV curves at different scan rates, shown as MP/O-PC500-0.75 at 1A g-1To 20A g-1GCD curve at current density; examples A-F CV curves and GCD curves were obtained for materials where the c plot is MP/O-PCs at a scan rate of 50mV s-1CV distribution of time, d is 1A g-1GCD distribution of temporal MP/O-PCs;
FIG. 5 is a graph of the results of electrochemical cycling stability tests on the MP/O-PC500-0.75 material obtained in example B.
Detailed Description
The preparation method for preparing the phosphorus/oxygen-doped nano porous carbon material by using the microwave comprises the following steps:
example A, 0.5g of phytic acid, 2g of potassium citrate and 2g of ethanol were mixed in a quartz crucible, and then placed in a microwave reactor for microwave heating with a reaction power of 500W and a reaction time of 2 min. And after the product is naturally cooled, treating the product with hydrochloric acid, washing with water to remove impurities, and drying in a 60 ℃ oven to obtain the phosphorus/oxygen doped nano porous carbon material MP/OPC 500-0.5.
Example B phytic acid 0.75g, potassium citrate 2g and ethanol 2g were mixed in a quartz crucible, and then placed in a microwave reactor for microwave heating at a reaction power of 500W for a reaction time of 2 min. And after the product is naturally cooled, treating the product with hydrochloric acid, washing with water to remove impurities, and drying in a 60 ℃ oven to obtain the phosphorus/oxygen doped nano porous carbon material MP/OPC 500-0.75.
Example C, 1g of phytic acid, 2g of potassium citrate and 2g of ethanol were mixed in a quartz crucible, and then placed in a microwave reactor for microwave heating with a reaction power of 500W and a reaction time of 2 min. And after the product is naturally cooled, treating the product with hydrochloric acid, washing with water to remove impurities, and drying in a 60 ℃ oven to obtain the phosphorus/oxygen doped nano porous carbon material MP/OPC500-1.
Example D phytic acid 1.25g, potassium citrate 2g and ethanol 2g were mixed in a quartz crucible, and then placed in a microwave reactor for microwave heating at a reaction power of 500W for a reaction time of 2 min. And after the product is naturally cooled, treating the product with hydrochloric acid, washing with water to remove impurities, and drying in a 60 ℃ oven to obtain the phosphorus/oxygen doped nano porous carbon material MP/OPC 500-1.25.
Example E phytic acid 0.75g, potassium citrate 2g and ethanol 2g were mixed in a quartz crucible, and then placed in a microwave reactor for microwave heating at a reaction power of 400W for a reaction time of 2 min. And after the product is naturally cooled, treating the product with hydrochloric acid, washing with water to remove impurities, and drying in a 60 ℃ oven to obtain the phosphorus/oxygen doped nano porous carbon material MP/OPC 400-0.75.
Example F, 0.75g of phytic acid, 2g of potassium citrate and 2g of ethanol were mixed in a quartz crucible, and then placed in a microwave reactor for microwave heating with a reaction power of 600W and a reaction time of 2 min. And after the product is naturally cooled, treating the product with hydrochloric acid, washing with water to remove impurities, and drying in a 60 ℃ oven to obtain the phosphorus/oxygen doped nano porous carbon material MP/OPC 600-0.75.
Example G, 0.75G of phytic acid, 2G of potassium citrate and 2G of ethanol were mixed in a quartz crucible, and then placed in a microwave reactor for microwave heating at a reaction power of 500W for 0.5 min. And after the product is naturally cooled, treating the product with hydrochloric acid, washing with water to remove impurities, and drying in a 60 ℃ oven to obtain the phosphorus/oxygen doped nano porous carbon material.
Example H phytic acid 0.75g, potassium citrate 2g and ethanol 2g were mixed in a quartz crucible, and then placed in a microwave reactor for microwave heating at a reaction power of 500W for 1 min. And after the product is naturally cooled, treating the product with hydrochloric acid, washing with water to remove impurities, and drying in a 60 ℃ oven to obtain the phosphorus/oxygen doped nano porous carbon material.
In example I, 0.75g of phytic acid, 2g of potassium citrate and 2g of ethanol are mixed in a quartz crucible, and then the mixture is placed in a microwave reactor for microwave heating, wherein the reaction power is 500W, and the reaction time is 2 min. And after the product is naturally cooled, treating the product with hydrochloric acid, washing with water to remove impurities, and drying in a 60 ℃ oven to obtain the phosphorus/oxygen doped nano porous carbon material.
Example J phytic acid 0.75g, potassium citrate 2g and ethanol 2g were mixed in a quartz crucible, and then placed in a microwave reactor for microwave heating at a reaction power of 500W for 3 min. And after the product is naturally cooled, treating the product with hydrochloric acid, washing with water to remove impurities, and drying in a 60 ℃ oven to obtain the phosphorus/oxygen doped nano porous carbon material.
Example K phytic acid 0.75g, potassium citrate 2g and ethanol 2g were mixed in a quartz crucible, and then placed in a microwave reactor for microwave heating at a reaction power of 500W for 4 min. And after the product is naturally cooled, treating the product with hydrochloric acid, washing with water to remove impurities, and drying in a 60 ℃ oven to obtain the phosphorus/oxygen doped nano porous carbon material.
Fig. 1-3 are scanning electron micrographs of materials prepared in examples a-K of the present invention, from which it can be seen that the phosphorus/oxygen doped nanoporous carbon is a porous structure, and ethanol is introduced during the mixing of potassium citrate and phytic acid to promote the uniform mixing of viscous phytic acid and potassium citrate. Microwave radiation is carried out in the air atmosphere, ethanol is heated and volatilized, phytic acid and water are emulsified under the action of hydrogen bonds, more vesicles are generated, and potassium citrate is uniformly distributed in the structures and on the surface layers of the vesicles. The phytic acid continuously absorbs the microwaves to increase the temperature, and the phytic acid is heated and decomposed into inositol and phosphoric acid. Inositol molecules are self-assembled on the surface of the vesicle and are dehydrated and carbonized in molecules to form a carbon shell when the temperature of a reaction system is higher, potassium citrate on the vesicle is carbonized at high temperature to form a porous structure, potassium element in the potassium forms more micropores and mesopores by etching the carbon material, phosphoric acid is dehydrated among molecules to form pyrophosphoric acid and is dehydrated at high temperature to carry out self-assembly to form polyphosphoric acid, the phosphoric acid and derivatives thereof achieve the effect of protecting the carbon material through the inhibition effect on air, and a large number of pore structures are also formed in a series of processes of thermal polycondensation, cyclization and the like of the phosphoric acid.
The reaction mechanism is further verified through different reaction times, observation can be carried out through SEM (scanning electron microscope), observation can be carried out under microwave irradiation for 0.5min, as shown in figure 1a, a plurality of small vesicles are observed, and the vesicles are in the foaming stage of phytic acid and grow up; upon microwave irradiation for 1min, as shown in FIG. 1b, the vesicles coexisted with the porous structure, at which point the growth of the vesicles had ended. In this process, potassium citrate decomposes to form potassium salt etched vesicles, and the vesicles begin to break down to form porous structures. When microwave irradiation is carried out for 2min, as shown in figure 1c, a uniform nano porous carbon structure is formed, and the etching of the vesicles by potassium salt is finished. Phosphoric acid and its derivatives are distributed on the surface of the porous carbon to prevent excessive oxidation of the material by air at high temperatures. With the increase of the microwave radiation time, the protection effect of the phosphoric acid and the derivatives thereof on the porous carbon is gradually weakened. Upon microwave irradiation for 3min, as shown in FIG. 1d, some of the porous structure began to collapse. Upon microwave irradiation for 4min, as shown in fig. 1e, the porous structure only left some larger carbon skeleton, and the sheet-like structure and porous structure largely disappeared and became more disordered. As shown in fig. 2, we explored the effect of varying amounts of phytic acid on the porous structure. When the dosage of the phytic acid is 0.5g (figure 2a), the generated vesicles are less, and the potassium citrate is greatly aggregated in the structure and the surface of the vesicles and is disorderly distributed after carbonization. When the dosage of the phytic acid is 0.75g (figure 2b), orderly arranged porous carbon is obtained after carbonization, and the pore diameter is relatively uniform. When the amount of phytic acid is 1g (fig. 2c), phytic acid is decomposed to generate more inositol and phosphoric acid, and the phosphoric acid further etches the porous carbon, so that the partial structure is collapsed. When the dosage of the phytic acid is 1.25g (shown in figure 2d), the potassium citrate distributed in the vesicle structure and on the surface is insufficient, the generated porous structure is distributed more sparsely, and larger pores are generated through excessive etching of more phosphoric acid, so that the nano flaky structure is damaged. When the microwave radiation power is 400W (figure 3a), more sheet structures are generated and the pore diameter is larger, probably because the decomposition speed of the emulsified phytic acid is slower and the temperature rise is slower. When the microwave power is 500W (figure 3b), the porous carbon with ordered arrangement is obtained, the aperture is smaller and the nano-sheet is very thin. At a microwave radiation power of 600W (fig. 3c), the sheet structure disappears, leaving only a porous structure with a disordered distribution, due to an excessively fast temperature rise and an excessively high temperature.
FIG. 4 is a graph showing (a) cyclic voltammogram and (B) charge-discharge curve of the electrode materials prepared in examples 1A to 1F of the present invention, and it can be seen from the curves that the specific capacitance of the electrode material prepared in example 1B is 330F g-1And has high specific capacitance. FIG. 4a shows CV curves for MP/O-PC500-0.75 at different sweep rates. In the range of 10 to 100mVs-1The similar shape is kept under the scanning speed, the oxidation peak of phosphorus/oxygen doping appears around-0.7V, and the reduction peak of phosphorus/oxygen doping appears around-0.6V, which proves that the MP/O-PC500-0.75 electrode material has the capability of fast transferring electrons and excellent capacitance performance. From 1A g-1To 20A g-1Also this is reflected by the triangle-like GCD curve of fig. 4 b. At 1A g-1Obtained at a current density of 330F g-1When the current density is increased to 20A g-1The retention rate of the capacitance value is 64.55% which is far superior to the phosphorus-containing doped carbon material reported previously. The specific capacitance value is reduced rapidly along with the increase of the current density, and the current degree is increased, so that a large amount of electricity is generatedThe adsorption of the electrolyte ions on the surface of the electrode material results in a rapid decrease in the interfacial electrolyte ion concentration, thereby inevitably increasing the concentration polarization. Fig. 4c shows CV curves of the electrode material obtained at different ratios and different powers, and fig. 4d shows that the GCD curves of the electrode material obtained at different ratios and different powers all maintain good triangle-like shapes. The capacitance values of the current density of the MP/O-PC500-0.5, the MP/O-PC500-0.75, the MP/O-PC500-1, the MP/O-PC500-1.25, the MP/O-PC400-0.75 and the MP/O-PC600-0.75 at 1Ag-1 are 261F g respectively-1，330F g-1，286F g-1，223F g-1，246F g-1，254F g-1And 313F g-1。
TABLE 1 electrochemical performance results for phosphorus/oxygen doped nanoporous carbon materials prepared by inventive examples A-F
Claims (8)
1. A method for preparing a phosphorus/oxygen doped nano porous carbon material by a microwave method is characterized by comprising the following steps: the method comprises the following steps:
(1) uniformly mixing a carbon source, a phosphorus source and a microwave absorbent according to different proportions to obtain a mixture;
(2) and placing the dispersing agent and the mixture in a microwave reactor, carrying out microwave reaction in the air atmosphere, after the product is naturally cooled, carrying out acid washing and water washing on the product to remove impurities, and drying to obtain the phosphorus/oxygen doped nano porous carbon material.
2. The method for preparing a phosphorus/oxygen-doped nanoporous carbon material according to claim 1, wherein: the carbon source is potassium citrate; the phosphorus source is phytic acid; the microwave absorbent is phytic acid.
3. The method for preparing a phosphorus/oxygen-doped nanoporous carbon material according to claim 2, wherein: the mass ratio of the potassium citrate to the phytic acid is 2: 0.5-1.25.
4. The method for preparing a phosphorus/oxygen-doped nanoporous carbon material according to claim 1, wherein: the dispersing agent is one or more of distilled water, ethanol, methanol and isopropanol.
5. The method for preparing a phosphorus/oxygen-doped nanoporous carbon material according to claim 4, wherein: the dispersing agent is ethanol.
6. The method for preparing a phosphorus/oxygen-doped nanoporous carbon material according to claim 1, wherein: the mass ratio of the dispersing agent to the mixture is 1-3: 2.
7. The method for preparing a phosphorus/oxygen-doped nanoporous carbon material according to claim 1, wherein: the power of the microwave reaction is 400-600W.
8. The method for preparing a phosphorus/oxygen-doped nanoporous carbon material according to claim 1, wherein: the microwave reaction time is 0.5-4 min.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114914424A (en) * | 2022-05-26 | 2022-08-16 | 湖北兴发化工集团股份有限公司 | Preparation method of carbon-phosphorus composite material derived from black phosphorus |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101181690A (en) * | 2007-12-14 | 2008-05-21 | 中山大学 | Microwave induction catalytic preparation method of nano tungsten carbide |
| CN103833006A (en) * | 2014-03-06 | 2014-06-04 | 安徽工业大学 | One-step preparation method of three-dimensional mesoporous nanometer cage-shaped carbon material for super capacitor |
| US20150352522A1 (en) * | 2013-02-21 | 2015-12-10 | Nippon Steel & Sumitomo Metal Corporation | Carbon material for catalyst support use |
| CN106672938A (en) * | 2017-03-22 | 2017-05-17 | 兰州理工大学 | Phosphor-doped mesoporous carbon material and microwave preparation method thereof |
| CN107892301A (en) * | 2017-10-26 | 2018-04-10 | 兰州理工大学 | A kind of phosphorus doping meso-porous carbon material and its microwave preparation and application |
| CN110127660A (en) * | 2019-05-08 | 2019-08-16 | 扬州大学 | The method that microwave prepares porous carbon nanomaterial |
| CN111463017A (en) * | 2020-03-20 | 2020-07-28 | 中国科学院山西煤炭化学研究所 | Asphalt alkenyl porous carbon nanosheet for supercapacitor and preparation method thereof |
-
2020
- 2020-07-29 CN CN202010747704.0A patent/CN111977633A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101181690A (en) * | 2007-12-14 | 2008-05-21 | 中山大学 | Microwave induction catalytic preparation method of nano tungsten carbide |
| US20150352522A1 (en) * | 2013-02-21 | 2015-12-10 | Nippon Steel & Sumitomo Metal Corporation | Carbon material for catalyst support use |
| CN103833006A (en) * | 2014-03-06 | 2014-06-04 | 安徽工业大学 | One-step preparation method of three-dimensional mesoporous nanometer cage-shaped carbon material for super capacitor |
| CN106672938A (en) * | 2017-03-22 | 2017-05-17 | 兰州理工大学 | Phosphor-doped mesoporous carbon material and microwave preparation method thereof |
| CN107892301A (en) * | 2017-10-26 | 2018-04-10 | 兰州理工大学 | A kind of phosphorus doping meso-porous carbon material and its microwave preparation and application |
| CN110127660A (en) * | 2019-05-08 | 2019-08-16 | 扬州大学 | The method that microwave prepares porous carbon nanomaterial |
| CN111463017A (en) * | 2020-03-20 | 2020-07-28 | 中国科学院山西煤炭化学研究所 | Asphalt alkenyl porous carbon nanosheet for supercapacitor and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114914424A (en) * | 2022-05-26 | 2022-08-16 | 湖北兴发化工集团股份有限公司 | Preparation method of carbon-phosphorus composite material derived from black phosphorus |
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