CN114334475A - One-step synthesized high-specific-surface-area hierarchical pore carbon electrode material and preparation method and application thereof - Google Patents
One-step synthesized high-specific-surface-area hierarchical pore carbon electrode material and preparation method and application thereof Download PDFInfo
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- CN114334475A CN114334475A CN202111208528.4A CN202111208528A CN114334475A CN 114334475 A CN114334475 A CN 114334475A CN 202111208528 A CN202111208528 A CN 202111208528A CN 114334475 A CN114334475 A CN 114334475A
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- 239000007772 electrode material Substances 0.000 title claims abstract description 40
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000002149 hierarchical pore Substances 0.000 title claims abstract description 24
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229960001484 edetic acid Drugs 0.000 claims abstract description 55
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 46
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 43
- 239000011148 porous material Substances 0.000 claims abstract description 40
- 239000002243 precursor Substances 0.000 claims abstract description 37
- 238000001354 calcination Methods 0.000 claims abstract description 29
- 239000007864 aqueous solution Substances 0.000 claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000003575 carbonaceous material Substances 0.000 claims description 66
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 24
- 239000003792 electrolyte Substances 0.000 claims description 23
- 239000003990 capacitor Substances 0.000 claims description 22
- -1 amine compounds Chemical class 0.000 claims description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 238000009826 distribution Methods 0.000 claims description 13
- 239000004088 foaming agent Substances 0.000 claims description 13
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- 238000004321 preservation Methods 0.000 claims description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 9
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 9
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 239000004604 Blowing Agent Substances 0.000 claims description 5
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 239000005486 organic electrolyte Substances 0.000 claims description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 3
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- 235000010333 potassium nitrate Nutrition 0.000 claims description 2
- 239000004323 potassium nitrate Substances 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 6
- IBZJNLWLRUHZIX-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole Chemical compound CCN1CN(C)C=C1 IBZJNLWLRUHZIX-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 20
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- 229910021641 deionized water Inorganic materials 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
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- 238000003756 stirring Methods 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
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- 229910052760 oxygen Inorganic materials 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
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- OTYYBJNSLLBAGE-UHFFFAOYSA-N CN1C(CCC1)=O.[N] Chemical compound CN1C(CCC1)=O.[N] OTYYBJNSLLBAGE-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
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- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
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Abstract
The application discloses a one-step method synthesized high-specific-surface hierarchical pore carbon electrode material and a preparation method and application thereof, wherein the preparation method of the one-step synthesized high-specific-surface hierarchical pore carbon electrode material comprises the steps of mixing and reacting an aqueous solution containing ethylene diamine tetraacetic acid with an aqueous solution of an alkali metal source to obtain ethylene diamine tetraacetic acid precursor gel; and calcining the ethylene diamine tetraacetic acid precursor gel to obtain the hierarchical porous carbon electrode material. The high specific surface area hierarchical pore carbon electrode material synthesized by the one-step method has the characteristics of low price, high specific surface area, large pore volume, adjustable particle size and morphology, and has the advantages of high specific capacity, long cycle life, high rate capability and the like after being used as an electrode material of an electrochemical energy storage device.
Description
Technical Field
The application relates to a one-step synthesized high-specific-surface hierarchical pore carbon electrode material, a preparation method and application thereof, and belongs to the technical field of electrochemical energy storage devices.
Background
The super capacitor is a novel energy storage device between a traditional capacitor and a battery, has the advantages of high energy density, high power density, high charge-discharge efficiency (99%), long service life (10 ten thousand times) and the like, and is widely applied to the fields of electronic equipment, transportation, engineering equipment, military equipment and the like.
The super capacitor is composed of components such as an electrode, a diaphragm, electrolyte and a battery shell, and the electric double layer super capacitor is used for adsorbing ions in the electrolyte to the surface of a porous electrode material by means of the action of an electric double layer so as to store electric charges. Generally, the voltage range of a super capacitor of the water-based electrolyte is only 1V, the voltage window is small, the application range is narrow, and the ionic liquid is used as the super capacitor electrolyte, so that the highest voltage range of 4V can be obtained, and higher energy density and power density can be obtained.
The ionic liquid electrolyte has a larger ionic radius than a common electrolyte, and the pore structure of the material needs to be matched with the ionic liquid electrolyte, so that the specific surface area and the pore structure of the electrode material are main factors influencing the capacitance of the electrode material. A porous crystalline material is commonly used as a precursor or a sacrificial template to prepare a derivative porous carbon material with high specific surface area, large pore volume and controllable particle size and morphology. Korean positive wave et al patent 201810126412.8 discloses that a nano-scale metal organic framework zn (tbip) is used as a precursor, and is calcined to obtain a carbon material with high specific capacity, high stability and high power density; in patent 202110033712.3, Huangdan lotus et al, a cobalt-based metal skeleton is used as a precursor, and the sea urchin-shaped amorphous carbon/foamed nickel composite material is obtained through hydrothermal treatment and calcination, and has the advantages of stable structure, high specific capacitance and the like.
However, the method using the metal organic framework MOF is complicated, requires a large amount of raw materials, requires a large number of steps, and is expensive. Therefore, it is a technical problem to be solved in the art to provide a one-step synthesized high-specific-surface hierarchical porous carbon electrode material.
Disclosure of Invention
The invention aims to provide preparation and application of a one-step synthesized high-specific-surface-area hierarchical porous carbon material.
According to an aspect of the present application, there is provided a method for preparing a one-step synthesized high surface area hierarchical porous carbon material, wherein the method for preparing the one-step synthesized high surface area hierarchical porous carbon material comprises:
mixing and reacting an aqueous solution containing ethylene diamine tetraacetic acid with an aqueous solution containing an alkali metal source to obtain ethylene diamine tetraacetic acid precursor gel; and calcining the ethylene diamine tetraacetic acid precursor gel to obtain the hierarchical porous carbon material.
Optionally, the alkali metal source is selected from at least one of a potassium source, a sodium source;
the potassium source is selected from KOH and CH3COOK、K2CO3At least one of;
the sodium source is selected from NaOH and CH3COONa、Na2CO3At least one of (1).
Optionally, the molar ratio of the ethylenediaminetetraacetic acid to the alkali metal source is (1:8) to (1: 2), wherein the number of moles of alkali metal source is based on the number of moles of alkali metal element;
optionally, the molar ratio of the ethylenediaminetetraacetic acid to the alkali metal source is (1:6) to (1: 4), wherein the number of moles of alkali metal source is based on the number of moles of alkali metal element;
alternatively, the upper limit of the molar ratio of the ethylenediaminetetraacetic acid to the alkali metal source may be independently selected from 1:2, 1:3, 1:4, 1:5, 1:6, 1: 7; the lower limit may be independently selected from 1:8, 1:7, 1:6, 1:5, 1:4, 1: 3.
Optionally, in the aqueous solution containing the alkali metal source, the mass volume ratio of the alkali metal source to water is 0.05-0.5 g/ml;
optionally, in the aqueous solution containing the alkali metal source, the mass volume ratio of the alkali metal source to water is 0.1-0.4 g/ml;
alternatively, the upper limit of the mass to volume ratio of the alkali metal source to water may be independently selected from 0.2g/ml, 0.3g/ml, 0.4 g/ml; the lower limit can be independently selected from 0.1g/ml, 0.2g/ml, 0.3 g/ml;
optionally, the obtaining of the ethylenediaminetetraacetic acid precursor gel comprises the following steps:
mixing an aqueous solution containing carbon source ethylene diamine tetraacetic acid with an alkali metal salt aqueous solution to obtain an ethylene diamine tetraacetic acid precursor solution; and drying the ethylene diamine tetraacetic acid precursor solution to obtain ethylene diamine tetraacetic acid precursor gel.
Optionally, the drying temperature is 60-160 ℃, and the time is 2-10 h;
optionally, the drying temperature is 80-120 ℃, and the time is 3-6 h.
Optionally, the upper drying temperature limit can be independently selected from 80 ℃, 100 ℃, 120 ℃, 140 ℃ and 160 ℃; the lower limit is selected independently from 60 deg.C, 80 deg.C, 100 deg.C, 120 deg.C, 140 deg.C;
alternatively, the upper time limit may be independently selected from 4h, 6h, 8h, 10 h; the lower limit can be independently selected from 2h, 4h, 6h and 8 h;
optionally, the calcining is performed under an atmosphere of an inert gas;
the inactive gas comprises one or a combination of several of nitrogen and argon.
The flow rate of the inactive gas is 50-150 sccm;
as used herein, "sccm" refers to Standard Cubic Centimeter per Minute, Standard milliliters per Minute.
Optionally, the calcination temperature is 600-1300 ℃, the heating rate is 1-10 ℃/min, and the calcination time is 2-6 h;
optionally, the calcination temperature is 600-1000 ℃, the heating rate is 2-6 ℃/min, and the calcination time is 3-5 h.
Alternatively, the upper limit of the calcination temperature may be independently selected from 800 ℃, 1000 ℃, 1300 ℃; the lower limit can be independently selected from 600 deg.C, 800 deg.C, 1000 deg.C;
optionally, the upper limit of the heating rate can be independently selected from 4 ℃/min, 5 ℃/min, 8 ℃/min, 10 ℃/min; the lower limit can be independently selected from 2 ℃/min, 4 ℃/min, 5 ℃/min and 8 ℃/min;
optionally, the calcining heat preservation time of the tube furnace is 1-6 h; more preferably, the calcination heat preservation time is 3-5 h.
Optionally, after the ethylene diamine tetraacetic acid precursor gel is calcined, grinding, washing with water, acid washing and drying processes are further included to obtain the hierarchical porous carbon electrode material,
in the above-described preparation method, the sample after calcination and in-situ carbonization activation is subjected to grinding and pulverization, preferably, manual grinding or mechanical grinding is used.
In the above-described preparation method, the ground sample is washed to be neutral in pH, and preferably, washing is repeated using deionized water, ethanol, and hydrochloric acid, nitric acid, or a mixed acid.
In the preparation method, the cleaned powder is dried, optionally, an oven or a vacuum oven is used, the temperature is 60-160 ℃, and the heat preservation time is 6-36 hours;
optionally, the temperature is 80-120 ℃, and the heat preservation time is 6-12 h.
According to another aspect of the application, the hierarchical pore carbon material prepared by the preparation method is provided, the hierarchical pore carbon material has a particle structure in a macroscopic view and has a blocky hierarchical pore structure in a microscopic appearance;
the hierarchical pores comprise micropores, mesopores and macropores;
the hierarchical porous carbon material comprises carbon, oxygen and nitrogen elements, and the surface activity of the material can be improved by a certain amount of doped oxygen and nitrogen elements, so that more sites are provided for the adsorption of electrolyte.
Optionally, in the hierarchical porous carbon material, the content of carbon element is 85-95%, the content of oxygen element is 5-15%, and the content of nitrogen element is 0-5%.
Optionally, the hierarchical porous carbon material has a high specific surface area of 1000-3500 m2Per g, pore volume of 0.5-3 cm3(ii)/g, the pore size distribution is 0.5-10 nm;
optionally, the specific surface area of the hierarchical porous carbon material is 1600-2800 m2Per g, pore volume of 1-2 cm3(ii)/g, the pore size distribution is 0.5 to 5 nm.
In another aspect of the present application, there is provided a method for preparing a one-step synthesized high surface area porous carbon material, wherein the method for preparing a one-step synthesized high surface area porous carbon material comprises:
mixing and reacting an aqueous solution containing ethylene diamine tetraacetic acid and a foaming agent with an aqueous solution containing an alkali metal source to obtain ethylene diamine tetraacetic acid precursor gel; and calcining the ethylene diamine tetraacetic acid precursor gel to obtain the hierarchical porous carbon material.
Optionally, the aqueous solution containing the carbon source ethylene diamine tetraacetic acid also comprises a foaming agent;
the foaming agent is selected from at least one of amine compounds, nitrate and carbonate;
optionally, the amine compound is selected from at least one of urea and melamine;
optionally, the nitrate is selected from at least one of potassium nitrate and sodium nitrate;
optionally, the carbonate is selected from at least one of potassium carbonate and sodium carbonate;
optionally, the molar ratio of the ethylene diamine tetraacetic acid to the blowing agent is 1: 5-2: 1.
optionally, the molar ratio of the ethylene diamine tetraacetic acid to the blowing agent is 1: 3-1: 1.
alternatively, the upper limit of the molar ratio of the ethylenediaminetetraacetic acid to the blowing agent may be independently selected from 2:1, 1:2, 1:3, 1: 4; the lower limit can be independently selected from 1:5, 1:4, 1:3, 1:2, 1: 1;
optionally, in the aqueous solution containing the ethylene diamine tetraacetic acid, the volume ratio of the total mass of the ethylene diamine tetraacetic acid and the foaming agent to the water is 0.04-0.4 g/ml.
Alternatively, the upper limit of the volume ratio of the total mass of the ethylenediamine tetraacetic acid and the foaming agent to the water can be independently selected from 0.12g/ml, 0.18g/ml, 0.24g/ml, 0.30g/ml and 0.4 g/ml; the lower limit can be independently selected from 0.04g/ml, 0.12g/ml, 0.18g/ml, 0.24g/ml, 0.30 g/ml;
optionally, the alkali metal source is selected from at least one of a potassium source, a sodium source;
the potassium source is selected from KOH and CH3COOK、K2CO3At least one of;
the sodium source is selected from NaOH and CH3COONa、Na2CO3At least one of (1).
Optionally, the molar ratio of the ethylenediaminetetraacetic acid to the alkali metal source is (1:8) to (1: 2), wherein the number of moles of alkali metal source is based on the number of moles of alkali metal element;
optionally, the molar ratio of the ethylenediaminetetraacetic acid to the alkali metal source is (1:6) to (1: 4), wherein the number of moles of alkali metal source is based on the number of moles of alkali metal element;
alternatively, the upper limit of the molar ratio of the ethylenediaminetetraacetic acid to the alkali metal source may be independently selected from 1:2, 1:3, 1:4, 1:5, 1:6, 1: 7; the lower limit may be independently selected from 1:8, 1:7, 1:6, 1:5, 1:4, 1: 3.
Optionally, in the aqueous solution containing the alkali metal source, the mass volume ratio of the alkali metal source to water is 0.05-0.5 g/ml;
optionally, in the aqueous solution containing the alkali metal source, the mass volume ratio of the alkali metal source to water is 0.1-0.4 g/ml;
alternatively, the upper limit of the mass to volume ratio of the alkali metal source to water may be independently selected from 0.2g/ml, 0.3g/ml, 0.4 g/ml; the lower limit can be independently selected from 0.1g/ml, 0.2g/ml, 0.3 g/ml;
optionally, the obtaining of the ethylenediaminetetraacetic acid precursor gel comprises the following steps:
mixing an aqueous solution containing carbon source ethylene diamine tetraacetic acid with an alkali metal salt aqueous solution to obtain an ethylene diamine tetraacetic acid precursor solution; and drying the ethylene diamine tetraacetic acid precursor solution to obtain ethylene diamine tetraacetic acid precursor gel.
Optionally, the drying temperature is 60-160 ℃, and the time is 2-10 h;
optionally, the drying temperature is 80-120 ℃, and the time is 3-6 h.
Optionally, the upper drying temperature limit can be independently selected from 80 ℃, 100 ℃, 120 ℃, 140 ℃ and 160 ℃; the lower limit is selected independently from 60 deg.C, 80 deg.C, 100 deg.C, 120 deg.C, 140 deg.C;
alternatively, the upper time limit may be independently selected from 4h, 6h, 8h, 10 h; the lower limit can be independently selected from 2h, 4h, 6h and 8 h.
Optionally, the calcining is performed under an atmosphere of an inert gas;
the inactive gas comprises one or more of nitrogen, argon and helium.
The flow rate of the inactive gas is 50-150 sccm;
as used herein, "sccm" refers to Standard Cubic Centimeter per Minute, Standard milliliters per Minute.
Optionally, the calcination temperature is 600-1300 ℃, the heating rate is 1-10 ℃/min, and the calcination heat preservation time is 2-6 h;
optionally, the calcination temperature is 600-1000 ℃, the heating rate is 2-6 ℃/min, and the calcination heat preservation time is 3-5 h.
Alternatively, the upper limit of the calcination temperature may be independently selected from 800 ℃, 1000 ℃, 1300 ℃; the lower limit can be independently selected from 600 deg.C, 800 deg.C, 1000 deg.C;
optionally, the upper limit of the heating rate can be independently selected from 4 ℃/min, 5 ℃/min, 8 ℃/min, 10 ℃/min; the lower limit can be independently selected from 2 deg.C/min, 4 deg.C/min, 5 deg.C/min, and 8 deg.C/min.
Optionally, the heat preservation time of the tube furnace is 1-6 h;
optionally, the calcination heat preservation time is 3-5 h.
After the ethylene diamine tetraacetic acid precursor gel is calcined, grinding, washing with water, pickling and drying to obtain the hierarchical porous carbon electrode material;
in the preparation method, the sample after calcination and in-situ carbonization activation is ground and crushed;
alternatively, manual grinding or mechanical grinding is used.
In the above-described preparation method, the ground sample is washed to be neutral in pH, and preferably, washing is repeated using deionized water, ethanol, and hydrochloric acid, nitric acid, or a mixed acid.
In the preparation method, the cleaned powder is dried, preferably, an oven or a vacuum oven is used, the temperature is 60-160 ℃, and the heat preservation time is 6-36 hours; more preferably, the temperature is 80-120 ℃, and the heat preservation time is 6-12 h.
According to another aspect of the application, a hierarchical porous carbon material prepared by the preparation method is provided, wherein the hierarchical porous carbon material has a particle structure in a macroscopic view and a lamellar hierarchical porous structure in a microscopic appearance;
the hierarchical pores comprise micropores, mesopores and macropores;
the hierarchical porous carbon material comprises carbon, oxygen and nitrogen elements, and the surface activity of the material can be improved by a certain amount of doped oxygen and nitrogen elements, so that more sites are provided for the adsorption of electrolyte.
Optionally, in the hierarchical porous carbon material, the content of carbon element is 85-95%, the content of oxygen element is 5-10%, and the content of nitrogen element is 0-5%.
The hierarchical porous carbon material has a high specific surface area of 1000-3500 m2Per g, pore volume of 0.5-3 cm3(ii)/g, the pore size distribution is 0.5-10 nm;
optionally, the specific surface area of the hierarchical porous carbon material is 1600-2800 m2Per g, pore volume of 1-2 cm3(ii)/g, the pore size distribution is 0.5 to 5 nm.
The high specific surface area hierarchical porous carbon material is synthesized by a one-step method, wherein the one-step method represents that the material is simply mixed and then is calcined and carbonized and activated in situ only by one step to obtain the final required high specific surface area hierarchical porous carbon material; the hierarchical pore means that the material has the structural characteristics of micropores, mesopores and macropores, and the pores are communicated with one another, so that the ion migration distance is reduced, and the high-rate performance of the material is facilitated.
According to still another aspect of the present application, there is provided an electrode material comprising the hierarchical porous carbon electrode material obtained by the preparation method or the hierarchical porous carbon electrode material.
Optionally, the specific capacity of the electrode material is 158-165F/g, the energy density is 71.1-74.24 Wh/kg, and the power density is 915.3-927.4W/kg under the current density of 0.5A/g.
According to another aspect of the present application, there is provided a supercapacitor comprising said electrode material.
The electrode material in the super capacitor is made of the high specific surface area hierarchical pore carbon material synthesized by the one-step method.
Optionally, the capacitor further comprises an electrolyte;
the electrolyte is selected from at least one of ionic liquid, commercial organic electrolyte and commercial water-based electrolyte;
optionally, the ionic liquid is selected from at least one of 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium bistrifluoromethylsulphonimide salt, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid.
In the present application, "ionic liquid" refers to a salt that is in a liquid state at room temperature and is composed entirely of anionic cations.
Optionally, the organic electrolyte is selected from at least one of AN acetonitrile solution of tetraethylammonium tetrafluoroborate salt (TEABF4/AN), AN acrylic carbonate solution of tetraethylammonium tetrafluoroborate salt (TEABF4/PC),
wherein TEABF4The concentration of/AN is 1mol/L, TEABF4The concentration of PC is 1 mol/L;
optionallyThe aqueous electrolyte is selected from KOH and H2SO4、Li2SO4At least one of;
wherein the concentration of KOH is 6mol/L, H2SO4Has a concentration of 1 to 3mol/L, Li2SO4The concentration of (b) is 1 to 2 mol/L.
The beneficial effects that this application can produce include:
1) according to the preparation method provided by the invention, Ethylene Diamine Tetraacetic Acid (EDTA) with low cost is used as a carbon source, alkali metal hydroxide or alkali metal salt is added for reaction, calcination and in-situ carbonization activation are carried out after drying, cleaning and drying are carried out, the high-specific-surface hierarchical pore carbon electrode material synthesized by the one-step method is obtained, and the high-specific-surface hierarchical pore carbon electrode material synthesized by the one-step method is used as an electrode material of a supercapacitor, so that the supercapacitor has the advantages of large capacitance, high energy density, high capacity retention rate, excellent rate capability and good cycle stability.
2) The preparation method provided by the invention has the advantages of low raw material price, simple operation and easy process, can easily realize batch preparation, can easily control the morphology, the pore structure and the specific surface area of the carbon material by adjusting the proportion of the alkali metal, and is suitable for industrial production.
Drawings
Fig. 1 is a scanning electron microscope picture of the one-step synthesized high specific surface area hierarchical pore carbon electrode material prepared in example 1 of the present invention, wherein (1-1), (1-2), (1-3), and (1-4) are scanning electron microscope pictures at different magnifications.
Fig. 2 is a pore size distribution graph of the one-step synthesized high specific surface area hierarchical pore carbon electrode material prepared in example 1 of the present invention.
Fig. 3 is a nitrogen adsorption and desorption graph of the one-step synthesized high-specific-surface-area hierarchical-pore carbon electrode material prepared in example 1 of the present invention.
Fig. 4 is a scanning electron microscope picture of the one-step synthesized hierarchical porous carbon electrode material with a high specific surface area prepared in example 2 of the present invention, wherein (4-1), (4-2), (4-3), and (4-4) are scanning electron microscope pictures at different magnifications.
Fig. 5 is a pore size distribution graph of the one-step synthesized high specific surface area hierarchical pore carbon electrode material prepared in example 2 of the present invention.
Fig. 6 is a scanning electron microscope picture of the one-step synthesized high specific surface area hierarchical pore carbon electrode material prepared in example 3 of the present invention.
Fig. 7 is a constant current charge and discharge curve diagram of a supercapacitor using the one-step synthesized high specific surface area hierarchical porous carbon electrode material according to example 4 of the present invention.
Fig. 8 is a plot of Cyclic Voltammetry (CV) for a supercapacitor using a one-step synthesized high surface area hierarchical porous carbon electrode material according to example 4 of the present invention.
Fig. 9 is a constant current charge and discharge curve diagram of a supercapacitor using the one-step synthesized high specific surface area hierarchical porous carbon electrode material according to example 5 of the present invention.
Fig. 10 is an X-ray photoelectron spectrum of the one-step synthesized high specific surface area hierarchical pore carbon electrode material prepared in example 1 of the present invention.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Unless otherwise specified, the starting materials in the examples of this application were all purchased commercially, wherein sodium hydroxide, potassium acetate, potassium carbonate, sodium carbonate, ethylenediaminetetraacetic acid, urea, tetraethylammonium tetrafluoroborate, acetonitrile, 1-ethyl-3-methylimidazolium tetrafluoroborate, polyvinylidene fluoride (PVDF) was purchased from the avastin reagent.
In the embodiment of the application, the specific capacity, the energy density and the power density are calculated as follows:
all capacitors of the invention are two electrodes, and the calculation mode of the specific capacity of the button cell type super capacitor is as follows:
wherein, Ctwo(Fg-1) The specific capacity of the super capacitor, i (a) is current, Δ t(s) is discharge time, and Δ v (v) is voltage interval of the super capacitor.
The energy density and power density of the super capacitor are calculated in the following mode:
wherein C iscell(Fg-1) Δ t(s), Δ V (V) are as above.
Example 1
The embodiment provides a preparation method of a precursor solution of a high-specific-surface-area hierarchical porous carbon material synthesized by a one-step method, wherein the preparation method comprises the following steps:
dispersing 6g of EDTA and 3g of urea in 50ml of deionized water, and uniformly stirring;
3g of KOH is used and dissolved in 30ml of deionized water, and the mixture is stirred until the KOH is completely dissolved;
mixing the two solutions, continuously stirring, and obtaining the precursor solution after the solution is clarified;
and transferring the prepared EDTA precursor aqueous solution into a corundum crucible, and drying in an oven at 60 ℃ for 10h to obtain the gel precursor.
Transferring the corundum crucible filled with the gel precursor into a tubular furnace, ventilating for 20 minutes by using 500sccm argon, discharging air in a quartz tube, then heating at the heating rate of 2 ℃/min to 800 ℃, preserving heat for 4 hours, continuously providing an inert gas atmosphere by using 150sccm argon, naturally cooling to room temperature after the constant-temperature reaction is finished, and then taking out a reaction product;
grinding the obtained reaction product, repeatedly cleaning the reaction product by using deionized water, ethanol and 1mol/L hydrochloric acid until the pH value is neutral, performing suction filtration, and putting the reaction product into an oven at 80 ℃ for 24 hours to obtain the one-step synthesisThe obtained high specific surface area hierarchical porous carbon material 1#。
Example 2
Dispersing 6g of EDTA in 50ml of deionized water without adding a foaming agent, and uniformly stirring;
dissolving 4g of KOH in 30ml of deionized water, and stirring until the KOH is completely dissolved;
mixing the two solutions, continuously stirring, and obtaining the precursor solution after the solution is clarified;
and transferring the prepared EDTA precursor aqueous solution into a corundum crucible, and drying in an oven at 100 ℃ for 4h to obtain the gel precursor.
Transferring the corundum crucible filled with the gel precursor into a tubular furnace, ventilating for 20 minutes by using 500sccm argon, discharging air in a quartz tube, then heating at the heating rate of 5 ℃/min to 1000 ℃, preserving heat for 4 hours, continuously providing an inert gas atmosphere by using 150sccm argon, naturally cooling to room temperature after the constant-temperature reaction is finished, and then taking out a reaction product;
grinding the obtained reaction product, repeatedly cleaning the reaction product by using deionized water, ethanol and 1mol/L hydrochloric acid until the pH value is neutral, performing suction filtration, and putting the reaction product into a 100 ℃ oven for 24 hours to obtain the one-step synthesized high-specific-surface-area hierarchical porous carbon material 2#。
Example 3
Dispersing 6g of EDTA in 50ml of deionized water without adding a foaming agent, and uniformly stirring;
use of 3gCH3COOK, dissolving in 30ml of deionized water, and stirring until the COOK is completely dissolved;
mixing the two solutions, continuously stirring, and obtaining the precursor solution after the solution is clarified;
and transferring the prepared EDTA precursor aqueous solution into a corundum crucible, and drying in an oven at 100 ℃ for 6h to obtain the gel precursor.
Transferring the corundum crucible filled with the gel precursor into a tubular furnace, ventilating for 20 minutes by using 500sccm argon, discharging air in a quartz tube, then heating at the heating rate of 4 ℃/min to 800 ℃, preserving heat for 2 hours, continuously providing an inert gas atmosphere by using 150sccm argon, naturally cooling to room temperature after the constant-temperature reaction is finished, and then taking out a reaction product;
grinding the obtained reaction product, repeatedly cleaning the reaction product by using deionized water, ethanol and 1mol/L hydrochloric acid until the pH value is neutral, performing suction filtration, and putting the reaction product into a 100 ℃ oven for 24 hours to obtain the one-step synthesized high-specific-surface-area hierarchical porous carbon material 3#。
Test example 1
The high-specific-surface-area hierarchical porous carbon material 1 obtained in examples 1 to 3 was subjected to a Hitachi S4800 field emission scanning electron microscope#～3#And (5) performing scanning electron microscope characterization.
FIG. 1 shows a carbon material 1 obtained in example 1 of the present invention#The material is seen to be lamellar in a scanning electron microscope, fig. 2 is a pore size distribution curve diagram of the carbon material obtained in example 1, and a great number of pore structure characteristics are distributed on the surface of the material in combination with fig. 1 and fig. 2.
FIG. 4 shows a carbon material 1 according to example 2 of the present invention#It can be seen from the scanning electron micrograph that the material obtained without adding the foaming agent is granular and has a large number of pores distributed on the surface, and FIG. 5 shows the carbon material 2 obtained in example 2 of the present invention#The pore size distribution diagram of (a) can be seen in conjunction with fig. 4 and 5, without the addition of blowing agent, the surface is also distributed with a large number of pores.
FIG. 6 shows a carbon material 3 according to example 3 of the present invention#In the scanning electron micrograph, it can be seen that CH was used without the addition of the foaming agent3After COOK, the electrode material of the invention can be obtained, which is granular and has a large number of pores distributed on the surface.
Test example 2
The high specific surface area hierarchical porous carbon material 1 obtained in examples 1-2 was analyzed by an ASAP2020M full-automatic specific surface area and porosity analyzer#、2#And (5) carrying out nitrogen adsorption and desorption tests.
FIG. 3 is a nitrogen adsorption/desorption graph of the carbon material No. 1 according to example 1 of the present invention, and the specific surface area of the carbon material was measuredProduct of 1925.9m2Per g, pore volume 1.06cm3/g。
FIG. 2 shows a carbon material 1 according to example 1 of the present invention#The pore size distribution curve chart shows that the material has a micropore and mesopore structure, the pore size is 0.5-5 nm, the macroporous structure of the material can be seen in an SEM picture, and the multi-stage pore size structure of the material is more favorable for the infiltration and adsorption of electrolyte.
FIG. 5 shows a carbon material 2 according to example 2 of the present invention#The material also has a micropore and mesopore structure, the pore diameter of the material is 0.5-10 nm, and the structure is favorable for infiltration and adsorption of electrolyte. For the multi-level pore carbon material 2 obtained in example 2#Performing nitrogen adsorption and desorption test to obtain the multi-level pore carbon material 2#Specific surface area of 2792.59m2Per g, pore volume 2.06cm3/g。
Test example 3
The high specific surface area hierarchical porous carbon material 1 obtained in example 1 is subjected to a KratosAxis Ultra DLDX ray photoelectron spectrometer#And (6) carrying out testing.
FIG. 10 shows a carbon material 1 according to example 1 of the present invention#The photoelectron spectrum of (1) wherein the carbon element is 91.524%, the oxygen element is 7.83%, and the nitrogen element is 0.643%.
Example 4
The embodiment provides a supercapacitor which takes the one-step synthesized high specific surface area hierarchical porous carbon material provided in embodiment 1 as an electrode material, and the assembly of the supercapacitor comprises the following specific steps:
1) according to the following steps of 8: 1:1, weighing a high-specific-surface multi-level pore carbon material synthesized by a one-step method prepared in the embodiment 1 of the invention, conductive carbon black and a polyvinylidene fluoride (PVDF) binder, and using nitrogen-methyl pyrrolidone (NMP) as a dispersing agent to obtain slurry after uniformly mixing by magnetic stirring;
2) soaking a foamed nickel pole piece with the diameter of 12mm in the slurry for 10s, taking out, drying in a 60 ℃ drying oven for 6h, and drying in a 120 ℃ vacuum drying oven for 12h to obtain a super capacitor pole piece;
3) the electrode plate with 2 active substances of the same mass is adopted to assemble a button type symmetrical electrode super capacitor, EMIMBF4 ionic liquid is used as electrolyte, and a 19mm cellulose diaphragm is used as a super capacitor diaphragm.
And (3) carrying out electrochemical performance test on the obtained super capacitor, wherein a Solartron analytical 1400CellTest System electrochemical workstation is adopted in the test process, and the voltage test interval is 0-3.6V.
FIG. 7 is a constant current charge and discharge curve diagram of a supercapacitor made of a high specific surface area hierarchical porous carbon material synthesized by a one-step method according to example 3 of the present invention, wherein an ionic liquid electrolyte allows a voltage to reach 3.6V, and the material has a specific capacity of 158F/g at a current density of 0.5A/g, wherein the energy density is 71.1Wh/kg, and the power density is as high as 927.4W/kg.
Fig. 8 is a Cyclic Voltammetry (CV) graph of a supercapacitor using a one-step synthesized high surface area hierarchical pore carbon material according to example 7 of the present invention, which corresponds to the CV curve characteristic of an electric double layer supercapacitor.
Example 5
The embodiment provides a supercapacitor which takes the one-step synthesized high-specific-surface-area hierarchical porous carbon material provided in embodiment 2 as an electrode material, and the assembly of the supercapacitor comprises the following specific steps:
1) according to the following steps of 8: 1: weighing the high-specific-surface multi-level pore carbon material synthesized by the one-step method prepared in the embodiment 2 of the invention, conductive carbon black and a polyvinylidene fluoride (PVDF) binder in a mass ratio of 1, and using nitrogen-methyl pyrrolidone (NMP) as a dispersing agent to obtain slurry after uniformly mixing by magnetic stirring;
2) soaking a foamed nickel pole piece with the diameter of 12mm in the slurry for 10s, taking out, drying in a 60 ℃ drying oven for 6h, and drying in a 120 ℃ vacuum drying oven for 12h to obtain a super capacitor pole piece;
3) the electrode plate with 2 active substances of the same mass is adopted to assemble a button type symmetrical electrode super capacitor, EMIMBF4 ionic liquid is used as electrolyte, and a 19mm cellulose diaphragm is used as a super capacitor diaphragm.
And (3) carrying out electrochemical performance test on the obtained super capacitor, wherein a Solartron analytical 1400CellTest System electrochemical workstation is adopted in the test process, and the voltage test interval is 0-3.6V.
FIG. 9 is a constant current charge and discharge curve diagram of a supercapacitor made of a high specific surface area hierarchical porous carbon material synthesized by a one-step method in example 5 of the invention, wherein an ionic liquid electrolyte expands the voltage to 3.6V, and the material has a specific capacity of 165F/g at a current density of 0.5A/g, wherein the energy density is 74.24Wh/kg, and the power density is as high as 915.3W/kg.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. A preparation method of a hierarchical porous carbon material is characterized in that an aqueous solution containing ethylene diamine tetraacetic acid and an aqueous solution containing an alkali metal source are mixed and reacted to obtain ethylene diamine tetraacetic acid precursor gel; and calcining the ethylene diamine tetraacetic acid precursor gel to obtain the hierarchical porous carbon material.
2. The production method according to claim 1,
the alkali metal source is selected from at least one of a potassium source and a sodium source;
the potassium source is selected from KOH and CH3COOK、K2CO3At least one of;
the sodium source is selected from NaOH and CH3COONa、Na2CO3At least one of;
preferably, the molar ratio of the ethylenediaminetetraacetic acid to the alkali metal source is 1: 8-1: 2, wherein the moles of the alkali metal source are based on the moles of the alkali metal element;
further preferably, the molar ratio of the ethylenediaminetetraacetic acid to the alkali metal source is 1: 6-1: 4, wherein the moles of the alkali metal source are based on the moles of the alkali metal element;
preferably, in the aqueous solution containing the alkali metal source, the mass volume ratio of the alkali metal source to water is 0.05-0.5 g/ml;
more preferably, in the aqueous solution containing the alkali metal source, the mass volume ratio of the alkali metal source to water is 0.1 to 0.4 g/ml.
3. The production method according to claim 1,
after the mixing reaction, drying to obtain the ethylene diamine tetraacetic acid precursor gel;
the drying temperature is 60-160 ℃, and the drying time is 2-10 h;
preferably, the calcination is carried out under an atmosphere of an inert gas;
the inactive gas is selected from one or more of nitrogen, argon and helium;
the flow rate of the inactive gas is 50-150 sccm;
preferably, the calcination temperature is 600-1300 ℃, the heating rate is 1-10 ℃/min, and the calcination heat preservation time is 2-6 h;
further preferably, the calcination temperature is 600-1000 ℃, the heating rate is 2-6 ℃/min, and the calcination heat preservation time is 3-5 h.
4. A hierarchical porous carbon material prepared by the preparation method according to any one of claims 1 to 3,
the microscopic morphology of the hierarchical porous carbon material is a blocky hierarchical porous structure;
the hierarchical pores comprise micropores, mesopores and macropores;
the specific surface area of the hierarchical porous carbon material is 1000-3500 m2Per g, pore volume of 0.5-3 cm3(ii)/g, the pore size distribution is 0.5-10 nm;
preferably, the specific surface area of the hierarchical porous carbon material is 1600-2800 m2Per g, pore volumeIs 1-2 cm3(ii)/g, the pore size distribution is 0.5 to 5 nm.
5. A preparation method of a hierarchical porous carbon material is characterized in that an aqueous solution containing ethylene diamine tetraacetic acid and a foaming agent is mixed with an aqueous solution containing an alkali metal source for reaction to obtain ethylene diamine tetraacetic acid precursor gel; and calcining the ethylene diamine tetraacetic acid precursor gel to obtain the hierarchical porous carbon material.
6. The production method according to claim 5,
the foaming agent is selected from at least one of amine compounds, nitrate and carbonate;
preferably, the amine compound is selected from at least one of urea and melamine;
preferably, the nitrate is at least one selected from potassium nitrate and sodium nitrate;
preferably, the carbonate is at least one selected from potassium carbonate and sodium carbonate;
the molar ratio of the ethylene diamine tetraacetic acid to the foaming agent is 1: 5-2: 1;
preferably, the molar ratio of the ethylene diamine tetraacetic acid to the blowing agent is 1: 3-1: 1;
the volume ratio of the total mass of the ethylenediamine tetraacetic acid and the foaming agent to the water is 0.04-0.4 g/ml.
7. The production method according to claim 5,
the preparation method further comprises the preparation method of any one of claims 2 to 4.
8. A hierarchical porous carbon material prepared by the preparation method according to any one of claims 5 to 7,
the microscopic morphology of the hierarchical porous carbon material is a lamellar hierarchical porous structure;
the hierarchical pores comprise micropores, mesopores and macropores;
the hierarchical porous carbon materialThe specific surface area of the material is 1000-3500 m2Per g, pore volume of 0.5-3 cm3(ii)/g, the pore size distribution is 0.5-10 nm;
preferably, the specific surface area of the hierarchical porous carbon material is 1600-800 m2Per g, pore volume of 1-2 cm3(ii)/g, the pore size distribution is 0.5 to 5 nm.
9. An electrode material, characterized in that the electrode material comprises at least one of the hierarchical porous carbon material obtained by the production method according to any one of claims 1 to 3, the hierarchical porous carbon material according to claim 4, the hierarchical porous carbon material obtained by the production method according to any one of claims 5 to 7, and the hierarchical porous carbon material according to claim 8;
preferably, the specific capacity of the electrode material is 158-165F/g, the energy density is 71.1-74.24 Wh/kg, and the power density is 915.3-927.4W/kg under the current density of 0.5A/g.
10. A supercapacitor, characterized in that it comprises the electrode material of claim 9;
preferably, the capacitor further comprises an electrolyte;
the electrolyte is selected from at least one of ionic liquid, organic electrolyte and aqueous electrolyte;
preferably, the ionic liquid is selected from at least one of 1-ethyl-3-methylimidazole tetrafluoroborate, 1-ethyl-3-methylimidazole bistrifluoromethylsulfonyl imide salt and 1-butyl-3-methylimidazole hexafluorophosphate;
preferably, the organic electrolyte is selected from at least one of an acetonitrile solution of tetraethylammonium tetrafluoroborate salt and an acrylic carbonate solution of tetraethylammonium tetrafluoroborate salt;
preferably, the aqueous electrolyte is selected from KOH, H2SO4、Li2SO4At least one of (1).
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