CN113200545B - Capacitance carbon and preparation method thereof - Google Patents
Capacitance carbon and preparation method thereof Download PDFInfo
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- CN113200545B CN113200545B CN202110483371.XA CN202110483371A CN113200545B CN 113200545 B CN113200545 B CN 113200545B CN 202110483371 A CN202110483371 A CN 202110483371A CN 113200545 B CN113200545 B CN 113200545B
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- C01B32/00—Carbon; Compounds thereof
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- C01B32/342—Preparation characterised by non-gaseous activating agents
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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
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
- C01B32/324—Preparation characterised by the starting materials from waste materials, e.g. tyres or spent sulfite pulp liquor
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention relates to capacitance carbon and a preparation method thereof, which mainly adopts the technical scheme that: the preparation method of the capacitance carbon comprises the following steps: soaking the crushed and sieved biomass raw material into an additive solution for soaking treatment, and drying the biomass raw material subjected to soaking treatment to obtain the biomass raw material impregnated with the additive; the additive is a compound containing nitrogen and phosphorus; calcining the biomass raw material impregnated with the additive in a protective atmosphere, heating the calcining temperature to 100-350 ℃, preserving the heat for a first set time, heating the calcining temperature to 400-1000 ℃, and preserving the heat for a second set time to obtain a calcined product; and (4) washing and drying the calcined product to obtain the capacitance carbon. The invention realizes four effects of carbon fixation, carbonization, activation and doping by using a calcination one-step method, has the advantages of cheap and easily obtained raw materials, short process flow, simple operation, low cost, high yield and good performance, and is beneficial to realizing the industrial production and commercial application of the capacitance carbon.
Description
Technical Field
The invention relates to the technical field of capacitance carbon, in particular to capacitance carbon and a preparation method thereof.
Background
The super capacitor is also called as an electrochemical capacitor, is a novel green pollution-free energy storage device, has the characteristics of high charging and discharging speed, long service life, high power density, high energy conversion efficiency and the like, and has wide application prospects in the fields of electric automobiles, smart power grids, portable electronic equipment and the like. The super capacitor is mainly composed of components such as an electrode material, a diaphragm, electrolyte, a current collector and the like, wherein the electrode material is the key for determining the electrochemical performance of the super capacitor. In order to realize the commercial application of the electrode material, a preparation technology with short process route, low cost, high yield and good performance must be developed.
The biomass-based capacitance carbon material has the characteristics of good conductivity, large specific surface area, stable physicochemical properties, rich pore structure, cheap and easily available raw materials and the like, and becomes a research hotspot of the electrode material for the super capacitor.
At present, the conventional preparation method of biomass-based capacitance carbon material mainly comprises carbonization and activation treatment of biomass raw material, and also comprises a doping step in related technology, wherein common doping methods comprise a chemical vapor deposition method, a separation growth method, a solvothermal method, an arc discharge method, a heat treatment method, a plasma treatment method, a hydrazine hydrate treatment method and the like. However, each step in the conventional preparation method of the biomass-based capacitance carbon material needs to be performed step by step, so that the preparation process has long route, long operation flow and high cost.
Aiming at the problems, the invention provides a preparation technology which takes the agricultural and forestry waste biomass as a raw material and realizes four effects of carbon fixation, carbonization, activation and doping through a one-step method of dipping an additive and calcining; the preparation technology has the advantages of simple operation, short process flow and low cost, and can obtain the high-performance biomass-based capacitance carbon material doped with two N-P elements with high yield. The preparation technology is beneficial to realizing the industrial production and the commercial application of the capacitance carbon.
Disclosure of Invention
The invention provides capacitance carbon and a preparation method thereof, and mainly aims to realize four effects of carbon fixation, carbonization, activation and doping through the steps of additive impregnation and calcination, thereby shortening the preparation process flow of the capacitance carbon, reducing the preparation cost and being beneficial to realizing the industrial production and the commercial application of biomass-based capacitance carbon.
In order to achieve the above-mentioned object, the invention mainly provides the following technical scheme:
in one aspect, an embodiment of the present invention provides a method for preparing capacitance carbon, where the method includes the following steps:
and (3) dipping an additive: soaking the crushed and sieved biomass raw material into an additive solution for soaking treatment, and then drying the biomass raw material subjected to soaking treatment to obtain the biomass raw material impregnated with the additive; wherein the additive is a nitrogen and phosphorus containing compound;
and (3) calcining: calcining the biomass raw material impregnated with the additive in a protective atmosphere, wherein the calcining temperature is firstly increased to 100-350 ℃, the temperature is maintained for a first set time, then the calcining temperature is increased to 400-1000 ℃, and the temperature is maintained for a second set time to obtain a calcined product;
and (3) post-treatment: and washing and drying the calcined product to obtain the capacitance carbon.
Preferably, in the step of impregnating with an additive: the additive is one or two of ammonium dihydrogen phosphate and diammonium hydrogen phosphate.
Preferably, in the step of impregnating with an additive: the mass ratio of the biomass raw material to the additive in the additive solution is 1: (0.1-10).
Preferably, the time of the impregnation treatment is 0.5 to 12 hours.
Preferably, the additive solution comprises an additive and water; wherein the amount of water is such that the additive solution will submerge the biomass feedstock during the impregnation process.
Preferably, in the step of impregnating with an additive: the biomass raw material after being crushed is sieved by a sieve with 40 to 200 meshes.
Preferably, before the step of impregnating the additive, the method further comprises: and cleaning and drying the biomass raw material.
Preferably, the biomass raw material is agricultural and forestry waste biomass, and any one of corn leaves, straws, rice hulls and fruit shells is preferably selected.
Preferably, in the calcining step:
the calcination step is carried out in a tube furnace; and/or
The protective atmosphere is selected from a nitrogen atmosphere or an argon atmosphere; and/or
The first set time is 0.5-10h; and/or
The heating rate is 0.1-20 ℃/min when the calcining temperature is heated to 100-350 ℃; and/or
The second set time is 0.5-10h; and/or
The heating rate is 0.1-20 ℃/min when the temperature is raised to 400-1000 ℃ during the calcination.
Preferably, in the post-treatment step: and washing the calcined product by using deionized water until the calcined product is neutral, and drying to obtain the capacitance carbon.
Preferably, the yield of the capacitance carbon is 45-58%.
On the other hand, the embodiment of the invention provides capacitance carbon, which is prepared by any one of the above capacitance carbon preparation methods; wherein, theThe capacitance carbon is doped with N element and P element, and the capacitance carbon has micropores less than 2nm and mesopores of 2-50 nm; preferably, the total specific surface area of the capacitance carbon is 500-2000m 2 Per g, preferably 553.6-1629.6m 2 (ii)/g; preferably, the specific surface area of micropores of the capacitance carbon is 400-1500m 2 /g, preferably 473.5-1389.2m 2 (iv) g; preferably, the specific surface area of the mesopores of the capacitance carbon is 50 to 300m 2 Per g, preferably from 80.1 to 240.4m 2 (ii)/g; preferably, the first discharge specific capacitance of the capacitance carbon is more than or equal to 35.0F/g under the conditions of an organic system and a current density of 50 mA/g; the specific capacitance of the capacitor carbon for the first discharge is more than or equal to 65.0F/g under the conditions of an inorganic system and the current density of 50 mA/g; preferably, the capacitance carbon has a relative content of N element of 2-8%, preferably 2.12-7.32%, and a relative content of P element of 1-4%, preferably 1.12-3.18%.
Compared with the prior art, the capacitance carbon and the preparation method thereof have the following beneficial effects:
on one hand, according to the preparation method of the capacitive carbon provided by the embodiment of the invention, the screened biomass raw material is subjected to impregnation treatment firstly, and then the impregnated biomass raw material is subjected to a set calcination treatment process, so that four effects of carbon fixation, carbonization, activation and doping are achieved by using a calcination one-step method, the yield of the biological carbon is improved, the regulation and control of a pore structure and a specific surface area and the doping modification of two kinds of hetero atoms N, P are completed, and the capacitive carbon (porous carbon electrode material) with low cost and excellent electrochemical performance is obtained. The invention realizes the preparation method of 'carbon fixation-carbonization-activation-doping' by a one-step method of impregnation and then calcination, greatly simplifies the process flow and is beneficial to realizing the industrial production and commercial application of the biomass-based capacitance carbon.
On the other hand, the capacitance carbon provided by the embodiment of the invention is prepared by the preparation method of the capacitance carbon, has larger specific surface area and better pore size distribution, is doped with N, P heteroatom, and has excellent electrochemical performance.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical solutions of the present invention more clearly understood and to implement them in accordance with the contents of the description, the following detailed description is given with reference to the preferred embodiments of the present invention and the accompanying drawings.
Drawings
FIG. 1 is a flow chart of a method of making a capacitive carbon provided by an embodiment of the present invention;
FIG. 2 is an XRD spectrum of the capacitance carbon prepared in example 1 of the present invention and comparative example 1;
FIG. 3 shows N values of the capacitor carbon prepared in example 1 of the present invention and comparative example 1 2 Adsorption and desorption isothermal curves;
FIG. 4 is a pore size distribution diagram of the capacitance carbon prepared in example 1 of the present invention and comparative example 1;
FIG. 5 is an XPS spectrum of capacitance carbon prepared in example 1 of the present invention and comparative example 1;
fig. 6 is a specific capacity curve diagram of the capacitance carbon prepared in example 1 and comparative example 1 of the present invention.
Detailed Description
To further explain the technical means and effects of the present invention adopted to achieve the predetermined object, the following detailed description of the embodiments, structures, features and effects according to the present invention will be made with reference to the accompanying drawings and preferred embodiments. In the following description, different "one embodiment" or "an embodiment" refers to not necessarily the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
According to the invention, four effects of carbon fixation, carbonization, activation and doping are achieved by utilizing a calcination one-step method through the steps of firstly impregnating the additive solution and then carrying out a set calcination treatment process on the impregnated biomass raw material. The yield of the biochar is improved, and meanwhile, the regulation and control of a pore structure and a specific surface area and the doping modification of N, P heteroatom are completed, so that the capacitive carbon (porous carbon electrode material) with low cost and excellent electrochemical performance is obtained. The invention emphasizes that the preparation method of 'carbon fixation-carbonization-activation-doping' is realized by a one-step method of impregnation and then calcination, has low cost, short process flow and simple operation, and is beneficial to realizing the industrial production and commercial application of the biomass-based capacitance carbon.
The main process flow of the preparation method of the capacitance carbon provided by the embodiment of the invention is shown in figure 1, and mainly comprises the steps of impregnating an additive and calcining; the method comprises the following specific steps:
1) The biomass feedstock is cleaned.
The biomass raw material of the invention is mainly agricultural and forestry waste biomass, preferably corn leaves, straws, rice hulls and fruit shells, but is not limited thereto.
2) And (3) dipping an additive: and crushing and screening the cleaned biomass raw material, immersing the biomass raw material into an additive solution for impregnation, and drying the impregnated biomass raw material to obtain the biomass raw material impregnated with the additive.
Wherein, the additive is one or two of ammonium dihydrogen phosphate and diammonium hydrogen phosphate. The mass ratio of the biomass raw material to the additive in the additive solution is 1: (0.1-10). The time of the dipping treatment is 0.5-12h. The additive solution comprises an additive and water; wherein the amount of water is such that the additive solution will submerge the biomass feedstock during the impregnation process.
Here, it should be noted that: the mass ratio of the biomass material to the additive and the dipping time can be appropriately adjusted depending on the type of the biomass material and the type of the additive to be used. And setting the mass ratio of the biomass raw material to the additive in the additive solution as 1: (0.1-10), and further controlling the time of the dipping treatment to be 0.5-12h, so that the effects (such as carbon fixation, activation and doping) generated by the dipping additive can be achieved. Here, the impregnation mass ratio and the time of the impregnation treatment are set to the above ranges in view of the process requirement and the economic requirement.
Preferably, the biomass raw material after the crushing treatment passes through a sieve with 40-200 meshes. The selection of the particle size of the raw material is directly related to the impregnation treatment and the calcination process. Too small a particle size may result in a reduced char yield. Too large a particle size can result in too large a particle size of the final capacitive carbon product, resulting in a decrease in electrochemical performance.
3) And (3) calcining: and calcining the biomass raw material impregnated with the additive in a protective atmosphere, wherein the calcining temperature is firstly increased to 100-350 ℃, the temperature is maintained for a first set time, then the calcining temperature is increased to 400-1000 ℃, and the temperature is maintained for a second set time to obtain a calcined product.
Wherein the first set time is 0.5-10h; the heating rate is 0.1-20 ℃/min when the calcining temperature is heated to 100-350 ℃.
The second set time is 0.5-10h; the heating rate is 0.1-20 ℃/min when the temperature is raised to 400-1000 ℃ during the calcination.
4) And (3) post-treatment: and washing and drying the calcined product to obtain the capacitance carbon.
The theory of the synergy of the above steps, the step of impregnating the additive and the step of calcining, and how to achieve the four effects of carbon fixation, carbonization, activation and doping, of the present invention are described as follows:
the biomass raw material is impregnated, and then the biomass raw material impregnated with the additive is calcined at 100-350 ℃, so that the additive in the biomass raw material impregnated with the additive is heated and decomposed to generate phosphoric acid and ammonia gas. Wherein (1) phosphoric acid and biomass energy are subjected to esterification reaction, H atoms in the phosphoric acid are combined with-OH groups in the biomass to form water molecules to be removed, so that the catalytic action is generated in the chemical dehydration process of the biomass, the thermal decomposition process of the biomass is facilitated to be carried out towards the direction of generating solid carbon, more carbon atoms are left on the solid carbon skeleton instead of being carried out together with oxygen atoms by CO or CO 2 The form of the carbon dioxide is volatilized, or macromolecular oxygen-containing compounds, namely tar liquid substances, are generated, so that the purpose of carbon fixation is achieved. Meanwhile, the esterification reaction generates a phosphorus-containing compound, and phosphate radical is introduced into a biomass precursor to complete the doping of P; in the subsequent calcining temperature rise process of 400-1000 ℃, phosphate radicals have a barrier effect on the stacking process of the carbon microcrystals, so that the graphite-like microcrystal carbon layer is incomplete in development, is twisted or deformed to form defects, and further forms a pore structure in a sample, thereby forming a pore structure in carbonizationThe process of (2) completes the activation pore-forming at the same time. (2) The ammonia gas can promote the thermal polycondensation of olefin structure in biomass, is favorable for the generation of carbon microcrystal structure, and has the carbon fixing effect. Meanwhile, N element is introduced into the biomass structure, so that N doping is realized. In addition, the carbon fixation provided by the method mainly reduces the loss of carbon element, improves the yield and reduces the production cost.
The invention is further described below by means of specific examples:
example 1
The embodiment of the preparation of the capacitance carbon comprises the following specific preparation steps:
1) Cleaning: cleaning and drying the biomass raw material corn leaves.
2) Impregnation of an additive: crushing the corn leaves cleaned in the step 1), and then sieving the crushed corn leaves with a 60-mesh sieve. 10g of the sieved corn leaf particles are soaked in a diammonium hydrogen phosphate solution (wherein the mass ratio of the corn leaves to the diammonium hydrogen phosphate is 1:2; the water content in the diammonium hydrogen phosphate solution ensures that the diammonium hydrogen phosphate solution can submerge the corn leaves), stirred, soaked and treated for 6 hours, and then dried to obtain the corn leaves soaked with diammonium hydrogen phosphate.
3) Calcining (carbon fixation-carbonization-activation-doping): putting the corn leaves soaked with diammonium hydrogen phosphate into a tubular furnace, and calcining in a nitrogen atmosphere; specifically, the temperature is increased to 200 ℃ at the heating rate of 2 ℃/min, the temperature is kept for 2h, then the temperature is increased to 700 ℃ at the heating rate of 2 ℃/min, and the temperature is kept for 1h. And cooling, taking out the calcined product, washing with deionized water to be neutral, and drying to obtain the capacitance carbon.
Example 2
This example prepared a capacitance carbon, and compared to example 1, the difference was step 2), and the other steps were identical. Wherein, step 2) of this embodiment is specifically as follows:
2) Impregnation of an additive: crushing the corn leaves cleaned in the step 1), and then sieving the crushed corn leaves with a 60-mesh sieve. Taking 10g of sieved corn She Jinyu diammonium phosphate solution (wherein the mass ratio of corn leaves to diammonium phosphate is 1:0.1, and the water content in the diammonium phosphate solution ensures that the diammonium phosphate solution can immerse the corn leaves), stirring, dipping for 12 hours, and drying to obtain the corn leaves dipped with diammonium phosphate.
And other steps are consistent.
Example 3
In this example, a capacitance carbon was prepared, and compared with example 1, the preparation steps of this example are different in step 2), and the other steps are the same. Wherein, step 2) of this embodiment is specifically as follows:
2) Impregnation of an additive: crushing the corn leaves cleaned in the step 1), and then sieving the crushed corn leaves with a 60-mesh sieve. Taking 10g of sieved corn She Jinyu diammonium hydrogen phosphate solution (wherein the mass ratio of corn leaves to diammonium hydrogen phosphate is 1.
And other steps are consistent.
Example 4
In this example, a capacitance carbon was prepared, and compared with example 1, the preparation steps of this example are different in step 2), and the other steps are the same. Wherein, step 2) of this embodiment is specifically as follows:
2) Impregnation of an additive: crushing the corn leaves cleaned in the step 1), and then sieving the crushed corn leaves with a 60-mesh sieve. 10g of sieved corn She Jinyu diammonium hydrogen phosphate solution (wherein the mass ratio of corn leaves to diammonium hydrogen phosphate is 1:5, and the water content in the diammonium hydrogen phosphate solution ensures that the diammonium hydrogen phosphate solution can submerge the corn leaves), stirring, soaking and drying for 6 hours to obtain the corn leaves soaked with diammonium hydrogen phosphate.
The other steps are consistent.
Example 5
In this example, a capacitance carbon was prepared, and compared with example 1, the preparation steps of this example are different in step 3), and the other steps are the same. Wherein, step 3) of this embodiment is specifically as follows:
3) And (3) calcining: putting the corn leaves soaked with diammonium hydrogen phosphate into a tubular furnace, and calcining in a nitrogen atmosphere; specifically, the temperature is raised to 350 ℃ at the heating rate of 2 ℃/min, the temperature is kept for 0.5h, then the temperature is raised to 1000 ℃ at the heating rate of 2 ℃/min, and the temperature is kept for 0.5h. And cooling, taking out the calcined product, washing with deionized water to be neutral, and drying to obtain the capacitance carbon.
Example 6
In this example, a capacitance carbon was prepared, and compared with example 1, the preparation steps of this example are different in step 3), and the other steps are the same. Wherein, step 3) of this embodiment is specifically as follows:
3) And (3) calcining: putting the corn leaves impregnated with diammonium hydrogen phosphate into a tubular furnace, and calcining in a nitrogen atmosphere; specifically, the temperature is increased to 100 ℃ at the heating rate of 2 ℃/min, the temperature is kept for 10h, then the temperature is increased to 400 ℃ at the heating rate of 2 ℃/min, and the temperature is kept for 10h. And cooling, taking out the calcined product, washing with deionized water to be neutral, and drying to obtain the capacitance carbon.
Example 7
In this example, compared with example 1, in this example, in the step of dipping treatment, the additive solution adopted is ammonium dihydrogen phosphate, and other steps and process parameters are consistent
Example 8
This example is a capacitance carbon, and compared with example 1, the difference is that rice hulls are used as raw materials, and other preparation steps are consistent.
Comparative example 1
Comparative example 1 a capacitive carbon was prepared with the following specific steps:
1) Cleaning and drying the corn leaves.
2) Crushing the corn leaves cleaned in the step 1), and then sieving the crushed corn leaves with a 60-mesh sieve. 10g of sieved corn leaves are placed in a tubular furnace and calcined in nitrogen atmosphere; specifically, the temperature is increased to 200 ℃ at the heating rate of 2 ℃/min, the temperature is kept for 2h, then the temperature is increased to 700 ℃ at the heating rate of 2 ℃/min, and the temperature is kept for 1h. And cooling, taking out the calcined product, washing with deionized water to be neutral, and drying to obtain the capacitance carbon.
The capacitive carbons prepared in examples 1-8 and comparative example 1 were characterized by the following structures:
1. the yields of the capacitance carbons prepared in examples 1 to 8 and comparative example 1 are shown in table 1.
TABLE 1
| Capacitance carbon | Yield (%) |
| Comparative example 1 | 26.5 |
| Example 1 | 45.9 |
| Example 2 | 45.0 |
| Example 3 | 58.0 |
| Example 4 | 53.7 |
| Example 5 | 48.6 |
| Example 6 | 54.9 |
| Example 7 | 47.2 |
| Example 8 | 51.4 |
As can be seen from Table 1, the yield of the capacitance carbon prepared in examples 1 to 8 of the present invention is greatly improved as compared with comparative example 1, and the purpose of expecting to improve the carbon yield is achieved.
2. The XRD patterns of the capacitive carbon prepared in example 1 and comparative example 1 are shown in fig. 2.
Fig. 2 is an XRD spectrum of the capacitive carbon prepared in example 1 and comparative example 1. As can be seen from fig. 2: the XRD pattern of the capacitive carbon prepared in example 1 has a relatively sharp small angle (2 θ < 10 °), high intensity, and a tendency of intensity decrease with an increase in scanning angle, i.e., a "tailing" shape, which indicates that a certain amount of pore structure exists in the capacitive carbon prepared in example 1 of the present invention. The XRD profile of the capacitive carbon prepared in comparative example 1 also exhibited a certain "tailing" phenomenon, but was not very significant. It was shown that the capacitive carbon prepared in example 1 had a more developed pore structure than comparative example 1.
3. N of capacitance carbon prepared in example 1 and comparative example 1 2 The adsorption and desorption isotherms are shown in FIG. 3.
As can be seen from FIG. 3, the method for preparing the capacity carbon according to example 1 of the present invention allows N of the capacity carbon to be increased through the step of impregnating the additive, as compared with comparative example 1 2 The adsorption and desorption amount is obviously increased, which shows that the capacitance carbon has larger specific surface area through impregnation modification, and the purpose of regulating and controlling the specific surface area is achieved.
4. The specific surface areas of the total, micropores and mesopores of the capacitor carbons prepared in examples 1 to 8 and comparative example 1 are shown in Table 2.
TABLE 2
| Sample (I) | S General assembly (m 2 /g) | S Micro-pores (m 2 /g) | S Mesopores (m 2 /g) |
| Comparative example 1 | 201.5 | 175.5 | 26.0 |
| Example 1 | 596.7 | 506.5 | 90.2 |
| Example 2 | 553.6 | 473.5 | 80.1 |
| Example 3 | 1629.6 | 1389.2 | 240.4 |
| Example 4 | 1287.9 | 1065.8 | 222.1 |
| Example 5 | 816.5 | 674.1 | 142.4 |
| Example 6 | 738.2 | 602.1 | 136.1 |
| Example 7 | 693.7 | 586.9 | 106.8 |
| Example 8 | 939.4 | 802.1 | 137.3 |
As can be seen from table 2: the total specific surface area of the capacitive carbon prepared in comparative example 1 was 201.5m 2 (g), the specific surface area of the carbon capacitors of examples 1 to 8 of the present invention was 553.6 to 1629.6m 2 The specific surface area of micropores (< 2 nm) and mesopores (2-50 nm) of the capacitance carbon prepared by the embodiment of the invention is increased, and the aim of increasing the specific surface area by activation is achieved.
5. The pore size distribution of the capacitance carbon prepared in example 1 and comparative example 1 is shown in fig. 4.
As can be seen from fig. 4: according to the preparation method of the capacitance carbon provided by the embodiment of the invention, through the step of impregnating the additive, the number of micropores and mesopores of the capacitance carbon can be obviously increased, which shows that the impregnation additive achieves the purpose of optimizing the pore structure, and the result is consistent with the XRD characterization result.
The above shows that: the preparation method of the capacitance carbon provided by the embodiment of the invention can achieve the purpose of activating and pore-forming through the step of dipping the additive, so that the capacitance carbon has larger specific surface area and better pore size distribution, and is beneficial to improving the electrochemical performance.
6. XPS spectra of the capacitance carbon prepared in example 1 and comparative example 1 are shown in fig. 5.
It can be seen from the XPS spectrum and the data in table 3 that the content of N, P element in the carbon materials prepared in examples 1-8 is much higher than the content of N, P element in the carbon material of comparative example 1, and the preparation scheme of the embodiment of the invention can realize the doping modification of N, P two kinds of hetero atoms, thereby achieving the design purpose of the doping modification of the invention.
Table 3 shows the comparison of the relative content of CONP in the capacitive carbon prepared in examples 1 to 8 and comparative example 1
TABLE 3
| Sample (I) | C(％) | O(％) | N(％) | P(％) |
| Comparative example 1 | 89.46 | 10.48 | 0.04 | 0.02 |
| Example 1 | 85.57 | 4.89 | 6.71 | 2.83 |
| Example 2 | 92.37 | 3.36 | 2.42 | 1.85 |
| Example 3 | 85.11 | 4.56 | 7.32 | 3.01 |
| Example 4 | 87.23 | 3.13 | 6.88 | 2.76 |
| Example 5 | 95.33 | 1.01 | 2.12 | 1.54 |
| Example 6 | 80.23 | 10.25 | 6.34 | 3.18 |
| Example 7 | 84.42 | 8.27 | 6.08 | 1.23 |
| Example 8 | 86.08 | 7.51 | 5.29 | 1.12 |
7. FIG. 6 is a graph showing the specific capacity of the capacitor carbon prepared in example 1 and comparative example 1.
As can be seen from fig. 6: the discharge time of the capacitor carbon prepared in example 1 is longer than that of the capacitor carbon prepared in comparative example 1, which shows that the specific capacity of the capacitor carbon is increased and the electrochemical performance is improved by the step of impregnating the additive in the capacitor carbon preparation method provided by the embodiment of the invention.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent change and modification made to the above embodiment according to the technical spirit of the present invention are still within the scope of the technical solution of the present invention.
Claims (17)
1. The preparation method of the capacitance carbon is characterized by comprising the following steps:
and (3) dipping an additive: soaking the crushed and sieved biomass raw material into an additive solution for soaking treatment, and then drying the biomass raw material subjected to soaking treatment to obtain the biomass raw material impregnated with the additive; wherein the additive is a nitrogen and phosphorus containing compound; wherein, the additive is one or two of ammonium dihydrogen phosphate and diammonium hydrogen phosphate; the mass ratio of the biomass raw material to the additive in the additive solution is 1: (0.1-10); the biomass raw material is corn leaves or rice hulls;
and (3) calcining: calcining the biomass raw material impregnated with the additive in a protective atmosphere, wherein the calcining temperature is firstly increased to 100-350 ℃, the temperature is maintained for a first set time, then the calcining temperature is increased to 400-1000 ℃, and the temperature is maintained for a second set time to obtain a calcined product; the first set time is 0.5-10h; the second set time is 0.5-10h;
and (3) post-treatment: and washing and drying the calcined product to obtain the capacitance carbon.
2. The method of making capacitive carbon of claim 1, wherein in the step of impregnating an additive: the time of the dipping treatment is 0.5-12h.
3. The method of making capacitive carbon of claim 1, wherein the additive solution comprises an additive and water; wherein the amount of water is such that the additive solution will submerge the biomass feedstock during the impregnation process.
4. The method of making capacitive carbon of claim 1, wherein in the step of impregnating an additive: sieving the crushed biomass raw material through a 40-200 mesh sieve; and/or
Before the step of impregnating the additive, the method further comprises the following steps: and cleaning and drying the biomass raw material.
5. The method of making capacitive carbon of claim 1, wherein in the calcining step:
the calcination step is carried out in a tube furnace; and/or
The protective atmosphere is selected from a nitrogen atmosphere or an argon atmosphere; and/or
The heating rate is 0.1-20 ℃/min when the calcining temperature is increased to 100-350 ℃; and/or
The heating rate is 0.1-20 ℃/min when the temperature of the calcination is raised to 400-1000 ℃.
6. The method of producing capacitive carbon according to claim 1, wherein in the post-treatment step:
and washing the calcined product by using deionized water until the calcined product is neutral, and drying to obtain the capacitance carbon.
7. The method of producing capacitive carbon according to any one of claims 1 to 6, wherein the yield of capacitive carbon is 45 to 58%.
8. A capacitive carbon, characterized in that the capacitive carbon is prepared by the method for preparing the capacitive carbon according to any one of claims 1 to 7;
the capacitor carbon is doped with N element and P element, and has micropores smaller than 2nm and mesopores of 2-50 nm.
9. The capacitive carbon of claim 8 having a total specific surface area of 500-2000m 2 /g。
10. The capacitive carbon of claim 9 having a total specific surface area of 553.6-1629.6m 2 /g。
11. The capacitive carbon of claim 8 having a specific surface area of micropores of 400-1500m 2 /g。
12. The capacitive carbon of claim 11 having a micropore specific surface area of 473.5 to 1389.2m 2 /g。
13. The capacitive carbon of claim 8, wherein the specific surface area of the mesopore of the capacitive carbon is 50 to 300m 2 /g。
14. The capacitive carbon of claim 13 having a specific surface area of mesopores of 80.1 to 240.4m 2 /g。
15. The capacitive carbon according to claim 8, wherein the first discharge specific capacitance of the capacitive carbon is not less than 35.0F/g under the condition of an organic system and a current density of 50 mA/g; the specific capacitance of the capacitance carbon for the first time is more than or equal to 65.0F/g under the conditions of an inorganic system and a current density of 50 mA/g.
16. The capacitive carbon of claim 8 wherein the capacitive carbon has a relative content of N elements of 2-8% and a relative content of P elements of 1-4%.
17. The capacitive carbon of claim 16 wherein the capacitive carbon has a relative content of N element of 2.12-7.32% and a relative content of P element of 1.12-3.18%.
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