CN113200545A - Capacitance carbon and preparation method thereof - Google Patents
Capacitance carbon and preparation method thereof Download PDFInfo
- Publication number
- CN113200545A CN113200545A CN202110483371.XA CN202110483371A CN113200545A CN 113200545 A CN113200545 A CN 113200545A CN 202110483371 A CN202110483371 A CN 202110483371A CN 113200545 A CN113200545 A CN 113200545A
- Authority
- CN
- China
- Prior art keywords
- carbon
- additive
- capacitance
- raw material
- biomass raw
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
- C01B32/342—Preparation characterised by non-gaseous activating agents
-
- 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
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Materials Engineering (AREA)
- Carbon And Carbon Compounds (AREA)
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 calcination temperature to 350-; 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 purpose, 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 raised to 350 ℃ for 100-;
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 0.5-10 h; and/or
The heating rate is 0.1-20 ℃/min when the calcining temperature is raised to 100-350 ℃; and/or
The second set time is 0.5-10 h; and/or
The heating rate is 0.1-20 ℃/min when the temperature of the calcination is raised to 400-1000 ℃.
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 the capacitance carbon, which is prepared by any one of the preparation methods of the capacitance carbon; the capacitor carbon is doped with N element and P element, and has micropores smaller than 2nm and mesopores of 2-50 nm; preferably, the total specific surface area of the capacitance carbon is 500-2000m2Per g, preferably from 553.6 to 1629.6m2(ii)/g; preferably, the specific surface area of the micropores of the capacitance carbon is 400-1500m2Per g, preferably 473.5 to 1389.2m2(ii)/g; preferably, the specific surface area of the mesopores of the capacitance carbon is 50 to 300m2Per g, preferably from 80.1 to 240.4m2(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 capacitance carbon has a first discharge specific capacitance of more than or equal to 65.0F/g under the conditions of an inorganic system and a current density of 50 mA/g; preferably, the relative content of the N element in the capacitance carbon is 2-8%, preferably 2.12-7.32%, and the relative content of the P element is 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 the pore structure and the 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 a larger specific surface area and a better pore size distribution, is doped with N, P heteroatoms, 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 12Adsorption 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 heteroatoms 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 0.5-12 h. 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 350 ℃ for 100-.
Wherein the first set time is 0.5-10 h; the heating rate is 0.1-20 ℃/min when the calcination temperature is raised to 100-350 ℃.
The second set time is 0.5-10 h; the heating rate is 0.1-20 ℃/min when the temperature of the calcination is raised to 400-1000 ℃.
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 method comprises the steps of impregnating the biomass raw material, calcining the biomass raw material impregnated with the additive at the temperature of 100-350 ℃ so as to thermally decompose the additive in the biomass raw material impregnated with the additive to generate phosphoric acid and ammoniaAnd (4) qi. 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 CO2The 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 calcination temperature rise process of 400-. (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 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), and the corn leaves soaked with the diammonium hydrogen phosphate are obtained after stirring, soaking and drying treatment for 6 hours.
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 1 h. 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. Soaking 10g of sieved corn leaves in a diammonium hydrogen phosphate solution (wherein the mass ratio of the corn leaves to the diammonium hydrogen phosphate is 1: 0.1, and the water content in the diammonium hydrogen phosphate solution ensures that the diammonium hydrogen phosphate solution can submerge the corn leaves), stirring, soaking for 12 hours, and drying to obtain the corn leaves soaked with diammonium hydrogen 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. Soaking 10g of sieved corn leaves in a diammonium hydrogen phosphate solution (wherein the mass ratio of the corn leaves to the diammonium hydrogen phosphate is 1: 10, and the water content in the diammonium hydrogen phosphate solution ensures that the diammonium hydrogen phosphate solution can submerge the corn leaves), stirring, soaking for 0.5h, and drying to obtain the corn leaves soaked with diammonium hydrogen phosphate.
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. Soaking 10g of sieved corn leaves in a diammonium hydrogen phosphate solution (wherein the mass ratio of the corn leaves to the 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 for 6h, and drying to obtain the corn leaves soaked with diammonium hydrogen phosphate.
And 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 0.5 h. 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 soaked 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 10 h. 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 1 h. 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 capacitance 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 12The adsorption and desorption isotherms are shown in FIG. 3.
As can be seen from FIG. 3, the capacitance carbon proposed in example 1 of the present invention is compared with comparative example 1The preparation method comprises the step of impregnating the additive to ensure that the N of the capacitance carbon2The 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) | SGeneral assembly(m2/g) | SMicro-pores(m2/g) | SMesopores(m2/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 carbon capacitor prepared in comparative example 1 was 201.5m2(g), the specific surface area of the carbon capacitors of examples 1 to 8 of the present invention was 553.6 to 1629.6m2The specific surface area of micropores (< 2nm) and mesopores (2-50nm) 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 fulfilled.
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 examples of the present invention can realize the doping modification of N, P two kinds of heteroatoms, so as to achieve the design purpose of the doping modification of the present invention.
Table 3 shows 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 capacitance carbon prepared in the embodiment 1 is longer than that of the capacitance carbon prepared in the comparison example 1, which shows that the capacitance carbon preparation method provided by the embodiment of the invention increases the specific capacity of the capacitance carbon and improves the electrochemical performance through the step of impregnating the additive.
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 (10)
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;
and (3) calcining: calcining the biomass raw material impregnated with the additive in a protective atmosphere, wherein the calcining temperature is firstly raised to 350 ℃ for 100-;
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 additive is one or two of ammonium dihydrogen phosphate and diammonium hydrogen phosphate; and/or
The mass ratio of the biomass raw material to the additive in the additive solution is 1: (0.1-10).
3. The method of preparing capacitive carbon according to claim 1 or 2, wherein in the step of impregnating an additive: the time of the dipping treatment is 0.5-12 h.
4. The method of making capacitive carbon of any one of claims 1-3, 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.
5. The method of making capacitive carbon of any one of claims 1-4, 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.
6. The method for preparing the capacitive carbon according to any one of claims 1 to 4, wherein the biomass raw material is agricultural and forestry waste biomass, preferably any one of corn leaves, straws, rice hulls and fruit shells.
7. The method of making capacitive carbon of any one of claims 1-6, 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 first set time is 0.5-10 h; and/or
The heating rate is 0.1-20 ℃/min when the calcining temperature is raised to 100-350 ℃; and/or
The second set time is 0.5-10 h; and/or
The heating rate is 0.1-20 ℃/min when the temperature of the calcination is raised to 400-1000 ℃.
8. The method for producing capacitive carbon according to any one of claims 1 to 7, 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.
9. The method of producing capacitive carbon according to any one of claims 1 to 8, wherein the yield of capacitive carbon is 45 to 58%.
10. A capacitance carbon, characterized in that the capacitance carbon is prepared by the method for preparing the capacitance carbon according to any one of claims 1 to 9;
the capacitor carbon is doped with N element and P element, and has micropores smaller than 2nm and mesopores of 2-50 nm;
preferably, the total specific surface area of the capacitance carbon is 500-2000m2Per g, preferably from 553.6 to 1629.6m2/g；
Preferably, the specific surface area of the micropores of the capacitance carbon is 400-1500m2Per g, preferably 473.5 to 1389.2m2/g；
Preferably, the specific surface area of the mesopores of the capacitance carbon is 50 to 300m2Per g, preferably from 80.1 to 240.4m2/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 capacitance carbon has a first discharge specific capacitance of more than or equal to 65.0F/g under the conditions of an inorganic system and a current density of 50 mA/g;
preferably, the relative content of the N element in the capacitance carbon is 2-8%, preferably 2.12-7.32%, and the relative content of the P element is 1-4%, preferably 1.12-3.18%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110483371.XA CN113200545B (en) | 2021-04-30 | 2021-04-30 | Capacitance carbon and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110483371.XA CN113200545B (en) | 2021-04-30 | 2021-04-30 | Capacitance carbon and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113200545A true CN113200545A (en) | 2021-08-03 |
| CN113200545B CN113200545B (en) | 2022-12-02 |
Family
ID=77029938
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110483371.XA Active CN113200545B (en) | 2021-04-30 | 2021-04-30 | Capacitance carbon and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113200545B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113479881A (en) * | 2021-08-24 | 2021-10-08 | 中国科学院山西煤炭化学研究所 | Method for improving purity of capacitance carbon |
| CN113880086A (en) * | 2021-10-30 | 2022-01-04 | 中国海洋大学 | Preparation method of nitrogen-phosphorus co-doped biomass derived capacitive deionization electrode |
Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6369155A (en) * | 1986-09-11 | 1988-03-29 | Toshiba Battery Co Ltd | Nonaqueous electrolyte secondary battery |
| US5102855A (en) * | 1990-07-20 | 1992-04-07 | Ucar Carbon Technology Corporation | Process for producing high surface area activated carbon |
| CN101475165A (en) * | 2008-12-25 | 2009-07-08 | 东华大学 | Method for preparing active carbon from straw stalk |
| CN101778794A (en) * | 2007-02-14 | 2010-07-14 | 肯塔基大学研究基金会 | Form the method for activated carbon |
| CN102583311A (en) * | 2012-02-07 | 2012-07-18 | 北京林业大学 | Method for preparing biomass carbon by utilizing agricultural and forestry waste |
| CN103011155A (en) * | 2013-01-05 | 2013-04-03 | 湖南奇异生物科技有限公司 | Method for preparing activated carbon by utilizing camellia oleifera shells |
| CN103771410A (en) * | 2012-10-24 | 2014-05-07 | 南京席瑞斯化工有限公司 | Preparation method for crop straw active carbon |
| CN108383119A (en) * | 2018-04-16 | 2018-08-10 | 吉林农业大学 | A kind of method that microorganism prepares maize straw multi-stage porous absorbent charcoal material |
| CN108389728A (en) * | 2018-02-07 | 2018-08-10 | 中国地质大学（武汉） | A kind of preparation method of nitrogen/phosphorus/oxygen heterogeneous element codope carbon electrode material |
| CN109019554A (en) * | 2018-07-31 | 2018-12-18 | 湖南理工学院 | A kind of nitrogen-phosphor codoping multiporous biological matter carbon material and preparation method thereof and the application in supercapacitor |
| CN109473291A (en) * | 2018-11-09 | 2019-03-15 | 天津工业大学 | A kind of N of the superelevation specific capacitance based on cotton, the novel preparation method of P codope Porous hollow Carbon fibe |
| CN109767927A (en) * | 2019-01-17 | 2019-05-17 | 中南大学 | A kind of preparation method of the supercapacitor biomass porous carbon of high-performance N doping |
| CN110015662A (en) * | 2019-04-25 | 2019-07-16 | 太原理工大学 | A kind of CO absorption2With the preparation method of nitrogen-doped porous carbon material |
| CN110858645A (en) * | 2018-08-23 | 2020-03-03 | 住友大阪水泥股份有限公司 | Positive electrode material for lithium ion secondary battery, method for producing same, positive electrode for lithium ion secondary battery, and lithium ion secondary battery |
| CN111268675A (en) * | 2020-02-28 | 2020-06-12 | 上海应用技术大学 | Method for preparing nitrogen-phosphorus co-doped carbon material by taking durian peel as raw material |
| CN112174136A (en) * | 2020-08-20 | 2021-01-05 | 浙江大学 | High-nitrogen biochar composite material and preparation method and application thereof |
-
2021
- 2021-04-30 CN CN202110483371.XA patent/CN113200545B/en active Active
Patent Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6369155A (en) * | 1986-09-11 | 1988-03-29 | Toshiba Battery Co Ltd | Nonaqueous electrolyte secondary battery |
| US5102855A (en) * | 1990-07-20 | 1992-04-07 | Ucar Carbon Technology Corporation | Process for producing high surface area activated carbon |
| CN101778794A (en) * | 2007-02-14 | 2010-07-14 | 肯塔基大学研究基金会 | Form the method for activated carbon |
| CN101475165A (en) * | 2008-12-25 | 2009-07-08 | 东华大学 | Method for preparing active carbon from straw stalk |
| CN102583311A (en) * | 2012-02-07 | 2012-07-18 | 北京林业大学 | Method for preparing biomass carbon by utilizing agricultural and forestry waste |
| CN103771410A (en) * | 2012-10-24 | 2014-05-07 | 南京席瑞斯化工有限公司 | Preparation method for crop straw active carbon |
| CN103011155A (en) * | 2013-01-05 | 2013-04-03 | 湖南奇异生物科技有限公司 | Method for preparing activated carbon by utilizing camellia oleifera shells |
| CN108389728A (en) * | 2018-02-07 | 2018-08-10 | 中国地质大学（武汉） | A kind of preparation method of nitrogen/phosphorus/oxygen heterogeneous element codope carbon electrode material |
| CN108383119A (en) * | 2018-04-16 | 2018-08-10 | 吉林农业大学 | A kind of method that microorganism prepares maize straw multi-stage porous absorbent charcoal material |
| CN109019554A (en) * | 2018-07-31 | 2018-12-18 | 湖南理工学院 | A kind of nitrogen-phosphor codoping multiporous biological matter carbon material and preparation method thereof and the application in supercapacitor |
| CN110858645A (en) * | 2018-08-23 | 2020-03-03 | 住友大阪水泥股份有限公司 | Positive electrode material for lithium ion secondary battery, method for producing same, positive electrode for lithium ion secondary battery, and lithium ion secondary battery |
| CN109473291A (en) * | 2018-11-09 | 2019-03-15 | 天津工业大学 | A kind of N of the superelevation specific capacitance based on cotton, the novel preparation method of P codope Porous hollow Carbon fibe |
| CN109767927A (en) * | 2019-01-17 | 2019-05-17 | 中南大学 | A kind of preparation method of the supercapacitor biomass porous carbon of high-performance N doping |
| CN110015662A (en) * | 2019-04-25 | 2019-07-16 | 太原理工大学 | A kind of CO absorption2With the preparation method of nitrogen-doped porous carbon material |
| CN111268675A (en) * | 2020-02-28 | 2020-06-12 | 上海应用技术大学 | Method for preparing nitrogen-phosphorus co-doped carbon material by taking durian peel as raw material |
| CN112174136A (en) * | 2020-08-20 | 2021-01-05 | 浙江大学 | High-nitrogen biochar composite material and preparation method and application thereof |
Non-Patent Citations (5)
| Title |
|---|
| HAN, JM ET AL.: "High-Surface-Area Nitrogen/Phosphorus Dual-Doped Hierarchical Porous Carbon Derived from Biochar for Sulfur Holder", 《CHEMISTRYSELECT》 * |
| LI, M ET AL.: "Removal of nitrogen and phosphorus pollutants from water by FeCl3-impregnated biochar", 《ECOLOGICAL ENGINEERING》 * |
| 林晓强: "生物质基多孔炭材料的制备及性能", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
| 王振: "炭基电极材料的制备及其表面性质对电化学性能的影响", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
| 王茜: "秸秆成型燃料提质及清洁燃烧特性研究", 《中国博士学位论文全文数据库 工程科技Ⅱ辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113479881A (en) * | 2021-08-24 | 2021-10-08 | 中国科学院山西煤炭化学研究所 | Method for improving purity of capacitance carbon |
| CN113880086A (en) * | 2021-10-30 | 2022-01-04 | 中国海洋大学 | Preparation method of nitrogen-phosphorus co-doped biomass derived capacitive deionization electrode |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113200545B (en) | 2022-12-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11370665B2 (en) | Method for producing activated carbon | |
| CN108483442B (en) | Preparation method of nitrogen-doped carbon electrode material with high mesoporous rate | |
| US20230115681A1 (en) | Nitrogen-doped porous carbon material and preparation method and application thereof | |
| KR100886365B1 (en) | Activated carbon with ultra-high specific surface area from corn and Production method of thereof | |
| CN113200545B (en) | Capacitance carbon and preparation method thereof | |
| CN108128773A (en) | A kind of method that electrode for electrochemical capacitor carbon material is prepared using peanut shell | |
| CN110817838B (en) | Nitrogen-sulfur co-doped porous carbon material and preparation method and application thereof | |
| CN107215871B (en) | A kind of preparation method of activated carbon for super capacitors | |
| CN109437165B (en) | Fluorine and nitrogen co-doped three-dimensional graphene material and one-step carbonization preparation method thereof | |
| Zhang et al. | Preparation and electrochemical performance of coconut shell activated carbon produced by the H3PO4 activation with rapid cooling method | |
| CN109637843A (en) | A method of supercapacitor is prepared by electrode material of celery | |
| KR100878262B1 (en) | Production method of high performance activated carbon from soybean curd residue | |
| CN108178141B (en) | Preparation method of microporous carbon with high conductivity, high tap density and high specific surface area | |
| CN109970056B (en) | Preparation method and application of biomass-based ordered microporous carbon material | |
| CN115547700A (en) | Derivative plant-based porous carbon and preparation method and application thereof | |
| CN115849377A (en) | Active carbon composite material and preparation method and application thereof | |
| CN114516627B (en) | Preparation method of soft and hard carbon composite nano material | |
| CN115010117A (en) | Preparation method and application of active metal modified carbon nanotube brush material | |
| KR20190073710A (en) | Method for manufacturing activated carbon for electrode material | |
| CN114613611A (en) | Preparation method and application of oxygen-enriched hollow tubular porous carbon | |
| CN114291806A (en) | Multi-scale regulation and control method for graphitization degree of low-order coal-based porous carbon | |
| CN111924842A (en) | Lotus stalk-based electrode material and preparation method thereof | |
| CN112520736A (en) | Method for preparing high-performance carbon-based electrode material by biomass full-component pyrolysis | |
| CN113511654B (en) | Capacitance carbon and preparation method thereof | |
| CN116443877B (en) | Coal-based three-dimensional porous carbon and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |