CN114477172A - Preparation method and application of straw-based porous carbon with honeycomb-shaped pore structure - Google Patents

Preparation method and application of straw-based porous carbon with honeycomb-shaped pore structure Download PDF

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CN114477172A
CN114477172A CN202210218023.4A CN202210218023A CN114477172A CN 114477172 A CN114477172 A CN 114477172A CN 202210218023 A CN202210218023 A CN 202210218023A CN 114477172 A CN114477172 A CN 114477172A
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straw
nitrogen
phosphorus
boron
porous carbon
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杨海霞
岳贤东
李浩铜
李浩坤
刘敬肖
史非
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Dalian Polytechnic University
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    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/30Active carbon
    • C01B32/312Preparation
    • C01B32/318Preparation characterised by the starting materials
    • C01B32/324Preparation characterised by the starting materials from waste materials, e.g. tyres or spent sulfite pulp liquor
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/30Active carbon
    • C01B32/312Preparation
    • C01B32/342Preparation characterised by non-gaseous activating agents
    • C01B32/348Metallic compounds
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/24Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their material
    • H01G11/32Carbon-based
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes

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Abstract

The invention discloses a preparation method of boron, nitrogen and phosphorus co-doped straw-based biomass carbon with honeycomb pores, and belongs to the technical field of functional material preparation. The invention solves the problem of high cost of the electrode material of the conventional super capacitor. According to the invention, straws are used as raw materials, boric acid, urea and disodium hydrogen phosphate are respectively used as cheap boron source, nitrogen source and phosphorus source, high-temperature treatment is carried out under the protection of nitrogen atmosphere after potassium hydroxide activation, and then acid pickling and drying are carried out, thus finally obtaining the boron, nitrogen, phosphorus and other multi-element co-doped biomass porous carbon. The invention has low production cost and simple process, and the obtained material can be used as an electrode material of a super capacitor, and has high specific capacitance and excellent cycle performance.

Description

Preparation method and application of straw-based porous carbon with honeycomb-shaped pore structure
Technical Field
The invention relates to a preparation method and application of waste straw biomass porous carbon with honeycomb-shaped pores, and belongs to the technical field of functional material preparation.
Background
With the continuous development of scientific technology and industrial engineering, a large amount of non-renewable resources such as coal, petroleum, natural gas and the like are consumed, so that fossil energy is increasingly deficient. In order to be able to continue to satisfy the development of global industry, research on new energy materials that can replace fossil energy is an urgent problem to be solved in the modern times. As a world agricultural kingdom, China has a great amount of waste straws which are incinerated or buried for treatment because the waste straws cannot be utilized every year, and the waste straws have great harm to the global environment. The data show that the total amount of the waste straws in China in 2021 is over 8 hundred million tons and is in a trend of increasing year by year. In order to respond to the idea of energy conservation and environmental protection advocated by the state, governments in various places actively take measures to forbid large-area burning of the waste straws, but the technical means of utilizing straw resources without forming is hindered. In order not to influence normal agricultural production, only packaging and centralized incineration can be finally adopted for thermal power generation. The power generation mode is not only low in efficiency, but also does not substantially improve the problem of environmental pollution, so that the conversion of waste straws into biomass energy materials with high utilization value is a problem to be solved urgently.
Super capacitors have attracted attention since the advent as a new generation of energy storage materials, and exhibit the advantages of fast charge and discharge rates, short time, high power density, good cycle stability, long service life, and the like, as compared to lithium ion batteries. The energy storage performance of the supercapacitor is mainly determined by a developed pore structure inside the electrode material. Therefore, designing an electrode material with excellent pore structure and conductivity plays a key role in the development of high-performance supercapacitors. The carbon-based material is widely used for supercapacitor electrode materials due to its excellent three-dimensional pore structure and electrical conductivity. Currently, commonly used carbon-based electrode materials include graphene, carbon nanotubes, carbon nanospheres, activated carbon, and the like. However, these electrode materials tend to have short service life and high price, which greatly limits the practical application of supercapacitors. Therefore, the waste straw with low cost and environmental friendliness is used as the electrode material of the super capacitor.
In recent years, natural biomass wastes such as crop straws, animal excreta and the like can have a better pore structure after being treated by a certain activation means due to the advantages of easy acquisition, simple preparation process, low cost, energy conservation, environmental protection and the like. Research has shown that biomass waste is generally produced with a relatively limited number of pores and a single pore structure by means of separate activation techniques.
Disclosure of Invention
The method takes the waste crop straws as a biomass carbon source, solves the problems of low utilization rate of the crop straws and environmental pollution caused by large-scale incineration treatment of the crop straws in China, adopts potassium hydroxide with excellent activation force as an activating agent, respectively uses boric acid, urea and disodium hydrogen phosphate as cheap boron source, nitrogen source and phosphorus source, and improves the surface wettability of the biomass carbon material by introducing boron, nitrogen and phosphorus atoms into a biomass carbon system, thereby further improving the pore structure and the electrical property of the biomass carbon material. The straw-based biomass porous carbon prepared by the method has excellent specific surface area and developed hierarchical pore structure, and is an ideal electrode material for a super capacitor. In addition, the method has important significance for reducing the environmental pollution caused by burning the straws.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of straw-based porous carbon with a honeycomb-shaped pore structure, which comprises the following steps:
step 1: cleaning straws with deionized water and absolute ethyl alcohol in sequence to remove surface impurities, then putting the straws into an oven for drying, and then crushing and sieving the dried straws to obtain straw powder;
step 2: uniformly mixing the straw powder obtained in the step 1 with potassium hydroxide, boric acid, urea, disodium hydrogen phosphate and deionized water, then carrying out cell disruption treatment for 5-10min, and then continuing stirring for 1-2 h;
and step 3: centrifuging the mixed solution obtained in the step 2, removing supernatant, drying the obtained lower precipitate at normal pressure for 24-48h, and then performing high-temperature carbonization in a nitrogen-filled tube furnace to obtain biomass carbon;
and 4, step 4: and (4) washing the biomass carbon obtained in the step (3) by using a hydrochloric acid solution, then washing by using deionized water until the pH value is 7, and drying at normal pressure to obtain the straw-based biomass carbon material.
In the above technical scheme, further, the straw powder, the potassium hydroxide, the boric acid, the urea, the disodium hydrogen phosphate and the deionized water are in a mass ratio of: 1:1-4: 0.5-2: 0.5-2: 0.5-2: 30-50.
In the above technical scheme, further, the straw includes corn straw, soybean straw, and rice straw.
In the technical scheme, furthermore, the particle size of the straw powder is not more than 0.125 mm.
In the above technical solution, further, the high temperature carbonization temperature is 700-.
In the above technical solution, further, the high temperature carbonization time is 1-2 hours.
In the technical scheme, the molar concentration of the hydrochloric acid is 1-4 mol/L.
The invention also provides a boron, nitrogen and phosphorus co-doped straw-based porous carbon material prepared by the preparation method, wherein the carbon material has honeycomb pores; the carbon material is codoped with boron, nitrogen and phosphorus, wherein the doping amount of boron is 1-4%, the doping amount of nitrogen is 1-4% and the doping amount of phosphorus is 0.2-1%.
The invention further provides application of the boron, nitrogen and phosphorus co-doped straw-based porous carbon material to an electrode material of a super capacitor.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention uses the straws as the biomass carbon source, the straws are used as the crop product with the highest output in China, the source is wide, the cost is low, and the problem of high cost of the electrode material of the supercapacitor at present is solved.
2. According to the invention, cheap potassium hydroxide is used as an activator, boric acid, urea and disodium hydrogen phosphate are used as a boron source, a nitrogen source and a phosphorus source respectively, and multiple atoms such as boron, nitrogen and phosphorus are used for replacing carbon atoms on a carbon skeleton to make defects, so that the pore structure of the biomass porous carbon is further optimized, and the pore structure can be optimized on the basis of reducing the production cost.
3. The invention crushes the straws, the particle size of the powder is less than or equal to 0.125mm, the contact area of the biomass raw material and the activating agent is greatly increased, and the uniformity of the pores of the biomass carbon material can be better optimized.
4. The specific surface area of the biomass porous carbon material prepared by the method can reach 3123.5m at most2Per g, pore volume reached 3.33cm3The specific capacitance of the prepared electrode plate of the super capacitor is up to 395.7F/g, and the electrode plate has excellent electrochemical performance.
Drawings
FIG. 1 is an SEM image of a porous carbon material prepared in example 1;
FIG. 2 is an SEM image of the porous carbon material prepared in example 2;
FIG. 3 is an SEM image of the porous carbon material prepared in example 3;
FIG. 4 is an SEM image of the porous carbon material prepared in comparative example 1;
FIG. 5 is a BET plot of the porous carbon material prepared in example 2;
FIG. 6 is an XRD pattern of the porous carbon material prepared in example 2;
FIG. 7 is a comparative graph of charge and discharge cycles of the porous carbon materials of examples 1 to 3 and comparative example 1.
Detailed Description
The following describes embodiments of the present invention in detail. The following examples are given by way of illustration only and are not to be construed as limiting the present invention.
Example 1
Step 1: washing corn straws with deionized water and absolute ethyl alcohol in sequence, putting the washed corn straws into an oven for drying, and crushing and sieving the dried corn straws by a crusher to obtain corn straw powder with the particle size of less than or equal to 0.125 mm;
step 2: mixing the corn straw powder obtained in the step 1 with potassium hydroxide and deionized water, uniformly stirring by magnetic force, sequentially adding boric acid, urea and disodium hydrogen phosphate, continuously stirring uniformly, performing cell disruption by using sound waves (Ningbo Xinzhi JY98-IIIDN) for 10min, and then continuously stirring by magnetic force for 2h to obtain a mixed solution, wherein the actual mass ratio is m (Cornstalk): m (KOH): m (Boric acid): m (urea): m (sodium Hydrogen phospate): m (H)2O)=3:8.25:1.5:1.5:1.5:40;
And 3, step 3: centrifuging the mixed solution obtained in the step 2, removing supernatant, drying for 36h under normal pressure, and carbonizing for 2h in a nitrogen-filled tube furnace at 800 ℃;
and 4, step 4: and (3) stirring the carbon powder obtained in the step (3) in a hydrochloric acid solution at a constant temperature of 60 ℃ for 2h, wherein the molar concentration of the used hydrochloric acid is 2mol/l, then washing the carbon powder with a large amount of deionized water until the pH value is 7, and drying the carbon powder at normal pressure to obtain the corn straw-based biomass porous carbon material.
Fig. 1 is an SEM image of the product obtained in this example, and it can be seen that the porosity of the biomass porous carbon is relatively uniform and the structure of the honeycomb-shaped pores can be seen, but the integrity of the pore structure is slightly deficient. The specific surface area is 1972.58m by the analysis of BET test2Per g, pore volume 1.30cm3(ii) in terms of/g. The specific capacitance was calculated to be 292.6F/g by the cyclic charge-discharge curve.
Example 2
Step 1: washing corn straws with deionized water and absolute ethyl alcohol in sequence, putting the washed corn straws into an oven for drying, and crushing and sieving the dried corn straws by a crusher to obtain corn straw powder with the particle size of less than or equal to 0.125 mm;
step 2: mixing the corn straw powder obtained in the step 1 with potassium hydroxide and deionized water, uniformly stirring by magnetic force, sequentially adding boric acid, urea and disodium hydrogen phosphate, continuously stirring uniformly, performing cell disruption treatment for 10min by using an ultrasonic cell disruption instrument (Ningbo Xinzhi JY98-IIIDN), and continuously stirring by magnetic force for 2h to obtain a mixed solution, wherein the actual mass ratio is m (Cor)nstalk):m(KOH):m(Boric Acid):m(Urea):m(Sodium Hydrogen Phosphate):m(H2O)=3:8.25:3:3:3:40;
And step 3: centrifuging the mixed solution obtained in the step 2, removing supernatant liquid, drying for 36h under normal pressure, and carbonizing for 2h at 800 ℃ in a nitrogen-filled tube furnace;
and 4, step 4: and (3) stirring the carbon powder obtained in the step (3) in a hydrochloric acid solution at a constant temperature of 60 ℃ for 2h, wherein the molar concentration of the used hydrochloric acid is 2mol/l, then washing the carbon powder with a large amount of deionized water until the pH value is 7, and drying the carbon powder at normal pressure to obtain the corn straw-based biomass porous carbon material.
Fig. 2 is an SEM image of the product obtained in this example, and it can be seen from the SEM image that the biomass porous carbon has dense and uniformly distributed pores, smaller pore size and honeycomb shape, and has more pores than the products of other examples under the same magnification. The specific surface area is 3123.5m by the analysis of BET test2Per g, pore volume 3.33cm3(ii) in terms of/g. The specific capacitance was calculated to be 395.7F/g from the cyclic charge-discharge curve.
Example 3
Step 1: washing corn straws with deionized water and absolute ethyl alcohol in sequence, putting the washed corn straws into an oven for drying, and crushing and sieving the dried corn straws by a crusher to obtain corn straw powder with the particle size of less than or equal to 0.125 mm;
step 2: mixing the corn straw powder obtained in the step 1 with potassium hydroxide and deionized water, uniformly stirring by magnetic force, sequentially adding boric acid, urea and disodium hydrogen phosphate, continuously stirring uniformly, performing cell disruption treatment for 10min by using an ultrasonic cell disruption instrument (Ningbo Xinzhi JY98-IIIDN), and then continuously stirring by magnetic force for 2h to obtain a mixed solution, wherein the actual mass ratio is m (Cornstalk): m (KOH): m (Boric acid): m (urea): m (sodium Hydrogen phospate): m (H)2O)=3:8.25:4.5:4.5:4.5:40;
And step 3: centrifuging the mixed solution obtained in the step 2, removing supernatant liquid, drying for 36h under normal pressure, and carbonizing for 2h at 800 ℃ in a nitrogen-filled tube furnace;
and 4, step 4: and (3) stirring the carbon powder obtained in the step (3) in a hydrochloric acid solution at a constant temperature of 60 ℃ for 2h, wherein the molar concentration of the used hydrochloric acid is 2mol/l, then washing the carbon powder with a large amount of deionized water until the pH value is 7, and drying the carbon powder at normal pressure to obtain the corn straw-based biomass porous carbon material.
Fig. 3 is an SEM image of the product obtained in this example, and it can be seen that the cellular pore structure of the biomass porous carbon is relatively developed and the pore structure is intact, but a small amount of thicker large pore walls exist. The specific surface area is 2604.88m by the analysis of BET test2Per g, pore volume 1.95cm3(ii) in terms of/g. The specific capacitance is calculated to be 337.5F/g through a cyclic charge-discharge curve.
Comparative example 1
The preparation method of the nitrogen and phosphorus doped biomass porous carbon material refers to example 1, and comprises the following steps:
step 1: washing corn straws with deionized water and absolute ethyl alcohol in sequence, putting the washed corn straws into an oven for drying, and crushing and sieving the dried corn straws by a crusher to obtain corn straw powder with the particle size of less than or equal to 0.125 mm;
step 2: mixing the corn straw powder obtained in the step 1 with potassium hydroxide and deionized water, uniformly stirring by magnetic force, sequentially adding urea and disodium hydrogen phosphate, continuously stirring uniformly, carrying out cell disruption treatment for 10min by using an ultrasonic cell disruption instrument of Ningbo Xinzhi JY98-IIIDN, and then continuously stirring by magnetic force for 2h to obtain a mixed solution, wherein the actual mass ratio is m (Cornstalk): m (KOH): m (urea): m (sodium Hydrogen phospate): m (H)2O)=3:8.25:3:3:40;
And step 3: centrifuging the mixed solution obtained in the step 2, removing supernatant liquid, drying for 36h under normal pressure, and carbonizing for 2h at 800 ℃ in a nitrogen-filled tube furnace;
and 4, step 4: and (3) stirring the carbon powder obtained in the step (3) in a hydrochloric acid solution at a constant temperature of 60 ℃ for 2h, wherein the molar concentration of the used hydrochloric acid is 2mol/l, then washing the carbon powder with a large amount of deionized water until the pH value is 7, and drying the carbon powder at normal pressure to obtain the corn straw-based biomass porous carbon material.
FIG. 4 is a graph of comparative example 1And obtaining an SEM image of the product, wherein the pores of the biomass porous carbon are dispersed and open, larger mesopores and macropores are more, the number of the pores is less, the compactness is insufficient, and the biomass porous carbon does not have a uniform honeycomb pore structure. The specific surface area is 1094.85m by the analysis of BET test2Per g, pore volume 0.32cm3(ii) in terms of/g. The specific capacitance was calculated to be 168.1F/g by cyclic charge and discharge curves.

Claims (9)

1. A preparation method of straw-based porous carbon with a honeycomb-shaped pore structure is characterized by comprising the following steps: the method comprises the following steps:
step 1: cleaning straws with deionized water and absolute ethyl alcohol in sequence to remove surface impurities, then putting the straws into an oven for drying, and then crushing and sieving the dried straws to obtain straw powder;
step 2: uniformly mixing the straw powder obtained in the step 1 with potassium hydroxide, boric acid, urea, disodium hydrogen phosphate and deionized water, then carrying out cell disruption treatment for 5-10min, and then continuing stirring for 1-2 h;
and step 3: centrifuging the mixed solution obtained in the step 2, removing supernatant, drying the obtained lower precipitate at normal pressure for 24-48h, and then performing high-temperature carbonization in a nitrogen-filled tube furnace to obtain biomass carbon;
and 4, step 4: and (4) washing the biomass carbon hydrochloric acid solution obtained in the step (3), then washing with deionized water until the pH value is 7, and drying under normal pressure to obtain the straw-based biomass carbon material.
2. The method of claim 1, wherein: the straw powder, the potassium hydroxide, the boric acid, the urea, the disodium hydrogen phosphate and the deionized water are in the following mass ratio: 1:1-4: 0.5-2: 0.5-2: 0.5-2: 30-50.
3. The production method according to claim 1, characterized in that: the straw comprises corn straw, soybean straw and rice straw.
4. The method of claim 1, wherein: the granularity of the straw powder is not more than 0.125 mm.
5. The method of claim 1, wherein: the high-temperature carbonization temperature is 700-900 ℃.
6. The method of claim 1, wherein: the high-temperature carbonization time is 1-2 h.
7. The method of claim 1, wherein: the molar concentration of the hydrochloric acid is 1-4 mol/L.
8. The boron, nitrogen and phosphorus co-doped straw-based porous carbon material prepared by the preparation method of any one of claims 1 to 7 is characterized in that: the carbon material has honeycomb-shaped pores; the carbon material is codoped with boron, nitrogen and phosphorus, wherein the doping amount of boron is 1-4%, the doping amount of nitrogen is 1-4% and the doping amount of phosphorus is 0.2-1%.
9. The application of the boron, nitrogen and phosphorus co-doped straw-based porous carbon material prepared by the preparation method of any one of claims 1 to 7 is characterized in that: the material is used for the electrode material of the super capacitor.
CN202210218023.4A 2022-03-07 2022-03-07 Preparation method and application of straw-based porous carbon with honeycomb-shaped pore structure Pending CN114477172A (en)

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CN115440965A (en) * 2022-10-13 2022-12-06 吉林大学 Nitrogen-sulfur co-doped mesoporous carbon composite material for depositing alkali metal and preparation method thereof
CN117208905A (en) * 2023-11-09 2023-12-12 广东韩研活性炭科技股份有限公司 Activated carbon for xylitol mother liquor decoloring working section and preparation method thereof

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Publication number Priority date Publication date Assignee Title
CN115116756A (en) * 2022-07-15 2022-09-27 东华理工大学 Preparation method of honeycomb porous carbon based on high-temperature activation method
CN115440965A (en) * 2022-10-13 2022-12-06 吉林大学 Nitrogen-sulfur co-doped mesoporous carbon composite material for depositing alkali metal and preparation method thereof
CN117208905A (en) * 2023-11-09 2023-12-12 广东韩研活性炭科技股份有限公司 Activated carbon for xylitol mother liquor decoloring working section and preparation method thereof
CN117208905B (en) * 2023-11-09 2024-03-01 广东韩研活性炭科技股份有限公司 Activated carbon for xylitol mother liquor decoloring working section and preparation method thereof

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