CN112670097B - Preparation method of loofah sponge-based derived carbon electrode material with three-dimensional network structure - Google Patents
Preparation method of loofah sponge-based derived carbon electrode material with three-dimensional network structure Download PDFInfo
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Abstract
The invention relates to a preparation method of a loofah sponge-based derived carbon electrode material with a three-dimensional network structure, and belongs to the technical field of new energy electronic materials. Except for the traditional activation carbonization method, the loofah sponge-based derived carbon with a three-dimensional network structure is obtained by adopting a Co ion catalytic graphitization method, and the preparation process comprises the following steps: pre-carbonizing retinervus Luffae fructus at 300 deg.C, soaking in 0.05mol/L cobalt nitrate solution for 24 hr, washing without centrifuging, oven drying, and drying according to mSample (A):mKOHMixing and drying according to the ratio of 1:1, carbonizing at 700 ℃ for 90min, cooling to room temperature, and then carrying out acid washing and drying to obtain the final product. The prepared loofah sponge-based derivative carbon with the three-dimensional network structure is used as an electrode material, and still has superior volume specific capacitance and mass specific capacitance when the loading amount of an active substance is high (10 mg). At 0.2A/g, the volume and the mass specific capacity are 1188.8F/cm respectively3653.3F/g, the rate performance is as high as 75%, the capacitance performance advantage is obvious, and the huge market application prospect of the loofah sponge-based derived carbon electrode material is shown.
Description
Technical Field
The invention belongs to the technical field of new energy electronic materials, and relates to a preparation method of a loofah sponge-based derived carbon electrode material with a three-dimensional network structure.
Background
The biomass-based material is widely researched due to the facts that developed pores can be obtained through physical/chemical activation carbonization, and high electric double layer capacitance and good rate performance can be obtained through adjustment of pore size and pore size distribution, and the biomass-based material has the advantages of being advantaged in structural characteristics, rich in heteroatoms such as N, O, S, low in price, green and efficient, and irreplaceable by other carbon materials. Many biomass-based materials such as phoenix tree batting, eggplants, ginkgo leaves, lotus seedpods and the like have been used as carbon precursors to prepare biomass porous carbon materials, have excellent electrochemical properties when being used as electrode materials in super capacitors, and show great development potential.
The loofah sponge mainly contains xylan and cellulose, has a communicated macroporous network structure, is endowed with superior electrochemical performance, and is widely researched by a plurality of researchers in the fields of microwave absorption, lithium ion batteries, supercapacitors and the like. Su et al prepared a series of loofah sponge porous derived carbons by using a KOH chemical activation method, and in a three-electrode system adopting 6M KOH electrolyte, the specific capacitance of the material at 1A/g was 309.6F/g, which shows a greater development potential of loofah sponge derived carbon electrode materials, but the method is too traditional, the dominant structure of loofah sponge is not fully utilized, and the electrochemical performance can be further improved. (Su X L, Chen J R, Zheng G P, et al, Three-dimensional perforated carbon derived from loo of horse spot biology for superparameter applications [ J ]. APPLID SURFACE SCIENCE, 2018.)
In order to improve the electrochemical performance of the supercapacitor based on the loofah sponge-based derived carbon material, a typical and effective strategy is to shear cleaned loofah sponge, carbonize the cleaned loofah sponge at a low temperature of 300 ℃, soak the loofah sponge in Co ion solution with a certain concentration, uniformly mix the loofah sponge with different amounts of KOH, and activate and carbonize the loofah sponge at a temperature of 700 ℃. The biomass-based carbon electrode material with a hierarchical porous structure with high ion accessible surface area and high specific capacitance is prepared by combining abundant micropores and mesopores. The invention takes loofah sponge with wide sources as raw materials, and prepares the loofah sponge-based derived carbon material after activation and carbonization by a method of catalyzing graphitization by Co ions. As an electrode material of a super capacitor, the super capacitor has very high volume specific capacitance and mass specific capacitance when the loading of an active substance is 10 mg. When the current density is 0.2A/g, the volume specific ratio value is 1188.8F/cm3When the current density is from 1A/g (968.8F/cm)3) The change was 10A/g (732.3F/cm)3) At this time, the volume specific capacitance value can be retained at 75.6%. The mass ratio capacitance value can reach 653.3F/g when the current density is 0.2A/g, 499.2F/g when 1A/g, 385.0F/g when 10A/g (the capacitance retention ratio is 77% when 1 to 10A/g), and the ultra-high capacitance value of 330.0F/g (the capacitance retention ratio is 66.1% when 1 to 30A/g) can be still maintained when 30A/g, so that the market application potential is huge.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a low-cost, green and efficient preparation method of the loofah sponge-based derived carbon electrode material with the three-dimensional network structure.
The technical scheme of the invention is as follows:
the electrode material for the super capacitor is prepared by activating and carbonizing a loofah sponge serving as a precursor material by a method of catalyzing graphitization by Co ions.
According to the invention, the preparation method of the loofah sponge-based derived carbon electrode material with the three-dimensional network structure comprises the following steps:
(1) weighing a proper amount of clean loofah sponge, placing the loofah sponge in a porcelain boat, pre-carbonizing the loofah sponge in a tube furnace, heating the loofah sponge to 300 ℃ at a heating rate of 5 ℃/min in an inert atmosphere, carbonizing the loofah sponge for 1-3 hours, cooling the loofah sponge to room temperature, and collecting a sample.
(2) Weighing 0.55g of sample, soaking the sample in 50ml of cobalt nitrate solution with the concentration of 0.035-0.65 mol/L, magnetically stirring for 24 hours, not centrifuging, not washing, and drying in an oven at 65 ℃.
(3) After drying, alkali treatment is carried out. According to mSample (A):mKOHAnd (3) =1: 0.5-3, dissolving KOH in a beaker by using a small amount of deionized water, mixing with the sample, and drying in an oven at 65 ℃.
(4) Transferring the sample into an iron crucible, carrying out activation carbonization in a tube furnace, heating to 600-800 ℃ at the heating rate of 5 ℃/min under the inert atmosphere, carbonizing for 60-180 min, cooling to room temperature, soaking with 1mol/L diluted hydrochloric acid in excess, carrying out centrifugal washing with deionized water and absolute ethyl alcohol to neutrality, and drying in a 65 ℃ oven to obtain the final product.
According to the present invention, it is preferable that the optimum pre-carbonization temperature in the step (1) is 300 ℃.
According to the present invention, it is preferred that the optimum concentration of cobalt nitrate in step (2) is 0.05 mol/L.
According to the present invention, it is preferable that the optimum m in the step (3)Sample (A):mKOHThe ratio was 1: 1.
According to the present invention, it is preferable that the optimum activating carbonization temperature in the step (4) is 700 ℃.
According to the present invention, it is preferable that the optimal carbonization time in the step (4) is 90 min.
The technical advantages of the invention are as follows:
(1) the raw material of the invention is cellulose waste, the source is rich, the price is low, and the resource utilization of the waste biomass is realized.
(2) The loofah sponge-based derived carbon electrode material with a three-dimensional network structure is obtained by activating and carbonizing a Co ion catalytic graphitization method, and still has outstanding volume specific capacitance and mass specific capacitance when the loofah sponge-based derived carbon electrode material has high active substance loading (10 mg).
Description of the figures and accompanying tables
Fig. 1 is a scanning electron microscope image of the loofah sponge-based derived carbon material prepared in example 1 of the present invention.
Fig. 2 is a graph of the volume specific capacitance value of the loofah sponge-based derived carbon material prepared in example 1 of the present invention.
Fig. 3 is a graph of mass specific capacitance values of the loofah sponge-based derived carbon material prepared in example 1 of the present invention.
FIG. 4 is a constant current charge/discharge diagram (0.2-3A/g) of the retinervus Luffae fructus-based derived carbon material of example 1.
FIG. 5 is a constant current charge/discharge diagram (5-30A/g) of the retinervus Luffae fructus-based derived carbon material of example 1.
Detailed Description
The present invention will be further described with reference to the following embodiments and drawings, but is not limited thereto.
Meanwhile, the experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Example 1:
weighing a proper amount of clean loofah sponge, placing the loofah sponge in a porcelain boat, pre-carbonizing the loofah sponge in a tube furnace, heating the loofah sponge to 300 ℃ at the heating rate of 5 ℃/min in an inert atmosphere, carbonizing the loofah sponge for 1h, cooling the loofah sponge to room temperature, and collecting a sample. 0.55g of sample was weighed, soaked in 50ml of cobalt nitrate solution with a concentration of 0.05mol/L, magnetically stirred for 24 hours, washed without centrifugation, and dried in an oven at 65 ℃.
After drying, the process is carried outAnd (5) adding alkali for treatment. According to mSample (A):mKOHIn a ratio of 1:1, KOH was dissolved in a beaker with a small amount of deionized water, mixed with the sample, and dried in an oven at 65 ℃. Transferring the sample into an iron crucible, carrying out activation carbonization in a tubular furnace, heating to 700 ℃ at the heating rate of 5 ℃/min under the inert atmosphere, carbonizing for 90min, cooling to room temperature, soaking with 1mol/L diluted hydrochloric acid in excess, carrying out centrifugal washing to neutrality by using deionized water and absolute ethyl alcohol, and drying in a drying oven at the temperature of 65 ℃ to obtain the final product.
Example 2:
weighing a proper amount of clean loofah sponge, placing the loofah sponge in a porcelain boat, pre-carbonizing the loofah sponge in a tube furnace, heating the loofah sponge to 300 ℃ at the heating rate of 5 ℃/min in an inert atmosphere, carbonizing the loofah sponge for 1h, cooling the loofah sponge to room temperature, and collecting a sample. 0.55g of sample was weighed, soaked in 50ml of cobalt nitrate solution with a concentration of 0.0375mol/L, magnetically stirred for 24 hours, washed without centrifugation, and dried in an oven at 65 ℃.
After drying, alkali treatment is carried out. According to mSample (A):mKOHIn a ratio of 1:1, KOH was dissolved in a beaker with a small amount of deionized water, mixed with the sample, and dried in an oven at 65 ℃. Transferring the sample into an iron crucible, carrying out activation carbonization in a tubular furnace, heating to 700 ℃ at the heating rate of 5 ℃/min under the inert atmosphere, carbonizing for 90min, cooling to room temperature, soaking with 1mol/L diluted hydrochloric acid in excess, carrying out centrifugal washing to neutrality by using deionized water and absolute ethyl alcohol, and drying in a drying oven at the temperature of 65 ℃ to obtain the final product.
Example 3:
weighing a proper amount of clean loofah sponge, placing the loofah sponge in a porcelain boat, pre-carbonizing the loofah sponge in a tube furnace, heating the loofah sponge to 300 ℃ at the heating rate of 5 ℃/min in an inert atmosphere, carbonizing the loofah sponge for 1h, cooling the loofah sponge to room temperature, and collecting a sample. 0.55g of a sample was weighed, soaked in 50ml of a cobalt nitrate solution having a concentration of 0.0625mol/L, magnetically stirred for 24 hours, and then dried in an oven at 65 ℃ without centrifugation and without washing.
After drying, alkali treatment is carried out. According to mSample (A):mKOHIn a ratio of 1:1, KOH was dissolved in a beaker with a small amount of deionized water, mixed with the sample, and dried in an oven at 65 ℃. Transferring the sample into an iron crucible, carrying out activation carbonization in a tubular furnace, heating to 700 ℃ at the heating rate of 5 ℃/min under the inert atmosphere, carbonizing for 90min, cooling to room temperature, soaking with 1mol/L diluted hydrochloric acid in excess, carrying out centrifugal washing to neutrality by using deionized water and absolute ethyl alcohol, and drying in a drying oven at the temperature of 65 ℃ to obtain the final product.
Comparative example:
weighing a proper amount of clean loofah sponge, placing the loofah sponge in a porcelain boat, pre-carbonizing the loofah sponge in a tube furnace, heating the loofah sponge to 300 ℃ at the heating rate of 5 ℃/min under the inert atmosphere, carbonizing the loofah sponge for 1h, cooling the loofah sponge to room temperature, collecting a sample, and adding alkali to the sample. According to mSample (A):mKOHIn a ratio of 1:1, KOH was dissolved in a beaker with a small amount of deionized water, mixed with the sample, and dried in an oven at 65 ℃. Transferring the sample into an iron crucible, carrying out activation carbonization in a tubular furnace, heating to 700 ℃ at the heating rate of 5 ℃/min under the inert atmosphere, carbonizing for 90min, cooling to room temperature, soaking with 1mol/L diluted hydrochloric acid in excess, carrying out centrifugal washing to neutrality by using deionized water and absolute ethyl alcohol, and drying in a drying oven at the temperature of 65 ℃ to obtain the final product.
Claims (1)
1. A preparation method of a supercapacitor electrode material comprises the following steps:
(1) weighing a proper amount of clean loofah sponge, placing the loofah sponge in a porcelain boat, pre-carbonizing the loofah sponge in a tube furnace, heating the loofah sponge to 300 ℃ at a heating rate of 5 ℃/min in an inert atmosphere, carbonizing the loofah sponge for 1h, cooling the loofah sponge to room temperature, and collecting a sample;
(2) weighing 0.55g of sample, soaking the sample in 50ml of cobalt nitrate solution with the concentration of 0.05mol/L, magnetically stirring for 24 hours, not centrifuging, not washing, and drying in a 65 ℃ oven;
(3) after drying, alkali treatment is carried out; according to mSample (A):mKOH1:1, dissolving KOH in a beaker with a small amount of deionized water, and mixing with the sampleMixing, and drying in a 65 deg.C oven;
(4) transferring the sample into an iron crucible, carrying out activation carbonization in a tubular furnace, heating to 700 ℃ at the heating rate of 5 ℃/min under the inert atmosphere, carbonizing for 90min, cooling to room temperature, soaking with 1mol/L diluted hydrochloric acid in excess, carrying out centrifugal washing to neutrality by using deionized water and absolute ethyl alcohol, and drying in a drying oven at the temperature of 65 ℃ to obtain the final product.
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| CN102867654A (en) * | 2012-09-10 | 2013-01-09 | 中国科学院大连化学物理研究所 | Graphitized activated carbon electrode material for supercapacitor and preparation method thereof |
| CN104098083A (en) * | 2014-07-15 | 2014-10-15 | 黑龙江大学 | Method for preparing porous nano carbon materials with biomass serving as carbon source |
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| CN103449433A (en) * | 2012-06-01 | 2013-12-18 | 中国科学院城市环境研究所 | Method for preparing novel active carbon by using potassium hydroxide activated vegetable luffa sponge |
| US10259714B2 (en) * | 2015-03-19 | 2019-04-16 | The University Of Akron | Method of making mesoporous carbon from natural wood and mesoporous carbon hollow tubes made thereby |
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| CN102867654A (en) * | 2012-09-10 | 2013-01-09 | 中国科学院大连化学物理研究所 | Graphitized activated carbon electrode material for supercapacitor and preparation method thereof |
| CN104098083A (en) * | 2014-07-15 | 2014-10-15 | 黑龙江大学 | Method for preparing porous nano carbon materials with biomass serving as carbon source |
| CN109205620A (en) * | 2018-11-16 | 2019-01-15 | 大连理工大学 | A kind of carbon bionic nano material and preparation method |
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