CN112661153A - Rhizome traditional Chinese medicine residue-based porous carbon electrode material and preparation and application thereof - Google Patents
Rhizome traditional Chinese medicine residue-based porous carbon electrode material and preparation and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of electrochemical materials, and discloses a rhizome type traditional Chinese medicine residue-based porous carbon electrode material and preparation and application thereof. The method comprises the following steps: 1) carbonizing: pre-carbonizing the rhizome traditional Chinese medicine residues in a protective atmosphere to obtain a pre-carbonized product; the rhizome Chinese medicinal residue is more than one of radix Sangusorbae, Saviae Miltiorrhizae radix, rhizoma Dioscoreae Septemlobae, radix Codonopsis, bupleuri radix, Scutellariae radix, radix Rhapontici and Polygoni Multiflori radix; 2) and (3) activation: and uniformly mixing the pre-carbonized product with an activating agent, performing activation pyrolysis in a protective atmosphere, and performing subsequent treatment to obtain the rhizome traditional Chinese medicine residue-based porous carbon electrode material. The rhizomatic traditional Chinese medicine residue porous carbon electrode material has high specific surface area and rich micropores; the prepared electrode has stable structure, higher capacity and cycling stability, improves the existing porous carbon preparation process, and realizes the resource utilization of the Chinese medicine residue. The electrode material disclosed by the invention is applied to a super capacitor and/or a lithium ion battery and is used for preparing an electrode.
Description
Technical Field
The invention belongs to the technical field of electrochemical materials, and particularly relates to a rhizome type traditional Chinese medicine residue-based porous carbon electrode material as well as preparation and application thereof.
Background
The traditional Chinese medicine is one of the cultural treasure of Chinese nationality, has been inherited and developed for thousands of years, has great potential in the aspects of preventing and treating various diseases, and is also an important resource for modern medicine research and innovation. Since the naebyo-yo of the nobel medical prize winner in 2015 extracted artemisinin from the traditional Chinese medicine artemisia annua, the traditional Chinese medicine attracted unprecedented attention, and many scholars strived to systematize and standardize the research on the traditional Chinese medicine, and the demand of the traditional Chinese medicine is increasing. Chinese medicine and natural medicinal biological resources are large in planting area and high in total medicinal material amount, and a large amount of solid wastes and byproducts are generated when the Chinese medicine and natural medicinal biological resources are utilized for pharmacy, preparation of formula particles, standard extracts and various types of health products. Most of the traditional Chinese medicine residues are mainly treated by burning or landfill and are not effectively utilized, which not only brings pressure to the environment, but also causes waste of resources.
The biomass charcoal is a porous charcoal material prepared by using biomass as a precursor, and has the advantages of wide source and simple preparation technology, and is often used as a supercapacitor electrode material. The invention prepares the traditional Chinese medicine residues into the porous carbon material, thereby not only improving the capacitance performance of the electrode material, but also effectively promoting the resource utilization of the traditional Chinese medicine residues and reducing the pressure of the traditional Chinese medicine residues on the ecological environment.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the invention aims to provide a rhizome type traditional Chinese medicine residue-based porous carbon electrode material and a preparation method thereof. The traditional Chinese medicine residue-based porous carbon utilizes rhizome traditional Chinese medicine residues as precursors, the raw materials are cheap and easy to obtain, the preparation process is simple, the obtained porous carbon material is rich in specific surface area, and the obtained porous carbon electrode is stable in structure and has high capacity and stability, so that the resource utilization of the traditional Chinese medicine residues is realized.
The invention also aims to provide the application of the rhizome traditional Chinese medicine residue-based porous carbon electrode material. The rhizome traditional Chinese medicine residue-based porous carbon electrode material is used for preparing super capacitor electrodes and/or lithium ion batteries, in particular super capacitors.
The purpose of the invention is realized by the following technical scheme:
the preparation method of the rhizome traditional Chinese medicine residue-based porous carbon electrode material comprises the following steps:
1) carbonizing: pre-carbonizing the rhizome traditional Chinese medicine residues in a protective atmosphere to obtain a pre-carbonized product; the rhizome Chinese medicinal residue is more than one of radix Sangusorbae, Saviae Miltiorrhizae radix, rhizoma Dioscoreae Septemlobae, radix Codonopsis, bupleuri radix, Scutellariae radix, radix Rhapontici and Polygoni Multiflori radix; the rhizome traditional Chinese medicine residues are dry rhizome traditional Chinese medicine residues;
2) and (3) activation: and uniformly mixing the pre-carbonized product with an activating agent, performing activation pyrolysis in a protective atmosphere, and performing subsequent treatment to obtain the rhizome traditional Chinese medicine residue-based porous carbon material.
The protective atmosphere in the step 1) is argon or nitrogen; the pre-carbonization temperature is 400-600 ℃; the pre-carbonization time is 1-3 h.
The temperature of the activation pyrolysis in the step 2) is 400-1000 ℃, preferably 600-900 ℃, and more preferably 700-900 ℃; the activation pyrolysis time is 0.5-6 h; the mass ratio of the rhizome traditional Chinese medicine residue-based porous carbon to the activating agent is 1 (0.25-5); the activator is potassium hydroxide.
The pre-carbonized product is crushed and ground before being uniformly mixed with the activating agent; the uniformly mixing refers to mixing and grinding the pre-carbonized product and the activating agent; the grinding time is 5-30 min.
The subsequent treatment in the step 2) is acid treatment, and water is washed to be neutral; the acid is hydrochloric acid, and the concentration of the hydrochloric acid is 1M;
the rhizome traditional Chinese medicine residue-based porous carbon electrode material is used for preparing electrodes.
The electrode is mainly prepared from a rhizome type traditional Chinese medicine residue-based porous carbon electrode material, a conductive substance and a binder;
the conductive substance is acetylene black, ketjen black or graphene; the binder is a PTFE solution.
The specific preparation steps of the electrode are
S1, uniformly mixing the rhizome type traditional Chinese medicine residue-based porous carbon electrode material, the conductive substance and the binder, and performing emulsion removal to obtain a coating material;
s2, tabletting: coating the coating material on a carrier, drying and compacting to obtain the traditional Chinese medicine residue-based porous carbon electrode.
In the step S1, the mass ratio of the rhizome traditional Chinese medicine residue-based porous carbon electrode material to the conductive substance is (7-9.5): 1;
in the step S1, the binder is a PTFE solution, and the mass fraction of the binder is 5-20%; the demulsifier for demulsification is absolute ethyl alcohol or diethyl ether; the addition amount of the demulsifier is 1-1.2 times of the mass of the PTFE solution.
In the step S2, the carrier is a nickel net, a titanium net, a stainless steel net, a titanium foil or a copper foil;
in the step S2, the drying temperature is 60-150 ℃ and the drying time is 2-12 hours; the compaction pressure is 5-30 MPa.
The rhizome traditional Chinese medicine residue-based porous carbon electrode is used for preparing a super capacitor and/or a lithium ion battery, in particular to a super capacitor.
The rhizome traditional Chinese medicine residue-based porous carbon electrode is an electrode of a super capacitor and/or a lithium ion battery.
The invention takes the rhizome traditional Chinese medicine residues as the precursor for preparing the porous carbon material, and has the following advantages: (1) the rhizome traditional Chinese medicine residues contain a large amount of cellulose, hemicellulose, lignin and protein, the ash content is low, and in the carbonization process, organic matters are decomposed into water and carbon dioxide to be beneficial to the formation of ordered pore channels of the porous carbon material; (2) oxygen, nitrogen, sulfur and phosphorus elements in the rhizome traditional Chinese medicine residues directly influence the doping of the final porous carbon material, and the abundant heteroatom doping can effectively improve the adsorption of cations in electrolyte, thereby enhancing the charge storage performance and widening the working voltage; (3) the rhizome traditional Chinese medicine residues have a relatively stable three-dimensional structure, and developed pore structures of the rhizome traditional Chinese medicine residues are still reserved after pyrolysis, so that the method is favorable for synthesizing a porous carbon material with a high specific surface area, and effectively improves the transportation and storage of electrolyte ions.
The specific surface area of the rhizome traditional Chinese medicine residue-based porous carbon electrode material is 2900-3500 m2 g-1。
Compared with the prior art, the invention has the following advantages:
1) the rhizome traditional Chinese medicine residue-based porous carbon material disclosed by the invention utilizes rhizome traditional Chinese medicine residues as precursors, is large in yield per year, cheap and easily available in raw materials, rich in cellulose, hemicellulose and lignin, excellent in primary pore structure, beneficial to preparation of a porous carbon material with a high specific surface area, and realizes resource utilization of the traditional Chinese medicine residues;
2) the invention adds activation in the process of preparing the porous carbon material, compared with the carbon material which is not activated, the activated material is 1A g-1Under the current density test condition, the specific capacitance is increased by more than 2 times;
3) the electrochemical performance of the electrode prepared by the porous carbon material prepared by the invention is 1A g the same as that of the commercially available Coly YP80F-1The specific capacitance is at least 20% higher than that of the capacitor under the test condition of the current density and is 10A g-1Under the current density, the specific capacitance is also 18 percent higher;
4) the rhizomatic traditional Chinese medicine residue porous carbon material prepared by the invention can also ensure the stability of specific capacitance under high current density.
In a word, the rhizome traditional Chinese medicine residue porous carbon material obtained by the invention has high specific surface area and rich micropores, and the prepared electrode has stable structure, higher capacity and cycling stability, improves the existing porous carbon preparation process, and realizes the resource utilization of the traditional Chinese medicine residue.
Drawings
FIG. 1 a) is a comparison graph of the cyclic voltammetry curves of sanguisorba officinalis (example 1), salvia miltiorrhiza (example 2), dioscorea tokoro hypoglauca (example 3), codonopsis pilosula (example 4), bupleurum chinense (example 5), scutellaria baicalensis (example 6), uniflower swisscentaury root (example 7) and polygonum multiflorum (example 8) residue-based porous carbon electrode prepared by carbonization-activation and the commercial porous carbon material Coly YP80F of comparative example 1; FIG. 1 b) is a graph showing the comparison of constant current charging and discharging curves of sanguisorba officinalis (example 1), salvia miltiorrhiza (example 2), dioscorea tokoro hypoglauca (example 3), codonopsis pilosula (example 4), radix bupleuri (example 5), scutellaria baicalensis (example 6), uniflower swisscentaury root (example 7) and polygonum multiflorum (example 8) decoction dreg-derived porous carbon electrode prepared by carbonization-activation and the commercial porous carbon material Coly YP80F of comparative example 1; fig. 1 c) is the electrochemical impedance spectrum curve of sanguisorba officinalis (example 1), salvia miltiorrhiza (example 2), dioscorea tokoro hypoglauca (example 3), codonopsis pilosula (example 4), radix bupleuri (example 5), scutellaria baicalensis (example 6), uniflower swisscentaury root (example 7) and polygonum multiflorum (example 8) residue-based porous carbon electrode prepared by carbonization activation method and the commercial porous carbon material cola YP80F of the comparative example 1;
in FIG. 2, a) is a comparison graph of cyclic voltammetry curves of the sanguisorba officinalis dreg-based porous carbon electrode in example 1 at different scanning speeds; FIG. 2 b) is a graph comparing constant current charge and discharge curves of example 1 at different current densities;
in fig. 3, a) is a comparison graph of cyclic voltammetry curves of the salvia miltiorrhiza residue-based porous carbon electrode in example 2 at different scanning speeds; FIG. 3 b) is a graph comparing constant current charge and discharge curves of example 2 at different current densities;
FIG. 4 a) is a comparison graph of cyclic voltammetry curves of the rhizoma Dioscoreae Septemlobae residue-based porous carbon electrode of example 3 at different scanning speeds; FIG. 4 b) comparative constant current charging and discharging curves of example 3 at different current densities;
in FIG. 5, a) is a comparison graph of cyclic voltammetry curves of the Codonopsis pilosula residue-based porous carbon electrode of example 4 at different scanning speeds; FIG. 5 b) comparative constant current charge and discharge curves of example 4 at different current densities;
FIG. 6 a) is a comparison graph of cyclic voltammetry curves of the Bupleurum scorzonerifolium-based porous carbon electrode of example 5 at different scanning speeds; FIG. 6 b) comparative constant current charge and discharge curves of example 5 at different current densities;
in FIG. 7, a) is a comparison graph of cyclic voltammetry curves of the Scutellaria baicalensis residue-based porous carbon electrode of example 6 at different scanning speeds; FIG. 7 b) comparative constant current charging and discharging curves of example 6 at different current densities;
in FIG. 8, a) is a comparison graph of cyclic voltammetry curves of the rhaponticum uniflorum dreg-based porous carbon electrode of example 7 at different scanning speeds; FIG. 8 b) comparative constant current charging and discharging curves of example 7 at different current densities;
FIG. 9 a) is a comparison graph of cyclic voltammetry curves of the polygonum multiflorum residue-based porous carbon electrode of example 8 at different scanning speeds; FIG. 9 b) comparative constant current charging and discharging curves of example 8 at different current densities;
in a) and b) in fig. 10, absorption, desorption curves and pore size distribution curves of the sanguisorba officinalis (example 1), salvia miltiorrhiza (example 2), dioscorea tokoro hypoglauca (example 3), codonopsis pilosula (example 4), radix bupleuri (example 5), scutellaria baicalensis (example 6), uniflower swisscentaury root (example 7) and polygonum multiflorum (example 8) medicine residue-derived porous carbon electrode prepared by a carbonization and activation method are respectively shown;
FIG. 11 is a scanning electron microscope image of a porous carbon material, wherein a), b), c), d), e), f), g) and h) are porous carbon materials based on sanguisorba, salvia miltiorrhiza, dioscorea tokoro, codonopsis pilosula, radix bupleuri, scutellaria baicalensis, uniflower swisscentaury root and polygonum multiflorum herb residues respectively.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto.
Example 1
1) Drying the garden burnet dregs in a constant-temperature drying box at the temperature of 80 ℃ until the weight is constant;
2) putting the dried sanguisorba dregs into a porcelain boat, then putting the porcelain boat into a tube furnace, introducing nitrogen, setting the temperature rise speed at 5K/min, raising the temperature to 500 ℃, and preserving the temperature for 1 hour to obtain a pre-carbonized product;
3) crushing and grinding the pre-carbonized sanguisorba officinalis charcoal, and adding potassium hydroxide (the mass ratio of the potassium hydroxide to the sanguisorba officinalis charcoal is 4: 1) uniformly mixing and grinding, putting into a corundum boat, putting into a tube furnace, introducing nitrogen for protection, setting the temperature rise speed at 5K/min, raising the temperature to 800 ℃, and preserving the temperature for 1 hour to obtain an activated product;
4) and soaking the activated product in 1M hydrochloric acid for 1 hour, washing the product to be neutral by deionized water, and drying the product in a constant-temperature drying oven at 80 ℃ to obtain the sanguisorba-based porous carbon material.
An electrode: mixing a sanguisorba-based porous carbon material, conductive carbon black and a 10% PTFE solution (the solvent of the solution is water) according to a mass ratio of 8:1:1, and adding 100mg of absolute ethyl alcohol into the mixture for demulsification to enable small droplets of the emulsion to agglomerate to form slurry easy to coat; coating the slurry on a nickel screen with a coating area of 1cm × 1cm, drying at 80 deg.C for 2h, tabletting under 20MPa, and drying to obtain radix Sangusorbae-based porous carbon electrode.
Example 2
1) Drying Saviae Miltiorrhizae radix residue in a constant temperature drying oven at 80 deg.C to constant weight;
2) putting the dried salvia miltiorrhiza dregs into a porcelain boat, then putting the porcelain boat into a tube furnace, introducing nitrogen, setting the temperature rise speed at 5K/min, raising the temperature to 500 ℃, and preserving the temperature for 1 hour to obtain a pre-carbonized product;
3) the pre-carbonized salvia miltiorrhiza charcoal is firstly crushed and ground, and then potassium hydroxide (the mass ratio of the alkali to the charcoal is 4: 1) uniformly mixing and grinding, putting into a corundum boat, putting into a tube furnace, introducing nitrogen for protection, setting the temperature rise speed at 5K/min, raising the temperature to 800 ℃, and preserving the temperature for 1 hour to obtain an activated product;
4) and (3) cleaning the activated product to be neutral by using 1M hydrochloric acid and deionized water, and drying in a constant-temperature drying oven at 80 ℃ to obtain the salvia-based porous carbon material.
An electrode: mixing a salvia miltiorrhiza based porous carbon material, conductive carbon black and a 10% PTFE solution according to a mass ratio of 8:1:1, and adding 100mg of absolute ethyl alcohol into the mixture for demulsification to enable small droplets of emulsion to agglomerate to form slurry easy to coat; coating the slurry on a nickel screen with a coating area of 1cm × 1cm, drying at 80 deg.C for 2h, tabletting under 20MPa, and drying to obtain the final product.
Example 3
1) Placing the residue of rhizoma Dioscoreae Septemlobae in a constant temperature drying oven, and drying at 80 deg.C to constant weight;
2) putting the dried residues of the yam rhizome into a porcelain boat, then putting the porcelain boat into a tube furnace, introducing nitrogen, heating to 500 ℃ at a heating speed of 5K/min, and preserving heat for 1 hour to obtain a pre-carbonized product;
3) crushing and grinding the pre-carbonized yam rhizome charcoal, and then adding potassium hydroxide (the mass ratio of alkali to charcoal is 4: 1) uniformly mixing and grinding, putting into a corundum boat, putting into a tube furnace, introducing nitrogen for protection, setting the temperature rise speed at 5K/min, raising the temperature to 800 ℃, and preserving the temperature for 1 hour to obtain an activated product;
4) and (3) cleaning the activated product to be neutral by using 1M hydrochloric acid and deionized water, and drying in a constant-temperature drying oven at 80 ℃ to obtain the product which is marked as the rhizoma dioscoreae hypoglaucae-based porous carbon material.
An electrode: mixing a yam rhizome-based porous carbon material, conductive carbon black and a 10% PTFE solution according to the mass ratio of 8:1:1, and adding 100mg of absolute ethyl alcohol into the mixture for demulsification to enable small droplets of emulsion to agglomerate to form slurry easy to coat; spreading the slurry on a nickel screen with a coating area of 1cm × 1cm, baking at 80 deg.C for 2 hr, tabletting under 20MPa, and drying to obtain porous carbon electrode.
Example 4
1) Drying the radix Codonopsis residue in a constant temperature drying oven at 80 deg.C to constant weight;
2) putting the dried codonopsis pilosula dregs into a porcelain boat, then putting the porcelain boat into a tube furnace, introducing nitrogen, setting the temperature rise speed at 5K/min, raising the temperature to 500 ℃, and preserving the temperature for 1 hour to obtain a pre-carbonized product;
3) crushing and grinding the pre-carbonized codonopsis pilosula charcoal, adding potassium hydroxide (the ratio of alkali to carbon is 4), uniformly mixing and grinding, putting into a corundum boat, putting into a tube furnace, introducing nitrogen for protection, setting the temperature rise speed at 5K/min, raising the temperature to 800 ℃, and preserving the heat for 1 hour to obtain an activated product;
4) and (3) cleaning the activated product to be neutral by using 1M hydrochloric acid and deionized water, and drying in a constant-temperature drying oven at 80 ℃ to obtain the codonopsis pilosula-based porous carbon material.
An electrode: mixing the codonopsis pilosula-based porous carbon material, the conductive carbon black and the 10% PTFE solution according to the mass ratio of 8:1:1, and then adding 100mg of absolute ethyl alcohol into the mixture for demulsification to enable small droplets of the emulsion to agglomerate to form slurry easy to coat; coating the slurry on a nickel screen with a coating area of 1cm × 1cm, drying at 80 deg.C for 2h, tabletting under 20MPa, and drying to obtain radix Codonopsis porous carbon electrode.
Example 5
1) Drying the radix bupleuri dregs in a constant-temperature drying box at the temperature of 80 ℃ to constant weight;
2) putting the dried radix bupleuri dregs into a porcelain boat, then putting the porcelain boat into a tube furnace, introducing nitrogen, setting the temperature rise speed at 5K/min, raising the temperature to 500 ℃, and preserving the temperature for 1 hour to obtain a pre-carbonized product;
3) crushing and grinding the pre-carbonized radix bupleuri charcoal, adding potassium hydroxide (the ratio of alkali to carbon is 4), uniformly mixing and grinding, putting into a corundum boat, putting into a tube furnace, introducing nitrogen for protection, setting the temperature rise speed at 5K/min, raising the temperature to 800 ℃, and preserving the heat for 1 hour to obtain an activated product;
4) and (3) cleaning the activated product to be neutral by using 1M hydrochloric acid and deionized water, and drying the product in a constant-temperature drying oven at 80 ℃ to obtain the Bupleurum-based porous carbon material.
An electrode: mixing the bupleurum-based porous carbon material, the conductive carbon black and a 10% PTFE solution according to the mass ratio of 8:1:1, and then adding 100mg of absolute ethyl alcohol (the mass ratio of the ethyl alcohol to the binder is 1:1.1) into the mixture for demulsification to enable small droplets of the emulsion to agglomerate to form slurry easy to coat; coating the slurry on a nickel screen with a coating area of 1cm × 1cm, drying at 80 deg.C for 2h, tabletting under 20MPa, and drying to obtain the final product.
Example 6
1) Placing the scutellaria residue in a constant-temperature drying box to be dried to constant weight at 80 ℃;
2) putting the dried scutellaria baicalensis dregs into a porcelain boat, then putting the porcelain boat into a tube furnace, introducing nitrogen, setting the temperature rise speed at 5K/min, raising the temperature to 500 ℃, and preserving the temperature for 1 hour to obtain a pre-carbonized product;
3) crushing and grinding the pre-carbonized scutellaria baicalensis carbon, adding potassium hydroxide (the ratio of alkali to carbon is 4), uniformly mixing and grinding, putting into a corundum boat, putting into a tube furnace, introducing nitrogen for protection, setting the temperature rise speed at 5K/min, raising the temperature to 800 ℃, and preserving the heat for 1 hour to obtain an activated product;
4) and (3) cleaning the activated product to be neutral by using 1M hydrochloric acid and deionized water, and drying in a constant-temperature drying oven at 80 ℃ to obtain the baical skullcap root-based porous carbon material.
An electrode: mixing a scutellaria-based porous carbon material, conductive carbon black and a 10% PTFE solution according to a mass ratio of 8:1:1, and adding 100mg of absolute ethyl alcohol into the mixture for demulsification to enable small droplets of emulsion to agglomerate to form slurry easy to coat; coating the slurry on a nickel screen with a coating area of 1cm × 1cm, drying at 80 deg.C for 2h, tabletting under 20MPa, and drying to obtain the final product.
Example 7
1) Placing the uniflower swisscentaury root dregs in a constant-temperature drying box, and drying at 80 ℃ to constant weight;
2) putting the dried uniflower swisscentaury root dregs into a porcelain boat, then putting into a tube furnace, introducing nitrogen, heating to 500 ℃ at a heating speed of 5K/min, and preserving heat for 1 hour to obtain a pre-carbonized product;
3) firstly crushing and grinding the pre-carbonized uniflower swisscentaury root carbon, then adding potassium hydroxide (the ratio of alkali to carbon is 4), uniformly mixing and grinding the mixture, putting the mixture into a corundum boat, putting the corundum boat into a tube furnace, introducing nitrogen for protection, setting the temperature rise speed at 5K/min, raising the temperature to 800 ℃, and preserving the heat for 1 hour to obtain an activated product;
4) and (3) cleaning the activated product to be neutral by using 1M hydrochloric acid and deionized water, and drying in a constant-temperature drying oven at 80 ℃ to obtain the rhaponticum-based porous carbon material.
An electrode: mixing the rhaponticum-based porous carbon material, the conductive carbon black and a 10% PTFE solution according to the mass ratio of 8:1:1, and then adding 100mg of absolute ethyl alcohol into the mixture for demulsification to enable small droplets of the emulsion to agglomerate to form slurry easy to coat; coating the slurry on a nickel screen with a coating area of 1cm multiplied by 1cm, drying at 80 ℃ for 2h, tabletting under the pressure of 20MPa, and continuously drying after tabletting to obtain the rhaponticum uniflorum-based porous carbon electrode.
Example 8
1) Placing the polygonum multiflorum dregs in a constant-temperature drying box to be dried at the temperature of 80 ℃ until the weight is constant;
2) putting the dried polygonum multiflorum dregs into a porcelain boat, then putting the porcelain boat into a tube furnace, introducing nitrogen, setting the temperature rise speed at 5K/min, raising the temperature to 500 ℃, and preserving the temperature for 1 hour to obtain a pre-carbonized product;
3) firstly crushing and grinding the pre-carbonized polygonum multiflorum carbon, then adding potassium hydroxide (the ratio of alkali to carbon is 4), uniformly mixing and grinding the polygonum multiflorum carbon, putting the polygonum multiflorum carbon into a corundum boat, putting the corundum boat into a tube furnace, introducing nitrogen for protection, setting the temperature rise speed at 5K/min, raising the temperature to 800 ℃, and preserving the temperature for 1 hour to obtain an activated product;
4) and (3) cleaning the activated product to be neutral by using 1M hydrochloric acid and deionized water, and drying in a constant-temperature drying oven at 80 ℃ to obtain the polygonum multiflorum-based porous carbon material.
An electrode: mixing a polygonum multiflorum-based porous carbon material, conductive carbon black and a 10% PTFE solution according to a mass ratio of 8:1:1, and adding 100mg of absolute ethyl alcohol into the mixture to demulsify so as to enable small droplets of emulsion to agglomerate to form slurry easy to coat; coating the slurry on a nickel screen with a coating area of 1cm multiplied by 1cm, drying at 80 ℃ for 2h, tabletting under the pressure of 20MPa, and continuously drying after tabletting to obtain the polygonum multiflorum-based porous carbon electrode.
Comparative example 1
Mixing the Coly YP80F, the conductive carbon black and the 10% PTFE solution according to the mass ratio of 8:1:1, and adding 100mg of absolute ethyl alcohol into the mixture to demulsify so as to enable small droplets of the emulsion to agglomerate to form slurry easy to coat; coating the slurry on a nickel screen with the coating area of 1cm multiplied by 1cm, drying at 80 ℃ for 2h, tabletting under the pressure of 20MPa, and continuously drying after tabletting to obtain the commercial YP80F porous carbon electrode.
And (3) performance testing:
s1: the electrodes prepared in examples 1 to 8 and comparative example 1 were subjected to electrode performance test:
(1) cyclic voltammetry testing: and performing cyclic voltammetry on the prepared electrode by using an electrochemical workstation with the model number of chi660e under the conditions that the scanning potential range is-1-0V and the scanning speed is 5, 10, 20, 50, 100 and 200mV/s, wherein for an ideal double-layer capacitor, an electric double layer can be rapidly and uniformly formed at an electrode/solution interface, so that the cyclic voltammetry curve is rectangular. Under the sweeping speed of 10mV/s and the potential window of-1-0V, as shown in a) in figure 1, when the cyclic scanning is carried out on the examples 1-8 and the commercial comparative example 1, the corresponding CV does not have a Faraday oxidation-reduction peak, the curve is close to a rectangle, the symmetry is good, and the porous carbon electrode has good electrochemical reversibility. Under the same electrode preparation process conditions, the electrochemical area of the commercial porous carbon material (comparative example) is smaller, and the specific capacitance is smallerAlso smaller than examples 1 to 8. With the increase of the sweeping speed, the curve is slightly distorted as shown in a) in figure 2, a) in figure 3, a) in figure 4), a) in figure 5, a) in figure 6, a) in figure 7, a) in figure 8) and a) in figure 9, mainly because the pore structure of the rhizome type dregs-based porous carbon material prepared by activation is mainly rich micropores and the specific surface area is basically more than 2900m2In terms of/g (as shown in Table 1).
(2) Constant current charge and discharge test: and (3) carrying out constant-current charge and discharge tests on the prepared electrode under the current densities of 1, 2, 5, 10, 20 and 50A/g by using an electrochemical workstation with the model number of chi660e and the charge and discharge potential range of-1-0V. Under the current density of 1A/g, the constant-current charge-discharge curves of the electrodes prepared in examples 1-8 and comparative example 1 are shown in a comparative graph of b) in FIG. 1, and the curves are relatively symmetrical isosceles triangles, which shows that the charge-discharge reversibility of the capacitor is good, and the charge-discharge efficiency is high, wherein the specific capacitance of example 1 is up to 349.1F/g, the specific capacitance of example 2 is 324.5F/g, the specific capacitance of example 3 is 321.4F/g, the specific capacitance of example 4 is 286.5F/g, the specific capacitance of example 5 is 265F/g, the specific capacitance of example 6 is 264.4F/g, the specific capacitance of example 7 is 240.7F/g, the specific capacitance of example 8 is 232.2F/g, the performance of the porous carbon material prepared after the eight-rhizome-type traditional Chinese medicine residues are activated is obviously improved compared with that of the carbon material before activation, and the specific capacitance is more than that of the commercial porous carbon material ColyYP-80F (comparative example 1, 192.8F/g) is at least 20% higher. As shown in tables 1 and 2, the specific capacitance was at least 18% higher than that of comparative example 1 even at a current density of 10A/g, and the capacity retention rate was substantially 70% or more. As shown in b) of fig. 2), b) of fig. 3, b) of fig. 4), b) of fig. 5), b) of fig. 6), b) of fig. 7), b) of fig. 8, and b) of fig. 9, the charge and discharge time of the electrode material becomes shorter and the specific capacitance tends to slightly decrease as the charge and discharge current density increases.
(3) Electrochemical impedance testing: the frequency range of the alternating potential wave is 0.1-100000 Hz. The comparison of the electrochemical impedance spectrum curves of the electrodes prepared in examples 1 to 8 and comparative example 1 is shown in c) of FIG. 1. The curve conforms to the typical trend of the porous carbon material, is approximately a vertical straight line in a low-frequency region, and shows that the material has good capacitance and ideal double-layer capacitance characteristics. In the high frequency region, the intercept with the real axis X axis represents the equivalent series resistance (Rs) of the electrode, namely the internal resistance of the electrode and the contact resistance with the electrolyte, and as can be seen from c) in FIG. 1, the equivalent series resistance of the rhizome type dregs-based porous carbon material is mostly close to that of a commercial electrode, wherein the resistances of example 3, example 6, example 7 and example 8 are obviously smaller than that of the commercial electrode (comparative example 1), which is beneficial to improving the power density and rate capability of the super capacitor.
FIG. 1 a) is a comparison graph of the cyclic voltammetry curves of sanguisorba officinalis (example 1), salvia miltiorrhiza (example 2), dioscorea tokoro hypoglauca (example 3), codonopsis pilosula (example 4), bupleurum chinense (example 5), scutellaria baicalensis (example 6), uniflower swisscentaury root (example 7) and polygonum multiflorum (example 8) residue-based porous carbon electrode prepared by carbonization-activation and the commercial porous carbon material Coly YP80F of comparative example 1; FIG. 1 b) is a graph showing the comparison of constant current charging and discharging curves of sanguisorba officinalis (example 1), salvia miltiorrhiza (example 2), dioscorea tokoro hypoglauca (example 3), codonopsis pilosula (example 4), radix bupleuri (example 5), scutellaria baicalensis (example 6), uniflower swisscentaury root (example 7) and polygonum multiflorum (example 8) decoction dreg-derived porous carbon electrode prepared by carbonization-activation and the commercial porous carbon material Coly YP80F of comparative example 1; in fig. 1, c) is an electrochemical impedance spectrum curve of sanguisorba officinalis (example 1), salviae miltiorrhizae (example 2), dioscorea tokoro hypoglauca (example 3), codonopsis pilosula (example 4), radix bupleuri (example 5), scutellaria baicalensis (example 6), uniflower swisscentaury root (example 7) and polygonum multiflorum (example 8) residue-based porous carbon electrode prepared by a carbonization-activation method and a commercial porous carbon material cola YP80F of the comparative example 1.
In FIG. 2, a) is a comparison graph of cyclic voltammetry curves of the sanguisorba officinalis dreg-based porous carbon electrode in example 1 at different scanning speeds; FIG. 2 b) is a graph comparing constant current charge and discharge curves of example 1 at different current densities; in fig. 3, a) is a comparison graph of cyclic voltammetry curves of the salvia miltiorrhiza residue-based porous carbon electrode in example 2 at different scanning speeds; FIG. 3 b) is a graph comparing constant current charge and discharge curves of example 2 at different current densities; FIG. 4 a) is a comparison graph of cyclic voltammetry curves of the rhizoma Dioscoreae Septemlobae residue-based porous carbon electrode of example 3 at different scanning speeds; FIG. 4 b) comparative constant current charging and discharging curves of example 3 at different current densities; in FIG. 5, a) is a comparison graph of cyclic voltammetry curves of the Codonopsis pilosula residue-based porous carbon electrode of example 4 at different scanning speeds; FIG. 5 b) comparative constant current charge and discharge curves of example 4 at different current densities; FIG. 6 a) is a comparison graph of cyclic voltammetry curves of the Bupleurum scorzonerifolium-based porous carbon electrode of example 5 at different scanning speeds; FIG. 6 b) comparative constant current charge and discharge curves of example 5 at different current densities; in FIG. 7, a) is a comparison graph of cyclic voltammetry curves of the Scutellaria baicalensis residue-based porous carbon electrode of example 6 at different scanning speeds; FIG. 7 b) comparative constant current charging and discharging curves of example 6 at different current densities; in FIG. 8, a) is a comparison graph of cyclic voltammetry curves of the rhaponticum uniflorum dreg-based porous carbon electrode of example 7 at different scanning speeds; FIG. 8 b) comparative constant current charging and discharging curves of example 7 at different current densities; FIG. 9 a) is a comparison graph of cyclic voltammetry curves of the polygonum multiflorum residue-based porous carbon electrode of example 8 at different scanning speeds; fig. 9 b) comparative plot of constant current charge and discharge curves of example 8 at different current densities.
S2: the rhizome-based slag-based porous carbon materials of examples 1 to 8 were subjected to a nitrogen adsorption and desorption test, and the test results are shown in fig. 10. In fig. 10, a) and b) are absorption/desorption curves and pore size distribution curves of the sanguisorba officinalis (example 1), salvia miltiorrhiza (example 2), dioscorea tokoro hypoglauca (example 3), codonopsis pilosula (example 4), radix bupleuri (example 5), scutellaria baicalensis (example 6), uniflower swisscentaury root (example 7) and polygonum multiflorum (example 8) medicine residue-derived porous carbon electrode prepared by the carbonization-activation method respectively.
In fig. 10, a) shows that the adsorption curves of examples 1 to 8 are mixed adsorption curves of type I and type IV. In the region with the relative pressure of less than 0.1, the adsorption capacity of the embodiments 1 to 8 is increased along with the increase of the relative pressure, which indicates that a large number of microporous structures exist in the rhizome-type decoction dreg based porous carbon material, and the curve shows hysteresis loops, which indicates that mesopores exist. Different rhizome dregs as precursors have different adsorption capacity and specific surface area under the same preparation method. In fig. 10 b), it can be seen that the pore diameter structure of the rhizome-type traditional Chinese medicine residue-based porous carbon material is mainly characterized by micropores and small mesopores of less than 10 nm.
S3: FIG. 11 is a scanning electron microscope image of a porous carbon material, wherein a), b), c), d), e), f), g) and h) are porous carbon materials based on sanguisorba, salvia miltiorrhiza, dioscorea tokoro, codonopsis pilosula, radix bupleuri, scutellaria baicalensis, uniflower swisscentaury root and polygonum multiflorum herb residues respectively.
S4: specific capacitance test data of the rhizome-based electrode prepared in examples 1 to 8 are shown in table 1, and specific capacitance test data of the electrode prepared in comparative example 1 are shown in table 2.
TABLE 1 specific capacitance of electrodes prepared in examples 1-8
TABLE 2 specific capacitance of electrode prepared in comparative example 1
| Sample number | Active substance | Specific capacitance (1A/g) | Specific capacitance (10A/g) | Capacity retention ratio | Stotal(m2 g-1) |
| Comparative example 1 | Colori YP-80F | 192.8 | 139 | 72.1％ | 2100 |
Claims (10)
1. The preparation method of the rhizome traditional Chinese medicine residue-based porous carbon electrode material is characterized by comprising the following steps of: the method comprises the following steps:
1) carbonizing: pre-carbonizing the rhizome traditional Chinese medicine residues in a protective atmosphere to obtain a pre-carbonized product; the rhizome Chinese medicinal residue is more than one of radix Sangusorbae, Saviae Miltiorrhizae radix, rhizoma Dioscoreae Septemlobae, radix Codonopsis, bupleuri radix, Scutellariae radix, radix Rhapontici and Polygoni Multiflori radix;
2) and (3) activation: and uniformly mixing the pre-carbonized product with an activating agent, performing activation pyrolysis in a protective atmosphere, and performing subsequent treatment to obtain the rhizome traditional Chinese medicine residue-based porous carbon material.
2. The method for preparing a rhizome-type traditional Chinese medicine residue-based porous carbon electrode material according to claim 1, which is characterized in that: the pre-carbonization temperature in the step 1) is 400-600 ℃; the pre-carbonization time is 1-3 h;
the temperature of the activation pyrolysis in the step 2) is 400-1000 ℃, and the time of the activation pyrolysis is 0.5-6 h;
in the step 2), the mass ratio of the rhizome traditional Chinese medicine residue-based porous carbon to the activating agent is 1 (0.25-5).
3. The method for preparing a rhizome-type traditional Chinese medicine residue-based porous carbon electrode material according to claim 1, which is characterized in that: the activating agent in the step 2) is potassium hydroxide;
the protective atmosphere in the step 1) is argon or nitrogen; the subsequent treatment in the step 2) is acid treatment, and water is washed to be neutral.
4. A rhizome Chinese medicine residue-based porous carbon electrode material obtained by the preparation method of any one of claims 1 to 3.
5. The application of the rhizome Chinese medicine residue-based porous carbon electrode material as claimed in claim 4, wherein: the rhizome traditional Chinese medicine residue-based porous carbon electrode material is used for preparing an electrode, and the electrode is a rhizome traditional Chinese medicine residue-based porous carbon electrode.
6. A rhizome traditional Chinese medicine residue-based porous carbon electrode is characterized in that: mainly prepared from a rhizome type traditional Chinese medicine residue-based porous carbon electrode material, a conductive substance and a binder; the electrode is mainly made of a rhizomatic dregs-based porous carbon electrode material as defined in claim 4.
7. The rhizome-based herb residue-based porous carbon electrode of claim 6, wherein: the conductive substance is acetylene black, ketjen black or graphene; the binder is a PTFE solution.
8. The rhizome-based herb residue-based porous carbon electrode of claim 6, wherein: the preparation method comprises the following specific steps
S1, uniformly mixing the rhizome type traditional Chinese medicine residue-based porous carbon electrode material, the conductive substance and the binder, and performing emulsion removal to obtain a coating material;
s2, tabletting: coating the coating material on a carrier, drying and compacting to obtain the traditional Chinese medicine residue-based porous carbon electrode.
9. The rhizome-based herb residue-based porous carbon electrode of claim 8, wherein: in the step S1, the mass ratio of the rhizome traditional Chinese medicine residue-based porous carbon electrode material to the conductive substance is (7-9.5): 1;
in the step S1, the binder is a PTFE solution, and the mass fraction of the PTFE solution is 5-20%; the demulsifier for demulsification is absolute ethyl alcohol or diethyl ether; the addition amount of the demulsifier is 1-1.2 times of the mass of the PTFE solution;
in the step S2, the carrier is a nickel net, a titanium net, a stainless steel net, a titanium foil or a copper foil;
in the step S2, the drying temperature is 60-150 ℃ and the drying time is 2-12 hours; the compaction pressure is 5-30 MPa.
10. The use of a rhizome-based herb residue-based porous carbon electrode according to any one of claims 6 to 9, wherein: the rhizome traditional Chinese medicine residue-based porous carbon electrode is used for preparing a super capacitor and/or a lithium ion battery.
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| CN114823160A (en) * | 2022-04-11 | 2022-07-29 | 中国石油大学(华东) | Coal/heavy oil hydrogenation co-refining residue-based porous carbon electrode material and preparation method and application thereof |
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| CN116462196A (en) * | 2023-03-13 | 2023-07-21 | 江西中医药大学 | Activated carbon adsorbent based on aconite dreg, preparation method and application thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113184843A (en) * | 2021-04-25 | 2021-07-30 | 华南理工大学 | Polygonum multiflorum residue-based porous carbon and preparation method and application thereof |
| CN114823160A (en) * | 2022-04-11 | 2022-07-29 | 中国石油大学(华东) | Coal/heavy oil hydrogenation co-refining residue-based porous carbon electrode material and preparation method and application thereof |
| CN114823160B (en) * | 2022-04-11 | 2024-02-27 | 中国石油大学(华东) | Coal/heavy oil hydrogenation co-refining residue-based porous carbon electrode material and preparation method and application thereof |
| CN116161640A (en) * | 2022-09-09 | 2023-05-26 | 广东容钠新能源科技有限公司 | Spherical long-circulation stable biomass hard carbon material, preparation method and application |
| CN116462196A (en) * | 2023-03-13 | 2023-07-21 | 江西中医药大学 | Activated carbon adsorbent based on aconite dreg, preparation method and application thereof |
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