CN113077997B - Preparation method of spirulina-based carbon material for super capacitor - Google Patents
Preparation method of spirulina-based carbon material for super capacitor Download PDFInfo
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- CN113077997B CN113077997B CN202110254490.8A CN202110254490A CN113077997B CN 113077997 B CN113077997 B CN 113077997B CN 202110254490 A CN202110254490 A CN 202110254490A CN 113077997 B CN113077997 B CN 113077997B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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
Abstract
The invention discloses a preparation method of a spirulina-based carbon material for a super capacitor. The method comprises the steps of mixing potassium oxalate and spiroThe mass ratio of spirulina is 1.5: 1, stirring spirulina and potassium oxalate in water until the spirulina and the potassium oxalate are uniformly mixed, centrifugally separating, collecting precipitate, freeze-drying, calcining a dried product at 200 ℃ in air atmosphere, and then carrying out N 2 Carbonizing at 500-800 ℃ in the atmosphere to obtain the three-dimensional porous spirulina-based carbon material. The spirulina-based carbon material prepared by the invention is simply stirred by potassium oxalate, and reacts to generate a more effective porous carbon structure with folds, so that abundant active sites and a smooth diffusion channel are provided, the charge transfer rate is accelerated, the volume effect in the electrochemical energy storage process is reduced, and the spirulina-based carbon material can be used as an electrode material and is suitable for a super capacitor.
Description
Technical Field
The invention belongs to the technical field of preparation of electrode materials, and relates to a preparation method of a spirulina-based carbon material for a super capacitor.
Background
With the development of consumer electronics, electric vehicles, and pulse technology, the demand for a super capacitor having a long service life, high coulombic efficiency, and capability of rapid charging/discharging is increasing. Supercapacitors can be divided into two broad categories based on their energy storage mechanism: electric double layer capacitors and pseudocapacitors. Electric double layer capacitance results primarily from ion adsorption and desorption at the electrode/electrolyte interface. Carbon materials have been widely used as electrode materials for supercapacitors due to their excellent electrical conductivity, tailorability and versatility.
Generally, carbon material precursors are typically derived from the by-products of fossil fuels, such as coal, petroleum coke, and pitch. Meanwhile, in consideration of environmental problems and economic benefits, the biomass serves as a novel green environment-friendly natural carbon material precursor, and the converted carbon material has rich porous structures, rich beneficial functional groups, high conductivity and other advantages. However, the cross-linking effect between cellulose and lignin of biomass makes the pore structure difficult to adjust and design, and the derived porous carbon material has interconnected macropores, so that the material accumulation and agglomeration are easily caused to cause general volume capacitance performance, and the application of the material is limited. Meanwhile, the literature (X.Liang, R.Liu and X.Wu, biological waste derived functional spore carbon with high gravi)(ii) metallic and volumetric capicients for supercapacitors, Microporous MeOporus mater.2021,310,110659.) use of KOH, NaOH, and ZnCl 2 When the chemical activation is carried out, the preparation process faces strongly corrosive chemical reagents, low carbon yield and complex preparation process flow, and the large-scale application of the preparation process is limited. The literature (A. Gopalakrishnan and S. Badhulika, Effect of selected-dependent catalysts on the performance of biological-dependent carbon for superparameter applications, J. Power Sources,2020,480,228830.) introduces heteroatoms into biomass by doping with precursors that add external agents (thiourea, phosphoric acid, melamine, boric acid, etc.). Such external doping generally involves multiple steps of pre-carbonization, activation, doping, etc., and the preparation process is complicated, time-consuming and tedious. These methods typically involve large energy consumption, cumbersome steps and extensive corrosion, resulting in high costs and contamination. Therefore, the green, simple and reasonable activation method for inducing the formation of the porous structure can promote the practical application of the biomass carbon. At present, no report is available for preparing the activated carbon material for the supercapacitor by using spirulina as a precursor and activating the activated carbon material by potassium oxalate.
Disclosure of Invention
The invention aims to provide a preparation method of a spirulina-based carbon material for a super capacitor. The method comprises the steps of fully stirring, mixing and culturing natural cylindrical spirulina and an activating agent potassium oxalate, calcining and shaping in air atmosphere, carbonizing in nitrogen atmosphere, and finally cleaning and drying to obtain the cylindrical porous activated carbon.
The technical scheme for realizing the purpose of the invention is as follows:
the preparation method of the spirulina-based carbon material for the super capacitor utilizes the best survival property of spirulina in alkalescent solution, takes potassium oxalate as an activating agent, fully mixes the materials and keeps the natural appearance of the spirulina under the condition of air calcination, and comprises the following steps:
step (ii) of2, calcining the product obtained in the step 1 at 200 ℃ for 1-3 h in the air atmosphere, and then carrying out N reaction 2 Carbonizing at 500-800 ℃ for 2h in the atmosphere, cleaning, and drying to obtain the three-dimensional porous spirulina-based carbon material.
Preferably, in step 1, the stirring time is 24 h.
Preferably, in step 2, the temperature rise rate of the calcination is 2 ℃ min -1 The temperature rise speed of carbonization is 1-5 ℃ min -1 。
In the step 1, the mass ratio of potassium oxalate to spirulina is 1.5: 1. when the mass ratio is too low, the prepared carbon material has too few channels, and when the mass ratio is too high, the channels are excessively activated, so that the channels are connected, and the specific surface area is reduced.
In step 2, the sample is shaped by calcination in an air atmosphere.
In the step 2, the carbonization temperature is 500-800 ℃. The temperature is too low, the time is too short, and the gasification is not facilitated to form a porous structure. Too high a temperature leads to too low a yield. Preferably, the carbonization temperature is 600 ℃ and the time is 2 h.
Compared with the prior art, the invention has the advantages that:
(1) the method is characterized in that cyanobacteria-spirulina generated by water eutrophication is selected as a biomass precursor, spirulina is a multicellular alga body, has a special cylindrical spiral filament, is rich in protein, saccharides, multiple vitamins and trace elements, has rich N, O functional groups, improves the surface wettability of the material, increases electrochemical active sites and improves the charge storage capacity;
(2) potassium oxalate is used as an activating agent, and the potassium oxalate is directly decomposed in a spirulina body phase to contribute to chemical activation, and CO decomposed in the formulas (1) and (2) can be used for secondary pore forming on the surface of spirulina. Meanwhile, the unique appearance of the spirulina is kept in the calcining process in the air, the carbonized product of the oxalate is carbon oxide, so that the activation effect on carbonization is realized, the subsequent material pore-forming is facilitated, the high utilization rate of atoms is realized, the prepared carbon material has large specific surface area and good energy storage performance, and the damage to equipment and the environment is lower compared with the traditional strong base KOH activator.
K 2 C 2 O 4 →K 2 CO 3 +CO (1)
K 2 CO 3 +2C→2K+3CO (2)
(3) Compared with the traditional activation mode, the potassium oxalate activation method can keep the appearance of the spirulina, and the activation condition is mild. In addition, the potassium oxalate activation provides higher product income, and a green and simple activation mode and high yield of activation play a very positive role in commercial utilization value.
Drawings
FIG. 1 is a microscopic view of Spirulina.
FIG. 2 is an SEM image of unactivated spirulina.
FIG. 3 is an SEM image of unactivated spirulina.
FIG. 4 is an SEM photograph of the spirulina carbon prepared in example 1.
FIG. 5 is an SEM photograph of the spirulina carbon prepared in example 1.
FIG. 6 is an X-ray diffraction pattern of the carbon material of Spirulina prepared in example 1.
FIG. 7 is a Raman spectrum of the carbon material of Spirulina prepared in example 1.
FIG. 8 is a fit electron spectrum of X-ray photoelectron spectroscopy analysis N1s of the spirulina carbon prepared in example 1.
FIG. 9 is a constant current charge and discharge curve of the carbon electrode material of Spirulina prepared in example 1.
FIG. 10 is a cyclic voltammogram of the carbon electrode material of Spirulina prepared in example 1.
FIG. 11 shows a carbon electrode material prepared in example 1 at 2A g -1 Performance plot for the first 10 cycles of cycling at current density.
Fig. 12 is an SEM image of the spirulina carbon prepared in comparative example 1.
Fig. 13 is an SEM image of the spirulina carbon prepared in comparative example 2.
Fig. 14 is a constant current charge and discharge graph of the carbon electrode materials of spirulina prepared in example 1 and comparative examples 1 and 2.
Fig. 15 is a graph showing the change of specific capacitance with current density of the carbon electrode materials of spirulina prepared in example 1 and comparative examples 1 and 2.
Fig. 16 is an SEM image of the spirulina carbon electrode material prepared in comparative example 3.
Detailed Description
The present invention will be described in more detail with reference to the following examples and the accompanying drawings.
The method filters and separates the spirulina in the water body, mixes the spirulina with activating agent potassium oxalate, and prepares the carbon material rich in heteroatom defects through secondary calcination. The electrolyte contains a large number of N, O heteroatom functional groups and carbon lattice defect structures, rich electrochemical active sites are exposed, and the transmission and ion adsorption of the electrolyte are promoted. Firstly, the spirulina is most suitable for the growth of the spirulina in a weak alkaline environment, so that the spirulina and the potassium oxalate are fully mixed and enter a bulk phase. In addition, the oxalate group of potassium oxalate itself realizes high atom utilization. Secondly, the unique cylindrical curved morphology of spirulina was well retained by calcination in air.
According to the three-dimensional porous active material prepared by the invention, the natural N, O functional groups in the bulk phase increase the surface wettability of the material, provide more ion transport channels and electrochemical reaction active sites, promote the free diffusion of electrolyte, and shorten the ion transfer path in the whole electrochemical reaction. Meanwhile, the volume change in electrochemical energy storage is relieved by the folds and the pore structure on the carbon surface of the spirulina, more electrochemical reaction active sites are provided, the free diffusion of electrolyte is promoted, and the transfer path of ions in the whole electrochemical reaction is shortened.
Example 1
(1) 0.5g of spirulina was uniformly dispersed in 100mL of distilled water, and 0.75g of potassium oxalate was added with stirring, and stirring was continued for 24 hours.
(2) The mixture was centrifuged to collect the precipitate, and lyophilized for 24 h.
(3) The product was kept at 2 ℃ for min under air -1 The temperature is raised to 200 ℃ at the rate of (1) and kept constant for 1 h. Then, in N 2 At 2 ℃ for min in an atmosphere of -1 The temperature is raised to 600 ℃ at the rate of (1) and kept constant for 120 min. Finally, the material is fully washed by hydrochloric acid solution until the pH value is 7, then washed by deionized water and ethanol, and dried at 60 ℃ to constant weight to obtain the carbon spirulinaA material.
FIG. 1 is a microscopic view of Spirulina. As can be seen in FIG. 1, the spirulina appeared to be in a curved cylindrical shape and was uniformly and widely distributed in the solution.
FIGS. 2 and 3 are SEM images of unactivated spirulina. As can be seen from FIGS. 2 and 3, the spirulina had a little slight wrinkles on its surface.
Fig. 4 and 5 are SEM images of the spirulina carbon prepared in example 1. As can be seen from fig. 4, the wrinkles and channels generated on the surface of the material are uniformly and widely distributed, which is beneficial to the penetration of the electrolyte and the entry of ions. As can be seen from fig. 5, the prepared material has a high disorder.
FIG. 6 is a carbon XRD pattern of Spirulina prepared in example 1.
FIG. 7 is a Raman spectrum of the carbon material of Spirulina prepared in example 1. As can be seen from fig. 7, the prepared material has a disordered structure and a graphite structure.
FIG. 8 is a fit electron spectrum of X-ray photoelectron spectroscopy analysis N1s of the spirulina carbon prepared in example 1. As can be seen from FIG. 8, N1s is divided into three peaks, which indicates that the surface of the activated carbon material has abundant nitrogen content, and the wettability and electrolyte compatibility of the material can be effectively enhanced, thereby improving the capacitance performance.
FIG. 9 is a constant current charge and discharge curve of the carbon electrode material of Spirulina prepared in example 1.
FIG. 10 is a cyclic voltammogram of the carbon electrode material of Spirulina prepared in example 1.
FIG. 11 shows a carbon electrode material prepared in example 1 at 2A g -1 Performance plots for the first 10 cycles of cycling at current density.
Comparative example 1
(1) 0.5g of spirulina was dispersed in 100mL of distilled water and stirred to be distributed uniformly, 1.0g of potassium oxalate was added with stirring, and stirring was continued for 24 hours.
(2) The mixture was centrifuged to collect the precipitate, and lyophilized for 24 h.
(3) The product was kept at 2 ℃ for min under air -1 The temperature rising rate of (2) was raised to 200 ℃ and activation was carried out at this temperature for 1 hour. Then, in N 2 At 2 ℃ for min in an atmosphere of -1 Temperature rise ofThe temperature is raised to 600 ℃ at a speed and kept constant for 120 min. And finally, fully washing the material with a hydrochloric acid solution until the pH value is 7, washing with deionized water and ethanol, and drying at 60 ℃ to constant weight to obtain the spirulina carbon material.
The SEM image of the spirulina carbon material prepared in comparative example 1 is shown in fig. 12, in which the pore structure of the material was interconnected to form large ravines, which were excessively activated to reduce the specific surface area.
Comparative example 2
(1) 0.5g of spirulina was dispersed in 100mL of distilled water and stirred to be distributed uniformly, 0.3g of potassium oxalate was added with stirring, and stirring was continued for 24 hours.
(2) The mixture was centrifuged to collect the precipitate, and lyophilized for 24 h.
(3) The product was kept at 2 ℃ for min under air -1 The temperature rising rate of (2) was raised to 200 ℃ and activation was carried out at this temperature for 1 hour. Then, in N 2 At 2 ℃ for min -1 The temperature is raised to 600 ℃ at the temperature raising rate, and the temperature is kept for 120 min. And finally, fully washing the material with a hydrochloric acid solution until the pH value is 7, washing with deionized water and ethanol, and drying at 60 ℃ to constant weight to obtain the spirulina carbon material.
Fig. 13 is an SEM image of the spirulina carbon material prepared in comparative example 2. It can be seen that there are few channels and the activation is insufficient.
Comparative example 3
(1) Mixing spirulina with potassium hydroxide in a ratio of 1: 1.5 into distilled water, continuously stirring and keeping for 24 h.
(2) The mixture was centrifuged to collect the precipitate, and lyophilized for 24 h.
(3) The product was kept at 2 ℃ for min under air -1 The temperature is raised to 200 ℃ at the rate of (1) and kept constant for 1 h. Then, in N 2 At 2 ℃ for min in an atmosphere of -1 The temperature is raised to 600 ℃ and kept constant for 120 min. And finally, fully washing the material with a hydrochloric acid solution until the pH value is 7, washing with deionized water and ethanol, and drying at 60 ℃ to constant weight to obtain the spirulina carbon material.
FIG. 16 SEM photograph of a Spirulina carbon material prepared in comparative example 3. It can be seen that the morphology of the carbon of the spirulina was changed without being completely retained by the activation with the strong base activator.
Example 2
Working electrodes were prepared using the spirulina carbon materials prepared in example 1 and comparative examples 1 and 2, respectively, as active materials, and electrochemical performance tests were performed thereon, including the following steps:
1) mixing an active material, conductive graphite and a binder Polytetrafluoroethylene (PTFE) in a weight ratio of 8: 1: 1 and proper amount of ethanol are mixed and coated on the foam nickel (1 multiplied by 1 cm) 2 ) Thus, a working electrode was obtained.
2) The foamed nickel working electrode was dried in an oven at 60 ℃ to constant weight and then pressed into tablets under 10 Mpa.
3) Preparing a working electrode, a reference electrode (silver-silver chloride electrode), a counter electrode (platinum electrode), a salt bridge and 6M KOH electrolyte, and assembling a three-electrode system.
Fig. 14 is a constant current charge and discharge graph of the carbon electrode materials of spirulina prepared in example 1 and comparative examples 1 and 2.
Fig. 15 is a graph showing the change of specific capacitance with current density of the carbon electrode materials of spirulina prepared in example 1 and comparative examples 1 and 2. As can be seen from FIG. 15, the specific capacitance of the electrode material prepared in example 1 is significantly higher than that of comparative examples 1 and 2, and when the current density is from 0.5A g -1 Increased to 10A g -1 In this case, the capacitance retention ratio of example 1 is also higher, which indicates that the interpenetrating stable pore structure has a significant effect of improving the capacitive performance.
In conclusion, the invention successfully synthesizes the three-dimensional porous cylindrical activated carbon taking spirulina as a precursor through simple potassium oxalate pretreatment and a subsequent one-step activation process. The spirulina carbon has the following advantages: (1) in the pretreatment process, the spirulina grows optimally in the alkalescent potassium oxalate aqueous solution, and is fully mixed and uniformly dispersed. Compared with other activating agents, the potassium oxalate can keep the appearance of the spirulina, and the activating condition is mild; (2) calcining in air, and keeping the cylindrical shape of the spirulina by rapid prototyping; (3) in the process of nitrogen calcination, potassium oxalate generates K at high temperature in the first step 2 O, CO and CO 2 Forming a pore structure with the carbon skeleton; second step CO 2 And the obtained spirulina carbon with the three-dimensional porous cylindrical structure provides rich active sites and open diffusion channels, accelerates the charge accumulation rate and lightens the volume effect of the electrode.
Claims (4)
1. The preparation method of the spirulina-based carbon material for the super capacitor is characterized by comprising the following steps of:
step 1, mixing potassium oxalate and spirulina according to a mass ratio of 1.5: 1, stirring spirulina and potassium oxalate in water until the spirulina and the potassium oxalate are uniformly mixed, carrying out centrifugal separation, collecting precipitate, and carrying out freeze drying;
step 2, calcining the product of the step 1 in the air atmosphere at 200 ℃ for 1-3 h, and then carrying out N 2 Carbonizing at 600 ℃ for 2h in the atmosphere, cleaning and drying to obtain the three-dimensional porous spirulina-based carbon material.
2. The method according to claim 1, wherein the stirring time in step 1 is 24 hours.
3. The method of claim 1, wherein the temperature of the calcination in step 2 is raised at a rate of 2 ℃ for min -1 。
4. The method according to claim 1, wherein the temperature increase rate of the carbonization in the step 2 is 1 to 5 ℃ for min -1 。
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| JP2006282444A (en) * | 2005-03-31 | 2006-10-19 | National Institute For Materials Science | Method for manufacturing spherical alga-like carbon having large specific surface area and electric double layer capacitor using the same |
| CN111547719A (en) * | 2020-04-13 | 2020-08-18 | 上海应用技术大学 | 3D porous carbon material and preparation method and application thereof |
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| CN104528720B (en) * | 2014-12-19 | 2016-08-24 | 浙江大学 | The preparation method of a kind of multi-stage porous Carbon Materials and product |
| KR101660313B1 (en) * | 2015-03-20 | 2016-09-27 | 한국과학기술원 | Method of preparing activated carbon |
| CN108128765B (en) * | 2017-12-26 | 2021-04-30 | 贵州大学 | Method for preparing nitrogen-doped porous carbon material and application |
| CN111943162B (en) * | 2019-05-14 | 2022-08-05 | 北京化工大学 | Microalgae bio-based nitrogen-doped carbon material and preparation method and application thereof |
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| JP2006282444A (en) * | 2005-03-31 | 2006-10-19 | National Institute For Materials Science | Method for manufacturing spherical alga-like carbon having large specific surface area and electric double layer capacitor using the same |
| CN111547719A (en) * | 2020-04-13 | 2020-08-18 | 上海应用技术大学 | 3D porous carbon material and preparation method and application thereof |
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