CN112624111B - Preparation method of metal-catalyzed corn straw derived carbon electrode material - Google Patents
Preparation method of metal-catalyzed corn straw derived carbon electrode material Download PDFInfo
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- CN112624111B CN112624111B CN202110042293.XA CN202110042293A CN112624111B CN 112624111 B CN112624111 B CN 112624111B CN 202110042293 A CN202110042293 A CN 202110042293A CN 112624111 B CN112624111 B CN 112624111B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/342—Preparation characterised by non-gaseous activating agents
- C01B32/348—Metallic compounds
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
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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
- H01G11/24—Electrodes 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
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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
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
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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 relates to a preparation method of a metal-catalyzed corn straw derived carbon electrode material, belonging to the technical field of new energy electronic materials. The obtained electrode material is cheap and easy to obtain, the process is simple, and the electrochemical performance is excellent. The preparation method comprises the following steps: pre-carbonizing the cleaned corn straw cores at 300 ℃ in Ar atmosphere; mixing the pre-carbonized product with 0.05 mol/L FeCl 3 ·6H 2 O doping, drying and then mixing the sample with KOH in a ratio of 1: 3, preserving the heat for 1 h at 700 ℃; the obtained product is washed by dilute hydrochloric acid solution, dried and subjected to sample preparation and test. The prepared metal-catalyzed corn straw derived carbon electrode material is prepared in 1 Ag ‑1 The specific capacitance value is 430.8 g ‑1 ，10 A g ‑1 The capacity retention rate reaches 1 Ag ‑1 74.2% of the total weight, the electrochemical performance was excellent. The metal-catalyzed straw-derived carbon electrode material prepared by the method has the advantages of low cost, stable structure, excellent electrochemical performance and high practical application value.
Description
Technical Field
The invention belongs to the technical field of new energy electronic materials, and relates to a preparation method of a corn straw derived carbon electrode material through metal catalysis.
Background
With the rapid development of the economy of China for the past decades, fossil fuels are widely exploited and utilized in various fields of economic construction of China. However, the development and use of fossil fuels without control causes serious damage to the natural environment and global warming of the climate, resulting in irreparable damage to the ecological environment. Therefore, the development of novel renewable energy storage devices, such as solar energy, wind energy, lithium ion batteries, super capacitors and the like, is considered as an effective measure for solving the problems of high pollution and high energy consumption of fossil fuels and realizing sustainable development of human beings. The super capacitor is favored by people due to the advantages of high charge-discharge rate, high specific capacity and the like, wherein the biomass material is widely distributed, cheap and easy to obtain, so the super capacitor is concerned by people in the research field of electrode materials.
The corn stalks are widely distributed in a wide area in northern China and consist of cellulose, hemicellulose and lignin, wherein the cellulose constitutes fibers, and the hemicellulose and the lignin are filled between microfine fibers and fiber cells as an adhesive, so that the plants are kept upright and have certain rigidity. The corn straw biomass carbon is prepared by carbonizing straws under the conditions of high temperature and oxygen deficiency, has the characteristics of developed pores, large specific surface area, rich organic functional groups on the surface and the like, and has the advantages of rich raw materials, low price and potential application prospect. In order to further develop the application of the corn stalks in the aspect of electrode materials of the super capacitor, the corn stalks are further researched to obtain better electrochemical performance. (preparation of pure plum, corn straw-based biomass carbon material and electrochemical performance research thereof [ D ] Jilin university, 2018.)
To improve the electrochemical performance of corn stover-derived carbon electrode materials, Li et al have used corn stover with LiCl/ZnCl 2 After mixing, the samples were heated at 800 ℃ for 10 h before mixing with K 2 C 2 O 4 、CaCO 3 Adding the materials according to the optimal proportion, carbonizing the materials at 800 ℃ for 2 hours, and then washing the materials by HCl and deionized water respectively, wherein the specific capacitance of the obtained product can reach 375F/g under the current density of 0.5A/g; gao et al, placing corn stalks into liquid nitrogen, freeze-drying, carbonizing the sample at 1100 deg.C for one hour in Ar gas environment, and obtaining a product with specific capacitance of 116F/g under current density of 0.25A/g; li et al prepared by mixing corn stover with K 2 C 2 O 4 、CaCO 3 Mixing and grinding, then carbonizing and preserving heat for one hour at 300 ℃, then preserving heat for two hours at 800 ℃, and obtaining the porous carbon material with the specific capacitance reaching 461F/g under the current density of 0.5A/g; wang et al added chopped corn stalks to a mixed solution of KCl and NaCl and soaked for 12 hours, then the mixture was carbonized by heat preservation at 800 ℃ for three hours in an air environment, the sample was washed with hydrochloric acid and dried, and the specific capacitance of the obtained sample was 407F/g at a current density of 1A/g. The invention takes the corn straws found in the farmland as the raw material, has rich sources, is cheap and is easy to obtain; the corn straw derived carbon electrode material catalyzed by metal ions obtained by doping metal ions with different concentrations, activating by KOH, carbonizing at high temperature and the like has excellent electrochemical performance as a super capacitor electrode material, the specific capacitance is 430.8F/g under the current density of 1A/g, and the specific capacitance is 320F/g under the current density of 10A/g; and 74.2% of the specific capacity under the current density of 1A/g can be reserved under the current density of 10A/g, and the high-power-factor-performance capacitor has good power performance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method and application of a metal-catalyzed corn straw derived carbon electrode material with higher specific capacitance and better cycle performance.
The technical scheme of the invention is as follows:
according to the invention, the preparation method of the biomass porous carbon material comprises the following steps:
(1) cleaning and drying fresh straws by deionized water, cutting corn straw cores into pieces, putting the cut corn straw cores into a clean porcelain boat, moving the porcelain boat into an Ar atmosphere tube furnace, heating the porcelain boat to 300 ℃ at the heating rate of 5 ℃/min, and preserving heat for 1 h at the temperature to obtain a pre-carbonized corn straw core product;
(2) taking 0.275 g of the pre-carbonized corn straw core obtained in the step (1), and respectively mixing with 25 ml of FeCl with the concentration of 0.04-0.06 mol/L 3 · 6H 2 Mixing the O solution, stirring for 24 hours, centrifuging, and drying in an oven at 55 ℃;
(3) immersing the dried metal ion-doped pre-carbonized product obtained in the step (2) into a KOH solution (the mass ratio of the pre-carbonized product to KOH is 1: 0.5-1: 5), stirring for one hour, and then putting the mixed solution into a 55 ℃ drying oven for drying:
(4) activating the sample obtained in the step (3) for 1-3 hours at 650-750 ℃ in Ar atmosphere;
(5) Washing the product obtained in the step (4) by using a dilute hydrochloric acid solution, and then washing the product by using deionized water and absolute ethyl alcohol until the solution is neutral;
(6) and (5) drying the product obtained in the step (5) at 55 ℃ for 12 h to obtain the metal catalytic straw derived carbon material.
According to the present invention, it is preferable that the concentration of the metal ions doped in the step (2) is 0.05 mol/L.
According to the present invention, it is preferred that the mass ratio of the pre-carbonized product to KOH in step (3) is 1: 3.
According to the present invention, it is preferred that the activation temperature in step (4) is 700 ℃.
According to the present invention, it is preferable that the activation time in the step (4) is 1 hour.
The technical advantages of the invention are as follows:
(1) the invention has the advantages of wide sources of raw materials, low price, easy obtainment, simple preparation process and controllability, and can change the catalytic action on the corn straw derived carbon by changing the concentrations of different metal ions.
(2) The metal-catalyzed corn straw derived carbon electrode material prepared by the invention has a three-dimensional porous shape.
(3) The metal-catalyzed corn straw derived carbon electrode material prepared by the invention has the advantages of stable structure, excellent electrochemical performance, good cycle performance, high specific capacitance and the like, and is very suitable for being applied to the field of supercapacitors as an electrode material.
Drawings
FIG. 1 is a scanning electron microscope image of the metal-catalyzed straw-derived carbon material prepared in example 1 of the present invention.
FIG. 2 is a constant current impulse discharge diagram of the metal-catalyzed straw-derived carbon material prepared in example 1 and comparative example of the present invention.
FIG. 3 is a specific capacitance diagram of the metal-catalyzed straw-derived carbon material prepared in example 1 of the present invention and a comparative example.
Detailed Description
The present invention will be further described with reference to the following detailed description and accompanying 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:
putting the cleaned corn straw cores into a clean porcelain boat, putting the porcelain boat into an atmosphere tube furnace, heating to 300 ℃ at a heating rate of 5 ℃/min under Ar atmosphere, preserving heat for 1 h at the temperature, and carrying out a pre-carbonization process; taking 0.275 g of pre-carbonized corn straw core and 25 ml of FeCl with the concentration of 0.05 mol/L 3 · 6H 2 Mixing O solution, stirring for 24 hr, centrifuging, and baking at 55 deg.CDrying in the box; immersing the pre-carbonized product doped with the dried metal ions into KOH solution (m) Pre-carbonized product ：m KOH =1: 3), after magnetically stirring for one hour, putting the mixed solution into an oven at 55 ℃ for drying; transferring the dried sample into an iron crucible, putting the iron crucible into an atmosphere tube furnace, heating to 700 ℃ at the heating rate of 5 ℃/min under the Ar atmosphere, and preserving heat for 1 h at the temperature to obtain a product; and finally, carrying out acid washing on the product by using 1 mol/L HCl solution, and drying the product to carry out sample preparation test.
Example 2:
putting the cleaned corn straw cores into a clean porcelain boat, putting the porcelain boat into an atmosphere tube furnace, heating to 300 ℃ at a heating rate of 5 ℃/min under Ar atmosphere, preserving heat for 1 h at the temperature, and carrying out a pre-carbonization process; taking 0.275g of pre-carbonized corn straw core and 25ml of FeCl with the concentration of 0.04 mol/L 3 · 6H 2 Mixing the O solution, stirring for 24 hours, centrifuging and drying in an oven at 55 ℃; immersing the pre-carbonized product doped with the dried metal ions into KOH solution (m) Pre-carbonized product ：m KOH =1: 3), after magnetically stirring for one hour, putting the mixed solution into an oven at 55 ℃ for drying; transferring the dried sample into an iron crucible, putting the iron crucible into an atmosphere tube furnace, heating to 700 ℃ at the heating rate of 5 ℃/min under the Ar atmosphere, and preserving heat for 1 h at the temperature to obtain a product; and finally, carrying out acid washing on the product by using 1 mol/L HCl solution, and drying the product to carry out sample preparation test.
Example 3:
putting the cleaned corn straw cores into a clean porcelain boat, putting the porcelain boat into an atmosphere tube furnace, heating to 300 ℃ at a heating rate of 5 ℃/min under Ar atmosphere, preserving heat for 1 h at the temperature, and carrying out a pre-carbonization process; taking 0.275 g of pre-carbonized corn straw core and 25 ml of FeCl with the concentration of 0.06 mol/L 3 · 6H 2 Mixing the O solution, stirring for 24 hours, centrifuging and drying in an oven at 55 ℃; immersing the pre-carbonized product doped with the dried metal ions into KOH solution (m) Pre-carbonized product ：m KOH =1: 3), after magnetically stirring for one hour, putting the mixed solution into an oven at 55 ℃ for drying; after dryingMoving the sample into an iron crucible, putting the iron crucible into an atmosphere tube furnace, heating to 700 ℃ at the heating rate of 5 ℃/min under the Ar atmosphere, and preserving heat for 1 h at the temperature to obtain a product; and finally, carrying out acid washing on the product by using 1 mol/L HCl solution, and drying the product to carry out sample preparation test.
Comparative example:
putting the cleaned corn straw cores into a clean porcelain boat, putting the porcelain boat into an atmosphere tube furnace, heating to 300 ℃ at a heating rate of 5 ℃/min under Ar atmosphere, preserving heat for 1 h at the temperature, and carrying out a pre-carbonization process; immersing the pre-carbonized product in KOH solution (m) Pre-carbonized product ：m KOH =1: 3), after magnetically stirring for one hour, putting the mixed solution into an oven at 55 ℃ for drying; transferring the dried sample into an iron crucible, putting the iron crucible into an atmosphere tube furnace, heating to 700 ℃ at the heating rate of 5 ℃/min under the Ar atmosphere, and preserving heat for 1h at the temperature to obtain a product; and finally, carrying out acid washing on the product by using 1 mol/L HCl solution, and drying the product to carry out sample preparation test.
Claims (1)
1. A preparation method of a metal-catalyzed corn straw derived carbon electrode material comprises the following steps:
(1) cleaning and drying fresh straws by deionized water, cutting corn straw cores into pieces, putting the cut corn straw cores into a clean porcelain boat, moving the porcelain boat into an Ar atmosphere tube furnace, heating the porcelain boat to 300 ℃ at the heating rate of 5 ℃/min, and preserving heat for 1h at the temperature to obtain a pre-carbonized corn straw core product;
(2) taking 0.275g of the pre-carbonized corn straw core in the step (1) and respectively mixing with 25ml of FeCl with the concentration of 0.04-0.06 mol/L 3 6H 2 Mixing the O solution, stirring for 24 hours, centrifuging, and drying in an oven at 55 ℃;
(3) immersing the metal ion-doped pre-carbonized product obtained in the step (2) into a KOH solution, wherein the mass ratio of the pre-carbonized product to KOH is 1: 0.5-1: 5, stirring for one hour, and then drying the mixed solution in a 55 ℃ oven;
(4) Activating the sample obtained in the step (3) for 1-3 h at 650-750 ℃ in Ar atmosphere;
(5) washing the product obtained in the step (4) by using a dilute hydrochloric acid solution, and then washing the product by using deionized water and absolute ethyl alcohol until the solution is neutral;
(6) drying the product obtained in the step (5) at 55 ℃ for 12h to obtain the metal-catalyzed corn straw porous carbon material;
the concentration of the doped metal ions in the step (2) is 0.05 mol/L;
the mass ratio of the pre-carbonized product to KOH in the step (3) is 1: 3;
the activation temperature in the step (4) is 700 ℃;
the activation time in step (4) is 1 hour.
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