CN111180220A - Preparation method of supercapacitor electrode material based on citrus peel biomass charcoal - Google Patents
Preparation method of supercapacitor electrode material based on citrus peel biomass charcoal Download PDFInfo
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- CN111180220A CN111180220A CN202010056398.6A CN202010056398A CN111180220A CN 111180220 A CN111180220 A CN 111180220A CN 202010056398 A CN202010056398 A CN 202010056398A CN 111180220 A CN111180220 A CN 111180220A
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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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- 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
- H01G11/44—Raw materials therefor, e.g. resins or coal
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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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- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses a preparation method of a supercapacitor electrode material based on citrus peel biomass charcoal. The invention has the following advantages and effects: the raw material used in the invention is the waste peel of citrus fruits, the peel of the fruits has extremely high yield per year, is easy to obtain and has lower cost, and the peel can still be used as the raw material for producing electrode materials after mildewing, so that the storage problem is not worried about; in the process of preparing the electrode material, the activation of the biochar is added, so that the problem that the specific capacitance is low due to the influence of relevant factors such as air tightness and the like because a large amount of biochar is fired only by an atmosphere furnace in the prior art is solved; the electrode material prepared by the invention can also ensure the stability of specific capacitance under high current density, and the electrode material has good cycling stability.
Description
Technical Field
The invention relates to an electrode material of a super capacitor, in particular to a super capacitor electrode material based on orange peel biomass charcoal and a preparation method thereof.
Background
Energy storage elements with high conversion efficiency and large energy density, such as Super capacitors (Super capacitors), are receiving much attention. The SC is regarded as one of green energy storage devices with the most development potential in the 21 st century because of the bright points of long cycle life, high power density (Pd), no memory effect, high charge and discharge rate and the like, has a great development prospect, and has achieved huge achievements in the fields of energy storage and electric automobiles nowadays. The main factor impeding the development of SC is its lower Energy Density (ED) relative to conventional batteries. The electrode material is directly related to the energy density, so the research on the electrode material is mainly focused on developing a novel electrode material. Carbon materials have long been used as SC electrode materials due to their low cost, stable electrochemical properties, and simple processing and production processes.
Biomass charcoal (Biochar), a porous carbon processed from various biomasses, has many unique advantages, rich sources and simple preparation technology, becomes a creditable hot material, and is widely used in the fields of aerospace, chemical metallurgy, green energy and the like. Biochar is the basis of the whole capacitor, and SC prepared by Biochar with excellent performance can have larger capacitance density. There are many methods for preparing activated Biochar, and acids or bases are generally used to mix with precursors and then pyrolyze them; after carbonization, the carbonized product is mixed with KOH solution, dried and activated at high temperature; further use of KOH and K2CO3The composite activation is carried out, and the activation temperature is generally 300-1000 ℃.
Only the pulp of citrus fruit is edible, while a large amount of the orange peel is discarded. The Biochar is prepared by utilizing waste orange peels, is utilized in the SC field, but is not easy to store peels and easy to rot and mildew, the rotten orange peels are prepared into biomass charcoal, and the prepared biomass charcoal has good capacitance performance when being used as an electrode material and has good economic, environmental and application values.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a preparation method of an orange peel biomass charcoal-based supercapacitor electrode material.
The invention also aims to provide a supercapacitor electrode material based on the citrus peel biomass charcoal. The electrode material has good capacitance performance.
The technical purpose of the invention is realized by the following technical scheme:
1. a preparation method of an orange peel biomass charcoal-based supercapacitor electrode material comprises the following steps:
(1) pretreatment
Cleaning fresh orange peel, placing in shade to naturally rot and mildew, and oven drying in a constant temperature drying oven;
(2) charring
Carbonizing the orange peel pretreated in the step (1) in an atmosphere furnace at 600-1000 ℃ for 2-3h at a heating rate of 5 ℃/min under the protection of nitrogen in the whole carbonization process, and grinding and crushing the carbonized orange peel to obtain carbon powder after the carbonized orange peel is cooled;
(3) activation of
Taking the carbon powder in the step (2), uniformly mixing the carbon powder with KOH in water, performing ultrasonic treatment for 1h, drying in an oven, centrifuging to obtain a precipitate, drying the precipitate for the first time, placing the precipitate in a tubular furnace heated to 600-900 ℃, performing heat preservation, and performing secondary drying and activation;
(4) purification of
And (4) cooling the activated product in the step (3) to room temperature, centrifuging, washing away KOH in the activated product, and drying to obtain the electrode material.
In the technical scheme, the mass ratio of the carbon powder to the KOH in the step (3) is 1:1-1: 4.
In the technical scheme, the drying temperature in the step (1) is 110 ℃, and the drying time is 22 h.
In the technical scheme, the baking temperature in the step (3) is 160 ℃, and the baking time is 15 hours.
In the above technical scheme, the temperature of the primary drying in the step (3) is 80 ℃.
In the above technical scheme, the time for the secondary drying in the step (3) is 2 hours.
In the above technical scheme, the drying temperature in the step (4) is 80 ℃.
In the technical scheme, the heat preservation time in the step (3) is 2 hours.
A supercapacitor electrode material based on citrus peel biomass charcoal is prepared by the method.
In conclusion, the preparation method and the obtained product have the following advantages and beneficial effects:
(1) the raw material used in the invention is the waste peel of citrus fruits, the peel of the fruits has extremely high yield per year, is easy to obtain and has lower cost, and the peel can still be used as the raw material for producing electrode materials after mildewing, so that the storage problem is not worried about;
(2) the method has the advantages that in the process of preparing the electrode material, the activation of the biomass charcoal is added, the problem that the specific capacitance is low due to the influence of relevant factors such as air tightness and the like because only an atmosphere furnace is used for firing in the prior art is solved, the specific capacitance can be improved by changing the mass ratio of the biomass charcoal to the KOH, the specific capacitance is increased by more than 1.5 times compared with a manufacturing method without an activation step when the temperature is 700 ℃ and the temperature is C: KOH =1:3 at the scanning speed of 10mV/s, and the specific capacitance is increased by more than 2 times compared with a manufacturing method without an activation step when the temperature is 700 ℃ and the temperature is C: KOH =1:3 at the scanning speed of 100 mV/s;
(3) in the activation process, two drying steps are added, the specific capacitance can be increased by more than 1.4 times compared with a manufacturing method without an activation step when the scanning speed is 10mV/s and the temperature is C: KOH =1:1 and 900 ℃, and the specific capacitance can be increased by more than 1.7 compared with the manufacturing method without the activation step when the scanning speed is 100mV/s and the temperature is C: KOH =1:1 and 900 ℃;
(4) the electrode material prepared by the invention can also ensure the stability of specific capacitance under high current density, and the electrode material has good cycling stability.
Drawings
FIG. 1 is a graph comparing carbonization at different temperatures, wherein (a) is a graph of CV for a differently carbonized molded citrus biomass at a scan rate of 10mV/s, (b) is a graph of CV for a differently carbonized molded citrus biomass at a scan rate of 100mV/s, and (c) (d) is a graph of CV for M-700 at different scan rates;
FIG. 2 is a graph comparing activation at 700 ℃ for different KOH ratios, wherein (a) is a graph showing CV of a molded tangerine Biochar activated at 700 ℃ for different KOH ratios at a scan rate of 10mV/s, (b) is a graph showing CV of a molded tangerine Biochar activated at 700 ℃ for different KOH ratios at a scan rate of 100mV/s, and (c) (d) is a graph showing CV of MK-1:3-700 at different scan rates;
FIG. 3 is a graph showing the CV of different temperature activations at KOH =1:1, wherein (a) is the CV of a mildewed citrus Biochar activated at different temperatures at a scan rate of 10mV/s, (b) is the CV of a mildewed citrus Biochar activated at different temperatures at a scan rate of 100mV/s at KOH =1:1, and (C) (d) is the CV of MK-1:1-900 at different scan rates;
FIG. 4 is a graph comparing the current density to capacitance of samples, where (a) is MK-1:3-700, MK-1:1-900 and M2-700 specific capacitance comparison line plots at different current densities, (b) M-700 and M-700-KN-700 specific capacitance comparison line plots at different current densities;
FIG. 5 is a graph of cycling stability tests for MK-1:3-700, MK-1:1-900, and M-700-KN-700;
FIG. 6 is an SEM topography, wherein (a), (b), (c), (d), (e) and (f) are SEM images of M-600, M-700, M-800, MK-1:3-700, MK-1:1-900 and M-700-KN-700, respectively.
Detailed Description
The present invention is described in detail below with reference to specific examples, but the use and purpose of the exemplary embodiments are merely to exemplify the present invention, and do not set forth any limitation on the actual scope of the present invention in any form, and the scope of the present invention is not limited thereto.
The pericarp of the orange fruit used in the invention is tangerine peel
Example 1
(1) Cleaning fresh tangerine peel, placing the tangerine peel in a shade place to naturally rot and mildew, and then placing the tangerine peel in a constant-temperature drying box for drying at the temperature of 110 ℃ for 22 hours;
(2) taking out the dried tangerine peel, putting the tangerine peel into a porcelain crucible, covering the porcelain crucible with a cover, putting the porcelain crucible into an atmosphere furnace chamber, closing a furnace door, introducing nitrogen, heating to 700 ℃ at a speed of 5 ℃/min, preserving heat for 2 hours, then cooling to room temperature at a speed of 10 ℃/min, and firing a large amount of Biochar under the protection of nitrogen in the whole process.
(3) After cooling, the nitrogen was turned off, the ceramic crucible was removed, the carbonized product was ground and sealed in a centrifuge tube, designated M2-700.
(4) 640.8mg of M2-700 is weighed by an electronic balance, 640.8mg of KOH is taken according to the ratio of C: KOH =1:1, water is added to the mixture to be uniformly mixed, the mixture is poured into an inner container of a reaction kettle, and ultrasound is carried out for one hour.
(5) The inner container is put into the outer container and screwed, and then dried in an oven for 15 hours at 160 ℃.
(6) Taking out, pouring into a centrifuge tube, centrifuging, drying the precipitate at 80 ℃, pouring into a porcelain boat, heating to 700 ℃ at 10 ℃/min in a tube furnace, preserving the heat for 2 hours, and then cooling to room temperature at 10 ℃/min.
(7) The activated product was removed and poured into a centrifuge tube for centrifugation to remove KOH present therein and dried at 80 ℃ and recorded as MK-1: 1-700.
Example 2
(1) Cleaning fresh tangerine peel, placing the tangerine peel in a shade place to naturally rot and mildew, and then placing the tangerine peel in a constant-temperature drying box for drying at the temperature of 110 ℃ for 22 hours;
(2) taking out the dried tangerine peel, putting the tangerine peel into a porcelain crucible, covering the porcelain crucible with a cover, putting the tangerine peel into an atmosphere furnace chamber, closing a furnace door, introducing nitrogen, heating to 1000 ℃ at the speed of 5 ℃/min, preserving heat for 3 hours, then cooling to room temperature at the speed of 10 ℃/min, and firing a large amount of Biochar under the protection of nitrogen in the whole process.
(3) After cooling, the nitrogen was turned off, the ceramic crucible was removed, the carbonized product was ground and sealed in a centrifuge tube, designated M2-700.
(4) 320.5 mg of M2-700 is weighed by an electronic balance, 640.8mg of KOH is weighed according to the ratio of C to KOH =1:2, water is added to the mixture to be uniformly mixed, the mixture is poured into an inner container of a reaction kettle, and ultrasound is carried out for one hour.
(5) The inner container is put into the outer container and screwed, and then dried in an oven for 15 hours at 160 ℃.
(6) Taking out, pouring into a centrifuge tube, centrifuging, drying the precipitate at 80 ℃, pouring into a porcelain boat, heating to 700 ℃ at 10 ℃/min in a tube furnace, preserving the heat for 2 hours, and then cooling to room temperature at 10 ℃/min.
(7) The activated product was removed and poured into a centrifuge tube for centrifugation to remove KOH present therein, and dried at 80 ℃ and recorded as MK-1: 2-700.
Example 3
(1) Cleaning fresh tangerine peel, placing the tangerine peel in a shade place to naturally rot and mildew, and then placing the tangerine peel in a constant-temperature drying box for drying at the temperature of 110 ℃ for 22 hours;
(2) taking out the dried tangerine peel, putting the tangerine peel into a porcelain crucible, covering the porcelain crucible with a cover, putting the tangerine peel into an atmosphere furnace chamber, closing a furnace door, introducing nitrogen, heating to 800 ℃ at a speed of 5 ℃/min, preserving heat for 3 hours, then cooling to room temperature at a speed of 10 ℃/min, and firing a large amount of Biochar under the protection of nitrogen in the whole process.
(3) After cooling, the nitrogen was turned off, the ceramic crucible was removed, the carbonized product was ground and sealed in a centrifuge tube, designated M2-700.
(4) Weighing 213.6 mg of M2-700 by an electronic balance, weighing 640.8mg of KOH according to the ratio of C to KOH =1:3, adding water, mixing uniformly, pouring into an inner container of a reaction kettle, and carrying out ultrasonic treatment for one hour.
(5) The inner container is put into the outer container and screwed, and then dried in an oven for 15 hours at 160 ℃.
(6) Taking out, pouring into a centrifuge tube, centrifuging, drying the precipitate at 80 ℃, pouring into a porcelain boat, heating to 700 ℃ at 10 ℃/min in a tube furnace, preserving the heat for 2 hours, and then cooling to room temperature at 10 ℃/min.
(7) The activated product was removed and poured into a centrifuge tube for centrifugation to remove KOH present therein, and dried at 80 ℃ and recorded as MK-1: 3-700.
Example 4
(1) Cleaning fresh tangerine peel, placing the tangerine peel in a shade place to naturally rot and mildew, and then placing the tangerine peel in a constant-temperature drying box for drying at the temperature of 110 ℃ for 22 hours;
(2) taking out the dried tangerine peel, putting the tangerine peel into a porcelain crucible, covering the porcelain crucible with a cover, putting the porcelain crucible into an atmosphere furnace chamber, closing a furnace door, introducing nitrogen, heating to 600 ℃ at a speed of 5 ℃/min, preserving heat for 3 hours, then cooling to room temperature at a speed of 10 ℃/min, and firing a large amount of Biochar under the protection of nitrogen in the whole process.
(3) After cooling, the nitrogen was turned off, the ceramic crucible was removed, the carbonized product was ground and sealed in a centrifuge tube, designated M2-700.
(4) Weighing 160.2 mg of M2-700 by using an electronic balance, weighing 640.8mg of KOH according to the ratio of C to KOH =1:4, adding water, uniformly mixing, pouring into an inner container of a reaction kettle, and carrying out ultrasonic treatment for one hour.
(5) The inner container is put into the outer container and screwed, and then dried in an oven for 15 hours at 160 ℃.
(6) Taking out, pouring into a centrifuge tube, centrifuging, drying the precipitate at 80 ℃, pouring into a porcelain boat, heating to 700 ℃ at 10 ℃/min in a tube furnace, preserving the heat for 2 hours, and then cooling to room temperature at 10 ℃/min.
(7) The activated product was removed and poured into a centrifuge tube for centrifugation to remove KOH present therein and dried at 80 ℃ and recorded as MK-1: 4-700.
Examples 5 to 7
The difference between the 3 examples and example 1 is that the holding temperature in the tube furnace is set to 600 deg.C, 800 deg.C and 900 deg.C respectively, and is recorded as MK-1:1-600, MK-1:1-800 and MK-1:1-900
Example 8
(1) Taking out flesh of the fresh mandarin orange, cleaning the peel, and placing the peel in a shade place to naturally rot and mildew.
(2) And (3) drying the mildewed tangerine peel in an oven for 22 hours at 110 ℃, taking out, grinding, sealing and storing.
(3) Taking out the ground tangerine powder, pouring the tangerine powder into a porcelain boat, lightly feeding the tangerine powder into the middle part of the tube furnace, screwing screws and checking the air tightness. And opening a nitrogen valve, removing air, setting the temperature to be 5 ℃/min, raising the temperature to 700 ℃, keeping the temperature at 700 ℃ for 2 hours, then cooling the temperature to room temperature at 10 ℃/min, and keeping the nitrogen in the whole process for conveying.
(4) And after cooling, closing the nitrogen, taking out the porcelain boat, filling the carbonized product into a centrifuge tube, sealing and marking by M-700.
Examples 9 to 12
The difference between these 3 examples and example 8 is that the holding temperatures in the tube furnace were set to 600 deg.C, 800 deg.C, 900 deg.C and 1000 deg.C, respectively, and labeled M-600, M-800, M-900 and M-1000, respectively.
Examples 8-12 are merely methods for preparing electrode materials that did not include an activation step, and are intended to compare the deficiencies of electrode materials prepared by the methods employed in the present invention.
Example 13
Preparation of porous N-doped biomass charcoal
(1) 357.5 mg of M-700 is weighed by an electronic balance, 1444.1 mg of KOH and 355.1mg of urea are weighed according to the ratio of C to KOH to N =1 to 4 to 1, water is added to the mixture, the mixture is uniformly mixed and poured into an inner container of a reaction kettle, and ultrasonic treatment is carried out for one hour.
(2) The inner container is put into the outer container and screwed, and then dried in an oven for 15 hours at 160 ℃.
(3) The liquid was poured into a petri dish, covered with a perforated aluminum foil paper, and dried in an oven at 100 ℃ for 5 hours.
(4) Scraping the dried product, placing the product in a porcelain boat, heating to 700 ℃ at a speed of 5 ℃/min in a tube furnace, preserving the heat for 2 hours, and then cooling to room temperature at a speed of 10 ℃/min.
(5) And (4) cooling, closing the nitrogen, taking out, centrifuging, washing away residual KOH, and drying.
(6) Drying, sealing, and marking as M-700-KN-700.
The invention also carries out the following research, the preparation of the electrode and the electrochemical performance test:
(1) three pieces of foamed nickel are cut into b shapes, marks which can be identified are made, the mass m1 of the marks is weighed respectively, and the records are made.
(2) M-700 was taken out, 11.1 mg of M-700 and 1.4 mg of acetylene black were weighed in a ratio of C: PTFE: acetylene black =8:1:1, 3.23. mu.l of PTFE was sucked by a pipette gun, a small amount of ethanol was added, and the mixture was ground into a paste.
(3) The mixture was evenly spread on three pieces of nickel foam using the tail of an iron spoon, baked under a strong light for 20 min, tabletted (9 MPa, 1 min), weighed, designated M2, and soaked in 6M KOH solution for 12 h.
(4) The mass of the active material component on the nickel foam was calculated to be m =80% (m 1-m 2).
(5) Starting an electrochemical workstation, assembling a three-electrode system, taking an Hg/HgO electrode (SCE) as a reference electrode, taking a platinum sheet electrode as a counter electrode, and taking a carbon-coated foamed nickel electrode as a working electrode.
(6) selecting Cyclic Voltammetry (CV), selecting a voltage window of-1.1-0.1V when the graph is closest to a rectangle by gradually changing the voltage window, testing three circles at the scanning rate of 1, 5, 10, 50, 100, 200, 400, 600, 800 and 1000mV/S respectively, storing data, selecting second circle data, calculating specific capacitance according to the following formula and recording, wherein Cm is mass specific capacitance, S integral area is integral area of a CV curve, m is mass of an active component, △ V is width of the voltage window, and r is the scanning rate.
Cm = S integral area/(2 m. DELTA. V. r)
(7) selecting a constant current charge-discharge method (CP), keeping a voltage window constant, respectively testing 6 sections of current densities of 0.3, 0.5, 1, 5, 10, 20, 40 and 80A/g, selecting a discharge curve of the middle section, calculating specific capacitance according to the following formula and recording the specific capacitance, wherein Cs is mass specific capacitance, I is current intensity, △ t is discharge time, m is the mass of an active component, and DeltaV is the width of the voltage window.
Cs=I·△t / (△V·m)
(8) And testing the cycle stability of the electrode, keeping the voltage window unchanged, setting the current density to be 80A/g, starting a cycle test, and drawing a relation graph of cycle times and specific capacitance.
(9) M-600, M-800, M-900, M-1000, M2-700, MK-1:1 (2, 3, 4) -700 and MK-1:1-600 (800, 900) were removed and the above experiments were repeated.
By electrochemical performance testing, the following conclusions were reached:
as shown in FIG. 1a, when the voltage window is-1.1-0.1V, the specific capacitance of M-700 is the largest at a scanning rate of 10mV/s, and the specific capacitance of M-700 is 139.1F/g, M-600 is 107.1F/g, M-800 is 123.1F/g, M-900 is 118.6F/g, and M-1000 is 76.6F/g, as calculated by the above formula;
as shown in FIG. 1b, when the voltage window is-1.1-0.1V, the specific capacitance of M-700 is the largest at a scanning rate of 100mV/s, and the specific capacitance of M-700 is 76.0F/g, M-600 is 42.0F/g, M-800 is 67.9F/g, M-900 is 71.6F/g, and M-1000 is 52.2F/g, as calculated by the above formula;
as shown in FIGS. 1c and 1d, the specific capacitance was 190.4F/g at a scan rate of 1 mV/s; 153.5F/g at 5 mV/s; 139.1F/g at 10 mV/s; 95F/g at 50 mV/s; 76.0F/g at 100 mV/s; 55.1F/g at 200 mV/s; 38.4F/g at 400 mV/s; 30.6F/g at 600 mV/s; 25.4F/g at 800 mV/s; the concentration at 1000mV/s was 21.8F/g. The specific capacitance continuously decreases along with the increase of the scanning speed;
as shown in FIG. 2a, the specific capacitance of MK-1:3-700 at a scan rate of 10mV/s is the greatest at a voltage window of-1.1-0.1V, and as calculated by the above formula, it is found that the specific capacitance of MK-1:3-700 is 155.0F/g, MK-1:1-700 is 135.8F/g, MK-1:2-700 is 151.4F/g, and MK-1:4-700 is 148.1F/g. Due to the use of M 2700 is formed by firing a large amount of atmosphere furnace, and the specific capacitance is only 98.6F/g due to the influence of relevant factors such as air tightness, so that it can be concluded that the activation is very helpful for the increase of the specific capacitance of the Biochar, and the influence of different proportions on the size of the increase of the specific capacitance is very large. At a scan rate of 10mV/s, 700 ℃ C: KOH =1:3, compared to M 2700, the increase of the specific capacitance is more than 1.5 times;
as shown in FIG. 2b, the specific capacitance of MK-1:3-700 at a scan rate of 100mV/s is the greatest at a voltage window of-1.1-0.1V, and as calculated by the above formula, it is found that the specific capacitance of MK-1:3-700 is 114.4F/g, MK-1:1-700 is 85.8F/g, MK-1:2-700 is 102.0F/g, and MK-1:4-700 is 99.2F/g. Relative to M2For a specific capacitance of-700 of only 56.7F/g, the improvement is obvious, and MK-1:3-700 is moreMore than twice the span is achieved;
as shown in FIGS. 2c and 2d, CV plots for different scan rates over a voltage window of-1.1-0.1V were calculated to have a specific capacitance of 182.1F/g at a scan rate of 1 mV/s; 164.2F/g at 5 mV/s; 155.0F/g at 10 mV/s; 130.0F/g at 50 mV/s; 114.4F/g at 100 mV/s; 93.9F/g at 200 mV/s; 68.8F/g at 400 mV/s; 50.4F/g at 600 mV/s; 43.6F/g at 800 mV/s; 36.1F/g at 1000 mV/s;
as shown in FIG. 3a, the specific capacitance of MK-1:1-900 at a scan rate of 10mV/s is the greatest at a voltage window of-1.1-0.1V, and as calculated by the above formula, it is found that the specific capacitance of MK-1:1-900 is 138.4F/g, MK-1:1-600 is 111.4F/g, MK-1:1-700 is 135.8F/g, and MK-1:1-800 is 136.7F/g. Due to the use of M 2700 is formed by firing a large amount in an atmosphere furnace, and the specific capacitance is only 98.6F/g due to the influence of factors such as airtightness, so that it can be concluded that activation is still very helpful for the increase of the specific capacitance of the Biochar, and the influence of different temperatures on the increase of the specific capacitance is also large. Comparison of M at a sweep rate of 10mV/s with C: KOH =1:1, 900 deg.C 2700, the increase of specific capacitance can reach more than 1.4 times;
as shown in FIG. 3b, the specific capacitance of MK-1:1-900 at a scan rate of 100mV/s is the greatest at a voltage window of-1.1-0.1V, and as calculated by the above formula, it is found that the specific capacitance of MK-1:1-900 is 95.6F/g, MK-1:1-600 is 70.7F/g, MK-1:1-700 is 85.8F/g, and MK-1:1-800 is 91.9F/g. Relative to M2For the specific capacitance of 700 only 56.7F/g, the improvement is obvious, and the highest MK-1:1-900 is increased by nearly 1.7 times;
as shown in FIGS. 3c and 3d, the specific capacitance was 169.2F/g at a scan rate of 1 mV/s; 148.5F/g at 5 mV/s; 138.4F/g at 10 mV/s; 110.2F/g at 50 mV/s; 95.6F/g at 100 mV/s; 79.6F/g at 200 mV/s; 61.7F/g at 400 mV/s; 51.3F/g at 600 mV/s; 43.2F/g at 800 mV/s; 37.2F/g at 1000 mV/s;
as shown in FIG. 4, this step of activation is for M at a voltage window of-1.1-0.1V2The improvement effect of the specific capacitance of-700 is very obvious,the proportion of KOH has more obvious influence on the specific capacitance, when the voltage window is-1.1-0.1V, the promotion effect of activation and N doping on the M-700 specific capacitance is very obvious, the stability of the specific capacitance can be ensured under larger current density, and the phenomenon that the M-700 seriously slides down under large current density is avoided;
as shown in fig. 5, it is clear from the graph that the specific capacitances of the three samples all have a tendency to decrease and then increase smoothly. All data values have small difference, and the specific capacitance can be basically kept in the same horizontal straight line within the allowable range of calculation error, which indicates that the circulation stability is good;
as shown in FIG. 6, it can be seen from the comparison of (a), (b) and (c) that the micro-surface pore distribution of the prepared carbon material is more and quite uniform at 700 degrees, which is one of the reasons for the larger specific capacitance; 600 degrees has less surface voids, while 800 degrees results in too large voids and more fine debris scattered, so that the specific capacitance of both is not very large. (d) (e) (f) the surface is rougher and the particles are smaller than (b), so that the specific surface area is larger, and therefore the specific capacitance is greatly improved. (f) Is the product after activation and N doping, the particles are finer and uneven, and thus the specific capacitance is the largest.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art will appreciate that they may still make modifications to the technical solutions described in the foregoing embodiments, or may make equivalents to some or all of the technical features; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (9)
1. A preparation method of a supercapacitor electrode material based on orange peel biomass charcoal is characterized by comprising the following steps: the method comprises the following steps:
(1) pretreatment
Cleaning fresh orange peel, placing in shade to naturally rot and mildew, and oven drying in a constant temperature drying oven;
(2) charring
Carbonizing the orange peel pretreated in the step (1) in an atmosphere furnace at 600-1000 ℃ for 2-3h at a heating rate of 5 ℃/min under the protection of nitrogen in the whole carbonization process, and grinding and crushing the carbonized orange peel to obtain carbon powder after the carbonized orange peel is cooled;
(3) activation of
Taking the carbon powder in the step (2), uniformly mixing the carbon powder with KOH in water, performing ultrasonic treatment for 1h, drying in an oven, centrifuging to obtain a precipitate, drying the precipitate for the first time, placing the precipitate in a tubular furnace heated to 600-900 ℃, performing heat preservation, and performing secondary drying and activation;
(4) purification of
And (4) cooling the activated product in the step (3) to room temperature, centrifuging, washing away KOH in the activated product, and drying to obtain the electrode material.
2. The preparation method of the orange peel biomass charcoal-based supercapacitor electrode material according to claim 1, wherein the preparation method comprises the following steps: the mass ratio of the carbon powder to the KOH in the step (3) is 1:1-1: 4.
3. The preparation method of the orange peel biomass charcoal-based supercapacitor electrode material according to claim 1, wherein the preparation method comprises the following steps: the drying temperature in the step (1) is 110 ℃, and the drying time is 22 h.
4. The preparation method of the orange peel biomass charcoal-based supercapacitor electrode material according to claim 1, wherein the preparation method comprises the following steps: the baking temperature in the step (3) is 160 ℃, and the baking time is 15 h.
5. The preparation method of the orange peel biomass charcoal-based supercapacitor electrode material according to claim 1, wherein the preparation method comprises the following steps: the temperature of the primary drying in the step (3) is 80 ℃.
6. The preparation method of the orange peel biomass charcoal-based supercapacitor electrode material according to claim 1, wherein the preparation method comprises the following steps: and (4) the time for secondary drying in the step (3) is 2 h.
7. The preparation method of the orange peel biomass charcoal-based supercapacitor electrode material according to claim 1, wherein the preparation method comprises the following steps: the drying temperature in the step (4) is 80 ℃.
8. The preparation method of the orange peel biomass charcoal-based supercapacitor electrode material according to claim 1, wherein the preparation method comprises the following steps: the heat preservation time in the step (3) is 2 hours.
9. The utility model provides a supercapacitor electrode material based on citrus peel biomass charcoal which characterized in that: prepared by the method of any one of claims 1-8.
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