CN114031076A - Biomass superstructure carbon, and preparation method and application thereof - Google Patents
Biomass superstructure carbon, and preparation method and application thereof Download PDFInfo
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- 239000002028 Biomass Substances 0.000 title claims abstract description 71
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
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- 238000002156 mixing Methods 0.000 claims abstract description 28
- 239000002243 precursor Substances 0.000 claims abstract description 24
- 240000008564 Boehmeria nivea Species 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000967 suction filtration Methods 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- 230000001681 protective effect Effects 0.000 claims abstract description 6
- 239000003990 capacitor Substances 0.000 claims description 25
- 239000000463 material Substances 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 239000003792 electrolyte Substances 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- 239000007772 electrode material Substances 0.000 claims description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- 239000002608 ionic liquid Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 239000004917 carbon fiber Substances 0.000 claims description 6
- 239000002033 PVDF binder Substances 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 5
- -1 polytetrafluoroethylene Polymers 0.000 claims description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 5
- 229910013872 LiPF Inorganic materials 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 239000006230 acetylene black Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 239000011888 foil Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
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- 238000006243 chemical reaction Methods 0.000 abstract description 34
- 238000000034 method Methods 0.000 abstract description 26
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- 230000008569 process Effects 0.000 description 9
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- 238000001027 hydrothermal synthesis Methods 0.000 description 6
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- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
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- 238000003775 Density Functional Theory Methods 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
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- 239000002055 nanoplate Substances 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
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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
- C01B32/324—Preparation characterised by the starting materials from waste materials, e.g. tyres or spent sulfite pulp liquor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
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- Environmental & Geological Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses biomass superstructure carbon and a preparation method and application thereof, wherein the method comprises the following steps: (1) preparing a biomass precursor: mixing ramie with 1-6 mol/L KOH solution according to the material-liquid ratio of 1 g: adding 30-40 mL of the KOH solution into a reaction lining, heating to 170-190 ℃, reacting for 5-7 h at 170-190 ℃, cooling after the reaction is finished, performing suction filtration to obtain ramie with KOH molecules pre-embedded, and drying to obtain the product; (2) preparing biomass superstructure carbon: uniformly mixing a biomass precursor and magnesium metal according to a mass ratio of 1-6: 1, heating to 650-750 ℃ in a protective gas environment, and introducing CO with a flow rate of 15-25 sccm2And reacting at 650-750 ℃ for 30-90 min to obtain the catalyst. The preparation method has the advantages of simple preparation process, low cost and batch production, and the prepared biomass superstructure carbon has a multi-level pore structure and a high specific surface area。
Description
Technical Field
The invention belongs to the technical field of microporous carbon material preparation, and particularly relates to biomass superstructure carbon and a preparation method and application thereof.
Background
Due to the special pore channel structure and the higher specific surface area, the microporous carbon material has a considerable effect in daily life. At present, microporous carbon materials have been widely used in the fields of storage and separation of gases, electrode materials for batteries or capacitors, catalysts or catalyst carriers for various chemical reactions, sewage treatment, recovery of precious metals, and the like.
The existing methods for preparing microporous carbon materials include physical activation methods, chemical activation methods and CVD methods. The porous carbon material prepared by adopting a physical activation or chemical activation method has a main pore structure, and large-size electrolyte ions have the problems of transmission and storage, and show the problems of poor rate performance and poor cycle stability. Although the preparation of the carbon composite material can be realized by adopting the CVD method, the carbon nano material prepared by the process is expensive and low in yield, and the specific surface area of the porous carbon material is greatly reduced, so that the transmission and storage of electrolyte ions are influenced.
Disclosure of Invention
Aiming at the prior art, the invention provides biomass superstructure carbon and a preparation method and application thereof, and aims to solve the problems of high cost, low yield, low specific surface area, difficult transmission and storage and the like of microporous carbon materials prepared by the existing method.
In order to achieve the purpose, the invention adopts the technical scheme that: provided is a preparation method of biomass superstructure carbon, comprising the following steps:
(1) preparing a biomass precursor: mixing ramie with 1-6 mol/L KOH solution according to the material-liquid ratio of 1 g: mixing 30-40 mL of the mixture, reacting at 170-190 ℃ for 5-7 h, filtering, and drying to obtain the product;
(2) preparing biomass superstructure carbon: uniformly mixing a biomass precursor and magnesium metal according to a mass ratio of 1-6: 1, heating to 650-750 ℃ in a protective gas environment, and introducing CO with a flow rate of 15-25 sccm2And reacting at 650-750 ℃ for 30-90 min to obtain the catalyst.
Further, the method also comprises the post-treatment of the biomass superstructure carbon, and the post-treatment method comprises the following steps: immersing the biomass superstructure carbon obtained in the step (2) in a hydrochloric acid solution with the concentration of 0.5-2 mol/L for 8-12h, then carrying out suction filtration, and drying for 10-14 h at 100-120 ℃ under a vacuum condition.
Further, the drying condition in the step (1) is drying for 10-14 h at 60-80 ℃.
Further, in the step (2), the biomass precursor and the magnesium metal are mixed for 1.5-2.5 hours at a rotation speed of 400-600 r/min.
Further, in the step (2), the protective gas is Ar or N2The gas flow rate is 30 to 50 sccm.
The invention also provides application of the biomass superstructure carbon in manufacturing capacitors.
Further, the capacitor is a button capacitor, and is prepared by the following steps:
s1: mixing biomass superstructure carbon, conductive carbon black and polytetrafluoroethylene according to a mass ratio of 7-9: 1:1, adding the mixture into isopropanol, uniformly stirring, and drying at 70-90 ℃ until the isopropanol is volatilized to dry to obtain a composite base material;
s2: preparing the composite base material into a wafer with the thickness of 70-90 mu m and the diameter of 11-13 mm, and drying at 110-130 ℃ for 22-26 h;
s3: pressing the dried wafer on the foamed nickel to obtain a porous carbon fiber electrode;
s4: by EMIMBF4The ionic liquid is used as electrolyte, the porous carbon fiber electrode is used as a positive electrode and a negative electrode, and the button capacitor is manufactured.
Further, the capacitor is a soft package capacitor and is prepared through the following steps:
s1: mixing biomass superstructure carbon, acetylene black and polyvinylidene fluoride according to a mass ratio of 7-9: 1:1, dissolving the mixture in N-methyl-2-pyrrolidone, coating on an aluminum foil, and vacuum-drying at 100-120 ℃ for 10-14 h to obtain an active electrode material;
s2: active electrode materials are used as positive and negative electrodes, and 0.5-1.5 mol.L-1LiPF of6the/EC + DMC solution is used as electrolyte to manufacture the soft package capacitor; the positive electrode and the negative electrode are separated by a polypropylene film.
The invention has the beneficial effects that:
1. the ramie has great potential in the aspect of energy storage as a natural biomass material, KOH molecules are embedded in a ramie precursor, a large number of defects can be generated by spontaneous reaction at high temperature, and magnesium powder is subjected to magnesium thermal reaction at high temperature to directly generate carbon atoms. The controllable construction of superstructure carbon can be well realized by utilizing the self-defect of the precursor material and the magnesium thermal reaction of magnesium atoms, the precise regulation and control of high specific surface area and pore structure are ensured, and the rapid transmission and storage of electrolyte ions are further realized.
2. By controlling the reaction temperature and the reaction time, the growth of carbon atoms with different sizes can be realized, and further the regulation and control of the superstructure carbon pore size distribution can be realized.
3. The method solves the problems of complicated preparation technology for preparing the biomass superstructure carbon material, poor rate capability in a large-size ionic liquid and organic electrolyte system and poor circulation stability, and realizes the batch preparation of the superstructure carbon material with simple preparation process and suitable aperture distribution by regulating and controlling the arrangement of carbon atoms.
4. The energy density of the whole device of the super capacitor is greatly improved. At room temperature, the devices exhibited a mass specific capacitance of up to 38.59F/g and 72.7Wh kg-1Energy density of (corresponding to a power density of 1.75kW kg)-1) And 36.3Wh kg-1Energy density of (corresponding to a power density of 175kW kg)-1). At an operating temperature of 100 ℃, the device exhibits a specific capacitance by mass of up to 43.22F/g and 80.3Wh kg-1Energy density of (corresponding to a power density of 1.75kW kg)-1) And 47.6Wh kg-1Energy density of (corresponding to a power density of 175kW kg)-1)。
Drawings
FIG. 1 is a structural design of superstructure carbon (DBSC) (a: DBSC synthetic self-assembly defect construction strategy; b: DBSC typical SEM image shows surface structure of a large number of defects; C: DBSC TEM image shows obvious interface, which can obviously reveal self-assembly growth of Mg atoms; d: representative AFM image for determining growth of upper layer structure; e: DBSC element mapping image of C, O, Mg, K elements; f: DBSC XPS data; g: DBSC C1s deconvolution curve; h: schematic diagram of self-assembly defect formation of superstructure carbon);
FIG. 2 is a physical characterization of superstructure carbon (DBSC) (a: infrared spectral curve; b: Raman spectrum. c: XRD analysis; d: N: XRD analysis)2Adsorption/desorption isotherms; e: pore size distribution obtained by DFT method; f: typical AFM images corresponding to linear scan analysis of DBSC nanoplates);
FIG. 3 is an electrochemical performance of a superstructure carbon (DBSC) based supercapacitor at room temperature in an ionic liquid system; FIG. 4 is an illustration of electrochemical performance of a superstructure carbon (DBSC) based supercapacitor exhibited under different operating temperature conditions in an ionic liquid system;
fig. 5 is a multi-scale control diagram of superstructure carbon.
Detailed Description
The following examples are provided to illustrate specific embodiments of the present invention.
A method for preparing biomass superstructure carbon, comprising the steps of:
(1) preparing a biomass precursor: mixing ramie with 1-6 mol/L KOH solution according to the material-liquid ratio of 1 g: adding 30-40 mL of the KOH solution into a reaction lining, heating to 170-190 ℃, reacting for 5-7 h at 170-190 ℃, cooling after the reaction is finished, performing suction filtration to obtain ramie with KOH molecules pre-embedded, and drying to obtain the product;
(2) preparing biomass superstructure carbon: uniformly mixing a biomass precursor and magnesium metal according to a mass ratio of 1-6: 1, heating to 650-750 ℃ in a protective gas environment, and introducing CO with a flow rate of 15-25 sccm2And reacting at 650-750 ℃ for 30-90 min to obtain the catalyst.
Example 1
A method for preparing biomass superstructure carbon, comprising the steps of:
(1) preparing a biomass precursor: mixing ramie with 3mol/L KOH solution according to the feed-liquid ratio of 1 g: adding 35mL of the KOH solution into the reaction lining, then placing the reaction lining into a hydrothermal reaction kettle, heating the reaction kettle to 180 ℃ in an air-blowing drying oven, reacting for 6 hours at 180 ℃, cooling after the reaction is finished, performing suction filtration to obtain the ramie with KOH molecules pre-embedded, and drying for 12 hours at 70 ℃ to obtain the product;
(2) preparing biomass superstructure carbon: mixing the biomass precursor and magnesium metal according to the mass ratio of 3:1 in a ball mill at the revolution of 500r/min for 2h, heating to 700 ℃ under the argon environment with the gas flow of 40sccm, and introducing CO with the gas flow of 20sccm2Reacting at 700 deg.C for 60min to obtain the final product.
(3) And (3) immersing the biomass superstructure carbon obtained in the step (2) in 1mol/L hydrochloric acid for 10h, removing impurities, performing suction filtration washing by using deionized water, and drying in a vacuum oven at 110 ℃ for 12 h.
Example 2
A method for preparing biomass superstructure carbon, comprising the steps of:
(1) preparing a biomass precursor: mixing ramie with 2mol/L KOH solution according to the feed-liquid ratio of 1 g: adding 30mL of the solution into a reaction liner, then placing the reaction liner into a hydrothermal reaction kettle, heating the reaction kettle to 170 ℃ in an air-blowing drying oven, reacting for 7 hours at 170 ℃, cooling after the reaction is finished, performing suction filtration to obtain the ramie with KOH molecules pre-embedded, and drying for 14 hours at 60 ℃ to obtain the product;
(2) preparing biomass superstructure carbon: mixing the biomass precursor and magnesium metal at a mass ratio of 2:1 in a ball mill at a rotation speed of 400r/min for 2.5h, heating to 750 ℃ under an argon environment with a gas flow of 30sccm, and introducing CO with a gas flow of 15sccm2Reacting at 750 deg.C for 30 min.
(3) And (3) immersing the biomass superstructure carbon obtained in the step (2) in 1mol/L hydrochloric acid for 12h, removing impurities, performing suction filtration washing by using deionized water, and drying in a vacuum oven at 100 ℃ for 14 h.
Example 3
A method for preparing biomass superstructure carbon, comprising the steps of:
(1) preparing a biomass precursor: mixing ramie with 1mol/L KOH solution according to the material-liquid ratio of 1 g: adding 35mL of the KOH solution into the reaction lining, then placing the reaction lining into a hydrothermal reaction kettle, heating the reaction kettle to 190 ℃ in an air-blowing drying oven, reacting for 5 hours at 190 ℃, cooling after the reaction is finished, performing suction filtration to obtain the ramie with KOH molecules pre-embedded, and drying for 10 hours at 80 ℃ to obtain the product;
(2) preparing biomass superstructure carbon: mixing the biomass precursor and magnesium metal according to the mass ratio of 1:1 in a ball mill at the rotation number of 600r/min for 1.5h, heating to 650 ℃ under the argon environment with the gas flow of 50sccm, and introducing CO with the gas flow of 25sccm2Reacting at 650 deg.C for 90 min.
(3) And (3) immersing the biomass superstructure carbon obtained in the step (2) in 1mol/L hydrochloric acid for 8h, removing impurities, performing suction filtration washing by using deionized water, and drying in a vacuum oven at 120 ℃ for 10 h.
Example 4
A method for preparing biomass superstructure carbon, comprising the steps of:
(1) preparing a biomass precursor: mixing ramie with a 4mol/L KOH solution according to the feed-liquid ratio of 1 g: adding 35mL of the KOH solution into the reaction lining, then placing the reaction lining into a hydrothermal reaction kettle, heating the reaction kettle to 180 ℃ in an air-blowing drying oven, reacting for 6 hours at 180 ℃, cooling after the reaction is finished, performing suction filtration to obtain the ramie with KOH molecules pre-embedded, and drying for 12 hours at 70 ℃ to obtain the product;
(2) preparing biomass superstructure carbon: mixing the biomass precursor and magnesium metal at a mass ratio of 4:1 in a ball mill at a revolution of 500r/min for 2h, heating to 700 ℃ under an argon atmosphere with a gas flow of 40sccm, and introducing CO with a gas flow of 20sccm2Reacting at 700 deg.C for 60min to obtain the final product.
Example 5
A method for preparing biomass superstructure carbon, comprising the steps of:
(1) preparing a biomass precursor: mixing ramie with 5mol/L KOH solution according to the material-liquid ratio of 1 g: adding 35mL of the KOH solution into the reaction lining, then placing the reaction lining into a hydrothermal reaction kettle, heating the reaction kettle to 180 ℃ in an air-blowing drying oven, reacting for 6 hours at 180 ℃, cooling after the reaction is finished, performing suction filtration to obtain the ramie with KOH molecules pre-embedded, and drying for 12 hours at 70 ℃ to obtain the product;
(2) preparing biomass superstructure carbon: mixing the biomass precursor and magnesium metal at a mass ratio of 5:1 in a ball mill at a revolution of 500r/min for 2h, and thenHeating to 700 ℃ under the argon atmosphere with the gas flow of 40sccm, and then introducing CO with the gas flow of 20sccm2Reacting at 700 deg.C for 60min to obtain the final product.
(3) And (3) immersing the biomass superstructure carbon obtained in the step (2) in 1mol/L hydrochloric acid for 10h, removing impurities, performing suction filtration washing by using deionized water, and drying in a vacuum oven at 110 ℃ for 12 h.
Example 6
A method for preparing biomass superstructure carbon, comprising the steps of:
(1) preparing a biomass precursor: mixing ramie with 6mol/L KOH solution according to the feed-liquid ratio of 1 g: adding 35mL of the KOH solution into the reaction lining, then placing the reaction lining into a hydrothermal reaction kettle, heating the reaction kettle to 180 ℃ in an air-blowing drying oven, reacting for 6 hours at 180 ℃, cooling after the reaction is finished, performing suction filtration to obtain the ramie with KOH molecules pre-embedded, and drying for 12 hours at 70 ℃ to obtain the product;
(2) preparing biomass superstructure carbon: mixing the biomass precursor and magnesium metal at a mass ratio of 6:1 in a ball mill at a rotation speed of 500r/min for 2h, heating to 700 ℃ under an argon environment with a gas flow of 40sccm, and introducing CO with a gas flow of 20sccm2Reacting at 700 deg.C for 60min to obtain the final product.
(3) And (3) immersing the biomass superstructure carbon obtained in the step (2) in 1mol/L hydrochloric acid for 12h, removing impurities, performing suction filtration washing by using deionized water, and drying in a vacuum oven at 110 ℃ for 12 h.
Comparative example 1
The ramie of example 1 was replaced with pine nut shells, and the procedure was the same as in example 1.
The following are the performance tests of the biomass superstructure carbon in the examples:
1. the alternating current impedance test is to measure the change rule of resistance along with frequency by inputting an alternating current signal with different frequencies. The internal resistance of the material or the device can be obtained through the alternating-current impedance spectrum, the dynamic process of the electrode interface electrochemistry can be analyzed, and then the related research on the energy storage mechanism of the material in the electrochemistry process can be favorably carried out. In the electrochemical test process, the frequency range is set to be 0.01Hz-100 kHz; the alternating current impedance test is divided into a high-frequency area, a medium-frequency area and a low-frequency area according to the difference of the speed in the electrochemical reaction process, the high-frequency area can obtain the equivalent series resistance, and the low-frequency area can obtain the equivalent diffusion resistance. As seen from the high frequency region of fig. 3a, the superstructure carbon exhibits less diffusion resistance in high viscosity ionic liquids. The linear area of the low-frequency area is close to 90 degrees, and the material is proved to have excellent rate capability.
2. The cyclic voltammetry test is to obtain the feedback of current by controlling the change of electrode potential, and the cyclic stability and the multiplying power performance of the material in the charging and discharging process are obtained by a cyclic voltammetry curve. Generally, the energy storage mechanism of the carbon nanomaterial is electrostatic adsorption of surface charges, and the corresponding cyclic voltammetry curve is similar to a rectangle. With the increase of the sweep rate, the shape is closer to an ellipse, so that the rate performance of the material is judged. After the device is assembled, the electrolyte used is EMIM BF4When the voltage is 0-3.5V, the sweep rate is 10-20000mV s-1And the obtained cyclic voltammetry curve can determine the multiplying power performance of the device. From FIGS. 3b and 3e, it can be seen that the superstructure carbon-based supercapacitor has a scan rate of 10000mV s-1The shape of a rectangle can be still displayed, and the ultrahigh magnification property is proved. When the service temperature of the capacitor is 100 ℃, the scan rate of the superstructure carbon-based supercapacitor can reach 20000mV s-1It shows that the material has excellent stability in a wide temperature range.
3. The constant current charge and discharge test is to obtain the change rule of the real-time potential along with the time by controlling the constant current density, and the specific capacity of the material and the device can be obtained by a constant current charge and discharge curve. The smaller the value of the voltage drop with increasing current density, the better the rate capability of the material. After the device is assembled, the electrolyte used is EMIM BF4At a current density of 1-100A g-1. From fig. 3c and 3f, it can be seen that the superstructure carbon-based supercapacitor has a current density of 100A g-1In the process, the shape of an isosceles triangle and extremely low voltage drop can still be shown, and the fact that the super capacitor not only has high specific capacity but also can realize charging and discharging of ultrahigh current density is proved.
4. From fig. 5, it can be seen that the preparation method of the present invention realizes the growth of carbon atoms with different sizes by controlling the reaction temperature and the reaction time, and further realizes the regulation and control of the superstructure carbon pore size distribution.
LiPF is adopted as the biomass superstructure carbon prepared by the invention6Electrolyte and EMIMBF4The ionic liquid electrolyte is used as electrolyte for manufacturing a button capacitor and a soft package capacitor:
manufacturing the button capacitor: mixing biomass superstructure carbon, conductive carbon black and PTFE according to a mass ratio of 8:1:1, taking isopropanol as a dispersing solvent, and stirring uniformly by using a scraper; then placing the mixture in a forced air drying oven at 80 ℃ until the solvent is volatilized to be dry; then repeatedly extruding the material by using a scraper until the strong dough appears; tabletting the pressed dough to obtain a sheet with a thickness of 80 μm; punching the pressed electrode material by using a punching machine, wherein the diameter of the punched electrode material is 12 mm; drying the punched electrode slice in a vacuum drying oven at 120 ℃ for 24 hours to obtain a porous carbon fiber electrode; and finally, weighing and pressing the dried small wafer on the foamed nickel to obtain the target porous carbon fiber electrode. EMIMBF is prepared4The ionic liquid is used as electrolyte of the supercapacitor, two electrodes with the same mass are selected as positive and negative electrodes, the button type symmetrical supercapacitor is manufactured, and the whole process needs to be operated in a glove box.
Manufacturing a soft package capacitor: uniformly mixing biomass superstructure carbon, a conductive agent acetylene black and a binder polyvinylidene fluoride (PVDF) according to a mass ratio of 8:1:1, dissolving the PVDF by adopting N-methyl-2-pyrrolidone (NMP) to obtain slurry, coating the slurry on an aluminum foil, and drying in vacuum at 110 ℃ for 12 hours to obtain the active electrode material. Manufacturing a soft package symmetrical super capacitor, taking electrodes made of active electrode materials as positive and negative electrodes, separating the positive and negative electrodes by adopting a polypropylene film, and adopting 1 mol.L electrolyte- 1LiPF6The entire process requires operation in a glove box, with/EC + DMC (i.e.ethylene carbonate and dimethyl carbonate, in a volume ratio of 1: 1).
The capacitors made from the biomass superstructure carbon material obtained in example 1 and comparative example 1 were subjected to performance tests as shown in table 1:
TABLE 1 capacitor Performance test results for Biomass superstructure carbon materials
While the present invention has been described in detail with reference to the embodiments, it should not be construed as limited to the scope of the patent. Various modifications and changes may be made by those skilled in the art without inventive step within the scope of the appended claims.
Claims (9)
1. A preparation method of biomass superstructure carbon is characterized by comprising the following steps:
(1) preparing a biomass precursor: mixing ramie with 1-6 mol/L KOH solution according to the material-liquid ratio of 1 g: mixing 30-40 mL of the mixture, reacting at 170-190 ℃ for 5-7 h, filtering, and drying to obtain the product;
(2) preparing biomass superstructure carbon: uniformly mixing a biomass precursor and magnesium metal according to a mass ratio of 1-6: 1, heating to 650-750 ℃ in a protective gas environment, and introducing CO with a flow rate of 15-25 sccm2And reacting at 650-750 ℃ for 30-90 min to obtain the catalyst.
2. The preparation method of claim 1, further comprising post-treatment of the biomass superstructure carbon by: immersing the biomass superstructure carbon obtained in the step (2) in a hydrochloric acid solution with the concentration of 0.5-2 mol/L for 8-12h, then carrying out suction filtration, and drying for 10-14 h at 100-120 ℃ under a vacuum condition.
3. The production method according to claim 1 or 2, characterized in that: the drying condition in the step (1) is drying for 10-14 h at 60-80 ℃.
4. The production method according to claim 1 or 2, characterized in that: in the step (2), the biomass precursor and the magnesium metal are mixed for 1.5-2.5 hours at the revolution of 400-600 r/min.
5. The production method according to claim 1 or 2, characterized in that: in the step (2), the protective gas is Ar or N2The gas flow rate is 30 to 50 sccm.
6. Biomass superstructure carbon produced by the production method according to any one of claims 1 to 5.
7. Use of the biomass superstructure carbon of claim 6 in the manufacture of capacitors.
8. Use according to claim 7, wherein the capacitor is a button capacitor, which is made by the following steps:
s1: mixing biomass superstructure carbon, conductive carbon black and polytetrafluoroethylene according to a mass ratio of 7-9: 1:1, adding the mixture into isopropanol, uniformly stirring, and drying at 70-90 ℃ until the isopropanol is volatilized to dry to obtain a composite base material;
s2: preparing the composite base material into a wafer with the thickness of 70-90 mu m and the diameter of 11-13 mm, and drying at 110-130 ℃ for 22-26 h;
s3: pressing the dried wafer on the foamed nickel to obtain a porous carbon fiber electrode;
s4: by EMIMBF4The ionic liquid is used as electrolyte, the porous carbon fiber electrode is used as a positive electrode and a negative electrode, and the button capacitor is manufactured.
9. Use according to claim 7, wherein the capacitor is a flexible package capacitor, which is produced by:
s1: mixing biomass superstructure carbon, acetylene black and polyvinylidene fluoride according to a mass ratio of 7-9: 1:1, dissolving the mixture in N-methyl-2-pyrrolidone, coating on an aluminum foil, and vacuum-drying at 100-120 ℃ for 10-14 h to obtain an active electrode material;
s2: active electrode materials are used as positive and negative electrodes, and 0.5-1.5 mol.L-1LiPF of6the/EC + DMC solution is used as electrolyte to manufacture the soft package capacitor; the positive electrode and the negative electrode are separated by a polypropylene film.
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| CN115206693A (en) * | 2022-06-24 | 2022-10-18 | 四川金时新能科技有限公司 | Biomass high-doping high-defect carbon material and preparation method and application thereof |
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| CN115672369A (en) * | 2022-10-19 | 2023-02-03 | 中钢集团鞍山热能研究院有限公司 | Preparation method of superstructure carbon material for catalytic oxidation and decoloration of desulfurization waste liquid |
| CN115672369B (en) * | 2022-10-19 | 2024-02-06 | 中钢集团鞍山热能研究院有限公司 | Preparation method of super-structure carbon material for catalytic oxidation and decoloration of desulfurization waste liquid |
| CN116573629A (en) * | 2023-04-14 | 2023-08-11 | 同济大学 | Carbon super-structure material based on crystal division growth and self-assembly and preparation method thereof |
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