CN112951618A - Biomass-based activated carbon loaded CuO nano-particle composite material and application thereof - Google Patents
Biomass-based activated carbon loaded CuO nano-particle composite material and application thereof Download PDFInfo
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- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- 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
- H01G11/24—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
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- 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
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- 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
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Abstract
The invention discloses a biomass-based activated carbon loaded CuO nano-particle composite material, a directional synthesis method thereof and application thereof in preparing a supercapacitor electrode. The composite material comprises biomass-based activated carbon, wherein CuO nano-particles are distributed in mesopores of the biomass-based activated carbon; the specific surface area of the biomass-based activated carbon is 2600 m2 g‑1(ii) a The particle size of the CuO nano-particles is 10-20 nm. The composite material of the invention not only maintains the originalThe super-large specific surface area of the activated carbon also loads CuO nano particles which can generate double oxidation-reduction reaction. When the composite material in which the carbon-based material with the double electric layer characteristic and the CuO pseudocapacitance material coexist cooperatively is used as the electrode material of the supercapacitor, the mass specific capacitance and the stability of the supercapacitor are improved remarkably.
Description
Technical Field
The invention belongs to the technical field of energy chemical engineering of energy storage materials and biomass solid waste recycling, and particularly relates to a biomass-based activated carbon loaded CuO nano particle composite material, a directional synthesis method thereof and application thereof in preparation of a supercapacitor electrode.
Background
Supercapacitors (SCs) are common energy storage devices, which are widely used in portable electronic devices due to their high specific capacitance, excellent cycling performance, long cycle life and charge-discharge rate, and are also advantageous for integration of power conversion devices. SCs can be classified into Electric Double Layer Capacitors (EDLC) and faraday Pseudocapacitors (PCs) according to the charge storage mechanism. EDLCs are the diffusion and accumulation of a double-layer charge formed by adsorption of electrolyte ions on the surface of an inert electrode whose electrode material is typically a carbon material with a large specific surface area and good hydrophilicity, which tend to have a low energy density. PCs are based on the rapid reversible faradaic reaction on the surface of active materials, such as the capacitance generated by metal oxides and conductive polymers, and their theoretical specific capacitance is often several times that of the electric double layer capacitance, but PC cannot obtain sufficient theoretical specific capacitance in applications due to its poor cycling stability and conductivity. In recent years, a supercapacitor having a high capacity and excellent stability can be obtained by performing synthetic modification of a metal oxide on the surface of a carbon material, which is also a focus of attention of researchers, and there has been an active attempt to synthesize a novel electrode material.
Due to noble metal oxides, e.g. RuO2And IrO2With their large specific capacitance, wide potential window and high electrochemical stability, they are used as ideal supercapacitor electrode materials, but the high cost of noble metals limits their widespread use. Therefore, in recent years, inexpensive transition metal oxides such as nickel oxide (NiO), manganese oxide (MnO), and copper oxide (CuO) have been increasingly usedThe more they are paid attention. The CuO has the advantages of high theoretical specific capacitance, low cost, wide source, environmental friendliness, good cycling stability and easiness in preparation, so that the carbon-based material and the CuO nanoparticles are mixed to form the composite material, which is a reliable means for improving the specific capacitance and stability of the material. In general, carbon-based materials mainly include activated carbon, graphene and carbon nanotubes, and among these carbon electrode materials, the graphene and carbon nanotubes are complex in manufacturing process and high in cost, and are not suitable for mass production. The biomass can be used as a promising activated carbon precursor, has the characteristics of greenness, renewability, low price and abundant resources, can meet the energy demand, and can promote the development of chemical and energy industries. Peanuts are one of the most important oil-producing crops in the world that are widely planted, and Peanut Shells (PS) are a major by-product of their planting process. Annual production of peanut shells is enormous worldwide, and the use of peanut shells as animal feed or fuel is currently very limited. However, the carbon content of the peanut shells is high, the carbon material has the potential of being prepared by conversion, and high-value development of the peanut shells can be realized.
Disclosure of Invention
The invention aims to provide a biomass-based activated carbon CuO-loaded nanoparticle composite material, and a directional synthesis method and application thereof. When the composite material in which the carbon-based material with the double electric layer characteristic and the CuO pseudocapacitance material coexist cooperatively is used as the electrode material of the supercapacitor, the mass specific capacitance and the stability of the supercapacitor can be improved remarkably.
In order to achieve the purpose, the invention adopts the following technical scheme:
a composite material of biomass-based activated carbon loaded with CuO nano-particles comprises biomass-based activated carbon, wherein CuO nano-particles are distributed in mesopores of the biomass-based activated carbon;
the specific surface area of the biomass-based activated carbon is 2600 m2 g-1(wherein the center hole 1943 m2 g-1Micro-hole 1302 m2 g-1) (ii) a The particle size of the CuO nano-particles is 10-20 nm.
Furthermore, the biomass-based activated carbon is obtained by carbonizing and then activating peanut shells serving as raw materials.
The oriented synthesis method of the composite material containing the biomass-based activated carbon loaded with the CuO nano particles comprises the following steps:
step 2, putting the peanut shell powder into a corundum boat, putting the corundum boat into an atmosphere tube furnace, and putting the corundum boat into an atmosphere tube furnace2Carbonizing in the atmosphere, and crushing the carbonized product to obtain the peanut shell semicoke;
step 3, mixing the peanut shell semicoke and potassium hydroxide, placing the mixture into a corundum boat, placing the corundum boat into an atmosphere tube furnace, and placing the corundum boat in an N atmosphere tube furnace2Activating under atmosphere, using 1 mol L of activating mixture-1Pickling with hydrochloric acid, washing with deionized water, and drying to obtain activated carbon powder;
step 4, dissolving copper acetate in deionized water, adding an ammonia water solution while stirring, then adding activated carbon powder into the mixed solution, continuously stirring, and then drying to obtain mixed powder;
and 5, putting the mixed powder into a tubular furnace, and calcining in an air atmosphere to obtain the biomass-based activated carbon-supported CuO nano-particle composite material.
Further, the temperature rise rate of the carbonization process in the step 2 is 5 ℃ min-1The carbonization temperature is 600 ℃, and the carbonization time is 3 h.
Further, the mass ratio of the semicoke and the KOH of the peanut shells in the step 3 is 1:4, and the heating rate in the activation process is 10 ℃ per minute-1The activation temperature is 800 ℃, and the activation time is 2 h.
Furthermore, the amount ratio of the ammonia water solution, copper acetate and activated carbon powder in step 4 was 5.5 mL:90 mg:0.56 g.
Further, the calcination conditions in step 5 are: the temperature is increased to 310 ℃ at the temperature increasing rate of 10 ℃/min for calcination for 2 h.
The composite material containing the biomass-based activated carbon loaded CuO nano particles is applied to preparation of the super capacitor.
Further, the application specifically is: grinding the composite material to 200 meshes, mixing the ground composite material with acetylene black and PTFE in a mortar according to the mass ratio of 8:1:1, adding ethanol to uniformly mix the materials, coating about 5 mg of the mixture on foamed nickel, tabletting for 60 s under the pressure of 10 MPa, and drying to ensure that the ethanol is completely removed to obtain the electrode material.
The invention provides a simple and convenient chemical deposition method for synthesizing and applying a composite electrode material of biomass-based activated carbon loaded with CuO nano particles. The CuO nano-particle composite electrode material loaded on the biomass-based activated carbon is prepared by using cheap and high-yield peanut shells and copper acetate. The produced composite carbon material not only maintains the super-large specific surface area of the original activated carbon, but also loads CuO nano-particles capable of generating double oxidation-reduction reaction. When the composite material in which the carbon-based material with the double electric layer characteristic and the CuO pseudocapacitance material coexist cooperatively is used as an electrode material of a super capacitor, the mass specific capacitance and the stability of the super capacitor are improved remarkably. In addition, the asymmetric capacitor assembled by the composite electrode material of the biomass-based activated carbon loaded CuO nano particles has higher energy density and successfully lights up a light-emitting diode. The method for preparing the biomass-based activated carbon CuO-loaded nano particle composite material by using the peanut shells with huge yield and the cheap copper acetate has the advantages of simple process, low cost, less pollution, higher mass specific capacitance, stability and energy density, realizes changing waste into valuable and has wide application prospect.
The method comprises the steps of taking peanut shells which are agricultural wastes with huge annual output as raw materials, activating by a potassium hydroxide two-step method to form activated carbon with a large specific surface area, then soaking the activated carbon in a mixed solution of ammonia water and copper acetate, calcining by air at 310 ℃ to directionally regulate the size and spatial position of CuO nano particles, and finally uniformly distributing the CuO particles in mesopores of a graded porous carbon material after potassium hydroxide activation without influencing a micropore structure, so that the generated composite material not only keeps the super-large specific surface area of the original activated carbon, but also loads CuO nano particles capable of generating double oxidation-reduction reaction and is applied to an electrode material of a super capacitor.
Compared with the prior art, the invention has the advantages that:
1. the raw materials have wide sources and low cost. In the aspect of selecting raw materials of electrode materials, materials such as graphene and carbon nanotubes cannot realize large-scale production due to high price, and peanut shells serving as agricultural wastes are huge in annual output, cannot be fully utilized, are low in cost, are wide and stable in source and are excellent biomass raw materials. The nano-source copper acetate also has the advantages of green, low price and the like.
2. The activated carbon obtained by activating the peanut shell by adopting a KOH two-step method is hierarchical porous carbon, and the huge specific surface area of the activated carbon is used as an advantageous condition for supporting the deposition of CuO nano particles.
3. The active carbon is dipped in a mixed solution of ammonia water and copper acetate, the grain diameter of the obtained CuO nano particles is 10-20nm and is uniformly distributed in a mesoporous pore passage without influencing the micropore structure by air calcination directional control, and the specific surface area of the composite material reaches 2600 m2 g-1The synthesis process not only introduces pseudo-capacitance, but also keeps the original double capacitance.
4. The CuO nano particles obtained by air calcination directional regulation can generate a double oxidation-reduction reaction, thereby providing higher pseudo capacitance.
Drawings
Fig. 1 is a flow chart of a biomass-based activated carbon-supported CuO nanoparticle composite material prepared in example 1;
fig. 2 is a diagram of a biomass-based activated carbon supported CuO nanoparticle composite prepared in example 1, (a) XRD, (b) Raman diagram;
fig. 3 is views of biomass-based activated carbon-supported CuO nanoparticle composite prepared in example 1, (a) and (b), TEM images at different magnifications, (c) HRTEM image, (d) elemental distribution diagram;
fig. 4 is an XPS spectrum of a biomass-based activated carbon supported CuO nanoparticle composite prepared in example 1, (a) O1 s; (b) cu 2 p;
fig. 5 is a diagram of a composite material of biomass-based activated carbon loaded with CuO nanoparticles prepared in example 1, (a) a nitrogen adsorption and desorption curve, and (b) a pore size distribution diagram;
fig. 6 is three-electrode system (a) (b) CV and (c) GCD diagrams of biomass-based activated carbon-supported CuO nanoparticle composite prepared in example 1;
fig. 7 is a cycle stability test chart of the biomass-based activated carbon-supported CuO nanoparticle composite electrode material prepared in example 1;
fig. 8 is CV and GCD curves of an asymmetric supercapacitor made of the biomass-based activated carbon supported CuO nanoparticle composite electrode material prepared in example 1 and the activated carbon electrode material prepared in comparative example 1;
fig. 9 is an electrochemical impedance spectrum of a biomass-based activated carbon-supported CuO nanoparticle composite prepared in example 1;
fig. 10 shows a diode lit by an asymmetric supercapacitor as a power supply.
Detailed Description
The invention is described in further detail below with reference to the figures and the specific examples, which should not be construed as limiting the invention. Modifications or substitutions to methods, procedures, or conditions of the invention may be made without departing from the spirit and scope of the invention. The experimental methods and reagents of the formulations not specified in the examples are in accordance with the conventional conditions in the art.
Example 1
A flow chart of the biomass-based activated carbon supported CuO nanoparticle composite material is shown in fig. 1.
Taking a proper amount of dried peanut shells, fully washing and drying at 105 ℃ for 72 hours, crushing the peanut shells into powder by using a crusher, and sieving the peanut shell powder by using a 80-mesh sieve.
Taking 10 g of peanut shell powder, carbonizing at 600 deg.C for 3h in a tube furnace at a heating rate of 5 deg.C for min-1While introducing 600 mL of min-1N of (A)2As a shielding gas. After the sample is naturally cooled to the room temperature, the sample is crushed again and passed throughSieving with 80 mesh sieve, and packaging in a sealed bag for later use.
Putting 2 g of peanut shell semicoke and 8 g of KOH in a boat, adding 10 mL of deionized water to uniformly mix, and heating at 80 ℃ for 30 min to obtain a slurry-like mixture. Placing the slurry mixture into an atmosphere tube furnace, activating at 800 deg.C for 2 hr in nitrogen atmosphere, and heating at 10 deg.C for 10 min-1. The activated mixture was ground and crushed, and 200 mL of hydrochloric acid (1 mol L) was poured-1) And sealing the solution by using a preservative film, heating the solution in water bath at 60 ℃ for 2 hours, and then carrying out suction filtration and drying on the solution to obtain the activated carbon powder.
90 mg of copper acetate is dissolved in 20 mL of deionized water, 5.5 mL of ammonia water solution is dropwise added while stirring, then 0.56 g of activated carbon powder is poured into the continuously stirred mixed solution, and the mixed solution is placed in a drying oven after 6 hours to obtain mixed powder.
And putting the mixed powder into a tubular furnace, heating to 310 ℃ at a heating rate of 10 ℃/min in an air atmosphere, and calcining for 2h to obtain the biomass-based activated carbon supported CuO nano-particle composite material.
Grinding the obtained biomass-based activated carbon loaded CuO nano-particle composite material to 200 meshes, mixing the biomass-based activated carbon loaded CuO nano-particle composite material and acetylene black in a mass ratio of PTFE =8:1:1, and adding ethanol to uniformly mix the materials. Applying about 5 mg of the mixture to 1 cm2And (3) tabletting for 60 s under the pressure of 10 MPa on the foamed nickel, and drying to obtain the biomass-based activated carbon CuO nano-particle loaded composite electrode material.
The biomass-based activated carbon CuO-loaded nanoparticle composite electrode material prepared in example 1 was subjected to characterization and electrochemical performance tests, CV and GCD tests were performed in a three-electrode system, and an asymmetric supercapacitor was assembled with the activated carbon electrode material prepared in comparative example 1 in a two-electrode system and CV, GCD and EIS thereof were tested. The electrolyte used was 6 mol L-1Adjusting parameters such as scanning speed and current density of the KOH solution to obtain the electrochemical properties of the electrode material under different parameters, and further calculating and solving the mass specific capacitance, energy density/power density and cycling stability of the electrodeAnd alternating current impedance parameters, wherein the calculation formula of each parameter is as follows:
three-electrode system:
wherein
Is the mass specific capacitance of a single electrode, with the unit of F g-1；
Is current, in units of A;
discharge time in units of s;
the unit is g and is the loading quantity of active substances on the electrode sheet;
the discharge voltage drop is given in V.
Wherein
Is a cycle stability parameter;
is at 10A g-1Current density of (1) measured specific capacitance by mass F g-1；
Is at 10A g-1Current density of (2) in units of F g-1。
Two-electrode system:
wherein
The specific capacitance by mass of a supercapacitor composed of two electrodes is F g-1。
Wherein
Is energy density in W h kg-1；
Mass specific capacitance of asymmetric supercapacitor, unit F g-1；
Discharge voltage drop in units of V;
is energy density in W kg-1；
Discharge time is given in units of s.
The results obtained were as follows:
XRD and Raman of the composite material of the CuO nano particles loaded on the biomass-based activated carbon are shown in figures 2a-b, and the sample impregnated with the copper acetate and the ammonia water respectively shows narrow and sharp peaks at 35.33 degrees, 38.46 degrees and 43.27 degrees in figure 2a,corresponding to the formation of CuO and Cu nanoparticles, the successful deposition of CuO nanoparticles into porous carbon is demonstrated. In addition to this, the sample shows a typical amorphous carbon structure on both broad peaks at 23 ° and 44 °, corresponding to the presence of (002) and (101) crystals of graphitic carbon, the Raman spectrum in fig. 2b showingI DAndI Gthe ratio of (a) to (b) is 1.01, which indicates that the sample is a carbon material mainly composed of amorphous carbon and having a certain graphite crystallite structure.
FIGS. 3a-b are TEM images of the composite material of the CuO nano-particles loaded on the biomass-based activated carbon under different magnifications, from which it is observed that the nano-particles are uniformly distributed on the surface of the porous carbon material and have a particle size of about 5-10 nm, and further analysis by a high resolution transmission electron microscope as shown in FIG. 3c confirms that CuO exists in the nano-particles distributed on the surface. As can be seen from the element distribution diagram shown in fig. 3d, Cu elements are uniformly distributed in the electron microscope image in addition to a large amount of C and O in the sample.
Fig. 4a-b are XPS spectra of a composite material of a biomass-based activated carbon loaded with CuO nanoparticles, and fig. 4a shows that the presence of oxygen-containing functional groups can effectively improve the hydrophilicity of the material, thereby improving the utilization rate of the specific surface area of the material and providing more active sites for charge storage; FIG. 4b demonstrates that Cu is contained in the sample2+. In conclusion, the prepared composite material not only contains a large amount of excellent surface functional groups, but also successfully loads CuO nano-particles, and can provide active sites for the material, generate pseudo-capacitance and improve the electrochemical performance of the material.
FIG. 5a and FIG. 5b are the nitrogen adsorption and desorption curves and the pore size distribution of the composite material of the biomass-based activated carbon loaded with CuO nanoparticles, respectively, and the nitrogen adsorption and desorption curves of the sample are H-containing4The IV-type isotherm of the hysteresis loop shows that the material contains a large number of micropores and mesopores. As can be seen from the pore size distribution, the composite material not only contains a large number of micropores with the pore size of less than 2 nm, but also has a large number of mesopores with the pore size of 2-4 nm. The micropores can provide a large amount of specific surface area and charge storage sites, and the mesopores provide a space position required by deposition for CuO loading, increase the specific surface area and effectively enhance the ion transferTransport capacity and reduced ion transfer resistance.
Fig. 6a-c are cyclic voltammetry Curves (CV) and constant current charge-discharge curves (GCD) of the biomass-based activated carbon loaded CuO nanoparticle composite electrode material under a three-electrode test, wherein the CV and the GCD of the sample have obvious redox peaks, and two obvious peaks appear in a discharge stage, which indicates that a pseudo-capacitance generated by CuO is provided by a double redox reaction, wherein the reaction increases the charge-discharge time in the pseudo-capacitance stage, thereby improving the mass specific capacitance of the biomass-based activated carbon loaded CuO nanoparticle composite electrode material. In addition, the composite electrode material shows better symmetry in initial charge and discharge of CV and GCD, which shows that the CuO nano-particle loaded biomass-based activated carbon composite electrode material not only retains the original electric double layer capacitance, but also introduces pseudo capacitance. According to the calculation formula of the three-electrode capacitor, the mass specific capacitance of the electrode is obtained at the current density of 1A g-1When it is 530F g-1At a current density of 10A g-1When it is 187F g-1. Fig. 7 is a cycle stability test of the electrode. At 10A g-1The capacity retention rate of 92.5 percent is still maintained after 10000 times of charge and discharge, which shows that the cycle stability of the material is improved after the metal oxide is combined with the carbon material; the CV and GCD curves of the asymmetric supercapacitor shown in FIG. 8 also show obvious redox peaks, and the asymmetric supercapacitor can be used in more practical places, and the mass specific capacitance of the asymmetric supercapacitor at the current density of 1A/g is calculated to be up to 338F/g.
FIG. 9a is an electrochemical impedance spectroscopy of a biomass-based activated carbon loaded CuO nanoparticle composite, wherein the intrinsic resistance of the electrode: (R e) 0.44 Ω, charge transfer resistance: (R ct) Is 0.26 omega. The slope of the sample perpendicular to the X-axis line in the high frequency region also indicates that the CuO nanocomposite electrode material has a lower ion transfer resistance.
FIG. 9b is a Ragong diagram of an asymmetric capacitor with an energy density of 46.8 Wkg-1The power density reaches 2514.9W kg-1The asymmetric capacitor is used as a power supply to successfully light a light emitting diode. As shown in fig. 10The brightness of the diode is strong and can still keep a certain brightness after being maintained for 90 s.
Comparative example 1
This example differs from example 1 in that: no CuO nanoparticles were loaded in the biomass-based activated carbon.
Taking a proper amount of dried peanut shells, fully washing and drying at 105 ℃ for 72 hours, crushing the peanut shells into powder by using a crusher, and sieving the peanut shell powder by using a 80-mesh sieve.
Taking 10 g of peanut shell powder in a beaker, then putting the sieved peanut shell powder in a tubular furnace, carbonizing at 600 ℃ for 3h at a heating rate of 5 ℃ per minute-1While introducing 600 mL/min-1N of (A)2As a shielding gas. After the sample is naturally cooled to room temperature, the sample is crushed again and sieved by a 80-mesh sieve, and the crushed sample is filled into a sealing bag for later use.
Putting 2 g of peanut shell semicoke and 8 g of KOH in a boat, adding 5 mL of deionized water to uniformly mix, and heating at 80 ℃ for 30 min to obtain a slurry-like mixture. Placing the slurry mixture into an atmosphere tube furnace, activating at 800 deg.C for 2 hr in nitrogen atmosphere, and heating at 10 deg.C/min-1. The activated mixture was ground and crushed, and 200 mL of hydrochloric acid (1 mol. L) was poured-1) Sealing with preservative film, heating in water bath at 60 deg.C for 2 hr, vacuum filtering and drying to obtain mixed powder, and placing into a tubular furnace at 10 deg.C for min in air atmosphere-1The temperature is increased to 310 ℃ at the temperature rising rate, and the active carbon is obtained after calcining for 2 h.
The obtained activated carbon material was ground to 200 mesh, mixed in a mortar in a mass ratio of porous carbon material to acetylene black to PTFE =8:1:1, and added with ethanol to be mixed uniformly. Applying about 5 mg of the mixture to 1 cm2Pressing the nickel foam into a sheet for 60 s under the pressure of 10 MPa, and drying to obtain the active carbon electrode material. The specific surface area of the material is 3200 m2 g-1Wherein the mesopore 1400 m2 g-1Micro-holes 1240 m2 g-1. The active carbon electrode material has no oxidation reduction peak in a three-electrode system test and is 1A g-1Mass ratio ofVolume 280F g-1The formed symmetrical capacitor is 1A g-1Has a mass specific capacitance of 235F g-1. At an energy density of 28.2W h kg-1The power density is 2309.6W kg-1. Intrinsic resistance of materialR e0.63 omega, charge transfer resistanceR ctIs 0.12 omega.
It can be obviously seen that compared with the biomass-based activated carbon loaded with the CuO nano-particle composite material, the original microporous structure is not damaged by the addition of CuO. The CuO nano-particle composite material loaded on the biomass-based activated carbon not only maintains the super-large specific surface area (the micropores are from 1302 m) of the original activated carbon2 g-1To 1240 m2 g-1) And CuO nano particles capable of generating double oxidation reduction reaction are also loaded. When the composite material in which the carbon-based material with the electric double layer characteristic and the CuO pseudocapacitance material coexist cooperatively is used as an electrode material of a super capacitor, the super capacitor has better conductivity, ultrahigh mass specific capacitance and cycle stability. The mass specific capacitance of the composite electrode material of the biomass-based activated carbon loaded with CuO nano particles obtained by the test of a three-electrode system is 530F g respectively-1Nearly doubled as compared to comparative example 1 (280F g)-1) The power density is from 2309.6W kg-1Increased to 2514.9W kg-1The energy density is from 28.2W h kg-1Increased to 46.8W h kg-1. Due to the higher conductivity of CuO and Cu, the intrinsic resistance of the composite electrode material of the biomass-based activated carbon loaded with CuO nano particles is reduced compared with that of the activated carbon electrode material of the comparative example 1. In conclusion, compared with the activated carbon electrode material in the comparative example 1, the electrochemical performance of the biomass-based activated carbon-supported CuO nanoparticle composite electrode material is obviously improved.
The above description is only a preferred embodiment of the present invention, and the scope of the present invention is not limited thereto, and any simple modifications or equivalent substitutions of the technical solutions that can be obviously obtained by those skilled in the art within the technical scope of the present invention are within the scope of the present invention.
Claims (9)
1. A biomass-based activated carbon loaded CuO nano-particle composite material is characterized in that: comprises biomass-based activated carbon, wherein CuO nano-particles are distributed in mesopores of the biomass-based activated carbon;
the specific surface area of the biomass-based activated carbon is 2600 m2 g-1(ii) a The particle size of the CuO nano-particles is 10-20 nm.
2. The composite material of claim 1, wherein: the biomass-based activated carbon is obtained by taking peanut shells as raw materials, carbonizing the peanut shells and then activating the peanut shells.
3. The oriented synthesis method of biomass-based activated carbon loaded CuO nanoparticle composite material as claimed in claim 1, characterized in that: the method comprises the following steps:
step 1, washing a peanut shell raw material with water, drying, and crushing to obtain peanut shell powder;
step 2, putting the peanut shell powder into a corundum boat, putting the corundum boat into an atmosphere tube furnace, and putting the corundum boat into an atmosphere tube furnace2Carbonizing in the atmosphere, and crushing the carbonized product to obtain the peanut shell semicoke;
step 3, mixing the peanut shell semicoke and potassium hydroxide, placing the mixture into a corundum boat, placing the corundum boat into an atmosphere tube furnace, and placing the corundum boat in an N atmosphere tube furnace2Activating under atmosphere, using 1 mol L of activating mixture-1Pickling with hydrochloric acid, washing with deionized water, and drying to obtain activated carbon powder;
step 4, dissolving copper acetate in deionized water, adding an ammonia water solution while stirring, then adding activated carbon powder into the mixed solution, continuously stirring, and then drying to obtain mixed powder;
and 5, putting the mixed powder into a tubular furnace, and calcining in an air atmosphere to obtain the biomass-based activated carbon-supported CuO nano-particle composite material.
4. The method of claim 3, wherein: the temperature rise rate of the carbonization process in the step 2 is 5 ℃ min-1The carbonization temperature is 600 ℃, and the carbonization time is 3 h.
5. The method of claim 3, wherein: the mass ratio of the semicoke of the peanut shell to the KOH in the step 3 is 1:4, and the heating rate in the activation process is 10 ℃ per minute-1The activation temperature is 800 ℃, and the activation time is 2 h.
6. The method of claim 3, wherein: in step 4, the dosage ratio of the ammonia water solution, the copper acetate and the activated carbon powder is 5.5 mL to 90 mg to 0.56 g.
7. The method of claim 3, wherein: the calcining conditions in the step 5 are as follows: the temperature is increased to 310 ℃ at the temperature increasing rate of 10 ℃/min for calcination for 2 h.
8. Use of a biomass-based activated carbon loaded CuO nanoparticle composite as claimed in claim 1 in the preparation of a supercapacitor.
9. Use according to claim 8, characterized in that: grinding the composite material to 200 meshes, mixing the ground composite material with acetylene black and PTFE in a mortar according to the mass ratio of 8:1:1, adding ethanol to uniformly mix the materials, coating 5 mg of the mixture on foamed nickel, tabletting for 60 s under the pressure of 10 MPa, and drying to ensure that the ethanol is completely removed to obtain the electrode material.
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|---|---|---|---|---|
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| CN111180214A (en) * | 2018-11-13 | 2020-05-19 | 北京化工大学 | Bamboo-based porous carbon/manganese dioxide nano composite electrode material for supercapacitor and preparation method thereof |
| CN112103091A (en) * | 2019-06-18 | 2020-12-18 | 华北电力大学（保定） | CuO/C composite material, preparation method and application thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN111180214A (en) * | 2018-11-13 | 2020-05-19 | 北京化工大学 | Bamboo-based porous carbon/manganese dioxide nano composite electrode material for supercapacitor and preparation method thereof |
| CN112103091A (en) * | 2019-06-18 | 2020-12-18 | 华北电力大学（保定） | CuO/C composite material, preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| YIJU LI等: "Anchoring CuO nanoparticles on nitrogen-doped reduced grapheme oxide nanosheets as electrode material for supercapacitors", 《JOURNAL OF ELECTROANALYTICAL CHEMISTRY》 * |
| YINBO ZHAN等: "Preparation of highly porous activated carbons from peanut shells as low-cost electrode materials for supercapacitors", 《JOURNAL OF ENERGY STORAGE》 * |
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