CN110697706A - Preparation method of three-dimensional biomass carbon/copper sulfide used as electrode material - Google Patents
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Abstract
The invention provides a preparation method of three-dimensional biomass carbon/copper sulfide used as an electrode material. The method comprises the steps of taking dry fruit shells as a carbon source of a biomass carbon material, washing, drying, ball milling and crushing, soaking with an alkaline activating agent solution, drying, and carbonizing at high temperature in a protective gas atmosphere to obtain the biomass carbon material. And then growing copper sulfide particles on the surface of the biomass carbon material by using copper nitrate and thiourea as a copper source and a sulfur source respectively through a hydrothermal synthesis method to prepare the three-dimensional biomass carbon/copper sulfide composite material. Electrochemical tests show that the three-dimensional biomass carbon/copper sulfide composite electrode material prepared from the material has high specific capacity, excellent rate capability and considerable electrochemical cycling stability, and is suitable for being applied to a super capacitor cathode material.
Description
The technical field is as follows:
the invention relates to the technical field of electrode materials of a super capacitor, in particular to a biomass carbon/copper sulfide composite electrode material, a preparation method thereof and application thereof in preparing a cathode material of the super capacitor.
Background art:
supercapacitors have received increasing attention over the past few decades due to their high power density, rapid charge and discharge, and excellent cycling stability. Supercapacitors can be classified into double layer capacitors and pseudocapacitors according to different energy storage mechanisms. The double-electric-layer super capacitor realizes energy storage through reversible absorption and desorption of charges on the surface of the material, and the electrode material of the double-electric-layer super capacitor mainly comprises a carbon material with a high specific surface area, including activated carbon, graphene, carbon nanotubes, carbon fibers, carbon aerogel and the like. The pseudocapacitance super capacitor energy storage is realized through a rapid reversible Faraday reaction, and electrode materials of the pseudocapacitance super capacitor energy storage mainly comprise conductive polymers, manganese dioxide, ruthenium oxide and the like.
Biomass, when considered as a renewable energy source, primarily refers to the carbohydrates found in plants and animals. The energy form is that the plants convert solar energy into chemical energy through photosynthesis and store the chemical energy in the bodies of the plants, is the fourth most energy behind coal, petroleum and natural gas, is one of important energy sources depending on the survival of human beings, and plays an important role in the whole energy system. At present, reports of biomass carbon materials as electrode materials of supercapacitors are frequent. The raw materials thereof are related to the fields of roots, stems, leaves, seeds, fruit peels, dried fruit shells, waste foods, fungi, shellfish, animal tissues, polysaccharides, proteins and the like of plants. Compared with carbon materials such as carbon nanotubes, carbon fibers and carbon quantum dots, the biomass carbon material has the advantages of environmental friendliness, low cost, reproducibility and the like. Patent CN 105197910A discloses a method for preparing a porous nano carbon material by using biomass as a carbon source, which adopts pleurotus eryngii as a raw material, obtains the biomass carbon material by methods of pre-carbonization, solvent freeze drying, secondary heat treatment and the like, and applies the biomass carbon material to a super capacitor. However, the raw material pleurotus eryngii is expensive, so that the method provides a challenge for large-scale industrial production, and simultaneously limits the application of the biomass carbon electrode material in actual production and life.
Copper-based sulfides (including copper sulfide, cuprous sulfide, heptacopper tetrasulfide and the like) are used as a series of materials and are widely applied to the fields of catalysis, energy storage, sensors and the like. Wherein, the theoretical capacity of copper sulfide (CuS) is up to (560mA hg) in electrochemical performance-1) And has good conductivity (10)-3S cm-1). Nevertheless, the severe capacity decay of CuS-based materials after many cycles is mainly due to structural damage and the "shuttling effect" of reactive polysulfide intermediates, inevitably limiting their widespread use in energy storage systems. Currently, these problems can be effectively solved by combining carbon materials with transition metal oxides or sulfur compounds. The introduction of transition metal oxides or sulfur compounds can increase the electrical conductivity of the carbon material. Meanwhile, the carbon material can remarkably increase the stability of the transition metal oxide or the sulfur compound. In Electrochimica Acta,2018,261:198-205, a biomass carbon material prepared by burning wheat straw is combined with iron oxide and applied to a cathode material of a supercapacitor. At 1A g-1At a current density of (2), a capacity of up to 987.9F g-1After 3000 cycles, the capacity remained at 82.6%. In Chemical Engineering Journal,2019, a method of compounding activated and carbonized chicken bone material with manganese dioxide by electrodeposition and applying to the electrode material of a supercapacitor is reported. At 1A g-1Porous biomass carbon (HPCS) possesses 231.5F g at current density of-1Capacity of (1), in contrast, HPCS @ MnO2Is 476.4F g-1. Meanwhile, 10A g-1The capacity of the HPCS still maintains 95 percent of the initial capacity after 10000 circles of continuous charging and discharging. At 1mol/L of Na2SO4Combined asymmetric capacitor HPCS// HPCS @ MnO in solution2Has 60.8Wh kg-1Energy density of 20.7kW kg-1The power density of (a).
The invention content is as follows:
the invention provides a method for preparing a three-dimensional porous carbon material by taking biomass as a carbon source and growing a copper sulfide composite material, which can be used for a supercapacitor electrode material and has the advantages of improving conductivity, slowing volume expansion, enhancing stability and the like.
The preparation method of the three-dimensional biomass carbon/copper sulfide composite electrode material comprises the following steps:
A. cleaning, drying and crushing the dried fruit shells; immersing dry fruit shell powder into an alkaline activator solution, wherein the mass ratio of the dry fruit shell to the alkaline activator is 3: 5-10, soaking the dry fruit shell powder and the alkaline activator in a vacuum environment with the pressure of 0.8-1 MPa for 6-12 h at normal temperature, filtering, and drying at the temperature of 60-120 ℃;
the dry fruit shell comprises sunflower seed shell, pumpkin seed shell, watermelon seed shell, peanut shell, pistachio nut shell, hazelnut shell and the like. The alkaline activator is one or a mixture of potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate which are mixed according to any proportion. The total molar concentration of the alkaline activator is 3-6 mol/L.
B. And B, placing the dried fruit shell powder pretreated in the step A into a tube furnace, and calcining in a protective gas atmosphere: raising the temperature to 240 ℃ under the air flow of 30-50 ml/min at the temperature rise rate of 2-5 ℃/min, and preserving the heat for 1-2 h; continuously raising the temperature to 450 ℃, and preserving the heat for 1-2 h; continuing to rise to 800 ℃ for 600-; filtering, washing with deionized water to neutrality, and drying to obtain biomass carbon material;
the protective gas is one or a mixture of several of nitrogen, argon, helium and carbon monoxide according to any proportion, and is used for isolating oxygen in the carbonization process. In practice, nitrogen is generally used as a protective gas due to cost problems.
The acid solution is hydrochloric acid, nitric acid, phosphoric acid or sulfuric acid solution, and the concentration of the acid solution is 1-2 mol/L;
C. adding the obtained biomass carbon material, copper nitrate and thiourea into ethylene glycol, and fully mixing to obtain mixed slurry, wherein the biomass carbon material: copper nitrate: the mass ratio of thiourea is 1: 1-3: 4-15, and the mass concentration of the biomass carbon material in ethylene glycol is 0.167-1.67 g/L; transferring the mixed slurry into a high-pressure reaction kettle, and carrying out hydrothermal reaction at the temperature of 150-180 ℃ for 12-24 h; and naturally cooling to room temperature, discharging, filtering, washing and drying to obtain the biomass carbon/copper sulfide composite material, wherein the chemical formula of the biomass carbon/copper sulfide composite material is represented as a C/CuS composite material, and the mass ratio of C to CuS is 1: 1-10.
The carbonization process adopts gradient temperature rise to ensure the porous structure of the carbon material. The first step (240 ℃) of the gradient temperature rise is heat preservation, which is helpful for removing the water and volatile oil in the dry shell powder; the second step (450 ℃) heat preservation is beneficial to the contact of the alkaline activator after the melting decomposition with the cellulose and the hemicellulose in the dry shell powder; under the high temperature condition, strong base reacts with carbon, so that a large number of interconnected holes appear in the dried fruit shell powder, a channel is provided for ion and electron diffusion, the ion diffusion distance is shortened, and the conductivity of the material is improved. Meanwhile, as the copper sulfide is attached to the surface of the biomass carbon material, the loading capacity of the copper sulfide is increased, a larger and more effective active area is provided, and the specific capacity of the copper sulfide is obviously increased. Therefore, the material is suitable for being used as an electrode material of a super capacitor.
FIG. 1 is a Scanning Electron Microscope (SEM) representation of the carbon material obtained in step (2) of example 1, and it can be seen that the carbon material is a honeycomb-like three-dimensional porous structure with pores of 200-500 nm diameter uniformly distributed on the surface.
FIG. 2 is a Scanning Electron Microscope (SEM) representation of the C/CuS composite material obtained in step (3) of example 1, from which it can be seen that copper sulfide particles are uniformly attached to the surface of the carbon material.
FIG. 3 is an X-ray diffraction (XRD) pattern of a curve a of the carbon material obtained in step (2) and a curve C/CuS-b obtained in step (3) in example 1. As can be seen from the a curve, around 20 ° and 43 °, the diffraction peaks are characteristic (002) and (101) diffraction peaks of the carbon material, and the intensity is weak and is related to the amorphous structure of the carbon material. As can be seen from the b-curve, the diffraction peaks 27.68 °, 29.27 °, 31.78 °, 32.88 °, 47.93 °, 52.72 ° and 59.36 ° correspond to the characteristic diffraction peaks of (101), (102), (103), (006), (110), (108) and (116) of CuS powder diffraction card (JCPDS card No. 06-0464). By comparing the two curves a and b, the diffraction peak of CuS can be obviously found, which shows that CuS crystal is successfully grown after hydrothermal treatment.
FIG. 4 is a Cyclic Voltammetry (CV) curve of the carbon material obtained in step (2) of example 5 and the electrode prepared from the C/CuS composite material obtained in step (3) in a KOH electrolyte of 1 mol/L.
Preparing the electrode: weighing 5mg of a material for preparing an electrode, adding 40-50 mu L of 5% adhesive (Nafion solution) and 1ml of ethanol solution, carrying out ultrasonic uniform treatment, and uniformly coating the material on the material which is subjected to ultrasonic cleaning and has the size of 1 multiplied by 1cm2And (5) drying the surface of the foamed nickel to obtain the electrode. Electrodes as mentioned in FIGS. 5-8 were prepared in the same manner as the method
The test method comprises the following steps: an Ag/AgCl electrode was used as a reference electrode, a Pt electrode as a counter electrode, and C/CuS as a working electrode. The test process is carried out at-1 to 0V, and the sweep rate is 100 mv/s. Wherein, curve a is carbon material CV curve, curve b is C/CuS composite material CV curve. As can be seen from the figure, the graph surrounded by the curve a approximately presents a parallelogram, which shows the electric double layer energy storage mechanism of the carbon material. Compared with a pure biomass carbon material, the biomass carbon/copper sulfide composite material has an obvious oxidation reduction peak, and meanwhile, the area enclosed by the CV curve is larger, which shows that the biomass carbon material has higher electric capacity than the biomass carbon material.
FIG. 5 is a constant current charge/discharge (GCD) curve of the carbon material obtained in step (2) of example 5 and the electrode prepared from the C/CuS composite material obtained in step (3) in a KOH electrolyte solution of 1 mol/L. Wherein the curve a is a GCD curve of the carbon material, and the charging and discharging process is carried out between-1.1V and 0V; the curve b is a GCD curve of the C/CuS composite material, and the charging and discharging process is carried out between-1V and 0V. At 1A g-1The pure carbon electrode has a capacity of 290F g at a current density of-1About, and the capacity of the C/CuS composite material is 700F g-1On the left and right, the capacity of the two materials clearly shows that the composition of the CuS and the carbon material can obviously improve the capacitance of the supercapacitor made of the materialCan, consistent with CV test results. The capacitance value can be calculated by the following formula:
c represents specific capacitance (F g)-1) I is a charge-discharge current (A), Δ t is a charge-discharge time(s), Δ V is a voltage (V), and m is a mass (g) of an electrode active component. By electrochemical testing, 1A g-1The capacity value of the composite material is 700F g under the current density-1The product has high specific capacity; at 10A g-1Under the current density, the capacity of 66.7 percent is still maintained, which shows that the composite material has excellent rate capability; at 20A g-1The capacity of the composite material still has 95.57% of the initial value after 1000 cycles under the current density, which indicates that the composite material has good electrochemical stability.
FIG. 6 is an alternating current impedance (EIS) curve of the carbon material obtained in step (2) of example 5 and the electrode prepared from the C/CuS composite material obtained in step (3) in a KOH electrolyte solution of 1 mol/L. Wherein, the curve a is a carbon material EIS curve, and the curve b is a C/CuS composite material EIS curve. According to the image display, the semicircle value of the carbon material curve in the high-frequency area is smaller, which indicates that the carbon material curve has smaller diffusion resistance; the slope of the line is greater in the low frequency region, indicating a smaller charge transfer resistance. In summary, it is shown that the carbon material still maintains a smaller impedance value, in other words, possesses a relatively excellent electrical conductivity, compared to the C/CuS composite material.
FIG. 7 is a Cyclic Voltammetry (CV) curve of an electrode prepared from the C/CuS composite obtained in step (3) of examples 1 and 4 in a KOH electrolyte of 1 mol/L. Wherein a is the material of the step (3) of the embodiment 1, and b is the material of the step (3) of the embodiment 4. The area enclosed by the curves a and b is larger than the area enclosed by the curve a in fig. 4, which shows that the two composite materials have better electrochemical capacity than carbon material.
FIG. 8 is a constant current charge and discharge (GCD) curve of electrodes made of the C/CuS composite obtained in step (3) of example 1 and step (3) of example 4 in a KOH electrolyte solution of 1 mol/L; wherein a is step (3) of example 1Material b is the material of example 4 step (3). By electrochemical testing, 1A g-1The capacity value of the composite material represented by the curve a is 800F g under the current density-1Left and right; the b curve represents the composite capacity value of 600F g-1And the left and right show that the composite material prepared by the method has good electrochemical performance.
The invention has the beneficial effects that:
the raw materials selected by the invention are green and environment-friendly, are easy to obtain and have low cost. The purposes of controlling the three-dimensional structure of the carbon material and regulating and controlling the loading capacity of the copper sulfide nanospheres can be achieved by controlling the gradient temperature-rising program and the proportion and the dosage of the copper source and the sulfur source. Because this product has fused carbon material and copper sulphide for this combined material has the advantage of electric double layer and pseudo-electric capacity concurrently, has better stability and excellent specific capacitance value simultaneously promptly. The method has wide application value in the aspect of the cathode material of the super capacitor.
Drawings
FIG. 1 is a scanning electron microscope photograph of a carbon material obtained in step (2) of example 1.
FIG. 2 is a scanning electron microscope photograph of the C/CuS composite material obtained in step (3) of example 1.
FIG. 3 is an X-ray diffraction chart of the materials obtained in steps (2) and (3) of example 1, wherein a is the material of step (2) and b is the material of step (3).
FIG. 4 is a Cyclic Voltammetry (CV) curve of an electrode material prepared from the material obtained in step (2) and step (3) of example 5; wherein a is the material of the step (2) and b is the material of the step (3).
FIG. 5 is a constant current charge and discharge (GCD) curve for electrode materials prepared from the materials obtained in step (2) and step (3) of example 5. Wherein a is the material of the step (2) and b is the material of the step (3).
FIG. 6 is an alternating current impedance (EIS) curve of electrode materials prepared from the materials obtained in step (2) and step (3) of example 5. Wherein a is the material of the step (2) and b is the material of the step (3).
FIG. 7 is a Cyclic Voltammetry (CV) curve of an electrode material prepared from the C/CuS composite of step (3) of examples 1 and 4; wherein a is the material of the step (3) of the embodiment 1, and b is the material of the step (3) of the embodiment 4.
FIG. 8 is a constant current charge and discharge (GCD) curve for electrode materials prepared from the C/CuS composite of example 1 and example 4 step (3); wherein a is the material of the step (3) of the embodiment 1, and b is the material of the step (3) of the embodiment 4.
Detailed Description
Example 1
(1) Pretreatment of dried fruit shells: cleaning hazelnut shells, drying, ball-milling and crushing; taking 3g of completely dried hazel nut shell powder, soaking the hazel nut shell powder into 30ml of 4mol/L KOH solution at normal temperature in a vacuum environment under the pressure of 0.8MPa for 12h, and then drying at the temperature of 60 ℃;
(2) and (3) an activation process: placing the dried fruit shell powder treated in the step (1) in a tube furnace, and calcining in a nitrogen atmosphere: raising the temperature to 240 ℃ at the heating rate of 2 ℃/min under the air flow of 30ml/min, and preserving the temperature for 1 h; continuously raising the temperature to 450 ℃, and preserving the temperature for 1 h; then continuously raising the temperature to 600 ℃, preserving the heat and carbonizing for 1 h; cooling to room temperature along with the furnace; taking out the carbon powder, and soaking the carbon powder into 2mol/L hydrochloric acid solution for 2 hours according to the proportion of 25mL acid solution per gram of carbon powder; filtering, washing with deionized water to neutrality, and drying to obtain carbon material;
(3) preparing a composite material: adding the 10mg biomass carbon material, 0.375g copper nitrate and 0.3g thiourea into 30ml ethylene glycol, and fully mixing to obtain a mixed solution; transferring the mixed solution into a high-pressure reaction kettle, and carrying out hydrothermal reaction for 12h at 150 ℃; naturally cooling to room temperature; discharging, filtering, washing and drying to obtain the biomass carbon/copper sulfide C/CuS composite material. The content of each element in C/CuS is measured by adopting an X-ray energy spectrum, and the result is shown in a table 1, wherein the carbon: copper: sulfur element mass ratio of about 1:6:3, carbon: the mass ratio of the copper sulfide is 1: 9.
TABLE 1C/CuS composite X-ray energy spectrum determination results
| Element(s) | Mass ratio% | Atom ratio% |
| C K | 9.81 | 30.16 |
| Cu K | 59.23 | 34.15 |
| S K | 30.96 | 35.69 |
| Total of | 100 | 100 |
Example 2
(1) Pretreatment of dried fruit shells: cleaning, drying and ball milling the watermelon seed shells; taking 3g of completely dried watermelon seed shell powder, soaking the watermelon seed shell powder into 30ml of mixed solution of 3mol/L sodium carbonate and sodium bicarbonate (the mass ratio of the substances is 1:1) at the pressure of 1MPa and the normal temperature in a vacuum environment for 8 hours, and then drying the watermelon seed shell powder at the temperature of 120 ℃;
(2) and (3) an activation process: placing the dried fruit shell powder treated in the step (1) in a tube furnace, and calcining in a carbon monoxide atmosphere: heating to 240 ℃ at the heating rate of 3 ℃/min under the air flow of 50ml/min, and preserving the heat for 1.5 h; continuously raising the temperature to 450 ℃, and preserving the temperature for 1 h; then continuously raising the temperature to 700 ℃, preserving the heat and carbonizing for 1 h; cooling to room temperature along with the furnace; taking out the carbon powder, and soaking the carbon powder into a sulfuric acid solution of 2mol/L for 2 hours according to the proportion of 30mL of acid solution per gram of carbon powder; filtering, washing with deionized water to neutrality, and drying to obtain carbon material;
(3) preparing a composite material: adding the obtained 25mg biomass carbon material, 0.1875g copper nitrate and 0.15g thiourea into 30ml ethylene glycol, and fully mixing to obtain a mixed solution; transferring the mixed solution into a high-pressure reaction kettle, and carrying out hydrothermal reaction for 18h at 160 ℃; naturally cooling to room temperature; discharging, filtering, washing and drying to obtain the biomass carbon/copper sulfide composite material; the content of each element in C/CuS is measured by adopting an X-ray energy spectrum, and the content of biomass carbon is as follows: the mass ratio of the copper sulfide is 1: 1.5.
Example 3
(1) Pretreatment of dried fruit shells: cleaning pumpkin seed shells, drying, and grinding by ball milling; taking 3g of completely dried pumpkin seed shell powder, soaking the pumpkin seed shell powder into 30ml of 5mol/L sodium bicarbonate solution at normal temperature in a vacuum environment under the pressure of 0.8MPa for 6h, and then drying the pumpkin seed shell powder at the temperature of 80 ℃;
(2) and (3) an activation process: placing the dried fruit shell powder treated in the step (1) in a tube furnace, and calcining in a helium atmosphere: raising the temperature to 240 ℃ at the temperature raising rate of 5 ℃/min under the air flow of 35ml/min, and preserving the temperature for 1 h; continuously raising the temperature to 450 ℃, and preserving the temperature for 1 h; then continuously raising the temperature to 750 ℃, and preserving heat for carbonization for 2 hours; cooling to room temperature along with the furnace; taking out the carbon powder, and soaking the carbon powder into 1mol/L nitric acid solution for 2 hours according to the proportion of 30mL acid solution per gram of carbon powder; filtering, washing with deionized water to neutrality, and drying to obtain carbon material;
(3) preparing a composite material: adding 30mg of the biomass carbon material, 0.09375g of copper nitrate and 0.125g of thiourea into 30ml of ethylene glycol, and fully mixing to obtain a mixed solution; transferring the mixed solution into a high-pressure reaction kettle, and carrying out hydrothermal reaction for 12h at 180 ℃; naturally cooling to room temperature; discharging, filtering, washing and drying to obtain the biomass carbon/copper sulfide composite material; the content of each element in C/CuS is measured by adopting an X-ray energy spectrum, and the content of biomass carbon is as follows: the mass ratio of the copper sulfide is 1:1.
Example 4
(1) Pretreatment of dried fruit shells: cleaning, drying and ball-milling the peanut shells; taking 3g of completely dried peanut shell powder, soaking the peanut shell powder into 30ml of mixed solution of 3mol/L sodium hydroxide and sodium carbonate (the mass ratio of the substances is 2:1) at the normal temperature in a vacuum environment under the pressure of 0.9MPa for 12h, and then drying the peanut shell powder at the temperature of 120 ℃;
(2) and (3) an activation process: placing the dried fruit shell powder treated in the step (1) in a tube furnace, and calcining in an argon atmosphere: raising the temperature to 240 ℃ at the heating rate of 4 ℃/min under 40ml/min air flow, and preserving the temperature for 2 h; continuously raising the temperature to 450 ℃, and preserving the temperature for 2 hours; then continuously raising the temperature to 800 ℃, preserving the heat and carbonizing for 2 hours; cooling to room temperature along with the furnace; taking out the carbon powder, and soaking the carbon powder into 2mol/L hydrochloric acid solution for 4 hours according to the proportion of 35mL acid solution per gram of carbon powder; filtering, washing with deionized water to neutrality, and drying to obtain carbon material;
(3) preparing a composite material: adding the obtained 50mg biomass carbon material, 0.375g copper nitrate and 0.3g thiourea into 30ml ethylene glycol, and fully mixing to obtain a mixed solution; transferring the mixed solution into a high-pressure reaction kettle, and carrying out hydrothermal reaction for 24 hours at 170 ℃; naturally cooling to room temperature; discharging, filtering, washing and drying to obtain the biomass carbon/copper sulfide composite material; and (3) measuring the content of each element in the C/CuS by adopting an X-ray energy spectrum, wherein the content of the biomass carbon is as follows: the mass ratio of the copper sulfide is 1: 2.
Example 5
(1) Pretreatment of dried fruit shells: cleaning sunflower seed shells, drying, and ball milling; taking 3g of completely dried sunflower seed shell powder, soaking the sunflower seed shell powder into 30ml of 6mol/L KOH solution at normal temperature in a vacuum environment under the pressure of 0.85MPa for 12h, and then drying at the temperature of 120 ℃;
(2) and (3) an activation process: placing the dried fruit shell powder treated in the step (1) in a tube furnace, and calcining in a nitrogen atmosphere: raising the temperature to 240 ℃ at the heating rate of 3 ℃/min under the air flow of 30ml/min, and preserving the temperature for 1 h; continuously raising the temperature to 450 ℃, and preserving the temperature for 1 h; then continuously raising the temperature to 700 ℃, preserving the heat and carbonizing for 2 hours; cooling to room temperature along with the furnace; taking out the carbon powder, and soaking the carbon powder into 1mol/L sulfuric acid solution for 2 hours according to the proportion of 35mL acid solution per gram of carbon powder; filtering, washing with deionized water to neutrality, and drying to obtain carbon material;
(3) preparing a composite material: adding the 10mg biomass carbon material, 0.375g copper nitrate and 0.3g thiourea into 30ml ethylene glycol, and fully mixing to obtain a mixed solution; transferring the mixed solution into a high-pressure reaction kettle, and carrying out hydrothermal reaction for 12h at 160 ℃; naturally cooling to room temperature; discharging, filtering, washing and drying to obtain the biomass carbon/copper sulfide composite material; and (3) measuring the content of each element in the C/CuS by adopting an X-ray energy spectrum, wherein the content of the biomass carbon is as follows: the mass ratio of the copper sulfide is 1: 9.
Claims (1)
1. A preparation method of three-dimensional biomass carbon/copper sulfide used as an electrode material comprises the following specific preparation steps:
A. cleaning, drying and crushing the dried fruit shells; immersing dry fruit shell powder into an alkaline activator solution, wherein the mass ratio of the dry fruit shell to the alkaline activator is 3: 5-10, soaking the dry fruit shell powder and the alkaline activator in a vacuum environment with the pressure of 0.8-1 MPa for 6-12 h at normal temperature, filtering, and drying at the temperature of 60-120 ℃;
the dry fruit shell comprises sunflower seed shell, pumpkin seed shell, watermelon seed shell, peanut shell, pistachio nut shell, hazelnut shell and the like; the alkaline activator is one or a mixture of potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate which are mixed according to any proportion; the total molar concentration of the alkaline activator is 3-6 mol/L;
B. and B, placing the dried fruit shell powder pretreated in the step A into a tube furnace, and calcining in a protective gas atmosphere: raising the temperature to 240 ℃ under the air flow of 30-50 ml/min at the temperature rise rate of 2-5 ℃/min, and preserving the heat for 1-2 h; continuously raising the temperature to 450 ℃, and preserving the heat for 1-2 h; continuing to rise to 800 ℃ for 600-; filtering, washing with deionized water to neutrality, and drying to obtain biomass carbon material;
the protective gas is nitrogen; the acid solution is hydrochloric acid, nitric acid, phosphoric acid or sulfuric acid solution, and the concentration of the acid solution is 1-2 mol/L;
C. adding the obtained biomass carbon material, copper nitrate and thiourea into ethylene glycol, and fully mixing to obtain mixed slurry, wherein the biomass carbon material: copper nitrate: the mass ratio of thiourea is 1: 1-3: 4-15, and the mass concentration of the biomass carbon material in ethylene glycol is 0.167-1.67 g/L; transferring the mixed slurry into a high-pressure reaction kettle, and carrying out hydrothermal reaction at the temperature of 150-180 ℃ for 12-24 h; naturally cooling to room temperature, discharging, filtering, washing and drying to obtain the biomass carbon/copper sulfide composite material, wherein the chemical formula of the biomass carbon/copper sulfide composite material is represented as C/CuS composite material, wherein C: the mass ratio of CuS is 1: 1-10.
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