CN113184830B - Preparation method of two-dimensional boron-nitrogen doped biomass derived carbon nanosheet - Google Patents
Preparation method of two-dimensional boron-nitrogen doped biomass derived carbon nanosheet Download PDFInfo
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
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- C—CHEMISTRY; METALLURGY
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- C01B32/00—Carbon; Compounds thereof
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- C01B32/318—Preparation characterised by the starting materials
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- C01B32/336—Preparation characterised by gaseous activating agents
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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
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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
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Abstract
A preparation method of a two-dimensional boron-nitrogen doped biomass derived carbon nanosheet relates to the technical field of supercapacitor electrode materials, and a precursor with an interlayer structure is formed in a manner of co-crystallization of boric acid and ampullaria gigas egg juice. Then carbonizing under the protection of nitrogen, and removing B from the obtained mixed material in deionized water 2 O 3 And finally obtaining the boron-nitrogen doped high-defect carbon two-dimensional nanosheet by using the template. According to the invention, the biomass macromolecules and boric acid are self-assembled into a two-dimensional structure through hydrogen bond acting force, and the activation of the carbon material is promoted by gas formed by decomposition of boric acid in subsequent carbonization. In addition, the boric acid used as the template can be recycled in a water-soluble mode, so that the purpose of environmental protection is achieved.
Description
Technical Field
The invention relates to the technical field of electrode materials of super capacitors.
Background
Since the 21 st century, rapid consumption of fossil fuels and severe greenhouse effect due to the rapid development of global economy have become major problems in the sustainable development of human society. The efficient energy storage device plays a key role in the aspects of low-carbon economy and renewable energy utilization. Super capacitors have received extensive attention from both academic and industrial circles as an important energy storage device. Compared to commercial rechargeable batteries that rely on an intercalation mechanism, supercapacitors have various advantages, such as high power density, excellent rate performance, long life, and rapid charge/discharge. This is because the charge storage mechanism is based on reactions such as adsorption on the surface of the electrode material, and there is no slow reaction limited by ion diffusion. Therefore, supercapacitors can compensate for the energy storage function of batteries or fuel cells by providing backup power and preventing power interruption, which are important supplements for military applications, electric vehicles, smart appliances and portable electronic devices.
In general, supercapacitors have two main types of charge storage mechanisms, electric double layer capacitors, whose capacitance results from the accumulation of pure electrostatic charges at the interface of the electrode and the electrolyte, and pseudocapacitors, whose capacitance results from rapid and reversible redox reactions in the active electrode material. When the electric double layer capacitor is charged by an external load, cations in the electrolyte move to the negative electrode, anions in the electrolyte move to the positive electrode, and electrons move from the negative electrode to the positive electrode through an external circuit, and double layer capacitance is formed at an interface with the electrodes. After the charging is completed, the positive electrode and the negative electrode attract anions and cations, respectively, from the electrolyte to each other, and stabilize the double layer of the electrode surface. The discharging process is exactly the reverse of the charging process. Thus, carbon materials are of interest because their higher surface area than metals allows more energy to be stored in them, such as graphene, CNTs, and other carbon nanostructures.
Activated Carbon (AC) based on biological precursors offers research opportunities to replace traditional fossil fuel derived carbon, such as wood, onion, phoenix tree, fish scales, willow catkin, and the like. The abundant earth resources are cheap and can be produced naturally. Through a suitable physical or chemical activation process, the resulting AC can possess a desirable hierarchical porous structure (macro-, meso-, and micro-pores), which has a positive effect on enhancing capacitance and good rate capability. Biomass is converted as a carbon precursor into activated carbon having a layered structure and a porous skeleton characteristic, thereby increasing the density of the carbon material and alleviating stacking/agglomeration of the porous layered material, which is an excellent electrode material for an electric double layer capacitor. Biomass, as a green sustainable resource, has unique intrinsic structure and rich heteroatom composition (e.g., O, N and S), facilitating the production of carbon with unique porous structure and heteroatom-rich surface functionality. The special pore structure can provide abundant active sites for rapid ion storage and diffusion to achieve excellent specific capacitance and rate capability. At the same time, surface redox reactions can contribute to the heteroatom functionalities creating additional pseudo-capacitance.
Furthermore, the electrochemical performance of the bio-waste derived AC may be further improved by doping. Dopants of heteroatoms such as nitrogen (N), sulfur (S), boron (B) and phosphorus (P) have been considered as an effective strategy to promote the electronic properties of adjacent carbon atoms. Due to their different electronegativity, these heteroatoms not only change the electron distribution, but can also form surface functional groups. Furthermore, heteroatom doping can synergistically improve charge storage capability by inducing defects, enhancing porosity, and optimizing carbon interlayers. Heteroatom doping in the carbon backbone can improve surface chemical reactivity and achieve higher capacitance performance. The biomass-derived nitrogen-doped hierarchical porous carbon has good capacitance performance and high rate capability.
Disclosure of Invention
The invention aims to provide a preparation method of a two-dimensional boron-nitrogen doped biomass derived carbon nanosheet for a supercapacitor.
The technical scheme of the invention is as follows: uniformly mixing boric acid and ampullaria gigas egg juice in deionized water, obtaining a crystalline solid in a low-temperature crystallization mode, drying the crystalline solid, carbonizing the crystalline solid under the protection of nitrogen to obtain an expanded carbon composite material, and dissolving the expanded carbon composite material in the deionized water to remove B 2 O 3 And (4) obtaining the two-dimensional boron-nitrogen doped biomass derived carbon nanosheet by using a template.
The invention has the beneficial effects that:
1. the invention breaks the dependence of conventional biologically-derived carbon on the natural structure of the biomass, and constructs the two-dimensional boron-nitrogen doped biomass-derived carbon nanosheet with the two-dimensional morphology with the high aspect ratio.
2. The two-dimensional boron-nitrogen-doped biomass-derived carbon nanosheet prepared by the invention has boron with a high defect structure and nitrogen-doped two-dimensional nanocarbon with excellent electrochemical performance, the conductivity of the carbon is enhanced due to the fact that boron and nitrogen atoms carrying unmatched electrons, and the lattice defects constructed in the carbon lattice provide high pseudocapacitance energy storage. The two-dimensional structure is beneficial to exposing more electroactive sites, and the morphology with a large aspect ratio can ensure the rapid transmission of electrons.
3. The chemical reagent (boric acid) used in the invention can be completely recycled, and meets the development requirements of environmental protection and low pollution. In addition, the recovered boric acid can be repeatedly used, and the production cost is effectively reduced.
In conclusion, the biomass carbon material self-assembles into a two-dimensional structure through the hydrogen bonding force between the biomass macromolecules and the boric acid, and the activation of the carbon material is promoted by the gas formed by the decomposition of the boric acid in the subsequent carbonization. In addition, the boric acid used as the template can be recycled in a water-soluble mode, so that the purpose of environmental protection is achieved.
Furthermore, the mixing mass ratio of the boric acid and the ampullaria gigas egg juice is 8: 1. In the process, the boric acid content directly affects the thickness of the derived carbon nanosheet and the uniformity of the two-dimensional morphology: if the boric acid is too little, the produced carbon nano-sheets can not maintain the two-dimensional morphology and have serious agglomeration; however, if the boric acid is too much, the nano carbon sheet is too thin, the stability of the structure is poor, and the nano carbon sheet is very easy to break and causes the reduction of the energy storage cycle performance.
The low-temperature crystallization mode is to stir and evaporate a mixed solution consisting of boric acid, ampullaria gigas egg juice and deionized water at 40-100 ℃. If the temperature is too low, the crystallization speed of the boric acid is too slow, and excessive energy loss can occur; if the temperature is too high, the crystallization rate of the boric acid is different from that of the ampullaria gigas egg juice, and uniform crystals cannot be formed.
The carbonization treatment is carried out at 2 deg.C for min -1 And annealing for two hours at the temperature of 400-700 ℃ at the temperature rise rate to obtain the expanded carbon composite material.
The annealing temperature is 400-700 ℃. When the temperature is too low, the boric acid cannot be completely decomposed, the activation effect on the biomass is low, and the boron doping efficiency is low; when the temperature is too high, heteroatom functional groups in the biomass-derived carbon are severely destroyed, losing the pseudocapacitance advantage.
The rate of the temperature rise is 2 ℃ min -1 . When the temperature rise speed is too low, pyrolysis gas generated by boric acid is released slowly, and the activation efficiency of the carbon material is low; when the temperature rising speed is too fast, pyrolysis gas generated by boric acid is released fast, and carbon sheets are excessively puffed and crushed.
Drawings
FIG. 1 is a scanning electron micrograph of the final product synthesized in example 1.
FIG. 2 is a transmission electron micrograph of the final product synthesized in example 1.
Fig. 3 is an XRD pattern of the final product synthesized in examples 1, 2 and 3.
Fig. 4 is a raman spectrum of the final product synthesized in examples 1, 2 and 3.
FIG. 5 is a scanning electron micrograph of the final product synthesized in example 2.
FIG. 6 is a scanning electron micrograph of the final product synthesized in example 3.
Fig. 7 is a graph of the three-electrode CV curves of the final products synthesized in examples 1 and 2.
Figure 8 is a three electrode GCD plot of the final product synthesized in example 1.
Figure 9 is a three electrode GCD plot of the final product synthesized in example 2.
Fig. 10 is a graph of a three-electrode cycle of the final product synthesized in example 1.
Fig. 11 is a graph of a three-electrode cycle of the final product synthesized in example 2.
Fig. 12 is a graph of two-electrode CV of the final product synthesized in example 1.
Fig. 13 is a graph of the GCD of the final product synthesized in example 1.
Fig. 14 is a graph of two-electrode cycle curves of the final product synthesized in example 1.
Detailed Description
1. The preparation process comprises the following steps:
example 1:
1) Evenly mixing boric acid and ampullaria gigas egg juice in a mass ratio of 8: 1 in deionized water to obtain a mixed solution. And heating the mixed solution to 60 ℃, and continuously stirring to evaporate water in the mixed solution to obtain a crystalline solid.
2) Drying the crystalline solid at 2 deg.C for min -1 The temperature is raised to 600 ℃ at the temperature raising rate, and annealing is carried out for two hours to obtain the expanded carbon composite material.
3) Deionizing expanded carbon compositesRemoving B by washing with water for multiple times 2 O 3 And (4) obtaining a final product, namely the two-dimensional boron-nitrogen doped biomass derived carbon nanosheet.
From the scanning electron micrograph of the two-dimensional boron nitrogen doped biomass-derived carbon nanosheets synthesized in example 1 depicted in fig. 1, it can be seen that: the carbon material has an obvious two-dimensional structure, and the matte carbon surface of the carbon material is beneficial to the infiltration of electrolyte.
As can be seen from the transmission electron micrograph of the two-dimensional boron nitrogen doped biomass-derived carbon nanosheet synthesized in example 1 illustrated in fig. 2: the carbon material has a stable two-dimensional structure.
Example 2:
1) Uniformly mixing boric acid and the ampullaria gigas egg juice in a mass ratio of 5:1 in deionized water to obtain a mixed solution. The mixed solution was stirred continuously at 40 ℃ to evaporate water therein to obtain a crystalline solid.
2) Drying the crystalline solid at 2 deg.C for min -1 And the temperature is raised to 400 ℃ for two hours for annealing, so as to obtain the expanded carbon composite material.
3) Washing the expanded carbon composite material with deionized water for multiple times to remove B 2 O 3 And (5) template to obtain the final product.
From the diagram of the final product synthesized in example 2 of fig. 5, it can be seen that: due to the fact that the content of the boric acid is too low, a two-dimensional structure does not appear, and serious agglomeration phenomenon exists.
Example 3:
1) Uniformly mixing boric acid and ampullaria gigas egg juice in a mass ratio of 10. The mixed solution was stirred continuously at 100 ℃ to evaporate water therein to obtain a crystalline solid.
2) Drying the crystalline solid at 2 deg.C for min -1 And the temperature is raised to 700 ℃ and annealed for two hours to obtain the expanded carbon composite material.
3) Washing the expanded carbon composite material with deionized water for multiple times to remove B 2 O 3 And (5) template to obtain the final product.
From the scanning electron micrograph of the final product synthesized in example 3 of fig. 6, it can be seen that: due to the fact that the content of boric acid is too high, although the boric acid has an obvious two-dimensional structure, the nanosheet structure is unstable, and more breakage phenomena occur.
FIG. 3 is an XRD spectrum of the synthesized carbon material of examples 1, 2 and 3. Example 1 can be observed at 23.5 o And 43.3 o Obvious peak response appears, which respectively corresponds to the crystal faces of the graphite type broad peak (002) and the disordered type weak peak (100). In addition, its (002) peak showed a very slight shift towards lower angular directions, which may be due to the incorporation of the B heteroatom into the carbon structure.
FIG. 4 shows Raman spectra of the synthetic carbon materials of examples 1, 2 and 3. All three of them were observed to be located at 1344 cm -1 (D-band) and 1592 cm -1 The (G-band) response peak represents the disordered and graphitized texture of the carbon material. Among these, example 1 has the highest disordered structure content, representing that boron successfully enters the carbon lattice under appropriate conditions, destroying the graphitization of the carbon lattice.
2. The application comprises the following steps:
the products obtained in the above examples 1 and 2 were used as active materials to prepare working electrodes, and electrochemical performance tests were performed in a three-electrode system, with the following results:
FIG. 7 is a cyclic voltammogram of the carbon material prepared in example 1. As can be seen from fig. 7: the CV curves appear as non-rectangular shapes with pseudocapacitance responses, indicating that abundant heteroatom functionalities provide a large amount of faradaic reactive capacitance.
FIG. 8 is a cyclic voltammogram of the carbon material prepared in example 2. As can be seen from fig. 8: in addition, the CV area of example 2 is significantly smaller than the voltammogram of example 1.
FIG. 9 is a plot of constant current charge and discharge for the carbon material prepared in example 1. As can be seen from fig. 9: when the current density is from 0.5 ag -1 Increased to 10 ag -1 In this case, the capacitor retention ratio of example 1 was excellent, and the rate capability was excellent.
FIG. 10 is a plot of constant current charge and discharge for the carbon material prepared in example 1. As can be seen from fig. 10: the specific capacitance of example 2 is significantly less than that of example 1.
FIG. 11 shows carbon electrodes prepared in examples 1 and 2The material is 2 ag -1 A performance diagram and a mass specific capacity change diagram of 5000 cycles under current density. As can be seen from fig. 11: the sample obtained in example 1 was found to be 2A g -1 The capacitance after 5000 cycles of cycling at the current density was still close to 100%, which indicates that the carbon active material of the chlorella of example 1 has good cycling stability.
Fig. 12 is a cyclic voltammogram of a symmetric supercapacitor assembled with a carbon electrode material prepared in example 1. As can be seen in fig. 12: the CV curve shows a highly symmetrical rectangular-like CV curve at different scan rates, which indicates that the CV curve has high reversible energy storage response.
Fig. 13 is a plot of constant current charge and discharge for a symmetrical supercapacitor assembled with the carbon electrode material prepared in example 1. As can be seen from fig. 13: it has a highly symmetrical triangle-like shape under different current densities and has a higher specific capacitance.
Fig. 14 is a cycle plot of a symmetric supercapacitor assembled with the carbon electrode material prepared in example 1. As can be seen from fig. 14: the cycle test shows high electrochemical stability, and represents that the structure has obvious advantages in electrical energy storage.
In conclusion, the two-dimensional boron nitrogen doped biomass-derived carbon shows excellent electrochemical performance in the super capacitor. The following aspects may be explained in detail: the two-dimensional structure of the derivatized carbon facilitates rapid electron transfer, ensuring that appreciable transport kinetics are maintained at high current densities. The boron-nitrogen highly-doped carbon material has abundant pseudocapacitance active sites, and the energy storage capacity of the material is increased.
Claims (2)
1. A preparation method of a two-dimensional boron-nitrogen doped biomass derived carbon nanosheet is characterized by comprising the following steps: uniformly mixing boric acid and ampullaria gigas egg juice in deionized water, wherein the mixing mass ratio of the boric acid to the ampullaria gigas egg juice is 8: 1, stirring and evaporating at 40-100 ℃ to obtain a crystalline solid, drying the crystalline solid, and then carbonizing under the protection of nitrogen, wherein the carbonizing is to anneal the dried crystalline solid at 400-700 ℃ for 2 hours to obtain an expanded carbon composite material, and placing the expanded carbon composite material in a containerDissolving in deionized water to remove B 2 O 3 And (4) obtaining the two-dimensional boron-nitrogen doped biomass derived carbon nanosheet by using a template.
2. The production method according to claim 1, characterized in that: the carbonization treatment is carried out at 2 ℃ for min -1 The temperature rise rate of (a) increases the temperature.
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