CN113206246B - Biomass hard carbon cathode material of sodium ion battery and preparation method thereof - Google Patents
Biomass hard carbon cathode material of sodium ion battery and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a biomass hard carbon negative electrode material of a sodium ion battery and a preparation method thereof. The hard carbon precursor material and the heteroatom organic compound are fully and uniformly mixed by adopting a ball milling method, so that the full reaction in the material pyrolysis carbonization process is facilitated; heteroatom doping can provide more active sites, and is beneficial to improving the sodium storage performance of the hard carbon material; the co-doping of various heteroatoms can generate a synergistic effect, so that the electrochemical performance of the material is obviously improved; the heating rate in the pyrolysis carbonization process is reduced, the surface defects of the hard carbon material are reduced, the irreversible capacity of the material is reduced, and the capacity and the first coulombic efficiency of the material are effectively improved.
Description
Technical Field
The invention belongs to the field of preparation of electrode materials of sodium-ion batteries, and particularly relates to a biomass hard carbon negative electrode material of a sodium-ion battery and a preparation method thereof.
Background
Lithium ion batteries have become one of the main electrochemical energy storage devices due to their advantages of high energy density, long cycle life, etc., and are widely used in the fields of portable electronic products, electric vehicles, renewable energy storage, etc. However, due to the limitations of lithium resource shortage, high cost, and the like, the development and application of lithium ion batteries in some large energy storage systems are hindered, and therefore, it is very important to develop a novel environment-friendly energy conversion method and storage technology. In various novel energy storage systems, the sodium ion battery has the advantages of low production cost, high safety, rich element reserves and the like, and meanwhile, the sodium ion battery has the working principle similar to that of a lithium ion battery, and the sodium ion battery is considered to be an ideal novel energy storage device.
The hard carbon material has large interlayer spacing and specific surface area, and shows the advantages of high capacity and low potential, which are widely noticed by researchers and considered as one of the most promising negative electrode materials of the sodium-ion battery. The biomass material is used as one of precursors of the hard carbon material, has a natural microstructure and is rich in carbon elements, and the derived carbon material has large interlamellar spacing, high disorder degree and rich active sites, has the advantages of low cost, reproducibility, environmental protection and the like, draws wide attention, and is regarded as a reliable large-scale carbon source.
In the research report of hard carbon materials, heteroatom doping is considered to be an effective method for effectively improving the electrochemical performance of the hard carbon negative electrode material of the sodium ion battery. The nitrogen-doped carbon microspheres prepared by simple hydrothermal method by strictly using oats as a carbon source and a nitrogen source at the university of east China have high reversible specific capacity and good cycling stability, and still have the reversible specific capacity of 104mA h/g after being cycled for 12500 times under the current density of 10A/g. The king of Nanjing university and the like prepares the fluorine-doped hard carbon material by using lotus petioles as a carbon source and a fluorine source and by a high-temperature carbonization method under the protection of argon, shows initial charging specific capacity of 230mAh/g under the current density of 50mA/g, and has excellent cycling stability. The nitrogen and sulfur co-doped hard carbon material is successfully prepared from gold and the like of the university of China science and technology through a one-step pyrolysis method, the nitrogen and sulfur co-doped electrochemical performance is superior to that of single heteroatom doping, the electrochemical performance of 223mA h/g is still achieved after the nitrogen and sulfur co-doped hard carbon material is circulated for 2000 times under the current density of 1A/g, and the nitrogen and sulfur co-doped hard carbon material has excellent rate capability and cycle stability.
At present, methods for doping a hard carbon material with a heteroatom organic compound are mostly focused on methods such as a hydrothermal method and a one-step pyrolysis method, most of the doped materials can obviously improve the electrochemical performance of the material, but the problems of insufficient capacity, low first coulombic efficiency and the like still exist, and therefore, the improvement of the capacity and the first coulombic efficiency of the material becomes one of the key problems of the hard carbon material.
Disclosure of Invention
The invention aims to provide a biomass hard carbon negative electrode material of a sodium ion battery and a preparation method thereof, and at least achieves the purpose of further improving the capacity and the first coulombic efficiency of the material.
The preparation method of the biomass hard carbon negative electrode material of the sodium-ion battery provided by the invention comprises the following steps.
Placing a biomass raw material in an ultrasonic cleaning machine for ultrasonic washing, and then performing suction filtration and drying to obtain a biomass precursor;
transferring the obtained biomass precursor to a muffle furnace, performing pyrolysis and pre-carbonization in the atmosphere of air, naturally cooling, placing in a crusher, and crushing to powder to obtain a pre-carbonization product;
step three, uniformly mixing the pre-carbonized product and the heteroatom organic compound according to a proportion, placing the obtained mixture in a planetary ball mill, and uniformly ball-milling to obtain a heteroatom-doped hard carbon precursor;
and step four, transferring the heteroatom-doped hard carbon precursor obtained in the step three into a high-temperature tube furnace, carbonizing at high temperature under the protection of inert gas, naturally cooling, placing into an acid solution for soaking, washing with deionized water and ethanol to be neutral, and placing the obtained product into a vacuum drying oven for vacuum drying to obtain the heteroatom-doped biomass-derived hard carbon material.
Further, in the first step, the biomass raw material is selected from one or more of camphor wood, bamboo wood, willow wood, peach wood and rosewood.
Further, in the step one, the ultrasonic time in the ultrasonic cleaning machine is 3-12 hours; drying by adopting an air-blast drying oven, wherein the temperature of the air-blast drying oven is 80 ℃, and the drying time is 12 hours.
Further, in the second step, when the pyrolysis pre-carbonization is carried out, the heating rate is 3-10 ℃/min, the pyrolysis temperature is 250-350 ℃, and the heat preservation time is 1-5 hours. Preferably, the heating rate is 3 ℃/min, the pyrolysis temperature is 250-350 ℃, and the heat preservation time is 2 hours.
Further, in the third step, the heteroatom organic compound is selected from one or more of urea, melamine, tetramethylurea, thiourea, thioacetamide and polyvinylidene fluoride, the mass ratio of the heteroatom organic compound to the pre-carbonized product is 0.1-1, and the preferred mass ratio of the heteroatom organic compound to the pre-carbonized product is 0.5-1.
Furthermore, in the third step, the rotating speed of the planetary ball mill is 500-800rpm, and the ball milling time is 8-24 hours.
Further, in the fourth step, during high-temperature carbonization, the temperature rise rate is 0.5-10 ℃/min, the pyrolysis temperature is 800-1600 ℃, and the heat preservation time is 2-6 hours. Preferably, the temperature rise rate is 0.5-3 ℃/min during high-temperature carbonization.
Further, in the fourth step, the acid solution is selected from one of dilute hydrochloric acid, dilute sulfuric acid or dilute nitric acid, the concentration of the acid solution is 1-3mol/L, and the soaking time is 3-12 hours; the temperature of the vacuum drying oven is 80 ℃, and the drying time is 12 hours.
The inert gas in the fourth step is selected from one of nitrogen, argon or helium.
According to another aspect of the invention, a biomass hard carbon negative electrode material of the sodium ion battery, which is prepared by the method, is provided.
According to another aspect of the invention, a sodium ion battery is provided, which comprises a negative electrode prepared from the above sodium ion battery biomass hard carbon negative electrode material.
The invention improves the existing preparation process of the biomass hard carbon cathode material of the sodium ion battery to obtain the heteroatom-doped biomass-derived hard carbon material for the sodium ion battery. By adopting a method of ball milling assisted heteroatom doping and low heating rate carbonization, the method of ball milling enables a hard carbon precursor material and a heteroatom organic compound to be fully and uniformly mixed, and is beneficial to full reaction in the material pyrolysis carbonization process; heteroatom doping can provide more active sites, and is beneficial to improving the sodium storage performance of the hard carbon material; the co-doping of various heteroatoms can generate a synergistic effect, so that the electrochemical performance of the material is obviously improved; the heating rate in the pyrolysis carbonization process is reduced, the surface defects of the hard carbon material are reduced, the irreversible capacity of the material is reduced, and the capacity and the first coulombic efficiency of the material are effectively improved.
The preparation method is simple, adopts easily-obtained and low-cost wood biomass as the carbon source, is environment-friendly, and is suitable for large-scale production.
Drawings
FIG. 1 is an XRD pattern of a heteroatom-doped biomass-derived hard carbon anode material prepared in examples 3,4,5 of the present invention;
fig. 2 is a Raman plot of a heteroatom-doped biomass-derived hard carbon anode material prepared according to examples 3,4,5 of the present invention;
fig. 3 is a CV curve graph of the heteroatom-doped derivatized biomass-derived hard carbon anode material prepared in example 1 of the present invention;
fig. 4 is a first charge-discharge curve diagram of the heteroatom-doped biomass-derived hard carbon negative electrode material prepared in example 4 of the present invention;
fig. 5 is a graph of the cycle performance of the heteroatom-doped biomass-derived hard carbon anode material prepared in example 1 of the present invention;
fig. 6 is a graph of the cycle performance of the heteroatom-doped biomass-derived hard carbon anode material prepared in example 4 of the present invention;
fig. 7 is a graph of the cycling performance of the heteroatom-doped biomass-derived hard carbon anode material prepared in example 6 of the present invention;
fig. 8 is a rate capability plot for the heteroatom-doped biomass-derived hard carbon anode material prepared in example 1 of the present invention;
fig. 9 is a rate performance graph of the heteroatom-doped biomass-derived hard carbon anode material prepared in example 4 of the present invention;
fig. 10 is a rate performance graph of the heteroatom-doped biomass-derived hard carbon anode material prepared in example 6 of the present invention.
Detailed Description
The claimed solution is further illustrated by the following examples. However, the examples and comparative examples are intended to illustrate the embodiments of the present invention without departing from the scope of the subject matter of the present invention, and the scope of the present invention is not limited by the examples. Unless otherwise specifically indicated, the materials and reagents used in the present invention are available from commercial products in the art.
Example 1
(1) The selected biomass is bamboo and wood, the bamboo and wood are placed in an ultrasonic cleaning machine for ultrasonic washing for 6 hours, and then the bamboo and wood are placed in a forced air drying oven for drying for 12 hours at 80 ℃ after suction filtration, so that a biomass precursor is obtained;
(2) Transferring the biomass precursor obtained in the step (1) into a muffle furnace, heating to 250 ℃ at a heating rate of 3 ℃/min in the atmosphere of air, preserving heat for 2 hours, naturally cooling, placing in a pulverizer, and pulverizing into powder to obtain a pre-carbonized product;
(3) Uniformly mixing the pre-carbonized product obtained in the step (2) with urea according to the mass ratio of 2;
(4) And (3) transferring the precursor of the nitrogen-doped hard carbon material obtained in the step (3) into a high-temperature tube furnace, heating to 1000 ℃ at a heating rate of 1 ℃/min under the protection of argon, preserving the heat for 2 hours, naturally cooling, placing into a dilute hydrochloric acid solution with the concentration of 2M for soaking for 3 hours, washing with deionized water and ethanol to be neutral, and placing the obtained product into a vacuum drying oven for vacuum drying for 12 hours at the temperature of 80 ℃ to obtain the nitrogen-doped hard carbon material.
Example 2
(1) The method comprises the following steps of (1) placing selected biomass into an ultrasonic cleaning machine for ultrasonic washing for 12 hours, then carrying out suction filtration, and then placing the biomass into a forced air drying oven for drying for 12 hours at 80 ℃ to obtain a biomass precursor;
(2) Transferring the biomass precursor obtained in the step (1) into a muffle furnace, heating to 300 ℃ at a heating rate of 3 ℃/min in the atmosphere of air, preserving heat for 2 hours, naturally cooling, placing in a pulverizer, and pulverizing into powder to obtain a pre-carbonized product;
(3) Uniformly mixing the pre-carbonized product obtained in the step (2) with urea according to the mass ratio of 2;
(4) And (4) transferring the precursor of the nitrogen-doped hard carbon material obtained in the step (3) into a high-temperature tube furnace, heating to 1300 ℃ at a heating rate of 1 ℃/min under the protection of argon, preserving the heat for 2 hours, naturally cooling, placing into a dilute hydrochloric acid solution with the concentration of 2M for soaking for 6 hours, washing with deionized water and ethanol to be neutral, and placing the obtained product into a vacuum drying oven for vacuum drying for 12 hours at the temperature of 80 ℃ to obtain the nitrogen-doped hard carbon material.
Example 3
(1) The method comprises the following steps of (1) placing selected biomass into an ultrasonic cleaning machine for ultrasonic washing for 12 hours, then carrying out suction filtration, and then placing the biomass into a forced air drying oven for drying for 12 hours at 80 ℃ to obtain a biomass precursor;
(2) Transferring the biomass precursor obtained in the step (1) into a muffle furnace, heating to 300 ℃ at a heating rate of 3 ℃/min in the atmosphere of air, preserving heat for 2 hours, naturally cooling, placing in a pulverizer, and pulverizing into powder to obtain a pre-carbonized product;
(3) Uniformly mixing the pre-carbonized product obtained in the step (2) with melamine according to the mass ratio of 2;
(4) And (4) transferring the precursor of the nitrogen-doped hard carbon material obtained in the step (3) into a high-temperature tube furnace, heating to 1300 ℃ at a heating rate of 1 ℃/min under the protection of argon, preserving the heat for 2 hours, naturally cooling, placing into a dilute hydrochloric acid solution with the concentration of 2M for soaking for 6 hours, washing with deionized water and ethanol to be neutral, and placing the obtained product into a vacuum drying oven for vacuum drying for 12 hours at the temperature of 80 ℃ to obtain the nitrogen-doped hard carbon material.
Example 4
(1) The method comprises the following steps of (1) placing selected biomass into an ultrasonic cleaning machine for ultrasonic washing for 12 hours, then carrying out suction filtration, and then placing the biomass into a forced air drying oven for drying for 12 hours at 80 ℃ to obtain a biomass precursor;
(2) Transferring the biomass precursor obtained in the step (1) into a muffle furnace, heating to 300 ℃ at a heating rate of 3 ℃/min in the atmosphere of air, preserving heat for 2 hours, naturally cooling, placing in a pulverizer, and pulverizing into powder to obtain a pre-carbonized product;
(3) Uniformly mixing the pre-carbonized product obtained in the step (2) with thiourea according to the mass ratio of 1;
(4) And (4) transferring the nitrogen and sulfur co-doped hard carbon material precursor obtained in the step (3) into a high-temperature tube furnace, heating to 1300 ℃ at a heating rate of 1 ℃/min under the protection of argon, preserving heat for 2 hours, naturally cooling, placing into a 2M dilute hydrochloric acid solution, soaking for 6 hours, washing with deionized water and ethanol to be neutral, and placing the obtained product into a vacuum drying oven, and performing vacuum drying at 80 ℃ for 12 hours to obtain the nitrogen and sulfur co-doped hard carbon material.
Example 5
(1) The method comprises the following steps of (1) placing selected biomass into an ultrasonic cleaning machine for ultrasonic washing for 12 hours, then carrying out suction filtration, and then placing the biomass into a forced air drying oven for drying for 12 hours at 80 ℃ to obtain a biomass precursor;
(2) Transferring the biomass precursor obtained in the step (1) into a muffle furnace, heating to 300 ℃ at a heating rate of 3 ℃/min in the atmosphere of air, preserving heat for 2 hours, naturally cooling, placing in a pulverizer, and pulverizing into powder to obtain a pre-carbonized product;
(3) Uniformly mixing the pre-carbonized product obtained in the step (2) with polyvinylidene fluoride according to the mass ratio of 2;
(4) And (4) transferring the fluorine-doped hard carbon material precursor obtained in the step (3) into a high-temperature tube furnace, heating up to 1000 ℃ at a heating rate of 1 ℃/min under the protection of argon, preserving heat for 2 hours, naturally cooling, placing into a dilute hydrochloric acid solution with the concentration of 2M for soaking for 6 hours, washing with deionized water and ethanol to be neutral, and placing the obtained product into a vacuum drying oven for vacuum drying at 80 ℃ for 12 hours to obtain the fluorine-doped hard carbon material.
Example 6
(1) The selected biomass is peach wood, the peach wood is placed in an ultrasonic cleaning machine for ultrasonic washing for 12 hours, and then the peach wood is placed in a forced air drying oven for drying for 12 hours at 80 ℃ after suction filtration, so that a biomass precursor is obtained;
(2) Transferring the biomass precursor obtained in the step (1) into a muffle furnace, heating to 300 ℃ at a heating rate of 3 ℃/min in the air atmosphere, preserving heat for 2 hours, naturally cooling, placing into a pulverizer, and pulverizing into powder to obtain a pre-carbonized product;
(3) Uniformly mixing the pre-carbonized product obtained in the step (2) with thioacetamide according to the mass ratio of 2;
(4) And (4) transferring the nitrogen and sulfur co-doped hard carbon material precursor obtained in the step (3) into a high-temperature tube furnace, heating up at 1200 ℃ at a heating rate of 1 ℃/min under the protection of argon, keeping the temperature for 2 hours, naturally cooling, placing the precursor into a dilute hydrochloric acid solution with the concentration of 2M for soaking for 6 hours, washing the precursor with deionized water and ethanol to be neutral, and placing the obtained product into a vacuum drying oven for vacuum drying at 80 ℃ for 12 hours to obtain the nitrogen and sulfur co-doped hard carbon material.
Example 7
(1) The selected biomass is peach wood, the peach wood is placed in an ultrasonic cleaning machine for ultrasonic washing for 12 hours, and then the peach wood is placed in a forced air drying oven for drying for 12 hours at 80 ℃ after suction filtration, so that a biomass precursor is obtained;
(2) Transferring the biomass precursor obtained in the step (1) into a muffle furnace, heating to 300 ℃ at a heating rate of 3 ℃/min in the atmosphere of air, preserving heat for 2 hours, naturally cooling, placing in a pulverizer, and pulverizing into powder to obtain a pre-carbonized product;
(3) Uniformly mixing the pre-carbonized product obtained in the step (2) with melamine and polyvinylidene fluoride according to the mass ratio of 4;
(4) And (4) transferring the nitrogen and fluorine co-doped hard carbon material precursor obtained in the step (3) into a high-temperature tube furnace, heating up to 1200 ℃ at a heating rate of 3 ℃/min under the protection of argon, preserving heat for 2 hours, naturally cooling, placing into a dilute hydrochloric acid solution with the concentration of 2M for soaking for 6 hours, washing with deionized water and ethanol to be neutral, and placing the obtained product into a vacuum drying oven for vacuum drying at 80 ℃ for 12 hours to obtain the nitrogen and fluorine co-doped hard carbon material.
Example 8
(1) The method comprises the following steps of (1) placing selected biomass as rosewood into an ultrasonic cleaning machine for ultrasonic washing for 3 hours, then carrying out suction filtration, and then placing the washed rosewood into a forced air drying oven for drying for 12 hours at 80 ℃ to obtain a biomass precursor;
(2) Transferring the biomass precursor obtained in the step (1) into a muffle furnace, heating to 350 ℃ at a heating rate of 3 ℃/min in the atmosphere of air, preserving heat for 2 hours, naturally cooling, placing in a pulverizer, and pulverizing into powder to obtain a pre-carbonized product;
(3) Uniformly mixing the pre-carbonized product obtained in the step (2) with thiourea according to the mass ratio of 10;
(4) And (4) transferring the nitrogen and sulfur co-doped hard carbon material precursor obtained in the step (3) into a high-temperature tube furnace, heating to 800 ℃ at a heating rate of 0.5 ℃/min under the protection of nitrogen, preserving heat for 6 hours, naturally cooling, placing into a 1M dilute hydrochloric acid solution, soaking for 12 hours, washing with deionized water and ethanol to be neutral, and placing the obtained product into a vacuum drying oven, and drying at 80 ℃ for 12 hours in vacuum to obtain the nitrogen and sulfur co-doped hard carbon material.
Example 9
The difference from the embodiment 8 is only that in the step (4), the nitrogen and sulfur co-doped hard carbon material precursor is transferred to a high-temperature tube furnace, the temperature is raised to 1600 ℃ at a heating rate of 1 ℃/min under the protection of helium, the temperature is kept for 2 hours, the precursor is placed in a dilute nitric acid solution with the concentration of 3M for soaking for 6 hours after natural cooling, the solution is washed to be neutral by deionized water and ethanol, and the obtained product is placed in a vacuum drying oven for vacuum drying for 12 hours at 80 ℃ to obtain the nitrogen and sulfur co-doped hard carbon material.
Comparative example 1
Comparative example 4, comparative example 1 provides a method for preparing an undoped heteroatom hard carbon material.
(1) The method comprises the following steps of (1) placing selected biomass into an ultrasonic cleaning machine for ultrasonic washing for 12 hours, then carrying out suction filtration, and then placing the biomass into a forced air drying oven for drying for 12 hours at 80 ℃ to obtain a biomass precursor;
(2) Transferring the biomass precursor obtained in the step (1) into a muffle furnace, heating to 300 ℃ at a heating rate of 3 ℃/min in the atmosphere of air, preserving heat for 2 hours, naturally cooling, placing in a pulverizer, and pulverizing into powder to obtain a pre-carbonized product;
(3) Placing the pre-carbonized product obtained in the step (2) in a planetary ball mill, and carrying out ball milling for 12 hours at the rotating speed of 800rpm to obtain a hard carbon material precursor;
(4) And (4) transferring the hard carbon material precursor obtained in the step (3) into a high-temperature tube furnace, heating to 1300 ℃ at a heating rate of 1 ℃/min under the protection of argon, preserving the heat for 2 hours, naturally cooling, placing into a dilute hydrochloric acid solution with the concentration of 2M for soaking for 6 hours, washing with deionized water and ethanol to be neutral, and placing the obtained product into a vacuum drying oven for vacuum drying for 12 hours at the temperature of 80 ℃ to obtain the hard carbon material.
Comparative example 2
Comparative example 4, comparative example 2 provides a method for preparing a high-heating-rate nitrogen carbide and sulfur carbide co-doped hard carbon material.
(1) The method comprises the following steps of (1) placing selected biomass into an ultrasonic cleaning machine for ultrasonic washing for 12 hours, then carrying out suction filtration, and then placing the biomass into a forced air drying oven for drying for 12 hours at 80 ℃ to obtain a biomass precursor;
(2) Transferring the biomass precursor obtained in the step (1) into a muffle furnace, heating to 300 ℃ at a heating rate of 3 ℃/min in the air atmosphere, preserving heat for 2 hours, naturally cooling, placing into a pulverizer, and pulverizing into powder to obtain a pre-carbonized product;
(3) Uniformly mixing the pre-carbonized product obtained in the step (2) with thiourea according to the mass ratio of 1;
(4) And (4) transferring the nitrogen and sulfur co-doped hard carbon material precursor obtained in the step (3) into a high-temperature tube furnace, heating to 1300 ℃ at a heating rate of 5 ℃/min under the protection of argon, preserving heat for 2 hours, naturally cooling, placing into a 2M dilute hydrochloric acid solution, soaking for 6 hours, washing with deionized water and ethanol to be neutral, and placing the obtained product into a vacuum drying oven, and performing vacuum drying at 80 ℃ for 12 hours to obtain the nitrogen and sulfur co-doped hard carbon material.
Uniformly grinding the heteroatom-doped biomass-derived hard carbon material obtained in each example and comparative example, acetylene black and sodium carboxymethylcellulose (CMC) according to the mass ratio of 8.
The electrode sheet obtained above was used as a negative electrode, a glass fiber (Whitman, GF/D) disc having a diameter of 19mm was used as a separator, a sodium metal sheet having a diameter of 12mm and a thickness of 0.2mm was used as a counter electrode and a reference electrode, and an electrolyte was 1mol/L sodium perchlorate/ethylene carbonate/dimethyl carbonate solution, and a sodium ion battery was assembled in a glove box filled with high-purity argon gas in accordance with the structure of a CR2016 standard button cell, and the battery was subjected to charge and discharge tests on a battery test platform at a current density of 30mA/g, and the results are shown in Table 1.
TABLE 1 main parameters and electrochemical Properties of examples 1 to 7 and comparative examples 1 to 2
| Biomass | Doping type/agent | Pyrolysis temperature/time | Rate of temperature rise | Initial specific capacity | First coulombic efficiency | |
| Example 1 | Bamboo and wood | Nitrogen doped/ |
1000℃/ |
1℃/min | 246.7mAh/g | 65% |
| Example 2 | Camphorwood | Nitrogen doped/urea | 1300℃/ |
1℃/min | 274.3mAh/g | 69% |
| Example 3 | Camphorwood | Nitrogen doped/melamine | 1300℃/ |
1℃/min | 284.4 mAh/g | 69% |
| Example 4 | Camphorwood | Nitrogen and sulfur co-doped/thiourea | 1300℃/ |
1℃/min | 303.7mAh/g | 70.7% |
| Example 5 | Camphorwood | Fluorine doped/ |
1000℃/ |
1℃/min | 278.2mAh/ |
68% |
| Example 6 | Peach wood | Nitrogen and sulfur codoped/ |
1200℃/ |
1℃/min | 268.2 mAh/g | 75% |
| Example 7 | Peach wood | Nitrogen and fluorine co-doping/polyvinylidene fluoride and |
1200℃/ |
1℃/min | 256.3mAh/g | 72% |
| Comparative example 1 | Camphorwood | Is not doped | 1300℃/ |
1℃/min | 268.2mAh/ |
68% |
| Comparative example 2 | Camphorwood | Nitrogen and sulfur co-doped/thiourea | 1300℃/ |
5℃/min | 288.2mAh/g | 61% |
The XRD pattern shown in figure 1 can see that the characteristic peaks of the three different doping type materials of examples 3,4 and 5 are all around 23 degrees and 43 degrees, no other obvious impurity peaks exist, and the characteristic peaks correspond to (002) diffraction crystal faces and (100) diffraction crystal faces respectively, which indicates that the three materials belong to amorphous carbon materials; the interlayer spacing of the three materials is respectively 0.379nm, 0.386nm and 0.382nm through Bragg equation analysis and calculation, and the nitrogen and sulfur co-doped hard carbon material prepared in the embodiment 4 has larger interlayer spacing and is more beneficial to the embedding and the extraction of sodium ions.
The Raman graph shown in fig. 2 shows that the three different doping types of materials of examples 3,4 and 5 all have two distinct characteristic peaks near 1350cm-1 and 1580cm-1, which correspond to the D peak and the G peak respectively, and indicate that the three materials all belong to amorphous carbon materials; by analyzing and calculating the integral area ratio of the D peak and the G peak, ID/IG representing the graphitization degrees of the three different doping type materials are respectively 1.06, 0.95, and 1.13, and the nitrogen-sulfur co-doped hard carbon material prepared in example 4 has a higher graphitization degree.
The CV curve graph shown in fig. 3 can see that the material of example 1 shows two distinct reduction peaks at 0.7V and 1.4V in the first round of charging and discharging and disappears after the second round, indicating that electrolyte decomposition and sodium ion deposition lead to the formation of SEI film when charging and discharging are authorized; the curves of the second and third circles almost coincide after the first cycle, indicating that the material has a high degree of electrochemical reversibility.
As can be seen from the charging and discharging curve diagram shown in FIG. 4, the material of example 3 shows 70.7% of first coulombic efficiency and 303.7mAh/g of initial specific capacity in a voltage region of 0-2V under the current density of 30mA/g, and has an obvious charging and discharging platform.
The cycle performance graphs shown in fig. 5, 6 and 7 show that the three different biomass materials of examples 1, 4 and 6 all show good cycle stability and capacity retention rate, wherein the nitrogen and sulfur co-doped camphorwood biomass-derived hard carbon material of example 4 has the highest reversible specific capacity, and shows the reversible specific capacity of 258.1mAh/g after 100 cycles under the current density of 30mA/g, and the capacity retention rate is 85%.
The rate performance graphs shown in fig. 8, 9 and 10 show that the three different biomass materials of examples 1, 4 and 6 all show good rate performance at 30mA/g, 100 mA/g, 200 mA/g, 500 mA/g, 1000mA/g and then 30mA/g, wherein the nitrogen and sulfur co-doped camphorwood biomass-derived hard carbon material of example 4 shows the highest reversible specific capacity no matter under small current or large current, and still has the reversible specific capacity of 103mAh/g under the large current density of 1000 mA/g.
As shown in table 1, by comparing example 4 with comparative example 1, it can be seen that the initial specific capacity of the material is increased from 268.2mAh/g to 303.7mAh/g and the first coulombic efficiency is increased from 68% to 70.7% by co-doping the hard carbon material with two kinds of heteroatoms, namely nitrogen and sulfur; by comparing the example 4 with the comparative example 2, the initial specific capacity of the material is improved from 288.2 mAh/g to 303.7mAh/g by reducing the temperature rise rate of the hard carbon material during pyrolysis and carbonization, and the first coulombic efficiency is improved from 61% to 70.7%; by carrying out heteroatom doping on the hard carbon material and reducing the heating rate, the capacity and the first coulombic efficiency of the material can be effectively improved, and the electrochemical performance of the material is improved.
Claims (6)
1. A preparation method of a biomass hard carbon negative electrode material of a sodium ion battery is characterized by comprising the following steps:
placing a biomass raw material in an ultrasonic cleaning machine for ultrasonic washing, and then performing suction filtration and drying to obtain a biomass precursor; the biomass raw material is selected from one or more of camphorwood, bamboo wood, willow, peach wood or rosewood;
transferring the obtained biomass precursor to a muffle furnace, performing pyrolysis and pre-carbonization in the atmosphere of air, naturally cooling, placing in a crusher, and crushing to powder to obtain a pre-carbonization product; when in pyrolysis and pre-carbonization, the heating rate is 3-10 ℃/min, the pyrolysis temperature is 250-350 ℃, and the heat preservation time is 1-5 hours;
step three, uniformly mixing the pre-carbonized product and the heteroatom organic compound according to a proportion, placing the obtained mixture in a planetary ball mill, and uniformly ball-milling to obtain a heteroatom-doped hard carbon precursor; the heteroatom organic compound is selected from one or more of urea, melamine, tetramethylurea, thiourea, thioacetamide and polyvinylidene fluoride, and the mass ratio of the heteroatom organic compound to the pre-carbonized product is 0.1-1;
transferring the heteroatom-doped hard carbon precursor obtained in the step three into a high-temperature tube furnace, and carrying out high-temperature carbonization under the protection of inert gas, wherein during the high-temperature carbonization, the heating rate is 1 ℃/min, the pyrolysis temperature is 1200-1300 ℃, and the heat preservation time is 2 hours; and naturally cooling, placing the obtained product in an acid solution for soaking, washing the obtained product to be neutral by using deionized water and ethanol, and placing the obtained product in a vacuum drying oven for vacuum drying to obtain the heteroatom-doped biomass-derived hard carbon material.
2. The method of claim 1, wherein: in the first step, the ultrasonic time in the ultrasonic cleaning machine is 3-12 hours; and drying by adopting an air-blast drying oven, wherein the temperature of the air-blast drying oven is 80 ℃, and the drying time is 12 hours.
3. The method of claim 2, wherein: in the third step, the rotating speed of the planetary ball mill is 500-800rpm, and the ball milling time is 8-24 hours.
4. The method of claim 3, wherein: in the fourth step, the acid solution is selected from one of dilute hydrochloric acid, dilute sulfuric acid or dilute nitric acid, the concentration of the acid solution is 1-3mol/L, and the soaking time is 3-12 hours; the temperature of the vacuum drying oven is 80 ℃, and the drying time is 12 hours.
5. The biomass hard carbon negative electrode material of the sodium-ion battery prepared by the method of any one of claims 1 to 4.
6. A sodium ion battery, characterized by: comprises preparing the biomass hard carbon negative electrode material of the sodium-ion battery as claimed in claim 5 to obtain a negative electrode.
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