CN114335524A - Heteroatom-doped porous carbon nanobelt material and preparation method and application thereof - Google Patents
Heteroatom-doped porous carbon nanobelt material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of nano composite materials, in particular to a heteroatom-doped porous carbon nanobelt material and a preparation method and application thereof. The porous carbon nanobelt material is prepared by electrostatic spinning of a spinning solution obtained by selecting a water-soluble carbon precursor, an alkali metal oxysalt and water. Hetero atoms doped with the porous carbon nanobelt material are uniformly distributed in the carbon material and can be used as nucleation sites to facilitate uniform deposition of metal lithium on the surface and inhibit formation of dendritic crystals; the porous and nano-belt structure widens the insertion and extraction channels of lithium ions in the circulation process, and ensures the rapid transmission and deposition of the lithium ions; the continuous and stable three-dimensional conductive network structure is not only beneficial to the rapid transmission of electrons, but also can accommodate a large amount of metal lithium deposition and buffer the volume expansion. Therefore, when the heteroatom-doped porous carbon nanobelt material obtained by the invention is used as a lithium ion battery cathode material, excellent energy storage and quick charge performances are shown.
Description
Technical Field
The invention relates to the technical field of nano composite materials, in particular to a heteroatom-doped porous carbon nanobelt material and a preparation method and application thereof.
Background
With the exhaustion of energy sources and the increasingly prominent global problems of environmental pollution and the like, electric energy is increasingly regarded as clean energy. The lithium ion battery is the most widely applied secondary battery at present, can be reversibly charged and discharged, has the advantages of long cycle life, high working voltage, high energy density, light transportation and the like, and occupies an important position in the field of energy storage devices. Meanwhile, along with the gradual development and popularization of the field of electric vehicles, how to realize rapid charging also becomes a key research direction in the field of electric vehicles, if the rapid storage of electric energy can be realized, the buffering time is greatly shortened, the electric energy can better replace the traditional energy, and the method has important significance for realizing low carbon.
However, the current electrode materials of lithium ion batteries still have some defects, which limit the further development of the lithium ion batteries in the field of quick charge. Different from graphite cathode materials, the porous carbon nanofiber material doped with heteroatoms can be used as an excellent lithium ion battery fast charging cathode material, so that the rapid storage of lithium ions is realized, and the formation of metal lithium dendrites is inhibited. However, the existing porous carbon nanofiber material often has the problems of poor structural continuity, limited heteroatom doping effect, residual inactive metal precursor and the like, and the improvement of the specific surface area, the heteroatom doping amount and the conductivity of the porous carbon nanofiber material is influenced, so that the improvement of the reversible capacity and the rate capability when the porous carbon nanofiber material is used as a negative electrode material is influenced. In addition, the limited lithium-philic sites and the unstable framework structure cannot effectively inhibit the formation of lithium dendrites and buffer volume expansion, so that the battery has a short-circuit risk, and the safety and stability of the battery are seriously affected.
Disclosure of Invention
Therefore, the technical problem to be solved by the present invention is to overcome the problem that the prior art cannot effectively solve the problems of reversible capacity and rate capability of the negative electrode material of the lithium ion battery, including: the problems of rapid transmission of lithium ions and electrons in the negative electrode material, uneven deposition of metal lithium on the surface of an electrode, easy formation of dendrite, irreversible volume expansion and the like. According to the invention, a three-dimensional porous nano-belt structure is designed, and water-soluble alkali metal oxysalt is selected as an auxiliary agent, so that alkali metal ions can be directly dissolved and removed by water, the obtained material is ensured to have no inactive metal residue, high reversible capacity is favorably shown when the material is used as a negative electrode material, the cycle stability and the rate capability are improved, the obtained porous nano-belt structure is doped with abundant heteroatoms, the doped heteroatoms are uniformly distributed in a carbon material, and the doped heteroatoms can be used as nucleation sites to be favorable for uniform deposition of metal lithium on the surface and inhibit formation of dendritic crystals; the porous and nano-belt structure widens the insertion and extraction channels of lithium ions in the circulation process, and ensures the rapid transmission and deposition of the lithium ions; the continuous and stable three-dimensional conductive network structure is not only beneficial to the rapid transmission of electrons, but also can accommodate a large amount of metal lithium deposition and buffer the volume expansion. Therefore, when the heteroatom-doped porous carbon nanobelt material is used as a lithium ion battery cathode material, excellent energy storage and quick charge performances are shown.
Therefore, the invention provides the following technical scheme:
the invention provides a heteroatom-doped porous carbon nanobelt material, which is doped with two or more heteroatoms, wherein the heteroatoms comprise: nitrogen, oxygen, sulfur, phosphorus or chlorine;
the aspect ratio of the porous carbon nanoribbon is 1000: 1-8000: 1; the width range is 0.05 μm to 10 μm.
Preferably, the nitrogen atom percentage is 0.2-10 at.%;
and/or the atomic percent of oxygen is 5-25 at.%;
and/or the atomic percent of sulfur is 0.1 to 10 at.%;
and/or the atomic percent of phosphorus is 0.1 to 10 at.%;
and/or the atomic percent of the chlorine is 0.1 to 10 at.%.
Preferably, the thickness range is 1 nm to 100 nm.
Preferably, the pore diameter range of the porous carbon nanoribbon is 0.5 nm-50 nm;
and/or a pore volume in the range of 0.1 cm3/g ~1.5 cm3/g；
And/or a specific surface area of 600 m2/g ~2000 m2/g。
The invention also provides a preparation method of the heteroatom-doped porous carbon nanobelt material, which comprises the following steps of: mixing a water-soluble carbon precursor, alkali metal oxysalt and water, taking the mixed solution as a spinning solution, carrying out electrostatic spinning to obtain protofilaments, and carrying out post-treatment on the obtained protofilaments to prepare the porous carbon nanobelt material.
Preferably, the water-soluble carbon precursor includes: at least one of polyaspartic acid, serine, glycine, vitamin B1, folic acid, carboxymethylcellulose, gelatin, and betaine;
the alkali metal oxyacid salts include: at least one of potassium sulfate, sodium sulfate, lithium sulfate, potassium phosphate, sodium phosphate, potassium nitrate, sodium nitrite, potassium tetraborate, sodium tetraborate, lithium tetraborate, and sodium hypochlorite.
Preferably, the mass ratio of the alkali metal oxysalt to the water-soluble carbon precursor is 1: 1-1: 10;
and/or the mass ratio of the water-soluble carbon precursor to water is 1: 1-1: 20;
and/or, the concentration range of the alkali metal oxysalt in the spinning solution is 0.0002g/cm3~1 g/cm3。
Preferably, the electrostatic spinning process conditions include: the spinning temperature is 40-80 ℃, the spinning time is 0.5-48 h, the positive pressure is 5-18 kV, the negative pressure is-8 to-1 kV, the receiving distance is 5-25 cm, and the advancing speed is 0.02-0.16 mm/min.
Preferably, the post-treatment comprises: pre-oxidizing, carbonizing, washing and drying the precursor;
and/or the pre-oxidation process comprises the following steps: placing a protofilament sample in a tube furnace, introducing air, raising the temperature from room temperature to 100-200 ℃ at a heating rate of 1-10 ℃/min, preserving the heat for 0.5-2 h, and raising the temperature to 200-350 ℃ at a heating rate of 0.2-5 ℃/min, preserving the heat for 0.5-2 h;
and/or the carbonization treatment process comprises the following steps: taking out the pre-oxidized protofilament, placing the protofilament in a tubular furnace, introducing argon under a closed condition, heating to 500-800 ℃ at a heating rate of 1-10 ℃/min in an inert gas atmosphere, preserving heat for 0.5-2 h, and then naturally cooling;
and/or the temperature of the drying treatment is 60-120 ℃.
The invention also provides an application of the porous carbon nanobelt material or the porous carbon nanobelt material prepared by the method in a battery cathode or a quick-charging lithium ion battery.
The technical scheme of the invention has the following advantages:
1. according to the invention, water-soluble alkali metal oxysalt is selected as an auxiliary agent, and can be directly dissolved by water to remove alkali metal ions, so that the obtained material is ensured to have no inactive metal residue, high reversible capacity is favorably shown when the material is used as a negative electrode material, the cycle stability and the rate capability are improved, the prepared three-dimensional porous nano belt-shaped material has good continuity and is doped with abundant heteroatoms, the doped heteroatoms are uniformly distributed in the carbon material and can be used as nucleation sites to be favorable for uniform deposition of metal lithium on the surface and inhibit formation of dendrites; the porous and nano-belt structure widens the insertion and extraction channels of lithium ions in the circulation process, and ensures the rapid transmission and deposition of the lithium ions; the continuous and stable three-dimensional conductive network structure is not only beneficial to the rapid transmission of electrons, but also can accommodate a large amount of metal lithium deposition and buffer the volume expansion. Meanwhile, the heteroatom is a non-metal heteroatom, so that the specific surface area is increased, and the capacity of the lithium electrode is improved.
2. The porous carbon nanobelt material provided by the invention selects alkali metal oxysalt as an auxiliary agent, and has multiple functions: the alkali metal oxysalt is used as a doping agent to introduce heteroatoms such as sulfur, phosphorus, nitrogen or chlorine, the alkali metal oxysalt is used as a template agent to introduce a mesoporous structure and a nanostructure structure, and the alkali metal oxysalt is used as an activating agent to introduce a microporous structure. The viscosity and rheological property of the spinning solution can be directly changed by adding the alkali metal oxysalt, and a nanostructure structure is directly formed in the spinning drying process instead of the traditional fiber structure.
3. The water-soluble carbon precursor selected by the porous carbon nanobelt material provided by the invention contains heteroatoms such as nitrogen and oxygen, so that the heteroatoms can be uniformly doped in situ in the carbonization process, and abundant heteroatoms can be used as additional lithium storage sites and can be used as uniform lithium-philic sites to inhibit the formation of possible metal lithium dendrites.
4. According to the preparation method of the porous carbon nanobelt material, provided by the invention, the alkali metal oxysalt is used as an auxiliary agent, the viscosity and rheological property of the whole mixed solution are regulated, water is used as a solvent, a three-dimensional nanobelt structure can be obtained by utilizing an environment-friendly electrostatic spinning process, the operation is simple and effective, meanwhile, multiple atoms contained in the alkali metal oxysalt can realize in-situ doping of two or more heteroatoms, and simultaneously, the alkali metal oxysalt can chemically react with biomass carbon to form a hierarchical porous structure with micropores and mesopores. The method realizes uniform pore forming on the surface and inside of the carbon material, introduces defects, effectively increases the pore volume and the specific surface area of the material, and can also introduce various non-metallic heteroatoms per se in the process of carbon formation to realize in-situ heteroatom doping of the material.
5. According to the invention, the porous carbon nanobelt material is used as the lithium battery cathode, the advantages of the carbon-based material can be continued, meanwhile, the nanobelt structure can provide a transmission channel for lithium ions, the rapid transmission of the lithium ions is ensured, the doped heteroatoms are uniformly distributed in the carbon material and are used as nucleation sites to facilitate the uniform deposition of metal lithium on the surface and inhibit the formation of dendrites, the porosity is greatly improved due to the porous structure, the insertion and extraction channels of the lithium ions in the circulation process are increased, the overall structural stability of the material is remarkably improved, meanwhile, the three-dimensional structure presented by the material is used as a frame to accommodate more metal lithium for rapid and uniform deposition, and thus, the excellent energy storage and rapid charging performances are realized.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
Fig. 1 is a scanning electron microscope image of the heteroatom-doped porous carbon nanobelt material prepared in example 1 of the present invention.
FIG. 2 is a transmission electron microscope image of the heteroatom-doped porous carbon nanobelt material prepared in example 1 of the present invention.
Fig. 3 is a nitrogen adsorption and desorption graph of the heteroatom-doped porous carbon nanobelt material prepared in example 1 of the present invention.
Fig. 4 is a graph of the pore size distribution of the heteroatom-doped porous carbon nanobelt material prepared in example 1 of the present invention.
FIG. 5 is a general X-ray photoelectron spectroscopy spectrum of the heteroatom-doped porous carbon nanobelt material prepared in example 1 of the present invention.
Fig. 6 is a high resolution spectrum of N element of the heteroatom-doped porous carbon nanobelt material prepared in example 1 of the present invention.
Fig. 7 is a high-resolution spectrum of S element of the heteroatom-doped porous carbon nanobelt material prepared in example 1 of the present invention.
Fig. 8 is a capacity-voltage curve test chart of the heteroatom-doped porous carbon nanobelt material prepared in example 1 of the present invention in a button-type half cell when the material is used as a negative electrode material of a lithium ion battery.
Fig. 9 is a rate performance test chart in a button-type half cell when the heteroatom-doped porous carbon nanobelt material prepared in example 1 of the present invention is used as a negative electrode material of a lithium ion cell.
Fig. 10 is a test chart of long cycle performance in a button-type half cell when the heteroatom-doped porous carbon nanobelt material prepared in example 1 of the present invention is used as a negative electrode material of a lithium ion cell.
Fig. 11 is a comparison graph of coulombic efficiency performance of lithium deposition in a button-type half cell when the heteroatom-doped porous carbon nanobelt material prepared in example 1 of the present invention is used as a negative electrode material of a lithium ion cell.
Fig. 12 is a graph of lithium-to-lithium test charge and discharge performance in a button-type half cell when the heteroatom-doped porous carbon nanobelt material prepared in example 1 of the present invention is used as a negative electrode material of a lithium ion cell.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
Example 1
A porous carbon nanobelt material is prepared by the following steps:
respectively weighing 1.588 g of polyaspartic acid, 0.570g of sodium sulfate and 9.000 g of deionized water, mixing in a beaker, uniformly stirring on a stirring table at 60 ℃ until completely dissolving, performing electrostatic spinning as a spinning stock solution after dissolving, setting the spinning temperature to be 60 ℃, setting the positive pressure to be 10 kV, setting the negative pressure to be-4 kV, setting the receiving distance to be 15 cm, setting the propelling speed to be 0.08 mm/min, setting the spinning time to be 6 h, obtaining protofilaments, and performing pre-oxidation on the protofilaments: putting the mixture into a tube furnace, introducing air, heating the mixture from room temperature to 150 ℃ at a heating rate of 3 ℃/min, preserving heat for 1h, heating the mixture to 270 ℃ at a heating rate of 1 ℃/min, preserving heat for 1h, naturally cooling the mixture to room temperature, and carbonizing the mixture: placing the mixture in a tubular furnace, introducing argon under a closed condition, heating to 700 ℃ in an inert gas atmosphere at the heating rate of 2.5 ℃/min, preserving the temperature for 1h, naturally cooling, taking out after cooling to room temperature, washing with water to remove non-carbohydrate soluble ions, and placing the mixture in an oven at 80 ℃ for drying to obtain the heteroatom-doped porous carbon nanoribbon active material.
The scanning electron microscope image of the heteroatom-doped porous carbon nanoribbon active material is shown in fig. 1, the transmission electron microscope image is shown in fig. 2, and as can be seen from fig. 1 and 2, the heteroatom-doped porous carbon nanoribbon active material obtained by the method is in a strip-shaped structure stacking morphology, the width range of the heteroatom-doped porous carbon nanoribbon active material is 0.2-1.5 mu m, and the thickness range of the heteroatom-doped porous carbon nanoribbon active material is 1-10 nm; obtaining a nitrogen absorption and desorption curve chart in figure 3 by using a nitrogen absorption and desorption method for the heteroatom doped porous carbon nanoribbon active material, and obtaining a pore size distribution chart in figure 4 by analyzing the pore size, so as to obtain the active material with the specific surface area of 937m2Per g, pore volume 0.56cm3The pore diameter is 1.5-8 nm; performing XPS detection on the heteroatom-doped porous carbon nanoribbon active material to obtain an X-ray photoelectron spectroscopy full spectrum and a target element high-resolution spectrum, as shown in fig. 5 to 7, wherein the heteroatom-doped porous carbon nanoribbon active material comprises nitrogen, sulfur and oxygen atoms, and the nitrogen atom percentage is as follows: 6.8 at.%, atomic percent of sulfur: 2.4 at.%, atomic percent of oxygen: 16.9 at.%.
Example 2
A porous carbon nanobelt material is prepared by the following steps:
1.589 g of polyaspartic acid, 0.571g of sodium phosphate and 9.002 g of deionized water are respectively weighed, mixed in a beaker, uniformly stirred on a stirring table at 60 ℃ until completely dissolved, and then taken as spinning stock solution for electrostatic spinning, the spinning temperature is set to be 60 ℃, the positive pressure is set to be 10 kV, the negative pressure is set to be-4 kV, the receiving distance is 15 cm, the propelling speed is set to be 0.08 mm/min, the spinning time is 6 h, protofilaments are obtained, and the protofilaments are pre-oxidized: putting the mixture into a tube furnace, introducing air, heating the mixture from room temperature to 150 ℃ at a heating rate of 3 ℃/min, preserving heat for 1h, heating the mixture to 270 ℃ at a heating rate of 1 ℃/min, preserving heat for 1h, naturally cooling the mixture to room temperature, and carbonizing the mixture: placing the mixture in a tubular furnace, introducing argon under a closed condition, heating to 700 ℃ in an inert gas atmosphere at the heating rate of 2.5 ℃/min, preserving the temperature for 1h, naturally cooling, taking out after cooling to room temperature, washing with water to remove non-carbohydrate soluble ions, and placing the mixture in an oven at 80 ℃ for drying to obtain the heteroatom-doped porous carbon nanoribbon active material.
Example 3
A porous carbon nanobelt material is prepared by the following steps:
respectively weighing 1.587 g of betaine, 0.569g of sodium sulfate and 9.001g of deionized water, mixing in a beaker, uniformly stirring on a stirring table at 60 ℃ until completely dissolving, performing electrostatic spinning as a spinning stock solution after dissolving, setting the spinning temperature to be 60 ℃, setting the positive pressure to be 10 kV, setting the negative pressure to be-4 kV, setting the receiving distance to be 15 cm, setting the propelling speed to be 0.08 mm/min, and setting the spinning time to be 6 h to obtain protofilaments, and performing pre-oxidation on the protofilaments: putting the mixture into a tube furnace, introducing air, heating the mixture from room temperature to 150 ℃ at a heating rate of 3 ℃/min, preserving heat for 1h, heating the mixture to 270 ℃ at a heating rate of 1 ℃/min, preserving heat for 1h, naturally cooling the mixture to room temperature, and carbonizing the mixture: placing the mixture in a tubular furnace, introducing argon under a closed condition, heating to 700 ℃ in an inert gas atmosphere at the heating rate of 2.5 ℃/min, preserving the temperature for 1h, naturally cooling, taking out after cooling to room temperature, washing with water to remove non-carbohydrate soluble ions, and placing the mixture in an oven at 80 ℃ for drying to obtain the heteroatom-doped porous carbon nanoribbon active material.
Example 4
A porous carbon nanobelt material is prepared by the following steps:
weighing 1.588 g of polyaspartic acid, 1.589 g of sodium sulfate and 9.002 g of deionized water respectively, mixing in a beaker, uniformly stirring on a stirring table at 60 ℃ until completely dissolving, performing electrostatic spinning as a spinning stock solution after dissolving, setting the spinning temperature to be 60 ℃, setting the positive pressure to be 10 kV, setting the negative pressure to be-4 kV, setting the receiving distance to be 15 cm, setting the propelling speed to be 0.08 mm/min, setting the spinning time to be 6 h, obtaining protofilaments, and performing pre-oxidation on the protofilaments: putting the mixture into a tube furnace, introducing air, heating the mixture from room temperature to 150 ℃ at a heating rate of 3 ℃/min, preserving heat for 1h, heating the mixture to 270 ℃ at a heating rate of 1 ℃/min, preserving heat for 1h, naturally cooling the mixture to room temperature, and carbonizing the mixture: placing the mixture in a tubular furnace, introducing argon under a closed condition, heating to 700 ℃ in an inert gas atmosphere at the heating rate of 2.5 ℃/min, preserving the temperature for 1h, naturally cooling, taking out after cooling to room temperature, washing with water to remove non-carbohydrate soluble ions, and placing the mixture in an oven at 80 ℃ for drying to obtain the heteroatom-doped porous carbon nanoribbon active material.
Example 5
A porous carbon nanobelt material is prepared by the following steps:
respectively weighing 1.586 g of polyaspartic acid, 0.571g of sodium sulfate and 12.702 g of deionized water, mixing in a beaker, uniformly stirring on a stirring table at 60 ℃ until completely dissolving, performing electrostatic spinning as a spinning stock solution after dissolving, setting the spinning temperature to be 60 ℃, setting the positive pressure to be 10 kV, setting the negative pressure to be-4 kV, setting the receiving distance to be 15 cm, setting the advancing speed to be 0.08 mm/min, and setting the spinning time to be 6 h to obtain protofilaments, and performing pre-oxidation on the protofilaments: putting the mixture into a tube furnace, introducing air, heating the mixture from room temperature to 150 ℃ at a heating rate of 3 ℃/min, preserving heat for 1h, heating the mixture to 270 ℃ at a heating rate of 1 ℃/min, preserving heat for 1h, naturally cooling the mixture to room temperature, and carbonizing the mixture: placing the mixture in a tubular furnace, introducing argon under a closed condition, heating to 700 ℃ in an inert gas atmosphere at the heating rate of 2.5 ℃/min, preserving the temperature for 1h, naturally cooling, taking out after cooling to room temperature, washing with water to remove non-carbohydrate soluble ions, and placing the mixture in an oven at 80 ℃ for drying to obtain the heteroatom-doped porous carbon nanoribbon active material.
Example 6
A porous carbon nanobelt material is prepared by the following steps:
respectively weighing 1.586 g of polyaspartic acid, 0.569g of sodium sulfate and 9.001g of deionized water, mixing in a beaker, uniformly stirring on a stirring table at 60 ℃ until completely dissolving, performing electrostatic spinning as a spinning stock solution after dissolving, setting the spinning temperature to be 60 ℃, setting the positive pressure to be 10 kV, setting the negative pressure to be-4 kV, setting the receiving distance to be 15 cm, setting the advancing speed to be 0.08 mm/min, and setting the spinning time to be 6 h to obtain protofilaments, and performing pre-oxidation on the protofilaments: putting the mixture into a tube furnace, introducing air, heating the mixture from room temperature to 150 ℃ at a heating rate of 3 ℃/min, preserving heat for 1h, heating the mixture to 300 ℃ at a heating rate of 1 ℃/min, preserving heat for 1h, naturally cooling the mixture to room temperature, and carbonizing the mixture: placing the mixture in a tubular furnace, introducing argon under a closed condition, heating to 700 ℃ in an inert gas atmosphere at the heating rate of 2.5 ℃/min, preserving the temperature for 1h, naturally cooling, taking out after cooling to room temperature, washing with water to remove non-carbohydrate soluble ions, and placing the mixture in an oven at 80 ℃ for drying to obtain the heteroatom-doped porous carbon nanoribbon active material.
Example 7
A porous carbon nanobelt material is prepared by the following steps:
respectively weighing 1.587 g of polyaspartic acid, 0.571g of sodium sulfate and 9.001g of deionized water, mixing in a beaker, uniformly stirring on a stirring table at 60 ℃ until the polyaspartic acid, the sodium sulfate and the 9.001g of deionized water are completely dissolved, carrying out electrostatic spinning as a spinning stock solution after the polyaspartic acid, the spinning temperature is set to be 60 ℃, the positive pressure is set to be 10 kV, the negative pressure is set to be-4 kV, the receiving distance is 15 cm, the propelling speed is set to be 0.08 mm/min, and the spinning time is 6 h to obtain protofilaments, and carrying out pre-oxidation on the protofilaments: putting the mixture into a tube furnace, introducing air, heating the mixture from room temperature to 150 ℃ at a heating rate of 3 ℃/min, preserving heat for 1h, heating the mixture to 270 ℃ at a heating rate of 1 ℃/min, preserving heat for 1h, naturally cooling the mixture to room temperature, and carbonizing the mixture: placing the mixture in a tubular furnace, introducing argon under a closed condition, heating to 800 ℃ in an inert gas atmosphere at the heating rate of 2.5 ℃/min, preserving the temperature for 1h, naturally cooling, taking out after cooling to room temperature, washing with water to remove non-carbohydrate soluble ions, and placing the mixture in an oven at 80 ℃ for drying to obtain the heteroatom-doped porous carbon nanoribbon active material.
Example 8
A porous carbon nanobelt material is prepared by the following steps:
respectively weighing 1.588 g of polyaspartic acid, 0.571g of sodium sulfate and 9.001g of deionized water, mixing in a beaker, uniformly stirring on a stirring table at 60 ℃ until completely dissolving, performing electrostatic spinning as a spinning stock solution after dissolving, setting the spinning temperature to be 60 ℃, setting the positive pressure to be 10 kV, setting the negative pressure to be-4 kV, setting the receiving distance to be 15 cm, setting the propelling speed to be 0.12 mm/min, and setting the spinning time to be 6 h to obtain protofilaments, and performing pre-oxidation on the protofilaments: putting the mixture into a tube furnace, introducing air, heating the mixture from room temperature to 150 ℃ at a heating rate of 3 ℃/min, preserving heat for 1h, heating the mixture to 270 ℃ at a heating rate of 1 ℃/min, preserving heat for 1h, naturally cooling the mixture to room temperature, and carbonizing the mixture: placing the mixture in a tubular furnace, introducing argon under a closed condition, heating to 700 ℃ in an inert gas atmosphere at the heating rate of 2.5 ℃/min, preserving the temperature for 1h, naturally cooling, taking out after cooling to room temperature, washing with water to remove non-carbohydrate soluble ions, and placing the mixture in an oven at 80 ℃ for drying to obtain the heteroatom-doped porous carbon nanoribbon active material.
Example 9
A porous carbon nanobelt material is prepared by the following steps:
respectively weighing 0.571g of polyaspartic acid, 0.570g of sodium sulfate and 11.401 g of deionized water, mixing in a beaker, uniformly stirring on a stirring table at 60 ℃ until the polyaspartic acid, the sodium sulfate and the 11.401 g of deionized water are completely dissolved, carrying out electrostatic spinning as a spinning stock solution after the polyaspartic acid, the spinning temperature is set to be 40 ℃, the positive pressure is set to be 18kV, the negative pressure is set to be-8 kV, the receiving distance is 5 cm, the propelling speed is set to be 0.02 mm/min, and the spinning time is 6 h to obtain protofilaments, and carrying out pre-oxidation on the protofilaments: putting the mixture into a tube furnace, introducing air, heating the mixture from room temperature to 200 ℃ at a heating rate of 10 ℃/min, preserving heat for 2h, heating the mixture to 200 ℃ at a heating rate of 0.2 ℃/min, preserving heat for 0.5h, naturally cooling the mixture to room temperature, and carbonizing the mixture: and (3) placing the mixture in a tubular furnace, introducing argon under a closed condition, heating to 500 ℃ in an inert gas atmosphere at the heating rate of 1 ℃/min, preserving the temperature for 2h, naturally cooling, taking out the mixture after cooling to room temperature, washing with water to remove non-carbohydrate soluble ions, and placing the mixture in a 120 ℃ oven for drying to obtain the heteroatom-doped porous carbon nanoribbon active material.
Example 10
A porous carbon nanobelt material is prepared by the following steps:
5.701 g of polyaspartic acid, 0.570g of sodium sulfate and 5.702 g of deionized water are respectively weighed, mixed in a beaker, uniformly stirred on a stirring table at 60 ℃ until completely dissolved, and then taken as spinning stock solution for electrostatic spinning after dissolution, the spinning temperature is set to 80 ℃, the positive pressure is set to 5kV, the negative pressure is set to-1 kV, the receiving distance is 25 cm, the propelling speed is set to 0.16 mm/min, the spinning time is 6 h, protofilaments are obtained, and the protofilaments are pre-oxidized: putting the mixture into a tube furnace, introducing air, heating the mixture from room temperature to 100 ℃ at a heating rate of 1 ℃/min, preserving heat for 0.5h, heating the mixture to 350 ℃ at a heating rate of 5 ℃/min, preserving heat for 2h, naturally cooling the mixture to room temperature, and carbonizing the mixture: placing the mixture in a tubular furnace, introducing argon under a closed condition, heating to 800 ℃ in an inert gas atmosphere at the heating rate of 10 ℃/min, preserving heat for 0.5h, naturally cooling, taking out after cooling to room temperature, washing with water to remove non-carbohydrate soluble ions, and placing the mixture in a 60 ℃ oven for drying to obtain the heteroatom-doped porous carbon nanoribbon active material.
Example 11
A porous carbon nanobelt material is prepared by the following steps:
respectively weighing 1.588 g of polyaspartic acid, 0.571g of sodium hypochlorite and 9.001g of deionized water, mixing in a beaker, uniformly stirring on a stirring table at 60 ℃ until the polyaspartic acid, the sodium hypochlorite and the 9.001g of deionized water are completely dissolved, setting the spinning temperature to be 60 ℃, the positive pressure to be 10 kV, the negative pressure to be-4 kV, the receiving distance to be 15 cm, the advancing speed to be 0.08 mm/min and the spinning time to be 6 h to obtain protofilaments, and pre-oxidizing the protofilaments: putting the mixture into a tube furnace, introducing air, heating the mixture from room temperature to 150 ℃ at a heating rate of 3 ℃/min, preserving heat for 1h, heating the mixture to 270 ℃ at a heating rate of 1 ℃/min, preserving heat for 1h, naturally cooling the mixture to room temperature, and carbonizing the mixture: placing the mixture in a tubular furnace, introducing argon under a closed condition, heating to 700 ℃ in an inert gas atmosphere at the heating rate of 2.5 ℃/min, preserving the temperature for 1h, naturally cooling, taking out after cooling to room temperature, washing with water to remove non-carbohydrate soluble ions, and placing the mixture in an oven at 80 ℃ for drying to obtain the heteroatom-doped porous carbon nanoribbon active material.
Comparative example 1
A heteroatom-doped carbon nanofiber material is prepared by the following steps:
weighing 1.588 g of polyaspartic acid, 0.020g of sodium sulfate and 9.000 g of deionized water respectively, mixing in a beaker, uniformly stirring on a stirring table at 60 ℃ until completely dissolving, performing electrostatic spinning as a spinning stock solution after dissolving, setting the spinning temperature to be 60 ℃, setting the positive pressure to be 10 kV, setting the negative pressure to be-14 kV, setting the receiving distance to be 15 cm, setting the propelling speed to be 0.12 mm/min, setting the spinning time to be 6 h, obtaining protofilaments, and performing pre-oxidation on the protofilaments: putting the mixture into a tube furnace, introducing air, heating the mixture from room temperature to 150 ℃ at a heating rate of 3 ℃/min, preserving heat for 1h, heating the mixture to 270 ℃ at a heating rate of 1 ℃/min, preserving heat for 1h, naturally cooling the mixture to room temperature, and carbonizing the mixture: placing the mixture in a tubular furnace, introducing argon under a closed condition, heating to 700 ℃ in an inert gas atmosphere at the heating rate of 2.5 ℃/min, preserving the heat for 1h, naturally cooling, taking out after cooling to room temperature, washing with water to remove non-carbohydrate soluble ions, and placing the mixture in an oven at 80 ℃ for drying to obtain the heteroatom-doped carbon nanofiber material, wherein the diameter range of the fibers is 0.5-30 mu m.
Comparative example 2
A cobalt and nitrogen doped porous carbon composite nanofiber is prepared by the following steps:
1) preparing a spinning solution: dissolving chitosan with the average molecular weight of 60 ten thousand in an aqueous solution of acetic acid, dissolving polyoxyethylene with the average molecular weight of 100 ten thousand in deionized water, diluting polyethyleneimine with the deionized water, adding cobalt acetate tetrahydrate, mixing and stirring the three solutions uniformly, and adding TritonX-100 to obtain a spinning solution, wherein the concentration of the chitosan is 2.9 wt%, the concentration of the acetic acid is 1.1 wt%, the concentration of the polyoxyethylene is 2.4wt%, the concentration of the polyethyleneimine is 0.5wt%, the concentration of the cobalt acetate is 0.2wt%, and the concentration of the TritonX-100 is 0.8 wt%; the mixed solution was stirred in a 30 ℃ water bath for 8 h.
2) Electrostatic spinning: and (3) filling the obtained spinning solution into an injector for electrostatic spinning, wherein the spinning distance is 10 cm, the solution flow is 0.3 mL/h, and the applied voltage is 15 kV.
3) And (3) heat treatment: placing the mixed polymer fiber obtained by spinning in a tubular furnace, pre-oxidizing for 4h at 150 ℃ in the air, then heating to 240 ℃ at 3 ℃/min under an inert atmosphere, keeping the temperature for 2h, heating to 340 ℃ at 3 ℃/min, keeping the temperature for 2h, then heating to 800 ℃ at 3 ℃/min, and keeping the temperature for 2h to finally obtain the cobalt and nitrogen doped porous carbon composite nanofiber, wherein the diameter range of the fiber is 0.05-0.08 mu m.
Experimental example 1:
SEM and TEM characterization tests are carried out on the porous carbon nanobelts prepared in the examples 1 to 11 and the nanofibers prepared in the comparative examples 1 to 2, and the experimental results are shown in Table 1:
TABLE 1 characterization test results of SEM and TEM of porous carbon nanobelt material
The experimental results show that: the porous carbon nanobelt material obtained in the embodiments 1 to 11 of the present invention has a shape of a stacked ribbon structure, a width range of 0.09 μm to 6.7 μm, a thickness range of 1 nm to 64 nm, and a pore structure uniformly distributed on the surface and inside.
Experimental example 2:
BET tests were performed on the porous carbon nanobelts prepared in examples 1 to 11 and the nanofibers of comparative examples 1 to 2, and the experimental results are shown in Table 2:
TABLE 2 BET test results
Experimental example 3: XPS spectrogram analysis is carried out on the porous carbon nanobelts prepared in the examples 1 to 11 and the nanofibers prepared in the comparative examples 1 to 2 to obtain the atomic percentage of the heteroatoms, and the experimental results are shown in Table 3.
TABLE 3 XPS Spectrum analysis results
Experimental example 4:
mixing the porous carbon nanobelt active material prepared in the examples 1-11 with the nanofiber material and the binder obtained in the comparative examples 1-2 in a mass ratio of 20:1, wherein the binder is PVDF (polyvinylidene fluoride), water is used as a solvent, the mixture is uniformly ground by a mortar, coated on a copper foil with the diameter of 14 mm, dried in a vacuum oven at 60 ℃ for 12 hours, taken out and used as a negative electrode, and a lithium sheet is a counter electrode, so as to assemble a button-type lithium ion half-cell;
the button-type lithium ion half-cell is assembled by taking commercial graphite as a negative electrode and a lithium sheet as a counter electrode, and is used as a comparative example 3, wherein the commercial graphite negative electrode is purchased from Xiancheng nanometer technology Co., Ltd and has the purity of 99.0 wt%, and the lithium sheet is purchased from Tianjin lithium industry Co., Ltd and has the diameter of 15.6 mm;
wherein, the button type lithium ion half-cell model is CR 2032.
A button-type lithium ion half cell was assembled using the porous carbon nanoribbon active material obtained in example 1 as a lithium ion cell negative electrode material, and a capacity voltage test was performed, and a test chart is shown in fig. 8, a rate performance test was performed on the porous carbon nanoribbon active material obtained in example 1 as a lithium ion cell negative electrode material, and a test chart is shown in fig. 9, and a long cycle performance test was performed on the button-type half cell using the porous carbon nanoribbon active material obtained in example 1 as a lithium ion cell negative electrode material, and the specific results shown in fig. 10 are shown in table 1.
Carrying out multiplying power and long cycle test on the prepared button type lithium ion half-cell, wherein a voltage window is 0.01-3V, and multiplying power test current density is selected in sequence as follows: 0.2C, 0.5C, 1C, 2C, 5C, 10C and 20C, and 6C is selected as the long-cycle test current density, and the test results are shown in Table 4.
TABLE 4 test results of multiplying power and long cycle of button-type lithium ion half-cell
It can be seen that when the porous carbon nanoribbon active material prepared in examples 1 to 11 is used as a negative electrode, the specific capacity of the battery is 576 to 620 mAh g at a current density of 0.2C-1When the specific capacity is increased to 20C, the specific capacity still remains 200-240 mAh g-1Showing good rate performance. And when the activated carbon is cycled for 400 circles after long-cycle test, the specific capacity can reach 507-570 mAh g-1The standard capacity of a commercial graphite cathode is 372 mAh g-1The capacity of the graphite anode is 1.5 times of the standard capacity of a commercial graphite anode, and the performance is excellent.
Experimental example 5:
taking a button-type half cell with surface deposited pure metal lithium as a cathode as a comparative example 4, performing a lithium deposition stripping test on the porous carbon nanoribbon active material prepared in the examples 1-11, the button-type half cell with the nanofiber material obtained in the comparative examples 1-2 as a lithium ion battery cathode material and the button-type half cell obtained in the comparative example 4, and firstly performing a lithium deposition stripping test on the button-type half cell with the surface deposited pure metal lithium as a cathode material at 1 mA cm-2Pre-depositing lithium 3 mAh cm-2Then at 1 mA cm-2，1 mAh cm-2The deposition stripping of lithium is carried out under the condition, the cut-off voltage is set to be 1V, and the ratio of the discharge capacity to the charge capacity of the lithium is calculated to obtain the coulombic efficiency;
when the heteroatom-doped porous carbon nanobelt material prepared in example 1 is used as a lithium ion battery negative electrode material, detection of the coulombic efficiency performance of lithium deposition and the charge-discharge performance of lithium-to-lithium tests is performed in a button-type half battery, and detection graphs are shown in fig. 11 to 12, and the results are shown in table 5.
TABLE 5 lithium deposition stripping test results
From the above results, it is apparent that at 1 mA cm-2，1 mAh cm-2The coulombic efficiency under the condition is obviously superior to that of a battery taking pure metal lithium deposited on the surface as a negative electrode, the coulombic efficiency of 93.9-96.6% can still be kept after 130 cycles of circulation, and the material is assembled into a symmetrical battery to be circulated in 500 cyclesThe voltage can still keep a stable state after h, and the long-cycle performance is good.
Compared with the negative electrode material reported at present, the material prepared by the method has more excellent energy storage and quick charge performance.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.
Claims (10)
1. A heteroatom-doped porous carbon nanoribbon material, characterized in that the porous carbon nanoribbon material is doped with two or more heteroatoms, the heteroatoms comprising: nitrogen, oxygen, sulfur, phosphorus or chlorine;
the aspect ratio of the porous carbon nanoribbon is 1000: 1-8000: 1; the width range is 0.05 μm to 10 μm.
2. The heteroatom-doped porous carbon nanobelt material of claim 1, wherein the atomic percent of nitrogen is 0.2 to 10 at.%;
and/or the atomic percent of oxygen is 5-25 at.%;
and/or the atomic percent of sulfur is 0.1 to 10 at.%;
and/or the atomic percent of phosphorus is 0.1 to 10 at.%;
and/or the atomic percent of the chlorine is 0.1 to 10 at.%.
3. The heteroatom-doped porous carbon nanoribbon material of any one of claims 1 to 2, wherein the porous carbon nanoribbon has a thickness in the range of 1 nm to 100 nm.
4. The heteroatom-doped porous carbon nanoribbon material of claim 1, wherein the porous carbon nanoribbon has a pore size in the range of 0.5 nm to 50 nm;
and/or a pore volume in the range of 0.1 cm3/g ~1.5 cm3/g；
And/or a specific surface area of 600 m2/g ~2000 m2/g。
5. The method for preparing a heteroatom-doped porous carbon nanobelt material according to any one of claims 1 to 4, comprising the steps of: mixing a water-soluble carbon precursor, alkali metal oxysalt and water, taking the mixed solution as a spinning solution, carrying out electrostatic spinning to obtain protofilaments, and carrying out post-treatment on the obtained protofilaments to prepare the porous carbon nanobelt material.
6. The method of preparing a heteroatom-doped porous carbon nanobelt material of claim 5, wherein the water-soluble carbon precursor comprises: at least one of polyaspartic acid, serine, glycine, vitamin B1, folic acid, carboxymethylcellulose, gelatin, and betaine;
and/or, the alkali metal oxyacid salt includes: at least one of potassium sulfate, sodium sulfate, lithium sulfate, potassium phosphate, sodium phosphate, potassium nitrate, sodium nitrite, potassium tetraborate, sodium tetraborate, lithium tetraborate, and sodium hypochlorite.
7. The method for preparing a heteroatom-doped porous carbon nanobelt material according to any one of claims 5 to 6, wherein the mass ratio of the alkali metal oxysalt to the water-soluble carbon precursor is 1:1 to 1: 10;
and/or the mass ratio of the water-soluble carbon precursor to water is 1: 1-1: 20;
and/or, the concentration range of the alkali metal oxysalt in the spinning solution is 0.0002g/cm3~1 g/cm3。
8. The method of preparing a heteroatom-doped porous carbon nanoribbon material of claim 5, wherein the process conditions of electrospinning comprise: the spinning temperature is 40-80 ℃, the spinning time is 0.5-48 h, the positive pressure is 5-18 kV, the negative pressure is-8 to-1 kV, the receiving distance is 5-25 cm, and the advancing speed is 0.02-0.16 mm/min.
9. The method of preparing a heteroatom-doped porous carbon nanobelt material of claim 5, wherein the post-treatment comprises: pre-oxidizing, carbonizing, washing and drying the precursor;
and/or the pre-oxidation process comprises the following steps: keeping the temperature of the precursor at 100-200 ℃ for 0.5-2 h in the air atmosphere, and then heating to 200-350 ℃ for 0.5-2 h;
and/or the carbonization treatment process comprises the following steps: preserving the temperature of the pre-oxidized protofilament for 0.5-2 h at 500-800 ℃ in an inert gas atmosphere;
and/or the temperature of the drying treatment is 60-120 ℃.
10. The use of the porous carbon nanobelt material according to any one of claims 1 to 4 in a battery negative electrode or in a fast-charging lithium ion battery.
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