CN111244412A - Nitrogen-doped porous carbon nanofiber composite material for lithium/sodium ion battery negative electrode and preparation method thereof - Google Patents
Nitrogen-doped porous carbon nanofiber composite material for lithium/sodium ion battery negative electrode and preparation method thereof Download PDFInfo
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Abstract
The invention provides a porous nitrogen-doped carbon nanofiber composite material and a preparation method thereof, wherein polyacrylonitrile and zinc acetate are added into dimethylformamide and stirred to obtain a mixed solution; transferring the mixed solution into an injector for electrostatic spinning to obtain a polyacrylonitrile/zinc acetate nanofiber composite material; soaking the composite material in an ethanol solution of 2-methylimidazole to enable zinc ions to react with dimethylimidazole to grow a ZIF-8 metal organic framework on the fiber, and drying to obtain a ZIF-8/polyacrylonitrile/zinc acetate composite nanofiber; the method comprises the steps of firstly pre-calcining the nanofiber composite material in air, then calcining the composite material in inert gas, generating a porous structure through acid etching, washing and drying the porous structure to obtain the porous nitrogen-doped carbon nanofiber composite material. The method has easy operation and repeatability, and the synthesized material has higher capacity and good cycle performance and can be used as a negative electrode material of a lithium/sodium ion battery.
Description
Technical Field
The invention belongs to the field of inorganic nano material synthesis. In particular to a method for preparing a nitrogen-doped porous carbon nanofiber (N-CHF) composite material by an electrospinning method.
Background
Recently, in order to meet the increasing energy demand worldwide, a large number of low-cost recyclable new energy devices are rapidly developed. Among them, the lithium/sodium ion battery is widely used in the fields of information technology, electric vehicles, aerospace and the like because of its characteristics of high specific energy density, high discharge voltage, long cycle life, no memory effect, no pollution and the like.
Compared with lithium resources, sodium reserves are abundant and account for about 2.64% of the earth crust reserves, the reserve of lithium with commercial exploitation value is only 1351.9 ten thousand metric tons, and sodium-ion batteries and lithium-ion battery energy storage technologies have certain similarity, and the sodium-ion batteries are rapidly developed. Because the radius of the sodium ions is larger and heavier than that of the lithium ions, the material can expand in a larger volume in the process of the sodium ions being inserted and removed, so that the structure of the material is damaged, and the circulation stability is further deteriorated. Therefore, in order to meet the market demand for high performance lithium/sodium ion batteries, materials with long cycle stability must be sought.
In lithium/sodium ion batteries, the negative electrode material is one of the important factors affecting the battery capacity and service life. At present, a human beingResearch on high lithium/sodium storage performance negative electrode materials has focused mainly on metals and alloy materials, oxides and sulfide materials, and carbon-based materials. Wherein the carbon-based material has higher theoretical specific capacity (372mAh g)-1) The lithium ion battery cathode material has the advantages of rich raw material sources, lower synthesis cost, no toxicity, environmental friendliness and the like, and is particularly suitable for serving as a cathode material of a new generation of lithium/sodium ion battery.
Although natural graphite does not have sodium storage activity, due to its successful application in lithium ion batteries and naturally abundant resources, it is desirable to modify graphite to store sodium. The larger radius of sodium ions can cause huge volume expansion of the material in the charge and discharge processes, thereby causing low capacity and poor cycle stability of the negative electrode material. Wen (WenY, He K, Zhu Y J, et al. expanded graphite as super anode for sodium-ionbateries [ J)]Nature Communications,2014,5:4033) and the like have synthesized graphite with an expanded carbon layer (0.43nm) by a method of oxidation followed by partial reduction. This work observed by in situ transmission electron microscopy that graphite with an expanded carbon layer was able to store sodium reversibly in an intercalated fashion. Constant current charge and discharge test shows that the graphite material is 20mA g-1The specific capacity of sodium storage under the current density of the sodium-containing lithium ion battery reaches 284mA h g-1At 100mA g-1184mAh g still remains after 2000 cycles of circulation under current density-1The reversible capacity of (2), capacity retention rate was 73.92%. The method for increasing the carbon layer spacing by doping can effectively improve the capacity of the carbon material in the sodium ion battery, but the cycling stability of the carbon material is not obviously improved. In the present research, the electrospinning technique is a commonly used method for manufacturing nanofiber materials. Ma D (Ma D, Li Y, et al. robust SnO2-xN optically-Impregnated Carbon Nanofibers with external electrochemical performance for Advanced Sodium-ion Batteries [ J]Angewandte chemical Edition,2018) and the like prepare a tin dioxide/carbon fiber composite electrode material by an electrostatic spinning technology, and the material has better cycling stability when applied to a sodium ion battery. However, the capacity of the one-dimensional fiber composite electrode material still needs to be improved because the one-dimensional fiber composite electrode material is not favorable for the sufficient contact between the electrode and the electrolyte. Root of herbaceous plantAccording to the reports of relevant documents, the porous structure design of the carbon material can effectively increase the contact between the electrode and the electrolyte. The MOFs metal organic framework is a crystalline porous material with a periodic network structure, the pore diameter of the MOFs metal organic framework can be adjusted from a few angstroms to a few nanometers (as high as 9.8nm) by increasing the length of rigid organic bridging molecules, and the MOFs metal organic framework also has a large specific surface area (1000-10000 cm)2g-1). The unique characteristics of flexible and controllable composition, structure and aperture of the MOFs bring diversity and operability of morphology design to the MOFs. Through the method of pyrolysis under inert gas, MOFs can be conveniently converted into the carbon-based nano porous material, and the problems of complicated preparation process and high cost of other traditional porous materials are solved. Therefore, the MOFs are often used for preparing nano porous structures with various shapes, and the contact area between an electrode and electrolyte can be effectively increased. Based on the above thought, the work utilizes the electrostatic spinning technology and the method of growing the ZIF-8 metal organic frame and then calcining and etching to synthesize the N-doped porous carbon nanofiber, which can be used as a negative electrode material of a lithium/sodium ion battery with high capacity and long cycle stability.
Disclosure of Invention
The invention aims to prepare a nitrogen-doped porous carbon nanofiber composite material through a series of processes of ZIF-8 growth coating, calcination, etching and the like after electrostatic spinning, and the nitrogen-doped porous carbon nanofiber composite material can be used for a lithium/sodium ion battery cathode. The composite material has a porous structure, nitrogen is doped in carbon fibers, and the porous fibers are mutually crosslinked to form a three-dimensional network structure. The porous structure in the carbon fiber can endow the material with a large specific surface area, so that the material is in full contact with electrolyte, the diffusion distance of lithium/sodium ions is reduced, the transmission of electrons and ions is facilitated, and the circulation stability of the material is enhanced. Meanwhile, the doping of the N element further improves the conductivity of the material and creates more active sites, which is beneficial to the adsorption of lithium/sodium ions, thereby increasing the specific capacity of the carbon material. Therefore, the method improves the specific capacity and the cycling stability of the carbon material as the negative electrode material of the lithium/sodium ion battery.
The invention provides a porous nitrogen-doped carbon fiber composite material for a lithium/sodium ion battery cathode, wherein the composite material is in a porous structure, nitrogen is doped in carbon fibers, and the porous carbon fibers are mutually crosslinked to form a three-dimensional network structure.
The invention provides a nitrogen-doped porous carbon nanofiber composite material prepared by using electrostatic spinning and suction filtration film-forming methods and then through calcination and etching synthesis and a method thereof.
The technical scheme of the invention is as follows:
a preparation method of a nitrogen-doped porous carbon nanofiber composite material for a lithium/sodium ion battery cathode; the method comprises the following steps:
1) adding Polyacrylonitrile (PAN) into Dimethylformamide (DMF), and stirring at 50-70 ℃ for 2-4h at 500r/min for 300-;
2) zinc acetate (Zn (Ac))2) Adding the solution into the solution prepared in the step 1), and stirring for 6-10h at the speed of 300-;
3) electrostatic spinning the solution obtained in step 2) to obtain PAN/Zn (Ac)2A composite material;
4) the PAN/Zn (Ac) obtained in step 3) is added2Soaking the composite material in an ethanol solution of 2-methylimidazole, and then performing suction filtration to obtain ZIF-8/PAN/Zn (Ac)2Compounding nano fiber;
5) putting the composite material prepared in the step 4) into a muffle furnace for calcining, and naturally cooling to room temperature; then transferring the mixture into a tubular furnace to calcine in argon, and naturally cooling the mixture to room temperature;
6) soaking the product prepared in the step 5) in acid to etch away zinc element, washing and drying to obtain the nitrogen-doped porous carbon nanofiber composite material.
The concentration of polyacrylonitrile in the step 1) is 0.05-0.14 g/mL.
The mass ratio of the zinc acetate to the polyacrylonitrile in the step 2) is 1:1-3: 1.
The electrostatic spinning conditions in the step 3) are as follows: the voltage is 18-22kV, the set flow is 0.4-0.8mL/h, and the distance is 15-20 cm.
The concentration of the 2-methylimidazole in the step 4) is 0.05-0.15g/mL, and the soaking time is 10-24 h.
The muffle furnace calcining condition in the step 5): the heating rate is 1-2 ℃/min, the temperature is kept at the temperature of 240-280 ℃ for 2-4h, and then the temperature is naturally cooled to the room temperature. And (3) calcining conditions of the tube furnace: the heating rate is 2-5 ℃/min, the temperature is kept at 650-750 ℃ for 6-10h, and then the temperature is naturally cooled to the room temperature.
In the step 6), the acid is one of sulfuric acid, nitric acid and hydrochloric acid, the soaking time is 6-24h, and the washing is carried out for 6-8 times by using ethanol and deionized water.
The step 6) drying conditions are as follows: drying at 50-80 deg.C for 10-18 h.
The method has the effect of preparing the nitrogen-doped porous carbon nanofiber composite material with high cycling stability for the cathode of the lithium/sodium ion battery. The composite material has a porous structure, and the nitrogen-doped carbon fibers are mutually crosslinked to form a three-dimensional network structure. The diameter of the nanofiber of the nitrogen-doped porous carbon nanofiber composite material is 150-200nm, the porous structure can endow the material with a large specific surface area, and the volume expansion of the carbon-based electrode in the process of sodium ion embedding and removing can be effectively relieved. Meanwhile, the doping of the N element further improves the conductivity of the material and creates more active sites. Thus, the method improves the cycling stability of the carbon material as a negative electrode material of a lithium/sodium ion battery. When used in a sodium ion battery, at 10A g-1The performance of the alloy is tested under the high current density, and the specific capacity of the alloy can reach 130mAh g after 1450 circles of circulation-1The coulombic efficiency is close to 100%, which shows that the coulombic efficiency is superior to the large-current long-cycle stability of the existing carbon-based negative electrode material, and the market demand of the high-performance lithium/sodium ion battery can be met.
Drawings
FIG. 1 is an X-ray diffraction pattern of a nitrogen-doped porous carbon nanofiber composite (N-CHF) prepared in example 1;
FIG. 2 is a scanning electron microscope image of the nitrogen-doped porous carbon nanofiber composite prepared in example 2;
FIG. 3 is a transmission electron microscope image of the nitrogen-doped porous carbon nanofiber composite prepared in example 3;
fig. 4 is a long cycle test plot of the nitrogen-doped porous carbon nanofiber composite prepared in example 3.
Detailed Description
Example 1:
1) adding 0.8g Polyacrylonitrile (PAN) into 16ml Dimethylformamide (DMF), and stirring at 50 ℃ at 500r/min for 2h to uniformly disperse PAN in DMF;
2) adding 2.4g of zinc acetate into the solution prepared in the step 1) (the mass ratio of the zinc acetate to the polyacrylonitrile is 3:1), and stirring for 6 hours at the speed of 500 r/min;
3) electrostatic spinning is carried out on the solution prepared in the step 2), the voltage is 18kV, the set flow is 0.4ml/h, the distance is 15cm, and PAN/Zn (Ac) is obtained2A composite material;
4) the PAN/Zn (Ac) obtained in step 3) is added2Soaking the composite material in 0.15g/mL 2-methylimidazole ethanol solution, and performing suction filtration after 10 hours to obtain ZIF-8/PAN/Zn (Ac)2Compounding nano fiber;
5) putting the composite material prepared in the step 4) into a muffle furnace for calcining at the heating rate of 2 ℃/min, preserving the heat at 280 ℃ for 2h, and naturally cooling to room temperature. Then transferring the mixture into a tubular furnace to calcine in argon, heating at a rate of 5 ℃/min, keeping the temperature at 750 ℃ for 6h, and naturally cooling to room temperature;
6) soaking the product prepared in the step 5) in sulfuric acid for 6 hours, repeatedly washing with ethanol and deionized water for 6 times, and drying at 80 ℃ for 10 hours to obtain the nitrogen-doped porous carbon nanofiber composite material.
As shown in FIG. 1, the XRD pattern of N-CHF showed two peaks at 23.4 ° and 43.5 °, respectively, corresponding to the (002) and (100) crystal planes of graphite (PDF #75-1621), and had better crystallinity. Further, it is noteworthy that the (002) diffraction peak of the N-CHF sample was shifted to a lower diffraction angle than that of the pure carbon fiber (2 θ ═ 25.3 °). According to the Bragg law, the (002) surface layer spacing of the N-CHF sample can be calculated to be 0.38nm, and the surface layer spacing of the sample is enlarged, so that the problem of volume expansion is favorably solved.
Example 2:
1) adding 1.52g Polyacrylonitrile (PAN) into 16mL Dimethylformamide (DMF), and stirring at 60 ℃ and 400r/min for 3h to uniformly disperse PAN in DMF;
2) mixing 3.04g vinegarZinc salt (Zn (Ac)2) Adding the mixture into the solution prepared in the step 1) (the mass ratio of the zinc acetate to the polyacrylonitrile is 2:1), and stirring for 8 hours at a speed of 400 r/min;
3) subjecting the solution prepared in the step 2) to electrostatic spinning at a voltage of 20kV and a set flow rate of 0.6mL/h and a distance of 17.5cm to obtain PAN/Zn (Ac)2A composite material;
4) the PAN/Zn (Ac) obtained in step 3) is added2Soaking the composite material in 0.1g/ml ethanol solution of 2-methylimidazole, and performing suction filtration after 17 hours to obtain ZIF-8/PAN/Zn (Ac)2Compounding nano fiber;
5) putting the composite material prepared in the step 4) into a muffle furnace for calcining at the heating rate of 1.5 ℃/min, preserving the temperature for 3h at 260 ℃, and naturally cooling to room temperature. Then transferring the mixture into a tubular furnace to calcine in argon, heating at the rate of 3.5 ℃/min, keeping the temperature at 700 ℃ for 15h, and naturally cooling to room temperature;
6) soaking the product prepared in the step 5) in hydrochloric acid for 15h, repeatedly washing with ethanol and deionized water for 7 times, and drying at 65 ℃ for 14h to obtain the nitrogen-doped porous carbon nanofiber composite material.
As shown in FIG. 2, it can be seen that the product is composed of porous carbon fibers having diameters distributed between 150 and 200 nm. The porous structure of carbon fiber is integrally in a coral reef shape, and the special porous structure endows the carbon material with larger specific surface area, so that the contact area of the electrode material and electrolyte is increased, the diffusion of sodium ions is facilitated, and the cycle performance and the rate capability of the electrode can be effectively improved.
Example 3:
1) adding 2.24g Polyacrylonitrile (PAN) into 16mL Dimethylformamide (DMF), and stirring at 70 ℃ for 4h at 300r/min to uniformly disperse PAN in DMF;
2) 2.24g of zinc acetate (Zn (Ac))2) Adding the mixture into the solution prepared in the step 1) (the mass ratio of the zinc acetate to the polyacrylonitrile is 1:1), and stirring for 10 hours at a speed of 300 r/min;
3) electrostatic spinning is carried out on the solution prepared in the step 2), the voltage is 22kV, the set flow is 0.8mL/h, the distance is 20cm, and PAN/Zn (Ac) is obtained2A composite material;
4) the PAN/Zn (Ac) obtained in step 3) is added2Soaking the composite material in 0.05g/ml ethanol solution of 2-methylimidazole, and performing suction filtration after 24 hours to obtain ZIF-8/PAN/Zn (Ac)2Compounding nano fiber;
5) putting the composite material prepared in the step 4) into a muffle furnace for calcining at the heating rate of 1 ℃/min, preserving the temperature for 4h at 240 ℃, and naturally cooling to the room temperature. Then transferring the mixture into a tubular furnace to calcine the mixture in argon, keeping the temperature at 650 ℃ for 24h at the heating rate of 2 ℃/min, and naturally cooling the mixture to room temperature;
6) soaking the product prepared in the step 5) in nitric acid for 24 hours, repeatedly washing with ethanol and deionized water for 8 times, and drying at 50 ℃ for 18 hours to obtain the nitrogen-doped porous carbon nanofiber composite material.
As shown in fig. 3, it can be seen that the product exhibits a hierarchical pore structure. The lattice spacing of C was 0.384nm, consistent with XRD results. The larger interlayer distance is more beneficial to the storage of sodium ions and the relief of volume expansion in the charge-discharge process. From the EDS spectrum of fig. 3, it can be seen that N element is uniformly distributed in the coral reef-like C material. The existence of nitrogen element further increases the conductivity of the material and improves the electrochemical active site.
As shown in FIG. 4, the product was prepared at 10A g when used in a sodium ion battery-1The performance of the alloy is tested under the current density, and the specific capacity of the alloy can reach 130mAh g after 1450 circles of circulation-1The above results show excellent long-cycle stability.
The attached drawings of the embodiments also clearly show that the product prepared by the invention is the nitrogen-doped porous carbon nanofiber composite material.
Claims (10)
1. A porous nitrogen-doped carbon fiber composite material for a lithium/sodium ion battery cathode is characterized in that the composite material is in a porous structure, nitrogen is doped in carbon fibers, and the porous carbon fibers are mutually crosslinked to form a three-dimensional network structure.
2. A preparation method of a nitrogen-doped porous carbon nanofiber composite material for a lithium/sodium ion battery cathode; the method comprises the following steps:
1) adding Polyacrylonitrile (PAN) into Dimethylformamide (DMF), and stirring at 50-70 ℃ for 2-4h at 500r/min for 300-;
2) zinc acetate (Zn (Ac))2) Adding the solution into the solution prepared in the step 1), and stirring for 6-10h at the speed of 300-500 r/min;
3) electrostatic spinning the solution obtained in step 2) to obtain PAN/Zn (Ac)2A composite material;
4) subjecting the PAN/Zn (Ac) obtained in step 3)2Soaking the composite material in an ethanol solution of 2-methylimidazole, and then performing suction filtration to obtain ZIF-8/PAN/Zn (Ac)2Compounding nano fiber;
5) putting the composite material prepared in the step 4) into a muffle furnace for calcining, and naturally cooling to room temperature; then transferring the mixture into a tubular furnace to calcine in argon, and naturally cooling the mixture to room temperature;
6) soaking the product prepared in the step 5) in acid to etch away zinc element, washing and drying to obtain the nitrogen-doped porous carbon nanofiber composite material.
3. The method as set forth in claim 2, wherein the concentration of polyacrylonitrile in the step 1) is 0.05-0.14 g/mL.
4. The method as set forth in claim 2, characterized in that the mass ratio of zinc acetate to polyacrylonitrile in the step 2) is 1:1 to 3: 1.
5. The method as set forth in claim 2, wherein the electrospinning conditions in the step 3) are: the voltage is 18-22kV, the set flow is 0.4-0.8mL/h, and the distance is 15-20 cm.
6. The method as set forth in claim 2, wherein the concentration of 2-methylimidazole in the step 4) is 0.05-0.15g/mL, and the soaking time is 10-24 h.
7. The method as set forth in claim 2, characterized in that the muffle furnace calcination conditions in step 5) are: the heating rate is 1-2 ℃/min, the temperature is kept at the temperature of 240-280 ℃ for 2-4h, and then the temperature is naturally cooled to the room temperature.
8. The method as set forth in claim 2, characterized in that the tube furnace calcination conditions in the step 5) are as follows: the heating rate is 2-5 ℃/min, the temperature is kept at 650-750 ℃ for 6-10h, and then the temperature is naturally cooled to the room temperature.
9. The method as set forth in claim 2, wherein in the step 6), the acid is one of sulfuric acid, nitric acid or hydrochloric acid, the soaking time is 6-24h, and the washing is performed 6-8 times by using ethanol and deionized water.
10. The method as set forth in claim 2, wherein the drying conditions in the step 6) are: drying at 50-80 deg.C for 10-18 h.
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| CN113279091A (en) * | 2021-07-22 | 2021-08-20 | 北京理工大学深圳汽车研究院(电动车辆国家工程实验室深圳研究院) | Porous carbon fiber, preparation method thereof and sodium ion battery |
| CN114267829A (en) * | 2021-12-08 | 2022-04-01 | 新疆大学 | Preparation method of coal-based porous carbon fiber negative electrode material of lithium/sodium ion battery |
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| CN114464810A (en) * | 2022-02-16 | 2022-05-10 | 广州大学 | Preparation method and application of sodium ion battery negative electrode material |
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