CN115831624A - Carbon nanofiber composite material, preparation method thereof and energy storage device - Google Patents
Carbon nanofiber composite material, preparation method thereof and energy storage device Download PDFInfo
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Abstract
The invention discloses a carbon nanofiber composite material, a preparation method thereof and an energy storage device, wherein the carbon nanofiber composite material takes a carbon nanofiber membrane as a matrix, the carbon nanofiber membrane comprises nitrogen-doped carbon nanofibers, holes are distributed on the surface and inside of the nitrogen-doped carbon nanofibers, nitrogen-doped carbon nanotubes grow on the surface and inside of the nitrogen-doped carbon nanofibers, and Co nanoparticles are packaged at the end openings of the nitrogen-doped carbon nanotubes. The carbon nanofiber composite material disclosed by the invention is large in specific surface area, good in conductivity, more in metal active sites, self-supporting and excellent in mechanical property, and the capacity and rate capability of the carbon nanofiber composite material are improved by utilizing the synergistic effect of the pseudocapacitance and the double electric layers by introducing Co and ZIF-8 into the carbon nanofiber composite material, so that the carbon nanofiber composite material can be widely applied to energy storage devices.
Description
Technical Field
The invention belongs to the technical field of new energy, and relates to a carbon nanofiber composite material, a preparation method thereof and an energy storage device.
Background
Among a plurality of carbon materials, the carbon nanofiber material has the characteristics of good conductivity, larger length-diameter ratio, larger specific surface area, better chemical corrosion resistance and the like, is a functional material with excellent performance, and is widely applied to the field of new energy. In addition, the Faraday electrode material has various special electrochemical properties and is widely applied to the field of new energy, the Faraday electrode material enhances charge transfer in a wider range due to oxidation-reduction reaction generated by the Faraday electrode material, and the generated Faraday capacitance (pseudo capacitance) is greatly improved compared with the electric double layer capacitance of a common carbon material. The typical representation of the Faraday electrode material is transition metal oxide, and the pseudocapacitance provided by the Faraday electrode material can greatly improve the capacitance performance of the material, so that the material has super capacitance and excellent electrochemical performance.
Currently, combining a carbon material with a faraday electrode material is a common method for improving the electrochemical performance of the material, for example, CN106449159A discloses a flexible electrode for a capacitor made of carbon fiber coated with a metal oxide and a preparation method thereof, which is a flexible film made of electrospun carbon nanofibers coated with metal oxide nanoparticles having pseudocapacitive characteristics, and can be used for a flexible supercapacitor. For example, CN114823153A discloses a flexible sodium ion capacitor electrode material, which is a carbon-based two-dimensional thin film loaded with a metal bismuth salt and instantaneously heated to obtain a carbon-based two-dimensional thin film electrode material loaded with bismuth nanoparticles. For example, CN114400325A discloses a preparation method of a silicon-carbon fiber film and its application as a negative electrode material of a lithium ion battery, wherein the fiber film is obtained by performing electrostatic spinning on a spinning solution containing polyacrylonitrile, F127 and nano silicon powder, and then carbonizing.
However, the material prepared by the method has the defects of small specific surface area, few metal active sites and unobvious conductivity improvement, and the improvement of the electrochemical performance of the material is limited. Therefore, it is desirable to provide a material with a large specific surface area, good conductivity, many metal active sites, and good electrochemical properties.
Disclosure of Invention
In view of the above problems in the prior art, the present invention is directed to a carbon nanofiber composite, a method for preparing the same, and an energy storage device.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a carbon nanofiber composite material, where a carbon nanofiber membrane is used as a substrate, the carbon nanofiber membrane includes nitrogen-doped carbon nanofibers, holes are distributed on the surface and inside of the nitrogen-doped carbon nanofibers, nitrogen-doped carbon nanotubes grow on the surface and inside of the nitrogen-doped carbon nanofibers, and Co nanoparticles are encapsulated at ports of the nitrogen-doped carbon nanotubes.
The carbon nanofiber composite material has excellent electrochemical performance, which is mainly attributed to the following aspects: first, the carbon nanofiber membrane has self-supporting characteristics and better mechanical properties. Secondly, the carbon nanofiber membrane comprises nitrogen-doped carbon nanofibers, and holes are distributed on the surface and in the nitrogen-doped carbon nanofibers, so that on one hand, the nitrogen doping improves the pseudocapacitance and the wettability of the carbon nanofiber composite material; on the other hand, the specific surface area of the carbon nanofiber composite material is increased due to the existence of the pores, the electric double layer capacitance is favorably improved, the transfer rate and the storage capacity of ions in the electrolyte in the carbon nanofiber composite material are improved, and the good metal active site distribution in the carbon nanofiber composite material is favorably realized. Thirdly, nitrogen-doped carbon nanotubes grow on the surface and inside of the nitrogen-doped carbon nanofiber, and the existence of the nitrogen-doped carbon nanotubes further improves the specific surface area, the conductivity, the pseudocapacitance and the wettability of the carbon nanofiber composite material. And fourthly, co nano particles are packaged at the ports of the nitrogen-doped carbon nano tubes, so that the pseudocapacitance of the carbon nano fiber composite material is improved, and the capacity and the rate capability of the carbon nano fiber composite material are improved under the synergistic effect of the pseudocapacitance provided by the Co nano particles and the electric double layer capacitance.
Preferably, the carbon nano-meterThe specific surface area of the fiber composite material is 90-420m 2 g -1 For example, it may be 90m 2 g -1 、140m 2 g -1 、210m 2 g -1 、280m 2 g -1 、350m 2 g -1 Or 420m 2 g -1 And the like.
Preferably, the pore volume of the carbon nanofiber composite is 0.09 to 0.42cm 3 g -1 For example, it may be 0.09cm 3 g -1 、0.13cm 3 g -1 、0.2cm 3 g -1 、0.27cm 3 g -1 、0.34cm 3 g -1 Or 0.42cm 3 g -1 And the like.
Preferably, the pores in the carbon nanofibers include micropores, mesopores, and macropores.
In the present invention, micropores refer to pores having a pore diameter of less than 2nm, mesopores refer to pores having a pore diameter of 2 to 50nm, and macropores refer to pores having a pore diameter of more than 50 nm.
Preferably, the content of Co nanoparticles in the carbon nanofiber composite is 0.04-0.3%, and may be, for example, 0.04%, 0.1%, 0.16%, 0.22%, 0.28%, 0.3%, or the like.
Preferably, the length of the nitrogen-doped carbon nanotube on the surface of the nitrogen-doped carbon nanofiber is 100-550nm, and may be, for example, 100nm, 200nm, 300nm, 400nm, 500nm, 550nm, or the like.
The length of the nitrogen-doped carbon nano tube on the surface of the nitrogen-doped carbon nano fiber is longer, and the reason is that under the action of staged temperature control and dicyanodiamide carrying, co ions are catalyzed to form a longer carbon tube; the advantage is that longer carbon tubes can have more beneficial conductivity, providing higher specific surface area.
Preferably, the doping amount of the N element in the carbon nanofiber composite material is 7 to 12%, and for example, may be 7%, 8%, 9%, 10%, 11%, 12%, or the like.
In a second aspect, the present invention provides a method for preparing a carbon nanofiber composite as described in the first aspect, the method comprising the steps of:
(1) Dispersing a polymer, ZIF-8 and a cobalt source in a solvent to obtain a precursor dispersion liquid;
(2) Performing electrostatic spinning on the precursor dispersion liquid obtained in the step (1) to obtain a nanofiber membrane;
(3) Carbonizing the nanofiber membrane and the nitrogen source in the step (2) in a protective atmosphere to prepare the carbon nanofiber composite material.
According to the preparation method, a precursor dispersion liquid formed by a polymer, ZIF-8 and a cobalt source is subjected to electrostatic spinning to prepare a nanofiber membrane, the cobalt source is successfully loaded into the nanofiber membrane, and through the subsequent carbonization step with a nitrogen source in a protective atmosphere, the ZIF-8 structure collapses to achieve the pore-forming effect, a graded porous structure is generated inside and on the surface of the carbon nanofiber, the electric double layer capacitance is greatly improved, the transfer rate and the storage capacity of ions in the electrolyte inside the carbon nanofiber membrane are improved, and the specific surface area of the carbon nanofiber composite material is also improved; meanwhile, a cobalt source is converted into cobalt nanoparticles, and the cobalt nanoparticles catalyze the growth of bamboo-like nitrogen-doped carbon nanotubes on the surface and in the carbon nanofibers, so that the specific surface area, the pseudocapacitance and the wettability of the carbon nanofiber composite material are improved, the graphitization degree of the carbon nanofiber composite material is also improved, and the conductivity of the carbon nanofiber composite material is further improved; on the other hand, the cobalt nanoparticles also improve the pseudocapacitance of the carbon nanofiber composite material.
The preparation method is simple, only utilizes the electrostatic spinning and carbonization processes, has low cost, and is suitable for large-scale industrial production.
Preferably, the mass ratio of the polymer, the ZIF-8 and the cobalt source in the step (1) is (7-9): (9-11): (4-6), wherein the polymer can be selected from 7-9, such as 7, 7.2, 7.4, 7.6, 7.8, 8, 8.2, 8.4, 8.6, 8.8 or 9, the ZIF-8 can be selected from 9, 9.2, 9.4, 9.6, 9.8, 10, 10.2, 10.4, 10.6, 10.8 or 11, the like, the ZIF-8 can be selected from 9-11, such as 9, 9.2, 9.4, 9.6, 9.8, 10, 10.2, 10.4, 10.6, 10.8 or 11, and the like, and the cobalt source can be selected from 4-6, such as 4, 4.2, 4.4, 4.6, 4.8, 5, 5.2, 5.4, 5.6, 5.8 or 6, and the like.
In the invention, when the mass ratio of the polymer, the ZIF-8 and the cobalt source is in the range, the carbon nanofiber composite material with better performance can be prepared, if the content of the ZIF-8 is more, more pore structures are formed inside the carbonized fibers, and if the content of the ZIF-8 is less, the pore structures inside the carbon fibers are greatly reduced; if the content of the cobalt source is high, more carbon nano tubes are generated, and if the content of the cobalt source is low, the generated carbon nano tubes are relatively reduced, but the content of the Co source is high, so that the spinning is adversely affected.
Preferably, the polymer of step (1) comprises at least one of polyacrylonitrile, polycaprolactone or polylactic acid.
Preferably, the cobalt source of step (1) comprises Co (NO) 3 ) 2 ·6H 2 O and/or C 10 H 16 CoO4。
Preferably, the precursor dispersion liquid in step (1) further comprises an excipient.
Preferably, the excipient comprises polyvinylpyrrolidone and/or polyvinyl alcohol.
Preferably, the precursor dispersion liquid in step (1) is prepared according to the following method:
firstly, dissolving a polymer in a solvent, then adding an excipient, sequentially adding ZIF-8 and a cobalt source after dissolving, and continuously stirring to obtain the precursor dispersion liquid.
The precursor dispersion prepared according to the above procedure has the advantage that the pore-forming agent ZIF-8 and Co source can be directly embedded into and on the surface of the fiber together.
Preferably, the material pushing speed of the electrostatic spinning in the step (2) is 0.5-1.0mL/h, such as 0.5mL/h, 0.6mL/h, 0.7mL/h, 0.8mL/h, 0.9mL/h or 1.0mL/h, etc.
Preferably, the voltage for electrospinning in step (2) is 20-25 kv, such as 20 kv, 21 kv, 22 kv, 23 kv, 24 kv or 25 kv.
Preferably, during the electrostatic spinning in step (2), the distance between the nanofiber membrane receiving device and the needle is 10-15cm, such as 10cm, 11cm, 12cm, 13cm, 14cm or 15 cm.
Preferably, the electrostatic spinning time in step (2) is 20-30h, such as 20h, 21h, 22h, 23h, 24h, 25h, 26h, 27h, 28h, 29h or 30h.
Preferably, the mass ratio of the nanofiber membrane and the nitrogen source in the step (3) is (2-7): 1, and the "2-7" can be, for example, 2, 3, 4, 5, 6 or 7.
In the present invention, when the content of the nitrogen source is too large, the structure of the fiber is broken at a high temperature, and when the content of the nitrogen source is too small, the growth of the carbon nanotube is not facilitated.
Preferably, the nitrogen source of step (3) comprises dicyandiamide and/or melamine.
Preferably, the carbonization in the step (3) is performed in the following manner:
heating at 200-500 deg.C for 1-4 hr, and then heating at 600-1200 deg.C for 0.5-3 hr, such as 200-500 deg.C, 300 deg.C, 350 deg.C, 400 deg.C, 450 deg.C or 500 deg.C; for example, "1-4h" can be 1h, 2h, 3h, or 4h, etc.; for example, "600 to 1200 ℃ may be 600 ℃, 700 ℃, 800 ℃, 900 ℃, 1000 ℃, 1100 ℃, 1200 ℃ or the like, and for example," 0.5 to 3 hours "may be 0.5 hours, 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours or the like.
In the invention, the staged heating aims at precipitating a Co source on the surface of the fiber and improving the stability of the fiber structure, and is beneficial to improving the mechanical property of the carbon nanofiber composite material.
Preferably, the nitrogen source of step (3) is heated upstream of the tube furnace.
The advantage of heating the nitrogen source upstream of the tube furnace is that the gas formed after heating the nitrogen source is effectively received by the fibres.
Preferably, the nanofiber membrane is preheated before the carbonization in step (3).
In the present invention, the purpose of preheating the nanofiber membrane is to stabilize the polymer structure, preventing direct carbonization from destroying the polymer structure until irreversible.
Preferably, the temperature of the preheating is 100-300 ℃, such as 100 ℃, 150 ℃, 200 ℃, 250 ℃ or 300 ℃ and the like.
Preferably, the preheating time is 1-3h, such as 1h, 1.5h, 2h, 2.5h or 3h, etc.
The gas in the protective atmosphere in step (3) is not limited, and the gas may include at least one of nitrogen or argon, for example.
In a third aspect, the present invention provides an energy storage device comprising the carbon nanofiber composite of the first aspect of the present invention.
The present invention is not limited to the kind of energy storage device, and the energy storage device includes, but is not limited to, a lithium battery, a sodium battery, a fuel cell, and a capacitor, by way of example.
Compared with the prior art, the invention has the following beneficial effects:
(1) The carbon nanofiber composite material disclosed by the invention is large in specific surface area, good in conductivity, more in metal active sites, self-supporting and excellent in mechanical property, and the capacity and rate capability of the carbon nanofiber composite material are improved by utilizing the synergistic effect of the pseudocapacitance and the double electric layers by introducing Co and ZIF-8 into the carbon nanofiber composite material, so that the carbon nanofiber composite material can be widely applied to energy storage devices.
(2) The preparation method is simple, the nanofiber membrane is obtained by performing electrostatic spinning on the precursor dispersion liquid formed by the polymer, the ZIF-8 and the cobalt source, and then the nanofiber membrane is carbonized to prepare the carbon nanofiber composite material, so that the carbon nanofiber composite material is low in cost and suitable for large-scale industrial production.
Drawings
FIG. 1 shows the flexibility test results of the carbon nanofiber composite in example 1 of the present invention;
FIG. 2 is a result of a conductivity test of a carbon nanofiber composite in example 1 of the present invention;
FIG. 3 is a Scanning Electron Microscope (SEM) image of a nanofiber membrane in example 1 of the present invention;
fig. 4 is an SEM image of the carbon nanofiber composite in example 1 of the present invention;
FIG. 5 shows the results of Raman testing of the carbon nanofiber composite in example 1 of the present invention;
FIG. 6 is X-ray photoelectron spectroscopy (XPS) results of a carbon nanofiber composite in example 1 of the present invention;
FIG. 7 is a graph showing adsorption and desorption curves of nitrogen gas by the carbon nanofiber composite in example 1 of the present invention;
FIG. 8 is a graph showing the impedance profile of the carbon nanofiber composite in example 1 of the present invention;
fig. 9 is a cyclic voltammogram of the carbon nanofiber composite in example 1 of the present invention.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
"room temperature" in the examples of the present invention means 25 ℃.
Example 1
The embodiment provides a carbon nanofiber composite material, which takes a carbon nanofiber membrane as a substrate, wherein the carbon nanofiber membrane comprises nitrogen-doped carbon nanofibers, holes are distributed on the surface and inside of the nitrogen-doped carbon nanofibers, nitrogen-doped carbon nanotubes grow on the surface and inside of the nitrogen-doped carbon nanofibers, and Co nanoparticles are encapsulated at the ports of the nitrogen-doped carbon nanotubes;
wherein the specific surface area of the carbon nanofiber composite material is 415.8m 2 g -1 The pore volume of the carbon nanofiber composite material is 0.415cm 3 g -1 (ii) a The content of Co nano particles in the carbon nanofiber composite material is 0.2%, the length of the nitrogen-doped carbon nano tube on the surface of the nitrogen-doped carbon nanofiber is 500nm, and the doping amount of N element in the carbon nanofiber composite material is 12%.
The preparation method of the carbon nanofiber composite material comprises the following steps:
(1) Adding 0.8g Polyacrylonitrile (PAN) to 10mL N, N-Dimethylformamide (DMF), stirring to dissolve completely, adding 0.2g polyvinylpyrrolidone (PVP), stirring at 50 deg.C to dissolve completely, mixing 1.0g ZIF-8 and 0.5g Co (NO) 3 ) 2 ·6H 2 O is in turnAdding into the above solution, and stirring at 40 deg.C for 12 hr to obtain precursor dispersion;
(2) Performing electrostatic spinning on the precursor dispersion liquid by using an electrostatic spinning device, transferring the precursor dispersion liquid into an injector with a stainless steel needle, connecting the stainless steel needle with a constant-pressure device, controlling the material pushing speed to be 0.8mL/h, controlling the voltage of the constant-pressure device to be 23 kilovolt, fixing the distance between a nanofiber membrane receiving device and the needle to be 13cm, controlling the humidity of a spinning chamber to be 75 +/-5%, controlling the temperature to be 25 +/-2 ℃, controlling the electrostatic spinning time to be 24h, and preparing to obtain a nanofiber membrane after the electrostatic spinning is finished;
(3) Preheating the nanofiber membrane in the step (2) in an oven at 220 ℃ for 2h, then respectively placing 40mg of the preheated nanofiber membrane and 8mg of dicyanodiamide in ceramic boats, placing the ceramic boats filled with dicyanodiamide at the upstream of a tube furnace, placing the ceramic boats in a nitrogen (with the purity of 99.999%) atmosphere, heating to 400 ℃ at a heating rate of 2 ℃/min, then preserving heat for 2h, heating to 900 ℃ at a heating rate of 5 ℃/min, preserving heat for 1h, and naturally cooling to room temperature to prepare the carbon nanofiber composite material.
Example 2
The embodiment provides a carbon nanofiber composite material, which takes a carbon nanofiber membrane as a substrate, wherein the carbon nanofiber membrane comprises nitrogen-doped carbon nanofibers, holes are distributed on the surface and inside of the nitrogen-doped carbon nanofibers, nitrogen-doped carbon nanotubes grow on the surface and inside of the nitrogen-doped carbon nanofibers, and Co nanoparticles are encapsulated at the ports of the nitrogen-doped carbon nanotubes;
wherein the specific surface area of the carbon nanofiber composite material is 157.2m 2 g -1 The pore volume of the carbon nanofiber composite material is 0.094cm 3 g -1 (ii) a The content of Co nanoparticles in the carbon nanofiber composite material is 0.04%, the length of the nitrogen-doped carbon nanotube on the surface of the nitrogen-doped carbon nanofiber is 100nm, and the doping amount of an N element in the carbon nanofiber composite material is 9.7%.
The preparation method of the carbon nanofiber composite material comprises the following steps:
(1) Adding 0.7g of polycaprolactone into 10mL of DMF, stirring until the polycaprolactone is completely dissolved, adding 0.2g of PVP, and stirring at 50 ℃ until the polycaprolactone is completely dissolved; mixing 0.9g ZIF-8, 0.4g Co (NO) 3 ) 2 ·6H 2 Sequentially adding O into the solution and stirring at 50 ℃ for 12h to obtain a precursor dispersion liquid;
(2) Performing electrostatic spinning on the precursor dispersion liquid by using an electrostatic spinning device, transferring the precursor dispersion liquid into an injector with a stainless steel needle, connecting the stainless steel needle with a constant-voltage device, controlling the material pushing speed to be 1mL/h, controlling the voltage of the constant-voltage device to be 25 kilovolts, fixing the distance between a nanofiber membrane receiving device and the needle to be 15cm, controlling the humidity of a spinning chamber to be 75 +/-5%, controlling the temperature to be 25 +/-2 ℃, controlling the electrostatic spinning time to be 20h, and preparing a nanofiber membrane after the electrostatic spinning is finished;
(3) Preheating the nanofiber membrane in the step (2) in an oven at 120 ℃ for 4h, then respectively placing 24mg of the preheated nanofiber membrane and 8mg of melamine in a porcelain boat, placing the porcelain boat filled with the melamine at the upstream of a tube furnace, placing the porcelain boat in a nitrogen (with the purity of 99.999%) atmosphere, heating to 200 ℃, then preserving heat for 4h, then heating to 700 ℃ at the heating rate of 5 ℃/min, preserving heat for 3h, and naturally cooling to room temperature to prepare the carbon nanofiber composite material.
Example 3
The embodiment provides a carbon nanofiber composite material, which takes a carbon nanofiber membrane as a substrate, wherein the carbon nanofiber membrane comprises nitrogen-doped carbon nanofibers, holes are distributed on the surface and inside of the nitrogen-doped carbon nanofibers, nitrogen-doped carbon nanotubes grow on the surface and inside of the nitrogen-doped carbon nanofibers, and Co nanoparticles are encapsulated at the ports of the nitrogen-doped carbon nanotubes;
wherein the specific surface area of the carbon nanofiber composite material is 97.4m 2 g -1 The pore volume of the carbon nanofiber composite material is 0.103cm 3 g -1 (ii) a The content of Co nano particles in the carbon nano fiber composite material is 0.3 percent, and the nitrogen-doped carbon nano on the surface of the nitrogen-doped carbon nano fiberThe length of the rice tube is 500nm, and the doping amount of the N element in the carbon nanofiber composite material is 7%.
The preparation method of the carbon nanofiber composite material comprises the following steps:
(1) Adding 0.9g of polylactic acid into 10mL of DMF, stirring until the polylactic acid is completely dissolved, then adding 0.2g of PVP, and stirring at 50 ℃ until the polylactic acid is completely dissolved; mixing ZIF-8 (1.1 g) and Co (NO) (0.6 g) 3 ) 2 ·6H 2 Sequentially adding O into the solution and stirring for 12h at 60 ℃ to obtain a precursor dispersion liquid;
(2) Performing electrostatic spinning on the precursor dispersion liquid by using an electrostatic spinning device, transferring the precursor dispersion liquid into an injector with a stainless steel needle, connecting the stainless steel needle with a constant-pressure device, controlling the material pushing speed to be 0.5mL/h, controlling the voltage of the constant-pressure device to be 20 kilovolts, fixing the distance between a nanofiber membrane receiving device and the needle to be 10cm, controlling the humidity of a spinning chamber to be 75 +/-5%, controlling the temperature to be 25 +/-2 ℃, controlling the electrostatic spinning time to be 30h, and preparing a nanofiber membrane after the electrostatic spinning is finished;
(3) Preheating the nanofiber membrane in the step (2) in an oven at 300 ℃ for 1h, then respectively placing 56mg of the preheated nanofiber membrane and 8mg of dicyanodiamide in ceramic boats, placing the ceramic boats filled with dicyanodiamide at the upstream of a tube furnace, placing the ceramic boats in a nitrogen (with the purity of 99.999%) atmosphere, heating to 300 ℃ at a heating rate of 2 ℃/min, then preserving heat for 3h, heating to 1100 ℃ at a heating rate of 5 ℃/min, preserving heat for 1.5h, and naturally cooling to room temperature to prepare the carbon nanofiber composite material.
Example 4
The embodiment provides a carbon nanofiber composite material, which takes a carbon nanofiber membrane as a substrate, wherein the carbon nanofiber membrane comprises nitrogen-doped carbon nanofibers, holes are distributed on the surface and inside of the nitrogen-doped carbon nanofibers, nitrogen-doped carbon nanotubes grow on the surface and inside of the nitrogen-doped carbon nanofibers, and Co nanoparticles are encapsulated at the ports of the nitrogen-doped carbon nanotubes;
wherein the specific surface area of the carbon nanofiber composite material is 215.4m 2 g -1 What is, what isThe pore volume of the carbon nanofiber composite material is 0.286cm 3 g -1 (ii) a The content of Co nano particles in the carbon nanofiber composite material is 0.08%, the length of the nitrogen-doped carbon nano tube on the surface of the nitrogen-doped carbon nanofiber is 500nm, and the doping amount of N element in the carbon nanofiber composite material is 11%.
The preparation method is different from that of example 1 only in that Co (NO) 3 ) 2 ·6H 2 The amount of O added was 0.2g.
Example 5
The embodiment provides a carbon nanofiber composite material, which takes a carbon nanofiber membrane as a substrate, wherein the carbon nanofiber membrane comprises nitrogen-doped carbon nanofibers, holes are distributed on the surface and inside of the nitrogen-doped carbon nanofibers, nitrogen-doped carbon nanotubes grow on the surface and inside of the nitrogen-doped carbon nanofibers, and Co nanoparticles are encapsulated at the ports of the nitrogen-doped carbon nanotubes;
wherein the specific surface area of the carbon nanofiber composite material is 408.3m 2 g -1 The pore volume of the carbon nanofiber composite material is 0.403cm 3 g -1 (ii) a The content of Co nano particles in the carbon nanofiber composite material is 0.4%, the length of the nitrogen-doped carbon nano tube on the surface of the nitrogen-doped carbon nanofiber is 500nm, and the doping amount of N element in the carbon nanofiber composite material is 13%.
The preparation method is different from that of example 1 only in that Co (NO) 3 ) 2 ·6H 2 The amount of O added was 0.7g.
Example 6
The embodiment provides a carbon nanofiber composite material, which takes a carbon nanofiber membrane as a substrate, wherein the carbon nanofiber membrane comprises nitrogen-doped carbon nanofibers, holes are distributed on the surface and inside of the nitrogen-doped carbon nanofibers, nitrogen-doped carbon nanotubes grow on the surface and inside of the nitrogen-doped carbon nanofibers, and Co nanoparticles are encapsulated at the ports of the nitrogen-doped carbon nanotubes;
wherein the carbon nanofiber compositeHas a specific surface area of 193.4m 2 g -1 The pore volume of the carbon nanofiber composite material is 0.135cm 3 g -1 (ii) a The content of Co nano particles in the carbon nanofiber composite material is 0.2%, the length of the nitrogen-doped carbon nano tube on the surface of the nitrogen-doped carbon nanofiber is 500nm, and the doping amount of N element in the carbon nanofiber composite material is 11%.
The preparation method was different from example 1 only in that 0.5g of ZIF-8 was added.
Example 7
The embodiment provides a carbon nanofiber composite material, which takes a carbon nanofiber membrane as a substrate, wherein the carbon nanofiber membrane comprises nitrogen-doped carbon nanofibers, holes are distributed on the surface and inside of the nitrogen-doped carbon nanofibers, nitrogen-doped carbon nanotubes grow on the surface and inside of the nitrogen-doped carbon nanofibers, and Co nanoparticles are encapsulated at the ports of the nitrogen-doped carbon nanotubes;
wherein the carbon nanofiber composite has a specific surface area of 395.4m 2 g -1 The pore volume of the carbon nanofiber composite material is 0.387cm 3 g -1 (ii) a The content of Co nano particles in the carbon nanofiber composite material is 0.1%, the length of the nitrogen-doped carbon nano tube on the surface of the nitrogen-doped carbon nanofiber is 500nm, and the doping amount of N element in the carbon nanofiber composite material is 12%.
The preparation method was different from example 1 only in that the amount of ZIF-8 added was 1.5g.
Example 8
The embodiment provides a carbon nanofiber composite material, which takes a carbon nanofiber membrane as a substrate, wherein the carbon nanofiber membrane comprises nitrogen-doped carbon nanofibers, holes are distributed on the surface and inside of the nitrogen-doped carbon nanofibers, nitrogen-doped carbon nanotubes grow on the surface and inside of the nitrogen-doped carbon nanofibers, and Co nanoparticles are encapsulated at the ports of the nitrogen-doped carbon nanotubes;
wherein the carbon nanofiber composite has a specific surface area of 336.2m 2 g -1 The pore volume of the carbon nanofiber composite material is 0.324cm 3 g -1 (ii) a The content of Co nano particles in the carbon nanofiber composite material is 0.2%, the length of the nitrogen-doped carbon nano tube on the surface of the nitrogen-doped carbon nanofiber is 300nm, and the doping amount of N element in the carbon nanofiber composite material is 10%.
The preparation process was compared with example 1, except that dicyanodiamide was added in an amount of 5g.
Example 9
The embodiment provides a carbon nanofiber composite material, which takes a carbon nanofiber membrane as a substrate, wherein the carbon nanofiber membrane comprises nitrogen-doped carbon nanofibers, holes are distributed on the surface and inside of the nitrogen-doped carbon nanofibers, nitrogen-doped carbon nanotubes grow on the surface and inside of the nitrogen-doped carbon nanofibers, and Co nanoparticles are encapsulated at the ports of the nitrogen-doped carbon nanotubes;
wherein the specific surface area of the carbon nanofiber composite material is 376.4m 2 g -1 The pore volume of the carbon nanofiber composite material is 0.372cm 3 g -1 (ii) a The content of Co nano particles in the carbon nanofiber composite material is 0.2%, the length of the nitrogen-doped carbon nano tube on the surface of the nitrogen-doped carbon nanofiber is 400nm, and the doping amount of N element in the carbon nanofiber composite material is 13%.
The preparation process was compared with example 1, except that the amount of dicyanodiamide added was 22g.
Example 10
The embodiment provides a carbon nanofiber composite material, which takes a carbon nanofiber membrane as a substrate, wherein the carbon nanofiber membrane comprises nitrogen-doped carbon nanofibers, holes are distributed on the surface and inside of the nitrogen-doped carbon nanofibers, nitrogen-doped carbon nanotubes grow on the surface and inside of the nitrogen-doped carbon nanofibers, and Co nanoparticles are encapsulated at ports of the nitrogen-doped carbon nanotubes;
wherein the carbon nanofiber composite has a specific surface area of 76.3m 2 g -1 The pore volume of the carbon nanofiber composite material is 0.068cm 3 g -1 (ii) a The content of Co nano particles in the carbon nanofiber composite material is 0.2%, the length of the nitrogen-doped carbon nano tube on the surface of the nitrogen-doped carbon nanofiber is 300nm, and the doping amount of N element in the carbon nanofiber composite material is 13%.
The only difference compared to example 1 is that the nanofiber membrane was not preheated.
Example 11
The embodiment provides a carbon nanofiber composite material, which takes a carbon nanofiber membrane as a substrate, wherein the carbon nanofiber membrane comprises nitrogen-doped carbon nanofibers, holes are distributed on the surface and inside of the nitrogen-doped carbon nanofibers, nitrogen-doped carbon nanotubes grow on the surface and inside of the nitrogen-doped carbon nanofibers, and Co nanoparticles are encapsulated at the ports of the nitrogen-doped carbon nanotubes;
wherein the specific surface area of the carbon nanofiber composite material is 281.1m 2 g -1 The pore volume of the carbon nanofiber composite material is 0.306cm 3 g -1 (ii) a The content of Co nano particles in the carbon nanofiber composite material is 0.1%, the length of the nitrogen-doped carbon nano tube on the surface of the nitrogen-doped carbon nanofiber is 80nm, the number of the nitrogen-doped carbon nano tubes is extremely small, and the doping amount of N elements in the carbon nanofiber composite material is 12%.
The preparation method is compared with example 1, and the difference is only that the heating at 400 ℃ is not carried out for 2h in the step (3), and the heating at 900 ℃ is directly carried out for 1h.
Comparative example 1
The only difference compared to example 1 is that in step (2) NO Co (NO) is added 3 ) 2 ·6H 2 O。
Comparative example 2
The only difference compared to example 1 is that no ZIF-8 was added in step (2).
Comparative example 3
The only difference compared to example 1 is that ZIF-8 in step (2) was replaced with ZIF-67.
Comparative example 4
In comparative example 4, there is provided a method of preparing a carbon nanofiber composite, comprising:
(1) Adding 0.8g of PAN into 10mL of DMF, stirring until the PAN is completely dissolved, adding 0.2g of PVP, and stirring at 50 ℃ until the PVP is completely dissolved to obtain a precursor dispersion liquid;
(2) Performing electrostatic spinning on the precursor dispersion liquid by using an electrostatic spinning device, transferring the precursor solution into an injector with a stainless steel needle, connecting the stainless steel needle with a constant-pressure device, controlling the material pushing speed to be 0.8mL/h, controlling the voltage of the constant-pressure device to be 23 kilovolt, fixing the distance between a nanofiber membrane receiving device and the needle to be 13cm, controlling the humidity of a spinning chamber to be 75 +/-5%, controlling the temperature to be 25 +/-2 ℃, controlling the electrostatic spinning time to be 24h, and preparing to obtain a nanofiber membrane after the electrostatic spinning is finished;
(3) Mixing ZIF-8 (1.0 g) and Co (NO) (0.5 g) 3 ) 2 ·6H 2 Adding O into 10mL of DMF to form a mixed dispersion liquid, cutting the nanofiber membrane (with the size of 5cm multiplied by 8 cm) in the step (2), immersing into the mixed dispersion liquid, and performing freeze drying after immersing for 1 h;
(4) Preheating the nanofiber membrane subjected to freeze drying in the step (3) in an oven at 220 ℃ for 2h, then respectively placing 40mg of the preheated nanofiber membrane and 8mg of dicyanodiamide in porcelain boats, placing the porcelain boats containing dicyanodiamide at the upstream of a tube furnace, placing the porcelain boats in a nitrogen (with the purity of 99.999%) atmosphere, raising the temperature at a rate of 2 ℃/min to 400 ℃, then preserving the heat for 2h, then raising the temperature at a rate of 5 ℃/min to 900 ℃, preserving the heat for 1h, and naturally cooling to room temperature to prepare the carbon nanofiber composite material.
And (3) performance detection:
the flexibility of the carbon nanofiber composite of example 1 was tested, and the results of the test are shown in fig. 1, where a in fig. 1 is a state where the carbon nanofiber composite is not bent, b in fig. 1 and c in fig. 1 are states where the carbon nanofiber composite is bent by 180 ° and 45 °, respectively, and it is seen from fig. 1 that the carbon nanofiber composite of example 1 exhibits good flexibility.
The carbon nanofiber composite material of example 1 was cut out and tested for electrical conductivity, and the results of the test are shown in fig. 2, where a in fig. 2 is the light emission of the LED lamp when two copper clips are placed at both ends of the carbon nanofiber composite material (the distance between the two copper clips is 5 cm), b in fig. 2 is the light emission of the LED lamp when the two copper clips are in direct contact, and c in fig. 2 is the light emission of the LED lamp when the two copper clips are placed at one end and inside of the carbon nanofiber composite material (the distance between the two copper clips is 0.5 cm), and it can be seen from fig. 2 that the brightness of the LED lamp is almost the same in the above three cases, indicating that the carbon nanofiber composite material of example 1 has better electrical conductivity.
SEM images of the nanofiber membrane of example 1 were tested, and the test results are shown in fig. 3, and it can be seen from fig. 3 that the nanofibers of the nanofiber membrane of example 1 are in a tubular shape and are distributed in a staggered manner, and the diameter of the tube is in the range of 300-350 nm.
SEM images of the carbon nanofiber composite in example 1 were tested, and the test results are shown in fig. 4, and it can be seen from fig. 4 that the carbon nanofiber composite includes nitrogen-doped carbon nanofibers, carbon nanotubes are grown on the surfaces of the nitrogen-doped carbon nanofibers, and Co nanoparticles are encapsulated at the ports of the carbon nanotubes, wherein the lengths of the carbon nanotubes are in the range of 400-500 nm.
The carbon nanofiber composite of example 1 was subjected to a raman test, and the results of the test are shown in fig. 5, and it can be seen from fig. 5 that the degree of disorder or defect of the carbon structure of the prepared material is high.
The carbon nanofiber composite of example 1 was subjected to XPS test, and the results of the test are shown in fig. 6, and it is seen from fig. 6 that the surface chemical composition elements and electronic structure of the sample.
The adsorption and desorption conditions of the carbon nanofiber composite material in example 1 to nitrogen were tested by using a full-automatic specific surface area and porosity analyzer (BET), and the test results are shown in fig. 7, and as seen from fig. 7, the type iv isotherm has a definite hysteresis loop and gradually absorbs in a relative pressure range of 0.45 to 1.0, indicating that a large number of mesopores exist, which is mainly due to the decomposition of the ZIF-8 structure under a high temperature condition. In addition, the two samples above also show a distinct absorption peak at relative pressure (< 0.1), which may be a micropore present by evaporation of a portion of the metallic zinc.
The specific surface area and pore volume of the composites in examples 1-11 and comparative examples 1-4 were tested on BET and the results are shown in table 1.
TABLE 1
As seen from table 1, the carbon nanofiber composites prepared in the examples of the present invention have a large specific surface area and a large pore structure.
The composite material of example 1 was subjected to the resistance test, and the test results are shown in fig. 8, and it can be seen from fig. 8 that the graphs of the material are composed of the semicircle of the high frequency region and the slant line of the low frequency region, the charge transfer resistance and the high frequency axis intercept of the material are small, and the material has more excellent conductivity, charge transfer rate and faster ion diffusion/transmission.
The carbon nanofiber composite material in example 1 was used as an electrode material of a capacitor to assemble a capacitor, and the capacitor was subjected to cyclic voltammetry.
The assembling method of the capacitor comprises the following steps: the composite material is used as an electrode material to assemble a symmetrical super capacitor, 6M KOH is used as electrolyte, a polypropylene film is used as a super capacitor diaphragm, and a current collector is foamed nickel.
The capacitor test conditions were: the tested voltage range is 0-0.55V, and cyclic voltammetry curves under different scanning rates are respectively tested.
The results of the test are shown in fig. 9, and the specific capacitance of the carbon nanofiber composite in example 1 was calculated to be 1281.78 fg -1 Example obtained by the same method2-11 and comparative examples 1-4, the results are shown in table 2.
TABLE 2
As can be seen from the data in table 2, the carbon nanofiber composites prepared in the examples of the present invention have higher specific capacitance.
And (3) analysis:
the data in the examples show that the carbon nanofiber composite material of the present invention has a large number of pores distributed therein, a large specific surface area, and a high content of nitrogen-doped carbon nanotubes in the carbon nanofiber composite material, and the above factors have combined effects to make the carbon nanofiber composite material of the present invention have good electrical conductivity and high specific capacitance.
It can be seen from the data of example 1 and examples 4-7 that the content of the polymer, cobalt source and ZIF-8 in the precursor dispersion has a great influence on the performance of the carbon nanofiber composite, and when the content of the cobalt source and ZIF-8 is more or less, the content affects the performance of the prepared carbon nanofiber composite.
It can be seen from the data of example 1 and examples 8-9 that the content of the nitrogen source also affects the performance of the carbon nanofiber composite, and only when the content of the nitrogen source is within a proper range, the carbon nanofiber composite with excellent performance can be obtained.
As can be seen from the data of example 1 and example 10, preheating the nanofiber membrane is advantageous for improving the properties of the prepared carbon nanofiber composite.
As can be seen from the data of example 1 and example 11, staged heating has an important effect on the performance of the carbon nanofiber composite material in the present invention, and heating is performed at a lower temperature so that part of Co in the nanofibers is diffused to the surface of the nanofibers, so that nitrogen-doped carbon nanotubes are grown on the surface and inside of the nanofibers during carbonization, thereby better improving the specific surface area and conductivity of the carbon nanofiber composite material.
As can be seen from the data of example 1 and comparative examples 1-2, the cobalt source and ZIF-8 have significant effects on the performance of the carbon nanofiber composites of the present invention, and the absence of either one affects the performance of the carbon nanofiber composites.
It can be seen from the data of example 1 and comparative example 3 that when ZIF-8 was replaced with ZIF-67, a carbon nanofiber composite having better properties could not be prepared.
As can be seen from the data of example 1 and comparative example 4, compared with the method of spinning with a solution of PAN to prepare a nanofiber membrane and then adding a cobalt source and ZIF-8 to the prepared nanofiber membrane, the method of directly electrospinning a precursor dispersion liquid composed of PAN, a cobalt source and ZIF-8 according to the present invention produces a composite material having a larger specific surface area, better electrical conductivity and more excellent electrochemical properties.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. The carbon nanofiber composite material is characterized in that a carbon nanofiber membrane is used as a matrix of the carbon nanofiber composite material, the carbon nanofiber membrane comprises nitrogen-doped carbon nanofibers, holes are distributed on the surface and inside of the nitrogen-doped carbon nanofibers, nitrogen-doped carbon nanotubes grow on the surface and inside of the nitrogen-doped carbon nanofibers, and Co nanoparticles are packaged at ports of the nitrogen-doped carbon nanotubes.
2. The carbon nanofiber composite according to claim 1, wherein the carbon nanofiber composite has a specific surface area of 90 to 420m 2 g -1 ；
Preferably, the pore volume of the carbon nanofiber composite is 0.09 to 0.42cm 3 g -1 ；
Preferably, the pores in the carbon nanofibers include mesopores, micropores, and macropores.
3. The carbon nanofiber composite according to claim 1 or 2, wherein the content of Co nanoparticles in the carbon nanofiber composite is 0.04-0.3%;
preferably, the length of the nitrogen-doped carbon nanotube on the surface of the nitrogen-doped carbon nanofiber is 100-500nm;
preferably, the doping amount of the N element in the carbon nanofiber composite material is 7-12%.
4. A method for preparing the carbon nanofiber composite as claimed in any one of claims 1 to 3, comprising the steps of:
(1) Dispersing a polymer, ZIF-8 and a cobalt source in a solvent to obtain a precursor dispersion liquid;
(2) Performing electrostatic spinning on the precursor dispersion liquid obtained in the step (1) to obtain a nanofiber membrane;
(3) Carbonizing the nanofiber membrane and the nitrogen source in the step (2) in a protective atmosphere to prepare the carbon nanofiber composite material.
5. The method according to claim 4, wherein the mass ratio of the polymer, ZIF-8 and cobalt source in step (1) is (7-9): (9-11): (4-6);
preferably, the polymer of step (1) comprises at least one of polyacrylonitrile, polycaprolactone or polylactic acid;
preferably, the cobalt source of step (1) comprises Co (NO) 3 ) 2 ·6H 2 O and/orC 10 H 16 CoO4；
Preferably, the precursor dispersion liquid in step (1) further comprises an excipient;
preferably, the excipient comprises polyvinylpyrrolidone and/or polyvinyl alcohol.
6. The method according to claim 4 or 5, wherein the precursor dispersion of step (1) is prepared by the following method:
firstly, dissolving a polymer in a solvent, then adding an excipient, sequentially adding ZIF-8 and a cobalt source after dissolving, and continuously stirring to obtain the precursor dispersion liquid.
7. The method according to any one of claims 4 to 6, wherein the material pushing speed of the electrospinning of step (2) is 0.5 to 1.0mL/h;
preferably, the voltage of the electrostatic spinning in the step (2) is 20-25 kilovolts;
preferably, in the electrostatic spinning process in the step (2), the distance between the nanofiber membrane receiving device and the needle is 10-15cm;
preferably, the electrostatic spinning time of the step (2) is 20-30h.
8. The method according to any one of claims 4 to 7, wherein the mass ratio of the nanofiber membrane and the nitrogen source in step (3) is (2-7): 1;
preferably, the nitrogen source of step (3) comprises dicyandiamide and/or melamine.
9. The method according to any one of claims 4 to 8, wherein the carbonization in step (3) is performed in the following manner:
heating at 200-500 deg.C for 1-4h, and heating at 600-1200 deg.C for 0.5-3h;
preferably, the nitrogen source of step (3) is heated upstream of the tube furnace;
preferably, the nanofiber membrane is preheated before the carbonization in step (3);
preferably, the preheating temperature is 100-300 ℃;
preferably, the preheating time is 1-3h.
10. An energy storage device comprising the carbon nanofiber composite as claimed in any one of claims 1 to 3.
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| CN115132499B (en) * | 2022-03-22 | 2024-01-19 | 中国石油大学(华东) | Nine cobalt octasulfide-sulfur co-doped carbon nanofiber composite material, preparation method thereof and sodium ion capacitor negative plate |
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