CN111223681A - Manganese monoxide/carbon nanofiber supercapacitor electrode material and preparation method thereof - Google Patents
Manganese monoxide/carbon nanofiber supercapacitor electrode material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a manganese monoxide/carbon nanofiber supercapacitor electrode material and a preparation method thereof, lithium manganese oxide is mixed in polyacrylonitrile spinning solution, and a manganese lowest valence state manganese monoxide/carbon nanofiber compound is obtained by combining an electrostatic spinning and a carbonization process, and the obtained low valence state manganese monoxide improves the conductivity and the specific surface area of carbon nanofibers to a great extent, so that the specific surface area and the conductivity of the compound are increased; the prepared composite is applied to the electrode material of the super capacitor, the obtained electrode material has the advantages of high specific capacity, wide electrochemical window, long service life and the like, and the electrode capacitance has better circulation holding capacity under high current density; the preparation method is simple and easy to implement, mild in reaction conditions, good in repeatability and easy for large-scale production.
Description
Technical Field
The invention belongs to the technical field of supercapacitor electrode materials, and relates to a supercapacitor electrode material of manganese monoxide/carbon nanofibers and a preparation method thereof.
Background
A super capacitor, also called an electrochemical capacitor, is a novel energy storage device between a battery and a conventional capacitor, has the advantages of fast charge and discharge speed, long service life, good temperature characteristics, environmental protection and the like, is widely concerned about, and relates to chemistry, materials, new energy, electronic devices and the like in the research field, which becomes one of the research hotspots of the interdisciplinary science. The electrode material is a core material of the super capacitor and plays a role in determining the performance of the super capacitor. The electrode materials of the super capacitor are divided into two categories according to the charge and discharge principle, one category is the double-layer electrode materials which form a double-layer on the surface of an electrode to store electric energy, and the other category is the pseudo-capacitance electrode materials which complete the electric energy storage by the two-dimensional or quasi-two-dimensional faradaic reaction between the electrode and electrolyte. The two methods are different from each other in that the former is a physical electrostatic adsorption process, the latter is realized by a rapid oxidation-reduction reaction between an electrode and an electrolyte interface and is a chemical reaction process, the rapid oxidation-reduction reaction can store high-density charges, so that the energy stored by the pseudo-capacitor super capacitor is generally higher than the capacitance of an electric double layer super capacitor, but the oxidation-reduction reaction of the pseudo-capacitor super capacitor has certain irreversibility, so that the cycle stability of the pseudo-capacitor super capacitor is poor. In fact, in order to achieve comprehensive optimization of capacitance performance and cycle stability performance, the electrode material of the supercapacitor generally comprises an active material with double electric layers and pseudo-capacitance properties, and the two active materials are combined to exert respective advantages to achieve a synergistic effect.
Among many pseudocapacitance electrode materials, manganese oxide (MnOx) is attracting attention because of its excellent theoretical capacity value, low price, environmental friendliness, and the like. However, MnOx has the defects of poor conductivity, large volume expansion, poor cycle performance and the like, and the application of MnOx is hindered. The carbon nanofiber has the advantages of large specific surface area, excellent conductivity and the like, and the combination of the carbon nanofiber and the carbon nanofiber is expected to obtain a composite material with high specific capacitance and excellent cycling stability. At present, there are some reports about the composite material of MnOx and carbon nanofiber, and the obtained electrochemical performance is greatly improved compared with that of a single material. However, all MnOx/carbon nanofiber composites have a high specific capacitance only in the positive electrode potential interval in a longitudinal view, and the specific capacitance in the negative electrode potential interval is smaller than that of pure carbon nanofibers. The fundamental reason for this is that manganese in MnOx has substantially higher valence states and has a higher pseudocapacitance only in the positive electrode potential interval. There are several reports reporting on composites of manganese monoxide (MnO) and carbon nanofibers, but the tests were only done to obtain high specific capacitance in the positive electrode potential interval. Thus, a high specific capacitance of the MnOx material in the negative electrode potential region requires not only the valence state of manganese but also the structure and morphology of the manganese oxygen compound.
Disclosure of Invention
Aiming at the defect that the existing MnOx/carbon nanofiber cannot provide high specific capacitance in a negative electrode potential interval, the invention provides a novel manganese monoxide/carbon nanofiber supercapacitor electrode material which can have high specific capacitance in the negative electrode potential interval. The invention adopts the electrostatic spinning technology to prepare the composite nanofiber of lithium manganese oxide and polyacrylonitrile, and then the composite nanofiber is subjected to high-temperature treatment to generate the synergistic effect of lithium removal by lithium manganese oxide and carbonization of polyacrylonitrile so as to finally obtain the novel manganese monoxide/carbon nanofiber composite material. The invention prepares the manganese monoxide/carbon nanofiber supercapacitor electrode material by combining electrostatic spinning with high-temperature carbonization, and the prepared electrode material is greatly improved in the aspects of conductivity and electrochemical performance.
The invention also aims to provide a method for preparing a manganese monoxide/carbon nanofiber supercapacitor electrode material by high-temperature carbonization after electrostatic spinning2O4) Mixing the mixture into polyacrylonitrile spinning solution, carbonizing polyacrylonitrile under high temperature and inert gas atmosphere, and removing lithium from lithium manganese oxide to obtain manganese monoxide with lowest valence and carbon nanofiber composite material with low nitrogen contentThe material has high conductivity and large specific surface area, has stronger electrochemical activity between a positive voltage area and a negative voltage area, makes up the defect that a manganese oxide compound has no capacitance or low capacitance between negative areas, has higher specific capacitance and good cycle performance, is a high-performance supercapacitor electrode material, and is originated by preparing MnO by lithium manganese oxide.
The manganese monoxide/carbon nanofiber supercapacitor electrode material is a carbon nanofiber film modified by manganese monoxide nanoparticles, the carbon nanofibers modified by the manganese monoxide nanoparticles are carbon nanofiber surfaces in which the manganese monoxide nanoparticles are uniformly distributed, the mass fraction of the manganese monoxide nanoparticles is 20% -60%, the particle size of the particles is 10-100 nm, the structure is a layered structure, and the diameter of the carbon nanofibers is 100-500 nm.
As a preferred technical scheme:
the conductivity of the manganese monoxide/carbon nanofiber supercapacitor electrode material is improved by two orders of magnitude compared with that of a carbon nanofiber electrode material, and the conductivity can be increased by 101～102S/m。
According to the manganese monoxide/carbon nanofiber supercapacitor electrode material, the specific surface area of the manganese monoxide/carbon nanofiber supercapacitor electrode material can be 150-400 m2/g。
The invention also provides a method for preparing the manganese monoxide/carbon nanofiber supercapacitor electrode material, which is characterized in that lithium manganese oxide is added into polyacrylonitrile electrospinning solution for electrospinning and then carbonized to obtain a manganese monoxide/carbon nanofiber compound, namely the manganese monoxide/carbon nanofiber supercapacitor electrode material.
As a preferred technical scheme:
according to the preparation method of the manganese monoxide/carbon nanofiber supercapacitor electrode material, the polyacrylonitrile electrostatic spinning solution is an N, N-dimethylformamide solution of polyacrylonitrile, and the concentration of the N, N-dimethylformamide solution is 8-15 wt%; the lithium manganese oxide is particles, and the average diameter of the lithium manganese oxide is 10 nm-200 nm; the mass ratio of the lithium manganese oxide to the polyacrylonitrile electrostatic spinning solution is 1: 100-10; the adding refers to pouring the lithium manganese oxide into the polyacrylonitrile electrostatic spinning solution and stirring the mixture to form a uniform suspension.
According to the preparation method of the manganese monoxide/carbon nanofiber supercapacitor electrode material, the main parameters of electrostatic spinning are as follows: the voltage is 10-28 KV, the flow rate is 0.5-2 mL/h, the height is 10-20 cm, the humidity is less than 50%, and the temperature is 20-40 ℃.
According to the preparation method of the manganese monoxide/carbon nanofiber supercapacitor electrode material, carbonization is carried out in an inert atmosphere at the temperature of 600-800 ℃ for 6-10 hours.
The preparation method of the manganese monoxide/carbon nanofiber supercapacitor electrode material comprises the following specific carbonization steps: drying the obtained electrostatic spinning fiber in hot air at 80-120 ℃ for 0.5-1h, preserving heat in the hot air at 260-300 ℃ for 1-5h, placing the nanofiber with stable heat preservation in a tubular furnace in an inert atmosphere, carrying out carbonization treatment, setting the temperature rise rate of heat treatment parameters of 2-5 ℃/min, raising the temperature to 600-800 ℃, preserving heat for 6-10 h, cooling along with the furnace, and sampling to obtain the manganese monoxide/carbon nanofiber composite.
The preparation method of the manganese monoxide/carbon nanofiber supercapacitor electrode material comprises the step of preparing the manganese monoxide/carbon nanofiber supercapacitor electrode material in an inert atmosphere of N2Or an atmosphere of Ar.
The invention also provides a manganese monoxide/carbon nanofiber supercapacitor electrode which is made of the manganese monoxide/carbon nanofiber supercapacitor electrode material, has good electrochemical activity between a positive voltage zone and a negative voltage zone, overcomes the defect that a manganese oxide compound has no capacitance or low capacitance between negative zones, can be used as a supercapacitor anode electrode and a supercapacitor cathode electrode, and can realize the specific capacitance of 300-350F/g.
The invention also provides a manganese monoxide/carbon nanofiber supercapacitor, wherein the electrode of the manganese monoxide/carbon nanofiber supercapacitor is made of the manganese monoxide/carbon nanofiber supercapacitor electrode material, the supercapacitor electrode has good cycle performance, the cycle is carried out for 2000 times, and the specific capacitance is still maintained to be more than 90%.
The invention mechanism is as follows:
the invention mixes lithium manganese oxide in polyacrylonitrile spinning solution, prepares lithium manganese oxide/polyacrylonitrile nano-fiber membrane by a conventional electrostatic spinning method, finishes the separation of lithium element, the formation of low-valence manganese and the carbonization of polyacrylonitrile in the process of finishing the calcination process, and specifically comprises the following steps: part of lithium element in lithium manganese oxide volatilizes, and part of lithium element and nitrogen element in polyacrylonitrile form lithium nitride which is finally dissolved in water, so that the nano fiber film can remove lithium and part of nitrogen element in carbon fiber; and 4-valent manganese in the lithium manganese oxide is changed into low-valent manganese monoxide in the atmosphere of lithium removal and inert gas calcination, and finally the manganese monoxide/carbon nanofiber membrane is obtained. The proportion of nitrogen elements in the carbon nanofibers is reduced, the conductivity of the low-valence manganese-oxygen compound is superior to that of the high-valence manganese-oxygen compound, so that the conductivity of the composite fiber membrane is improved, and the low-valence manganese can contribute to the capacity in a negative region, so that the composite material has higher specific capacitance in a negative potential region.
In addition, the addition of the manganese monoxide enables the carbon nanofibers to generate more mesopores, the specific surface area of the fiber membrane is increased, more electron transmission channels are provided, more charges can be stored, the rate capability of the electrode material is improved, and the super capacitor has good capacitance performance and cycle performance.
The loading capacity of the active manganese monoxide is controllable, the manganese monoxide can be uniformly dispersed in the carbon nanofiber substrate to form a composite material with a one-dimensional porous structure, the special structure enables more diffusion paths of electron charge carriers, and the diffusion rate of electrons and electrolyte ions in the nanostructure is improved. In addition, gaps existing among the materials can relieve external stress or volume change and the like brought by the materials in the charging and discharging processes, so that the electrode material has better stability; therefore, the preparation method can realize the preparation of the excellent supercapacitor electrode material without additionally combining any other electrochemical active substances, has few preparation steps and simple operation, and has wider development prospect and practical application space.
Has the advantages that:
(1) according to the preparation method of the supercapacitor electrode material of the manganese monoxide/carbon nanofiber, lithium manganese oxide is mixed in polyacrylonitrile spinning solution, and a low-valence manganese monoxide/carbon nanofiber compound is obtained by combining an electrostatic spinning and a carbonization process;
(2) in the supercapacitor electrode material of the manganese monoxide/carbon nanofiber, the obtained low-valence manganese monoxide improves the conductivity and the specific surface area of the carbon nanofiber to a great extent, so that the specific surface area and the conductivity of the composite are increased;
(3) the prepared compound is applied to electrodes and super capacitors, the obtained electrodes have the advantages of high specific capacity, wide electrochemical window, long service life and the like, and the electrode capacitance has good cyclic retention capacity under high current density;
(4) the preparation method of the manganese monoxide/carbon nanofiber supercapacitor electrode material is simple and easy to implement, mild in reaction conditions, good in repeatability and easy for large-scale production.
Drawings
FIG. 1 is an SEM image of a manganese monoxide/carbon nanofiber of the present invention.
Fig. 2 XRD of the composite nanofiber and carbon nanofiber prepared using lithium manganese oxide according to embodiment 1 of the present invention.
FIG. 3 is a comparison of cyclic voltammetry curves of the manganese monoxide/carbon nanofibers and pure carbon nanofibers obtained in example 1 of the present invention.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
The preparation method of the manganese monoxide/carbon nanofiber supercapacitor electrode material comprises the following steps:
(1) pouring lithium manganese oxide particles with the average diameter of 10nm into N, N-dimethylformamide electrostatic spinning solution of polyacrylonitrile with the concentration of 8%, stirring to form uniform suspension, and performing electrostatic spinning, wherein the mass ratio of the lithium manganese oxide particles to the electrostatic spinning solution is 1: 50; the main parameters of electrostatic spinning are: the voltage is 15KV, the flow rate is 1mL/h, the height is 15cm, the humidity is 45%, and the temperature is 25 ℃;
(2) then in an inert atmosphere (N)2The atmosphere of (2) is performed, and the specific process of carbonization is as follows: drying the obtained electrostatic spinning fibers in hot air at 100 ℃ for 1h, preserving heat in hot air at 260 ℃ for 6h, then placing the stabilized nanofibers in a tubular furnace in inert atmosphere, carrying out carbonization treatment, setting the heating rate of the heat treatment parameters at 2 ℃/min, heating to 800 ℃, preserving heat for 6h, finally cooling along with the furnace, and sampling to obtain a manganese monoxide/carbon nanofiber compound, namely the manganese monoxide/carbon nanofiber supercapacitor electrode material.
The prepared manganese monoxide/carbon nanofiber supercapacitor electrode material is a manganese monoxide/carbon nanofiber composite membrane, and is an electrostatic spinning membrane with manganese monoxide uniformly distributed in carbon nanofibers, an SEM picture of the membrane is shown in figure 1, X-ray diffraction is performed on Lithium Manganese Oxide (LMO) used in the embodiment and the prepared composite nanofibers, an obtained XRD spectrogram is shown in figure 2, and compared with a standard card, the diffraction peak of the lithium manganese oxide disappears and the diffraction peak of MnO appears after electrostatic spinning and carbonization. Thermogravimetric analysis is carried out on the manganese monoxide/carbon nanofiber membrane, and the result shows that the content of manganese monoxide in the composite fiber membrane accounts for 48% of the total mass; the specific surface area and the conductivity of the obtained manganese monoxide/carbon nanofiber are tested, and the conductivity of the supercapacitor electrode material of the manganese monoxide/carbon nanofiber is improved by two orders of magnitude compared with that of the carbon nanofiber electrode material, the conductivity reaches 14S/m, and the specific surface area reaches 260m2/g。
The supercapacitor electrode of the manganese monoxide/carbon nanofiber is prepared from the prepared supercapacitor electrode material of the manganese monoxide/carbon nanofiber, and the circulating volt-ampere curve shows that the surrounding area of the supercapacitor electrode of the manganese monoxide/carbon nanofiber is greatly improved in a negative voltage range (-0.8-0V) compared with that of a pure carbon nanofiber electrode (shown in figure 3), so that the composite material still has good electrochemical activity in the negative range, and the specific capacitance reaches 350F/g through calculation.
The electrode made of the prepared manganese monoxide/carbon nanofiber supercapacitor electrode material is used as the electrode of the manganese monoxide/carbon nanofiber supercapacitor, the supercapacitor electrode has good cycle performance, and the specific capacitance is still maintained at 94.8% after the supercapacitor electrode is cycled for 2000 times.
Example 2
The preparation method of the manganese monoxide/carbon nanofiber supercapacitor electrode material comprises the following steps:
(1) pouring lithium manganese oxide particles with the average diameter of 91nm into N, N-dimethylformamide electrostatic spinning solution of polyacrylonitrile with the concentration of 10%, stirring to form uniform suspension, and performing electrostatic spinning, wherein the mass ratio of the lithium manganese oxide particles to the electrostatic spinning solution is 1: 40; the main parameters of electrostatic spinning are: the voltage is 20KV, the flow rate is 1mL/h, the height is 19cm, the humidity is 45%, and the temperature is 21 ℃;
(2) then carbonizing in an inert atmosphere (Ar atmosphere), wherein the specific process of carbonizing is as follows: drying the obtained electrostatic spinning fibers in hot air at 110 ℃ for 1h, preserving heat in hot air at 280 ℃ for 1h, then placing the nanofibers with stable low temperature in a tubular furnace in inert atmosphere, carrying out carbonization treatment, setting the heating rate of 2 ℃/min as the heat treatment parameter, heating to 780 ℃, preserving heat for 7h, finally cooling along with the furnace, and sampling to obtain a manganese monoxide/carbon nanofiber compound, namely the manganese monoxide/carbon nanofiber supercapacitor electrode material.
The prepared manganese monoxide/carbon nanofiber supercapacitor electrode material is a manganese monoxide/carbon nanofiber composite membrane which is an electrostatic spinning membrane with manganese monoxide uniformly distributed in carbon nanofibers, and the content of the manganese monoxide accounts for 52% of the total mass; the manganese monoxide/carbon nanofiber super capacitorThe conductivity of the electrode material is improved by two orders of magnitude compared with that of a carbon nanofiber electrode material, and the conductivity can be 6S/m; the specific surface area of the manganese monoxide/carbon nanofiber supercapacitor electrode material can achieve 190m2/g。
The supercapacitor electrode of the manganese monoxide/carbon nanofiber is prepared from the prepared supercapacitor electrode material of the manganese monoxide/carbon nanofiber, has good electrochemical activity in a negative voltage region, and can realize the specific capacitance of 310F/g.
The electrode made of the prepared manganese monoxide/carbon nanofiber supercapacitor electrode material is used as the electrode of the manganese monoxide/carbon nanofiber supercapacitor, the supercapacitor electrode has good cycle performance, and the specific capacitance is still maintained at 90% after the cycle is carried out for 2000 times.
Example 3
The preparation method of the manganese monoxide/carbon nanofiber supercapacitor electrode material comprises the following steps:
(1) pouring lithium manganese oxide particles with the average diameter of 107nm into N, N-dimethylformamide electrostatic spinning solution of polyacrylonitrile with the concentration of 12%, stirring to form uniform suspension, and performing electrostatic spinning, wherein the mass ratio of the lithium manganese oxide particles to the electrostatic spinning solution is 1: 15; the main parameters of electrostatic spinning are: the voltage is 24KV, the flow rate is 1.2mL/h, the height is 19cm, the humidity is 44%, and the temperature is 22 ℃;
(2) then in an inert atmosphere (N)2The atmosphere of (2) is performed, and the specific process of carbonization is as follows: drying the obtained electrostatic spinning fibers in hot air at 85 ℃ for 1h, preserving heat in hot air at 270 ℃ for 3h, then placing the nanofibers with stable low temperature in a tubular furnace in inert atmosphere, carrying out carbonization treatment, setting the heating rate of 2 ℃/min as the heat treatment parameter, heating to 680 ℃, preserving heat for 6h, finally cooling along with the furnace, and sampling to obtain a manganese monoxide/carbon nanofiber compound, namely the manganese monoxide/carbon nanofiber supercapacitor electrode material.
The prepared manganese monoxide/carbon nanofiber supercapacitor electrode material is a manganese monoxide/carbon nanofiber composite membrane, and manganese monoxide is uniformly distributed in carbon nanotubesThe content of manganese monoxide in the electrostatic spinning film in the rice fiber accounts for 58 percent of the total mass; the conductivity of the manganese monoxide/carbon nanofiber supercapacitor electrode material is improved by two orders of magnitude compared with that of a carbon nanofiber electrode material, and the conductivity can be 7S/m; the specific surface area of the manganese monoxide/carbon nanofiber supercapacitor electrode material can reach 300m2/g。
The supercapacitor electrode of the manganese monoxide/carbon nanofiber is prepared from the prepared supercapacitor electrode material of the manganese monoxide/carbon nanofiber, has good electrochemical activity in a negative voltage interval, and can realize the specific capacitance of 301F/g.
The electrode made of the prepared manganese monoxide/carbon nanofiber supercapacitor electrode material is used as the electrode of the manganese monoxide/carbon nanofiber supercapacitor, the supercapacitor electrode has good cycle performance, and the specific capacitance is still maintained at 92% after the cycle is carried out for 2000 times.
Example 4
The preparation method of the manganese monoxide/carbon nanofiber supercapacitor electrode material comprises the following steps:
(1) pouring lithium manganese oxide particles with the average diameter of 69nm into N, N-dimethylformamide electrostatic spinning solution of polyacrylonitrile with the concentration of 15%, stirring to form uniform suspension, and performing electrostatic spinning, wherein the mass ratio of the lithium manganese oxide particles to the electrostatic spinning solution is 1: 90; the main parameters of electrostatic spinning are: the voltage is 24KV, the flow rate is 1.5mL/h, the height is 20cm, the humidity is 43%, and the temperature is 27 ℃;
(2) then carbonizing in an inert atmosphere (Ar atmosphere), wherein the specific process of carbonizing is as follows: drying the obtained electrostatic spinning fibers in hot air at 105 ℃ for 1h, preserving heat in hot air at 280 ℃ for 4h, then placing the nanofibers with stable low temperature in a tubular furnace in inert atmosphere, carrying out carbonization treatment, setting the heating rate of 2 ℃/min as the heat treatment parameter, heating to 770 ℃, preserving heat for 7h, finally cooling along with the furnace, and sampling to obtain a manganese monoxide/carbon nanofiber compound, namely the manganese monoxide/carbon nanofiber supercapacitor electrode material.
The obtained manganese monoxide/carbonThe electrode material of the nanofiber super capacitor is a manganese monoxide/carbon nanofiber composite membrane, which is an electrostatic spinning membrane with manganese monoxide uniformly distributed in carbon nanofibers, and the content of manganese monoxide accounts for 26% of the total mass; the conductivity of the manganese monoxide/carbon nanofiber supercapacitor electrode material is improved by two orders of magnitude compared with that of a carbon nanofiber electrode material, and the conductivity can be 8S/m; the specific surface area of the manganese monoxide/carbon nanofiber supercapacitor electrode material can reach 200m2/g。
The supercapacitor electrode of the manganese monoxide/carbon nanofiber prepared from the supercapacitor electrode material of the manganese monoxide/carbon nanofiber has good electrochemical activity in a negative voltage interval, and the specific capacitance can achieve 318F/g.
The electrode made of the prepared manganese monoxide/carbon nanofiber supercapacitor electrode material is used as the electrode of the manganese monoxide/carbon nanofiber supercapacitor, the supercapacitor electrode has good cycle performance, and the specific capacitance is still maintained at 91% after the cycle is carried out for 2000 times.
Example 5
The preparation method of the manganese monoxide/carbon nanofiber supercapacitor electrode material comprises the following steps:
(1) pouring lithium manganese oxide particles with the average diameter of 68nm into N, N-dimethylformamide electrostatic spinning solution of polyacrylonitrile with the concentration of 9%, stirring to form uniform suspension, and performing electrostatic spinning, wherein the mass ratio of the lithium manganese oxide particles to the electrostatic spinning solution is 1: 60; the main parameters of electrostatic spinning are: the voltage is 25KV, the flow rate is 1.7mL/h, the height is 12cm, the humidity is 43%, and the temperature is 29 ℃;
(2) then in an inert atmosphere (N)2The atmosphere of (2) is performed, and the specific process of carbonization is as follows: drying the obtained electrostatic spinning fiber in hot air at 115 ℃ for 1h, preserving heat in hot air at 290 ℃ for 2h, then placing the nanofiber with stable low temperature in a tubular furnace in inert atmosphere for carbonization treatment, setting the temperature rise rate of the heat treatment parameter of 2 ℃/min, raising the temperature to 600 ℃, preserving heat for 6h, finally cooling along with the furnace, and sampling to obtain the manganese monoxide/carbon nanofiber compositeNamely the manganese monoxide/carbon nanofiber supercapacitor electrode material.
The prepared manganese monoxide/carbon nanofiber supercapacitor electrode material is a manganese monoxide/carbon nanofiber composite membrane which is an electrostatic spinning membrane with manganese monoxide uniformly distributed in carbon nanofibers, and the content of the manganese monoxide accounts for 42% of the total mass; the conductivity of the manganese monoxide/carbon nanofiber supercapacitor electrode material is improved by two orders of magnitude compared with that of a carbon nanofiber electrode material, and the conductivity can be 11S/m; the specific surface area of the manganese monoxide/carbon nanofiber supercapacitor electrode material can be 380m2/g。
The supercapacitor electrode of the manganese monoxide/carbon nanofiber is prepared from the prepared supercapacitor electrode material of the manganese monoxide/carbon nanofiber, has good electrochemical activity in a negative voltage interval, and can realize the specific capacitance of 320F/g.
The electrode made of the supercapacitor electrode material of the prepared manganese monoxide/carbon nanofiber is used as the electrode of the supercapacitor of the manganese monoxide/carbon nanofiber, the supercapacitor electrode has good cycle performance, the specific capacitance is still maintained at 92 percent after the cycle is carried out for 2000 times
Example 6
The preparation method of the manganese monoxide/carbon nanofiber supercapacitor electrode material comprises the following steps:
(1) pouring lithium manganese oxide particles with the average diameter of 54nm into N, N-dimethylformamide electrostatic spinning solution of polyacrylonitrile with the concentration of 10%, stirring to obtain uniform suspension, and performing electrostatic spinning, wherein the mass ratio of the lithium manganese oxide particles to the electrostatic spinning solution is 1: 70; the main parameters of electrostatic spinning are: the voltage is 27KV, the flow rate is 1.9mL/h, the height is 15cm, the humidity is 41%, and the temperature is 29 ℃;
(2) then carbonizing in an inert atmosphere (Ar atmosphere), wherein the specific process of carbonizing is as follows: drying the obtained electrostatic spinning fibers in hot air at 95 ℃ for 1h, preserving heat in hot air at 280 ℃ for 3h, then placing the nanofibers with stable low temperature in a tubular furnace in inert atmosphere, carrying out carbonization treatment, setting the heating rate of 2 ℃/min as the heat treatment parameter, heating to 750 ℃, preserving heat for 7h, finally cooling along with the furnace, and sampling to obtain a manganese monoxide/carbon nanofiber compound, namely the manganese monoxide/carbon nanofiber supercapacitor electrode material.
The prepared manganese monoxide/carbon nanofiber supercapacitor electrode material is a manganese monoxide/carbon nanofiber composite membrane which is an electrostatic spinning membrane with manganese monoxide uniformly distributed in carbon nanofibers, and the content of manganese monoxide accounts for 37% of the total mass; the conductivity of the manganese monoxide/carbon nanofiber supercapacitor electrode material is improved by two orders of magnitude compared with that of a carbon nanofiber electrode material, and the conductivity can be 14S/m; the specific surface area of the manganese monoxide/carbon nanofiber supercapacitor electrode material can reach 280m2/g。
The supercapacitor electrode of the manganese monoxide/carbon nanofiber is prepared from the prepared supercapacitor electrode material of the manganese monoxide/carbon nanofiber, has good electrochemical activity in a negative voltage interval, and can realize the specific capacitance of 330F/g.
The electrode made of the prepared manganese monoxide/carbon nanofiber supercapacitor electrode material is used as the electrode of the manganese monoxide/carbon nanofiber supercapacitor, the supercapacitor electrode has good cycle performance, and the specific capacitance is still maintained to be more than 93% after the supercapacitor electrode is cycled for 2000 times.
Example 7
The preparation method of the manganese monoxide/carbon nanofiber supercapacitor electrode material comprises the following steps:
(1) pouring lithium manganese oxide particles with the average diameter of 34nm into N, N-dimethylformamide electrostatic spinning solution of polyacrylonitrile with the concentration of 10%, stirring to obtain uniform suspension, and performing electrostatic spinning, wherein the mass ratio of the lithium manganese oxide particles to the electrostatic spinning solution is 1: 45; the main parameters of electrostatic spinning are: the voltage is 28KV, the flow rate is 2mL/h, the height is 17cm, the humidity is 40%, and the temperature is 32 ℃;
(2) then in an inert atmosphere (N)2The atmosphere of (2) is performed, and the specific process of carbonization is as follows: drying the obtained electrostatic spinning fiber in 105 deg.C hot air for 1h, and keeping the temperature in 275 deg.C hot airAnd 4h, then placing the nanofiber with stable low temperature in a tubular furnace in inert atmosphere, carrying out carbonization treatment, setting the heat treatment parameter as the heating rate of 2 ℃/min, heating to 650 ℃, keeping the temperature for 6.5h, finally cooling along with the furnace, and sampling to obtain a manganese monoxide/carbon nanofiber compound, namely the manganese monoxide/carbon nanofiber supercapacitor electrode material.
The prepared manganese monoxide/carbon nanofiber supercapacitor electrode material is a manganese monoxide/carbon nanofiber composite membrane which is an electrostatic spinning membrane with manganese monoxide uniformly distributed in carbon nanofibers, and the content of manganese monoxide accounts for 51% of the total mass; the conductivity of the manganese monoxide/carbon nanofiber supercapacitor electrode material is improved by two orders of magnitude compared with that of a carbon nanofiber electrode material, and the conductivity can be 5S/m; the specific surface area of the manganese monoxide/carbon nanofiber supercapacitor electrode material can achieve 290m2/g。
The supercapacitor electrode of the manganese monoxide/carbon nanofiber is prepared from the prepared supercapacitor electrode material of the manganese monoxide/carbon nanofiber, has good electrochemical activity in a negative voltage interval, and can realize the specific capacitance of 310F/g.
The electrode made of the prepared manganese monoxide/carbon nanofiber supercapacitor electrode material is used as the electrode of the manganese monoxide/carbon nanofiber supercapacitor, the supercapacitor electrode has good cycle performance, and the specific capacitance is still maintained to be more than 93% after the supercapacitor electrode is cycled for 2000 times.
Example 8
The preparation method of the manganese monoxide/carbon nanofiber supercapacitor electrode material comprises the following steps:
(1) pouring lithium manganese oxide particles with the average diameter of 200nm into N, N-dimethylformamide electrostatic spinning solution of polyacrylonitrile with the concentration of 15%, stirring to form uniform suspension, and performing electrostatic spinning, wherein the mass ratio of the lithium manganese oxide particles to the electrostatic spinning solution is 1: 100; the main parameters of electrostatic spinning are: the voltage is 28KV, the flow rate is 2mL/h, the height is 20cm, the humidity is 40%, and the temperature is 40 ℃;
(2) then carbonizing in an inert atmosphere (Ar atmosphere), wherein the specific process of carbonizing is as follows: drying the obtained electrostatic spinning fibers in hot air at 120 ℃ for 1h, preserving heat in hot air at 300 ℃ for 5h, then placing the nanofibers with stable low temperature in a tubular furnace in inert atmosphere, carrying out carbonization treatment, setting the heating rate of 2 ℃/min as the heat treatment parameter, heating to 800 ℃, preserving heat for 8h, finally cooling along with the furnace, and sampling to obtain a manganese monoxide/carbon nanofiber compound, namely the manganese monoxide/carbon nanofiber supercapacitor electrode material.
The prepared manganese monoxide/carbon nanofiber supercapacitor electrode material is a manganese monoxide/carbon nanofiber composite membrane which is an electrostatic spinning membrane with manganese monoxide uniformly distributed in carbon nanofibers, and the content of manganese monoxide accounts for 21% of the total mass; the conductivity of the manganese monoxide/carbon nanofiber supercapacitor electrode material is improved by two orders of magnitude compared with that of a carbon nanofiber electrode material, and the conductivity can be improved by 2S/m; the specific surface area of the manganese monoxide/carbon nanofiber supercapacitor electrode material can reach 150m2/g。
The supercapacitor electrode of the manganese monoxide/carbon nanofiber is prepared from the prepared supercapacitor electrode material of the manganese monoxide/carbon nanofiber, has good electrochemical activity in a negative voltage interval, and can realize the specific capacitance of 300F/g.
The electrode made of the prepared manganese monoxide/carbon nanofiber supercapacitor electrode material is used as the electrode of the manganese monoxide/carbon nanofiber supercapacitor, the supercapacitor electrode has good cycle performance, and the specific capacitance is still maintained at 90% after the cycle is carried out for 2000 times.
Claims (10)
1. The manganese monoxide/carbon nanofiber supercapacitor electrode material is characterized in that: the supercapacitor electrode material of the manganese monoxide/carbon nanofiber is a carbon nanofiber film modified by manganese monoxide nano particles, the carbon nanofiber modified by the manganese monoxide nano particles is formed by uniformly distributing the manganese monoxide nano particles on the surface of the carbon nanofiber, the mass fraction of the manganese monoxide nano particles is 20-60%, the particle size is 10-100 nm, the structure is a layered structure, and the diameter of the carbon nanofiber is 100-500 nm.
2. The manganese monoxide/carbon nanofiber supercapacitor electrode material according to claim 1, wherein the conductivity of the manganese monoxide/carbon nanofiber supercapacitor electrode material is improved by two orders of magnitude compared with that of a carbon nanofiber electrode material, and the conductivity can be increased by 101～102S/m。
3. The manganese monoxide/carbon nanofiber supercapacitor electrode material according to claim 1, wherein the specific surface area of the manganese monoxide/carbon nanofiber supercapacitor electrode material can achieve 150-400 m2/g。
4. The method for preparing the manganese monoxide/carbon nanofiber supercapacitor electrode material as claimed in claims 1 to 3, which is characterized by comprising the following steps: and adding lithium manganese oxide into the polyacrylonitrile electrostatic spinning solution for electrostatic spinning, and then carbonizing to obtain a manganese monoxide/carbon nanofiber compound, namely the manganese monoxide/carbon nanofiber super capacitor electrode material.
5. The preparation method of the manganese monoxide/carbon nanofiber supercapacitor electrode material according to claim 4, wherein the polyacrylonitrile electrospinning solution is an N, N-dimethylformamide solution of polyacrylonitrile, and the concentration of the N, N-dimethylformamide solution is 8-15%; the lithium manganese oxide is particles, and the average diameter of the lithium manganese oxide is 10 nm-200 nm; the mass ratio of the lithium manganese oxide to the polyacrylonitrile electrostatic spinning solution is 1: 100-10; the adding refers to pouring the lithium manganese oxide into the polyacrylonitrile electrostatic spinning solution and stirring the mixture to form a uniform suspension.
6. The method for preparing the manganese monoxide/carbon nanofiber supercapacitor electrode material according to claim 4, wherein the main parameters of the electrostatic spinning are as follows: the voltage is 10-28 KV, the flow rate is 0.5-2 mL/h, the height is 10-20 cm, the humidity is less than 50%, and the temperature is 20-40 ℃.
7. The preparation method of the manganese monoxide/carbon nanofiber supercapacitor electrode material according to claim 4, wherein the carbonization is carried out in an inert atmosphere at 600-800 ℃ for 6-10 hours; the inert atmosphere is N2Or an atmosphere of Ar.
8. The preparation method of the manganese monoxide/carbon nanofiber supercapacitor electrode material according to claim 4 or 7, wherein the carbonization is carried out in the following specific steps: drying the obtained electrostatic spinning fiber in hot air at 80-120 ℃ for 0.5-1h, preserving heat in the hot air at 260-300 ℃ for 1-5h, placing the nanofiber with stable heat preservation in a tubular furnace in an inert atmosphere, carrying out carbonization treatment, setting the temperature rise rate of heat treatment parameters of 2-5 ℃/min, raising the temperature to 600-800 ℃, preserving heat for 6-10 h, cooling along with the furnace, and sampling to obtain the manganese monoxide/carbon nanofiber composite.
9. The manganese monoxide/carbon nanofiber supercapacitor electrode is characterized in that: the supercapacitor electrode of the manganese monoxide/carbon nanofiber is made of the supercapacitor electrode material of the manganese monoxide/carbon nanofiber, has good electrochemical activity between a positive voltage zone and a negative voltage zone, overcomes the defect that a manganese oxide compound has no capacitance or low capacitance between negative zones, can be used as a supercapacitor anode electrode and a supercapacitor cathode electrode, and can realize the specific capacitance of 300-350F/g.
10. The manganese monoxide/carbon nanofiber supercapacitor is characterized in that: the electrode of the manganese monoxide/carbon nanofiber supercapacitor is made of the manganese monoxide/carbon nanofiber supercapacitor electrode material, the supercapacitor electrode has good cycle performance, and the specific capacitance is still maintained to be more than 90% after the cycle is carried out for 2000 times.
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