CN109728287B - One-dimensional coaxial double-nanotube composite material and preparation method and application thereof - Google Patents

One-dimensional coaxial double-nanotube composite material and preparation method and application thereof Download PDF

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CN109728287B
CN109728287B CN201910014494.1A CN201910014494A CN109728287B CN 109728287 B CN109728287 B CN 109728287B CN 201910014494 A CN201910014494 A CN 201910014494A CN 109728287 B CN109728287 B CN 109728287B
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刘代伙
吕晓
杨林
白正宇
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Henan Normal University
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Abstract

The invention discloses a one-dimensional coaxial double-nanotube composite material and a preparation method and application thereof, belonging to the technical field of lithium ion battery cathode materials. The technical scheme of the invention is as follows: can quickly synthesize the alpha-MnO in batches under the conditions of room temperature and liquid phase2NTs precursors, followed by a-MnO2Coating a layer of polydopamine on the surface of the NTs precursor to obtain alpha-MnO2The intermediate product of @ PDA DNTs is subjected to two-step solid phase heat treatment to obtain the one-dimensional coaxial double-nanotube composite material alpha-MnSe2The synthesis process of the @ N-C DNTs is simple and the cost is low, and the prepared one-dimensional coaxial double-nanotube composite material is used as the cathode material of the lithium ion battery, because the one-dimensional coaxial double-nanotube composite material is alpha-MnSe2The @ N-C DNTs has special structural morphology and high conductivity, and shows excellent lithium storage rate capability and overlong high-rate cycle capability.

Description

One-dimensional coaxial double-nanotube composite material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of lithium ion battery cathode materials, and particularly relates to a one-dimensional coaxial double-nanotube composite material and a preparation method and application thereof.
Background
The lithium ion battery becomes a new generation of high-energy green energy storage material by virtue of the advantages of high energy density, high power density, long cycle life, environmental friendliness and the like. At present, lithium ion batteries are widely applied to the fields of energy storage devices such as various portable electronic products, wearable electronic products, electric vehicles and the like. In the lithium ion battery commercially applied at present, the negative electrode material is mainly graphite, and the theoretical specific capacity of the negative electrode material is only 372mA h g-1The energy density of the battery as a whole is limited. Therefore, the research and development of novel high-performance negative electrode materials are effective strategies for improving the performance of the lithium ion battery. alpha-MnSe based on multi-electron conversion mechanism2Has better mechanical stability, electrode dynamics, thermal stability and higher conductivity when being used as a cathode material, but still has the advantages of high stability, high conductivity, high stability and high stabilityHas the disadvantage of alpha-MnSe2The large volume change during cycling, slow kinetics, poor rate and cycling performance, greatly hinder the realization of its excellent electrochemical performance. To improve alpha-MnSe2The most effective method is to prepare functionalized carbon-based composite materials, especially carbon-based composite materials doped with different atoms, and through physical and electronic direct contact between the active materials and the highly conductive carbon materials, the ion transmission kinetics can be effectively promoted and the electrode conductivity can be improved. In addition, designing a unique nanostructure is also a key strategy for improving the electrochemical properties of the composite material, can more effectively relieve large volume change during cycling, and provides abundant interface space for lithium ion transmission and electron migration, so that the transmission distance of lithium ions is more effectively shortened and the electron migration rate of the lithium ions is accelerated. The design concept of the shape and the structure of the material and the synthesis method have very important guiding significance for the development of the cathode material and the anode material of the lithium ion battery.
Disclosure of Invention
The invention aims to provide a one-dimensional coaxial double-nanotube composite material and a preparation method thereof, and the one-dimensional coaxial double-nanotube composite material alpha-MnSe is explored for the first time2The lithium storage performance of the @ N-C DNTs has good application in the negative electrode material of the lithium ion battery, and shows excellent lithium storage rate performance and ultra-long high rate cycle performance.
The invention adopts the following technical scheme for realizing the aim, and the one-dimensional coaxial double-nanotube composite material is characterized in that: the composite material is prepared from alpha-MnSe2One-dimensional coaxial double-nanotube alpha-MnSe formed by the inner tube and the nitrogen-doped carbon nanotube outer tube (N-C outer tube) and having the average length of 0.5-10 mu m and the average diameter of about 100nm2@ N-C DNTs (note: DNTs is an abbreviation for double nanotubes), wherein alpha-MnSe2The inner tube and the nitrogen-doped carbon nanotube outer tube are tightly grown together to form a coaxial hollow double-nanotube structure.
Further limit, the one-dimensional coaxial double nano-tube alpha-MnSe2alpha-MnSe in @ N-C DNTs2The mass percentage of the N-C is 5 to 90 percentThe mass percentage of the DNTs is 10-95%.
Further defined, the average wall thickness of the nitrogen-doped carbon nanotube outer tube is 2-50 nm.
The preparation method of the one-dimensional coaxial double-nanotube composite material is characterized by comprising the following specific steps:
Step S1: mixing KMnO4Adding the mixture into water, stirring, adding a hydrochloric acid solution with the mass fraction of 36%, stirring and mixing uniformly, transferring the mixed solution into a stainless steel high-pressure kettle, and carrying out hydrothermal reaction at 140 ℃ to obtain alpha-MnO2NTs precursors;
step S2: subjecting the alpha-MnO obtained in step S1 to2Adding NTs precursor into trihydroxymethyl aminomethane buffer solution, adding dopamine hydrochloride to react in alpha-MnO2Coating a layer of polydopamine on the surface of the NTs precursor to obtain alpha-MnO2Intermediates of @ PDA DNTs;
step S3: under the protection of inert gas, the alpha-MnO obtained in the step S22Putting the intermediate product of @ PDA DNTs in a tubular furnace, heating to 300-900 ℃ at the heating rate of 1-10 ℃/min, and calcining to obtain MnO @ N-C DNTs;
step S4: mixing MnO @ N-C DNTs obtained in the step S3 with Se powder according to the molar ratio of MnO to Se of 1:1.1, placing the mixture in a quartz glass tube, vacuumizing, then placing the quartz glass tube in a tube furnace, heating to 300-750 ℃ at the heating rate of 1-15 ℃/min, and calcining to obtain the one-dimensional coaxial double-nanotube composite material alpha-MnSe2@N-C DNTs。
Further limited, the preparation method of the one-dimensional coaxial double-nanotube composite material is characterized by comprising the following specific steps:
step S1: 0.658g KMnO 4Adding 70mL of water, stirring for 25min, adding 2.5mL of hydrochloric acid solution with the mass fraction of 36%, stirring for 15min, uniformly mixing, transferring the mixed solution into a 100mL stainless steel autoclave, carrying out hydrothermal reaction at 140 ℃ for 10h, carrying out vacuum filtration, repeatedly washing and precipitating with deionized water, and drying at 80 ℃ for 10h to obtain alpha-MnO2NTs precursor;
step S2: 600mg of the alpha-MnO obtained in step S12NTs precursor addition to 750mL of trihydroxymethyl aminomethane buffer solution with the molar concentration of 10mmol/L is stirred for 5min at room temperature and then is subjected to ultrasonic treatment for 5min, then is magnetically stirred for 30min at room temperature, then 300mg of dopamine hydrochloride is added, the stirring is continued for 6h, centrifugal separation is carried out, ethanol and deionized water are used for repeatedly washing and precipitating, and the precipitate is dried for 8h at 80 ℃ to obtain alpha-MnO2@ PDA NTs intermediate;
step S3: under the protection of high-purity nitrogen, the alpha-MnO obtained in the step S22Putting the intermediate product of @ PDA DNTs in a tubular furnace, heating to 400 ℃ at a heating rate of 3 ℃/min, calcining for 2h, and naturally cooling to room temperature to obtain MnO @ N-C DNTs;
step S4: mixing MnO @ N-C DNTs obtained in the step S3 with Se powder according to the molar ratio of MnO to Se being 1:1.1, placing the mixture in a quartz glass tube, vacuumizing, then placing the quartz glass tube in a tube furnace, heating to 500 ℃ at the heating rate of 10 ℃/min, calcining for 50h, and naturally cooling to room temperature to obtain the one-dimensional coaxial double-nanotube composite material alpha-MnSe 2@N-C DNTs。
The application of the one-dimensional coaxial double-nanotube composite material in the lithium ion battery cathode material is that the one-dimensional coaxial double-nanotube composite material is alpha-MnSe2The @ N-C DNTs has special structural morphology and high conductivity, and shows excellent lithium storage rate capability and overlong high-rate cycle capability.
The invention has the following advantages:
1. the one-dimensional coaxial nano composite material alpha-MnSe prepared by the invention2@ N-C DNTs is composed of alpha-MnSe2One-dimensional coaxial double nano-tube, alpha-MnSe, composed of inner tube and N-C outer tube2The inner tube and the N-C outer tube are tightly grown together to form a coaxial hollow double nanotube structure, the structure can more effectively relieve large volume change during circulation, and provide rich interface space for lithium ion transmission and electron migration, thereby more effectively shortening the transmission distance of lithium ions and accelerating the electron migration rate of the lithium ions, and the alpha-MnSe alloy material has the advantages of high strength, high heat resistance and high heat resistance2The @ N-C DNTs composite material shows excellent rate capability and overlong high-rate cycle performance when used as a lithium ion battery cathode material;
2. the invention can be quickly carried out under the conditions of room temperature and liquid phaseBatch synthesis of alpha-MnO2NTs precursors, followed by in alpha-MnO2Coating a layer of polydopamine on the surface of the NTs precursor to obtain alpha-MnO 2The intermediate product of @ PDA DNTs is subjected to two-step solid phase heat treatment to obtain the one-dimensional coaxial double-nanotube composite material alpha-MnSe2@ N-C DNTs, simple synthesis process and low cost, and has better popularization and application prospects.
Drawings
FIG. 1 is a view of alpha-MnSe2A synthesis process flow chart of the @ N-C DNTs composite material;
FIG. 2 is a view of alpha-MnSe2The molecular structure of the @ N-C DNTs composite material is shown in a schematic diagram;
FIG. 3 is a view showing that α -MnSe obtained in example 1 is2XRD patterns of @ N-C DNTs composites;
FIG. 4 shows the result of example 1 to obtain alpha-MnSe2SEM and TEM images of the @ N-C DNTs composite material, wherein (a) is a Scanning Electron Microscope (SEM) photograph and (b) is a Transmission Electron Microscope (TEM) photograph;
FIG. 5 shows that alpha-MnSe obtained in example 12A rate performance graph of the @ N-C DNTs composite material as a lithium ion battery cathode material;
FIG. 6 shows the production of α -MnSe in example 12The constant current charge-discharge curve diagram corresponding to the corresponding multiplying power in figure 5 when the @ N-C DNTs composite material is used as the lithium ion battery cathode material;
FIG. 7 shows the production of α -MnSe in example 12And the long cycle performance diagram under high current density when the @ N-C DNTs composite material is used as the lithium ion battery cathode material.
Detailed Description
The present invention is described in further detail below with reference to examples, but it should not be construed that the scope of the above subject matter of the present invention is limited to the following examples, and that all the technologies realized based on the above subject matter of the present invention belong to the scope of the present invention.
Example 1
Step S1: 0.658g KMnO4Adding 70mL of water, stirring for 25min, adding 2.5mL of hydrochloric acid solution with the mass fraction of 36%, stirring for 15min, mixing uniformly, and transferring the mixed solution to 100mHydrothermal reaction in L-shaped stainless steel high-pressure kettle at 140 deg.c for 10 hr, vacuum filtering, repeated washing of precipitate with deionized water, and drying at 80 deg.c for 10 hr to obtain alpha-MnO2NTs precursor;
step S2: 600mg of the alpha-MnO obtained in step S12Adding NTs precursor into 750mL trihydroxymethyl aminomethane buffer solution with molar concentration of 10mmol/L, stirring at room temperature for 5min, performing ultrasonic treatment for 5min, magnetically stirring at room temperature for 30min, adding 300mg dopamine hydrochloride, continuously stirring for 6h, centrifuging, washing precipitate with ethanol and deionized water repeatedly, and drying at 80 deg.C for 8h to obtain alpha-MnO2Intermediates of @ PDA DNTs;
step S3: under the protection of high-purity nitrogen, the alpha-MnO obtained in the step S22Putting the intermediate product of @ PDA DNTs in a tubular furnace, heating to 400 ℃ at the heating rate of 3 ℃/min, calcining for 2h, and naturally cooling to room temperature to obtain MnO @ N-C DNTs;
step S4: mixing MnO @ N-C DNTs obtained in the step S3 with Se powder according to the molar ratio of MnO to Se being 1:1.1, placing the mixture in a quartz glass tube, vacuumizing, then placing the quartz glass tube in a tube furnace, heating to 500 ℃ at the heating rate of 10 ℃/min, calcining for 50h, and naturally cooling to room temperature to obtain the one-dimensional coaxial double-nanotube composite material alpha-MnSe 2@N-C DNTs。
Example 2
Step S1: 0.658g KMnO4Adding 70mL of water, stirring for 25min, adding 2.5mL of hydrochloric acid solution with the mass fraction of 36%, stirring for 15min, uniformly mixing, transferring the mixed solution into a 100mL stainless steel autoclave, carrying out hydrothermal reaction at 140 ℃ for 10h, carrying out vacuum filtration, repeatedly washing and precipitating with deionized water, and drying at 80 ℃ for 10h to obtain alpha-MnO2NTs precursor;
step S2: 600mg of the alpha-MnO obtained in step S12Adding NTs precursor into 750mL trihydroxymethyl aminomethane buffer solution with molar concentration of 10mmol/L, stirring at room temperature for 5min, performing ultrasonic treatment for 5min, magnetically stirring at room temperature for 30min, adding 300mg dopamine hydrochloride, continuously stirring for 6h, centrifuging, washing precipitate with ethanol and deionized water repeatedly, and drying at 80 deg.C for 8h to obtain alpha-MnO2Intermediates of @ PDA DNTs;
step S3: under the protection of high-purity nitrogen, the alpha-MnO obtained in the step S22Putting the @ PDA NTs intermediate product into a tubular furnace, heating to 400 ℃ at the heating rate of 3 ℃/min, calcining for 2h, and naturally cooling to room temperature to obtain MnO @ N-C DNTs;
step S4: mixing MnO @ N-C DNTs obtained in the step S3 with Se powder according to the molar ratio of MnO to Se being 1:1.1, placing the mixture in a quartz glass tube, vacuumizing, then placing the quartz glass tube in a tube furnace, heating to 400 ℃ at the heating rate of 10 ℃/min, calcining for 12 hours, and naturally cooling to room temperature to obtain the one-dimensional coaxial double-nanotube composite material alpha-MnSe 2@N-C DNTs。
Example 3
Step S1: 0.658g KMnO4Adding 70mL of water, stirring for 25min, adding 2.5mL of hydrochloric acid solution with the mass fraction of 36%, stirring for 15min, uniformly mixing, transferring the mixed solution into a 100mL stainless steel autoclave, carrying out hydrothermal reaction at 140 ℃ for 10h, carrying out vacuum filtration, repeatedly washing and precipitating with deionized water, and drying at 80 ℃ for 10h to obtain alpha-MnO2NTs precursor;
step S2: 600mg of the alpha-MnO obtained in step S12Adding NTs precursor into 750mL trihydroxymethyl aminomethane buffer solution with molar concentration of 10mmol/L, stirring at room temperature for 5min, performing ultrasonic treatment for 5min, magnetically stirring at room temperature for 30min, adding 300mg dopamine hydrochloride, continuously stirring for 6h, centrifuging, washing precipitate with ethanol and deionized water repeatedly, and drying at 80 deg.C for 8h to obtain alpha-MnO2Intermediates of @ PDA DNTs;
step S3: under the protection of high-purity nitrogen, the alpha-MnO obtained in the step S22Putting the intermediate product of @ PDA DNTs in a tubular furnace, heating to 400 ℃ at the heating rate of 3 ℃/min, calcining for 2h, and naturally cooling to room temperature to obtain MnO @ N-C DNTs;
step S4: mixing MnO @ N-C DNTs obtained in the step S3 with Se powder according to the molar ratio of MnO to Se being 1:1.1, placing the mixture into a quartz glass tube, vacuumizing, then placing the quartz glass tube into a tube furnace, heating to 450 ℃ at the heating rate of 5 ℃/min, calcining for 20 hours, and naturally cooling to room temperature to obtain the one-dimensional coaxial double-nanotube composite material alpha-MnSe 2@N-C DNTs。
Example 4
Step S1: 0.658g KMnO4Adding 70mL of water, stirring for 25min, adding 2.5mL of hydrochloric acid solution with the mass fraction of 36%, stirring for 15min, uniformly mixing, transferring the mixed solution into a 100mL stainless steel autoclave, carrying out hydrothermal reaction at 140 ℃ for 10h, carrying out vacuum filtration, repeatedly washing and precipitating with deionized water, and drying at 80 ℃ for 10h to obtain alpha-MnO2NTs precursor;
step S2: 600mg of the alpha-MnO obtained in step S12Adding NTs precursor into 750mL trihydroxymethyl aminomethane buffer solution with molar concentration of 10mmol/L, stirring at room temperature for 5min, performing ultrasonic treatment for 5min, magnetically stirring at room temperature for 30min, adding 300mg dopamine hydrochloride, continuously stirring for 6h, centrifuging, washing precipitate with ethanol and deionized water repeatedly, and drying at 80 deg.C for 8h to obtain alpha-MnO2Intermediates of @ PDA DNTs;
step S3: under the protection of high-purity nitrogen, the alpha-MnO obtained in the step S22Putting the intermediate product of @ PDA DNTs in a tubular furnace, heating to 400 ℃ at the heating rate of 3 ℃/min, calcining for 2h, and naturally cooling to room temperature to obtain MnO @ N-C DNTs;
step S4: mixing MnO @ N-C DNTs obtained in the step S3 with Se powder according to the molar ratio of MnO to Se being 1:1.1, placing the mixture into a quartz glass tube, vacuumizing, then placing the quartz glass tube into a tube furnace, heating to 550 ℃ at the heating rate of 15 ℃/min, calcining for 30 hours, and naturally cooling to room temperature to obtain the one-dimensional coaxial double-nanotube composite material alpha-MnSe 2@N-C DNTs。
The foregoing embodiments illustrate the principles, principal features and advantages of the invention, and it will be understood by those skilled in the art that the invention is not limited to the foregoing embodiments, which are merely illustrative of the principles of the invention, and that various changes and modifications may be made therein without departing from the scope of the principles of the invention.

Claims (6)

1. A one-dimensional coaxial double-nanotube composite material is characterized in that: the composite material is prepared from alpha-MnSe2Inner tube and nitrogen dopingOne-dimensional coaxial double-nanotube alpha-MnSe with the average length of 0.5-10 mu m and the average diameter of about 100nm and composed of outer tubes of the hybrid carbon nanotubes (N-C outer tubes)2@ N-C DNTs, wherein alpha-MnSe2The inner tube and the nitrogen-doped carbon nanotube outer tube are tightly grown together to form a coaxial hollow double-nanotube structure.
2. The one-dimensional coaxial double nanotube composite of claim 1, wherein: the one-dimensional coaxial double-nanotube alpha-MnSe2alpha-MnSe in @ N-C DNTs2The content of the N-C DNTs is 5-90% by mass, and the content of the N-C DNTs is 10-95% by mass.
3. The one-dimensional coaxial double nanotube composite of claim 1, wherein: the average wall thickness of the nitrogen-doped carbon nanotube outer tube is 2-50 nm.
4. A method for preparing a one-dimensional coaxial double nanotube composite material according to any one of claims 1 to 3, which is characterized by comprising the following specific steps:
step S1: mixing KMnO4Adding the mixture into water, stirring, adding a hydrochloric acid solution with the mass fraction of 36%, stirring and mixing uniformly, transferring the mixed solution into a stainless steel high-pressure kettle, and carrying out hydrothermal reaction at 140 ℃ to obtain alpha-MnO2NTs precursors;
step S2: the alpha-MnO obtained in step S12Adding NTs precursor into trihydroxymethyl aminomethane buffer solution, adding dopamine hydrochloride for reaction in alpha-MnO2Coating a layer of polydopamine on the surface of the NTs precursor to obtain alpha-MnO2Intermediates of @ PDA DNTs;
step S3: under the protection of inert gas, the alpha-MnO obtained in the step S22Putting the intermediate product of @ PDA DNTs in a tubular furnace, heating to 300-900 ℃ at the heating rate of 1-10 ℃/min, and calcining to obtain MnO @ N-C DNTs;
step S4: mixing MnO @ N-C DNTs obtained in the step S3 with Se powder according to the molar ratio of MnO: Se =1:1.1, placing the mixture into a quartz glass tube, vacuumizing, and then placing the quartz glass tube into a tube furnace at the temperature of 1-15 ℃/minThe temperature is raised to 300-750 ℃ at a speed rate and calcined to obtain the one-dimensional coaxial double-nanotube composite material alpha-MnSe2@N-C DNTs。
5. The preparation method of the one-dimensional coaxial double-nanotube composite material according to claim 4, which is characterized by comprising the following specific steps:
Step S1: 0.658g KMnO4Adding 70mL of water, stirring for 25min, adding 2.5mL of hydrochloric acid solution with the mass fraction of 36%, stirring for 15min, uniformly mixing, transferring the mixed solution into a 100mL stainless steel autoclave, carrying out hydrothermal reaction at 140 ℃ for 10h, carrying out vacuum filtration, repeatedly washing and precipitating with deionized water, and drying at 80 ℃ for 10h to obtain alpha-MnO2NTs precursor;
step S2: 600mg of the alpha-MnO obtained in step S12Adding NTs precursor into 750mL trihydroxymethyl aminomethane buffer solution with molar concentration of 10mmol/L, stirring at room temperature for 5min, performing ultrasonic treatment for 5min, magnetically stirring at room temperature for 30min, adding 300mg dopamine hydrochloride, continuously stirring for 6h, centrifuging, washing precipitate with ethanol and deionized water repeatedly, and drying at 80 deg.C for 8h to obtain alpha-MnO2Intermediates of @ PDA DNTs;
step S3: under the protection of high-purity nitrogen, the alpha-MnO obtained in the step S22Putting the intermediate product of @ PDA DNTs in a tubular furnace, heating to 400 ℃ at the heating rate of 3 ℃/min, calcining for 2h, and naturally cooling to room temperature to obtain MnO @ N-C DNTs;
step S4: mixing MnO @ N-C DNTs obtained in the step S3 with Se powder according to the molar ratio of MnO: Se =1:1.1, placing the mixture in a quartz glass tube for vacuumizing, then placing the quartz glass tube in a tube furnace, heating to 500 ℃ at the heating rate of 10 ℃/min for calcining for 50h, and naturally cooling to room temperature to obtain the one-dimensional coaxial double-nanotube composite material alpha-MnSe 2@N-C DNTs。
6. The use of the one-dimensional co-axial double nanotube composite of any of claims 1-3 in a lithium ion battery anode material due to the one-dimensional co-axial double nanotube composite alpha-MnSe2The @ N-C DNTs has special structural morphology and high conductivity and shows excellent lithium storageRate capability and ultra-long high rate cycle capability.
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