CN111924827B - Three-dimensional nitrogen and fluorine co-doped carbon nanotube potassium electrical anode material and preparation method thereof - Google Patents

Three-dimensional nitrogen and fluorine co-doped carbon nanotube potassium electrical anode material and preparation method thereof Download PDF

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CN111924827B
CN111924827B CN202010750175.XA CN202010750175A CN111924827B CN 111924827 B CN111924827 B CN 111924827B CN 202010750175 A CN202010750175 A CN 202010750175A CN 111924827 B CN111924827 B CN 111924827B
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CN111924827A (en
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章立清
洪果
仲云雷
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Jiangsu Zhaowei Plastic Technology Co ltd
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Abstract

The invention relates to the field of electrode material preparation, in particular to a preparation method for controllably constructing a three-dimensional nitrogen and fluorine co-doped carbon nanotube potassium electric anode material by a template growth method; the three-dimensional nitrogen and fluorine co-doped carbon nanotube is calcined by a polypyrrole fiber and polyvinylidene fluoride microsphere mixture precursor; the microsphere mixture precursor is obtained by carrying out solution polymerization on pyrrole, ammonium sulfate, polyvinylidene fluoride, hexadecyl ammonium bromide and hydrochloric acid; the polymerization method for constructing the polypyrrole fiber and polyvinylidene fluoride microsphere precursor solution is simple, the fluorine doping amount can be controllably adjusted by adjusting the input amount of the polyvinylidene fluoride microspheres, the nitrogen and fluorine co-doped carbon nanotube is synthesized for the first time and is applied as a potassium ion battery cathode material, and the dynamic diffusion coefficient of the nitrogen and fluorine co-doped carbon nanotube as a carbon-based potassium electricity cathode material is higher; the nitrogen and fluorine co-doped carbon nanotube has higher surface pseudocapacitance effect under the condition of proper doping amount.

Description

Three-dimensional nitrogen and fluorine co-doped carbon nanotube potassium electrical anode material and preparation method thereof
Technical Field
The invention relates to the field of electrode material preparation, in particular to a preparation method for controllably constructing a three-dimensional nitrogen and fluorine co-doped carbon nanotube potassium electric anode material by a template growth method.
Background
Electrochemical cell systems play a key role in renewable energy networks and can be used for portable energy storage and for supplementing the intermittent output power of renewable energy sources. Hitherto, a large amount of alkali metals have been usedAnd alkaline earth metals (Li, na, K, mg and Al) are used for developing storage and conductive materials. Among them, rechargeable Lithium Ion Batteries (LIBs) have enjoyed great success over the past several decades. However, the limitation of lithium resources is an urgent problem to be solved in the field of charging systems. The potassium ion battery which can be charged and discharged is considered as an ideal new energy storage system capable of replacing the lithium ion battery due to rich potassium storage and strong interaction with the traditional carbon cathode, so that the new energy storage system can be rapidly developed. It is worth mentioning that the potential of potassium ion batteries compared to standard hydrogen electrodes is-2.93 v, which is closest to-3.04 v for lithium ion batteries, and has a higher operating voltage than sodium ion batteries. Therefore, the method has wider application prospect. However, the rate performance of the potassium ion battery is poor and the cycle life is short, because the intercalation/deintercalation of potassium during charge and discharge causes huge volume and structure changes. In addition, since a large ionic radius of potassium ions causes severe pulverization of a solid electrolyte membrane (SEI) and an active material during cycling to aggravate side reactions, researchers have made great efforts to find alternative electrode materials that are structurally stable and have excellent electrochemical properties. For the anode material, the two-dimensional metal compound has a larger interlayer spacing so that K is + Can be freely migrated without unnecessary structural change and thus is gaining wide attention. Based on this theory, ten thousand and his colleagues reported a unique SnS 2 The composite negative electrode material with substance encapsulated in graphene has a laminated porous structure K + Storage provides sufficient reaction sites to significantly improve reversible capacity and rate performance. However, too high a potential plateau for transition metal sulfides leads to low energy density and the shuttle effect produced by liquid polysulfides also shortens battery life.
In recent years, carbon materials have received increasing attention due to their low potential plateau and structurally stable charge/discharge processes. Low cost, high capacity graphite is a "hard carbon" with good electrical conductivity and interlayer spacing support K + And (4) diffusion. An expanded graphite cathode was fabricated at 0.01mAg -1 May provide 263mahg -1 Near the theoretical capacity of graphite (279 mAhg) -1 ，K 8 C) In that respect However, the reversible capacity and rate capability of graphite as a potassium electrical negative electrode remain obstacles to its practical application. To address these problems, researchers have designed and applied new "soft carbon" anodes with larger interlayer spacing to potassium ion batteries. Based on this, mai et al proposed a well-defined novel soft carbon with polycrystalline semi-hollow microarray structure as PIBs negative electrode at a current density of 500mAg -1 Next, 172mAh was exhibited -1 And can sustain 500 cycles. This is mainly due to the large inter-layer space and the ability of the semi-hollow nanostructures to slow down volume expansion, promote interfacial interactions, K + And electrons provide an efficient diffusion path. In order to further improve the cycle life and rate capability of the carbon material, other potassium storage mechanisms need to be introduced to break through the theoretical capacity limit of potassium storage of the carbon material. The most direct and effective method for modifying the carbon material is doping of hetero atoms, including non-metal elements such as P, F, S, O, N and the like, so as to replace carbon atoms in a network, change the overall potential and achieve the purpose of functional modification. For example, doped carbon has higher electronegativity and more defects than undoped carbon, which is beneficial to improve the conductivity of the electrode and is beneficial to K + Can be inserted into and separated from carbon to increase K + The storage active site of (1). Xu et al synthesized bamboo-type nitrogen-doped carbon nanowires by CVD, the first-turn reversible capacity of which was 323mAhg -1 After 100 cycles, the concentration of the active ingredient is finally maintained at 236mAhg -1 When the current density is 1Ag -1 Time rate performance of 75mAhg -1 . In addition, it is reported that the fluorine doping with the highest electronegativity can also greatly improve the disorder of the carbon material surface and is beneficial to increase K + Is stored. Living et al synthesized a few layers of F-doped graphene foam at 500mA -1 The reversible capacity of the foam can be kept at 165.9mAhg after the foam is used as a PIBs negative electrode to circulate for 200 circles -1 . The reason for the improvement of the electrochemical performance is that a C-F covalent bond is formed, which is helpful to change the hybridization state of carbon and cause local change of the structure, and has great significance. Except for single atomsBesides doping systems, polyatomic doping systems are also in the field of view of researchers. Chen and the like construct an oxygen-fluorine co-doped carbon nano polyhedron with a porous structure as a novel potassium ion battery cathode, and the initial reversible capacity of the oxygen-fluorine co-doped carbon nano polyhedron is 481mAhg -1 The cycling stability is excellent, and the reversible capacity retention rate after 2000 cycles is up to 92%. However, the electrode material is often affected by large volume change in charge and discharge cycles, so that the lateral strain of the three-dimensional carbon material is large, and the electrochemical performance of the three-dimensional carbon material is affected. To avoid these inherent defects of carbon materials, low dimensional structures and efficient heteroatom doping to achieve excellent PIBs performance have become a focus of research in recent years.
Disclosure of Invention
The purpose of the invention is: the defects in the prior art are overcome, the three-dimensional nitrogen and fluorine co-doped carbon nanotube potassium electric anode material is provided, and the hollow structure of the three-dimensional carbon nanotube can relieve the damage to the structure of the carbon nanotube when the potassium ions are embedded and separated.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the three-dimensional nitrogen and fluorine co-doped carbon nanotube potassium cathode material is prepared by calcining a polypyrrole fiber and polyvinylidene fluoride microsphere mixture precursor.
Furthermore, the precursor of the microsphere mixture is obtained by carrying out solution polymerization on pyrrole, ammonium sulfate, polyvinylidene fluoride, hexadecyl ammonium bromide and hydrochloric acid.
Further, the three-dimensional nitrogen and fluorine co-doped carbon nano tube is of a hollow structure, wherein the doping content of F is 0.4wt% -1.2 wt%.
Furthermore, the diameter of the three-dimensional nitrogen and fluorine co-doped carbon nano tube is about 20-100 nm.
Furthermore, the surface of the three-dimensional nitrogen and fluorine co-doped carbon nanotube potassium electric anode material is coated with rough carbon particles.
Another object of the invention is: the preparation method for the three-dimensional nitrogen and fluorine co-doped carbon nano tube potassium electricity negative electrode material is simple in polymerization method for constructing polypyrrole fibers and polyvinylidene fluoride microsphere precursor solution, and the nitrogen and fluorine co-doped carbon nano tube is synthesized for the first time and applied as a potassium ion battery negative electrode material.
A preparation method of a three-dimensional nitrogen and fluorine co-doped carbon nanotube potassium electric anode material comprises the following steps:
s1, dissolving hexadecyl ammonium bromide in HCl solution at 0-3 ℃, stirring for dissolving, then adding polyvinylidene fluoride, continuously stirring until the polyvinylidene fluoride is completely dispersed, then adding ammonium persulfate while stirring, finally slowly dropwise adding pyrrole monomer, and continuously stirring for polymerization at constant temperature after the addition is finished;
s2, at room temperature, carrying out suction filtration on the liquid to obtain a cake-shaped substance;
s3, washing the cake with deionized water and absolute ethyl alcohol for three times respectively at room temperature to obtain a precursor of a mixture of polypyrrole fibers and polyvinylidene fluoride microspheres;
and S4, drying the mixture at room temperature, and calcining the dried mixture in a furnace body to obtain the three-dimensional nitrogen and fluorine co-doped carbon nano tube.
Further, the mass ratio of the polyvinylidene fluoride to the pyrrole is 1.32.
Furthermore, the mass ratio of the hexadecyl ammonium bromide to the pyrrole is (0.48-0.55): 1, and the mass ratio of the ammonium persulfate to the pyrrole is (0.75-0.78): 1.
Further, the reaction temperature after all the materials are added in the step S1 is-5 ℃ to 10 ℃, and the reaction time is 3 hours.
Further, the calcination in the step S4 is to perform calcination at a temperature rising rate of 5 ℃/min to 650 ℃ for 2h under an atmosphere of high-purity argon.
The technical scheme adopted by the invention has the beneficial effects that:
the polymerization method for constructing the polypyrrole fiber (PPy) and polyvinylidene fluoride (PVDF) microsphere precursor solution is simple, the fluorine doping amount can be controllably adjusted by adjusting the input amount of the polyvinylidene fluoride (PVDF) microspheres, the nitrogen and fluorine co-doped carbon nano tube is synthesized for the first time and is applied as a potassium ion battery cathode material, and the dynamic diffusion coefficient of the nitrogen and fluorine co-doped carbon nano tube as a carbon-based potassium electricity cathode material is higher. The nitrogen and fluorine co-doped carbon nanotube has higher surface pseudocapacitance effect under the condition of proper doping amount.
Drawings
FIG. 1 is an SEM image of polypyrrole fiber (PPy) and polyvinylidene fluoride (PVDF) microsphere precursor-1 a), precursor-2 b), precursor-3 c), and precursor-4 d);
FIG. 2 is SEM of N-F co-doped carbon nanotube-1, N-F co-doped carbon nanotube-2 and N-F co-doped carbon nanotube-3;
FIG. 3 is a TEM image of N-F co-doped carbon nanotube-2;
FIG. 4 is a graph showing the rate performance of a battery assembled by nitrogen and fluorine co-doped carbon nanotube-1, nitrogen and fluorine co-doped carbon nanotube-2 and nitrogen and fluorine co-doped carbon nanotube-3;
FIG. 5 is a graph showing the cycle performance of an assembled battery of N/F-codoped carbon nanotube-1, N/F-codoped carbon nanotube-2, and N/F-codoped carbon nanotube-3;
FIG. 6 is a graph showing the ratio of pseudocapacitance of N/F-co-doped carbon nanotube-1, N/F-co-doped carbon nanotube-2, and N/F-co-doped carbon nanotube-3 at different CV scanning speeds;
FIG. 7 shows K of N/F-codoped carbon nanotube-1, N/F-codoped carbon nanotube-2, and N/F-codoped carbon nanotube-3 + A graph of the diffusion coefficient of the ions.
Detailed Description
The invention will now be described in further detail with reference to specific embodiments and drawings attached to the description.
In the three-dimensional nitrogen and fluorine co-doped carbon nanotube potassium electric cathode material, the three-dimensional nitrogen and fluorine co-doped carbon nanotube is calcined by a polypyrrole fiber and polyvinylidene fluoride microsphere mixture precursor. The precursor of the microsphere mixture is obtained by solution polymerization of pyrrole, ammonium sulfate, polyvinylidene fluoride, hexadecyl ammonium bromide and hydrochloric acid, and the raw materials are simple and easy to obtain and have low cost.
The hollow structure of the three-dimensional carbon nano tube can relieve the damage to the structure of the carbon nano tube when potassium ions are embedded and removed. In addition, the three-dimensional nitrogen and fluorine co-doped carbon nanoThe rice tube has abundant mesoporous/microporous structures, active sites for storing K ions are increased, and the multiplying power capability and the capacitance characteristic of the electrode at a high-voltage scanning speed are improved. And the high content of N doping helps to improve the active sites and conductivity. While the additional F doping further reduces K + And binding energy between carbon nanotubes. The synergistic effect promotes the electrode material to show higher specific capacity of 238mAhg -1 At 0.2Ag -1 Superior rate capability (83 mAhg) at current density -1 At 10Ag -1 At current density), and good cycle stability (at current density 1 Ag) -1 After 1000 cycles of lower circulation, the specific capacity can still be kept at 187mAhg -1 ) The carbon-based potassium ion battery anode is one of the best representatives of the electrochemical performances of all the carbon-based potassium ion battery anodes at present. Meanwhile, density functional theory calculation shows that the interaction of different heteroatoms has positive influence on active sites in soft carbon and is accompanied by K + The transmission path of (2) is reduced, and the conductivity of the three-dimensional nitrogen and fluorine co-doped carbon nano tube is increased. Therefore, this finding greatly promoted the development of soft carbon anodes, driving them to have better rate performance and cycle performance in PIBs. Therefore, the three-dimensional nitrogen and fluorine co-doped carbon nanotube prepared by the method can be widely used in potassium ion batteries and has potential good economic benefits.
The three-dimensional nitrogen and fluorine co-doped carbon nanotube is of a hollow structure, wherein the doping content of F is 0.4-1.2 wt%.
The diameter of the three-dimensional nitrogen and fluorine co-doped carbon nano tube is about 20-100 nm; the nano material is beneficial to relieving the problem of volume expansion in the charging and discharging process, is beneficial to shortening the diffusion distance of K ions and improves the multiplying power performance of the material.
The surface of the three-dimensional nitrogen and fluorine co-doped carbon nanotube potassium electric negative electrode material is coated with rough carbon particles, so that K adsorption sites are increased, and the specific capacity is increased.
A preparation method of a three-dimensional nitrogen and fluorine co-doped carbon nanotube potassium electric anode material comprises the following steps:
s1, dissolving cetyl ammonium bromide in HCl solution at 0-3 ℃, stirring for dissolving, then adding polyvinylidene fluoride, continuously stirring until the polyvinylidene fluoride is completely dispersed, then adding ammonium persulfate while stirring, finally slowly dropwise adding pyrrole monomer, and continuously stirring for polymerization at constant temperature; the mass ratio of polyvinylidene fluoride to pyrrole is 1.32-1, and the reaction temperature is-5 ℃ to 10 ℃ after all the materials are added, and the reaction time is 3h. Cetyl ammonium bromide serves to bubble disperse polyvinylidene fluoride, and disperse Py.
S2, at room temperature, carrying out suction filtration on the liquid to obtain a cake-shaped substance;
s3, washing the cake with deionized water and absolute ethyl alcohol for three times respectively at room temperature to obtain a precursor of a mixture of polypyrrole fibers and polyvinylidene fluoride microspheres;
and S4, drying the precursor at room temperature, drying the product in a forced air drying oven at 80 ℃ for 10 hours, removing water and ethanol, placing the product in a furnace body for calcination to obtain the three-dimensional nitrogen and fluorine co-doped carbon nanotube, and performing calcination by raising the temperature to 650 ℃ at a heating rate of 5 ℃/min in the atmosphere of high-purity argon for 2 hours.
The following examples are intended to provide those skilled in the art with a more complete understanding of the present invention, and are not intended to limit the scope of the present invention. Reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic may be included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Example 1
A three-dimensional nitrogen and fluorine co-doped carbon nanotube potassium electric cathode material is prepared by calcining a polypyrrole fiber and polyvinylidene fluoride microsphere mixture precursor, wherein the microsphere mixture precursor is prepared by carrying out solution polymerization on pyrrole, ammonium sulfate, polyvinylidene fluoride, hexadecyl ammonium bromide and hydrochloric acid.
The three-dimensional nitrogen and fluorine co-doped carbon nanotube is of a hollow structure, the content of F doping is continuously adjustable by 0.4% -1.2%, the diameter of the three-dimensional nitrogen and fluorine co-doped carbon nanotube is about 20-100 nm, and rough carbon particles are coated on the surface of the three-dimensional nitrogen and fluorine co-doped carbon nanotube potassium electric cathode material.
The preparation method of the three-dimensional nitrogen and fluorine co-doped carbon nanotube potassium electric anode material comprises the following steps:
(1) Preparation of a mixture of polypyrrole fibres (PPy) and polyvinylidene fluoride (PVDF) microspheres:
0.803g of cetylammonium bromide (CTAB) was dissolved in 240mL at 0 to 3 ℃ and 1mol L was added thereto –1 In HCl solution. After complete dissolution and foaming, 0.235g of polyvinylidene fluoride (PVDF) was added and dispersed completely under magnetic stirring at 800 r/min. Subsequently, 1.2g of ammonium persulfate (NH) 4 ) 2 S 2 O 8 ) The mixture was poured into the above solution under stirring. 1.6mL of pyrrole monomer was then slowly added dropwise to the above white suspension and polymerized for 3h with magnetic stirring. And (3) carrying out suction filtration on the reactant, wherein the obtained product is black powder, namely the mixture of polypyrrole fibers (PPy) and polyvinylidene fluoride (PVDF) microspheres. The obtained product is dried in a drying oven at 80 ℃ for 10 hours after being washed by deionized water and absolute ethyl alcohol for three times respectively, and is named as a precursor-1, and an SEM picture is shown in figure 1.
(2) Preparing a carbon-based negative electrode material of the nitrogen and fluorine co-doped carbon nanotube potassium ion battery:
at room temperature, the precursor-1 is placed in a tube furnace, the temperature is raised to 650 ℃ at the heating rate of 5 ℃/min under the atmosphere of high-purity argon gas, and the precursor is calcined for 2 hours, the obtained black product is the nitrogen and fluorine co-doped carbon nanotube-1 (NFDCN 1), an SEM image of the nitrogen and fluorine co-doped carbon nanotube is shown in figure 2, and the doping amounts of nitrogen and fluorine in the nitrogen and fluorine co-doped carbon nanotube-1 (NFDCN 1) are shown in table 1.
Example 2
A three-dimensional nitrogen and fluorine co-doped carbon nanotube potassium electric cathode material is prepared by calcining a polypyrrole fiber and polyvinylidene fluoride microsphere mixture precursor, wherein the microsphere mixture precursor is prepared by carrying out solution polymerization on pyrrole, ammonium sulfate, polyvinylidene fluoride, hexadecyl ammonium bromide and hydrochloric acid.
The three-dimensional nitrogen and fluorine co-doped carbon nano tube is of a hollow structure, the content of F doping is continuously adjustable (0.4% -1.2%), the diameter of the three-dimensional nitrogen and fluorine co-doped carbon nano tube is about 20-100 nm, and rough carbon particles are coated on the surface of the three-dimensional nitrogen and fluorine co-doped carbon nano tube potassium electric cathode material.
The preparation method of the three-dimensional nitrogen and fluorine co-doped carbon nanotube potassium electric anode material comprises the following steps:
(1) Preparation of a mixture of polypyrrole fibres (PPy) and polyvinylidene fluoride (PVDF) microspheres:
the PVDF content was adjusted to 0.704g under the same experimental procedure as in example 1, and the resulting mixture of polypyrrole fibers (PPy) and polyvinylidene fluoride (PVDF) microspheres was named as precursor-2, and the SEM image is shown in FIG. 1.
(2) Preparing a carbon-based negative electrode material of the nitrogen and fluorine co-doped carbon nanotube potassium ion battery:
and at room temperature, placing the precursor-2 in a tube furnace, heating to 650 ℃ at a heating rate of 5 ℃/min in the atmosphere of high-purity argon, and calcining for 2h to obtain a black product, namely the nitrogen-fluorine co-doped carbon nanotube-2 (NFDCN 2). The SEM image of the nitrogen and fluorine co-doped carbon nanotube is shown in FIG. 2, and the TEM image of the nitrogen and fluorine co-doped carbon nanotube-2 is shown in FIG. 3. The doping amounts of nitrogen and fluorine in the nitrogen and fluorine co-doped carbon nanotube-2 (NFDCN 2) are shown in Table 1.
Example 3
A three-dimensional nitrogen and fluorine co-doped carbon nanotube potassium electricity negative electrode material is prepared by calcining a polypyrrole fiber and polyvinylidene fluoride microsphere mixture precursor, wherein the microsphere mixture precursor is prepared by carrying out solution polymerization on pyrrole, ammonium sulfate, polyvinylidene fluoride, hexadecyl ammonium bromide and hydrochloric acid.
The three-dimensional nitrogen and fluorine co-doped carbon nanotube is of a hollow structure, the content of F doping is continuously adjustable (0.4% -1.2%), the diameter of the three-dimensional nitrogen and fluorine co-doped carbon nanotube is about 20-100 nm, and rough carbon particles are coated on the surface of the three-dimensional nitrogen and fluorine co-doped carbon nanotube potassium electric cathode material.
The preparation method of the three-dimensional nitrogen and fluorine co-doped carbon nanotube potassium electric anode material comprises the following steps:
(1) Preparation of a mixture of polypyrrole fibres (PPy) and polyvinylidene fluoride (PVDF) microspheres:
the PVDF content was adjusted to 1.173g under the same experimental procedure, and the resulting product polypyrrole fiber (PPy) and polyvinylidene fluoride (PVDF) microsphere blends were named as precursor-3, respectively, and the SEM image is shown in FIG. 1.
(2) Preparing a carbon-based negative electrode material of the nitrogen and fluorine co-doped carbon nanotube potassium ion battery:
and at room temperature, placing the precursor-3 in a tube furnace, heating to 650 ℃ at a heating rate of 5 ℃/min in the atmosphere of high-purity argon, and calcining for 2h to obtain a black product, namely the nitrogen-fluorine co-doped carbon nanotube-1 (NFDCN 3). The SEM image of the nitrogen and fluorine co-doped carbon nanotube is shown in fig. 2, and the amounts of nitrogen and fluorine doping in the nitrogen and fluorine co-doped carbon nanotube-3 (NFDCN 3) are shown in table 1.
Example 4
A three-dimensional nitrogen and fluorine co-doped carbon nanotube potassium electric cathode material is prepared by calcining a polypyrrole fiber and polyvinylidene fluoride microsphere mixture precursor, wherein the microsphere mixture precursor is prepared by carrying out solution polymerization on pyrrole, ammonium sulfate, polyvinylidene fluoride, hexadecyl ammonium bromide and hydrochloric acid.
The three-dimensional nitrogen and fluorine co-doped carbon nanotube is of a hollow structure, the content of F doping is continuously adjustable (0.4% -1.2%), the diameter of the three-dimensional nitrogen and fluorine co-doped carbon nanotube is about 20-100 nm, and rough carbon particles are coated on the surface of the three-dimensional nitrogen and fluorine co-doped carbon nanotube potassium electric cathode material.
The preparation method of the three-dimensional nitrogen and fluorine co-doped carbon nanotube potassium electric anode material comprises the following steps:
(1) Preparation of a mixture of polypyrrole fibres (PPy) and polyvinylidene fluoride (PVDF) microspheres:
the PVDF content was adjusted to 1.645g under the same experimental procedure, and the resulting microsphere mixtures of polypyrrole fibers (PPy) and polyvinylidene fluoride (PVDF) were named as precursors-4 respectively, and the SEM image is shown in FIG. 1.
It was found through experimentation that when the amount of PVDF was increased to 1.645g, py polymerization was hindered, so precursor 4 was not discussed in the following characterization of properties. As can be seen from the SEM image of precursor-4 d) in fig. 1.
Performance detection
The performance of the battery with the carbon nanotube-1 co-doped with nitrogen and fluorine, the carbon nanotube-2 co-doped with nitrogen and fluorine, and the carbon nanotube-3 potassium ion carbon-based negative electrode material in the embodiments 1 to 3 is detected as follows:
punching a wafer with the diameter of 15mm from the prepared nitrogen and fluorine co-doped carbon nano tube-1, nitrogen and fluorine co-doped carbon nano tube-2 and nitrogen and fluorine co-doped carbon nano tube-3 potassium ion carbon-based negative electrode material to serve as a negative electrode piece, taking a lithium foil as a positive electrode piece, taking a glass fiber membrane (Whatman, gradeGF/B) as a diaphragm, selecting electrolyte (the concentration of KPF6 in the electrolyte is 0.8mol/L, and the rest is ethylene carbonate and diethyl carbonate in the volume ratio of 1: 1), assembling a CR2025 button type simulation battery in a glove box filled with argon, sealing by using a battery packaging machine, packaging to obtain a half battery, performing charge-discharge test by using constant current, wherein the charge-discharge voltage is 0.01-3.0V. Multiplying power performance and cycle performance are shown in figures 4 and 5, pseudocapacitance ratio calculation under different CV sweeping speeds is shown in figure 6 + The diffusion coefficient of the ions is shown in FIG. 7.
Table 1 shows the structure, properties and surface chemical properties of the nitrogen and fluorine co-doped carbon nanotube-1, the nitrogen and fluorine co-doped carbon nanotube-2 and the nitrogen and fluorine co-doped carbon nanotube-3.
TABLE 1
Figure BDA0002609823980000131
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.

Claims (6)

1. The utility model provides a three-dimensional nitrogen and fluorine codope carbon nanotube potassium ion battery cathode material which characterized in that: the three-dimensional nitrogen and fluorine co-doped carbon nano tube is calcined by a polypyrrole fiber and polyvinylidene fluoride microsphere mixture precursor;
the three-dimensional nitrogen and fluorine co-doped carbon nano tube is of a hollow structure, wherein the doping content of F is 0.4-1.2 wt%;
the surface of the three-dimensional nitrogen and fluorine co-doped carbon nanotube potassium ion battery cathode material is coated with rough carbon particles;
the preparation method of the three-dimensional nitrogen and fluorine co-doped carbon nanotube potassium ion battery negative electrode material comprises the following steps:
s1, dissolving CTAB in HCl solution at 0-3 ℃, stirring for dissolving, then adding polyvinylidene fluoride, continuously stirring until the polyvinylidene fluoride is completely dispersed, then adding ammonium persulfate while stirring, finally slowly dropwise adding pyrrole monomer, and continuously stirring for polymerization at constant temperature;
s2, at room temperature, carrying out suction filtration on the liquid to obtain a cake-shaped substance;
s3, washing the cake with deionized water and absolute ethyl alcohol for three times respectively at room temperature to obtain a precursor of a mixture of polypyrrole fibers and polyvinylidene fluoride microspheres;
and S4, drying the mixture at room temperature, and calcining the dried mixture in a furnace body to obtain the three-dimensional nitrogen and fluorine co-doped carbon nano tube.
2. The three-dimensional nitrogen and fluorine co-doped carbon nanotube potassium ion battery anode material of claim 1, which is characterized in that: the diameter of the three-dimensional nitrogen and fluorine co-doped carbon nano tube is 20-100 nm.
3. The three-dimensional nitrogen and fluorine co-doped carbon nanotube potassium ion battery anode material of claim 1, which is characterized in that: the mass ratio of the polyvinylidene fluoride to the pyrrole is 1.32.
4. The three-dimensional nitrogen and fluorine co-doped carbon nanotube potassium ion battery anode material of claim 1, which is characterized in that: the mass ratio of CTAB to pyrrole is (0.48-0.55): 1, and the mass ratio of ammonium persulfate to pyrrole is (0.75-0.78): 1.
5. The three-dimensional nitrogen and fluorine co-doped carbon nanotube potassium ion battery anode material of claim 1, which is characterized in that: the reaction temperature after all the materials are added in the step S1 is-5 ℃ to 10 ℃, and the reaction time is 3 hours.
6. The preparation method of the three-dimensional nitrogen and fluorine co-doped carbon nanotube potassium ion battery anode material according to claim 1, characterized by comprising the following steps: the calcination in the step S4 is to perform calcination for 2h at the temperature rising rate of 5 ℃ per minute under the atmosphere of high-purity argon and at the temperature rising rate of 650 ℃.
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