CN114455569B - Phosphorus-doped nitrogen-rich porous carbon nano sheet and preparation method and application thereof - Google Patents

Phosphorus-doped nitrogen-rich porous carbon nano sheet and preparation method and application thereof Download PDF

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CN114455569B
CN114455569B CN202210129876.0A CN202210129876A CN114455569B CN 114455569 B CN114455569 B CN 114455569B CN 202210129876 A CN202210129876 A CN 202210129876A CN 114455569 B CN114455569 B CN 114455569B
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phosphorus
porous carbon
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doped nitrogen
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CN114455569A (en
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周国伟
董旭晟
赵瑞正
孙彬
高婷婷
李华鹏
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Qilu University of Technology
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Abstract

The invention belongs to the technical field of potassium ion batteries, and relates to a phosphorus-doped nitrogen-rich porous carbon nano sheet, and a preparation method and application thereof. And forming a metal hexamine frame precursor by hydrogen bonding of transition metal nitrate and hexamethylenetetramine in an ethanol solution, carrying out pyrolysis on the metal hexamine frame precursor in an inert atmosphere to obtain an N/C precursor, carrying out heating phosphating treatment on the N/C precursor and sodium hypophosphite in the inert atmosphere, and cooling to obtain the N/C precursor. The invention constructs the N-doped carbon material with enough defects and edge sites by doping phosphorus, realizes higher active N proportion, improves the storage performance of potassium, and can obtain the advanced electrode material with high conductivity, good multiplying power performance and strong cycle stability by an economic and efficient method.

Description

Phosphorus-doped nitrogen-rich porous carbon nano sheet and preparation method and application thereof
Technical Field
The invention belongs to the technical field of potassium ion batteries, and relates to a phosphorus-doped nitrogen-rich porous carbon nano sheet, and a preparation method and application thereof.
Background
The disclosure of this background section is only intended to increase the understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art already known to those of ordinary skill in the art.
Nitrogen atom doping is one of effective methods for improving the potassium storage performance of a carbonaceous material serving as a cathode material of a potassium ion battery, and can effectively adjust surface functional groups, local electronic structures and chemical properties, improve electronic conductivity and electrolyte wettability, and generate stronger potassium storage active sites so as to improve the potassium storage performance. The inventors have found that the type of N-defect site (pyridine-N, pyrrole-N or graphite-N) plays a key role in the energy storage device and that the active N content of the doped carbon may determine its reaction characteristics. pyridine-N and pyrrole-N are energetically more favorable for ion storage than graphite-N because they can induce enough defects, provide more active sites, and improve reactivity and electron conductivity. The existing nitrogen-doped carbonaceous material has fewer defects and edge sites, so that the proportion of active nitrogen is lower, and the storage performance of the nitrogen-doped carbonaceous material potassium is required to be improved.
Disclosure of Invention
In order to solve the defects of the prior art, the invention aims to provide a phosphorus-doped nitrogen-rich porous carbon nano sheet, a preparation method and application thereof, wherein an N-doped carbon material with enough defects and edge sites is constructed by doping phosphorus, so that a higher active N proportion is realized, the storage performance of potassium is improved, and an advanced electrode material with high conductivity, good multiplying power performance and strong cycling stability can be obtained by an economic and efficient method.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
on the one hand, the preparation method of the phosphorus-doped nitrogen-rich porous carbon nano-sheet comprises the steps of forming a metal hexamine framework precursor through hydrogen bonding action of transition metal nitrate and hexamine in an ethanol solution, carrying out pyrolysis on the metal hexamine framework precursor in an inert atmosphere to obtain an N/C precursor, carrying out heating phosphating treatment on the N/C precursor and sodium hypophosphite in the inert atmosphere, and cooling to obtain the nitrogen-rich porous carbon nano-sheet.
The phosphorus-doped nitrogen-rich porous carbon nano-sheet (P-N/C) prepared by the invention has a two-dimensional porous structure, and the two-dimensional porous structure has larger interlayer spacing, rich pore defects and edges, and can effectively reduce K + Diffusion distance and promote K + Diffusion kinetics. Meanwhile, the P-N/C negative electrode has larger specific surface area and superior performance through additional P dopingThe conductivity and the higher pyrrole-N and pyridine-N content of the polymer not only can expose more accessible active sites and increase the interface K + Adsorption reaction, acceleration of electron transfer, promotion of charge transfer kinetics in the circulation process, and excellent electrochemical performance.
In addition, the invention discovers that anions in the transition metal nitrate influence the morphology structure of the material, and the morphology structure can be obtained when the nitrate is adopted.
On the other hand, the phosphorus-doped nitrogen-rich porous carbon nano-sheet is obtained by the preparation method. The P-N/C prepared by the invention has a two-dimensional porous structure, a large specific surface area, a unique phosphorus-doped nitrogen-rich structural system, excellent electronic conductivity and more active sites, and the characteristics of the P-N/C show excellent electrochemical performance through excellent synergistic effect.
In a third aspect, the application of the phosphorus-doped nitrogen-rich porous carbon nano-sheet in a potassium ion battery is provided. In particular to the application in the cathode of a potassium ion battery.
In a fourth aspect, a negative electrode of a potassium ion battery includes a current collector and an active ingredient, where the active ingredient is the above-mentioned phosphorus doped nitrogen-rich porous carbon nanosheet.
In a fifth aspect, a potassium ion battery comprises the negative electrode, the counter electrode, the diaphragm and the electrolyte of the potassium ion battery.
Compared with the prior art, the invention has the following beneficial effects:
(1) Transition metal nitrate and Hexamethylenetetramine (HMT) are selected to form a metal hexamine framework precursor with a special structure through hydrogen bonding in an ethanol solution.
(2) The preparation process of the N/C precursor adopts a hydrogen bond assembly and pyrolysis strategy, and is simple and efficient.
(3) The phosphorus-doped nitrogen-rich porous carbon nano-sheet improves the content of active nitrogen, and has the advantages of simple preparation method and strong operability.
(4) The invention has low temperature and short calcination time in the calcination and phosphorylation process, and can reduce energy consumption.
(5) The synthesized P-N/C has large specific surface area, unique two-dimensional porous structure, excellent conductivity and more active sites, and the characteristics have excellent electrochemical performance through excellent synergistic effect.
(6) The invention relates to a phosphorus-doped nitrogen-rich porous carbon nano sheet, wherein the content of active nitrogen is regulated by P atom doping, so that more active sites are provided for electron conduction, and a certain reference function is played for widening an energy material system.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention.
FIG. 1 is an X-ray diffraction pattern (XRD) of a two-dimensional porous N/C nanoplatelet and a phosphorus-doped nitrogen-rich porous carbon nanoplatelet prepared in example 1 of the present invention.
FIG. 2 is a Scanning Electron Microscope (SEM) of two-dimensional N/C nanoplatelets prepared during preparation of example 1 of the present invention.
FIG. 3 is a Transmission Electron Microscope (TEM) of the phosphorus-doped nitrogen-rich porous carbon nanoplatelets prepared in example 1 of the present invention.
Fig. 4 is a Mapping diagram of the element C, N, P of the phosphorus-doped nitrogen-rich porous carbon nano-sheet prepared in example 1 of the present invention.
Fig. 5 is an XPS diagram of N1s of the phosphorus-doped nitrogen-rich porous carbon nanoplatelets prepared in example 1 of the present invention.
Fig. 6 is a graph showing the rate performance of the potassium ion battery prepared in example 4 of the present invention.
Fig. 7 is a graph showing the long cycle performance curve and coulombic efficiency of the potassium ion battery prepared in example 4 of the present invention.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the present invention. As used herein, the singular is also intended to include the plural unless the context clearly indicates otherwise, and furthermore, it is to be understood that the terms "comprises" and/or "comprising" when used in this specification are taken to specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof.
In view of the problems that the prior preparation method for constructing a pore structure, doping hetero atoms and preparing a carbon-based nano composite material is uncontrollable in structure, few in active sites, low in reversible capacity and the like, the invention provides a phosphorus-doped nitrogen-enriched porous carbon nano sheet, and a preparation method and application thereof.
According to an exemplary embodiment of the invention, a preparation method of a phosphorus-doped nitrogen-rich porous carbon nano sheet is provided, transition metal nitrate and hexamethylenetetramine form a metal hexamine frame precursor through hydrogen bonding in an ethanol solution, the metal hexamine frame precursor is pyrolyzed in an inert atmosphere to obtain an N/C precursor, and the N/C precursor and sodium hypophosphite are subjected to heating and phosphating treatment in the inert atmosphere and cooled to obtain the nitrogen-rich porous carbon nano sheet.
The preparation method can prepare the phosphorus-doped nitrogen-rich porous carbon nano-sheet, and can solve the problems of low content and low activity of pyrrole-N and pyridine-N, complex reaction in the preparation process, environmental pollution and the like.
The transition metal nitrate is a nitrate compound with cations as transition metal ions, and the transition metal can be cadmium, zinc, copper and the like. The invention preferably selects cadmium salt, wherein the cadmium salt is a compound with cadmium ion as cation, and Cd (NO 3 ) 2 ·4H 2 In the O process, the problem of low activity of pyrrole-N and pyridine-N contents can be better solved.
In some examples of this embodiment, the molar ratio of transition metal nitrate to hexamethylenetetramine is from 1:1 to 3. In this case, more metal hexamine framework precursor can be ensured.
In some examples of this embodiment, the transition metal nitrate is reacted with hexamethylenetetramine at a temperature of 25 to 45℃for a period of 18 to 30 hours.
In some examples of this embodiment, the material after reaction of the transition metal nitrate with hexamethylenetetramine is carefully centrifuged, washed and dried sequentially. The drying temperature is 75-85 ℃ and the drying time is 10-15 h.
In some examples of this embodiment, the pyrolysis treatment is carried out at a temperature of 800 to 1000 ℃ for a time of 1 to 3 hours.
In some examples of this embodiment, the mass ratio of the N/C precursor to sodium hypophosphite is 1:5-10.
In some examples of this embodiment, the N/C precursor is purged with an inert atmosphere for 0.5 to 1 hour and then subjected to a thermal phosphating treatment. The material effect obtained by the method is better.
In some examples of this embodiment, the ramp rate of the phosphating treatment is 2 to 5 ℃/min. When the temperature rising rate is 3 ℃/min, the obtained material has better effect.
In some examples of this embodiment, the phosphating time is 3 to 5 hours. When the heat preservation time is 4 hours, the obtained material effect is better.
In some examples of this embodiment, the temperature of the phosphating treatment is 350 to 450 ℃.
In another embodiment of the invention, a phosphorus-doped nitrogen-rich porous carbon nanosheet is provided, which is obtained by the preparation method. The P-N/C prepared by the invention has a two-dimensional porous structure, a large specific surface area, a unique phosphorus-doped nitrogen-rich structural system, excellent electronic conductivity and more active sites, and the characteristics of the P-N/C show excellent electrochemical performance through excellent synergistic effect.
The third embodiment of the invention provides an application of the phosphorus-doped nitrogen-rich porous carbon nano-sheet in a potassium ion battery. In particular to the application in the cathode of a potassium ion battery.
The fourth embodiment of the invention provides a negative electrode of a potassium ion battery, which comprises a current collector and an active ingredient, wherein the active ingredient is the phosphorus-doped nitrogen-rich porous carbon nano-sheet.
In some examples of this embodiment, the method of preparation is: and ball-milling the nitrogen-rich porous carbon nano-sheet doped with phosphorus to regulate the activity of nitrogen into powder, uniformly mixing with an adhesive and conductive carbon black, adding a solvent, uniformly mixing to form a colloid, and rolling the colloid onto a current collector.
In a fifth embodiment of the present invention, a potassium ion battery is provided, which includes the above-described negative electrode, counter electrode, separator, and electrolyte.
In some examples of this embodiment, the counter electrode is potassium metal.
In some examples of this embodiment, the separator is a fiberglass membrane.
In some examples of this embodiment, the electrolyte is potassium hexafluorophosphate (KPF) 6 ) The solution obtained by dissolving the mixed solvent of Ethylene Carbonate (EC) and diethyl carbonate (DEC) is electrolyte (the volume ratio of EC to DEC is 1:1, KPF in the electrolyte 6 At a concentration of 0.8 mol/L).
The potassium ion battery is a 2032 button battery.
In order to enable those skilled in the art to more clearly understand the technical scheme of the present invention, the technical scheme of the present invention will be described in detail below with reference to specific examples and comparative examples.
Example 1
And (3) preparing the phosphorus-doped nitrogen-rich porous carbon nano-sheet.
(1) Preparation of two-dimensional N/C nanosheets:
①Cd(NO 3 ) 2 ·4H 2 o, HMT to the ethanol solution of 340mL and 560mL respectively, and stirring well.
(2) The Cd (NO) obtained in the step (1) 3 ) 2 The solution was added dropwise to the HMT solution to give a white precipitate, and the mixed solution was stirred for an additional 24 hours in order to obtain sufficient Cd-HMT MHF.
(3) And (3) repeatedly washing the precipitate obtained in the step (2) with ethanol for a plurality of times, and drying the precipitate in an oven at 80 ℃ for 12 hours to obtain the Cd-HMT MHF.
(4) And heating the obtained Cd-HMT MHF to 1000 ℃ in Ar atmosphere at the heating rate of 3 ℃/min under Ar flow, and then maintaining for 2 hours to obtain the two-dimensional N/C nano-sheet, as shown in figures 1-4.
(2) And (3) preparing the phosphorus-doped nitrogen-rich porous carbon nano-sheet.
Mixing two-dimensional N/C nano-sheet precursor powder with excessive NaH 2 PO 2 ·H 2 O (the mass ratio is greater than 1:2 and is excessive, and the mass ratio of the embodiment is 1:2.5), placing the two ends of the same sintering boat in argon gas flow, and calcining at 400 ℃ to obtain the phosphorus-doped nitrogen-enriched porous carbon nano-sheet, as shown in figure 1. Ventilating for 1h at normal temperature before heating, wherein the heating rate is 3 ℃/min, and the heat preservation time is 2h.
Wherein, the raw material Cd (NO) used for preparing Cd-HMT MHF 3 ) 2 ·4H 2 O and HMT are added according to the mol ratio of 1:1 to prepare the two-dimensional N/C nano-sheet, the pyrolysis temperature is 1000 ℃, and the heat preservation is carried out for 2 hours.
The Cd (NO) 3 ) 2 ·4H 2 Molecular weights of O and HMT are 308.49 gmol respectively -1 And 140.19g mol -1 。
FIG. 5 is an XPS spectrum of N1s demonstrating the increase in pyridine-N and pyrrole-N content and the decrease in graphite-N and oxidation-N content after P doping.
Example 2
The preparation method of the two-dimensional N/C nano-sheet is the same as the step (1) in the example 1.
(2) Preparing the phosphorus doped nitrogen-rich porous carbon nano-sheet.
(1) Mixing two-dimensional N/C nano-sheet powder with excessive NaH 2 PO 2 ·H 2 O (mass ratio 1:2) is respectively placed in two burning boats to make NaH in a tube furnace 2 PO 2 ·H 2 O is placed upstream of the gas flow and two-dimensional N/C nanoplatelet powder is placed downstream of the gas flow.
(2) And (5) vacuumizing the tube furnace and introducing argon for three times.
(3) Setting the heating rate to 2 ℃/min in argon gas flow at the constant temperature of 30 ℃ for 1h, heating to 400 ℃ and preserving heat for 2h. Finally obtaining the phosphorus doped nitrogen-rich porous carbon nano-sheet.
Example 3:
as described in example 1, the difference is that:
zinc nitrate (Zn (NO) 3 ) 2 .4H 2 O), copper nitrate (Cu (NO) 3 ) 2 .4H 2 O) and other transition metal nitrates, the morphology and pore size distribution of the derived N/C have certain difference. The charge transfer and ion diffusion channels formed by the phosphorus doped nitrogen-rich porous carbon nano-sheet are not affected, the electrochemical kinetics is accelerated, and the cycling stability and the rate capability of the electrode material are not affected.
Example 4:
the phosphorus-doped nitrogen-rich porous carbon nanosheets prepared in example 1 were prepared into coin cells.
The phosphorus doped nitrogen-rich porous carbon nanoplatelets, binder PVDF, and conductive carbon black upper P LI were mixed in a weight ratio of 70:15:15, and then dissolved in NMP to form a uniform slurry. After the uniform slurry was coated on a Cu foil and vacuum-dried at 60 ℃ for 12 hours, the electrode was cut into disk electrode pieces having a diameter of 12 mm. Next, a potassium ion battery (2025 button cell) was assembled by using a metal potassium (aladine) as a counter electrode, a glass fiber membrane (GF/D whatman) as a separator, a mixed solvent of potassium hexafluorophosphate (KPF 6) dissolved in Ethylene Carbonate (EC) and diethyl carbonate (DEC) as an electrolyte (the volume ratio of EC to DEC was 1:1, the concentration of KPF6 in the electrolyte was 0.8 mol/L), and a disk electrode sheet having a diameter of 12mm as a working electrode.
As shown in FIGS. 6-7, the cycle performance curve of the potassium ion battery can be seen that the phosphorus doped nitrogen-rich porous carbon nano-sheet electrode is shown in 1 A.g -1 Has a reversible capacity of 265.8mAh g after 2000 cycles at a current density of (2) -1 。
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (9)

1. The preparation method of the phosphorus doped nitrogen-rich porous carbon nano sheet comprises the steps of forming a metal hexamine frame precursor by hydrogen bonding of transition metal nitrate and hexamethylenetetramine in an ethanol solution, carrying out pyrolysis on the metal hexamine frame precursor in an inert atmosphere to obtain an N/C precursor, carrying out heating phosphating treatment on the N/C precursor and sodium hypophosphite in the inert atmosphere, and cooling to obtain the nitrogen doped nitrogen-rich porous carbon nano sheet;
the mol ratio of the transition metal nitrate to the hexamethylenetetramine is 1:1-3;
the mass ratio of the N/C precursor to the sodium hypophosphite is 1:5-10.
2. The method for preparing the phosphorus-doped nitrogen-rich porous carbon nano sheet according to claim 1, wherein in the reaction process of transition metal nitrate and hexamethylenetetramine, the temperature is 25-45 ℃ and the reaction time is 18-30 hours;
or the pyrolysis treatment is carried out at 800-1000 ℃ for 1-3 hours.
3. The method for preparing the phosphorus-doped nitrogen-rich porous carbon nano-sheet according to claim 1, wherein the materials after the reaction of the transition metal nitrate and the hexamethylenetetramine are sequentially centrifuged, washed and dried.
4. The method for preparing the phosphorus-doped nitrogen-rich porous carbon nano-sheet according to claim 1, wherein the method is characterized in that inert atmosphere gas is introduced into the N/C precursor for 0.5-1 h, and then the heating phosphating treatment is carried out.
5. The method for preparing the phosphorus-doped nitrogen-rich porous carbon nano sheet according to claim 1, wherein the temperature rising rate of the phosphating treatment is 2-5 ℃/min;
or, the phosphating treatment time is 3-5 hours;
or, the temperature of the phosphating treatment is 350-450 ℃.
6. A phosphorus doped nitrogen enriched porous carbon nanoplatelet characterized by being obtained by the preparation method of any one of claims 1 to 5.
7. Use of the phosphorus-doped nitrogen-rich porous carbon nanoplatelets of claim 6 in a potassium ion battery.
8. A negative electrode of a potassium ion battery, comprising a current collector and an active ingredient, wherein the active ingredient is the phosphorus-doped nitrogen-rich porous carbon nano-sheet of claim 6.
9. A potassium ion battery, which is characterized by comprising the negative electrode, the counter electrode, the diaphragm and the electrolyte of the potassium ion battery of claim 8.
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