CN115498194A - Nitrogen-doped hollow mesoporous carbon nanosheet, preparation method thereof and application of nanosheet in potassium ion battery - Google Patents
Nitrogen-doped hollow mesoporous carbon nanosheet, preparation method thereof and application of nanosheet in potassium ion battery Download PDFInfo
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- 239000002135 nanosheet Substances 0.000 title claims abstract description 118
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 229910001414 potassium ion Inorganic materials 0.000 title claims abstract description 60
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 75
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 59
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
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- 239000000463 material Substances 0.000 claims abstract description 16
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- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 4
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 14
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- 239000011347 resin Substances 0.000 abstract description 21
- 229920005989 resin Polymers 0.000 abstract description 21
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 19
- DGXAGETVRDOQFP-UHFFFAOYSA-N 2,6-dihydroxybenzaldehyde Chemical compound OC1=CC=CC(O)=C1C=O DGXAGETVRDOQFP-UHFFFAOYSA-N 0.000 abstract description 15
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 229910004298 SiO 2 Inorganic materials 0.000 description 7
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- AAMATCKFMHVIDO-UHFFFAOYSA-N azane;1h-pyrrole Chemical compound N.C=1C=CNC=1 AAMATCKFMHVIDO-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- MGJURKDLIJVDEO-UHFFFAOYSA-N formaldehyde;hydrate Chemical compound O.O=C MGJURKDLIJVDEO-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
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- 238000003780 insertion Methods 0.000 description 2
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- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 208000032953 Device battery issue Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
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- -1 and among them Substances 0.000 description 1
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- 239000010406 cathode material Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
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- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
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- 239000007773 negative electrode material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
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- H01M10/00—Secondary cells; Manufacture thereof
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- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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Abstract
The nitrogen-doped hollow mesoporous carbon nanosheet comprises a carbon shell and wrapped reduced graphene oxide; mesopores vertically communicated with the inner wall and the outer wall are distributed on the carbon shell. The preparation method comprises the following steps: carrying out hydrolysis polycondensation reaction on tetrapropoxysilane in a graphene solution to obtain a silicon dioxide nanosheet template, carrying out resorcinol-formaldehyde resin coating reaction by using resorcinol and formaldehyde as carbon source precursors, ammonia water as an alkaline catalyst and a nitrogen source and tetrapropoxysilane as a pore-forming agent, calcining the product at high temperature, and finally etching to remove the silicon dioxide nanosheets. The nitrogen-doped hollow mesoporous carbon nanosheet provides considerable specific mass capacity, shows excellent rate capability and cycle stability, can be used as an ideal carbon-based current collector material of a potassium ion negative electrode, and is further used for constructing a safe potassium ion battery with high specific mass capacity and long cycle life.
Description
Technical Field
The invention relates to the field of electrode materials of potassium ion batteries, in particular to a nitrogen-doped hollow mesoporous carbon nanosheet, a preparation method thereof and application thereof in a potassium ion battery.
Background
Lithium ion batteries have become a necessity of our lives, however, the demand of people for energy has rapidly increased with the development of scientific technology. The main electrode materials of the lithium ion battery commercialized at present, namely, the mineral resources of lithium and cobalt, are scarcely stored in the earth crust and are extremely unevenly distributed, so that the production cost of the lithium ion battery is greatly increased. While the content of the potassium element in the crust is two orders of magnitude higher than that of the lithium element. And the Stokes radius of potassium ions in the common electrolyte solvent propylene carbonate is
Smaller than lithium ions
This means that potassium ions have better diffusion kinetics than lithium ions, and macroscopically show larger diffusion coefficients and higher diffusion rates. Although the voltage of the potassium ion electrode relative to the standard hydrogen electrode is slightly higher-2.93V than the voltage of the lithium ion electrode relative to the hydrogen standard electrode-3.04V, cyclic voltammetry tests under the electrolyte system show that the potassium metal deposition potential is lower by about 0.1V relative to the lithium metal deposition potential, which means that the potassium ion battery can achieve a higher operating voltage range and also means that the potassium ion battery with a higher energy density can be achieved.
Potassium ions have many advantages over lithium ions in electrolyte systems. At present, many different kinds of materials have been considered as potential potassium ion battery negative electrode materials, and among them, carbon-based materials are considered as one of the ideal potassium ion battery negative electrodes due to their low cost, simple preparation process and excellent mechanical properties. However, the mass-to-capacity ratio of the carbon-based material is not high due to the large ionic radius of the potassium ion and the corresponding intercalation/deintercalation mechanism. And the electrode undergoes a large volume change during battery cycling, resulting in destruction of the electrode material and thus battery failure.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a nitrogen-doped hollow mesoporous carbon nanosheet, a preparation method thereof and application thereof in a potassium ion battery. The method comprises the steps of taking monodisperse silicon dioxide nanosheets as templates, resorcinol-formaldehyde resin as a carbon source, ammonia water as an alkaline catalyst and a nitrogen source, and tetrapropoxysilane as a pore-forming agent, and carrying out surface coating, heat treatment carbonization and hydrofluoric acid etching on the silicon dioxide nanosheets to obtain the product, namely the nitrogen-doped hollow mesoporous carbon nanosheets with large cavities. The carbon nano-sheet has a very large specific surface area, can provide rich potassium ion embedding sites, and thus can obtain higher specific capacity of quality. The mesopores distributed on the carbon nano-sheet shell can not only improve the specific surface area of the carbon nano-sheet, but also buffer the volume change generated when potassium ions are removed/inserted at active sites. The carbon nano sheet still keeps stable structure after multiple cycles of the potassium ion removal/insertion process.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a nitrogen-doped hollow mesoporous carbon nanosheet, wherein the nitrogen-doped hollow mesoporous carbon nanosheet comprises a carbon shell and reduced graphene oxide in a hollow inner cavity of the carbon shell, and the carbon shell is formed by nitrogen-doped mesoporous amorphous carbon.
Further, the specific surface area of the carbon shell is 1300-1450 m 2 /g。
Furthermore, the nitrogen atom doping amount of the carbon shell is 2.5mol% -4 mol%.
Further, the thickness of the carbon shell is 30-60 nm.
Furthermore, the carbon shell is distributed over mesopores vertically communicated with the inner wall and the outer wall, and the pore diameter of the mesopores is intensively distributed at 6-9 nm. As can be seen from observation of a transmission electron microscope, nitrogen is uniformly distributed in the carbon nanosheets, which means that a large number of uniformly distributed active sites can be provided for potassium ion deintercalation, and considerable specific mass capacity is provided.
The invention also provides a preparation method of the nitrogen-doped hollow mesoporous carbon nanosheet, which comprises the following steps:
s1, uniformly dispersing graphene oxide in a reaction system, and then performing hydrolytic polycondensation reaction on tetrapropoxysilane under an alkaline condition to coat the surface of the graphene oxide to obtain a monodisperse silica nanosheet coated with the graphene oxide;
s2, taking the silicon dioxide nanosheet obtained in the S1 as a template, resorcinol and formaldehyde as a carbon source precursor, taking ammonia water remained in the reaction in the step S1 as an alkaline catalyst and a nitrogen source, and taking tetrapropoxysilane remained in the reaction in the step S1 as a pore-forming agent to perform resorcinol-formaldehyde resin coating reaction to obtain a silicon dioxide nanosheet coated with resorcinol-formaldehyde resin on the surface;
and S3, calcining the silicon dioxide nanosheets coated with the resorcinol-formaldehyde resin at high temperature to carbonize the resorcinol-formaldehyde resin contained in the silicon dioxide nanosheets, and etching the high-temperature calcined products to remove the template silicon dioxide nanosheets to obtain the nitrogen-doped hollow mesoporous carbon nanosheets.
Further, in the step S1, the graphene oxide is dispersed by adding the graphene oxide powder into a mixed solution of ethanol, water and ammonia water, and then performing ultrasonic dispersion to obtain a monodisperse graphene oxide suspension; the hydrolysis polycondensation reaction mode is that the tetrapropoxysilane is added into the suspension, and then the mixture is stirred and reacts in a water bath at the temperature of 20-40 ℃ for 5-20 min to obtain the monodisperse silicon dioxide nanosheet suspension.
Further, relative to 1mg of graphene oxide, the dosage of ethanol is 10-30 mL, the dosage of deionized water is 1-2 mL, the dosage of ammonia water is 0.5-1 mL, and the dosage of tetrapropoxysilane is 0.5-1 mL.
Further, in the step S2, the resorcinol-formaldehyde resin coating reaction is performed by sequentially adding resorcinol and formaldehyde into the monodisperse silica nanosheet suspension, performing magnetic stirring reaction for 20-30 h, performing centrifugal cleaning, and drying to obtain the silica nanosheet coated with the resorcinol-formaldehyde resin on the surface.
Further, the amount of resorcinol is 20 to 50mg and the amount of formaldehyde is 0.4 to 0.7mL, relative to the mentioned 1mg of graphene oxide.
Further, in step S3, the high-temperature calcination is performed by grinding the silica nanosheet coated with the resorcinol-formaldehyde resin on the surface (the grinding degree is only required to disperse the agglomerated particles), then heating the ground product to 700-900 ℃ at a rate of 1-5 ℃/h under the protection of inert gas or nitrogen, reacting for 2-6 hours while maintaining the temperature, and cooling to room temperature after the reaction is finished, so as to obtain a high-temperature calcined product.
Further, in step S3, the etching manner is to dissolve the high-temperature calcined product in a hydrofluoric acid solution with a concentration of 5wt% to 15wt%, magnetically stir for reaction for 8 to 15 hours, then perform solid-liquid separation, centrifugally clean the obtained solid (for example, through three times of centrifugal cleaning with deionized water/ethanol), and dry to obtain the nitrogen-doped hollow mesoporous carbon nanosheet.
The invention also provides application of the nitrogen-doped hollow mesoporous carbon nanosheet as a carbon nanosheet current collector material of a potassium ion negative electrode.
In addition, the invention also provides a potassium ion battery which comprises a potassium ion negative electrode, wherein the potassium ion negative electrode takes the nitrogen-doped hollow mesoporous carbon nanosheet as a current collector material.
The nitrogen-doped hollow mesoporous carbon nanosheet prepared by the method provided by the invention can provide abundant potassium ion active sites, limit the volume change in the potassium ion de-intercalation/de-intercalation process, and can be used as an ideal carbon-based current collector material of a potassium ion negative electrode, so that the nitrogen-doped hollow mesoporous carbon nanosheet can be used for constructing a safe, high-quality and long-life potassium ion battery. In addition, the nitrogen-doped hollow mesoporous carbon nanosheet provided by the invention is simple in preparation process and low in material cost, and is expected to become a potassium ion battery negative electrode current collector material with excellent electrochemical performance and commercial potential.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
(1) The nitrogen-doped hollow mesoporous carbon nanosheet provided by the invention has a mesoporous hollow structure and a high specific surface area (1300-1450 m) 2 Per g) largePore volume (1.8-2.3 cm) 3 The characteristics of/g), can effectively promote the transmission of ions/electrons, reduce the effective current density of the electrode;
(2) The nitrogen atom doping amount of the nitrogen-doped hollow mesoporous carbon nanosheet is 2.5-4 mol%, wherein the nitrogen atoms exist in the forms of pyrrole nitrogen (prN) and pyridine nitrogen (pdN) respectively, a small amount of O atoms exist at the same time, and the existence of the N atoms and the O atoms can obviously improve the affinity of amorphous carbon and potassium ions and promote the de-intercalation/intercalation behavior of the potassium ions in the amorphous carbon, so that higher mass-to-volume capacity and stable coulombic efficiency are obtained;
(3) The nitrogen-doped hollow mesoporous carbon nanosheet provided by the invention has a larger hollow inner cavity structure, and simultaneously mesoporous channels which are vertically communicated with the inner wall and the outer wall and have the diameter of 6-9 nm are distributed on the carbon shell, so that the specific surface area of the material is greatly increased, the wettability of electrolyte on an electrode material is improved, the migration rate of potassium ions in the electrolyte can be accelerated through the capillary action, and the diffusion coefficient of the potassium ions is increased;
(4) The thickness of the carbon shell of the nitrogen-doped hollow mesoporous carbon nanosheet is 30-60 nm, and the volume change in the potassium ion de-intercalation/de-intercalation process can be effectively buffered due to the excellent mechanical property of amorphous carbon.
Drawings
FIG. 1 is a flow chart of the present invention for preparing nitrogen-doped hollow mesoporous carbon nanosheets;
FIG. 2 is a morphology characterization diagram of the nitrogen-doped hollow mesoporous carbon nanosheet obtained in example 1, wherein a is an SEM image, b is a TEM image, and c is a high-resolution TEM image;
FIG. 3 is a dark field photograph and an element distribution diagram of the nitrogen-doped hollow mesoporous carbon nanosheet obtained in example 1, wherein a is an HADDF photograph, b is a C element distribution diagram, C is an O element distribution diagram, and d is an N element distribution diagram;
FIG. 4 is an XPS spectrum of the nitrogen-doped hollow mesoporous carbon nanosheet obtained in example 1, wherein a is a full spectrum and b is an N1s fine spectrum;
fig. 5 is a nitrogen adsorption/desorption curve (a) and a pore diameter distribution diagram (b) of the nitrogen-doped hollow mesoporous carbon nanosheet obtained in example 1 and a nitrogen adsorption/desorption curve (c) and a pore diameter distribution diagram (d) of the nitrogen-doped hollow microporous carbon nanosheet obtained in comparative example 1;
FIG. 6 is a cyclic voltammogram measured at different scanning rates using the nitrogen-doped hollow mesoporous carbon nanosheet obtained in example 1 as the potassium ion cathode and the pseudocapacitance contribution ratio calculated therefrom;
FIG. 7 is a constant current intermittent titration technical chromatogram obtained by using the nitrogen-doped hollow mesoporous carbon nanosheet obtained in example 1 and the nitrogen-doped hollow microporous carbon nanosheet obtained in comparative example 1 as potassium ion cathodes respectively;
FIG. 8 is a morphology characterization graph of the nitrogen-doped hollow microporous carbon nanosheet obtained in comparative example 1, wherein a is an SEM image, b is a TEM image, and c is a high-resolution TEM image;
FIG. 9 is a graph showing the electrochemical performance of the nitrogen-doped hollow mesoporous carbon nanosheets obtained in example 1 and the nitrogen-doped hollow microporous carbon nanosheets obtained in comparative example 1 as potassium ion negative electrodes, wherein a is Ag at a current density of 0.1 -1 The specific mass capacity and coulombic efficiency of the lower cycle, b is the rate capability of the cycle under different current densities, and c is the current density 2Ag -1 The specific mass capacity and coulombic efficiency of the lower cycle.
Detailed Description
In order to make the technical problems, technical solutions and beneficial effects to be solved by the present invention clearer and clearer, the present invention is further described in detail below with reference to the accompanying drawings and embodiments.
Example 1
The embodiment is used to illustrate a preparation method of a nitrogen-doped hollow mesoporous carbon nanosheet provided by the invention, and is specifically shown in fig. 1:
s1, uniformly dispersing 10mg of graphene oxide powder into a mixed solution of 70mL of ethanol, 10mL of deionized water and 3mL of ammonia water (the mass fraction is 25%, the same applies below), then adding 3.5mL of tetrapropoxysilane, and carrying out magnetic stirring reaction in a water bath at 30 ℃ for 15min to obtain the graphene oxide-coated monodisperse silicon dioxide nanosheets.
S2, adding 0.4g of resorcinol and 0.56mL of formaldehyde solution (the mass fraction is 36 percent, the same is applied below) into the solution, and carrying out magnetic stirring reaction in a water bath at 30 ℃ for 25 percenth, performing centrifugal separation, performing three-time centrifugal cleaning on the obtained solid through deionized water/ethanol, collecting a sample, and drying in an oven at 60 ℃ for 12h to obtain the silicon dioxide nanosheet SiO with the surface coated with the resorcinol-formaldehyde resin 2 &resin@SiO 2 。
S3, coating resorcinol-formaldehyde resin on the surface of the silicon dioxide nanosheet SiO 2 &resin@SiO 2 Grinding, placing in an alumina crucible, placing in a tube furnace, and adding N 2 Heating to 800 ℃ at a heating rate of 2 ℃/h as a gas source, keeping the temperature for 4h, cooling to room temperature after the reaction is finished to obtain a high-temperature calcined product, collecting the high-temperature calcined product, dispersing the high-temperature calcined product into a hydrofluoric acid (HF) aqueous solution with the concentration of 15wt%, magnetically stirring to react for 12h, performing centrifugal separation, cleaning the obtained solid by deionized water/ethanol, and finally drying to obtain the nitrogen-doped hollow mesoporous carbon nanosheet, which is marked as N-HMCNS.
The morphology characterization result of the nitrogen-doped hollow mesoporous carbon nanosheet N-HMCNS is shown in FIG. 2, wherein a is an SEM image, b is a TEM image, and c is a high-resolution TEM image. The results of a to c in fig. 2 show that the nitrogen-doped hollow mesoporous carbon nanosheet N-HMCNS comprises a carbon shell and a hollow inner cavity, the thickness of the carbon shell is 50nm, mesoporous channels which are vertically communicated with the inner wall and the outer wall and densely distributed are distributed on the carbon shell from scanning and transmission photos, and the diameters of the mesoporous channels are 6 to 9nm.
The HADDF photograph and the element distribution of the nitrogen-doped hollow mesoporous carbon nanosheet N-HMCNS are shown in fig. 3, wherein a is the HADDF photograph, b is a C element distribution diagram, C is an O element distribution diagram, and d is an N element distribution diagram. The results of fig. 3 show that the C, N, O elements are uniformly distributed in the N-HMCNS of the nitrogen-doped hollow mesoporous carbon nanosheets.
The XPS spectrum of the N-HMCNS of the nitrogen-doped hollow mesoporous carbon nanosheet is shown in FIG. 4, wherein a is the full spectrum of a sample, b is the N1s fine scanning spectrum, and the fitting result shows the measurement peaks: pyridine nitrogen (pnN, 397.6 eV) and pyrrole nitrogen (prN, 400.1 eV). As can be seen from a and b in fig. 4, the carbon shell of the nitrogen-doped hollow mesoporous carbon nanosheet N-HMCNS is formed of nitrogen-doped mesoporous amorphous carbon, the doping amount of nitrogen atoms is 3.2mol%, and pyrrole nitrogen is the main component.
The nitrogen adsorption and desorption curves and the pore size distribution of the nitrogen-doped hollow mesoporous carbon nanosheet N-HMCNS are shown as a and b in figure 5, wherein a is the nitrogen adsorption and desorption curve, and b is the pore size distribution diagram. From fig. 5-a, it can be seen that the nitrogen adsorption and desorption curves of the nitrogen-doped hollow mesoporous carbon nanosheet N-HMCNS exhibit typical type IV curve characteristics, indicating that capillary condensation occurs during adsorption. From fig. 5-b, it can be seen that the pore size of the nitrogen-doped hollow mesoporous carbon nanosheet N-HMCNS is primarily distributed within the range of 6-9 nm. According to calculation, the specific surface area of the N-HMCNS of the nitrogen-doped hollow mesoporous carbon nanosheet is 1433.15m 2 Per g, pore volume of 2.03cm 3 And/g, proving that the material has extremely high specific surface area and abundant pore structure.
The cyclic voltammetry test result of the half-cell assembled by using the nitrogen-doped hollow mesoporous carbon nanosheet N-HMCNS as the potassium ion cathode is shown in FIG. 6, wherein a is a voltage-current curve at different scanning rates, and b is a pseudocapacitance contribution diagram at different scanning rates. As can be seen from FIG. 6-a, the N-HMCNS of the nitrogen-doped hollow mesoporous carbon nanosheet has good cycling stability. As can be seen from FIG. 6-a, the N-HMCNS of the N-doped hollow mesoporous carbon nanosheet has a dominant position of pseudocapacitance contribution in the circulation process, and the N-HMCNS of the N-doped hollow mesoporous carbon nanosheet has a very large specific surface area which can provide abundant potassium ion adsorption sites so as to obtain a large specific capacity.
Fig. 7 shows the result of a constant current intermittent titration test of a half-cell assembled by using the nitrogen-doped hollow mesoporous carbon nanosheet N-HMCNS as a potassium ion negative electrode, wherein a is a specific capacity-voltage curve during charge/discharge, and b is a voltage-diffusion coefficient curve during charge/discharge calculated based on the curve. As can be seen from a and b of fig. 7, the N-HMCNS of the nitrogen-doped hollow mesoporous carbon nanosheet has a large diffusion coefficient during charge/discharge, i.e., exhibits a high diffusion rate of potassium ions.
Example 2
The embodiment is used to illustrate a preparation method of a nitrogen-doped hollow mesoporous carbon nanosheet provided by the invention, and is specifically shown in fig. 1:
s1, uniformly dispersing 10mg of graphene oxide powder into a mixed solution of 70mL of ethanol, 10mL of deionized water and 2.5mL of ammonia water (the mass fraction is 25%, the same below), then adding 3mL of tetrapropoxysilane, and carrying out magnetic stirring reaction in a water bath at 30 ℃ for 15min to obtain the monodisperse silicon dioxide nanosheet coated with graphene oxide.
S2, adding 0.3g of resorcinol and 0.42mL of formaldehyde water solution (the mass fraction is 36%, the same below) into the solution, reacting the mixture with magnetic stirring in a water bath at 30 ℃ for 20 hours, performing centrifugal separation, centrifugally cleaning the obtained solid for three times by using deionized water/ethanol, collecting a sample, and drying the sample in a drying oven at 60 ℃ for 12 hours to obtain a silicon dioxide nanosheet SiO coated with resorcinol-formaldehyde resin on the surface 2 &resin@SiO 2 。
S3, coating the surface with silicon dioxide nano-sheets SiO of resorcinol-formaldehyde resin 2 &resin@SiO 2 Grinding, placing in an alumina crucible, placing in a tube furnace, and adding N 2 Heating to 900 ℃ at a heating rate of 2 ℃/h as a gas source, preserving heat for 4h, cooling to room temperature after the reaction is finished to obtain a high-temperature calcined product, collecting the high-temperature calcined product, dispersing the high-temperature calcined product in a hydrofluoric acid (HF) aqueous solution with the concentration of 15wt%, magnetically stirring for reaction for 12h, performing centrifugal separation, cleaning the obtained solid by deionized water/ethanol, and finally drying to obtain the nitrogen-doped hollow mesoporous carbon nanosheet, which is recorded as N-HMCNS.
The nitrogen-doped hollow mesoporous carbon nanosheet N-HMCNS comprises a carbon shell and a hollow inner cavity, wherein the thickness of the carbon shell is 35nm, mesoporous pore channels which are vertically communicated with the inner wall and the outer wall and are densely distributed are distributed on the carbon shell, the diameter of each pore channel is 6-9 nm, the doping amount of nitrogen atoms is 2.8mol%, and the specific surface area is 1232.42m 2 G, pore volume of 1.70cm 3 /g。
Example 3
The embodiment is used to illustrate a preparation method of a nitrogen-doped hollow mesoporous carbon nanosheet provided by the invention, and is specifically shown in fig. 1:
s1, uniformly dispersing 15mg of graphene oxide powder into a mixed solution of 70mL of ethanol, 10mL of deionized water and 4mL of ammonia water (the mass fraction is 25%, the same below), then adding 5mL of tetrapropoxysilane, and magnetically stirring and reacting in a water bath at 40 ℃ for 15min to obtain the monodisperse silicon dioxide nanosheet coated with graphene oxide.
S2, adding 0.5g of resorcinol and 0.7mL of formaldehyde water solution (the mass fraction is 36%, the same below) into the solution, magnetically stirring the solution and a water bath at 40 ℃ for reaction for 30 hours, carrying out centrifugal separation, then carrying out centrifugal washing on the obtained solid for three times through deionized water/ethanol, collecting a sample, and drying the sample in a 60 ℃ oven for 12 hours to obtain a silicon dioxide nanosheet SiO with the surface coated with resorcinol-formaldehyde resin 2 &resin@SiO 2 。
S3, coating the surface with silicon dioxide nano-sheets SiO of resorcinol-formaldehyde resin 2 &resin@SiO 2 Grinding, placing in an alumina crucible, placing in a tube furnace, and adding N 2 Heating to 900 ℃ at a heating rate of 2 ℃/h as a gas source, preserving heat for 2h, cooling to room temperature after the reaction is finished to obtain a high-temperature calcined product, collecting the high-temperature calcined product, dispersing the high-temperature calcined product in a hydrofluoric acid (HF) aqueous solution with the concentration of 15wt%, magnetically stirring for reaction for 12h, performing centrifugal separation, cleaning the obtained solid by deionized water/ethanol, and finally drying to obtain the nitrogen-doped hollow mesoporous carbon nanosheet, which is recorded as N-HMCNS.
The nitrogen-doped hollow mesoporous carbon nanosheet N-HMCNS comprises a carbon shell and a hollow inner cavity, wherein the thickness of the carbon shell is 40nm, mesoporous pore channels which are vertically communicated with the inner wall and the outer wall and are densely distributed are distributed on the carbon shell, the diameter of each pore channel is 6-9 nm, the doping amount of nitrogen atoms is 3.3mol%, and the specific surface area is 1432.42m 2 Per g, pore volume 1.92cm 3 /g。
Comparative example 1
Nitrogen-doped hollow microporous carbon nanosheets were prepared as in example 1, except that tetrapropoxysilane was replaced with tetraethoxysilane (same amount of tetraethoxysilane as in example 1) in steps S1 and S2, and the rest was the same as in example 1, to give nitrogen-doped hollow microporous carbon nanosheets, denoted as N-HPCNS.
The morphology characterization result of the nitrogen-doped hollow microporous carbon nanosheet N-HPCNS is shown in FIG. 8, wherein a is an SEM image, b is a TEM image, and c is a high-resolution TEM image. The results of a-c in fig. 8 show that the nitrogen-doped hollow microporous carbon nanosheet N-HPCNS comprises a carbon shell and a hollow inner cavity, the thickness of the carbon shell being 50nm. However, the carbon shell of the N-HPCNS of the N-doped hollow microporous carbon nanosheet is loose and has irregular pore channels, and the diameter of the pore channels is less than 3nm, so that the N-HMCNS of the N-doped hollow mesoporous carbon nanosheet is different from the N-HMCNS of the N-doped hollow mesoporous carbon nanosheet which is vertically communicated with the inner wall and the outer wall and has densely distributed mesoporous pore channels.
The nitrogen adsorption and desorption curves and the pore size distribution of the nitrogen-doped hollow microporous carbon nanosheet N-HPCNS are shown as c and d in figure 5, wherein c is the nitrogen adsorption and desorption curve, and d is the pore size distribution diagram. As can be seen from FIG. 5, the specific surface area of the N-HPCNS of the nitrogen-doped hollow microporous carbon nanosheet is 1046.20m 2 Per g, pore volume 1.22cm 3 The pore diameter is mainly distributed below 3 nm.
Test example
The nitrogen-doped hollow mesoporous carbon nanosheet N-HMCNS obtained in example 1 and the nitrogen-doped hollow microporous carbon nanosheet N-HPCNS obtained in comparative example 1 were used as potassium ion negative electrode assembly half-cells respectively to test the potassium ion diffusion coefficient and at 0.1Ag -1 、2Ag -1 Long cycle performance at different current densities and rate performance at different current densities. The test results are shown in FIGS. 7 and 9, in which FIG. 7-a is a voltage-specific capacity curve obtained by the constant current intermittent titration technique, and FIG. 7-b is a calculated diffusion coefficient of potassium ion according to the results. FIG. 9-a shows Ag at a current density of 0.1 -1 The specific mass capacity and the coulombic efficiency of the lower cycle, 9-b is the multiplying power performance of the lower cycle under different current densities, and 9-c is the current density of 2Ag -1 Specific capacity of lower cycle and coulombic efficiency. According to test results, the N-HMCNS of the nitrogen-doped hollow mesoporous carbon nanosheet has better electrochemical performance than the N-HPCNS of the nitrogen-doped hollow microporous carbon nanosheet under different test conditions. Specifically, the half-cell assembled by using the nitrogen-doped hollow mesoporous carbon nanosheet N-HMCNS as the potassium ion negative electrode has a larger potassium ion diffusion coefficient in the charging or discharging process compared with the half-cell assembled by using the nitrogen-doped hollow microporous carbon nanosheet N-HPCNS as the potassium ion negative electrode. And the half cells assembled by using the nitrogen-doped hollow mesoporous carbon nanosheet N-HMCNS as the potassium ion negative electrode respectively have the current density of 0.1Ag -1 Lower cycle 120 cycles and currentDensity 2Ag -1 After 1000 cycles of lower circulation, the batteries respectively maintain 310mAh g -1 And 145mAh g -1 The specific capacity of the mass and the coulombic efficiency are stabilized at about 100 percent. In contrast, the nitrogen-doped hollow microporous carbon nanosheet N-HPCNS only retained 203mAh g after cycling as a potassium ion negative assembled half-cell -1 And 116mAh g -1 The mass to capacity of (d). After the nitrogen-doped hollow mesoporous carbon nanosheets are sequentially cycled under different current densities, a half cell assembled by taking the N-HMCNS as a potassium ion cathode is 4Ag -1 Can reach 112mAh g under the current density -1 After a second time at 0.05Ag -1 365mAh g can still be obtained when the current is circulated under the current density -1 The mass to capacity of (d). In contrast, the nitrogen-doped hollow microporous carbon nanosheet N-HPCNS is taken as a potassium ion cathode assembled half-cell, and only 56mAh g is obtained after the half-cell is sequentially circulated under different current densities -1 And 248mAh g -1 The mass to capacity ratio of (2). The results show that the N-HMCNS is an ideal potassium ion battery cathode material.
According to various material characteristics and electrochemical test results, the unique mesoporous pore channel design which is vertically communicated with the inner wall and the outer wall and is possessed by the nitrogen-doped hollow mesoporous carbon nanosheet N-HMCNS obtained according to the embodiment is shown to not only greatly increase the specific surface area of the material, but also provide rich potassium ion de/clamping points under the combined action of the material and nitrogen doping, and the capillary action of the pore channel enhances the wettability of the electrolyte, so that the positive and large advantages of the specific surface of the material can be fully exerted, the diffusion rate of potassium ions in the electrolyte is improved, and finally, the large mass specific capacity is obtained. Meanwhile, due to the excellent mechanical properties of the carbon-based material and the larger pore diameter of the mesopores, the volume expansion of the material during the removal/insertion of potassium ions can be well buffered, so that the N-HMCNS of the nitrogen-doped hollow mesoporous carbon nanosheet has excellent cycling stability, and the failure of the battery caused by the damage of the active material can be avoided.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made in the above embodiments by those of ordinary skill in the art without departing from the principle and spirit of the present invention.
Claims (10)
1. A nitrogen-doped hollow mesoporous carbon nanosheet is characterized in that: the nitrogen-doped hollow mesoporous carbon nanosheet comprises a carbon shell, wherein the carbon shell is provided with a hollow inner cavity, and reduced graphene oxide is wrapped in the hollow inner cavity; the carbon shell is made of porous amorphous carbon doped with nitrogen, and the doping amount of nitrogen atoms is 2.5-4 mol%; mesopores vertically communicated with the inner wall and the outer wall are distributed on the carbon shell, and the aperture of the mesopores is 6-9 nm.
2. The nitrogen-doped hollow mesoporous carbon nanosheet of claim 1, wherein: the specific surface area of the carbon shell is 1300-1450 m 2 The thickness of the carbon shell is 30-60 nm.
3. The method for preparing nitrogen-doped hollow mesoporous carbon nanosheets as claimed in any one of claims 1 to 2, comprising the steps of:
1) Dispersing graphene oxide in a mixed solution of ethanol, deionized water and ammonia water, then adding tetrapropoxysilane, and stirring for reaction under the water bath condition;
2) Adding resorcinol and formaldehyde aqueous solution into the solution obtained in the step 1), stirring and reacting under the condition of water bath, and then centrifuging, washing and drying;
3) Calcining the product obtained in the step 2), then dispersing the calcined product into hydrofluoric acid aqueous solution, stirring for reaction, and finally centrifuging, washing and drying.
4. The method of claim 3, wherein: in the step 1), relative to 1mg of graphene oxide, the dosage of ethanol is 10-30 mL, the dosage of deionized water is 1-2 mL, the dosage of ammonia water is 0.2-0.8 mL, and the dosage of tetrapropoxysilane is 0.5-1 mL.
5. The method of claim 3, wherein: in the step 2), the dosage of the resorcinol and the aqueous solution of formaldehyde is 20-50 mg and 0.4-0.7 mL respectively relative to 1mg of graphene oxide.
6. The method of claim 3, wherein: in the step 1) and the step 2), the water bath temperature is 20-40 ℃; the stirring reaction time in the step 1) is 5-20 min, and the stirring reaction time in the step 2) is 20-30 h.
7. The method of claim 3, wherein: in the step 3), the calcination adopts nitrogen or inert atmosphere, the temperature is raised to 700-900 ℃ at the speed of 1-5 ℃/h, and the reaction is carried out for 2-6 h under the condition of heat preservation.
8. The method of claim 3, wherein: in the step 3), the concentration of the hydrofluoric acid aqueous solution is 5wt% -15 wt%, and the stirring reaction time is 8-15 h.
9. The use of the nitrogen-doped hollow mesoporous carbon nanosheets of claims 1-2 or of the nitrogen-doped hollow mesoporous carbon nanosheets prepared by the preparation method of any one of claims 3-8, characterized in that: the nitrogen-doped hollow mesoporous carbon nanosheet is used as a carbon nanosheet current collector material of a potassium ion negative electrode.
10. A potassium ion battery, the potassium ion battery includes potassium ion negative pole, its characterized in that: the potassium ion negative electrode takes the nitrogen-doped hollow mesoporous carbon nanosheet disclosed in claims 1-2 or the nitrogen-doped hollow mesoporous carbon nanosheet prepared by the preparation method disclosed in any one of claims 3-8 as a current collector material.
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