CN115784204B - Ultra-high edge nitrogen doped carbon nano sheet and preparation method and application thereof - Google Patents
Ultra-high edge nitrogen doped carbon nano sheet and preparation method and application thereof Download PDFInfo
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 186
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 127
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 93
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 69
- 239000002135 nanosheet Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 49
- 229910001414 potassium ion Inorganic materials 0.000 claims abstract description 21
- 239000007864 aqueous solution Substances 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 19
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 229920000642 polymer Polymers 0.000 claims abstract description 13
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- 238000004108 freeze drying Methods 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 7
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 5
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- 238000010000 carbonizing Methods 0.000 claims abstract description 3
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- 238000003763 carbonization Methods 0.000 claims description 12
- 229920000877 Melamine resin Polymers 0.000 claims description 11
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 11
- 125000003277 amino group Chemical group 0.000 claims description 10
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- 238000000034 method Methods 0.000 claims description 9
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- 239000004584 polyacrylic acid Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052700 potassium Inorganic materials 0.000 abstract description 12
- 239000011591 potassium Substances 0.000 abstract description 12
- 238000003860 storage Methods 0.000 abstract description 10
- 150000003384 small molecules Chemical class 0.000 abstract description 4
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- 239000012298 atmosphere Substances 0.000 description 8
- LBSPZZSGTIBOFG-UHFFFAOYSA-N bis[2-(4,5-dihydro-1h-imidazol-2-yl)propan-2-yl]diazene;dihydrochloride Chemical compound Cl.Cl.N=1CCNC=1C(C)(C)N=NC(C)(C)C1=NCCN1 LBSPZZSGTIBOFG-UHFFFAOYSA-N 0.000 description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
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- 238000000926 separation method Methods 0.000 description 8
- 239000003575 carbonaceous material Substances 0.000 description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
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- 239000010405 anode material Substances 0.000 description 3
- 239000007833 carbon precursor Substances 0.000 description 3
- 238000009831 deintercalation Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- AAMATCKFMHVIDO-UHFFFAOYSA-N azane;1h-pyrrole Chemical compound N.C=1C=CNC=1 AAMATCKFMHVIDO-UHFFFAOYSA-N 0.000 description 2
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 description 2
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- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- XZRMXDPWEPRYMF-UHFFFAOYSA-N (4-ethenylphenoxy)boronic acid Chemical compound OB(O)OC1=CC=C(C=C)C=C1 XZRMXDPWEPRYMF-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229920001410 Microfiber Polymers 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
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- 230000033228 biological regulation Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
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- 239000011229 interlayer Substances 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
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- 239000003658 microfiber Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- XFTALRAZSCGSKN-UHFFFAOYSA-M sodium;4-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 XFTALRAZSCGSKN-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
An ultra-high edge nitrogen doped carbon nano-sheet, a preparation method and application thereof, wherein the preparation method comprises the following steps: grafting a reactive polymer containing an acid group on the surface of graphene oxide to prepare a graphene oxide-polymer molecular brush; adding small nitrogen-rich molecules containing amino into an aqueous solution of graphene oxide-polymer molecules, stirring, performing hydrothermal reaction and freeze-drying to obtain a self-assembled compound; carbonizing the self-assembled composite in inert gas to obtain the ultra-high edge nitrogen doped carbon nano sheet. According to the invention, the carbon nano-sheet can be assembled by changing the types and the proportions of reactive polymers and small molecules, the ultrahigh edge nitrogen content in the prepared carbon nano-sheet provides developed potassium storage active sites for a carbon skeleton, the two-dimensional nano-sheet morphology and the high conductivity graphene skeleton provided by graphene oxide remarkably improve the active site utilization rate and the ion transmission capacity, and the carbon nano-sheet shows excellent multiplying power performance and cycle stability when being used as a negative electrode of a potassium ion battery.
Description
Technical Field
The invention relates to the field of nano carbon materials and potassium ion batteries, in particular to an ultra-high edge nitrogen doped carbon nano sheet and a preparation method and application thereof.
Background
The lithium ion battery has the advantages of high energy density, long cycle life, environmental friendliness and the like, and has dominant role in the field of rechargeable batteries. However, lithium resources are scarce and unevenly distributed on earth, while their increasing cost greatly limits their further use in the increasingly large-scale energy storage industry. On the other hand, the potassium resources are widely distributed in the crust and have low cost, and the energy storage mechanism of the potassium ion battery is similar to that of the lithium ion battery, so that the potassium ion battery is hopeful to become a low-cost substitute of the lithium ion battery. However, the ionic radius of potassium ions is large, the intercalation/deintercalation kinetics process in the traditional lithium ion battery cathode material (such as graphite and the like) is relatively difficult, and the large volume expansion of the electrode material in the charge-discharge cycle process is inevitably brought, so that the performance is unsatisfactory, and further the further application of the potassium ion battery is limited.
Development of a novel high-performance anode material is one of keys for promoting development of potassium ion batteries. The carbon material has the advantages of low cost, high conductivity, stable physicochemical property and the like, and is one of ideal anode materials. However, commercial graphite has smaller graphite layer spacing, is unfavorable for potassium ion intercalation/deintercalation, and has unsatisfactory potassium storage capacity and cycle stability. In recent years, heteroatom doping has proven to be one of the strategies for effectively improving the potassium storage performance of carbon materials. The introduction of hetero atoms such as nitrogen, oxygen, phosphorus and the like into the hard carbon skeleton can not only enlarge the interlayer spacing of graphite microcrystals, be beneficial to the intercalation/deintercalation of potassium ions, but also provide defect sites rich in electronegativity for the adsorption/desorption of potassium ions on the surface of the material. Theory and experiment prove that the electrochemical activity of the material can be improved by doping edge nitrogen (pyridine nitrogen and pyrrole nitrogen) in the carbon skeleton, so that the capacity and stability of the anode material are obviously improved.
However, most of the nitrogen-doped carbon materials reported at present have low nitrogen doping content and unreasonable edge nitrogen proportion, and meanwhile, the nano morphology is amorphous, which is unfavorable for the full exposure of active sites. In addition, nitrogen-rich doped carbon materials often need to be prepared at lower heat treatment conditions, which inevitably results in undesirable conductivity of the material.
Therefore, the preparation of the carbon material with high edge nitrogen content and high conductivity and fully exposed active sites can be expected to improve the potassium storage capacity and the cycling stability, thereby promoting the development of the field of potassium ion batteries.
Disclosure of Invention
Based on the above, the invention provides an ultra-high edge nitrogen doped carbon nano sheet, and a preparation method and application thereof, so as to solve the technical problems of low nitrogen doping content, unreasonable edge nitrogen proportion, amorphous nano morphology and the like in the nitrogen doped carbon material in the prior art.
In order to achieve the above purpose, the invention provides a preparation method of an ultra-high edge nitrogen doped carbon nano sheet, which comprises the following steps:
1) Grafting a reactive polymer containing an acid group on the surface of graphene oxide to prepare a graphene oxide-polymer molecular brush;
2) Adding small nitrogen-rich molecules containing amino into the aqueous solution of graphene oxide-polymer molecules prepared in the step 1), stirring, performing hydrothermal reaction and freeze-drying to obtain a self-assembled compound;
3) Carbonizing the self-assembled compound prepared in the step 2) in inert gas to obtain the ultra-high edge nitrogen doped carbon nano-sheet.
As a further preferable technical scheme of the invention, in the step 1), the reactive polymer is one or more of polyacrylic acid, poly-p-styrenesulfonic acid and poly-p-styreneboric acid; in the step 2), the nitrogen-rich micromolecule is one or more of melamine, urea, thiourea, cyanamide and dicyandiamide.
As a further preferable embodiment of the present invention, in step 1), the proportion of the reactive polymer in the graphene oxide-polymer molecular brush is 30wt% or more.
In the step 2), the reactive polymer and the nitrogen-rich small molecule are self-assembled and compounded according to the molar ratio of the acid group in the reactive polymer to the amino group in the nitrogen-rich small molecule of 1:1-10.
As a further preferable technical scheme of the invention, the hydrothermal reaction temperature in the step 2) is 100-120 ℃ and the reaction time is 12-36 h.
As a further preferable technical scheme of the invention, the carbonization reaction temperature in the step 3) is 550-900 ℃ and the carbonization time is 1-4 h.
As a further preferable technical scheme of the invention, the inert gas in the step 3) is one or more of nitrogen, argon or helium, the gas flow rate is 100-300 mL min < -1 >, and the temperature rising rate is 2-5 ℃ min -1 。
According to another aspect of the invention, the invention also provides the ultra-high edge nitrogen doped carbon nano-sheet prepared by the preparation method.
According to another aspect of the invention, the invention further provides an application of the ultra-high edge nitrogen doped carbon nano-sheet in a potassium ion battery.
The ultra-high edge nitrogen doped carbon nano sheet and the preparation method and the application thereof can achieve the following beneficial effects by adopting the technical scheme:
1) The ultra-high edge nitrogen doped carbon nano sheet prepared by the method has an ultra-high nitrogen doping proportion and a high edge nitrogen proportion, wherein the nitrogen doping proportion is up to 20.6at%, and the edge nitrogen doping proportion is up to 16.2at%;
2) The preparation method has good universality, can be used for assembling by changing the types and the proportion of reactive macromolecules and micromolecules, can obtain carbon nano-sheets with different heteroatom doping types and contents according to the requirements, and is convenient to regulate and control;
3) The materials used in the preparation method can be purchased commercially, and the method is simple and convenient to operate, low in production cost and convenient for large-scale industrial production;
4) The ultra-high edge nitrogen doped carbon nano-sheet prepared by the invention has remarkable structural advantages in the application aspect of potassium ion batteries: firstly, the ultrahigh edge nitrogen content provides rich potassium storage active sites for the material, so that the potassium storage capacity is effectively improved; secondly, the two-dimensional nano sheet shape provides a shorter distance for ion diffusion, and is also beneficial to full exposure of active sites, so that the utilization rate of the active sites is improved; finally, the graphene substrate not only provides a two-dimensional nano sheet template, but also provides a high-conductivity framework, so that the charge transmission capacity and the electrode conductivity are improved; the structural advantages mentioned above synergistically improve the kinetics of the potassium storage reaction of the electrode material, and are beneficial to improving the capacity and the cycling stability of the potassium ion battery.
Drawings
The invention will be described in further detail with reference to the drawings and the detailed description.
FIG. 1 is a scanning electron microscope photograph of an ultra-high edge nitrogen-doped carbon nano-sheet I prepared in example 1 of the present invention.
FIG. 2 is a scanning electron microscope photograph of an ultra-high edge nitrogen-doped carbon nano-sheet II prepared in example 2 of the present invention.
FIG. 3 is a scanning electron microscope photograph of an ultra-high edge nitrogen-doped carbon nano-sheet III prepared in example 3 of the present invention.
FIG. 4 is a scanning electron microscope photograph of an ultra-high edge nitrogen-doped carbon nano-sheet four prepared in example 4 of the present invention.
FIG. 5 is a scanning electron microscope photograph of an ultra-high edge nitrogen-doped carbon nano-sheet five prepared in example 5 of the present invention.
FIG. 6 is a graph of N1s fine XPS spectrum and a fitted curve of the ultra-high edge nitrogen doped carbon nanoplatelets one prepared in example 1 of the present invention.
FIG. 7 is a graph of N1s fine XPS spectrum and a fitted curve of a second ultra-high edge nitrogen-doped carbon nano-sheet prepared in example 2 of the present invention.
FIG. 8 is a graph of N1s fine XPS spectrum and a fitted curve of an ultra-high edge nitrogen doped carbon nanoplate III prepared in example 3 of the present invention.
FIG. 9 is a graph of N1s fine XPS spectrum and a fitted curve of an ultra-high edge nitrogen doped carbon nanoplate four prepared in example 4 of the present invention.
FIG. 10 is a graph of N1s fine XPS spectrum and a fitted curve of an ultra-high edge nitrogen doped carbon nanoplatelet five prepared in example 5 of the present invention.
FIG. 11 is a graph showing the rate performance of the ultra-high edge nitrogen-doped carbon nanoplatelets prepared in examples 1 to 5 of the present invention when used as a negative electrode material for potassium ion batteries, and the current density is 0.05 to 10Ag -1 。
FIG. 12 shows the use of ultra-high edge nitrogen doped carbon nanoplatelets prepared in example 1 of the present invention as negative electrode for potassium ion batteriesCycle performance graph at polar material with current density of 10Ag -1 。
FIG. 13 is an electrochemical impedance diagram of the ultra-high edge nitrogen doped carbon nanoplatelets prepared in example 1 of the present invention as a negative electrode material for potassium ion batteries.
The achievement of the objects, functional features and advantages of the present invention will be further described with reference to the accompanying drawings, in conjunction with the embodiments.
Detailed Description
The following describes specific embodiments of the present invention in detail with reference to the drawings. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
Unless defined otherwise, technical terms used in the following examples have the same meaning as commonly understood by one of ordinary skill in the art to which the inventive concepts pertain. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
The principle of the invention is that: according to the preparation method, the self-assembled compound is prepared by utilizing the liquid phase assembly of the reactive polymer grafted on the graphene oxide surface and the nitrogen-rich micromolecules, and the ultra-high edge nitrogen doped carbon nano sheet is obtained after carbonization. Taking graphene oxide-polyacrylic acid and melamine as examples of raw materials, reacting rich carboxylic acid groups on a side chain of a polymer molecular brush with amino groups of nitrogen-rich micromolecules to form covalent bonds, and obtaining a nitrogen-rich carbon precursor serving as a whole nitrogen source and a part of carbon source. In the assembly process, the graphene oxide plays a role of a structure guiding template, and is beneficial to realizing uniform loading of the nitrogen-rich carbon precursor on the surface of the graphene oxide framework. After carbonization, the nitrogen-rich carbon precursor is successfully converted into an ultra-high edge nitrogen doped carbon coating on the surface of the graphene template, and meanwhile, graphene in the carbon nano sheet provides a high-conductivity skeleton, so that the two-dimensional carbon nano sheet with high edge nitrogen and high conductivity is obtained. The ultra-high edge nitrogen doped carbon nano sheet has high nitrogen doping content and edge nitrogen content, good two-dimensional morphology and conductive graphene skeleton, and good potassium storage capacity and cycle stability when being used as a cathode material of a potassium ion battery.
The present invention will be further described in detail by means of specific examples in order to enable those skilled in the art to better understand and realize the technical aspects of the present invention.
Example 1
The preparation method of the ultra-high edge nitrogen doped carbon nano sheet comprises the following steps:
step (1): 7.2mL of acrylic acid monomer is added into 80mL of aqueous solution containing 100mg of graphene oxide, inert atmosphere protection is introduced, 161.64mg of 2, 2-azo bis [2- (2-imidazolin-2-yl) propane ] dihydrochloride is added, the mixture is uniformly mixed, the temperature is raised to 56 ℃ for reaction for 48 hours, the mixed solution is washed by water, and the graphene oxide-polyacrylic acid polymer molecular brush is obtained after centrifugal separation.
Step (2): preparing the graphene oxide-polyacrylic acid polymer molecular brush obtained in the step (1) into a graphene oxide-polyacrylic acid polymer molecular brush with the concentration of 6-7 mgmL -1 About 60mL of aqueous solution, carboxyl: adding melamine into the mixture at the same time of stirring in the molar ratio of the amino groups of 1:5, transferring the mixture to a hydrothermal kettle liner after stirring for 10 hours, reacting for 24 hours at 110 ℃ after sealing the hydrothermal kettle, and then freeze-drying the resultant to obtain the self-assembled compound.
Step (3): placing the self-assembled complex obtained in the step (2) in 200mLmin -1 In a nitrogen atmosphere at 5℃for a period of minutes -1 And (3) raising the temperature to 600 ℃ and preserving heat for 2 hours, naturally cooling to room temperature, and taking out to obtain the ultra-high edge nitrogen doped carbon nano-sheet I.
Example 2
The preparation method of the ultra-high edge nitrogen doped carbon nano sheet comprises the following steps:
step (1): 7.2mL of acrylic acid monomer is added into 80mL of aqueous solution containing 100mg of graphene oxide, inert atmosphere protection is introduced, 161.64mg of 2, 2-azo bis [2- (2-imidazolin-2-yl) propane ] dihydrochloride is added, the mixture is uniformly mixed, the temperature is raised to 56 ℃ for reaction for 48 hours, the mixed solution is washed by water, and the graphene oxide-polyacrylic acid polymer molecular brush is obtained after centrifugal separation.
Step (2): polymerizing the graphene oxide-polyacrylic acid obtained in the step (1)The molecular brush is prepared into a concentration of 6-7 mgmL -1 About 60mL of aqueous solution, carboxyl: adding melamine into the mixture at the same time of stirring in the molar ratio of the amino groups of 1:5, transferring the mixture to a hydrothermal kettle liner after stirring for 10 hours, reacting for 24 hours at 110 ℃ after sealing the hydrothermal kettle, and then freeze-drying the resultant to obtain the self-assembled compound.
Step (3): placing the self-assembled complex obtained in the step (2) in 200mLmin -1 In a nitrogen atmosphere at 5℃for a period of minutes -1 And (3) raising the temperature to 550 ℃ and preserving heat for 2 hours, naturally cooling to room temperature, and taking out to obtain the ultra-high edge nitrogen doped carbon nano-sheet II.
Example 3
The preparation method of the ultra-high edge nitrogen doped carbon nano sheet comprises the following steps:
step (1): 7.2mL of acrylic acid monomer is added into 80mL of aqueous solution containing 100mg of graphene oxide, inert atmosphere protection is introduced, 161.64mg of 2, 2-azo bis [2- (2-imidazolin-2-yl) propane ] dihydrochloride is added, the mixture is uniformly mixed, the temperature is raised to 56 ℃ for reaction for 48 hours, the mixed solution is washed by water, and the graphene oxide-polyacrylic acid polymer molecular brush is obtained after centrifugal separation.
Step (2): preparing the graphene oxide-polyacrylic acid polymer molecular brush obtained in the step (1) into a graphene oxide-polyacrylic acid polymer molecular brush with the concentration of 6-7 mgmL -1 About 60mL of aqueous solution, carboxyl: adding melamine into the mixture at the same time of stirring in the molar ratio of the amino groups of 1:5, transferring the mixture to a hydrothermal kettle liner after stirring for 10 hours, reacting for 24 hours at 110 ℃ after sealing the hydrothermal kettle, and then freeze-drying the resultant to obtain the self-assembled compound.
Step (3): placing the self-assembled complex obtained in the step (2) in 200mLmin -1 In a nitrogen atmosphere at 5℃for a period of minutes -1 And (3) raising the temperature to 650 ℃ and preserving heat for 2 hours, naturally cooling to room temperature, and taking out to obtain the ultra-high edge nitrogen doped carbon nano-sheet III.
In order to further illustrate the beneficial effects of the invention, the ultra-high edge nitrogen doped carbon nano-sheet prepared in the embodiment 1-3 is subjected to scanning electron microscope characterization, and as shown in the figure 1-3, when the carbonization temperature is 550-650 ℃, a two-dimensional nano-sheet structure can be obtained after carbonization.
Example 4
The preparation method of the ultra-high edge nitrogen doped carbon nano sheet comprises the following steps:
step (1): 7.2mL of acrylic acid monomer is added into 80mL of aqueous solution containing 100mg of graphene oxide, inert atmosphere protection is introduced, 161.64mg of 2, 2-azo bis [2- (2-imidazolin-2-yl) propane ] dihydrochloride is added, the mixture is uniformly mixed, the temperature is raised to 56 ℃ for reaction for 48 hours, the mixed solution is washed by water, and the graphene oxide-polyacrylic acid polymer molecular brush is obtained after centrifugal separation.
Step (2): preparing the graphene oxide-polyacrylic acid polymer molecular brush obtained in the step (1) into a graphene oxide-polyacrylic acid polymer molecular brush with the concentration of 6-7 mgmL -1 About 60mL of aqueous solution, carboxyl: adding melamine into the mixture at the same time of stirring in the molar ratio of the amino groups of 1:1, transferring the mixture to a hydrothermal kettle liner after stirring for 10 hours, reacting for 24 hours at 110 ℃ after sealing the hydrothermal kettle, and then freeze-drying the product to obtain the self-assembled compound.
Step (3): placing the self-assembled complex obtained in the step (2) in 200mLmin -1 In a nitrogen atmosphere at 5℃for a period of minutes -1 And (3) raising the temperature to 600 ℃ and preserving heat for 2 hours, naturally cooling to room temperature, and taking out to obtain the ultra-high edge nitrogen doped carbon nano-sheet IV.
Example 5
The preparation method of the ultra-high edge nitrogen doped carbon nano sheet comprises the following steps:
step (1): 7.2mL of acrylic acid monomer is added into 80mL of aqueous solution containing 100mg of graphene oxide, inert atmosphere protection is introduced, 161.64mg of 2, 2-azo bis [2- (2-imidazolin-2-yl) propane ] dihydrochloride is added, the mixture is uniformly mixed, the temperature is raised to 56 ℃ for reaction for 48 hours, the mixed solution is washed by water, and the graphene oxide-polyacrylic acid polymer molecular brush is obtained after centrifugal separation.
Step (2): preparing the graphene oxide-polyacrylic acid polymer molecular brush obtained in the step (1) into a graphene oxide-polyacrylic acid polymer molecular brush with the concentration of 6-7 mgmL -1 About 60mL of aqueous solution, carboxyl: adding melamine into the mixture at the same time of stirring in the molar ratio of amino of 1:10, stirring for 10 hours, transferring the mixture into a hydrothermal kettle liner, and sealing the hydrothermal kettle linerThe reaction was carried out at 110℃for 24 hours after the autoclave, and then the resultant was freeze-dried to obtain a self-assembled composite.
Step (3): placing the self-assembled complex obtained in the step (2) in 200mLmin -1 In a nitrogen atmosphere at 5℃for a period of minutes -1 And (5) raising the temperature to 600 ℃ and preserving heat for 2 hours, naturally cooling to room temperature, and taking out to obtain the ultra-high edge nitrogen doped carbon nano-sheet five.
In order to further illustrate the beneficial effects of the invention, scanning electron microscope characterization is carried out on the ultra-high edge nitrogen doped carbon nano-sheets prepared in the embodiment 1 and the embodiment 4-5, and as shown in the fig. 1 and the fig. 4-5, the two-dimensional nano-sheet structure can be obtained after carbonization when the molar ratio of carboxyl of graphene oxide-polyacrylic acid to amino of melamine is 1:1-10.
To further illustrate the beneficial effects of the present invention, the ultra-high edge nitrogen doped carbon nanoplatelets prepared in examples 1-5 were characterized by X-ray photoelectron spectroscopy and the resulting curves were fitted as shown in fig. 6-10 and table 1.
TABLE 1 Nitrogen element types and ratios of different ultra high edge Nitrogen doped carbon nanoplates
Note that: total edge nitrogen= (pyridine nitrogen ratio + pyrrole nitrogen ratio) total nitrogen element
The results illustrate: examples 1-3 differ in that the carbonization temperature is different, and as the carbonization temperature increases, the ratio of total nitrogen element to edge nitrogen decreases; examples 1 and 4-5 differ in the ratio of carboxyl groups to amino groups, with the total nitrogen element to edge nitrogen ratio increasing as the nitrogen source ratio increases.
The improvement of the nitrogen content at the edge can improve the potassium ion adsorption capacity of the material so as to improve the potassium storage performance, however, the too high nitrogen content can reduce the conductivity of the material so as to influence the electrochemical performance, and two factors influencing the nitrogen content in the invention are carbonization temperature and nitrogen-rich small molecule proportion respectively, and as can be seen from comprehensive analysis of table 1, the embodiment 1 is an optimal regulation example integrating the consideration of the conductivity and the edge nitrogen content of the material. In order to further illustrate the beneficial effects of the present invention, electrochemical impedance tests were performed on the ultra-high edge nitrogen-doped carbon nano-sheet prepared in example 1, as shown in fig. 13, and the prepared ultra-high edge nitrogen-doped carbon nano-sheet has good electrical conductivity.
Example 6
The preparation method of the ultra-high edge nitrogen doped carbon nano sheet comprises the following steps:
step (1): 10.31g of sodium p-styrenesulfonate monomer is added into 80mL of aqueous solution containing 100mg of graphene oxide, inert atmosphere protection is introduced, 161.64mg of 2, 2-azo bis [2- (2-imidazolin-2-yl) propane ] dihydrochloride is added, the temperature is raised to 56 ℃ for reaction for 48 hours after uniform mixing, the mixed solution is washed by water, 0.1M dilute hydrochloric acid is used for dispersion for ion exchange, and the graphene oxide-poly (p-styrenesulfonic acid) polymer molecular brush is obtained after centrifugal separation.
Step (2): preparing the graphene oxide-poly (p-styrenesulfonic acid) polymer molecular brush obtained in the step (1) into a molecular brush with the concentration of 6-7 mgmL -1 About 60mL of aqueous solution, as sulfonic acid group: adding melamine into the mixture at the same time of stirring in the molar ratio of the amino groups of 1:5, transferring the mixture to a hydrothermal kettle liner after stirring for 10 hours, reacting for 24 hours at 110 ℃ after sealing the hydrothermal kettle, and then freeze-drying the resultant to obtain the self-assembled compound.
Step (3): placing the self-assembled complex obtained in the step (2) in 200mLmin -1 In a nitrogen atmosphere at 5℃for a period of minutes -1 And (3) raising the temperature to 600 ℃ and preserving heat for 2 hours, naturally cooling to room temperature, and taking out to obtain the ultra-high edge nitrogen doped carbon nano-sheet six.
Example 7
The preparation method of the ultra-high edge nitrogen doped carbon nano sheet comprises the following steps:
step (1): 7.40g of p-vinylphenyl boric acid monomer is added into 80mL of aqueous solution containing 100mg of graphene oxide, inert atmosphere protection is introduced, 161.64mg of 2, 2-azo bis [2- (2-imidazolin-2-yl) propane ] dihydrochloride is added, the mixture is heated to 56 ℃ for reaction for 48 hours after uniform mixing, the mixed solution is washed by water, 0.1M dilute hydrochloric acid is used for dispersion and ion exchange, and the graphene oxide-poly-p-vinylphenyl boric acid polymer molecular brush is obtained after centrifugal separation.
Step (2): preparing the graphene oxide-poly (p-vinylphenyl) boric acid polymer molecular brush obtained in the step (1) into a molecular brush with the concentration of 6-7 mgmL -1 About 60mL of aqueous solution, as sulfonic acid group: adding melamine into the mixture at the same time of stirring in the molar ratio of the amino groups of 1:5, transferring the mixture to a hydrothermal kettle liner after stirring for 10 hours, reacting for 24 hours at 110 ℃ after sealing the hydrothermal kettle, and then freeze-drying the resultant to obtain the self-assembled compound.
Step (3): placing the self-assembled complex obtained in the step (2) in 200mLmin -1 In a nitrogen atmosphere at 5℃for a period of minutes -1 And (3) raising the temperature to 600 ℃ and preserving heat for 2 hours, naturally cooling to room temperature, and taking out to obtain the ultra-high edge nitrogen doped carbon nano-sheet seven.
Example 8
The preparation method of the ultra-high edge nitrogen doped carbon nano sheet comprises the following steps:
step (1): 7.2mL of acrylic acid monomer is added into 80mL of aqueous solution containing 100mg of graphene oxide, inert atmosphere protection is introduced, 161.64mg of 2, 2-azo bis [2- (2-imidazolin-2-yl) propane ] dihydrochloride is added, the mixture is uniformly mixed, the temperature is raised to 56 ℃ for reaction for 48 hours, the mixed solution is washed by water, and the graphene oxide-polyacrylic acid polymer molecular brush is obtained after centrifugal separation.
Step (2): preparing the graphene oxide-polyacrylic acid polymer molecular brush obtained in the step (1) into a graphene oxide-polyacrylic acid polymer molecular brush with the concentration of 6-7 mgmL -1 About 60mL of aqueous solution, carboxyl: adding thiourea while stirring at the amino molar ratio of 1:5, transferring the mixture to a hydrothermal kettle liner after stirring for 10 hours, sealing the hydrothermal kettle, reacting at 110 ℃ for 24 hours, and then freeze-drying the resultant to obtain the self-assembled compound.
Step (3): placing the self-assembled complex obtained in the step (2) in 200mLmin -1 In a nitrogen atmosphere at 5℃for a period of minutes -1 And (3) raising the temperature to 600 ℃ and preserving heat for 2 hours, naturally cooling to room temperature, and taking out to obtain the ultra-high edge nitrogen doped carbon nano-sheet eight.
Application example 1
In order to further illustrate the beneficial effects of the present invention, the ultra-high edge nitrogen doped carbon nanoplatelets (hereinafter referred to as carbon nanoplatelets) prepared in examples 1-5 were used as the negative electrode material of the potassium ion battery. Mixing the carbon nano-sheet, the binder polyvinylidene fluoride and the conductive carbon black SuperP of the conductive agent according to the mass ratio of 7:1:2, adding a small amount of N-methyl pyrrolidone, and grinding and mixing to obtain slurry with certain viscosity. Subsequently, the slurry was uniformly coated on the surface of the copper foil using a coater, vacuum-dried at 60 ℃, and then electrode sheets having a diameter of 12mm were cut. Next, the battery assembly was performed in a glove box under an argon atmosphere (water oxygen content of less than 0.5 ppm). The active material electrode slice is taken as an anode, the metal potassium slice is taken as a cathode, and the electrolyte is KPF of 0.8M 6 Dissolving in ethylene carbonate and diethyl carbonate with a volume ratio of 1:1, and adopting Whatman glass microfiber filter paper as a diaphragm to assemble the CR2032 button battery according to the corresponding sequence. The battery is tested for charge and discharge performance by using a LandCT2001A battery test system, and the charge and discharge termination range is 0.01-3.0V. As shown in FIG. 11, the carbon nanoplates prepared in examples 1, 2, 3, 4 and 5 were prepared at 0.1. 0.1A g -1 Reversible specific capacities at current densities are 319, 277, 290, 284 and 342mA h g, respectively -1 When the current density increases to 10A g -1 The reversible specific capacities were 144, 100, 125, 135 and 95mA h g, respectively -1 It is apparent that example 1 has the highest potassium storage capacity and rate capability. Further, as shown in FIG. 12, example 1 is shown at 10A g -1 After 400 circles of stable circulation under the current density, the reversible specific capacity still keeps 100mA h g -1 And exhibits excellent cycle stability.
While particular embodiments of the present invention have been described above, it will be appreciated by those skilled in the art that these are merely illustrative, and that many variations or modifications may be made to the embodiments without departing from the principles and spirit of the invention, the scope of which is defined only by the appended claims.
Claims (6)
1. The preparation method of the ultra-high edge nitrogen doped carbon nano sheet is characterized by comprising the following steps of:
1) Grafting a reactive polymer containing an acid group on the surface of graphene oxide to prepare a graphene oxide-polymer molecular brush;
2) Adding small nitrogen-rich molecules containing amino into the aqueous solution of the graphene oxide-polymer molecules prepared in the step 1), and obtaining a self-assembled compound through stirring, hydrothermal reaction and freeze drying;
3) Carbonizing the self-assembled compound prepared in the step 2) in inert gas to obtain an ultrahigh-edge nitrogen-doped carbon nano sheet;
in the step 1), the reactive polymer is one or more of polyacrylic acid, poly-p-styrenesulfonic acid and poly-p-styreneboric acid; in the step 2), the nitrogen-rich micromolecule is one or more of melamine, urea, thiourea, cyanamide and dicyandiamide;
in the step 2), the reactive polymer and the nitrogen-rich micromolecule are subjected to self-assembly compounding according to the molar ratio of acid groups in the reactive polymer to amino groups in the nitrogen-rich micromolecule of 1:1-10;
the carbonization reaction temperature in the step 3) is 550-900 ℃, and the carbonization time is 1-4 h.
2. The method for preparing ultra-high edge nitrogen-doped carbon nano-sheets according to claim 1, wherein in step 1), the proportion of the reactive polymer in the graphene oxide-polymer molecular brush is more than 30wt%.
3. The method for preparing ultra-high edge nitrogen-doped carbon nano-sheets according to claim 1, wherein the hydrothermal reaction temperature in the step 2) is 100-120 ℃ and the reaction time is 12-36 h.
4. The method for preparing the ultra-high edge nitrogen-doped carbon nano-sheet according to claim 1, wherein the inert gas in the step 3) is one or more of nitrogen, argon or helium, the gas flow rate is 100-300 mL min < -1 >, and the temperature rising rate is 2-5 ℃ for min -1 。
5. An ultra-high edge nitrogen-doped carbon nanoplatelet made by the method of any one of claims 1-4.
6. Use of the ultra-high edge nitrogen doped carbon nanoplatelets of claim 5 in potassium ion batteries.
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