CN115312744A - Nitrogen-sulfur co-doped carbon dot regulated polypyrrole derived carbon material, preparation method thereof and application thereof in potassium ion battery - Google Patents

Nitrogen-sulfur co-doped carbon dot regulated polypyrrole derived carbon material, preparation method thereof and application thereof in potassium ion battery Download PDF

Info

Publication number
CN115312744A
CN115312744A CN202211126703.XA CN202211126703A CN115312744A CN 115312744 A CN115312744 A CN 115312744A CN 202211126703 A CN202211126703 A CN 202211126703A CN 115312744 A CN115312744 A CN 115312744A
Authority
CN
China
Prior art keywords
nitrogen
sulfur
polypyrrole
doped carbon
carbon material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202211126703.XA
Other languages
Chinese (zh)
Inventor
杨莉
任芷彤
侯红帅
邹国强
纪效波
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hunan University of Technology
Original Assignee
Hunan University of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hunan University of Technology filed Critical Hunan University of Technology
Priority to CN202211126703.XA priority Critical patent/CN115312744A/en
Publication of CN115312744A publication Critical patent/CN115312744A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • H—ELECTRICITY
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H—ELECTRICITY
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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

The invention discloses a nitrogen-sulfur co-doped carbon point regulation polypyrrole derived carbon material, a preparation method thereof and application thereof in a potassium ion battery. Dissolving and dispersing the nitrogen-sulfur co-doped carbon points into a dilute acid solution, adding an initiator and a pyrrole monomer for polymerization, and calcining a polymerization product to obtain the nitrogen-sulfur co-doped carbon point regulation polypyrrole derived carbon material. Compared with the existing strip-shaped fiber polypyrrole derived carbon material, the carbon material can provide a shorter ion transmission and transfer path, expose more active sites, increase the contact area with electrolyte when used for a potassium ion battery, and slow down the structural breakage caused by the embedding and releasing of potassium ions, thereby improving the cycle performance of the potassium ion battery and obtaining high capacity.

Description

Nitrogen-sulfur co-doped carbon dot regulated polypyrrole derived carbon material, preparation method thereof and application thereof in potassium ion battery
Technical Field
The invention relates to a potassium ion battery cathode material, in particular to a nitrogen and sulfur co-doped carbon point regulated polypyrrole derived carbon material, a preparation method thereof and application of the material as a potassium ion battery cathode material, and belongs to the fields of new energy storage materials and electrochemistry.
Background
Potassium ion batteries have great potential in large-scale energy storage applications due to their low cost, high energy density, abundant potassium reserves, and redox potentials similar to lithium. However, since the potassium ion battery has a large ionic radius, it causes large volume change and slow diffusion kinetics during charge and discharge, resulting in poor cycle stability and low capacity, which severely limits the development of PIBs. One of the major challenges of PIBs is to find suitable anode materials that can stably accommodate potassium ions for reversible rapid insertion/extraction. In order to solve the above problems, the negative electrode materials having potential at present are mainly focused on carbon materials, transition metal oxides and sulfides, alloy materials, silicon materials, and the like. Among them, carbon materials are promising candidate materials for PIBs cathodes because of their adjustable microstructure, high electrical conductivity, low cost, and environmental friendliness. However, the battery has low reversible capacity, poor rate performance and poor cycling stability due to huge volume expansion and structural deformation generated in the charging and discharging processes. In order to improve the potassium storage capacity of the carbon material and improve the performance of KIB, the carbon material is modified mainly by means of carbon structure and morphology design, graphite interlayer spacing regulation, electronic structure regulation and the like. Among them, adjustment of the electronic structure and microstructure of carbon materials has proven to be an effective strategy for improving electrochemical performance by creating more active sites or a large number of defects, enlarging the interlayer spacing and thereby significantly increasing K + And (4) storing the performance.
The design of a carbon structure with a specific structure and high stability mainly adopts means such as surface modification assembly, carbonization process control and the like, wherein carbon points can exert unique advantages in the material surface assembly and carbonization evolution process. Since carbon points were reported in 2004 (X.Y.Xu, et al, electrophoretic analysis and purification of fluorescent single-walled carbon nanotubes fragments, journal of the American Chemical Society,2004,126, 12736-12737), with the rapid progress of research on carbon points, the advantages of abundant active sites, large specific surface area, small volume, etc. have a positive effect on promoting ion transfer and storage. Carbon dots as a new Carbon source can be used to prepare functional Carbon composite materials with specific morphology, such as (Wanwan Hong, yu Zhang, li Yang, ye Tian, peng Ge, jiugang Hu, weifen Wei, guoqiang zuo, hongshuai Hou, xiaoo Ji, carbon four dot microorganisms tall organic hole Carbon anode for fast void storage and sodium storage, nano Energy 65 (2019) 104038, doi 10.1016/j.nanoen.2019.038) report that Carbon dots as a new template can regulate and control the synthesized nitrogen-doped Carbon material with hollow structure, when the nitrogen-doped Carbon material is applied to a potassium ion battery, the larger specific surface area and the multi-level pore electrolyte structure are favorable for infiltration and the potassium ion can be rapidly transferred, and the buffer capacity of potassium ion can be changed, thereby improving the potassium ion cycling performance and the potassium ion cycling stability.
Disclosure of Invention
Aiming at the defects in the prior art, the first object of the invention is to provide a nitrogen and sulfur co-doped carbon point regulated polypyrrole derived carbon material, wherein the carbon material utilizes nitrogen and sulfur co-doped carbon points to induce pyrrole to polymerize to generate polypyrrole tending to a nanoparticle shape, and finally a granular polypyrrole derived carbon material is obtained.
The second purpose of the invention is to provide a preparation method of a nitrogen-sulfur co-doped carbon point regulation polypyrrole derived carbon material, which has the advantages of rich and cheap raw materials, simple and convenient operation and high yield, and can achieve the purpose of large-scale production.
The third purpose of the invention is to provide an application of a nitrogen and sulfur co-doped carbon point regulation polypyrrole derived carbon material, wherein the nitrogen and sulfur co-doped carbon point regulation polypyrrole derived carbon material is used as a potassium ion battery negative electrode material, and the obtained potassium ion battery shows excellent cycling stability and high specific capacity.
In order to achieve the technical purpose, the invention provides a preparation method of a nitrogen and sulfur co-doped carbon dot regulation and control polypyrrole derived carbon material, which comprises the steps of dissolving and dispersing nitrogen and sulfur co-doped carbon dots into a dilute acid solution under the action of a surfactant in an environment with the temperature of not higher than 5 ℃, adding an initiator and a pyrrole monomer into the dilute acid solution to perform a polymerization reaction to obtain a nitrogen and sulfur co-doped carbon dot-polypyrrole composite material, and calcining the nitrogen and sulfur co-doped carbon dot-polypyrrole composite material to obtain the nitrogen and sulfur co-doped carbon dot-polypyrrole composite material.
The key point of the invention is that nitrogen and sulfur co-doped carbon points are used as an inducer in the pyrrole polymerization process, so that the morphology of the generated polypyrrole is essentially changed, common fibrous morphology is converted into granular morphology, and the nano polypyrrole derived carbon material is obtained, and compared with the fibrous polypyrrole derived carbon material, the nano granular polypyrrole derived carbon material can provide a shorter ion transmission and transfer path and expose more active sites, and meanwhile, the nitrogen and sulfur co-doped carbon points are high-activity carbon materials, and the nitrogen and sulfur co-doped carbon points can improve the conductivity of the composite carbon material by doping the polypyrrole derived carbon material and accelerate the ion transfer rate and charge transfer dynamics in the electrochemical process, so that when the nitrogen and sulfur co-doped carbon points are used for regulating and controlling the polypyrrole derived carbon material in a potassium ion battery, the contact area between the carbon material and an electrolyte can be increased, and the structural breakage caused by embedding and removing of potassium ions in the carbon material is relieved, and the cycle performance of the potassium ion battery is improved.
The nitrogen and sulfur co-doped carbon dot has a good regulation effect on the morphology of polypyrrole, and common non-doped carbon dots, nitrogen-doped carbon dots and the like in the prior art almost have no regulation effect on the morphology of polypyrrole, which is unexpected.
As a preferred scheme, the concentration of the nitrogen and sulfur co-doped carbon dots in a dilute acid solution is 80-400 mg/L. The concentration of nitrogen and sulfur co-doped carbon dots is in an optimal range, the morphology adjusting effect on polypyrrole is more obvious along with the improvement of the concentration of the nitrogen and sulfur co-doped carbon dots, for example, when the concentration of the nitrogen and sulfur co-doped carbon dots is 80mg/L, fibrous particles with the size of about 50nm can be still observed, when the concentration of the nitrogen and sulfur co-doped carbon dots is 200mg/L, a morphology structure with the particles arranged into strips can be seen, when the concentration of the nitrogen and sulfur co-doped carbon dots is improved to 400mg/L, the particle accumulation state is appeared, the nitrogen and sulfur co-doped carbon dots finally formed by the polypyrrole accumulated by nanoparticles can regulate and control the polypyrrole carbon material to have the best electrochemical performance, and if the concentration of the nitrogen and sulfur co-doped carbon dots is further improved, the agglomeration phenomenon can be caused. Therefore, the concentration of the carbon dots in the diluted acid solution is preferably 100 to 400mg/L, more preferably 200 to 400mg/L, and most preferably 300 to 400mg/L.
In a preferred embodiment, the surfactant is at least one of quaternary ammonium surfactant, sodium stearyl sulfate, sodium stearate, sodium dioctyl sulfosuccinate, sodium dodecyl benzene sulfonate, and sodium glycocholate. The preferred surfactant can promote the dissolution and dispersion of the nitrogen and sulfur co-doped carbon dots in the solution. Quaternary ammonium surfactants such as cetyl trimethyl ammonium bromide and the like.
As a preferred embodiment, the initiator is a persulfate. Persulfates are common redox initiators, such as ammonium persulfate, potassium persulfate, and the like.
As a preferable scheme, the concentration of the surfactant in the dilute acid solution is 2-4 g/L.
As a preferable scheme, the concentration of the initiator in the dilute acid solution is 6-10 g/L.
As a preferable scheme, the concentration of the dilute acid solution is 0.5-1.5 mol L -1 Dilute hydrochloric acid of (2).
As a preferable scheme, the concentration of the pyrrole monomer in the dilute acid solution is 8-20 g/L.
As a preferred embodiment, the calcination conditions are: under the protective atmosphere, at the temperature of 2-10 ℃ for min -1 The temperature is raised to 500-800 ℃ at the temperature raising rate, and the temperature is kept for 5-10 h. Protective atmospheres such as argon, nitrogen, and the like.
The nitrogen-sulfur co-doped carbon dots are prepared by the following preparation method: dissolving sulfur-containing amino acid in aldehyde solution, slowly adding alkaline compound, and performing ultrasonic treatment, dialysis and freeze drying to obtain nitrogen and sulfur co-doped carbon dots (NSCDs). Preferred sulfur-containing amino acids include at least one of methionine, cystine, and cysteine. All the amino acids are sulfur-containing amino acids, and the sulfur-nitrogen co-doped carbon dots can be synthesized by an acetaldehyde method, and most preferably cysteine. Preferred aldehyde solutions include at least one of acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, caproaldehyde, heptaldehyde, caprylic aldehyde, succinaldehyde, glutaraldehyde, hexanedial, nonanal, decanal. Preferred basic compounds include at least one of lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, potassium phosphate, sodium acetate, and potassium acetate. The mass ratio of the alkaline substance to the sulfur-containing amino acid is 2-4; preferably 2.5 to 3.
The invention also provides a nitrogen-sulfur co-doped carbon point regulation polypyrrole derived carbon material, which is obtained by the preparation method.
The invention also provides application of the nitrogen-sulfur co-doped carbon point regulated polypyrrole derived carbon material as a negative electrode material of a potassium ion battery.
The nitrogen-sulfur co-doped carbon point regulated polypyrrole derived carbon material is used for a potassium ion battery: uniformly mixing a nitrogen-sulfur co-doped carbon point regulation polypyrrole derived carbon material, a sodium carboxymethylcellulose binder and a Super P conductive agent according to a mass ratio of 70. The dried, active material-coated copper foil was cut into disks with a diameter of 13mm, pressed at a pressure of 10MPa and used as working electrode for button cells, potassium metal as comparative electrode and Celgard 2400 membrane as separator.
Compared with the prior art, the technical scheme of the invention has the following beneficial technical effects:
1) The preparation method of the nitrogen and sulfur co-doped carbon point regulation polypyrrole derived carbon material provided by the invention is characterized in that the nitrogen and sulfur co-doped carbon point is used, and has two main functions: induction and regulation. On one hand, the nitrogen and sulfur co-doped functionalized carbon dots are used as an inducer and can generate a driving force for directional aggregation, so that effective regulation and control of specific morphology are realized, the morphology of the nitrogen and sulfur co-doped carbon dots regulated polypyrrole derived carbon material is substantially changed compared with that of a common polypyrrole derived carbon material, the granular polypyrrole derived carbon material can be obtained, a shorter ion transmission and transfer path can be provided, more active sites are exposed, the contact area with an electrolyte can be increased when the carbon material is used for a potassium ion battery, and structural breakage caused by the fact that potassium ions are removed from the carbon material, so that the cycle performance of the potassium ion battery is improved, and the dispersibility and stability of a material structure are improved; on the other hand, the nitrogen and sulfur co-doped carbon dot is used for doping the polypyrrole derived carbon material, so that the conductivity of the composite carbon material can be improved, and the ion transfer rate and charge transfer kinetics in the electrochemical process are accelerated.
2) According to the preparation method of the nitrogen-sulfur co-doped carbon point regulation polypyrrole derived carbon material, the appearance of the nitrogen-sulfur co-doped carbon point regulation polypyrrole derived carbon material can be effectively regulated and controlled by regulating the addition amount of the nitrogen-sulfur co-doped carbon point, the polypyrrole derived carbon material is converted from fibrous to beaded and then to granular, and after electrochemical tests, the fact that the potassium storage performance of polypyrrole is more excellent along with the increase of the introduction amount of the carbon point is found, the NSCDs regulated ppy-NSCDs-100 carbon-based negative electrode material shows electrochemical performance obviously superior to ppy, and the electrochemical performance is 0.1A g -1 The specific capacity is kept at 265.2mAh g after the current density is cycled for 100 circles -1 At 1.0A g -1 The current density of the lithium battery is excellent in potassium storage performance, and the specific capacity of the lithium battery is still 155.4mAh g after the lithium battery is cycled for 495 circles -1 . At 0.05, 0.1, 0.2, 0.4, 0.6, 0.8, 1.0, 1.5 and 2.0ag -1 Has a reversible specific capacity of 354.4, 283.0, 252.4, 224.1,195.1, 181.5, 168.5, 140.7, and 108.4mAh g -1 When the current density suddenly changes from 2.0ag -1 Return to 0.1 ag -1 When the specific capacity is higher than the standard, the specific capacity can be recovered to 278.4mAh g -1 While pure ppy under the same conditions is only 246.7mAh g -1 Indicating that ppy-NSCDs-100 has good cycle reversibility. The improvement of the performance of the carbon nano-material is closely related to the great change of the morphology structure caused by the addition of the carbon dots, and the fact that the carbon dots are used as a novel carbon nano-material is proved, so that the carbon nano-material has very important application value in the aspects of preparation and regulation of electrode materials.
3) The preparation method of the nitrogen-sulfur co-doped carbon point regulation polypyrrole derived carbon material provided by the invention has the advantages of high yield, simplicity and convenience in operation, good repeatability and the like, overcomes the defect of complex traditional synthetic process, is rich and cheap in raw materials, and can realize the purpose of large-scale production.
4) The nitrogen-sulfur co-doped carbon point regulation polypyrrole derived carbon material provided by the invention can show the characteristics of high capacity, good cycle stability and the like when being applied as a potassium ion battery material.
Drawings
FIG. 1 is a TEM image of a nitrogen and sulfur co-doped carbon dot-modulated polypyrrole derived carbon material (ppy-NSCD-20) prepared in example 1.
FIG. 2 is a TEM image of a nitrogen and sulfur co-doped carbon dot-modulated polypyrrole derived carbon material (ppy-NSCD-50) prepared in example 2.
FIG. 3 is a TEM image of nitrogen and sulfur co-doped carbon dot-modulated polypyrrole derived carbon material (ppy-NSCD-100) prepared in example 3.
Fig. 4 is a TEM image of a nitrogen and sulfur co-doped pure polypyrrole derived carbon material product (ppy) prepared in comparative example 1.
FIG. 5 is an X-ray diffraction pattern of nitrogen and sulfur co-doped carbon point-regulated polypyrrole derived carbon material products prepared in examples 1, 2 and 3.
FIG. 6 is an X-ray diffraction pattern of a pure polypyrrole derived carbon material product prepared in comparative example 1.
Fig. 7 is a cycle performance diagram and a rate diagram of a potassium ion battery assembled by the nitrogen and sulfur co-doped carbon point-regulated polypyrrole derived carbon material (ppy-NSCD-20) prepared in example 1.
Fig. 8 is a cycle performance diagram and a rate diagram of a potassium ion battery assembled by the nitrogen and sulfur co-doped carbon point controlled polypyrrole derived carbon material (ppy-NSCD-50) prepared in example 2.
Fig. 9 is a cycle performance diagram and a rate diagram of a potassium ion battery assembled by the nitrogen and sulfur co-doped carbon point controlled polypyrrole derived carbon material (ppy-NSCD-100) prepared in example 3.
Fig. 10 is a cycle performance diagram and a rate diagram of a potassium ion battery assembled with pure polypyrrole-derived carbon material (ppy) prepared in comparative example 1.
Fig. 11 is a cycle performance diagram and a rate diagram of a potassium ion battery assembled by nitrogen-doped carbon dots (NCDs) modulated polypyrrole derived carbon materials (ppy-NCD-100) prepared in comparative example 2.
Fig. 12 is a cycle performance diagram of a potassium ion battery assembled by the nitrogen and sulfur co-doped carbon point-controlled polypyrrole derived carbon material (ppy-NSCD-20) prepared in example 4.
Fig. 13 is a graph showing cycle performance of a potassium ion battery assembled from a nitrogen and sulfur co-doped carbon dot-modulated polypyrrole derived carbon material (ppy-NSCD-20) prepared in comparative example 3.
FIG. 14 is a TEM image of a nitrogen and sulfur co-doped carbon dot-modulated polypyrrole derived carbon material (ppy-NSCD-120) prepared in comparative example 4.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
4g of cysteine was dissolved in 40mL of acetaldehyde, and then 12g of NaOH was slowly added thereto, and the mixture was stirred at normal temperature and pressure for 2 hours. And after the reaction is finished, adding a proper amount of deionized water (only by immersion) and carrying out ultrasonic treatment for 30min, then transferring into a dialysis bag for dialysis and purification, transferring the dialyzate into a beaker after the dialyzate is neutral, placing the beaker into a vacuum freeze dryer for freeze drying, and obtaining nitrogen-sulfur co-doped carbon dots (NSCDs) after the completion of the freeze drying.
0.8g of hexadecaneTrimethylammonium bromide (CTAB) and 20mg NSCDs were dissolved in 250mL of 1mol L under ice bath conditions (0-5 ℃ C.) -1 Then 2g ammonium persulfate is added into the solution, the solution is stirred for 30min, then 2.5mL pyrrole monomer is added, the solution is stirred for 8h on a magnetic stirrer, and the whole process is carried out under the ice-bath condition. After the reaction is finished, the obtained material is filtered by suction and 1mol L of the obtained material is used -1 Respectively cleaning with dilute hydrochloric acid, deionized water and ethanol, drying in a forced air drying oven for 24h, and drying at 5 deg.C for 5 min in argon atmosphere -1 The temperature is raised to 600 ℃ at the heating rate, the temperature is kept for 5 hours, and the required sample (ppy-NSCD-20) is obtained after the temperature is naturally reduced.
And regulating the polypyrrole derived carbon material by using the nitrogen and sulfur co-doped carbon point of the obtained product, and assembling the CR2016 type button cell in an inert gas glove box. Uniformly mixing a nitrogen-sulfur co-doped carbon point regulation polypyrrole derived carbon material (ppy-NSCD-20), a sodium carboxymethylcellulose binder and a Super P conductive agent according to a mass ratio of 70. The dried active material-coated copper foil was cut into a circular sheet with a diameter of 13mm, pressed at a pressure of 10MPa and used as a working electrode for a button cell, sodium metal as a comparative electrode and Celgard 2400 membrane as a separator. After assembly, performance testing was performed, and when applied to a potassium ion battery, only 79.9mAh g remained after 495 cycles of cycling -1 The capacity retention was also only 43.6%. At 0.05, 0.1, 0.2, 0.4, 0.6, 0.8, 1.0, 1.5 and 2.0ag -1 Has a reversible specific capacity of 361.3, 264.2, 225.5, 193.6, 177.5, 163.6, 153.3, 134.9 and 119.9mAh g respectively -1 When the current density suddenly changes from 2.0Ag -1 Return to 0.1 ag -1 When the specific capacity is high, the specific capacity can be recovered to 246.6mAh g -1 。
Example 2
NSCDs were prepared according to example 1.
0.8g of cetyltrimethylammonium bromide (CTAB) and 50mg of NSCDs are dissolved in 250mL of 1mol L under ice bath conditions (0-5 ℃ C.) -1 Then 2g ammonium persulfate is added into the solution, the solution is stirred for 30min, then 2.5mL pyrrole monomer is added, the solution is stirred for 8h on a magnetic stirrer, and the whole process is carried out under the ice-bath condition. After the reaction is finished, the obtained material is filtered by suction and 1mol L of the obtained material is used -1 Respectively cleaning with dilute hydrochloric acid, deionized water and ethanol, drying in a forced air drying oven for 24h, and drying at 5 deg.C for 5 min in argon atmosphere -1 The temperature is raised to 600 ℃ at the temperature raising rate, the temperature is kept for 5 hours, and the required sample (ppy-NSCD-50) is obtained after the temperature is naturally lowered.
And (3) regulating a polypyrrole derived carbon material by using the nitrogen and sulfur co-doped carbon point of the obtained product, and assembling the CR2016 type button cell in an inert gas glove box. Uniformly mixing the obtained product, namely the nitrogen-sulfur co-doped carbon point regulation polypyrrole derived carbon material (ppy-NSCD-50), the sodium carboxymethylcellulose binder and the Super P conductive agent according to a mass ratio of 15. The dried active material-coated copper foil was cut into a circular sheet with a diameter of 13mm, pressed at a pressure of 10MPa and used as a working electrode for a button cell, sodium metal as a comparative electrode and Celgard 2400 membrane as a separator. After assembly, the performance was tested at 1.0A g when applied to a potassium ion battery -1 After 495 cycles, the discharge specific capacity of 136 is still kept, and the capacity retention rate reaches 91.1%. At 0.05, 0.1, 0.2, 0.4, 0.6, 0.8, 1.0, 1.5 and 2.0ag -1 Has a reversible specific capacity of 540.3, 282.0, 223.8, 183.7, 162.4, 149.8, 141.2, 128.7 and 120.2mAh g, respectively -1 When the current density suddenly changes from 2.0ag -1 Return to 0.1 ag -1 When the specific capacity is higher than the standard, the specific capacity can be recovered to 265.4mAh g -1 。
Example 3
NSCDs were prepared according to example 1.
0.8g of cetyltrimethylammonium bromide (CTAB) and 100mg of NSCDs were dissolved in 250mL of 1mol L under ice bath conditions (0-5 ℃ C.) -1 After 2g of persulfuric acid was added to the solutionAmmonium, stirring for 30min, then adding 2.5mL pyrrole monomer, and stirring for 8h on a magnetic stirrer, wherein the whole process is carried out under ice bath conditions. After the reaction is finished, the obtained material is filtered by suction and 1mol L of the filtrate is used -1 Respectively cleaning with dilute hydrochloric acid, deionized water and ethanol, drying in a forced air drying oven for 24h, and drying at 5 deg.C for 5 min in argon atmosphere -1 The temperature is raised to 600 ℃ at the temperature raising rate, the temperature is kept for 5 hours, and the required sample (ppy-NSCD-100) is obtained after the temperature is naturally lowered.
And regulating the polypyrrole derived carbon material by using the nitrogen and sulfur co-doped carbon point of the obtained product, and assembling the CR2016 type button cell in an inert gas glove box. Uniformly mixing the obtained product, namely a nitrogen-sulfur co-doped carbon point regulation and control polypyrrole derived carbon material (ppy-NSCD-100), a sodium carboxymethylcellulose binder and a Super P conductive agent according to a mass ratio of 15. The dried copper foil coated with active material was cut into a circular sheet with a diameter of 13mm, pressed under a pressure of 10MPa and used as a working electrode for a button cell, sodium metal was used as a comparative electrode, and Celgard 2400 membrane was used as a separator. After assembly, the performance was tested at 0.1A g when applied to a potassium ion battery -1 The specific capacity is kept at 265.2mAh g after the current density is cycled for 100 circles -1 At 1.0A g -1 The current density of the alloy is excellent in potassium storage performance, and the specific capacity of the alloy is still 155.4mAh g after the alloy is circulated for 495 circles -1 . At 0.05, 0.1, 0.2, 0.4, 0.6, 0.8, 1.0, 1.5 and 2.0ag -1 Has a reversible specific capacity of 354.4, 283.0, 252.4, 224.1, 195.1, 181.5, 168.5, 140.7 and 108.4mAh g respectively -1 When the current density suddenly changes from 2.0ag -1 Return to 0.1 Ag -1 When the specific capacity is increased, the specific capacity can be recovered to 278.4mAh g -1 While pure ppy under the same conditions is only 246.7mAh g -1 The potassium storage performance of ppy-NSCDs-100 is obviously improved.
Example 4
NSCDs were prepared according to example 1.
0.8g of cetyltrimethylammonium bromide (CTAB) and 20mg of NSCDs are dissolved in 250mL of 1mol L under ice bath conditions (0-5 ℃ C.) -1 Then 2g ammonium persulfate is added into the solution, the solution is stirred for 30min, then 2.5mL pyrrole monomer is added, and the solution is stirred for 8h on a magnetic stirrer, and the whole process is carried out under the ice-bath condition. After the reaction is finished, the obtained material is filtered by suction and 1mol L of the obtained material is used -1 Respectively cleaning with dilute hydrochloric acid, deionized water and ethanol, drying in a forced air drying oven for 24h, and drying at 5 deg.C for 5 min in argon atmosphere -1 The temperature is raised to 500 ℃ at the heating rate, the temperature is kept for 5 hours, and the required sample (ppy-NSCD-20) is obtained after the temperature is naturally reduced.
And (3) regulating a polypyrrole derived carbon material by using the nitrogen and sulfur co-doped carbon point of the obtained product, and assembling the CR2016 type button cell in an inert gas glove box. Uniformly mixing the obtained product, namely the nitrogen-sulfur co-doped carbon point regulation polypyrrole derived carbon material (ppy-NSCD-20), the sodium carboxymethylcellulose binder and the Super P conductive agent according to a mass ratio of 15. The dried copper foil coated with active material was cut into a circular sheet with a diameter of 13mm, pressed under a pressure of 10MPa and used as a working electrode for a button cell, sodium metal was used as a comparative electrode, and Celgard 2400 membrane was used as a separator. After assembly, the performance was tested at 0.1A g for potassium ion batteries -1 Can only keep 86.3mAh g after circulating for 100 circles under the current density -1 Specific capacity.
Comparative example 1
0.8g of cetyltrimethylammonium bromide (CTAB) was dissolved in 250mL of 1mol L under ice-bath conditions (0-5 ℃ C.) -1 Then 2g ammonium persulfate is added into the solution, the solution is stirred for 30min, then 2.5mL pyrrole monomer is added, and the solution is stirred for 8h on a magnetic stirrer, and the whole process is carried out under the ice-bath condition. After the reaction is finished, the obtained material is filtered by suction and 1mol L of the obtained material is used -1 Respectively cleaning with dilute hydrochloric acid, deionized water and ethanol, drying in a forced air drying oven for 24 hr, and dryingDrying the sample at 5 deg.C for min under argon atmosphere -1 The temperature is raised to 600 ℃ at the heating rate, the temperature is kept for 5 hours, and the carbon material derived from pure polypyrrole is obtained after the carbon material is naturally cooled.
And assembling the polypyrrole derived carbon material in an inert gas glove box to obtain the CR2016 type button cell. Uniformly mixing the obtained product polypyrrole derived carbon material (ppy), sodium carboxymethylcellulose binder and Super P conductive agent according to a mass ratio of 70. The dried copper foil coated with active material was cut into a circular sheet with a diameter of 13mm, pressed under a pressure of 10MPa and used as a working electrode for a button cell, sodium metal was used as a comparative electrode, and Celgard 2400 membrane was used as a separator. After the assembly, the performance test is carried out, when the battery is applied to a potassium ion battery, the specific capacity is attenuated continuously, and the current density is 0.1A g -1 Under the condition of (1), the specific discharge capacity is only 192.7mAh g after circulating for 100 circles -1 The specific capacity of (2) is only 77.7mAh g left after 495 cycles of circulation -1 . At 0.05, 0.1, 0.2, 0.4, 0.6, 0.8, 1.0, 1.5 and 2.0ag -1 Has a reversible specific capacity of 366.3, 280.6, 241.5, 213.6, 191.4, 174.1, 157.9, 135.8 and 117.8mAh g respectively -1 When the current density suddenly changes from 2.0ag -1 Return to 0.1 Ag -1 When the specific capacity is increased, the specific capacity can be recovered to 240.8mAh g -1
Comparative example 2
4g of urea was dissolved in 40mL of acetaldehyde, and then 12g of NaOH was slowly added thereto, followed by stirring at normal temperature and pressure for 2 hours. And after the reaction is finished, adding a proper amount of deionized water (soaking), carrying out ultrasonic treatment for 30min, then transferring into a dialysis bag for dialysis and purification, transferring into a beaker after the dialysate is neutral, placing into a vacuum freeze dryer for freeze drying, and obtaining nitrogen-doped carbon dots (NCDs).
0.8g of cetyltrimethylammonium bromide (CTAB) and 100mg of NCDs carbon dots were dissolved in 250mL of 1mol L under ice bath conditions (0 to 5 ℃ C.) -1 After adding 2g of ammonium persulfate to the solution, stirringStirring for 30min, then adding 2.5mL of pyrrole monomer, and stirring for 8h on a magnetic stirrer, wherein the whole process is carried out under the ice-bath condition. After the reaction is finished, the obtained material is filtered by suction and 1mol L of the obtained material is used -1 Respectively cleaning with dilute hydrochloric acid, deionized water and ethanol, drying in a forced air drying oven for 24h, and drying at 5 deg.C for 5 min in argon atmosphere -1 The temperature is raised to 600 ℃ at the heating rate, the temperature is kept for 5 hours, and a required sample (ppy-NCD-100) is obtained after the temperature is naturally reduced.
And regulating the polypyrrole derived carbon material by using the nitrogen-doped carbon point of the obtained product, and assembling the CR2016 type button cell in an inert gas glove box. Uniformly mixing the obtained product nitrogen-doped carbon point control polypyrrole derived carbon material (ppy-NCD-100), the sodium carboxymethyl cellulose binder and the Super P conductive agent according to a mass ratio of 15. The dried active material-coated copper foil was cut into a circular sheet with a diameter of 13mm, pressed at a pressure of 10MPa and used as a working electrode for a button cell, sodium metal as a comparative electrode and Celgard 2400 membrane as a separator. After assembly, the performance was tested at 0.1A g for potassium ion batteries -1 The specific capacity is only kept at 237.1mAh g after the current density is cycled for 100 circles -1 At 1.0A g -1 The current density of the alloy is excellent in potassium storage performance, and the specific capacity is 53.8mAh g after the alloy is circulated for 495 circles -1 . At 0.05, 0.1, 0.2, 0.4, 0.6, 0.8, 1.0, 1.5 and 2.0Ag -1 Has a reversible specific capacity of 326.5, 249.7, 215.2, 191.3, 168.8, 151.1, 132.0, 112.2 and 87.3mAh g respectively -1 When the current density suddenly changes from 2.0ag -1 Return to 0.1 ag -1 When the specific capacity is higher than the specific capacity, the specific capacity can be recovered to 193.9mAh g -1 Compared with the potassium storage performance of a pure polypyrrole derived carbon material (ppy), the potassium storage performance is not obviously improved but is reduced, which indicates that the purpose of improving the cycle performance and rate capability of the final carbon material cannot be achieved by adding the nitrogen-doped carbon point.
Comparative example 3
NSCDs were prepared according to example 1.
0.8g of cetyltrimethylammonium bromide (CTAB) and 20mg of NSCDs are dissolved in 250mL of 1mol L under ice bath conditions (0-5 ℃ C.) -1 Then 2g ammonium persulfate is added into the solution, the solution is stirred for 30min, then 2.5mL pyrrole monomer is added, and the solution is stirred for 8h on a magnetic stirrer, and the whole process is carried out under the ice-bath condition. After the reaction is finished, the obtained material is filtered by suction and 1mol L of the obtained material is used -1 Respectively cleaning with dilute hydrochloric acid, deionized water and ethanol, drying in a forced air drying oven for 24h, and drying at 5 deg.C for 5 min in argon atmosphere -1 The temperature is raised to 400 ℃ at the heating rate, the temperature is kept for 5 hours, and a required sample (ppy-NSCD-20) is obtained after the temperature is naturally reduced.
And (3) regulating a polypyrrole derived carbon material by using the nitrogen and sulfur co-doped carbon point of the obtained product, and assembling the CR2016 type button cell in an inert gas glove box. Uniformly mixing the obtained product, namely a nitrogen-sulfur co-doped carbon point regulation and control polypyrrole derived carbon material (ppy-NSCD-100), a sodium carboxymethylcellulose binder and a Super P conductive agent according to a mass ratio of 15. The dried copper foil coated with active material was cut into a circular sheet with a diameter of 13mm, pressed under a pressure of 10MPa and used as a working electrode for a button cell, sodium metal was used as a comparative electrode, and Celgard 2400 membrane was used as a separator. After assembly, the performance was tested at 0.1A g for potassium ion batteries -1 The specific capacity can only be kept at 106.9mAh g after the current density is cycled for 100 circles -1 The potassium storage performance is somewhat different from the electrochemical performance of the product obtained in example 1.
Comparative example 4
NSCDs were prepared according to example 1.
0.8g of cetyltrimethylammonium bromide (CTAB) and 120mg of NSCDs are dissolved in 250mL of 1mol L under ice bath conditions (0-5 ℃ C.) -1 Then 2g ammonium persulfate is added into the solution, the solution is stirred for 30min, then 2.5mL pyrrole monomer is added, the solution is stirred for 8h on a magnetic stirrer,the whole process is carried out under ice bath conditions. After the reaction is finished, the obtained material is filtered by suction and 1mol L of the obtained material is used -1 Respectively cleaning with dilute hydrochloric acid, deionized water and ethanol, drying in a forced air drying oven for 24h, and drying at 5 deg.C for 5 min in argon atmosphere -1 The temperature is raised to 600 ℃ at the heating rate, the temperature is kept for 5 hours, and the required sample (ppy-NSCD-120) is obtained after the temperature is naturally reduced.
As can be seen from fig. 14, when the concentration of the sulfur-nitrogen co-doped carbon quantum dots is increased to a certain concentration, the polypyrrole-derived carbon material is agglomerated.

Claims (8)

1. A preparation method of a nitrogen and sulfur co-doped carbon dot regulated polypyrrole derived carbon material is characterized by comprising the following steps: in the environment with the temperature not higher than 5 ℃, the nitrogen and sulfur co-doped carbon dots are dissolved and dispersed into a dilute acid solution under the action of a surfactant, then an initiator and a pyrrole monomer are added into the dilute acid solution to carry out polymerization reaction to obtain a nitrogen and sulfur co-doped carbon dot-polypyrrole composite material, and the nitrogen and sulfur co-doped carbon dot-polypyrrole composite material is calcined to obtain the nitrogen and sulfur carbon dot-polypyrrole composite material.
2. The preparation method of the nitrogen and sulfur co-doped carbon point controlled polypyrrole derived carbon material according to claim 1, wherein the preparation method comprises the following steps: the concentration of the nitrogen and sulfur co-doped carbon dots in the dilute acid solution is 80-400 mg/L.
3. The preparation method of the nitrogen and sulfur co-doped carbon point controlled polypyrrole derived carbon material according to claim 1, wherein the preparation method comprises the following steps:
the surfactant is at least one of quaternary ammonium salt surfactant, sodium octadecyl sulfate, sodium stearate, dioctyl sodium sulfosuccinate, sodium dodecyl benzene sulfonate and sodium glycocholate;
the initiator is persulfate.
4. The preparation method of the nitrogen and sulfur co-doped carbon point controlled polypyrrole derived carbon material according to claim 1 or 3, characterized in that:
the concentration of the surfactant in the dilute acid solution is 2-4 g/L;
the concentration of the initiator in the dilute acid solution is 6-10 g/L;
the concentration of the dilute acid solution is 0.5-1.5 mol L -1 Dilute hydrochloric acid in the range.
5. The preparation method of the nitrogen and sulfur co-doped carbon point controlled polypyrrole derived carbon material according to claim 1, wherein the preparation method comprises the following steps: the concentration of the pyrrole monomer in the dilute acid solution is 8-20 g/L.
6. The preparation method of the nitrogen and sulfur co-doped carbon point controlled polypyrrole derived carbon material according to claim 1, wherein the preparation method comprises the following steps: the calcining conditions are as follows: under the protective atmosphere, at the temperature of 2-10 ℃ for min -1 The temperature is raised to 500-800 ℃ at the temperature raising rate, and the temperature is kept for 5-10 h.
7. The utility model provides a nitrogen and sulfur codoped carbon dot regulation and control polypyrrole derived carbon material which characterized in that: obtained by the production method according to any one of claims 1 to 7.
8. The application of the nitrogen and sulfur co-doped carbon point regulation polypyrrole derived carbon material according to claim 7 is characterized in that: the material is applied as a negative electrode material of a potassium ion battery.
CN202211126703.XA 2022-09-16 2022-09-16 Nitrogen-sulfur co-doped carbon dot regulated polypyrrole derived carbon material, preparation method thereof and application thereof in potassium ion battery Pending CN115312744A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202211126703.XA CN115312744A (en) 2022-09-16 2022-09-16 Nitrogen-sulfur co-doped carbon dot regulated polypyrrole derived carbon material, preparation method thereof and application thereof in potassium ion battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202211126703.XA CN115312744A (en) 2022-09-16 2022-09-16 Nitrogen-sulfur co-doped carbon dot regulated polypyrrole derived carbon material, preparation method thereof and application thereof in potassium ion battery

Publications (1)

Publication Number Publication Date
CN115312744A true CN115312744A (en) 2022-11-08

Family

ID=83866148

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202211126703.XA Pending CN115312744A (en) 2022-09-16 2022-09-16 Nitrogen-sulfur co-doped carbon dot regulated polypyrrole derived carbon material, preparation method thereof and application thereof in potassium ion battery

Country Status (1)

Country Link
CN (1) CN115312744A (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120244429A1 (en) * 2009-08-27 2012-09-27 Lan Trieu Lam Electrical storage device and electrode thereof
WO2015031461A1 (en) * 2013-08-28 2015-03-05 Massachusetts Institute Of Technology Seed for metal dichalcogenide growth by chemical vapor deposition
CN104934232A (en) * 2015-05-13 2015-09-23 东南大学 Titanium dioxide or titanium nitride supported carbon quantum dot modification polypyrrole nanometer array material and preparation method and application thereof
CN110212178A (en) * 2019-05-18 2019-09-06 福建师范大学 A kind of preparation method of nitrogen sulphur codope VN/CNF kalium ion battery negative electrode material

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120244429A1 (en) * 2009-08-27 2012-09-27 Lan Trieu Lam Electrical storage device and electrode thereof
WO2015031461A1 (en) * 2013-08-28 2015-03-05 Massachusetts Institute Of Technology Seed for metal dichalcogenide growth by chemical vapor deposition
CN104934232A (en) * 2015-05-13 2015-09-23 东南大学 Titanium dioxide or titanium nitride supported carbon quantum dot modification polypyrrole nanometer array material and preparation method and application thereof
CN110212178A (en) * 2019-05-18 2019-09-06 福建师范大学 A kind of preparation method of nitrogen sulphur codope VN/CNF kalium ion battery negative electrode material

Similar Documents

Publication Publication Date Title
CN111362254B (en) Preparation method and application of nitrogen-doped carbon nanotube-loaded phosphorus-doped cobaltosic oxide composite material
CN107331867B (en) Preparation method of nitrogen-doped porous carbon material used as negative electrode of sodium-ion battery
CN109037625B (en) Composite material of hierarchical porous carbon and cobalt sulfide, and preparation method and application thereof
CN107275578B (en) Method for manufacturing potassium ion battery cathode by adopting nitrogen-doped porous carbon material
CN112635706B (en) Preparation method of graphene-manganese dioxide nanorod-shaped negative electrode material
CN111146424B (en) Metal sulfide/carbon composite material, and preparation method and application thereof
CN111463418B (en) Carbon-coated nickel selenide ultrathin nanosheet composite material and preparation method thereof
CN108767203B (en) Titanium dioxide nanotube-graphene-sulfur composite material and preparation method and application thereof
CN111180700B (en) Preparation method of N-doped Co nanocluster/N-doped porous carbon/S composite material for high-performance potassium-sulfur battery positive electrode
CN113161533A (en) MOF-derived ZnO @ C composite material and application thereof
CN114702022B (en) Preparation method and application of hard carbon anode material
CN115132981A (en) Binary doped iron-based fluorophosphate sodium ion positive electrode material and preparation method thereof
CN111276694A (en) Preparation method of polyimide derived carbon/molybdenum disulfide negative electrode material and application of polyimide derived carbon/molybdenum disulfide negative electrode material in potassium ion battery
CN114933293A (en) Preparation of sodium vanadium fluorophosphate and application thereof in sodium-ion battery
CN111554874A (en) FeS2-xSexSolid solution cathode material and preparation method thereof
CN116247188A (en) Core-shell structure antimony@porous carbon anode material for sodium ion battery and preparation method and application thereof
CN115966666A (en) Sodium ion battery carbon-based negative electrode material and preparation method thereof
CN115498183A (en) Modified vanadium manganese sodium phosphate cathode material, preparation and application thereof
CN115312744A (en) Nitrogen-sulfur co-doped carbon dot regulated polypyrrole derived carbon material, preparation method thereof and application thereof in potassium ion battery
CN112421027B (en) Surface modified porous hexagonal Na3V2(PO4)2F3Carbon-coated microsphere and preparation method and application thereof
CN115084509A (en) Preparation method and application of selenium indium sulfide/carbon cathode material for potassium ion battery
CN114540989A (en) Preparation method and application of carbon fiber loaded bismuth sulfide material
CN114243007A (en) Nickel disulfide/carbon nanotube composite electrode material and preparation method and application thereof
CN113346064A (en) Sulfur-doped graphene-coated bimetallic sulfide composite material, preparation method and application thereof in sodium-ion battery
CN113193191B (en) Manganous-manganic oxide nanocrystalline @3D honeycomb-shaped hierarchical porous network framework carbon composite material and preparation and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination