CN117443429A - Manganese monoatomic catalyst with high S/N atomic content, preparation method and application thereof in lithium-sulfur battery - Google Patents

Manganese monoatomic catalyst with high S/N atomic content, preparation method and application thereof in lithium-sulfur battery Download PDF

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CN117443429A
CN117443429A CN202311417536.9A CN202311417536A CN117443429A CN 117443429 A CN117443429 A CN 117443429A CN 202311417536 A CN202311417536 A CN 202311417536A CN 117443429 A CN117443429 A CN 117443429A
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catalyst
manganese
ppy
sulfur
atom content
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张凤祥
乔少明
王倩
黄春宏
张强
王旭
蔡川
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Dalian University of Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/417—Polyolefins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/497—Ionic conductivity

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Abstract

Manganese monoatomic catalyst with high S/N atom content, preparation method and application thereof in lithium-sulfur battery, and first, flaky g-C is prepared in a pyrolysis mode 3 N 4 Template, through pyrrole sheetPolymerization reaction of the body A layer of polypyrrole is coated on the surface of the template to form g-C 3 N 4 @ppy composite material. Because the polypyrrole surface has rich nitrogen atoms, a large amount of Mn can be adsorbed 2+ Forming pyrolytic precursor g-C 3 N 4 @Mn-PPy. And fully mixing the precursor with sulfur powder, pyrolyzing, pickling and drying to obtain the catalyst. Due to g-C 3 N 4 The gas with etching effect generated by the template decomposition can regulate and control the pore structure of the catalyst. Meanwhile, in the pyrolysis process, the template decomposition and the sulfur powder evaporation can enable the pyrolysis atmosphere to be rich in S/N atoms, fully contact with the precursor, increase the doping amount and ensure that the S and N atoms in the catalyst are high. The catalytic and polysulfide adsorption capacity of the metal active site is improved due to a large number of nonmetallic atoms; meanwhile, the conductivity of the PPy derivative nitrogen doped carbon carrier is obviously improved. The catalyst, when applied to a lithium sulfur battery as a separator modification material, exhibits excellent specific capacity and excellent cycle stability.

Description

Manganese monoatomic catalyst with high S/N atomic content, preparation method and application thereof in lithium-sulfur battery
Technical Field
The invention belongs to the field of electrochemistry, relates to a manganese monoatomic catalyst with high S/N atomic content, and a preparation method and application thereof, and particularly relates to a preparation method of the manganese monoatomic catalyst with high S/N atomic content and application of the manganese monoatomic catalyst as a modification material in a lithium sulfur battery, so that the catalysis and adsorption effects of the catalyst on polysulfide are improved.
Background
As a novel secondary battery, the lithium-sulfur battery has theoretical specific capacity and energy density respectively as high as 1675mAh g -1 And 2600Wh kg -1 The method comprises the steps of carrying out a first treatment on the surface of the Meanwhile, the sulfur material serving as the main material for redox of the battery anode has the advantages of abundant reserve, low cost, environmental friendliness and the like. Therefore, a lithium-sulfur battery is a promising secondary energy storage system. However, many existing problems greatly limit the commercialization process: (1) Poor conductivity of sulfur and its discharge products results in low sulfur utilization; (2) About 80% of the volume inside the battery changes during charge and discharge; (3) Multiple onesThe "shuttle effect" of the sulfide results in faster decay of specific capacity and lower coulombic efficiency. A series of problems cause degradation in performance and poor safety of the battery, and need to be solved immediately.
Numerous solutions to the above problems are sequentially proposed, and researches show that the catalyst with high conductivity and catalytic activity is supported on a lithium sulfur battery diaphragm, so that the shuttle effect of polysulfide can be effectively inhibited, and the performance of the battery is improved. The catalyst is supported on one side of the diaphragm to block the polysulfide transferring process, so that a positive electrode protection area is formed, and the polysulfide is effectively prevented from entering a negative electrode area. At the same time, due to the high conductivity of the catalyst, the surface discharge product Li of the catalyst can be improved 2 S/Li 2 S 2 The utilization rate of the battery is obviously improved. However, current research on single-atom catalysts has made it difficult to achieve desirable electrochemical performance.
When the metal single-atom catalyst is applied to a lithium sulfur battery as a novel catalyst, the excellent catalysis and anchoring effects of the metal active site can accelerate the transformation of polysulfide and limit the diffusion of polysulfide; meanwhile, the outstanding conductivity of the carbon substrate material can effectively improve the utilization rate of sulfur and discharge products. However, the activity of the metal active site and the conductivity of the support are still not satisfactory for current lithium sulfur battery applications. The non-metal atom doping mode can simultaneously promote the properties of active sites and carriers, and can promote the rate capability and the cycling stability of the battery. Therefore, the content of the hetero atoms in the catalyst is improved, so that the commercialization process of the lithium-sulfur battery can be effectively promoted. At present, research on improving the content of nonmetallic atoms in a monoatomic catalyst is deficient, and the research on a preparation process capable of effectively increasing the content of nonmetallic atoms is necessary for a lithium-sulfur battery.
In order to increase the content of metal atoms in the catalyst, the invention adopts a gas phase doping mode to prepare the manganese monoatomic catalyst rich in S/N atoms, and the process has the following advantages: (1) By using g-C capable of generating gases having etching properties 3 N 4 As a template, the product is of a porous sheet structure, which is beneficial to the transmission of ions/electrons;(2) The template and the sulfur source can generate gas rich in S/N atoms, fully contact and dope the precursor, and can improve the content of heterogeneous S/N atoms in the catalyst; (3) A large number of nonmetallic atoms improve the conductivity and the catalytic/adsorption capacity of the catalyst and improve the battery performance; (4) The preparation process is convenient and quick, has low cost and can realize batch production.
Disclosure of Invention
Aiming at the defects of the synthesis method in the prior art, the invention provides a gas phase doping strategy for preparing a manganese monoatomic catalyst rich in S/N atoms and application of the manganese monoatomic catalyst to a lithium-sulfur battery. For the preparation of the catalyst, first of all sheet-like g-C is prepared by pyrolysis 3 N 4 The template is coated with a layer of polypyrrole on the surface of the template to form g-C through polymerization reaction of pyrrole monomers 3 N 4 @ppy composite material. Because the polypyrrole surface has rich nitrogen atoms, a large amount of Mn can be adsorbed 2+ I.e. forming pyrolytic precursor g-C 3 N 4 @Mn-PPy. And fully mixing the precursor with a certain amount of sulfur powder, performing pyrolysis, and performing acid washing and drying to obtain the catalyst. Due to g-C 3 N 4 The template is decomposed to generate gas with etching effect, and the pore structure of the catalyst can be regulated and controlled. Meanwhile, in the pyrolysis process, the template decomposition and the sulfur powder evaporation can enable the pyrolysis atmosphere to be rich in S/N atoms, fully contact with the precursor, increase the doping amount, and respectively reach the S and N atom contents of 6.38at% and 12.20at% in the prepared catalyst. The catalytic and polysulfide-adsorbing capacity of the metal active site is improved due to a large number of nonmetallic atoms; meanwhile, the conductivity of the PPy derivative nitrogen doped carbon carrier is obviously improved. The catalyst, when applied to a lithium sulfur battery as a separator modification material, exhibits excellent specific capacity and excellent cycle stability.
Based on the above description, the technical scheme of the invention is as follows:
a manganese monoatomic catalyst with high S/N atom content, which is prepared by using g-C 3 N 4 the@PPy is used as a precursor and is obtained by mixing manganese ions and sulfur powder for pyrolysis. Gas generation due to the intrinsic high nitrogen atom content of PPy and template decompositionThe nitrogen atom doping effect of the bulk can increase the nitrogen atom content of the catalyst. The sulfur atom-containing gas generated by the evaporation of the sulfur powder can be fully contacted with the precursor, so that the sulfur atom content is improved. The S and N atom content in the manganese monoatomic catalyst can reach 5.50at% to 6.30at% and 6.32at% to 12.00at%.
A preparation method of a manganese monoatomic catalyst with high S/N atom content comprises the following steps:
the first step: synthesis of g-C 3 N 4 Template
1.1 Placing dicyandiamide in a closed porcelain boat, keeping the temperature at 550-650 ℃ for 4-6h at a heating rate of 2-5 ℃/min in an air atmosphere, and fully grinding the product after naturally cooling to room temperature to obtain a block-shaped g-C 3 N 4 And (3) powder.
1.2 g-C) in block form 3 N 4 Placing in an open porcelain boat, maintaining at 500-600deg.C for 2-4 hr at a heating rate of 3-5deg.C/min under air atmosphere, cooling to room temperature to obtain sheet g-C 3 N 4 And (3) powder.
And a second step of: synthesis of g-C 3 N 4 @PPy composite material
2.1 At room temperature, flaky g-C 3 N 4 Placing in deionized water and carrying out ultrasonic treatment for 15-30 min to enable the solution to be dispersed uniformly, and dripping pyrrole monomer into the solution under the ice bath condition to obtain a mixed solution with uniform dispersion.
2.2 Ammonium persulfate (NH) at room temperature 4 ) 2 S 2 O 8 Slowly add to the mixed solution obtained in step 2.1) and continue stirring for 6-10h. In the process, pyrrole monomers can be in a flake shape g-C under the action of an ammonium persulfate initiator 3 N 4 The surface reacts to form polypyrrole.
2.3 Washing the product with deionized water for several times, and lyophilizing for 12 hr to obtain g-C 3 N 4 @ppy composite material.
In the step 2.1), 0.2-0.3 mu L of pyrrole monomer is added to 1mL of solution.
In the step 2.2), 1.5-2.0g of ammonium persulfate is added to 1mL of the mixed solution.
And a third step of: synthesis of manganese monoatomic catalyst with high S/N atomic content
3.1 g-C at room temperature 3 N 4 Placing the@PPy composite material into deionized water for ultrasonic treatment to uniformly disperse the@PPy composite material, wherein the concentration of the@PPy composite material is 2-3mg/mL; then manganese acetate [ Mn (CH) 3 COO) 2 ]Adding into the above solution, stirring for 6-10 hr, washing with deionized water by suction filtration for several times, and drying to obtain g-C 3 N 4 @Mn-PPy. In this process, positively charged Mn 2+ Ions are adsorbed on the surface of the composite material due to electrostatic adsorption.
3.2 Fully mixing the product obtained in the step 3.1) with sulfur powder, and then carrying out step pyrolysis, specifically: in Ar atmosphere, heating to 500-600 ℃ at a heating rate of 2-3 ℃/min, and keeping for 4-6h, wherein in the process, sulfur powder is evaporated to form sulfur-rich atom atmosphere; heating to 900-950 deg.C at a heating rate of 4-6deg.C/min, maintaining for 2-3 hr, and naturally cooling to obtain g-C 3 N 4 The template decomposes to produce an etching gas rich in nitrogen atoms.
3.3 (ii) subjecting the product obtained in step 3.2) to a temperature of 60-90℃with 0.5-1mol/L H 2 SO 4 Washing with deionized water to neutrality after 5-8h of acid washing, and vacuum drying to obtain the manganese monoatomic catalyst with high S/N atom content.
In the step 3.1), the addition amount of the manganese acetate is g-C 3 N 4 0.5-1 times of the mass of the@PPy composite material.
In the step 3.2), the addition amount of the sulfur powder is g-C 3 N 4 1 to 1.5 times of the mass of the@PPy composite material.
The application of the manganese monoatomic catalyst with high S/N atom content in the lithium sulfur battery is characterized in that the synthesized catalyst is used for modifying a PP diaphragm of a commercial battery and is applied to the lithium sulfur battery, and the specific operation steps are as follows:
the first step: preparation of modified separator
The prepared catalyst, carbon nano tube and binder (PVDF) are mixed according to the mass ratio of 8:1:1, mixing and grinding fully, adding the obtained mixture into a proper amount of isopropanol for ultrasonic treatment to uniformly disperse the mixture, loading a catalyst on a PP diaphragm by adopting a suction filtration mode, and drying at 60 ℃ for 12 hours to obtain the modified diaphragm.
And a second step of: preparation of Sulfur/carbon cathode
Sublimated sulfur and BP-2000 are mixed according to the mass ratio of 75:25 was sufficiently ground and then kept at 155℃for 12 hours under Ar atmosphere. Mixing the obtained powder with Super P and PVDF according to the mass ratio of 7:2:1 after mixing and grinding thoroughly, NMP was added and stirred for 12h. The resulting homogeneously mixed slurry was knife coated on aluminum foil and dried at 60 ℃ for 12h.
And a third step of: assembled lithium sulfur battery
The prepared composite diaphragm, the sulfur/carbon positive electrode and the lithium sheet are assembled into a lithium-sulfur battery, the addition amount of electrolyte on the positive electrode side is 25 mu L, the addition amount on the negative electrode side is 15 mu L, and the sulfur load is 1mg/cm 2 。
The beneficial effects of the invention are as follows:
1) The preparation process of the catalyst is convenient and quick, the raw material cost is low, and the catalyst is environment-friendly, and on the basis, the process can effectively improve the nonmetallic S/N atom content in the single-atom catalyst, so that the catalyst has a good benefit effect.
2) The content of nonmetallic atoms in the catalyst is improved by adopting a gas phase doping strategy, and the doping steps are completed in the pyrolysis process by selecting a decomposable template and evaporated sulfur powder as S and N sources, so that the content and uniformity of nonmetallic atoms can be improved, complex steps such as template removal and the like are avoided, and mass production is easy to carry out.
3) The catalyst has a large amount of S/N atoms, so that on one hand, the catalytic and polysulfide adsorption capacity of Mn-N active sites can be improved, the reaction kinetics of polysulfide is improved, and the shuttle effect is inhibited; on the other hand, the conductivity of the carrier can be improved, and the utilization rate of sulfur and discharge products thereof can be improved. Based on the above effects, the lithium-sulfur battery assembled by the modified separator has excellent multiplying power and cycle performance.
4) The loading of the catalyst on the modified membrane is only 0.15mg/cm 2 Good performance (specific capacity decay is only 0.016% per cycle after 1600 cycles at 2C current density) can be achieved at low loadings, for this catalyst on the cellHas good prospect in application.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) picture of the catalyst prepared in example 1;
FIG. 2 is a Transmission Electron Microscope (TEM) image of the catalyst prepared in example 1;
FIG. 3 is the result of an X-ray absorption fine structure (XAFS) test of the catalyst prepared in example 1;
FIG. 4 is a wavelet transform EXAFS signal (color depth in the figure represents bond concentration) for the catalyst prepared in example 1;
FIG. 5 is the rate capability of the lithium sulfur battery catalyst prepared in example 1;
fig. 6 shows the cycle performance of the lithium sulfur battery catalyst prepared in example 1.
Detailed Description
The following further describes the preparation method of the S/N atom-enriched manganese monoatomic catalyst by the specific embodiment
Embodiment case 1: preparation of MnSNC catalyst
The first step: synthesis of g-C 3 N 4 Template
Placing a proper amount of dicyandiamide into a closed porcelain boat, keeping the temperature at 550 ℃ for 6 hours at a heating rate of 5 ℃/min in an air atmosphere, and fully grinding the product after naturally cooling to room temperature to obtain a block-shaped g-C 3 N 4 And (3) powder. Then, a proper amount of block-shaped g-C is taken 3 N 4 Placing into an open porcelain boat, maintaining at 600deg.C for 4 hr at a heating rate of 5 deg.C/min under air atmosphere, and cooling to room temperature to obtain sheet g-C 3 N 4 A powder;
and a second step of: synthesis of g-C 3 N 4 @PPy composite material
Sheet-like g-C 3 N 4 Put into deionized water and ultrasonic to disperse evenly (the concentration is 1.25 g/mL), and pyrrole monomer is added dropwise into the solution under ice bath condition and stirred for a period of time (the addition amount is 0.3 mu L/mL). Subsequently, a certain amount of ammonium persulfate [ (NH) 4 ) 2 S 2 O 8 The addition amount is 2.0g/mL]Slowly add to the solution and continue stirringAnd stirring for 10 hours. Finally, the product is washed for a plurality of times by deionized water, and is frozen and dried for 12 hours to obtain g-C 3 N 4 A @ PPy composite;
and a third step of: synthesis of manganese monoatomic catalyst with high S/N atomic content
The prepared g-C 3 N 4 Placing the@PPy composite material into deionized water for ultrasonic treatment to uniformly disperse the@PPy composite material (the concentration is 3 mg/mL); subsequently, manganese acetate [ Mn (CH) 3 COO) 2 ]Adding into the above solution, stirring (adding amount is g-C) 3 N 4 1 time of the mass of the@PPy composite material), washing the composite material with deionized water for a plurality of times, and drying the composite material to obtain g-C 3 N 4 @Mn-PPy. Mixing the obtained product with sulfur powder (sulfur powder with addition amount of g-C) 3 N 4 1.5 times the mass of the @ PPy composite material) to be subjected to step pyrolysis: in Ar atmosphere, heating to 600 ℃ at a heating rate of 3 ℃/min, and keeping for 6 hours; then heating to 950 ℃ at a heating rate of 6 ℃/min, keeping for 3 hours, and naturally cooling. The obtained product was treated with 1mol/L H at a temperature of 90 DEG C 2 SO 4 Washing with deionized water to neutrality after 8h of acid washing, and vacuum drying to obtain the manganese monoatomic catalyst with high S/N atom content. The S and N atom content in the manganese monoatomic catalyst is 6.38at% and 12.20at%.
The morphology of the prepared catalyst is shown in figure 1, and the catalyst is in a flake shape due to g-C 3 N 4 And (3) a template effect, wherein the appearance of the obtained catalyst is a sheet structure. Meanwhile, in order to show the internal structure of the sample, TEM test (as shown in fig. 2) was performed, and the catalyst contained a large amount of graphitic carbon structure. At the same time, a large number of pore structures are present due to the etching gas of the template. The coordination structure of the Mn atom was analyzed by X-ray absorption fine structure test (FIG. 3), and it was confirmed that Mn was immobilized by the N atom and exists in the form of a single atom without bonding to the S atom, and the coordination manner of Mn and N atom was MnN 4 Configuration. Further, the wavelet transform contour map (fig. 4) also demonstrates this conclusion.
Fourth step, application of the obtained catalyst in lithium-sulfur battery
1. Preparation of modified separator
The prepared catalyst, carbon nano tube and binder (PVDF) are mixed according to the mass ratio of 8:1:1, mixing and grinding fully, adding the obtained mixture into a proper amount of isopropanol for ultrasonic treatment to uniformly disperse the mixture, loading a catalyst on a PP diaphragm by adopting a suction filtration mode, and drying at 60 ℃ for 12 hours to obtain the modified diaphragm.
2. Preparation of Sulfur/carbon cathode
Sublimated sulfur and BP-2000 are mixed according to the mass ratio of 75:25 was sufficiently ground and then kept at 155℃for 12 hours under Ar atmosphere. Mixing the obtained powder with Super P and PVDF according to the mass ratio of 7:2:1 after mixing and grinding thoroughly, NMP was added and stirred for 12h. The resulting homogeneously mixed slurry was knife coated on aluminum foil and dried at 60 ℃ for 12h.
3. Assembled lithium sulfur battery
The prepared composite diaphragm, the sulfur/carbon positive electrode and the lithium sheet are assembled into a lithium-sulfur battery, the addition amount of electrolyte on the positive electrode side is 25 mu L, the addition amount on the negative electrode side is 15 mu L, and the sulfur load is 1mg/cm 2 。
The assembled lithium sulfur battery was used for electrochemical performance testing, and the results are shown in fig. 5 and 6. When the current density is 0.1C, the first-circle specific capacity of the battery is up to 1526.3mAh/g; when the current density rises to 5C, the specific capacity of the battery is still kept at 486.5mAh/g; at a current density of 2C, the specific capacity decay after 1600 cycles is only 0.016% per cycle. The rate and cycle stability tests show that the prepared catalyst has good conductivity and polysulfide limiting/catalyzing capability.
Embodiment case 2: preparation of MnSNC catalyst
The first step: synthesis of g-C 3 N 4 Template
Placing a proper amount of dicyandiamide into a closed porcelain boat, keeping the temperature at 650 ℃ for 4 hours at a heating rate of 2 ℃/min in an air atmosphere, and fully grinding the product after naturally cooling to room temperature to obtain a block-shaped g-C 3 N 4 And (3) powder. Then, a proper amount of block-shaped g-C is taken 3 N 4 Placing into an open porcelain boat, maintaining at 500deg.C for 2 hr at a heating rate of 3deg.C/min under air atmosphere, and cooling to room temperature to obtain sheet g-C 3 N 4 A powder;
and a second step of: synthesis of g-C 3 N 4 @PPy composite material
Sheet-like g-C 3 N 4 Placing in deionized water and ultrasonic to make it disperse uniformly (concentration is 0.75 g/mL), under ice bath condition, adding pyrrole monomer dropwise into the above-mentioned solution and stirring for a period of time (adding quantity is 0.2 mu L/mL). Subsequently, a certain amount of ammonium persulfate [ (NH) 4 ) 2 S 2 O 8 The addition amount is 1.5g/mL]Slowly add to the solution and continue stirring for 6h. Finally, the product is washed for a plurality of times by deionized water, and is frozen and dried for 12 hours to obtain g-C 3 N 4 A @ PPy composite;
and a third step of: synthesis of manganese monoatomic catalyst with high S/N atomic content
The prepared g-C 3 N 4 Placing the@PPy composite material into deionized water for ultrasonic treatment to uniformly disperse the@PPy composite material (the concentration is 2 mg/mL); subsequently, manganese acetate [ Mn (CH) 3 COO) 2 ]Adding into the above solution, stirring (adding amount is g-C) 3 N 4 0.5 times of the mass of the@PPy composite material), washing the composite material with deionized water for a plurality of times, and drying the composite material to obtain g-C 3 N 4 @Mn-PPy. Mixing the obtained product with sulfur powder (sulfur powder with addition amount of g-C) 3 N 4 1 times the mass of the @ PPy composite material) to be subjected to step pyrolysis: in Ar atmosphere, heating to 500 ℃ at a heating rate of 2 ℃/min, and keeping for 4 hours; then heating to 900 ℃ at a heating rate of 4 ℃/min, keeping for 2 hours, and naturally cooling. The resulting product was purified at 60℃using 0.5mol/L H 2 SO 4 Washing with deionized water to neutrality after 5h of acid washing, and vacuum drying to obtain the manganese monoatomic catalyst with high S/N atom content. The S and N atom content in the manganese monoatomic catalyst is 6.40at% and 12.25at%.
Fourth step, application of the obtained catalyst in lithium-sulfur battery
1. Preparation of modified separator
The prepared catalyst, carbon nano tube and binder (PVDF) are mixed according to the mass ratio of 8:1:1, mixing and grinding fully, adding the obtained mixture into a proper amount of isopropanol for ultrasonic treatment to uniformly disperse the mixture, loading a catalyst on a PP diaphragm by adopting a suction filtration mode, and drying at 60 ℃ for 12 hours to obtain the modified diaphragm.
2. Preparation of Sulfur/carbon cathode
Sublimated sulfur and BP-2000 are mixed according to the mass ratio of 75:25 was sufficiently ground and then kept at 155℃for 12 hours under Ar atmosphere. Mixing the obtained powder with Super P and PVDF according to the mass ratio of 7:2:1 after mixing and grinding thoroughly, NMP was added and stirred for 12h. The resulting homogeneously mixed slurry was knife coated on aluminum foil and dried at 60 ℃ for 12h.
3. Assembled lithium sulfur battery
The prepared composite diaphragm, the sulfur/carbon positive electrode and the lithium sheet are assembled into a lithium-sulfur battery, the addition amount of electrolyte on the positive electrode side is 25 mu L, the addition amount on the negative electrode side is 15 mu L, and the sulfur load is 1mg/cm 2 。
The assembled lithium sulfur battery was used for electrochemical performance testing. When the current density is 0.1C, the first-circle specific capacity of the battery is up to 1541.2mAh/g; when the current density rises to 5C, the specific capacity of the battery is still kept at 512.3mAh/g; at a current density of 2C, the specific capacity decay was only 0.014% per revolution after 1600 cycles. The rate and cycle stability tests show that the prepared catalyst has good conductivity and polysulfide limiting/catalyzing capability.
Embodiment 3: preparation of MnSNC catalyst
The first step: synthesis of g-C 3 N 4 Template
Placing a proper amount of dicyandiamide into a closed porcelain boat, keeping the temperature at 600 ℃ for 3 hours at a heating rate of 3 ℃/min in an air atmosphere, and fully grinding the product after naturally cooling to room temperature to obtain a block-shaped g-C 3 N 4 And (3) powder. Then, a proper amount of block-shaped g-C is taken 3 N 4 Placing in an open porcelain boat, maintaining at 550deg.C at a heating rate of 4deg.C/min under air atmosphere for 3 hr, and cooling to room temperature to obtain sheet g-C 3 N 4 A powder;
and a second step of: synthesis of g-C 3 N 4 @PPy composite material
Sheet-like g-C 3 N 4 Placing into deionized water, ultrasonic dispersing to obtain solution (concentration of 1 g/mL), adding pyrrole monomer dropwise into the solution under ice bath condition, and stirring for a period of time (adding amount of 0.25)Mu L/mL). Subsequently, a certain amount of ammonium persulfate [ (NH) 4 ) 2 S 2 O 8 The addition amount is 1.75g/mL]Slowly add to the solution and continue stirring for 8h. Finally, the product is washed for a plurality of times by deionized water, and is frozen and dried for 12 hours to obtain g-C 3 N 4 A @ PPy composite;
and a third step of: synthesis of manganese monoatomic catalyst with high S/N atomic content
The prepared g-C 3 N 4 Placing the@PPy composite material into deionized water for ultrasonic treatment to uniformly disperse the@PPy composite material (the concentration is 2.5 mg/mL); subsequently, manganese acetate [ Mn (CH) 3 COO) 2 ]Adding into the above solution, stirring (adding amount is g-C) 3 N 4 0.75 times of the weight of the@PPy composite material), washing the composite material with deionized water for a plurality of times, and drying the composite material to obtain g-C 3 N 4 @Mn-PPy. Mixing the obtained product with sulfur powder (sulfur powder with addition amount of g-C) 3 N 4 1.25 times the mass of the @ PPy composite material) to be subjected to step pyrolysis: heating to 550 ℃ at a heating rate of 2.5 ℃/min in Ar atmosphere, and keeping for 5 hours; then heating to 920 ℃ at a heating rate of 4 ℃/min, keeping for 2.5 hours, and naturally cooling. The resulting product was purified at 80℃using 0.75mol/L H 2 SO 4 Washing with deionized water to neutrality after acid washing for 7h, and vacuum drying to obtain the manganese monoatomic catalyst with high S/N atom content. The S and N atom content in the manganese monoatomic catalyst is 6.52at% and 12.20at%.
Fourth step, application of the obtained catalyst in lithium-sulfur battery
1. Preparation of modified separator
The prepared catalyst, carbon nano tube and binder (PVDF) are mixed according to the mass ratio of 8:1:1, mixing and grinding fully, adding the obtained mixture into a proper amount of isopropanol for ultrasonic treatment to uniformly disperse the mixture, loading a catalyst on a PP diaphragm by adopting a suction filtration mode, and drying at 60 ℃ for 12 hours to obtain the modified diaphragm.
2. Preparation of Sulfur/carbon cathode
Sublimated sulfur and BP-2000 are mixed according to the mass ratio of 75:25 was sufficiently ground and then kept at 155℃for 12 hours under Ar atmosphere. Mixing the obtained powder with Super P and PVDF according to the mass ratio of 7:2:1 after mixing and grinding thoroughly, NMP was added and stirred for 12h. The resulting homogeneously mixed slurry was knife coated on aluminum foil and dried at 60 ℃ for 12h.
3. Assembled lithium sulfur battery
The prepared composite diaphragm, the sulfur/carbon positive electrode and the lithium sheet are assembled into a lithium-sulfur battery, the addition amount of electrolyte on the positive electrode side is 25 mu L, the addition amount on the negative electrode side is 15 mu L, and the sulfur load is 1mg/cm 2 。
The assembled lithium sulfur battery was used for electrochemical performance testing. When the current density is 0.1C, the first-circle specific capacity of the battery is up to 1554.3mAh/g; when the current density rises to 5C, the specific capacity of the battery is still kept at 540.2mAh/g; at a current density of 2C, the specific capacity decay after 1600 cycles is only 0.015% per cycle. The rate and cycle stability tests show that the prepared catalyst has good conductivity and polysulfide limiting/catalyzing capability.
Embodiment 4: preparation of SNC catalyst
The first step: synthesis of g-C 3 N 4 Template
Placing a proper amount of dicyandiamide into a closed porcelain boat, keeping the temperature at 650 ℃ for 4 hours at a heating rate of 2 ℃/min in an air atmosphere, and fully grinding the product after naturally cooling to room temperature to obtain a block-shaped g-C 3 N 4 And (3) powder. Then, a proper amount of block-shaped g-C is taken 3 N 4 Placing into an open porcelain boat, maintaining at 600deg.C for 2 hr at a heating rate of 3deg.C/min under air atmosphere, and cooling to room temperature to obtain sheet g-C 3 N 4 A powder;
and a second step of: synthesis of g-C 3 N 4 @PPy composite material
Sheet-like g-C 3 N 4 Placing in deionized water and ultrasonic to make it disperse uniformly (concentration is 0.75 g/mL), under ice bath condition, adding pyrrole monomer dropwise into the above-mentioned solution and stirring for a period of time (adding quantity is 0.2 mu L/mL). Subsequently, a certain amount of ammonium persulfate [ (NH) 4 ) 2 S 2 O 8 The addition amount is 1.5g/mL]Slowly add to the solution and continue stirring for 6h. Finally, the product is washed for a plurality of times by deionized water, and is frozen and dried for 12 hours to obtain g-C 3 N 4 A @ PPy composite;
and a third step of: synthesis of manganese monoatomic catalyst with high S/N atomic content
The prepared g-C 3 N 4 The @ PPy composite material is fully mixed with sulfur powder (the addition amount of the sulfur powder is g-C) 3 N 4 1.25 times the mass of the @ PPy composite material) to be subjected to step pyrolysis: in Ar atmosphere, heating to 500 ℃ at a heating rate of 2 ℃/min, and keeping for 4 hours; then heating to 900 ℃ at a heating rate of 4 ℃/min, keeping for 2 hours, and naturally cooling. The resulting product was purified at 60℃using 0.5mol/L H 2 SO 4 Washing with deionized water to neutrality after 5h acid washing, and vacuum drying to obtain the catalyst with high S/N atom content. The S and N atom content in the manganese monoatomic catalyst is 6.45at% and 12.30at%.
Fourth step, application of the obtained catalyst in lithium-sulfur battery
1. Preparation of modified separator
The prepared catalyst, carbon nano tube and binder (PVDF) are mixed according to the mass ratio of 8:1:1, mixing and grinding fully, adding the obtained mixture into a proper amount of isopropanol for ultrasonic treatment to uniformly disperse the mixture, loading a catalyst on a PP diaphragm by adopting a suction filtration mode, and drying at 60 ℃ for 12 hours to obtain the modified diaphragm.
2. Preparation of Sulfur/carbon cathode
Sublimated sulfur and BP-2000 are mixed according to the mass ratio of 75:25 was sufficiently ground and then kept at 155℃for 12 hours under Ar atmosphere. Mixing the obtained powder with Super P and PVDF according to the mass ratio of 7:2:1 after mixing and grinding thoroughly, NMP was added and stirred for 12h. The resulting homogeneously mixed slurry was knife coated on aluminum foil and dried at 60 ℃ for 12h.
3. Assembled lithium sulfur battery
The prepared composite diaphragm, the sulfur/carbon positive electrode and the lithium sheet are assembled into a lithium-sulfur battery, the addition amount of electrolyte on the positive electrode side is 25 mu L, the addition amount on the negative electrode side is 15 mu L, and the sulfur load is 1mg/cm 2 。
The assembled lithium sulfur battery was used for electrochemical performance testing. When the current density is 0.1C, the first-circle specific capacity of the battery is up to 1550.9mAh/g; when the current density rises to 5C, the specific capacity of the battery is still kept at 530.8mAh/g; at a current density of 2C, the specific capacity decay was only 0.014% per revolution after 1600 cycles. The rate and cycle stability tests show that the prepared catalyst has good conductivity and polysulfide limiting/catalyzing capability.
Embodiment case 5: preparation of NC catalyst
The first step: synthesis of g-C 3 N 4 Template
Placing a proper amount of dicyandiamide into a closed porcelain boat, keeping the temperature at 550 ℃ for 4 hours at a heating rate of 2 ℃/min in an air atmosphere, and fully grinding the product after naturally cooling to room temperature to obtain a block-shaped g-C 3 N 4 And (3) powder. Then, a proper amount of block-shaped g-C is taken 3 N 4 Placing into an open porcelain boat, maintaining at 500deg.C for 2 hr at a heating rate of 3deg.C/min under air atmosphere, and cooling to room temperature to obtain sheet g-C 3 N 4 A powder;
and a second step of: synthesis of g-C 3 N 4 @PPy composite material
Sheet-like g-C 3 N 4 Placing in deionized water and ultrasonic to make it disperse uniformly (concentration is 0.75 g/mL), under ice bath condition, adding pyrrole monomer dropwise into the above-mentioned solution and stirring for a period of time (adding quantity is 0.2 mu L/mL). Subsequently, a certain amount of ammonium persulfate [ (NH) 4 ) 2 S 2 O 8 The addition amount is 1.5g/mL]Slowly add to the solution and continue stirring for 6h. Finally, the product is washed for a plurality of times by deionized water, and is frozen and dried for 12 hours to obtain g-C 3 N 4 A @ PPy composite;
and a third step of: synthesis of manganese monoatomic catalyst with high S/N atomic content
The prepared g-C 3 N 4 Carrying out step-by-step pyrolysis on the@PPy composite material: in Ar atmosphere, heating to 500 ℃ at a heating rate of 2 ℃/min, and keeping for 4 hours; then heating to 900 ℃ at a heating rate of 4 ℃/min, keeping for 2 hours, and naturally cooling. The resulting product was purified at 60℃using 0.5mol/L H 2 SO 4 Washing with deionized water to neutrality after pickling for 5h, and vacuum drying to obtain NC manganese monoatomic catalyst. The S and N atom content in the manganese monoatomic catalyst is 6.32at% and 12.15at%。
Fourth step, application of the obtained catalyst in lithium-sulfur battery
1. Preparation of modified separator
The prepared catalyst, carbon nano tube and binder (PVDF) are mixed according to the mass ratio of 8:1:1, mixing and grinding fully, adding the obtained mixture into a proper amount of isopropanol for ultrasonic treatment to uniformly disperse the mixture, loading a catalyst on a PP diaphragm by adopting a suction filtration mode, and drying at 60 ℃ for 12 hours to obtain the modified diaphragm.
2. Preparation of Sulfur/carbon cathode
Sublimated sulfur and BP-2000 are mixed according to the mass ratio of 75:25 was sufficiently ground and then kept at 155℃for 12 hours under Ar atmosphere. Mixing the obtained powder with Super P and PVDF according to the mass ratio of 7:2:1 after mixing and grinding thoroughly, NMP was added and stirred for 12h. The resulting homogeneously mixed slurry was knife coated on aluminum foil and dried at 60 ℃ for 12h.
3. Assembled lithium sulfur battery
The prepared composite diaphragm, the sulfur/carbon positive electrode and the lithium sheet are assembled into a lithium-sulfur battery, the addition amount of electrolyte on the positive electrode side is 25 mu L, the addition amount on the negative electrode side is 15 mu L, and the sulfur load is 1mg/cm 2 。
The assembled lithium sulfur battery was used for electrochemical performance testing. When the current density is 0.1C, the first-circle specific capacity of the battery is up to 1490.2mAh/g; when the current density rises to 5C, the specific capacity of the battery is still kept at 469.3mAh/g; at a current density of 2C, the specific capacity decay after 1600 cycles was only 0.018% per cycle. The rate and cycle stability tests show that the prepared catalyst has good conductivity and polysulfide limiting/catalyzing capability.
The above examples merely represent embodiments of the present invention and are not to be construed as limiting the scope of the patent. It should be noted that variations and modifications can be made by those skilled in the art without departing from the spirit of the invention, which falls within the scope of the invention.

Claims (10)

1. A manganese monoatomic catalyst with high S/N atom content is characterized in thatThe catalyst is expressed in g-C 3 N 4 the@PPy is used as a precursor and is obtained by mixing manganese ions and sulfur powder for pyrolysis; the S and N atom content in the manganese monoatomic catalyst can reach 5.50at% to 6.30at% and 6.32at% to 12.00at%.
2. A process for preparing a manganese monoatomic catalyst having a high S/N atom content as claimed in claim 1 or 2, characterized in that, firstly, the sheet-like g-C is prepared by pyrolysis 3 N 4 A template; secondly, coating a layer of polypyrrole on the surface of the template through polymerization reaction of pyrrole monomers to form g-C 3 N 4 A @ PPy composite; again, the composite material is adsorbed with Mn 2+ Forming pyrolytic precursor g-C 3 N 4 @Mn-PPy; and finally, fully mixing the precursor with sulfur powder, pyrolyzing, pickling and drying to obtain the catalyst.
3. The method for preparing the manganese monoatomic catalyst with high S/N atomic content according to claim 2, comprising the following steps:
the first step: synthesis of g-C 3 N 4 Template
1.1 Placing dicyandiamide in a closed porcelain boat, keeping the temperature at 550-650 ℃ for 4-6h at a heating rate of 2-5 ℃/min in an air atmosphere, and fully grinding the product after naturally cooling to room temperature to obtain a block-shaped g-C 3 N 4 A powder;
1.2 g-C) in block form 3 N 4 Placing into an open porcelain boat, heating to 500-600deg.C under air atmosphere, maintaining for 2-4 hr, cooling to room temperature to obtain sheet g-C 3 N 4 A powder;
and a second step of: synthesis of g-C 3 N 4 @PPy composite material
2.1 Plate-like g-C 3 N 4 Placing the solution in deionized water and carrying out ultrasonic treatment to uniformly disperse the solution, and dropwise adding pyrrole monomers into the solution under the ice bath condition to obtain a uniformly dispersed mixed solution;
2.2 Ammonium persulfate (NH) 4 ) 2 S 2 O 8 Slow and slowAdding the mixture obtained in the step 2.1) into the mixed solution and continuously stirring for 6-10h;
2.3 Washing with deionized water, and lyophilizing to obtain g-C 3 N 4 A @ PPy composite;
and a third step of: synthesis of manganese monoatomic catalyst with high S/N atomic content
3.1 g-C) 3 N 4 Placing the@PPy composite material into deionized water for ultrasonic treatment to uniformly disperse the@PPy composite material; then manganese acetate [ Mn (CH) 3 COO) 2 ]Adding into the above solution, stirring for 6-10 hr, washing with deionized water for several times, and drying to obtain g-C 3 N 4 @Mn-PPy；
3.2 Fully mixing the product obtained in the step 3.1) with sulfur powder, and then carrying out fractional pyrolysis;
3.3 (ii) subjecting the product obtained in step 3.2) to H at a temperature of 60-90 DEG C 2 SO 4 Washing with deionized water to neutrality after acid washing, and vacuum drying to obtain the manganese monoatomic catalyst with high S/N atom content.
4. The method for preparing a manganese monoatomic catalyst having a high S/N atom content according to claim 3, wherein in the step 2.1), 0.2 to 0.3. Mu.L of the pyrrole monomer is added to 1mL of the solution.
5. The method for preparing a manganese monoatomic catalyst having a high S/N atom content according to claim 3, wherein in the step 2.2), 1.5 to 2.0g of ammonium persulfate is added to 1mL of the mixed solution.
6. The method for preparing a manganese monoatomic catalyst having a high S/N atom content according to claim 3, wherein in step 3.1), g-C 3 N 4 The concentration of the @ PPy composite in deionized water is 2-3mg/mL.
7. The method for preparing a manganese monoatomic catalyst having a high S/N atom content according to claim 3, wherein in step 3.1), the manganese acetate is added in an amount of g-C 3 N 4 @PPy composite material0.5-1 times of the mass of the material.
8. The method for preparing a manganese monoatomic catalyst having a high S/N atom content according to claim 3, wherein the sulfur powder is added in an amount of g-C in step 3.2) 3 N 4 1 to 1.5 times of the mass of the@PPy composite material.
9. The method for preparing a manganese monoatomic catalyst with high S/N atom content according to claim 3, wherein in the step 3.2) step pyrolysis process: in Ar atmosphere, heating from room temperature to 500-600 ℃ and keeping for 4-6 h; heating to 900-950 deg.C, maintaining for 2-3 hr, and naturally cooling.
10. The application of the manganese monoatomic catalyst with high S/N atom content in a lithium sulfur battery is characterized in that the catalyst synthesized by the preparation method of any one of claims 2-9 is applied to the lithium sulfur battery and used for modifying a PP diaphragm of the commercial battery.
CN202311417536.9A 2023-10-30 2023-10-30 Manganese monoatomic catalyst with high S/N atomic content, preparation method and application thereof in lithium-sulfur battery Pending CN117443429A (en)

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