CN113649043A - Preparation method of high-load Mn-N active site doped carbon material catalyst and application of catalyst in lithium-sulfur battery - Google Patents
Preparation method of high-load Mn-N active site doped carbon material catalyst and application of catalyst in lithium-sulfur battery Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229910018648 Mn—N Inorganic materials 0.000 title claims abstract 17
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- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 7
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 7
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- 238000011068 loading method Methods 0.000 description 14
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
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- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- AAMATCKFMHVIDO-UHFFFAOYSA-N azane;1h-pyrrole Chemical compound N.C=1C=CNC=1 AAMATCKFMHVIDO-UHFFFAOYSA-N 0.000 description 1
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 description 1
- RBVYPNHAAJQXIW-UHFFFAOYSA-N azanylidynemanganese Chemical compound [N].[Mn] RBVYPNHAAJQXIW-UHFFFAOYSA-N 0.000 description 1
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- 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
-
- B01J35/33—
-
- 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
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
-
- 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 provides a preparation method of a high-load Mn-N active site doped carbon material catalyst and application of the catalyst in a lithium-sulfur battery, and belongs to the field of energy storage batteries. The catalyst adopts a manganese-doped zinc-based metal organic framework Mn-ZIF-8 as a precursor, and zinc Zn atoms and ammonia NH are evaporated through high-temperature pyrolysis3The treatment increases the number of the anchoring sites of vacancies and nitrogen atoms on the substrate material, and then secondary adsorption of manganese ions increases the doping amount of Mn-N sites. The synthesis method adopts the in-situ supported Mn-N sites in two steps, and simultaneously optimizes the catalystThe aperture structure improves the doping amount of nitrogen atoms. When the catalyst prepared by the method is applied to a lithium-sulfur battery, the high-load Mn-N active sites and nitrogen atoms not only increase the catalytic and adsorption effects of the catalyst on polysulfide, but also ensure elemental sulfur and Li on the high-conductivity carbon material substrate2S/Li2S2Higher utilization ratio.
Description
Technical Field
The invention belongs to the field of electrochemistry, relates to a Mn-N active site doped carbon material catalyst, and a preparation method and application thereof, and particularly relates to a preparation method of a high-load Mn-N active site doped carbon material catalyst, and application of the high-load Mn-N active site doped carbon material catalyst as a modification material to a lithium-sulfur battery diaphragm modification material, so that the effects of catalysis and adsorption on polysulfide are achieved.
Background
The lithium-sulfur battery is a novel secondary energy storage battery and has higher theoretical specific capacity (1675mAh g)-1) And energy density (2600Wh kg)-1) (ii) a Meanwhile, the elemental sulfur as the anode material has the advantages of wide source, low price, small pollution and the like. Therefore, the method is a promising secondary energy storage system. However, its many deficiencies greatly limit its development: (1) the low utilization of elemental sulfur (conductivity of about 5 x 10) due to its insulating properties-30S cm-125 ℃); (2) the volume change inside the battery is large (about 80%) during the charging and discharging process; (3) the specific capacity due to the "shuttle effect" of polysulfides decays faster and with lower coulombic efficiency.
A plurality of solutions are provided for researchers of the problems, and the results show that the introduction of a high-conductivity material (carbon material, MXene) and the compounding of elemental sulfur can effectively improve the utilization rate of sulfur. By adopting the high specific surface area (hollow structure and core-shell structure), the volume change in the charging and discharging process can be effectively relieved, and the safety of the battery is guaranteed. The "shuttle effect" is inhibited by both physical/chemical effects, one is the use of a "molecular sieve" effect to prevent the polysulfide from diffusing to the negative region; another approach is to limit the diffusion by forming chemical bonds with polysulfides.
When metal-nitrogen (M-N) active sites are supported on a carbon material as a catalyst for application to a lithium-sulfur battery, the excellent catalytic and anchoring effects of the M-N active sites can accelerate the conversion of polysulfides and limit their diffusion; meanwhile, the outstanding conductivity of the carbon substrate material can also effectively improve the utilization rate of sulfur and discharge products. However, the low loading of M-N active sites on carbon materials has been the biggest problem faced by this type of catalyst. Particularly, the preparation of the high-load manganese-nitrogen (Mn-N) active site doped carbon catalyst is realized because the manganese element has more valence states (0 to +7) and is easy to form a compound; meanwhile, the catalyst is very easy to agglomerate into clusters or particle structures in the pyrolysis process, and the like, so that the preparation of the catalyst is more difficult.
In order to solve the problems, the invention adopts a two-step in-situ preparation process of a high-load Mn-N active site, and the process has the following advantages: (1) the used process can effectively improve the loading capacity of the Mn-N active sites on the carbon material; (2) the intrinsic high nitrogen content of a Metal Organic Framework (MOF) and the ammonia gas treatment can greatly increase the doping amount of nitrogen atoms; (3) the ammonia etching effect and the zinc atom evaporation can greatly optimize the pore diameter structure of the catalyst; (4) the preparation steps of the whole experimental process are in-situ doping of active sites, which is beneficial to further optimization of the catalyst performance.
Disclosure of Invention
Aiming at the defects of a synthesis method in the prior art, the invention provides a preparation method for preparing a high-load Mn-N active site doped carbon material catalyst in situ and application of the catalyst in a lithium-sulfur battery. For the preparation of the catalyst, Mn is first introduced using a "doping" step2+Manganese acetate forms a Mn-ZIF-8 precursor in ZIF-8 to be used as a first step for in-situ preparation of the Mn-N active site supported catalyst. After two-step pyrolysis (NH3+ Ar), extra N element can be doped into the catalyst due to the etching effect of ammonia gas; meanwhile, Zn atoms can be provided with holes to limit Mn atoms under the high-temperature condition through evaporation, so that the catalyst after the first step is finished has enough defect nitrogen anchoring sites and spaces to limit Mn atoms2+. On the basis of the first step, the catalyst is mixed with Mn2+Mixing (manganese acetate, manganese chloride and the like) solution for secondary in-situ adsorption of Mn2+The catalyst prepared by the steps of adsorption, pyrolysis and acid washing is the catalyst of the high-load Mn-N active site doped carbon material. The prepared catalyst has Mn-N active sites with higher loading capacity; at the same time, the content of nitrogen atoms is also due to NH3The treatment is promoted; the carbon material derived from the metal organic framework also has high conductivity, so that the catalyst has good performance on polysulfideCatalysis and adsorption effects. When the catalyst is used as a diaphragm modification material to be applied to a lithium-sulfur battery, excellent specific capacity and outstanding cycling stability are shown.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a high-load Mn-N active site doped carbon catalyst takes Mn-ZIF-8 as a precursor and is prepared by NH3The atmosphere treatment and the evaporation effect of Zn atoms provide enough nitrogen atom anchoring sites and space confinement effect for the catalyst, and further the high-load Mn-N site catalyst is prepared. The Mn atom content in the prepared catalyst is 2.31 wt% (ICP-MS), and the Mn-N bond content is up to 11.75% (XPS).
A preparation method for preparing a high-load Mn-N active site doped carbon material catalyst comprises the following steps:
the first step is as follows: synthesis of Mn-ZIF-8 precursor
Dissolving 2-methylimidazole in a methanol solution, and fully stirring to obtain a solution A with the concentration of 1.0-1.4 mmol/mL; dissolving zinc nitrate hexahydrate and manganese acetate in a methanol solution, and uniformly stirring to obtain a solution B with the concentrations of the zinc nitrate hexahydrate and the manganese acetate being 0.18-0.22mmol/mL and 0.04-0.06mmol/mL respectively. And (3) adding the solution B into the solution A with the same volume at room temperature, slowly stirring for 30-60min, standing for 20-26h to obtain a precipitate, washing the precipitate with ethanol for multiple times, and vacuum-drying at 60-80 ℃ for 12-16h to obtain the Mn-ZIF-8 precursor.
The second step is that: catalyst for synthesizing low-load Mn-N active site doped carbon material
Pyrolyzing a Mn-ZIF-8 precursor, controlling the heating rate to be 3-5 ℃/min in an argon atmosphere, heating to 750 ℃ and keeping for 0.5-1.5 h; then introducing ammonia gas, keeping the temperature constant for 1.5-2h, replacing with argon gas atmosphere, continuously heating to 900-; the obtained product is used for 0.5mol/L H at the temperature of 70-80 DEG C2SO4Stirring the solution for 5-8h for acid washing, washing the acid-washed material with deionized water to neutrality (pH 7), and drying in vacuum at 60-80 ℃ for 12-16h to obtain the low-load Mn-N active site doped carbon material catalyst.
The third step: catalyst for synthesizing high-load Mn-N active site doped carbon material
Dissolving the catalyst obtained in the second step in deionized water, performing ultrasonic treatment for 1.5-2h to form uniformly dispersed suspension, adding a manganese ion-containing compound into the solution to provide manganese ions, wherein the mass of the manganese ion compound is 1/4-1/3 of the mass of the catalyst, and stirring the mixed solution for 2-3 h. And (3) performing suction filtration and cleaning on the product after the reaction is finished for multiple times by using deionized water, performing vacuum drying for 12-16h at the temperature of 60-80 ℃, heating the obtained powder sample from room temperature to 900-950 ℃ in an argon atmosphere, performing pyrolysis for 2.5-3h, cooling to room temperature, and performing an acid cleaning step to obtain the final product.
The compound containing manganese ions in the third step is manganese acetate and manganese chloride.
And the temperature rise rate in the third step is 3-5 ℃/min.
The acid washing in the third step is carried out at 70-80 ℃ by adopting 0.5mol/L H2SO4The solution was stirred for 5-8 h.
The application of a high-load Mn-N active site doped carbon material catalyst in a lithium sulfur battery is characterized in that the synthesized catalyst is used for modifying a commercial PP diaphragm of the lithium sulfur battery and is applied to the lithium sulfur battery, and the specific operation steps are as follows:
the first step is as follows: preparation of modified membranes
Mixing the prepared catalyst and a binder (PVDF) in a mass ratio of 9: 1, fully mixing and grinding, adding NMP into the obtained mixture, stirring at room temperature for 12 hours to obtain catalyst slurry, coating the catalyst slurry on a PP diaphragm by a scraper, and drying at 60 ℃ for 12 hours.
The second step is that: preparation of Sulfur/carbon anodes
Sublimed sulfur and carbon black are mixed according to the mass ratio of 7: 3 grinding fully, and keeping at 155 ℃ for 12h under Ar atmosphere. Mixing the obtained powder with Super P and PVDF according to a mass ratio of 7: 2: 1 and adding NMP and stirring for 12 hours after fully mixing and grinding. The resulting homogeneously mixed slurry was knife coated on aluminum foil (sulfur loading was adjusted by knife thickness) and dried at 60 ℃ for 12 h.
The third step: assembled lithium-sulfur battery
Assembling the prepared composite diaphragm, a sulfur/carbon positive electrode and a lithium sheet into a lithium-sulfur battery, wherein the addition amount of electrolyte on the positive electrode side is 25 mu L and the negative electrode side is negativeThe amount of the added electrode side was 15. mu.L, and the sulfur loading amount was 1.2mg/cm2。
The invention has the beneficial effects that:
1) the preparation raw materials of the catalyst are low in price and easy to obtain, and on the basis, the process can effectively improve the loading capacity of Mn-N active sites and nitrogen atoms on the carbon material, so that the catalyst has a good benefit effect.
2) The prepared catalyst firstly adopts an in-situ doping process and then adopts an in-situ adsorption process, the whole process flow adopts in-situ preparation defects, the removal process of a coating layer and a template is not involved, and good guarantee can be provided for the subsequent performance optimization of the catalyst.
3) The high-load Mn-N active sites and defect N atoms in the catalyst can effectively improve the conversion speed of polysulfide in the lithium-sulfur battery, and can limit the shuttle effect of the polysulfide to a great extent by being used as a modified diaphragm material, so that the polysulfide is limited in an anode region and a lithium cathode is protected; on the other hand, the carbon material derived from the Metal Organic Framework (MOF) as the carrier of the active site can inherit the advantage of the MOF material of high specific surface area, has excellent conductivity, and can promote sulfur simple substance and discharge product (Li)2S/Li2S2) The utilization ratio of (2).
4) When the catalyst is applied to a lithium-sulfur battery as a diaphragm modification material, the specific capacity and the cycling stability of the lithium-sulfur battery can be effectively improved.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) picture of the catalyst prepared in example 1;
FIG. 2 is a graph of XPS N1 s peak fitting results for the catalyst prepared in example 1;
FIG. 3 is a graph of rate performance of a lithium sulfur battery using the catalyst prepared in example 1;
FIG. 4 shows the cycle performance of the catalyst prepared in example 1 applied to a lithium sulfur battery;
FIG. 5 is a flow chart of the present invention for preparing a highly loaded Mn-N site doped carbon catalyst.
Detailed description of the preferred embodiments
The preparation method of the highly loaded Mn-N active site catalyst is further illustrated by the following specific embodiment
Example 1 (schematic preparation scheme shown in fig. 5):
first, synthesizing Mn-ZIF-8 precursor
Taking 30mL of 2-methyl imidazole methanol solution A with the concentration of 1.2 mmol/mL; adding 30mL of methanol into zinc nitrate hexahydrate and manganese acetate to ensure that the concentrations of the two are 0.2mmol/mL and 0.05mmol/mL respectively, and stirring for 30min to obtain a solution B. And (3) adding the solution B into the solution A at room temperature, slowly stirring for 50min, standing for 24h to obtain a precipitate, washing the precipitate with ethanol for multiple times, and performing vacuum drying at 70 ℃ for 14h to obtain the Mn-ZIF-8 precursor.
Second step, synthesizing low load Mn-N active site catalyst
Pyrolyzing a Mn-ZIF-8 precursor, controlling the heating rate to be 5 ℃/min in an argon atmosphere, heating to 750 ℃ and keeping for 1 h; then introducing ammonia gas, keeping the temperature constant for 1.5h, replacing with argon gas atmosphere, continuously heating to 950 ℃, keeping the temperature constant for 2.5h, and naturally cooling to room temperature; the obtained product is used for 0.5mol/L H at the temperature of 80 DEG C2SO4The solution is stirred for 5H for acid washing (H)2SO4The ratio of the solution to the catalyst is 1mg/mL), washing the material after acid washing to be neutral (pH is 7) by using deionized water, and drying the material in vacuum at 70 ℃ for 14h to obtain the low-load Mn-N active site doped carbon material catalyst.
Step three, synthesizing a high-load Mn-N active site catalyst
Dissolving the catalyst obtained in the second step in deionized water, performing ultrasonic treatment for 1.5h to form uniformly dispersed suspension, adding manganese acetate into the solution, adding 1/4 taking the mass of the manganese acetate as the mass of the catalyst, and stirring the mixed solution for 2 h. Performing suction filtration and cleaning on the product after the reaction is finished for multiple times by using deionized water, performing vacuum drying at 70 ℃ for 14h, heating the obtained powder sample to 900 ℃ in an argon atmosphere, performing pyrolysis for 2.5h (the heating rate is 5 ℃/min), cooling to room temperature, and performing acid cleaning (0.5 mol/L H is used at 80℃)2SO4The solution is stirred for 5h) to obtain the final product.
The morphology of the prepared catalyst is shown in figure 1, the morphology of ZIF-8 is still maintained after different post-treatments, and the surface of a sample is in a rough state due to the etching effect of ammonia treatment. Meanwhile, in order to show the contents of Mn-N active sites and N atoms in the sample, XPS test (as shown in FIG. 2) is performed, and after fitting and calculation, the contents of Mn-N bonds, pyridine nitrogen and pyrrole nitrogen in the sample are respectively: 11.75%, 28.98%, and 20.74%, indicating that the samples have a higher content of Mn — N active sites and defective nitrogen atoms for catalyzing polysulfide conversion and limiting its "shuttling effect".
The fourth step, the use of the obtained catalyst in lithium-sulfur batteries
Preparing a modified diaphragm:
mixing the prepared catalyst and a binder (PVDF) in a mass ratio of 9: 1, fully mixing and grinding, adding NMP into the obtained mixture, stirring at room temperature for 12 hours to obtain catalyst slurry, coating the catalyst slurry on a PP diaphragm by a scraper, and drying at 60 ℃ for 12 hours.
Preparing a sulfur/carbon positive electrode:
sublimed sulfur and carbon black are mixed according to the mass ratio of 7: 3 grinding fully, and keeping at 155 ℃ for 12h under Ar atmosphere. Mixing the obtained powder with Super P and PVDF according to a mass ratio of 7: 2: 1 and adding NMP and stirring for 12 hours after fully mixing and grinding. The resulting homogeneously mixed slurry was knife coated on aluminum foil (sulfur loading was adjusted by knife thickness) and dried at 60 ℃ for 12 h.
Assembling the lithium-sulfur battery:
assembling the prepared composite diaphragm, a sulfur/carbon positive electrode and a lithium sheet into a lithium-sulfur battery, wherein the adding amount of electrolyte on the positive electrode side is 25 mu L, the adding amount of electrolyte on the negative electrode side is 15 mu L, and the sulfur loading amount is 1.2mg/cm2。
The assembled lithium sulfur battery was used for electrochemical performance tests, and the results are shown in fig. 3 and 4. When the current density is 0.1C, the specific capacity of the first circle of the battery is up to 1596 mAh/g; when the current density is increased to 2C, the specific capacity of the battery is still maintained at 581 mAh/g; under the condition that the current density is 0.5C, after 200 cycles, the specific volume retention rate is 91.0%. Rate test and cycle stability test show that the prepared catalyst has good conductivity and polysulfide limiting/catalyzing capability.
Example 2:
first, synthesizing Mn-ZIF-8 precursor
Taking 30mL of 2-methyl imidazole methanol solution A with the concentration of 1.0 mmol/mL; adding 30mL of methanol into zinc nitrate hexahydrate and manganese acetate to ensure that the concentrations of the two are 0.18mmol/mL and 0.04mmol/mL respectively, and stirring for 30min to obtain a solution B. And (3) adding the solution B into the solution A at room temperature, slowly stirring for 30min, standing for 20h to obtain a precipitate, washing the precipitate with ethanol for multiple times, and vacuum-drying at 60 ℃ for 12h to obtain the Mn-ZIF-8 precursor.
Second step, synthesizing low load Mn-N active site catalyst
Pyrolyzing a Mn-ZIF-8 precursor, controlling the heating rate to be 3 ℃/min in an argon atmosphere, heating to 750 ℃ and keeping for 0.5 h; then introducing ammonia gas, keeping the temperature constant for 1.5h, replacing with argon gas atmosphere, continuously heating to 900 ℃, keeping the temperature constant for 2.5h, and naturally cooling to room temperature; the obtained product is used for 0.5mol/L H at the temperature of 70 DEG C2SO4The solution is stirred for 5H for acid washing (H)2SO4The ratio of the solution to the catalyst is 1mg/mL), the material after acid washing is washed to be neutral (PH is 7) by deionized water, and the material is dried in vacuum at 60 ℃ for 12h to obtain the low-load Mn-N active site doped carbon material catalyst.
Step three, synthesizing a high-load Mn-N active site catalyst
Dissolving the catalyst obtained in the second step in deionized water, performing ultrasonic treatment for 1.5h to form uniformly dispersed suspension, adding manganese chloride into the solution, adding 1/4 (mass of the manganese chloride is equal to that of the catalyst), and stirring the mixed solution for 2 h. Repeatedly filtering and cleaning the product after the reaction is finished with deionized water, drying for 12h under vacuum at 60 ℃, heating the obtained powder sample to 900 ℃ in argon atmosphere for pyrolysis for 2.5h (the heating rate is 3 ℃/min), cooling to room temperature, and then pickling (0.5 mol/L H is used under the condition of 70℃)2SO4The solution is stirred for 5h) to obtain the final product.
The fourth step, the use of the obtained catalyst in lithium-sulfur batteries
Preparing a modified diaphragm:
mixing the prepared catalyst and a binder (PVDF) in a mass ratio of 9: 1, fully mixing and grinding, adding NMP into the obtained mixture, stirring at room temperature for 12 hours to obtain catalyst slurry, coating the catalyst slurry on a PP diaphragm by a scraper, and drying at 60 ℃ for 12 hours.
Preparing a sulfur/carbon positive electrode:
sublimed sulfur and carbon black are mixed according to the mass ratio of 7: 3 grinding fully, and keeping at 155 ℃ for 12h under Ar atmosphere. Mixing the obtained powder with Super P and PVDF according to a mass ratio of 7: 2: 1 and adding NMP and stirring for 12 hours after fully mixing and grinding. The resulting homogeneously mixed slurry was knife coated on aluminum foil (sulfur loading was adjusted by knife thickness) and dried at 60 ℃ for 12 h.
Assembling the lithium-sulfur battery:
assembling the prepared composite diaphragm, a sulfur/carbon positive electrode and a lithium sheet into a lithium-sulfur battery, wherein the adding amount of electrolyte on the positive electrode side is 25 mu L, the adding amount of electrolyte on the negative electrode side is 15 mu L, and the sulfur loading amount is 1.2mg/cm2。
Example 3:
first, synthesizing Mn-ZIF-8 precursor
Taking 30mL of 2-methyl imidazole methanol solution A with the concentration of 1.4 mmol/mL; adding 30mL of methanol into zinc nitrate hexahydrate and manganese acetate to ensure that the concentrations of the two are 0.22mmol/mL and 0.06mmol/mL respectively, and stirring for 30min to obtain a solution B. And (3) adding the solution B into the solution A at room temperature, slowly stirring for 60min, standing for 26h to obtain a precipitate, washing the precipitate with ethanol for multiple times, and vacuum-drying at 80 ℃ for 16h to obtain the Mn-ZIF-8 precursor.
Second step, synthesizing low load Mn-N active site catalyst
Pyrolyzing a Mn-ZIF-8 precursor, controlling the heating rate to be 5 ℃/min in an argon atmosphere, heating to 750 ℃ and keeping for 1.5 h; then introducing ammonia gas, keeping the temperature constant for 2 hours, replacing the ammonia gas with argon gas, continuously heating to 950 ℃, keeping the temperature constant for 2.5 hours, and naturally cooling to room temperature; the obtained product is used for 0.5mol/L H at the temperature of 80 DEG C2SO4The solution is stirred for 8H for acid washing (H)2SO4The ratio of the solution to the catalyst was 1.5mg/mL), the material after acid washing was washed to neutrality (PH 7) with deionized water, and dried under vacuum at 80 ℃ for 16h to obtain a low-load Mn — N active site doped carbon material catalyst.
Step three, synthesizing a high-load Mn-N active site catalyst
Dissolving the catalyst obtained in the second step in deionized water, performing ultrasonic treatment for 2 hours to form uniformly dispersed suspension, adding manganese acetate into the solution, adding 1/3 taking the mass of the manganese acetate as the mass of the catalyst, and stirring the mixed solution for 3 hours. Performing suction filtration and cleaning on the product after the reaction is finished for multiple times by using deionized water, performing vacuum drying for 16h at 80 ℃, heating the obtained powder sample to 950 ℃ in argon atmosphere for pyrolysis for 2.5h (the heating rate is 5 ℃/min), cooling to room temperature, and performing acid cleaning (0.5 mol/L H is used at 80℃)2SO4The solution is stirred for 8h) to obtain the final product.
The fourth step, the use of the obtained catalyst in lithium-sulfur batteries
Preparing a modified diaphragm:
mixing the prepared catalyst and a binder (PVDF) in a mass ratio of 9: 1, fully mixing and grinding, adding NMP into the obtained mixture, stirring at room temperature for 12 hours to obtain catalyst slurry, coating the catalyst slurry on a PP diaphragm by a scraper, and drying at 60 ℃ for 12 hours.
Preparing a sulfur/carbon positive electrode:
sublimed sulfur and carbon black are mixed according to the mass ratio of 7: 3 grinding fully, and keeping at 155 ℃ for 12h under Ar atmosphere. Mixing the obtained powder with Super P and PVDF according to a mass ratio of 7: 2: 1 and adding NMP and stirring for 12 hours after fully mixing and grinding. The resulting homogeneously mixed slurry was knife coated on aluminum foil (sulfur loading was adjusted by knife thickness) and dried at 60 ℃ for 12 h.
Assembling the lithium-sulfur battery:
assembling the prepared composite diaphragm, a sulfur/carbon positive electrode and a lithium sheet into a lithium-sulfur battery, wherein the adding amount of electrolyte on the positive electrode side is 25 mu L, the adding amount of electrolyte on the negative electrode side is 15 mu L, and the sulfur loading amount is 1.2mg/cm2。
Example 4:
first, synthesizing Mn-ZIF-8 precursor
Taking 30mL of 2-methyl imidazole methanol solution A with the concentration of 1.0 mmol/mL; adding 30mL of methanol into zinc nitrate hexahydrate and manganese acetate to ensure that the concentrations of the two are 0.20mmol/mL and 0.04mmol/mL respectively, and stirring for 30min to obtain a solution B. And (3) adding the solution B into the solution A at room temperature, slowly stirring for 60min, standing for 20h to obtain a precipitate, washing the precipitate with ethanol for multiple times, and vacuum-drying at 60 ℃ for 16h to obtain the Mn-ZIF-8 precursor.
Second step, synthesizing low load Mn-N active site catalyst
Pyrolyzing a Mn-ZIF-8 precursor, controlling the heating rate to be 3 ℃/min in an argon atmosphere, heating to 750 ℃ and keeping for 1.5 h; then introducing ammonia gas, keeping the temperature constant for 1.5h, replacing with argon gas atmosphere, continuously heating to 950 ℃, keeping the temperature constant for 2.5h, and naturally cooling to room temperature; the obtained product is used for 0.5mol/L H at the temperature of 70 DEG C2SO4The solution is stirred for 8H for acid washing (H)2SO4The ratio of the solution to the catalyst was 1.5mg/mL), the material after acid washing was washed to neutrality (PH 7) with deionized water, and dried under vacuum at 60 ℃ for 16h to obtain a low-load Mn — N active site doped carbon material catalyst.
Step three, synthesizing a high-load Mn-N active site catalyst
Dissolving the catalyst obtained in the second step in deionized water, performing ultrasonic treatment for 1.5h to form uniformly dispersed suspension, adding manganese chloride into the solution, adding 1/4 (mass of the manganese chloride is equal to that of the catalyst), and stirring the mixed solution for 3 h. Repeatedly filtering and cleaning the product after the reaction is finished by deionized water, drying for 16h under vacuum at 60 ℃, heating the obtained powder sample to 950 ℃ in argon atmosphere for pyrolysis for 3h (the heating rate is 3 ℃/min), cooling to room temperature, and then pickling (0.5 mol/L H is used under the condition of 80℃)2SO4The solution is stirred for 8h) to obtain the final product.
The fourth step, the use of the obtained catalyst in lithium-sulfur batteries
Preparing a modified diaphragm:
mixing the prepared catalyst and a binder (PVDF) in a mass ratio of 9: 1, fully mixing and grinding, adding NMP into the obtained mixture, stirring at room temperature for 12 hours to obtain catalyst slurry, coating the catalyst slurry on a PP diaphragm by a scraper, and drying at 60 ℃ for 12 hours.
Preparing a sulfur/carbon positive electrode:
sublimed sulfur and carbon black are mixed according to the mass ratio of 7: 3 grinding fully, and keeping at 155 ℃ for 12h under Ar atmosphere. Mixing the obtained powder with Super P and PVDF according to a mass ratio of 7: 2: 1 and adding NMP and stirring for 12 hours after fully mixing and grinding. The resulting homogeneously mixed slurry was knife coated on aluminum foil (sulfur loading was adjusted by knife thickness) and dried at 60 ℃ for 12 h.
Assembling the lithium-sulfur battery:
assembling the prepared composite diaphragm, a sulfur/carbon positive electrode and a lithium sheet into a lithium-sulfur battery, wherein the adding amount of electrolyte on the positive electrode side is 25 mu L, the adding amount of electrolyte on the negative electrode side is 15 mu L, and the sulfur loading amount is 1.2mg/cm2。
The above examples merely represent embodiments of the present invention and are not to be construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.
Claims (8)
1. A preparation method for preparing a high-load Mn-N active site doped carbon material catalyst is characterized by comprising the following steps:
the first step is as follows: synthesis of Mn-ZIF-8 precursor
Dissolving 2-methylimidazole in a methanol solution, and fully stirring to obtain a solution A with the concentration of 1.0-1.4 mmol/mL; dissolving zinc nitrate hexahydrate and manganese acetate in a methanol solution, and uniformly stirring to obtain a solution B with the concentrations of the zinc nitrate hexahydrate and the manganese acetate being 0.18-0.22mmol/mL and 0.04-0.06mmol/mL respectively; adding the solution B into the solution A with the same volume at room temperature, slowly stirring for 30-60min, standing for 20-26h to obtain precipitate, washing the precipitate with ethanol for multiple times, and vacuum drying to obtain a Mn-ZIF-8 precursor;
the second step is that: catalyst for synthesizing low-load Mn-N active site doped carbon material
Pyrolyzing a Mn-ZIF-8 precursor, controlling the heating rate to be 3-5 ℃/min in an argon atmosphere, heating to 750 ℃ and keeping for 0.5-1.5 h; then introducing ammonia gas, keeping the temperature constant for 1.5-2h, continuing to heat to 900-year heat-preservation temperature of 950 ℃ in the argon atmosphere, keeping the temperature constant for 2.5h, and naturally cooling to room temperature; subjecting the obtained product to reaction with H at 70-80 deg.C2SO4The solution is stirred for 5 to 8 hoursCarrying out acid washing, washing the material after acid washing to be neutral by using deionized water, and carrying out vacuum drying to obtain the low-load Mn-N active site doped carbon material catalyst;
the third step: catalyst for synthesizing high-load Mn-N active site doped carbon material
Dissolving the catalyst obtained in the second step in deionized water, performing ultrasonic treatment to obtain uniformly dispersed suspension, adding a manganese ion-containing compound into the solution to provide manganese ions, wherein the mass of the manganese ion compound is 1/4-1/3 of the mass of the catalyst, and stirring the mixed solution for 2-3 hours; and (3) performing suction filtration and cleaning on the product after the reaction is finished for multiple times by using deionized water, heating the powder sample from room temperature to 900-950 ℃ in an argon atmosphere after vacuum drying, pyrolyzing for 2.5-3h, cooling to room temperature, and performing an acid cleaning step to obtain the final product.
2. The method for preparing a catalyst of a highly loaded Mn-N active site doped carbon material as claimed in claim 1, wherein the vacuum drying temperature is 60-80 ℃ and the drying time is 12-16 h.
3. The method for preparing a catalyst of a highly loaded Mn-N active site doped carbon material as claimed in claim 1, wherein the sonication time in the second step is 1.5-2 h.
4. The method for preparing a catalyst of a highly loaded Mn-N active site doped carbon material as claimed in claim 1, wherein the manganese ion-containing compound in the third step is manganese acetate or manganese chloride.
5. The method for preparing a catalyst of a highly loaded Mn-N active site doped carbon material as claimed in claim 1, wherein the temperature increase rate in the third step is 3-5 ℃/min.
6. The method for preparing a catalyst of a highly loaded Mn-N active site doped carbon material as claimed in claim 1, wherein the acid washing in the third step isAt 70-80 deg.C using 0.5mol/L H2SO4The solution was stirred for 5-8 h.
7. A method for preparing a highly loaded Mn-N active site doped carbon material catalyst, wherein the highly loaded Mn-N active site doped carbon material catalyst is not prepared by the preparation method according to any one of claims 1 to 6.
8. The application of the high-load Mn-N active site doped carbon material catalyst in the lithium sulfur battery according to claim 7, wherein the synthesized catalyst is used for modifying a commercial PP (propene polymer) diaphragm of the lithium sulfur battery and is applied to the lithium sulfur battery.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114361454A (en) * | 2022-01-07 | 2022-04-15 | 中创新航科技股份有限公司 | Composite carbon material for lithium-sulfur battery, preparation method thereof and lithium-sulfur battery comprising same |
| CN114774972A (en) * | 2022-04-13 | 2022-07-22 | 浙江大学衢州研究院 | Method for synthesizing nitrogen-doped carbon-based single-atom catalyst through metal solid phase diffusion, product and application thereof |
| CN114904548A (en) * | 2022-04-18 | 2022-08-16 | 电子科技大学 | Bifunctional material capable of adsorbing and catalyzing polysulfide conversion and preparation method thereof |
| CN114944494A (en) * | 2022-06-01 | 2022-08-26 | 厦门大学 | Method for preparing high-purity M-N type monatomic carbon-based catalyst on large scale at low temperature and application |
| CN114976484A (en) * | 2022-07-11 | 2022-08-30 | 大连理工大学 | Loaded with Ni 2 P-Co Schottky junction active site urchin-shaped carbon material electrocatalyst, preparation method and application thereof |
| CN115057488A (en) * | 2022-07-12 | 2022-09-16 | 合肥国轩高科动力能源有限公司 | Lithium ion battery positive electrode material with special morphology and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018034501A1 (en) * | 2016-08-17 | 2018-02-22 | 부산대학교 산학협력단 | Multi-layered separator, coated with catalyst layer, for lithium sulfur batteries and lithium sulfur battery using same |
| CN110085822A (en) * | 2019-04-18 | 2019-08-02 | 江苏理工学院 | A kind of F-N-C composite material and preparation method and application |
| CN110752380A (en) * | 2019-09-10 | 2020-02-04 | 东南大学 | ZIF-8 derived hollow Fe/Cu-N-C type oxygen reduction catalyst and preparation method and application thereof |
| CN112239230A (en) * | 2020-10-15 | 2021-01-19 | 北京理工大学 | Hierarchical structure coating diaphragm for lithium-sulfur battery and preparation method thereof |
| CN112973754A (en) * | 2021-03-01 | 2021-06-18 | 南开大学 | Preparation method of novel transition metal monoatomic catalyst loaded on carbon-based material |
-
2021
- 2021-08-17 CN CN202110942517.2A patent/CN113649043B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018034501A1 (en) * | 2016-08-17 | 2018-02-22 | 부산대학교 산학협력단 | Multi-layered separator, coated with catalyst layer, for lithium sulfur batteries and lithium sulfur battery using same |
| CN110085822A (en) * | 2019-04-18 | 2019-08-02 | 江苏理工学院 | A kind of F-N-C composite material and preparation method and application |
| CN110752380A (en) * | 2019-09-10 | 2020-02-04 | 东南大学 | ZIF-8 derived hollow Fe/Cu-N-C type oxygen reduction catalyst and preparation method and application thereof |
| CN112239230A (en) * | 2020-10-15 | 2021-01-19 | 北京理工大学 | Hierarchical structure coating diaphragm for lithium-sulfur battery and preparation method thereof |
| CN112973754A (en) * | 2021-03-01 | 2021-06-18 | 南开大学 | Preparation method of novel transition metal monoatomic catalyst loaded on carbon-based material |
Non-Patent Citations (1)
| Title |
|---|
| LONGTAO REN ET AL.: "Catalytic separators with Co-N-C nanoreactors for high-performance lithium-sulfur batteries", 《INORGANIC CHEMISTRY FRONTIERS》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114361454A (en) * | 2022-01-07 | 2022-04-15 | 中创新航科技股份有限公司 | Composite carbon material for lithium-sulfur battery, preparation method thereof and lithium-sulfur battery comprising same |
| CN114361454B (en) * | 2022-01-07 | 2023-08-15 | 中创新航科技股份有限公司 | Composite carbon material for lithium-sulfur battery, preparation method of composite carbon material and lithium-sulfur battery comprising composite carbon material |
| CN114774972A (en) * | 2022-04-13 | 2022-07-22 | 浙江大学衢州研究院 | Method for synthesizing nitrogen-doped carbon-based single-atom catalyst through metal solid phase diffusion, product and application thereof |
| CN114774972B (en) * | 2022-04-13 | 2023-12-08 | 浙江大学衢州研究院 | Method for synthesizing nitrogen-doped carbon-based single-atom catalyst by metal solid-phase diffusion, product and application thereof |
| CN114904548A (en) * | 2022-04-18 | 2022-08-16 | 电子科技大学 | Bifunctional material capable of adsorbing and catalyzing polysulfide conversion and preparation method thereof |
| CN114944494A (en) * | 2022-06-01 | 2022-08-26 | 厦门大学 | Method for preparing high-purity M-N type monatomic carbon-based catalyst on large scale at low temperature and application |
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| CN115057488A (en) * | 2022-07-12 | 2022-09-16 | 合肥国轩高科动力能源有限公司 | Lithium ion battery positive electrode material with special morphology and preparation method and application thereof |
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