CN113649043B - 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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- 239000003054 catalyst Substances 0.000 title claims abstract description 114
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229910018648 Mn—N Inorganic materials 0.000 title claims abstract 14
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims abstract description 23
- 239000002243 precursor Substances 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910001437 manganese ion Inorganic materials 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 51
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- 238000004140 cleaning Methods 0.000 claims description 9
- 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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- 239000011565 manganese chloride Substances 0.000 claims description 7
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- 239000011701 zinc Substances 0.000 abstract description 3
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- 239000012621 metal-organic framework Substances 0.000 description 6
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- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
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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
- 238000006555 catalytic reaction Methods 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
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- 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
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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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
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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
- H01M10/42—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
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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
- 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
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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
- 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
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- 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
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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 pyrolysis 3 The 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 loaded Mn-N sites in two steps, simultaneously optimizes the pore diameter structure of the catalyst and 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 substrate 2 S/Li 2 S 2 Higher utilization of the process.
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 (1675 mAh g) -1 ) And energy density (2600 Wh 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, many of its own deficiencies have greatly limited its development: (1) The low utilization of elemental sulfur (conductivity of about 5 x 10) due to its insulating properties -30 S cm -1 25 ℃); (2) The volume change inside the battery is large (about 80%) during charging and discharging; (3) The specific capacity due to the "shuttle effect" of polysulfides decays more rapidly and with lower coulombic efficiency.
A plurality of solutions are provided for researchers aiming at the problems, and the results show that the utilization rate of sulfur can be effectively improved by introducing a high-conductivity material (carbon material and MXene) to be compounded with sulfur simple substances. 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 two physical/chemical actions, one is to use the "molecular sieve" action to prevent the polysulfide from diffusing to the negative electrode area; 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 the 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 flow 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 is toIn the preparation of the catalyst, mn is first introduced by means of a "doping" step 2+ 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 (NH 3+ Ar), extra N element enters the catalyst due to the etching effect of ammonia gas and the doping of the extra N element; 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 atoms 2+ . On the basis of the first step, the catalyst is mixed with Mn 2+ Mixing (manganese acetate, manganese chloride and the like) solution for secondary in-situ adsorption of Mn 2+ 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 NH 3 The treatment is promoted; the carbon material derived from the metal organic framework also has higher conductivity, so that the catalyst has good catalytic and adsorption effects on polysulfide. 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 highly loaded Mn-N active site doped carbon catalyst takes Mn-ZIF-8 as a precursor and passes through NH 3 The 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 2.31wt% (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 at room temperature, adding the solution B into the solution A with the same volume, slowly stirring for 30-60min, standing for 20-26h to obtain a precipitate, washing the precipitate with ethanol for multiple times, and performing 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 0.5-1.5h; then introducing ammonia gas, keeping the temperature constant for 1.5-2h, replacing with argon gas atmosphere, continuously heating to 900-950 ℃, keeping the temperature constant for 2.5h, and naturally cooling to room temperature; the obtained product is treated with 0.5mol/L H at 70-80 DEG C 2 SO 4 Stirring the solution for 5-8h for acid washing, washing the acid-washed material with deionized water to be neutral (PH = 7), and drying the material 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 that of the catalyst, and stirring the mixed solution for 2-3h. 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, pyrolyzing for 2.5-3h, cooling to room temperature, and performing an acid washing step to obtain the final product.
The manganese ion-containing compound in the third step is manganese acetate or manganese chloride.
And the temperature rise rate in the third step is 3-5 ℃/min.
The third step is that 0.5mol/L H is adopted at 70-80 DEG C 2 SO 4 The solution was stirred for 5-8h.
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: 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 uniformly mixed slurry was knife coated on aluminum foil (sulfur loading was adjusted by knife coating thickness) and dried at 60 ℃ for 12h.
The third step: assembled lithium-sulfur battery
The prepared composite diaphragm, the sulfur/carbon anode and the lithium sheet are assembled into the lithium-sulfur battery, the addition of the electrolyte on the anode side is 25 mu L, the addition of the electrolyte on the cathode side is 15 mu L, and the sulfur loading capacity is 1.2mg/cm 2 。
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 be used as a modified diaphragm material to limit the shuttle effect of the polysulfide to the maximum extent, so that the polysulfide is limited in the positive electrode area, and the lithium negative electrode is protected; on the other hand, metal Organic Framework (MOF) -derived carbon materials as active sitesThe carrier can inherit the advantage of high specific surface area of the MOF material, has excellent conductivity, and can promote sulfur simple substances and discharge products (Li) 2 S/Li 2 S 2 ) 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 methanol solution A with the concentration of 2-methylimidazole being 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.
Secondly, synthesizing the low-load Mn-N active site catalyst
Pyrolyzing a Mn-ZIF-8 precursor, firstly controlling the heating rate to be 5 ℃/min in the argon atmosphere, heating to 750 ℃ and keeping for 1h; 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; will be provided withThe obtained product is treated with 0.5mol/L H at 80 DEG C 2 SO 4 The solution was stirred for 5H for acid washing (H) 2 SO 4 The ratio of the solution to the catalyst is 1 mg/mL), the material after acid washing is washed to be neutral (pH = 7) by deionized water, and vacuum drying is carried out at 70 ℃ for 14h, so as 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, wherein the mass of the manganese acetate is 1/4 of that of the catalyst, and stirring the mixed solution for 2h. 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, pyrolyzing for 2.5H (the heating rate is 5 ℃/min), cooling to room temperature, and performing acid cleaning (using 0.5mol/L H at 80 ℃) after the temperature is cooled to room temperature 2 SO 4 The solution is stirred for 5 h) 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, mixing and fully grinding, adding NMP into the obtained mixture, stirring for 12 hours at room temperature to obtain catalyst slurry, coating the catalyst slurry on a PP diaphragm by scraping, and drying for 12 hours at 60 ℃.
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. And mixing the obtained powder with Super P and PVDF according to the 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 12h.
Assembling the lithium-sulfur battery:
the prepared composite diaphragm, the sulfur/carbon anode and the lithium sheet are assembled into the lithium-sulfur battery, the addition of the electrolyte on the anode side is 25 mu L, the addition of the electrolyte on the cathode side is 15 mu L, and the sulfur loading capacity is 1.2mg/cm 2 。
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 1596mAh/g; when the current density is increased to 2C, the specific capacity of the battery is still maintained at 581mAh/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 methanol solution A with the concentration of 2-methylimidazole being 1.0 mmol/mL; adding zinc nitrate hexahydrate and manganese acetate into 30mL of methanol to enable the concentrations of the zinc nitrate hexahydrate and the manganese acetate to be 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 drying in vacuum at 60 ℃ for 12h to obtain the Mn-ZIF-8 precursor.
Secondly, synthesizing the low-load Mn-N active site catalyst
Pyrolyzing a Mn-ZIF-8 precursor, firstly controlling the heating rate to be 3 ℃/min in the argon atmosphere, heating to 750 ℃, and keeping for 0.5h; 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 treated with 0.5mol/L H at 70 DEG C 2 SO 4 The solution is stirred for 5H for acid washing (H) 2 SO 4 The ratio of solution to catalyst was 1 mg/mL),and washing the material subjected to acid washing by using deionized water to be neutral (pH = 7), and drying the material in vacuum at 60 ℃ for 12 hours 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, wherein the mass of the manganese chloride is 1/4 of that of the catalyst, and stirring the mixed solution for 2h. 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 at 70℃) 2 SO 4 The solution is stirred for 5 h) 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, mixing and grinding fully, adding NMP and stirring for 12h. The resulting uniformly mixed slurry was knife coated on aluminum foil (sulfur loading was adjusted by knife coating thickness) and dried at 60 ℃ for 12h.
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/cm 2 。
Example 3:
first, synthesizing Mn-ZIF-8 precursor
Taking 30mL of methanol solution A with the concentration of 2-methylimidazole being 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 at room temperature, adding the solution B into the solution A, slowly stirring for 60min, standing for 26h to obtain a precipitate, washing the precipitate with ethanol for multiple times, and drying in vacuum 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 1.5h; then ammonia gas is introduced into the mixture, the mixture is kept at a constant temperature for 2 hours, the mixture is replaced by argon atmosphere, the temperature is continuously raised to 950 ℃, the mixture is kept at the constant temperature for 2.5 hours, and then the mixture is naturally cooled to the room temperature; the obtained product is treated with 0.5mol/L H at 80 DEG C 2 SO 4 The solution is stirred for 8H for acid washing (H) 2 SO 4 The ratio of the solution to the catalyst is 1.5 mg/mL), the material after acid washing is washed to be neutral (PH = 7) by deionized water, and vacuum drying is carried out at 80 ℃ for 16h, so that the low-load Mn-N active site doped carbon material catalyst is obtained.
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, wherein the mass of the added manganese acetate is 1/3 of that 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 ℃) 2 SO 4 The solution is stirred for 8 h) 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 12h.
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/cm 2 。
Example 4:
first, synthesizing Mn-ZIF-8 precursor
Taking 30mL of methanol solution A with the concentration of 2-methylimidazole 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 1.5h; 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 treated with 0.5mol/L H at 70 DEG C 2 SO 4 The solution is stirred for 8H for acid washing (H) 2 SO 4 The ratio of the solution to the catalyst is 1.5 mg/mL), the material after acid washing is washed to be neutral (PH = 7) by deionized water, and vacuum drying is carried out at 60 ℃ for 16h, so that the low-load Mn-N active site doped carbon material catalyst is obtained.
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, and adding the suspension into the solutionAdding manganese chloride, wherein the mass of the added manganese chloride is 1/4 of that of the catalyst, and stirring the mixed solution for 3 hours. Repeatedly filtering and cleaning the product after the reaction is finished with deionized water, drying for 16H under vacuum at 60 ℃, heating the obtained powder sample to 950 ℃ in argon atmosphere for pyrolysis for 3H (heating speed is 3 ℃/min), cooling to room temperature, and then pickling (0.5 mol/L H is used at 80℃) 2 SO 4 The solution is stirred for 8 h) 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, mixing and fully grinding, adding NMP into the obtained mixture, stirring for 12 hours at room temperature to obtain catalyst slurry, coating the catalyst slurry on a PP diaphragm by scraping, and drying for 12 hours at 60 ℃.
Preparing a sulfur/carbon positive electrode:
sublimed sulfur and carbon black are mixed according to the mass ratio of 7:3 grinding fully, and then keeping at 155 ℃ for 12h under Ar atmosphere. And mixing the obtained powder with Super P and PVDF according to the mass ratio of 7:2:1, mixing and grinding fully, adding NMP and stirring for 12h. The resulting uniformly mixed slurry was knife coated on aluminum foil (sulfur loading was adjusted by knife coating thickness) and dried at 60 ℃ for 12h.
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/cm 2 。
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 (6)
1. The application of a high-load Mn-N active site doped carbon material catalyst in a lithium sulfur battery is characterized in that the catalyst is used for modifying a PP (polypropylene) diaphragm of the lithium sulfur battery, and the preparation method of the 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; 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: 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 0.5-1.5h; then ammonia gas is introduced into the mixture for keeping the temperature constant for 1.5 to 2 hours, the mixture is continuously heated to 900 to 950 ℃ in the argon atmosphere and kept at the temperature for 2.5 hours, and then the mixture is naturally cooled to the room temperature; subjecting the obtained product to reaction with H at 70-80 deg.C 2 SO 4 Stirring the solution for 5-8h for acid washing, washing the acid-washed material to be neutral by using deionized water, and drying in vacuum to obtain a 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 h; 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 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 use of the highly loaded Mn-N active site doped carbon material catalyst in a lithium sulfur battery according to claim 1, wherein the vacuum drying temperature is 60-80 ℃ and the drying time is 12-16 h.
3. The application of the highly-loaded Mn-N active site doped carbon material catalyst in the lithium-sulfur battery as claimed in claim 1, wherein the ultrasonic time in the third step is 1.5-2 h.
4. The use of a highly loaded Mn-N active site doped carbon material catalyst in a lithium sulfur battery as claimed in claim 1, wherein the manganese ion containing compound of the third step is manganese acetate or manganese chloride.
5. The use of a highly loaded Mn-N active site doped carbon material catalyst in a lithium sulfur battery as claimed in claim 1, wherein the temperature increase rate in the third step is 3-5 ℃/min.
6. The use of a highly loaded Mn-N active site doped carbon material catalyst in a lithium sulfur battery as claimed in claim 1, wherein the acid washing in the third step is performed at 70-80 ℃ with 0.5mol/L H 2 SO 4 The solution was stirred for 5-8h.
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