CN110890504A - Functional diaphragm coating material for lithium-sulfur battery and preparation method thereof - Google Patents
Functional diaphragm coating material for lithium-sulfur battery and preparation method thereof Download PDFInfo
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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
- 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
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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
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- H01M10/05—Accumulators with non-aqueous 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
- 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
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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
- 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
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Abstract
The invention belongs to the technical field of lithium-sulfur battery diaphragms, and discloses a functional diaphragm coating material for a lithium-sulfur battery and a preparation method thereof, wherein the functional diaphragm coating material mainly comprises metalloporphyrin and an adhesive, wherein the metalloporphyrin mainly comprises porphyrin ligands and intermediate metal elements, and the intermediate metal elements are metal elements excluding lithium elements; the mass ratio of the metalloporphyrin to the adhesive is 9: 1-2: 1. According to the invention, by improving the key composition and structure of the functional diaphragm coating material, the whole process design of the preparation method and the conditions and parameters of each step, the finally formed functional diaphragm coating material can provide an interaction force generated by the polar element and the polysulfide compound to inhibit the shuttle of the polysulfide compound and promote the interconversion between the polysulfide compounds, so that the dissolution and shuttle of the polysulfide compound in the charging and discharging process are reduced, and the utilization rate and the cycle stability of the active substance of the lithium-sulfur battery are finally improved.
Description
Technical Field
The invention belongs to the technical field of lithium-sulfur battery diaphragms, and particularly relates to a functional diaphragm coating material for a lithium-sulfur battery and a preparation method thereof.
Background
The lithium-sulfur battery has higher theoretical specific capacity (1675mAh g)-1) High energy density (2600Wh kg)-1) Low cost of elemental sulfur, rich natural content, environmental protection and the like. However, the presence of some drawbacks hinders their practical application. For example, long-chain polysulfide dissolves in the liquid electrolyte, and the soluble polysulfide shuttles between the positive and negative electrodes to corrode the negative lithium metal and cause serious self-discharge, so-called "shuttle effect", and finally cause rapid decrease in the specific capacity, cycle life and coulombic efficiency of the lithium-sulfur battery.
In recent years, various strategies such as sulfur carrier design, electrolyte system innovation, separator modification and the like have been pursued to overcome the "shuttle effect" in order to improve the electrochemical performance of lithium sulfur batteries. Among them, separator modification is a promising strategy to prevent polysulfide from dissolving into the electrolyte, further improving the utilization of active sulfur materials in the positive electrode. A large number of functional materials are used for modifying the diaphragm, wherein the nano carbon material has the advantages of large specific surface area, good conductivity and the like, and is widely applied by physically blocking shuttle of polysulfide compounds. However, their poor affinity for polar polysulfides limits their ability to maintain high specific capacities. On the contrary, polar hetero elements such as oxygen, nitrogen, sulfur and the like can generate electrostatic interaction force with polysulfide, and the weak physical barrier property of the carbon material can more effectively inhibit the shuttle effect.
In addition, during the charging and discharging processes of the lithium-sulfur battery, the interconversion reaction of the intermediate products of the polysulfide compound is slow, and especially the dissolution of the polysulfide compound is increased during the ultra-long cycle. Therefore, it is imperative to prepare a functional membrane coating material which has an interaction force with polysulfide compounds and can catalyze the interconversion between polysulfide compounds.
Disclosure of Invention
In view of the above defects or improvement needs of the prior art, an object of the present invention is to provide a functional separator coating material for a lithium-sulfur battery and a preparation method thereof, in which by improving key composition and structure of the functional separator coating material (especially, structure of porphyrin ligand, selection of intermediate metal element), and overall process design of the preparation method and conditions and parameters of each step (such as type and ratio of reaction raw materials, reaction temperature and time during synthesis of porphyrin ligand, etc.), the finally formed functional separator coating material can provide interaction force between polar elements and polysulfide compounds to inhibit shuttling of the polysulfide compounds, and can promote interconversion between the polar polysulfide compounds through activation of the interface between metal in metalloporphyrin and electrolyte, and further, the dissolution and shuttling of polysulfide compounds in the charging and discharging processes are reduced, and finally the utilization rate and the cycling stability of active substances of the lithium-sulfur battery are improved.
In order to achieve the above objects, according to one aspect of the present invention, there is provided a functional separator coating material for a lithium-sulfur battery, characterized in that the functional separator coating material is mainly composed of a metalloporphyrin and a binder, wherein the metalloporphyrin is mainly composed of a porphyrin ligand and an intermediate metal element located inside the porphyrin ligand, the intermediate metal element being a metal element excluding lithium; the mass ratio of the metalloporphyrin to the adhesive is 9: 1-2: 1.
As a further preferred aspect of the present invention, the metalloporphyrin has a chemical structure represented by formula (I):
in the formula (I), R1Is a hydrocarbon group, a phenyl group, a carboxylic acid group or an ester group; r2Is a hydrocarbyl, cyano, phenyl or halogen element; x represents the intermediate metal element, specifically Co, Ti, Fe, Zn, Ni, Cr or Sc.
As a further preferred aspect of the present invention, the binder is one of polyvinylidene fluoride (PVDF), Styrene Butadiene Rubber (SBR), hydroxymethyl cellulose (CMC), polyacrylic acid (PAA), Polyacrylonitrile (PAN), or Polyacrylate (PEA).
According to another aspect of the present invention, the present invention provides a method for preparing the above functional separator coating material for a lithium-sulfur battery, which is characterized by comprising the following steps:
(1) adding the adhesive into N-methyl pyrrolidone or deionized water, and performing magnetic stirring to assist dispersion to obtain a first mixture;
(2) adding metalloporphyrin into the first blend obtained in the step (1), and performing magnetic stirring to assist dispersion to obtain a second blend; the second blend contains the functional diaphragm coating material for the lithium-sulfur battery, and can be used for preparing the functional diaphragm coating for the lithium-sulfur battery.
As a further preferred aspect of the present invention, in the step (2), metalloporphyrin is synthesized, and then metalloporphyrin is added to the first mixture obtained in the step (1); the synthesis of the metalloporphyrin satisfies the following synthetic route:
wherein R is1Is a hydrocarbon group, a phenyl group, a carboxylic acid group or an ester group; r2Is a hydrocarbyl, cyano, phenyl or halogen element; x is specifically Co, Ti, Fe, Zn, Ni, Cr or Sc.
As a further preferred aspect of the present invention, the synthesis of the metalloporphyrin comprises the following substeps:
(S1) adding the compound of the formula (III) into a mixture of acetic anhydride and propionic acid to obtain a first solution, and refluxing and stirring at 100-180 ℃ for 20-60 min to obtain a homogeneous solution of the compound of the formula (III); the blend of acetic anhydride and propionic acid is obtained by mixing acetic anhydride and propionic acid according to the volume ratio of 0.5/20-1.5/20; the ratio of the mass of the compound of formula (III) to the volume of the blend of acetic anhydride and propionic acid is from 1g:10ml to 1g:40 ml;
(S2) adding the compound of formula (II) to the homogeneous solution of the compound of formula (III) obtained in the step (S1) to obtain a second solution, stirring under reflux at 100 to 180 ℃ for 0.5 to 2 hours, cooling, washing, and drying at 60 to 100 ℃ to obtain a first powder; in the second solution, the mass ratio of the compound of the formula (II) to the compound of the formula (III) is 1/2-1/3;
(S3) adding the first powder obtained in the step (S2) into an acetone solution to obtain a third solution, performing reflux extraction with a soxhlet extractor at 80-120 ℃ until the acetone in the soxhlet extractor is transparent in color, and drying at 70-90 ℃ to obtain a second powder; in the third solution, the ratio of the mass of the first powder to the volume of the acetone solution is 10g:400 mL-50 g:400 mL;
(S4) adding the second powder obtained in the step (S3) to pyridine to obtain a fourth solution, dissolving the fourth solution at 100 to 150 ℃ for 1 to 3 hours under reflux to obtain a homogeneous solution of the second powder, cooling the homogeneous solution at 1 to 5 ℃ for 10 to 24 hours, filtering the homogeneous solution, washing the homogeneous solution, and drying the homogeneous solution at 50 to 100 ℃ to obtain a compound of formula (IV); in the fourth solution, the ratio of the mass of the second powder to the volume of the pyridine is 10g:10 mL-50 g:10 mL;
(S5) adding the compound of formula (IV) obtained in the step (S4) and acetate for providing an intermediate metal element to anhydrous dimethylformamide to obtain a fifth solution, refluxing at 130 to 170 ℃ under nitrogen for 12 to 24 hours, cooling, filtering, washing, and drying at 50 to 80 ℃ to obtain a compound of formula (I); in the fifth solution, the mass ratio of the compound of the formula (IV) to the acetate is 0.5/1-1.8/1, the volume ratio of the anhydrous dimethylformamide to the compound of the formula (IV) is 30mL:0.5 g-30 mL:1.5g, and the intermediate metal element is Co, Ti, Fe, Zn, Ni, Cr or Sc.
As a further preferred aspect of the present invention, in the step (1), the binder is one of polyvinylidene fluoride (PVDF), Styrene Butadiene Rubber (SBR), hydroxymethyl cellulose (CMC), polyacrylic acid (PAA), Polyacrylonitrile (PAN), or Polyacrylate (PEA); the ratio of the mass of the adhesive to the volume of the N-methylpyrrolidone or the deionized water is 1g:4 mL-1 g:10 mL;
for the second blend obtained in the step (2), the mass ratio of the metalloporphyrin contained in the second blend to the adhesive is 9: 1-2: 1;
in the step (S2), the cooling is specifically room temperature cooling, and the cleaning is specifically cleaning with water, methanol, and dichloromethane in sequence;
in the step (S4), the washing is specifically washing with tetrahydrofuran and water in sequence;
in the step (S5), the cooling is specifically room temperature cooling, and the washing is specifically washing with water and methanol in sequence.
According to another aspect of the invention, the invention provides the application of the second blend prepared by the method, which is characterized in that the second blend prepared by the method is coated on a separator, and the separator covered by the functional separator coating material can be obtained after drying.
As a further preference of the invention, the coating is in particular a doctor blade coating of the second blend on the separator.
As a further preferred aspect of the present invention, the thickness of the coating is 60 μm to 120 μm; the drying temperature is 60-100 ℃.
Through the technical scheme, compared with the prior art, the invention has the following beneficial effects:
1. aiming at the lithium-sulfur battery, the metalloporphyrin mainly composed of porphyrin ligand and intermediate metal element is adopted, and for the porphyrin ligand, nitrogen element on pyrrole in the porphyrin ligand can generate interaction force with polysulfide, so that shuttle of polysulfide compound is effectively inhibited. Metalloporphyrin is an organometallic complex in which an intermediate metal element is coordinated to the center of a ligand (i.e., located inside a porphyrin ligand) by covalent bonding, and thus the intermediate metal element may also be referred to as a central metal element.
The invention is particularly directed to porphyrin ligands having the chemical structure shown in formula IV, wherein R is1And R2Some polar groups (such as carboxylic acid groups and cyano groups) can be selected to further generate interaction with the polysulfide compound, thereby further inhibiting the shuttling of the polysulfide compound.
2. And taking the intermediate metal element as x for example, the metalloporphyrin shown in the formula I is obtained by introducing the metal element excluding lithium element into the porphyrin ligand shown in the formula IV, so that the porphyrin ligand can provide nitrogen element, and other metal elements introduced by coordination, especially transition metal elements including Co, Ti, Fe, Zn, Ni, Cr, Sc and the like, can effectively catalyze the conversion of polysulfide compound. The metalloporphyrin adopted in the invention has the internal intermediate metal surrounded by the porphyrin ligand, and the metal not only has good electron conduction effect and can improve the utilization rate of the active substance sulfur material; in addition, metals (such as Co, Ti, Fe, Zn, Ni, Cr, Sc) can catalyze interconversion between polysulfide compounds, particularly interconversion between long-chain compounds and short-chain compounds, by activation of polar polysulfide compounds by the interface between the metal and the electrolyte, thereby contributing to improvement of the specific capacity retention rate and coulombic efficiency of the battery.
3. The invention adopts the metalloporphyrin and the adhesive to be directly blended and blade-coated on the diaphragm, and the preparation method is simple and easy to operate.
In conclusion, the coating material in the invention enables the diaphragm to have good lithium ion selective permeability, pyrrole in porphyrin can generate interaction force with polysulfide compound so as to have more freely conducted lithium ions, and simultaneously, intermediate metal can effectively catalyze the interconversion of the polysulfide compound, which is beneficial to reducing the dissolution and shuttling of the polysulfide compound in the charging and discharging process, and finally improves the utilization rate and the cycling stability of active substances of the lithium-sulfur battery.
Drawings
FIG. 1 is a scanning electron micrograph of porphyrin prepared in comparative example 1 of the present invention.
FIG. 2 is a projection electron micrograph of porphyrin prepared in comparative example 1 of the present invention.
Figure 3 is a linear sweep voltammogram of the separator (commercially available polypropylene separator without any coating), the separator obtained in comparative example 1 (i.e., porphyrin-functionalized separator), and the separator obtained in example 1 (i.e., cobalt porphyrin-functionalized separator).
Fig. 4 is a graph showing impedance spectra of the separator, the separator obtained in comparative example 1, and the separator obtained in example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The functional diaphragm coating material and the preparation method thereof are prepared by directly blending metalloporphyrin and an adhesive, and can be further coated on a diaphragm (such as blade coating on the diaphragm), wherein the metalloporphyrin is composed of a porphyrin ligand and an intermediate metal.
Using PVDF as the binder, various embodiments of the invention are as follows (of course, other binders known in the art may be used in addition to PVDF):
example 1:
benzaldehyde, pyrrole and cobalt acetate are taken as materials. The cobalt porphyrin based functional membrane material was prepared according to the following procedure.
(1) Adding 8g of benzaldehyde into a mixed solution of 10mL of acetic anhydride and 200mL of propionic acid solution, refluxing and stirring at 130 ℃ for 30min, adding 5mL of pyrrole, refluxing at 130 ℃ for 1h, cooling to room temperature, washing with water, methanol and dichloromethane, and drying at 70 ℃ to obtain a first powder; soxhlet extracting the first powder with 250mL of acetone at 100 deg.C until the acetone in the Soxhlet extractor is transparent, and drying at 80 deg.C to obtain a second powder;
(2) adding the second powder obtained in the step (1) into 10mL of pyridine, refluxing for 1.5h at 120 ℃, then cooling for 15h at 25 ℃, filtering, washing with tetrahydrofuran, washing with water, and drying at 60 ℃ to obtain a compound porphyrin ligand of the formula IV;
(3) adding 0.2g of porphyrin ligand obtained in the step (2) and 0.6g of cobalt acetate into 30mL of anhydrous dimethylformamide, refluxing for 14h at 140 ℃ under the nitrogen atmosphere, cooling at room temperature, filtering, washing with water and methanol, and drying at 65 ℃ to obtain cobalt porphyrin (x in the formula I is Co element) as a compound of the formula I;
(4) 0.2g of PVDF was added to 7mL of N-methylpyrrolidone and dispersed with the aid of magnetic stirring; then adding 0.8g of cobalt porphyrin obtained in the step (3), and performing magnetic stirring to assist dispersion; scraping the membrane with a scraper with the thickness of 80 mu m, and drying at 75 ℃ to obtain the cobalt porphyrin-based functional membrane material.
Example 2:
benzaldehyde, pyrrole and titanium acetate are taken as materials. The titanium porphyrin based functional membrane material was prepared as follows.
(1) Adding 8g of benzaldehyde into a mixed solution of 10mL of acetic anhydride and 200mL of propionic acid solution, refluxing and stirring at 130 ℃ for 30min, adding 5mL of pyrrole, refluxing at 130 ℃ for 1h, cooling to room temperature, washing with water, methanol and dichloromethane, and drying at 70 ℃ to obtain a first powder; soxhlet extracting the first powder with 250mL of acetone at 100 deg.C until the acetone in the Soxhlet extractor is transparent, and drying at 80 deg.C to obtain a second powder;
(2) adding the second powder obtained in the step (1) into 10mL of pyridine, refluxing for 1.5h at 120 ℃, then cooling for 15h at 25 ℃, filtering, washing with tetrahydrofuran, washing with water, and drying at 60 ℃ to obtain a compound porphyrin ligand of the formula IV;
(3) adding 0.2g of porphyrin ligand obtained in the step (2) and 0.6g of titanium acetate into 30mL of anhydrous dimethylformamide, refluxing for 14h at 140 ℃ under the nitrogen atmosphere, cooling at room temperature, filtering, washing with water and methanol, and drying at 65 ℃ to obtain titanium porphyrin (x in the formula I is Ti element) as a compound of the formula I;
(4) 0.2g of PVDF was added to 7mL of N-methylpyrrolidone and dispersed with the aid of magnetic stirring; then adding 0.8g of titanium porphyrin obtained in the step (3), and stirring by magnetic force to assist dispersion; scraping the membrane with a scraper with the thickness of 80 mu m, and drying at 75 ℃ to obtain the titanium porphyrin-based functional membrane material.
Example 3:
benzaldehyde, pyrrole and ferric acetate are taken as materials. The ferriporphyrin-based functional separator material was prepared as follows.
(1) Adding 8g of benzaldehyde into a mixed solution of 10mL of acetic anhydride and 200mL of propionic acid solution, refluxing and stirring at 130 ℃ for 30min, adding 5mL of pyrrole, refluxing at 130 ℃ for 1h, cooling to room temperature, washing with water, methanol and dichloromethane, and drying at 70 ℃ to obtain a first powder; soxhlet extracting the first powder with 250mL of acetone at 100 deg.C until the acetone in the Soxhlet extractor is transparent, and drying at 80 deg.C to obtain a second powder;
(2) adding the second powder obtained in the step (1) into 10mL of pyridine, refluxing for 1.5h at 120 ℃, then cooling for 15h at 25 ℃, filtering, washing with tetrahydrofuran, washing with water, and drying at 60 ℃ to obtain a compound porphyrin ligand of the formula IV;
(3) adding 0.2g of porphyrin ligand obtained in the step (2) and 0.6g of iron acetate into 30mL of anhydrous dimethylformamide, refluxing for 14h at 140 ℃ under the nitrogen atmosphere, cooling at room temperature, filtering, washing with water and methanol, and drying at 65 ℃ to obtain iron porphyrin (in the formula I, x is Fe element);
(4) 0.2g of PVDF was added to 7mL of N-methylpyrrolidone and dispersed with the aid of magnetic stirring; then adding 0.8g of the ferriporphyrin obtained in the step (3), and stirring by magnetic force to assist dispersion; scraping the membrane with a scraper with the thickness of 80 mu m, and drying at 75 ℃ to obtain the functional membrane material based on ferriporphyrin.
Example 4:
benzaldehyde, pyrrole and zinc acetate are taken as materials. The zinc porphyrin based functional separator material was prepared as follows.
(1) Adding 8g of benzaldehyde into a mixed solution of 10mL of acetic anhydride and 200mL of propionic acid solution, refluxing and stirring at 130 ℃ for 30min, adding 5mL of pyrrole, refluxing at 130 ℃ for 1h, cooling to room temperature, washing with water, methanol and dichloromethane, and drying at 70 ℃ to obtain a first powder; soxhlet extracting the first powder with 250mL of acetone at 100 deg.C until the acetone in the Soxhlet extractor is transparent, and drying at 80 deg.C to obtain a second powder;
(2) adding the second powder obtained in the step (1) into 10mL of pyridine, refluxing for 1.5h at 120 ℃, then cooling for 15h at 25 ℃, filtering, washing with tetrahydrofuran, washing with water, and drying at 60 ℃ to obtain a compound porphyrin ligand of the formula IV;
(3) adding 0.2g of porphyrin ligand obtained in the step (2) and 0.6g of zinc acetate into 30mL of anhydrous dimethylformamide, refluxing for 14h at 140 ℃ under the nitrogen atmosphere, cooling at room temperature, filtering, washing with water and methanol, and drying at 65 ℃ to obtain a compound zinc porphyrin (in the formula I, x is Zn element);
(4) 0.2g of PVDF was added to 7mL of N-methylpyrrolidone and dispersed with the aid of magnetic stirring; then adding 0.8g of zinc porphyrin obtained in the step (3), and stirring by magnetic force to assist dispersion; scraping the membrane with a scraper with the thickness of 80 mu m, and drying at 75 ℃ to obtain the functional membrane material based on zinc porphyrin.
Example 5:
benzaldehyde, pyrrole and nickel acetate are taken as materials. The nickel porphyrin based functional separator material was prepared as follows.
(1) Adding 8g of benzaldehyde into a mixed solution of 10mL of acetic anhydride and 200mL of propionic acid solution, refluxing and stirring at 130 ℃ for 30min, adding 5mL of pyrrole, refluxing at 130 ℃ for 1h, cooling to room temperature, washing with water, methanol and dichloromethane, and drying at 70 ℃ to obtain a first powder; soxhlet extracting the first powder with 250mL of acetone at 100 deg.C until the acetone in the Soxhlet extractor is transparent, and drying at 80 deg.C to obtain a second powder;
(2) adding the second powder obtained in the step (1) into 10mL of pyridine, refluxing for 1.5h at 120 ℃, then cooling for 15h at 25 ℃, filtering, washing with tetrahydrofuran, washing with water, and drying at 60 ℃ to obtain a compound porphyrin ligand of the formula IV;
(3) adding 0.2g of porphyrin ligand obtained in the step (2) and 0.6g of nickel acetate into 30mL of anhydrous dimethylformamide, refluxing for 14h at 140 ℃ under the nitrogen atmosphere, cooling at room temperature, filtering, washing with water and methanol, and drying at 65 ℃ to obtain nickel porphyrin (in the formula I, x is Ni element);
(4) 0.2g of PVDF was added to 7mL of N-methylpyrrolidone and dispersed with the aid of magnetic stirring; then adding 0.8g of nickel porphyrin obtained in the step (3), and stirring by magnetic force to assist dispersion; scraping the membrane with a scraper with the thickness of 80 mu m, and drying at 75 ℃ to obtain the nickel porphyrin-based functional membrane material.
Example 6:
benzaldehyde, pyrrole and chromium acetate are taken as materials. The chromium porphyrin based functional membrane material was prepared according to the following procedure.
(1) Adding 8g of benzaldehyde into a mixed solution of 10mL of acetic anhydride and 200mL of propionic acid solution, refluxing and stirring at 130 ℃ for 30min, adding 5mL of pyrrole, refluxing at 130 ℃ for 1h, cooling to room temperature, washing with water, methanol and dichloromethane, and drying at 70 ℃ to obtain a first powder; soxhlet extracting the first powder with 250mL of acetone at 100 deg.C until the acetone in the Soxhlet extractor is transparent, and drying at 80 deg.C to obtain a second powder;
(2) adding the second powder obtained in the step (1) into 10mL of pyridine, refluxing for 1.5h at 120 ℃, then cooling for 15h at 25 ℃, filtering, washing with tetrahydrofuran, washing with water, and drying at 60 ℃ to obtain a compound porphyrin ligand of the formula IV;
(3) adding 0.2g of porphyrin ligand obtained in the step (2) and 0.6g of chromium acetate into 30mL of anhydrous dimethylformamide, refluxing for 14h at 140 ℃ under the nitrogen atmosphere, cooling at room temperature, filtering, washing with water and methanol, and drying at 65 ℃ to obtain the compound chromium porphyrin (in the formula I, x is Cr element);
(4) 0.2g of PVDF was added to 7mL of N-methylpyrrolidone and dispersed with the aid of magnetic stirring; then adding 0.8g of chromium porphyrin obtained in the step (3), and stirring by magnetic force to assist dispersion; scraping the diaphragm with a scraper with the thickness of 80 mu m, and drying at 75 ℃ to obtain the functional diaphragm material based on the chromium porphyrin.
Example 7:
benzaldehyde, pyrrole and scandium acetate are used as materials. The functional scandium porphyrin-based separator material was prepared according to the following procedure.
(1) Adding 8g of benzaldehyde into a mixed solution of 10mL of acetic anhydride and 200mL of propionic acid solution, refluxing and stirring at 130 ℃ for 30min, adding 5mL of pyrrole, refluxing at 130 ℃ for 1h, cooling to room temperature, washing with water, methanol and dichloromethane, and drying at 70 ℃ to obtain a first powder; soxhlet extracting the first powder with 250mL of acetone at 100 deg.C until the acetone in the Soxhlet extractor is transparent, and drying at 80 deg.C to obtain a second powder;
(2) adding the second powder obtained in the step (1) into 10mL of pyridine, refluxing for 1.5h at 120 ℃, then cooling for 15h at 25 ℃, filtering, washing with tetrahydrofuran, washing with water, and drying at 60 ℃ to obtain a compound porphyrin ligand of the formula IV;
(3) adding 0.2g of porphyrin ligand obtained in the step (2) and 0.6g of scandium acetate into 30mL of anhydrous dimethylformamide, refluxing for 14h at 140 ℃ in a nitrogen atmosphere, cooling at room temperature, filtering, washing with water and methanol, and drying at 65 ℃ to obtain a compound scandium porphyrin (in the formula I, x is Sc element);
(4) 0.2g of PVDF was added to 7mL of N-methylpyrrolidone and dispersed with the aid of magnetic stirring; then adding 0.8g of scandium porphyrin obtained in the step (3), and performing magnetic stirring to assist dispersion; and (3) scraping the membrane by using a scraper with the thickness of 80 mu m, and drying at 75 ℃ to obtain the scandium porphyrin-based functional membrane material.
Comparative example 1:
benzaldehyde and pyrrole are used as materials. The porphyrin-based functional separator material was prepared as follows.
(1) Adding 8g of benzaldehyde into a mixed solution of 10mL of acetic anhydride and 200mL of propionic acid solution, refluxing and stirring at 130 ℃ for 30min, adding 5mL of pyrrole, refluxing at 130 ℃ for 1h, cooling to room temperature, washing with water, methanol and dichloromethane, and drying at 70 ℃ to obtain a first powder; soxhlet extracting the first powder with 250mL of acetone at 100 deg.C until the acetone in the Soxhlet extractor is transparent, and drying at 80 deg.C to obtain a second powder;
(2) adding the second powder obtained in the step (1) into 10mL of pyridine, refluxing for 1.5h at 120 ℃, then cooling for 15h at 25 ℃, filtering, washing with tetrahydrofuran, washing with water, and drying at 60 ℃ to obtain a compound porphyrin ligand of the formula IV;
(3) 0.2g of PVDF was added to 7mL of N-methylpyrrolidone and dispersed with the aid of magnetic stirring; then adding 0.8g of porphyrin ligand obtained in the step (2), and stirring by magnetic force to assist dispersion; scraping the membrane with a scraper with the thickness of 80 mu m, and drying at 75 ℃ to obtain the functional membrane material based on porphyrin.
FIG. 1 is a scanning electron micrograph of porphyrin prepared in comparative example 1 of the present invention, and FIG. 2 is a projection electron micrograph of porphyrin prepared in comparative example 1 of the present invention. As can be seen from FIG. 1, the porphyrin prepared has a uniform granular structure; as can be seen from FIG. 2, the porphyrin prepared has a layered structure.
Figure 3 is a linear sweep voltammogram of the membrane (i.e., a commercially available polypropylene membrane without any coating), the membrane obtained in comparative example 1 (i.e., a porphyrin-functionalized membrane), and the membrane obtained in example 1 (i.e., a cobalt porphyrin-functionalized membrane). Fig. 4 is a graph showing impedance spectra of the separator, the separator obtained in comparative example 1, and the separator obtained in example 1. By comparing the function of the separator without any coating with that of the separator obtained in comparative example 1 (i.e., porphyrin-functionalized separator) and that of the separator obtained in example 1 (i.e., cobalt porphyrin-functionalized separator), it can be seen that both porphyrin and cobalt porphyrin have good electrochemical stability, and the electrochemical stability window of the separator is not affected by the coating (as shown in fig. 3); both the porphyrin-functionalized membrane and the cobalt porphyrin-functionalized membrane had good ionic conductivity (as shown in fig. 4).
The environment in which the operation such as the reflow is performed is an air environment unless otherwise specified.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A functional diaphragm coating material for a lithium-sulfur battery is characterized by mainly comprising metalloporphyrin and an adhesive, wherein the metalloporphyrin mainly comprises a porphyrin ligand and an intermediate metal element positioned in the porphyrin ligand, and the intermediate metal element is a metal element excluding lithium; the mass ratio of the metalloporphyrin to the adhesive is 9: 1-2: 1.
2. The functional separator coating material for a lithium sulfur battery as claimed in claim 1, wherein the metalloporphyrin has a chemical structure according to formula (I):
in the formula (I), R1Is a hydrocarbon group, a phenyl group, a carboxylic acid group or an ester group; r2Is a hydrocarbyl, cyano, phenyl or halogen element; x represents the intermediate metal element, specifically Co, Ti, Fe, Zn, Ni, Cr or Sc.
3. The functional separator coating material for a lithium sulfur battery according to claim 1, wherein the binder is one of polyvinylidene fluoride (PVDF), Styrene Butadiene Rubber (SBR), hydroxymethyl cellulose (CMC), polyacrylic acid (PAA), Polyacrylonitrile (PAN), or Polyacrylate (PEA).
4. The method for preparing the functional separator coating material for the lithium-sulfur battery according to any one of claims 1 to 3, comprising the following steps:
(1) adding the adhesive into N-methyl pyrrolidone or deionized water, and performing magnetic stirring to assist dispersion to obtain a first mixture;
(2) adding metalloporphyrin into the first blend obtained in the step (1), and performing magnetic stirring to assist dispersion to obtain a second blend; the second blend, i.e. containing the functional separator coating material for lithium-sulfur batteries as claimed in any one of claims 1 to 3, can be used for preparing functional separator coatings for lithium-sulfur batteries.
5. The method of claim 4, wherein step (2) comprises synthesizing metalloporphyrin and then adding metalloporphyrin to the first mixture obtained in step (1); the synthesis of the metalloporphyrin satisfies the following synthetic route:
wherein R is1Is a hydrocarbon group, a phenyl group, a carboxylic acid group or an ester group; r2Is a hydrocarbyl, cyano, phenyl or halogen element; x is specifically Co, Ti, Fe, Zn, Ni, Cr or Sc.
6. The method of claim 5, wherein the synthesis of metalloporphyrin comprises the following sub-steps:
(S1) adding the compound of the formula (III) into a mixture of acetic anhydride and propionic acid to obtain a first solution, and refluxing and stirring at 100-180 ℃ for 20-60 min to obtain a homogeneous solution of the compound of the formula (III); the blend of acetic anhydride and propionic acid is obtained by mixing acetic anhydride and propionic acid according to the volume ratio of 0.5/20-1.5/20; the ratio of the mass of the compound of formula (III) to the volume of the blend of acetic anhydride and propionic acid is from 1g:10ml to 1g:40 ml;
(S2) adding the compound of formula (II) to the homogeneous solution of the compound of formula (III) obtained in the step (S1) to obtain a second solution, stirring under reflux at 100 to 180 ℃ for 0.5 to 2 hours, cooling, washing, and drying at 60 to 100 ℃ to obtain a first powder; in the second solution, the mass ratio of the compound of the formula (II) to the compound of the formula (III) is 1/2-1/3;
(S3) adding the first powder obtained in the step (S2) into an acetone solution to obtain a third solution, performing reflux extraction with a soxhlet extractor at 80-120 ℃ until the acetone in the soxhlet extractor is transparent in color, and drying at 70-90 ℃ to obtain a second powder; in the third solution, the ratio of the mass of the first powder to the volume of the acetone solution is 10g:400 mL-50 g:400 mL;
(S4) adding the second powder obtained in the step (S3) to pyridine to obtain a fourth solution, dissolving the fourth solution at 100 to 150 ℃ for 1 to 3 hours under reflux to obtain a homogeneous solution of the second powder, cooling the homogeneous solution at 1 to 5 ℃ for 10 to 24 hours, filtering the homogeneous solution, washing the homogeneous solution, and drying the homogeneous solution at 50 to 100 ℃ to obtain a compound of formula (IV); in the fourth solution, the ratio of the mass of the second powder to the volume of the pyridine is 10g:10 mL-50 g:10 mL;
(S5) adding the compound of formula (IV) obtained in the step (S4) and acetate for providing an intermediate metal element to anhydrous dimethylformamide to obtain a fifth solution, refluxing at 130 to 170 ℃ under nitrogen for 12 to 24 hours, cooling, filtering, washing, and drying at 50 to 80 ℃ to obtain a compound of formula (I); in the fifth solution, the mass ratio of the compound of the formula (IV) to the acetate is 0.5/1-1.8/1, the volume ratio of the anhydrous dimethylformamide to the compound of the formula (IV) is 30mL:0.5 g-30 mL:1.5g, and the intermediate metal element is Co, Ti, Fe, Zn, Ni, Cr or Sc.
7. The method of claim 6, wherein in the step (1), the binder is one of polyvinylidene fluoride (PVDF), Styrene Butadiene Rubber (SBR), hydroxymethyl cellulose (CMC), polyacrylic acid (PAA), Polyacrylonitrile (PAN) or Polyacrylate (PEA); the ratio of the mass of the adhesive to the volume of the N-methylpyrrolidone or the deionized water is 1g:4 mL-1 g:10 mL;
for the second blend obtained in the step (2), the mass ratio of the metalloporphyrin contained in the second blend to the adhesive is 9: 1-2: 1;
in the step (S2), the cooling is specifically room temperature cooling, and the cleaning is specifically cleaning with water, methanol, and dichloromethane in sequence;
in the step (S4), the washing is specifically washing with tetrahydrofuran and water in sequence;
in the step (S5), the cooling is specifically room temperature cooling, and the washing is specifically washing with water and methanol in sequence.
8. Use of the second blend prepared according to any of claims 4 to 7 for coating a separator with the second blend prepared according to the above method, and drying the coated separator to obtain a separator covered with a functional separator coating material.
9. The use according to claim 8, wherein the coating is carried out by knife coating the second blend on the separator.
10. The use according to claim 8, wherein the coating has a thickness of 60 μm to 120 μm; preferably, the drying temperature is 60-100 ℃.
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