CN115232326A - Metal organic framework material, preparation thereof and application thereof in electrode material - Google Patents
Metal organic framework material, preparation thereof and application thereof in electrode material Download PDFInfo
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Abstract
A metal organic framework material, a preparation method thereof and an application thereof in an electrode material. The invention belongs to the field of lithium-sulfur battery cathode materials. The invention aims to solve the technical problems that the existing metal organic framework material applied to the lithium-sulfur battery is weak in charge transfer capacity, low in specific capacity and poor in cycling stability. The metal organic framework material is MOF-ET8 with a chemical formula of [ Zr ] 2 (L) 3 ]Wherein L is an organic ligand C 22 H 20 N 2 O 6 . The metal organic framework material is used for preparing an electrode material applied to a lithium-sulfur battery.
Description
Technical Field
The invention belongs to the field of lithium-sulfur battery positive electrode materials, and particularly relates to a metal organic framework material, a preparation method thereof and application thereof in an electrode material.
Background
In recent years, conventional fuel-powered automobiles are being "replaced" by new energy automobiles step by step. As a power source of the new energy automobile, the performance of the battery is directly related to the driving mileage and the cruising ability of the automobile, and the key for determining whether the new energy automobile can replace the traditional fuel oil automobile in the future is also provided. However, the energy density of the ternary lithium battery widely applied to new energy automobiles is close to the theoretical limit, and the endurance capacity of the lithium iron phosphate battery system is poor, so that a new battery system is urgently needed. As an important component of a new generation of battery technology, the lithium-sulfur battery has higher energy density, stronger cruising ability and richer resources, and is widely concerned by the scientific research community and the industrial community.
The lithium-sulfur battery utilizes sulfur as the positive electrode of the battery and metal lithium as the negative electrode of the battery, and is a battery system for effectively realizing mutual conversion of electric energy and chemical energy. The lithium-sulfur battery using sulfur as the anode material has light weight and can improve the overall energy density of the battery; in addition, elemental sulfur is abundant in reserves, friendly to the environment and capable of realizing large-scale production, so that the lithium sulfur battery is considered as the most competitive candidate in new energy automobile batteries. However, the lithium-sulfur battery still faces some unsolved problems such as low capacity utilization rate and shuttling effect. Therefore, focusing on solving the shuttling effect of the polysulfide of the lithium-sulfur battery and improving the utilization rate of the capacity are important issues facing the research field.
Metal Organic Frameworks (MOFs) are porous materials formed by highly orderly connecting Metal ions and Organic ligands, and have wide application prospects in the fields of gas storage, biomedicine, catalysis and the like. Its pore size tunability, designability of chemically active sites, and high porosity make it extremely potential in limiting the shuttling of polysulfides. However, the technical problems of weak charge transfer capability, low specific capacity, poor cycling stability and the like still exist in the existing Metal Organic Frameworks (MOFs) applied to the lithium-sulfur battery are urgently needed to be solved.
Disclosure of Invention
The invention aims to solve the technical problems of weak charge transfer capacity, low specific capacity and poor cycling stability of the existing metal organic framework material applied to a lithium-sulfur battery, and provides a metal organic framework material, a preparation method thereof and application thereof in an electrode material.
One of the objectives of the present invention is to provide a metal organic framework material, which is MOF-ET8 with the chemical formula [ Zr ] 2 (L) 3 ]Wherein L is an organic ligand C 22 H 20 N 2 O 6 。
Further defined, the organic ligand has the structure:
。
the second purpose of the invention is to provide a preparation method of the organic ligand, which comprises the following steps:
s1: sequentially adding n-butyllithium, 1, 5-dibromo-2, 4-dimethoxybenzene and tetrahydrofuran into n-hexane at the temperature of-78 ℃, heating to 0 ℃, stirring for 12 hours at the temperature of 0 ℃, cooling to-78 ℃, adding trimethyl borate, heating to 25 ℃, stirring for 18 hours at the temperature of 25 ℃, adding hydrochloric acid, stirring for 0.5 hour at the temperature of 25 ℃, washing and drying to obtain an intermediate 1;
s2: sequentially adding an intermediate 1, 2-amino-4-methyl bromobenzoate, cesium fluoride and palladium dichloride into a water/dioxane mixed solution, heating, stirring and refluxing for 24 hours under the protection of argon, cooling to 25 ℃, adding dichloromethane, standing for layering, washing, drying, spin-drying an organic phase, and finally performing silica gel column chromatography by using dichloromethane/ethyl acetate as an eluent to obtain an intermediate 2;
s3: and (3) mixing the intermediate 2, tetrahydrofuran, methanol and a sodium hydroxide solution, heating, refluxing and stirring for 24 hours, cooling to 25 ℃, then spin-drying an organic phase, then adjusting the pH value to 5, centrifuging, washing the precipitate with water, and finally drying in vacuum to obtain the organic ligand.
In a more specific aspect, the molar ratio of n-butyllithium, 1, 5-dibromo-2, 4-dimethoxybenzene, and trimethyl borate in S1 is (90-100): 30: (30-32).
Further limiting, washing with water, diethyl ether and chloroform is carried out in the S1 sequence.
More particularly, the molar ratio of the intermediate 1, the methyl 2-amino-4-bromobenzoate, the cesium fluoride and the palladium dichloride in the S2 is 2: (4-6): (11-12): (0.1-0.2).
Further limited, the volume ratio of water to dioxane in the mixed solution of water/dioxane in S2 is 1.
More specifically, in S2, washing is performed by using water and a saturated sodium chloride solution in sequence.
More specifically, the ratio of the molar amount of the intermediate 2 in the S3 to the volume of the tetrahydrofuran solution, the methanol solution and the sodium hydroxide solution is 1mmol: (15-25) mL: (35-45) mL: (25-35) mL.
More specifically, the concentration of the sodium hydroxide solution in S3 is 0.3 to 0.35mol/L.
The invention also aims to provide a preparation method of the metal organic framework material, which comprises the following steps:
dissolving zirconium tetrachloride and an organic ligand in a mixed solution of N, N-dimethylformamide and hydrochloric acid, performing ultrasonic treatment, heating for reaction, centrifuging after the reaction, washing, and drying to obtain MOF-ET8, namely the metal organic framework material.
Further defined, the molar ratio of zirconium tetrachloride to organic ligand is 0.27: (0.35-0.4).
Further defined, the ratio of the mass of zirconium tetrachloride to the volume of the mixed solution is 63mg: (7-9) mL.
Further, the concentration of hydrochloric acid is 1mol/L.
Further limiting, the heating reaction temperature is 70-90 ℃, and the time is 10-14h.
The fourth purpose of the present invention is to provide an application of the metal organic framework material in an electrode material.
Further defined, the electrode material is CNT @ MOF-ET8-S.
The invention also aims to provide a preparation method of the electrode material CNT @ MOF-ET8-S, which comprises the following steps:
step 1: carrying out acid treatment on Carbon Nano Tubes (CNT), then washing with water and freeze-drying;
and 2, step: adding the MOF-ET8, the CNT and a hydrochloric acid solution into N, N-dimethylformamide, performing ultrasound treatment, performing a heating reaction, centrifuging, washing and drying in vacuum to obtain CNT @ MOF-ET8;
and 3, step 3: mixing CNT @ MOF-ET8 and sulfur, transferring the mixture into an autoclave under the protection of argon, heating the mixture for 8 to 12 hours at the temperature of between 150 and 170 ℃, and heating the mixture for 1 to 3 hours at the temperature of between 150 and 250 ℃ in a nitrogen atmosphere to obtain a positive electrode material CNT @ MOF-ET8-S.
Further limiting, the acid treatment process in the step 1: and adding CNT into mixed acid of sulfuric acid/nitric acid, and soaking for 5-7h.
Further limiting, the volume ratio of the sulfuric acid to the nitric acid is 7.
Further defined, the mass to volume ratio of CNT to mixed acid is 200mg: (8-12) mL.
Further defining that the mass ratio of the MOF-ET8 to the CNT in the step 2 is 2:3.
further defined, the mass to hydrochloric acid volume ratio of CNTs in step 2 is 35mg: (0.45-0.55) mL, and the concentration of hydrochloric acid is 1mol/L.
Further limiting, the volume ratio of hydrochloric acid to N, N-dimethylformamide in step 2 is (0.45-0.55): 7.5.
further limiting, in the step 2, the heating reaction temperature is 70-90 ℃, the time is 10-14h, the vacuum drying temperature is 110-130 ℃, and the time is 10-14h.
Further limiting, the mass ratio of CNT @ MOF-ET8 to sulfur in step 3 is 1: (2-4).
The invention aims at providing an application of an electrode material CNT @ MOF-ET8-S in a lithium sulfur battery.
Compared with the prior art, the invention has the advantages that:
the invention provides a novel metal organic framework material, which is applied to the preparation of a co-polysulfide positive electrode, and the positive electrode material can promote the transformation of polysulfide, inhibit the shuttle effect of a lithium-sulfur battery and promote Li 2 S is uniformly deposited and converted in the anode, so that the specific capacity and the cycling stability of the lithium-sulfur battery are greatly improved, and the lithium-sulfur battery can be applied to the field of new energy automobile batteriesHas prominent market potential and the specific advantages are as follows:
1) According to the results of single crystal X-ray diffraction tests, the MOF-ET8 is in a hexagonal crystal system, the space group is P42 (68), the MOF-ET8 crystal structure is an infinite chain structure formed by connecting zirconium ions and ligands along the a-axis direction, and the structure is favorable for effective transmission of electrons and improves the conductivity of the electrode material.
2) The lithium sulfur battery based on the positive electrode material CNT @ MOF-ET8-S of the porous metal organic framework material MOF-ET8 has the charge transfer resistance of 27.6 omega and excellent charge transfer capacity. In addition, a cycle performance test was carried out, and the specific capacity of initial discharge was 1425.8 mA · hg −1 After circulation, the specific capacity of the lithium-sulfur battery can be still maintained at 1325.7 mA-hg −1 The coulombic efficiency is 99.8%, and the composite material has good cycling stability and high specific capacity.
Drawings
FIG. 1 is a synthesis scheme of organic ligands in the metal organic framework material of example 1;
FIG. 2 is a schematic view of the structural composition of a lithium sulfur battery in application example 1;
fig. 3 is an ac impedance test chart of the lithium sulfur battery of application example 1 before non-discharge cycle;
FIG. 4 is a graph showing the AC impedance test after the charge-discharge cycle of the lithium sulfur battery of application example 1;
fig. 5 is a cycle performance test chart of the lithium sulfur battery of application example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention.
The experimental procedures used in the following examples are conventional unless otherwise specified. The materials, reagents, methods and apparatus used, unless otherwise specified, are conventional in the art and are commercially available to those skilled in the art.
The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," or any other variation thereof, as used in the following embodiments, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or range defined by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when the range "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range. In the present description and claims, range limitations may be combined and/or interchanged, including all sub-ranges contained therein if not otherwise stated.
Example 1: as shown in fig. 1, the preparation method of a metal organic framework material of this embodiment is performed according to the following steps:
the 1, 4-dibromo-2, 5-dimethoxybenzene (feed 1, CAS: 2674-34-2) and methyl 2-amino-4-bromobenzoate (feed 2, CAS: 135484-83-2) described in the following procedure were obtained from Sigma-Aldrich company as direct purchases.
Synthesis of intermediate 1:
at-78 ℃, n-butyllithium (60 ml, 96 mmol), 1, 5-dibromo-2, 4-dimethoxybenzene (8.88 g, 30 mmol) and 10 ml of tetrahydrofuran are sequentially added to 50 ml of n-hexane, the mixed solution is heated to 0 ℃, stirred at 0 ℃ for 12 hours, cooled to-78 ℃, added with trimethyl borate (3.5 ml, 31 mmol), heated to 25 ℃, stirred at 25 ℃ for 18 hours, added with 10 ml of hydrochloric acid solution with the concentration of 2mol/L, stirred at 25 ℃ for 0.5 hours, and finally the precipitate is washed with water, diethyl ether and chloroform in sequence and dried to obtain 0.59 g of solid, namely intermediate 1 with the yield of 85%.
Nuclear magnetic characterization and identification results of the intermediate 1:
hydrogen spectrum: 1 H NMR (400 MHz, DMSO): δ 3.86 (6 H, s), 6.54(1 H, s), 7.41(4 H, s), 7.90(1 H, s) 。
carbon spectrum: 13 C NMR (100 MHz, DMSO): δ 55.3, 93.8, 111.9, 144.4, 167.7。
and (3) mass spectrum characterization results: ESI (M/z) < M + H] + Calcd. for C 8 H 12 B 2 O 6 , 225.8; Found, 226.6。
Elemental analysis test results: calcd, for C 8 H 12 B 2 O 6 , C, 42.55, H, 5.36, O, 42.51; Found, C, 43.28, H, 6.02, O, 43.29。
Synthesis of intermediate 2:
in a 500 ml three-necked flask, 80 ml of a mixed solution of water/dioxane (water/dioxane v: v = 1), followed by sequentially adding intermediate 1 (0.45 g, 2 mmol), methyl 2-amino-4-bromobenzoate (1.15 g, 5 mmol), cesium fluoride (1.8 g, 11.8 mmol) and palladium dichloride (0.1 g, 0.14 mmol), and the mixture was heated under argon with stirring at reflux for 24 hours, the reaction system was cooled to 25 ℃, 200 ml of dichloromethane was added for standing and layering, then washed sequentially with 500 ml of water and 200 ml of a saturated sodium chloride solution, followed by drying over sodium sulfate, followed by spin-drying of the organic phase, and finally, silica gel column chromatography was performed with dichloromethane/ethyl acetate as an eluent to obtain 0.69 g of a yellow solid in a yield of 80%.
And the nuclear magnetic characterization and identification result of the intermediate 2:
hydrogen spectrum: 1 H NMR (400 MHz, DMSO): δ 7.99 (d, 2 H), 7.52 (d, 2 H), 7.36 (s, 4 H), 7.24 (d, 2 H), 7.05 (d, 2 H), 3.983 (s, 6 H), 3.854 (s, 6 H)。
carbon spectrum: 13 C NMR (100 MHz, DMSO): δ 166.79, 151.14, 148.97, 139.97,133.32, 130.90, 116.79, 112.90, 112.38, 110.13, 55.99, 51.52。
and (3) mass spectrum characterization results: ESI (M/z) < M + H] + Calcd. for C 24 H 24 N 2 O 6 , 436.46; Found, 437.21。
Elemental analysis test results: calcd, for C 24 H 24 N 2 O 6 , C, 66.05, H, 5.54, O, 21.99; Found, C, 66.75, H, 5.91, O, 20.89。
Organic ligand C 22 H 20 N 2 O 6 The synthesis of (2):
to a three-necked flask was added intermediate 2 (0.33 g, 1 mmol), 20 ml of tetrahydrofuran, 40 ml of methanol, and 30 ml of an aqueous solution of sodium hydroxide (0.41 g, 10 mmol), and after heating under reflux and stirring for 24 hours, the reaction system was cooled to 25 ℃ and the organic phase was spun off, and then a hydrochloric acid solution having a concentration of 1mol/L was added to adjust the pH to 5 to obtain a pale yellow paste, and after centrifugation, the precipitate was washed with 40 ml of water, washed three times, and then dried under vacuum to obtain 0.38 g of a yellow solid with a yield of 92%.
Organic ligand C 22 H 20 N 2 O 6 The nuclear magnetic characterization identification result is as follows:
hydrogen spectrum: 1 H NMR (400 MHz, DMSO): δ 8.16 (d, 2 H), 7.52 (d, 2 H), 7.31 (d, 2 H), 7.15 (d, 2 H),7.03 (s, 4 H), 3.86 (s, 6 H)。
carbon spectrum: 13 C NMR (100 MHz, DMSO): δ 168.77, 151.14, 149.64, 139.83,
132.57, 130.90, 116.08, 113.69, 112.36, 110.13, 55.99。
and (3) mass spectrum characterization results: ESI (M/z) < M + H] + Calcd. for C 22 H 20 N 2 O 6 , 408.41; Found, 409.21。
Elemental analysis test results: calcd, for C 22 H 20 N 2 O 6 , C, 64.7, H, 4.94, O, 23.50; Found, C, 65.45, H, 5.42, O, 22.49。
MOF-ET8[ Zr ] metal organic framework material 2 (C 22 H 20 N 2 O 6 ) 3 ]The preparation of (1):
zirconium tetrachloride (63 mg, 0.27 mmol) and organic ligand C 22 H 20 N 2 O 6 (155 mg, 0.38 mmol) is dissolved in a mixed solution consisting of 500 microliters of 1mol/L hydrochloric acid solution and 7.5 milliliters of N, N-dimethylformamide, then ultrasonic treatment is carried out for 5 minutes, heating is carried out for 12 hours at 80 ℃, then a centrifuge is used for centrifuging for 20 minutes at the rotating speed of 10000 r/min, the precipitate is washed for three times by methanol, 10 milliliters each time, and finally vacuum drying is carried out for 12 hours at 120 ℃, thus obtaining the porous MOF-ET8.
Characterization of the porous metal organic framework material MOF-ET 8:
the synthesized MOF-ET8 crystal is stored in a glass capillary, a crystal structure is tested by adopting a monocrystal X-ray, an instrument is a Bruker-Apex II type CCD detector, a Cu Ka (lambda = 1.54178A) X-ray source is used for collecting, data are corrected for absorption by adopting an SADABS program, extinction or decay is not corrected, a SHELXTL software package is used for directly solving, and a test result is shown in Table 1.
TABLE 1 MOF-ET8 Crystal Structure parameters
| Sample (I) | MOF-ET8 |
| Chemical formula (II) | C 66 H 60 N 6 O 18 Zr 2 |
| Molecular weight | 1407.68 |
| Crystal system | Hexagonal system hexagonal |
| Space group | P 42（68） |
| a/Å | 19.9686(6) |
| b/Å | 19.9686(6) |
| c/Å | 7.2437(3) |
| α/° | 90 |
| β/° | 90 |
| γ/° | 120 |
| Volume of | 2931.71(8) |
| Number of molecules contained in |
6 |
| Unit cell density | 0.509 |
| Coefficient of absorption | 1.948 |
| Number of electrons in unit cell | 2578.0 |
| Crystal size | 0.06 × 0.04 × 0.03 |
| Radiation rays | CuKα (λ = 1.54178) |
| Angle of collection by diffraction | 11.59 to 99.58 |
| Range of diffraction indices | -34 ≤ h ≤ 35, -38 ≤ k ≤ 32, -16 ≤ l ≤ 15 |
| Collection of diffraction points | 52289 |
| Independent diffraction points | 4275 [Rint = 0.0619, Rsigma = 0.0288] |
| Data restrictive parameters | 4275/175/168 |
| GOF value based on F2 | 1.085 |
| Residual factor R value of observable diffraction point | R 1 = 0.0575, wR 2 = 0.1123 |
| Residual factor R value of all diffraction points | R 1 = 0.0584, wR 2 = 0.1350 |
| Peak and valley values of residual electron density | 1.00/-0.93 |
| CCDC | 1989619 |
Example 2: application of the metal organic framework material MOF-ET8 prepared in example 1 in the electrode material of CNT @ MOF-ET8-S.
The preparation method of the positive electrode material CNT @ MOF-ET8-S comprises the following steps:
step 1: adding 200mg of Carbon Nano Tubes (CNT) into a mixed solution of 7 ml of sulfuric acid with the mass concentration of 98% and 3 ml of nitric acid with the mass concentration of 68%, soaking for 6 hours, washing the CNT with deionized water, and then freezing and drying the CNT after acid treatment;
step 2: adding the MOF-ET8 obtained in the step 1, 35mg of CNT and 500 microliters of hydrochloric acid solution with the concentration of 1mol/L into 7.5 milliliters of N, N-dimethylformamide, carrying out ultrasonic treatment for 5 minutes, heating at 80 ℃ for 12 hours, centrifuging, washing the precipitate with methanol for three times, 10 milliliters each time, and finally carrying out vacuum drying on the sample at 120 ℃ for 12 hours to obtain CNT @ MOF-ET8;
and step 3: and (3) mixing the CNT @ MOF-ET8 obtained in the step (2) with sulfur according to the mass ratio of 1: 3, transferring the mixture into an autoclave under the protection of argon, heating the mixture for 10 hours at 160 ℃, and heating the mixture for 2 hours at 200 ℃ in a nitrogen atmosphere to obtain the positive electrode material CNT @ MOF-ET8-S with high charge transfer performance.
Application example 1: the positive electrode material CNT @ MOF-ET8-S prepared in example 2 is used for preparing the lithium sulfur battery, and the specific steps are as follows:
(1) Preparing a positive plate: the positive electrode material CNT @ MOF-ET8-S of example 2 is mixed with a conductive agent and polyvinylidene fluoride according to the mass ratio of 7 to 1, N-methylpyrrolidone is added, stirring reaction is carried out at 25 ℃ for 24 hours, then the mixture is uniformly coated on an aluminum foil, the aluminum foil is placed into a vacuum oven at 60 ℃ for drying for 12 hours, and then an electrode slice with the diameter of 12 mm is manufactured by a puncher.
(2) Preparing a negative electrode: mixing polyvinylpyrrolidone and polyethyleneimine according to a volume ratio of 2 to obtain a binder, then mixing propylene carbonate, ethyl methyl carbonate and polyether sulfone according to a volume ratio of 3; and heating the negative plate at 70 ℃, and flattening the negative plate to obtain the negative plate of the battery.
(3) Assembling the battery: the prepared positive plate and negative plate were assembled into a lithium sulfur battery as shown in fig. 2.
Characterization of lithium sulfur battery performance:
the method comprises the following steps of (I) alternating current impedance spectrum testing: and standing the battery for 24 hours, and testing the alternating current impedance spectrum of the lithium-sulfur battery through an electrochemical workstation, wherein the alternating current impedance test frequency range is 100 KHz to 10 mHz, and the alternating current disturbance signal is 5 mV.
The test results are shown in FIG. 3, and it can be seen from FIG. 3 that the charge transfer resistance of the lithium sulfur battery with the positive electrode material of CNT @ MOF-ET8-S is 27.6 Ω, which indicates that the lithium sulfur battery with the positive electrode material of CNT @ MOF-ET8-S has excellent charge transfer capability.
In addition, after cycling for 100 cycles under the rate condition of 1C, the test results are shown in fig. 4, and it is apparent from fig. 4 that the impedance after 100 cycles is significantly smaller than that without discharge, which is seen from the impedance spectrum before and after charging and discharging, due to Li during charging and discharging 2 S/Li 2 S 2 And S 8 And (4) mutual transformation is carried out.
(II) cycle performance test: the cycle performance test is carried out by a Xinwei battery test system, the charge-discharge voltage range is 1.7V-2.8V, and the discharge multiplying power is 0.2C.
As shown in FIG. 5, it can be seen from FIG. 5 that the lithium-sulfur battery with the positive electrode material of CNT @ MOF-ET8-S has a high specific capacity, the initial specific discharge capacity is 1425.8 mA · hg −1 After 100 cycles, the specific capacity can still be maintained at 1325.7 mA · hg −1 The attenuation rate was 0.012%, showing good battery performance.
Meanwhile, as can be seen from the accompanying drawing 5 of the specification, the coulombic efficiency of the lithium sulfur battery with the positive electrode material of CNT @ MOF-ET8-S is 99.8%, which indicates that the lithium sulfur battery with the positive electrode material of CNT @ MOF-ET8-S has good cycling stability, and metal ions contained in the material can react with polysulfide, so that the shuttle effect of polysulfide is inhibited.
While the invention has been described with reference to specific preferred embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but is intended to cover various modifications and alternative embodiments, which may be apparent to those skilled in the art, within the spirit and scope of the invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.
Claims (10)
1. The metal organic framework material is characterized in that the metal organic framework material is MOF-ET8 with the chemical formula of [ Zr ] 2 (L) 3 ]Wherein L is an organic ligand C 22 H 20 N 2 O 6 。
2. The metal-organic framework material of claim 1, wherein the organic ligand has the structure:
。
3. a process for the preparation of an organic ligand according to claim 2, characterised in that the process comprises the steps of:
s1: sequentially adding n-butyllithium, 1, 5-dibromo-2, 4-dimethoxybenzene and tetrahydrofuran into n-hexane at the temperature of-78 ℃, heating to 0 ℃, stirring for 12 hours at the temperature of 0 ℃, cooling to-78 ℃, adding trimethyl borate, heating to 25 ℃, stirring for 18 hours at the temperature of 25 ℃, adding hydrochloric acid, stirring for 0.5 hour at the temperature of 25 ℃, washing and drying to obtain an intermediate 1;
s2: sequentially adding an intermediate 1, 2-amino-4-methyl bromobenzoate, cesium fluoride and palladium dichloride into a water/dioxane mixed solution, heating, stirring and refluxing for 24 hours under the protection of argon, cooling to 25 ℃, adding dichloromethane, standing for layering, washing, drying, spin-drying an organic phase, and finally performing silica gel column chromatography by using dichloromethane/ethyl acetate as an eluent to obtain an intermediate 2;
s3: and mixing the intermediate 2, tetrahydrofuran, methanol and a sodium hydroxide solution, heating, refluxing and stirring for 24 hours, cooling to 25 ℃, then spin-drying an organic phase, then adjusting the pH value to 5, centrifuging, washing with water, precipitating, and finally drying in vacuum to obtain the organic ligand.
4. A method for preparing a metal-organic framework material according to claim 1 or 2, characterized in that the method is carried out as follows:
dissolving zirconium tetrachloride and an organic ligand in a mixed solution of N, N-dimethylformamide and hydrochloric acid, firstly performing ultrasonic treatment, then heating for reaction, centrifuging after reaction, washing and drying to obtain MOF-ET8, namely the metal organic framework material.
5. The process according to claim 4, wherein the molar ratio between zirconium tetrachloride and organic ligand is 0.27: (0.35-0.4), heating to react at 70-90 ℃ for 10-14h.
6. Use of a metal-organic framework material according to claim 1 or 2 in an electrode material.
7. Use according to claim 6, wherein the electrode material is CNT @ MOF-ET8-S.
8. A process for the preparation of CNT @ MOF-ET8-S as claimed in claim 7, wherein said process is carried out by the following steps:
step 1: performing acid treatment on CNT, then washing with water and freeze-drying;
and 2, step: adding the MOF-ET8, the CNT and a hydrochloric acid solution into N, N-dimethylformamide, performing ultrasound treatment, performing a heating reaction, centrifuging, washing and drying in vacuum to obtain CNT @ MOF-ET8;
and step 3: mixing CNT @ MOF-ET8 and sulfur, transferring the mixture into an autoclave under the protection of argon, heating the mixture for 8 to 12 hours at the temperature of between 150 and 170 ℃, and then heating the mixture for 1 to 3 hours at the temperature of between 150 and 250 ℃ in a nitrogen atmosphere to obtain the positive electrode material CNT @ MOF-ET8-S.
9. The method according to claim 8, wherein the acid treatment process in step 1: adding CNT into mixed acid of sulfuric acid/nitric acid, and soaking for 5-7h; heating in the step 2 at 70-90 ℃ for 10-14h; the mass ratio of CNT @ MOF-ET8 to sulfur in step 3 is 1: (2-4).
10. Use of the electrode material CNT @ MOF-ET8-S of claim 7 in a lithium sulfur battery.
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