CN113097467B - Preparation method of lithium ion battery composite material with double-layer shell structure - Google Patents
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Abstract
The invention discloses a preparation method of a lithium ion battery composite material with a double-shell structure, which comprises the steps of adding cobalt nitrate hexahydrate into N, N-dimethylformamide, carrying out ultrasonic dissolution to obtain a solution I, adding 2, 5-dihydroxyterephthalic acid into an absolute ethyl alcohol solution, carrying out ultrasonic dissolution to obtain a solution II, mixing and stirring the solutions I and II, adding distilled water, moving the solution I and II into a polytetrafluoroethylene reaction kettle, reacting at 110-120 ℃ for 24-30 h, cooling to obtain a metal organic framework Co-MOF-74, adding copper nitrate trihydrate into a methanol solution, carrying out ultrasonic dissolution, adding the metal organic framework Co-MOF-74 in the step S1, carrying out magnetic stirring at room temperature for 3-6 h, adding citric acid for ultrasonic stirring, moving to the polytetrafluoroethylene reaction kettle, reacting at 60-80 ℃ for 3-5 h, cooling, filtering and drying; and (3) placing the dried product in a tubular furnace, heating to 580-520 ℃ at a heating rate of 5-8 ℃/min in an air atmosphere, keeping the temperature for 4-7 h, and then cooling to room temperature at a rate of 0.5-1.2 ℃/min to obtain the composite material.
Description
Technical Field
The invention belongs to the technical field of preparation of lithium ion battery composite materials, and particularly relates to a preparation method of a lithium ion battery composite material with a double-shell structure.
Background
Lithium ion batteries are becoming the main carrying power source of electric vehicles due to the performance advantages of high specific energy, durability, stability and the like, and chemical energy storage technologies represented by the lithium ion batteries are also being actively researched and developed. The cathode material of the current commercial lithium ion battery is a graphite carbon material, but the theoretical capacity of the cathode material is only 372 mAh/g; on the other hand, the lithium insertion potential of the material is mainly concentrated in 0-0.1V (vs. Li/Li) + ) In the range very close to the deposition potential of metallic lithium, is detrimental to the safety of the battery. In order to meet the requirement of high-capacity lithium ion batteries, research and development of high-specific-capacity and reliable-safety lithium ion battery electrode materials are urgent and necessary.
The metal organic framework Material (MOF) is a novel porous material with a network structure, is formed by inputting organic ligands through coordination bonds, and is widely applied to lithium battery electrode materials in the existing energy raw materials due to the fact that the metal organic framework material has a large specific surface area, good porosity, good thermal stability and an ordered crystal structure, but the electrode material obtained from the MOF material has poor conductivity due to the poor conductivity of the MOF, and further the application of the metal organic framework material in the electrode material is limited.
Disclosure of Invention
The invention aims to provide a preparation method of a lithium ion battery composite material with a double-layer shell structure, which comprises the following steps:
s1: adding cobalt nitrate hexahydrate into N, N-dimethylformamide, performing ultrasonic dissolution to obtain a solution I, adding 2, 5-dihydroxyterephthalic acid into an absolute ethyl alcohol solution, performing ultrasonic dissolution to obtain a solution II, mixing and stirring the solutions I and II, adding distilled water, transferring the solution I and II into a polytetrafluoroethylene reaction kettle, reacting for 24-30 hours at 110-120 ℃, and cooling to obtain a metal organic framework Co-MOF-74 for later use.
S2: adding copper nitrate trihydrate into a methanol solution, adding the metal organic framework Co-MOF-74 obtained in the step S1 after ultrasonic dissolution, magnetically stirring for 3-6 hours at room temperature, adding citric acid for ultrasonic treatment, moving to a polytetrafluoroethylene reaction kettle, reacting for 3-5 hours at 60-80 ℃, cooling, filtering and drying. In the step, a methanol solution is adopted to carry out displacement activation on solvent molecules in one-dimensional pore channels of the metal organic framework Co-MOF-74, so that Cu is obtained 2+ Entering the pore channel, and then adding citric acid which is easy to react with the exposed metal sites of the metal organic framework Co-MOF-74 to coat Cu 2+ On the inner wall of the duct.
S3: and (4) placing the dried product in the step S2 in a tubular furnace, rapidly heating to 480-520 ℃ at a heating rate of 5-8 ℃/min in an air atmosphere, keeping the temperature for 4-7 h, and then cooling to room temperature at a rate of 0.5-1.2 ℃/min to obtain the composite material. In the step, the temperature is increased at a faster temperature increase rate when the calcination is started, so that a larger temperature gradient exists, a layer of shell substance is formed on the surface of the composite, the shell substance on the outer surface is hardened along with the rapid temperature increase, a layer of protective substance is formed, the organic ligand 2, 5-dihydroxyterephthalic acid and the citric acid which plays a complexing role are oxidized and decomposed along with the continuation of the calcination to generate a contractility, the contractility is contracted towards the core, and finally the inner core begins to diffuse outwards, and a double-shell structure is formed inside.
Preferably, the mass ratio of the cobalt nitrate hexahydrate to the 2, 5-dihydroxy terephthalic acid is (1.2-2.8) to (0.46-0.85).
Preferably, the volume ratio of the N, N-dimethylformamide to the absolute ethyl alcohol to the distilled water is (15-20): (10-14): 1.5-3.
Preferably, the mass-volume ratio of the copper nitrate trihydrate, the methanol solution and the citric acid is (1.02-1.28) g, (14-20) mL and (1.36-1.69) g.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, a metal organic framework material is synthesized by using a hydrothermal synthesis method, then a methanol solution of copper salt with a certain concentration is adopted for solvent replacement activation, copper ions further enter the Co-MOF-74 pore channels, citric acid is added to generate an affinity effect with metal sites inside the metal organic framework material, more copper ions enter the pore channels, and then the composite material is obtained after calcination.
Drawings
FIG. 1 is a TEM image of a composite material prepared in example 1 of the present invention;
FIG. 2 is a constant current charge and discharge curve of the composite material prepared in example 1 of the present invention;
FIG. 3 is a graph of electrochemical cycle performance of a composite material prepared in example 1 of the present invention;
FIG. 4 is a Nyquist plot of composites prepared in example 1 of the present invention.
Detailed Description
The following embodiments of the present invention are described in detail, and the embodiments are implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, it should be noted that, for those skilled in the art, a plurality of modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Example 1
A preparation method of a lithium ion battery composite material with a double-shell structure specifically comprises the following steps:
s1: adding cobalt nitrate hexahydrate into N, N-dimethylformamide, performing ultrasonic dissolution to obtain a solution I, adding 2, 5-dihydroxyterephthalic acid into an absolute ethyl alcohol solution, performing ultrasonic dissolution to obtain a solution II, mixing and stirring the solutions I and II, adding distilled water, transferring the solution I and II into a polytetrafluoroethylene reaction kettle, reacting for 24 hours at 110 ℃, and cooling to obtain a metal organic framework Co-MOF-74 for later use; wherein the mass ratio of the cobalt nitrate hexahydrate to the 2, 5-dihydroxy terephthalic acid is 1.2: 0.46; the volume ratio of the N, N-dimethylformamide to the absolute ethyl alcohol to the distilled water is 15:10: 1.5.
S2: adding copper nitrate trihydrate into a methanol solution, adding the metal organic framework Co-MOF-74 obtained in the step S1 after ultrasonic dissolution, magnetically stirring for 3 hours at room temperature, adding citric acid for ultrasonic treatment, moving to a polytetrafluoroethylene reaction kettle, reacting for 3 hours at 60 ℃, cooling, filtering and drying.
S3: placing the dried product in the step S2 in a tubular furnace, rapidly heating to 480 ℃ at a heating rate of 5 ℃/min under the air atmosphere, then keeping the temperature for 4h, and then cooling to room temperature at a rate of 0.5 ℃/min to obtain the composite material; wherein the mass-volume ratio of the copper nitrate trihydrate, the methanol solution and the citric acid is 1.02g to 14mL to 1.36 g.
Example 2
A preparation method of a lithium ion battery composite material with a double-shell structure specifically comprises the following steps:
s1: adding cobalt nitrate hexahydrate into N, N-dimethylformamide, performing ultrasonic dissolution to obtain a solution I, adding 2, 5-dihydroxyterephthalic acid into an absolute ethyl alcohol solution, performing ultrasonic dissolution to obtain a solution II, mixing and stirring the solutions I and II, adding distilled water, transferring the solution I and II into a polytetrafluoroethylene reaction kettle, reacting for 30 hours at 120 ℃, and cooling to obtain a metal organic framework Co-MOF-74 for later use; wherein the mass ratio of the cobalt nitrate hexahydrate to the 2, 5-dihydroxy terephthalic acid is 2.8: 0.85; the volume ratio of the N, N-dimethylformamide to the absolute ethyl alcohol to the distilled water is 20:14: 3.
S2: adding copper nitrate trihydrate into a methanol solution, adding the metal organic framework Co-MOF-74 obtained in the step S1 after ultrasonic dissolution, magnetically stirring for 6 hours at room temperature, adding citric acid for ultrasonic treatment, moving to a polytetrafluoroethylene reaction kettle, reacting for 5 hours at 80 ℃, cooling, filtering and drying.
S3: placing the dried product in the step S2 in a tube furnace, rapidly heating to 520 ℃ at a heating rate of 8 ℃/min under the air atmosphere, then keeping the temperature for 7h, and then cooling to room temperature at a rate of 1.2 ℃/min to obtain the composite material; wherein the mass-volume ratio of the copper nitrate trihydrate, the methanol solution and the citric acid is 1.28g, 20mL and 1.69 g.
Example 3
A preparation method of a lithium ion battery composite material with a double-shell structure specifically comprises the following steps:
s1: adding cobalt nitrate hexahydrate into N, N-dimethylformamide, performing ultrasonic dissolution to obtain a solution I, adding 2, 5-dihydroxyterephthalic acid into an absolute ethyl alcohol solution, performing ultrasonic dissolution to obtain a solution II, mixing and stirring the solutions I and II, adding distilled water, transferring the solution I and II into a polytetrafluoroethylene reaction kettle, reacting for 26 hours at 115 ℃, and cooling to obtain a metal organic framework Co-MOF-74 for later use; wherein the mass ratio of the cobalt nitrate hexahydrate to the 2, 5-dihydroxy terephthalic acid is 1.8: 0.54; the volume ratio of the N, N-dimethylformamide to the absolute ethyl alcohol to the distilled water is 16:12: 1.9.
S2: adding copper nitrate trihydrate into a methanol solution, adding the metal organic framework Co-MOF-74 obtained in the step S1 after ultrasonic dissolution, magnetically stirring for 4 hours at room temperature, adding citric acid for ultrasonic treatment, moving to a polytetrafluoroethylene reaction kettle, reacting for 4 hours at 70 ℃, cooling, filtering and drying.
S3: placing the dried product in the step S2 in a tube furnace, rapidly heating to 500 ℃ at a heating rate of 6 ℃/min in an air atmosphere, then keeping the temperature for 5h, and then cooling to room temperature at a rate of 0.7 ℃/min to obtain the composite material; wherein the mass-volume ratio of the copper nitrate trihydrate, the methanol solution and the citric acid is 1.16g to 16mL to 1.49 g.
Example 4
A preparation method of a lithium ion battery composite material with a double-shell structure specifically comprises the following steps:
s1: adding cobalt nitrate hexahydrate into N, N-dimethylformamide, performing ultrasonic dissolution to obtain a solution I, adding 2, 5-dihydroxyterephthalic acid into an absolute ethyl alcohol solution, performing ultrasonic dissolution to obtain a solution II, mixing and stirring the solutions I and II, adding distilled water, transferring the solution I and II into a polytetrafluoroethylene reaction kettle, reacting for 28 hours at 118 ℃, and cooling to obtain a metal organic framework Co-MOF-74 for later use; wherein the mass ratio of the cobalt nitrate hexahydrate to the 2, 5-dihydroxy terephthalic acid is 2.5: 0.82; the volume ratio of the N, N-dimethylformamide to the absolute ethyl alcohol to the distilled water is 18:13: 2.6.
S2: adding copper nitrate trihydrate into a methanol solution, adding the metal organic framework Co-MOF-74 obtained in the step S1 after ultrasonic dissolution, magnetically stirring for 5 hours at room temperature, adding citric acid for ultrasonic treatment, moving to a polytetrafluoroethylene reaction kettle, reacting for 4 hours at 75 ℃, cooling, filtering and drying.
S3: placing the dried product in the step S2 in a tube furnace, rapidly heating to 510 ℃ at a heating rate of 7 ℃/min in an air atmosphere, then keeping the temperature for 6h, and then cooling to room temperature at a rate of 1 ℃/min to obtain the composite material; wherein the mass-volume ratio of the copper nitrate trihydrate, the methanol solution and the citric acid is 1.25g to 18mL to 1.64 g.
Examples of the experiments
Performance test-the composite material prepared in example 1, acetylene black and polyvinylidene fluoride were mixed at a mass ratio of 8:1:1, and then an appropriate amount of N-methylpyrrolidone was added as a dispersant, and the mixture was dispersed with a high-speed disperser, and the resulting slurry was applied to a clean sheet of paperDrying the copper sheet for 24 hours at 60 ℃ in vacuum to obtain an electrode; the electrochemical performance tests of the electrodes prepared from the composite material in the example 1 are all assembled into a 2032 type button cell, the test is carried out at room temperature, the cell is assembled in a glove box filled with argon, the button cell uses a high-purity lithium sheet as a reference electrode, a polypropylene membrane is adopted as a diaphragm, and 1mol/L LiPF is used as an electrolyte 6 The solvent comprises ethylene carbonate, dimethyl carbonate and diethyl carbonate, wherein the ethylene carbonate, the dimethyl carbonate and the diethyl carbonate are 1:1:1, the battery needs to be kept still for 24 hours before testing, an electrochemical workstation is used for testing, and the test result is shown in fig. 2-4.
As can be seen from fig. 1, the composite material prepared in example 1 has a double-shell structure, as can be seen from fig. 2, the composite material has a higher specific capacity, as can be seen from fig. 3, after 50 cycles, the composite electrode material still maintains the discharge specific capacity of 1120.4mA · h/g, and has a higher capacity performance, as can be seen from fig. 4, the resistance value of the composite material is 147 Ω, which is beneficial to the improvement of the capacity of a lithium battery, and the cycle stability of the composite material is better.
It should be specifically noted that the composite materials prepared in the other embodiments of the present invention have the same or similar properties as the composite material prepared in example 1, and are not repeated herein.
Claims (4)
1. A preparation method of a lithium ion battery composite material with a double-shell structure is characterized by comprising the following steps:
s1: adding cobalt nitrate hexahydrate into N, N-dimethylformamide, performing ultrasonic dissolution to obtain a solution I, adding 2, 5-dihydroxyterephthalic acid into an absolute ethyl alcohol solution, performing ultrasonic dissolution to obtain a solution II, mixing and stirring the solutions I and II, adding distilled water, transferring the solution I and II into a polytetrafluoroethylene reaction kettle, reacting for 24-30 hours at 110-120 ℃, and cooling to obtain a metal organic framework Co-MOF-74 for later use;
s2: adding copper nitrate trihydrate into a methanol solution, performing ultrasonic dissolution, adding the metal organic framework Co-MOF-74 obtained in the step S1, performing magnetic stirring at room temperature for 3-6 hours, adding citric acid, performing ultrasonic treatment, moving to a polytetrafluoroethylene reaction kettle, reacting at 60-80 ℃ for 3-5 hours, cooling, filtering and drying;
s3: and (4) placing the dried product in the step S2 in a tubular furnace, rapidly heating to 480-520 ℃ at a heating rate of 5-8 ℃/min in an air atmosphere, keeping the temperature for 4-7 h, and then cooling to room temperature at a rate of 0.5-1.2 ℃/min to obtain the composite material.
2. The method for preparing the lithium ion battery composite material with the double-shell structure according to claim 1, wherein the mass ratio of the cobalt nitrate hexahydrate to the 2, 5-dihydroxy terephthalic acid is (1.2-2.8) to (0.46-0.85).
3. The method for preparing the lithium ion battery composite material with the double-shell structure according to claim 1, wherein the volume ratio of the N, N-dimethylformamide to the absolute ethyl alcohol to the distilled water is (15-20) to (10-14) to (1.5-3).
4. The preparation method of the lithium ion battery composite material with the double-shell structure according to claim 1, wherein the mass-volume ratio of the copper nitrate trihydrate, the methanol solution and the citric acid is (1.02-1.28) g, (14-20) mL and (1.36-1.69) g.
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| WO2021037428A1 (en) * | 2019-08-23 | 2021-03-04 | Technische Universität Berlin | Supercapacitors comprising phosphonate and arsonate metal organic frameworks (mofs) as active electrode materials |
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| CN103992339A (en) * | 2014-05-21 | 2014-08-20 | 哈尔滨工业大学 | Method for synthesizing metal organic framework material Mg-MOF-74 |
| CN105037444A (en) * | 2015-06-19 | 2015-11-11 | 哈尔滨工业大学 | Synthetic method of metal organic frameworks Co-MOF-74 |
| CN108321358A (en) * | 2017-01-16 | 2018-07-24 | 北京化工大学 | A kind of lithium ion battery negative material and preparation method thereof |
| KR20190036700A (en) * | 2017-09-28 | 2019-04-05 | 주식회사 엘지화학 | A carbon -surfur complex, manufacturing method thereof and lithium secondary battery comprising the same |
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