CN110854375A - Preparation method and application of Ti-MOF metal organic framework material, lithium titanate and carbon-coated lithium titanate - Google Patents
Preparation method and application of Ti-MOF metal organic framework material, lithium titanate and carbon-coated lithium titanate Download PDFInfo
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Abstract
The invention relates to the technical field of lithium ion batteries, and particularly discloses a preparation method and application of a Ti-MOF metal organic framework material, lithium titanate and carbon-coated lithium titanate. The preparation method of the Ti-MOF metal organic framework material comprises the following steps: adding a titanium source and benzene polycarboxylic acid into a solvent, taking 4-dimethylaminopyridine as an accelerator, preparing Ti-MOF by adopting a hydrothermal method, and using the Ti-MOF to prepare lithium titanate and carbon-coated lithium titanate. The carbon-coated lithium titanate provided by the invention has larger specific surface area, and the surface of the carbon-coated lithium titanate is coated by carbon, so that the carbon-coated lithium titanate can be more fully contacted with an electrolyte, more active sites are obtained, and higher capacity and conductivity are obtained.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a preparation method and application of a Ti-MOF metal organic framework material, lithium titanate and carbon-coated lithium titanate.
Background
The lithium ion battery is used as a power energy source and has good application prospect in electric vehicles and various energy storage systems. At present, various lithium intercalation carbon materials are often used for the negative electrode of a lithium ion battery, but since the potential of a carbon electrode material is close to that of metallic lithium, when the battery is overcharged, metallic lithium is easily precipitated on the surface of the carbon electrode to form dendrite, so that the battery is short-circuited, and thermal runaway and the like are easily caused when the temperature of the carbon electrode is too high. Meanwhile, in the process of repeated insertion and extraction of lithium ions, the structure of the carbon material is damaged, and the capacity of the material is attenuated.
Lithium titanate (Li)4Ti5O12LTO) is a spinel crystal having defects, and is widely spotlighted as a novel negative electrode material for a lithium ion battery due to its excellent structural stability and electrochemical properties. The lithium titanate negative electrode material with the spinel structure has a high de-intercalation lithium potential platform, excellent cycle stability, a fast charging process and outstanding safety performance, is considered as a very potential lithium ion battery negative electrode material, and has great development potential in a lithium ion power battery. However, the lithium titanate with the spinel structure has poor conductivity, so that the lithium titanate has serious polarization degree, fast capacity attenuation and poor rate capability under the condition of large-current charge and discharge, and the large-scale application of the lithium titanate is seriously limited.
Disclosure of Invention
Aiming at the technical problems of the existing lithium titanate negative electrode material, the invention provides a preparation method and application of a Ti-MOF metal organic framework material, lithium titanate and carbon-coated lithium titanate.
In order to achieve the purpose of the invention, the embodiment of the invention adopts the following technical scheme:
a preparation method of a Ti-MOF metal organic framework material comprises the following steps: mixing a titanium source and polybasic aromatic carboxylic acid, taking 4-dimethylamino pyridine as an accelerant, and preparing the Ti-MOF metal organic framework material by adopting a hydrothermal method.
Compared with the prior art, the preparation method of the Ti-MOF metal organic framework material provided by the invention has the advantages that the MOF is used for inducing and generating the Ti-MOF precursor Ti-MOF metal organic framework material, 4-dimethylaminopyridine is added as an accelerating agent, and the Ti-MOF obtains a more complete and uniform morphology through the interaction between the accelerating agent and benzene polycarboxylic acid, so that the preparation method is favorable for obtaining the titanium dioxide precursor with a porous cake-shaped structure. If 4-dimethylaminopyridine is not used as an accelerator, the Ti-MOF is difficult to form in morphology, and a titanium dioxide precursor with a porous cake-like structure cannot be obtained.
Further, the titanium source is titanium tetrachloride, titanium sulfate, tetrabutyl titanate or isopropyl titanate; the polybasic aromatic carboxylic acid is terephthalic acid, isophthalic acid, hemimellitic acid or trimesic acid. In the hydrothermal reaction, Ti provided by a titanium source and the benzene polycarboxylic acid organic ligand form a Ti-MOF metal organic framework material with complete and uniform appearance better.
Further, the mass ratio of the titanium source, the benzene polycarboxylic acid and the 4-dimethylamino pyridine is (1-10): (0.5-50): (0.1-5); the reaction solvent is a mixed solvent of anhydrous methanol and anhydrous N, N-dimethylformamide with the volume ratio of 3: 10-50.
Further, the reaction temperature of the hydrothermal method is 100-200 ℃, and the reaction time is 12-72 hours. The formation of Ti-MOF and the completeness and uniformity of the morphology of the Ti-MOF are further ensured by controlling the reactant dosage, the reaction temperature and the reaction time.
The invention also provides a preparation method of the lithium titanate, which comprises the following steps:
s1: calcining the obtained Ti-MOF metal organic framework material in an air atmosphere to obtain a titanium dioxide precursor;
s2: and mixing the titanium dioxide precursor with a lithium salt solution to obtain a lithium titanate precursor, and calcining to obtain the lithium titanate.
The preparation method of the lithium titanate provided by the invention comprises the steps of calcining Ti-MOF in an air atmosphere, removing organic matters, obtaining a titanium dioxide precursor with a porous cake-shaped structure, and then forming lithium titanate with a porous structure with lithium salt, so that the specific surface area of the lithium titanate is increased.
Further, the lithium salt is one of lithium hydroxide, lithium carbonate or lithium acetate, the concentration of the lithium salt solution is 0.5-5M, and sufficient lithium ions are provided to react with the titanium dioxide precursor to form a lithium titanate precursor.
Further, in step S1, the calcination treatment temperature is 200 to 400 ℃, the time is 2 to 4 hours, the temperature is raised to the calcination temperature at a temperature rise rate of 1 to 5 ℃/min, the calcination is directly carried out in an air atmosphere, and organic matters are burned off to obtain a titanium dioxide precursor with a porous structure; in step S2, the temperature of the calcination treatment is 300-600 ℃, and the time is 1-5 h.
The invention also provides a preparation method of the carbon-coated lithium titanate, which comprises the following steps: grinding and mixing the obtained lithium titanate and a carbon source according to the mass ratio of 1: 0.5-2, and calcining at 300-500 ℃ for 10-30 min to obtain the carbon-coated lithium titanate.
According to the preparation method of the carbon-coated lithium titanate, provided by the invention, the lithium titanate with the porous structure and the carbon source are ground, so that the carbon source can be completely and fully attached to the lithium titanate, and the carbon-coated lithium titanate is further obtained. The carbon-coated lithium titanate prepared by the preparation method has larger specific surface area, and the surface of the carbon-coated lithium titanate is coated by carbon, so that the carbon-coated lithium titanate can be more fully contacted with an electrolyte, more active sites are obtained, and higher capacity and conductivity are obtained.
Further, the carbon source is at least one of starch, glucose, maltose or cyclodextrin.
The carbon source is β -cyclodextrin, gamma-cyclodextrin, methyl- β -cyclodextrin, 2-hydroxypropyl- β -cyclodextrin, (2-hydroxypropyl) -gamma-cyclodextrin, 2, 6-di-O-methyl- β -cyclodextrin or at least one of hepta (2,3, 6-tri-O-methyl) - β -cyclodextrin, the cyclodextrin can fully coat lithium titanate after the lithium titanate is ground and mixed with the cyclodextrin, and the cyclodextrin is carbonized to form a graphitized carbon layer after being calcined to coat the surface of the lithium titanate, and the specific surface porosity of the lithium titanate is further improved, so that the lithium titanate has better conductivity and capacitance.
The invention also provides carbon-coated lithium titanate prepared by the preparation method of the carbon-coated lithium titanate.
The invention also provides application of the carbon-coated lithium titanate in a lithium ion battery.
The carbon-coated lithium titanate provided by the invention has a porous structure and a large specific surface area, and the surface of the carbon-coated lithium titanate is coated with a graphitized carbon layer. The carbon-coated lithium titanate is used in an ion battery and used as a negative electrode material, can be in contact with an electrolyte more fully, obtains more active sites, obtains higher specific discharge capacity, improves the conductivity of an electrode, and further improves the rate capability of the battery.
Drawings
FIG. 1 is an SEM image of a titanium dioxide precursor in an example of the present invention;
FIG. 2 is an SEM image of a Ti-MOF metal organic framework material in a comparative example;
FIG. 3 is an SEM image of a Ti-MOF metal organic framework material in an example of the invention;
fig. 4 is an SEM image of lithium titanate in the comparative example;
fig. 5 is an SEM image of lithium titanate in an example of the present invention;
FIG. 6 is a graph showing BET and nitrogen adsorption of lithium titanate in a comparative example;
FIG. 7 shows BET and N-absorption diagrams of lithium titanate according to an embodiment of the present invention.
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 are not intended to limit the invention.
Example 1
A preparation method of a Ti-MOF metal organic framework material comprises the following steps:
adding 3.0g of terephthalic acid and 1.56mL of tetrabutyl titanate into a mixed solvent of anhydrous methanol (6mL) and anhydrous N, N-dimethylformamide (54mL), uniformly stirring, adding 0.2g of 4-dimethylaminopyridine, reacting at 150 ℃ for 72h, cooling to room temperature after the reaction is finished, centrifugally washing for 3 times by using methanol, and then drying in vacuum at room temperature to obtain the Ti-MOF metal organic framework material.
The Ti-MOF metal organic framework material is used for preparing lithium titanate, and the specific preparation method is as follows:
s1: placing the Ti-MOF metal organic framework material in a muffle furnace, heating to 400 ℃ at the heating rate of 1 ℃/min, and calcining for 2h in the air atmosphere to obtain a titanium dioxide precursor with a porous cake-shaped structure (as shown in figure 1);
s2: dispersing the titanium dioxide precursor in 30mL of 2M LiOH solution, reacting at 60 ℃ for 10h, centrifuging, washing with deionized water for 3 times, drying at 60 ℃ for 12h to obtain a lithium titanate precursor, and calcining at 550 ℃ for 2h in an air atmosphere to obtain lithium titanate.
The preparation method of the carbon-coated lithium titanate is as follows:
and grinding and mixing the lithium titanate with 200mg of 2, 6-di-O-methyl- β -cyclodextrin and 200mg of hepta (2,3, 6-tri-O-methyl) - β -cyclodextrin, and calcining at 300 ℃ for 10min under an argon atmosphere to obtain the carbon-coated lithium titanate.
Example 2
A preparation method of a Ti-MOF metal organic framework material comprises the following steps:
adding 1g of isophthalic acid and 0.5mL of isopropyl titanate into a mixed solvent of anhydrous methanol (6mL) and anhydrous N, N-dimethylformamide (20mL), uniformly stirring, adding 0.1g of 4-dimethylaminopyridine, reacting at 200 ℃ for 12h, cooling to room temperature after the reaction is finished, centrifugally washing for 3 times by using methanol, and then drying in vacuum at room temperature to obtain a Ti-MOF metal organic framework material;
the Ti-MOF metal organic framework material is used for preparing lithium titanate, and the specific preparation method is as follows:
s1: placing the Ti-MOF metal organic framework material in a muffle furnace, heating to 200 ℃ at a heating rate of 5 ℃/min, and calcining for 4h in an air atmosphere to obtain a titanium dioxide precursor;
s2: dispersing the titanium dioxide precursor in 10mL of 0.5M lithium acetate solution, reacting at 80 ℃ for 1h, centrifuging, washing with deionized water for 3 times, drying at 80 ℃ for 12h to obtain a lithium titanate precursor, and calcining at 600 ℃ for 1h in an air atmosphere to obtain lithium titanate;
the preparation method of the carbon-coated lithium titanate is as follows:
and grinding and mixing the lithium titanate with the mass ratio of 1:0.5 and glucose, and calcining at 400 ℃ for 30min under the argon atmosphere to obtain the carbon-coated lithium titanate.
Example 3
A preparation method of a Ti-MOF metal organic framework material comprises the following steps:
adding 10g of trimesic acid and 50g of titanium tetrachloride into a mixed solvent of anhydrous methanol (6mL) and anhydrous N, N-dimethylformamide (100mL), uniformly stirring, adding 5g of 4-dimethylaminopyridine, reacting at 100 ℃ for 50h, cooling to room temperature after the reaction is finished, carrying out centrifugal washing for 3 times by using methanol, and then carrying out vacuum drying at room temperature to obtain the Ti-MOF metal organic framework material;
the Ti-MOF metal organic framework material is used for preparing lithium titanate, and the specific preparation method is as follows:
s1: placing the Ti-MOF metal organic framework material in a muffle furnace, heating to 300 ℃ at a heating rate of 3 ℃/min, and calcining for 3h in an air atmosphere to obtain a titanium dioxide precursor;
s2: dispersing the titanium dioxide precursor in 20mL of 5M lithium carbonate solution, reacting at 40 ℃ for 20h, centrifuging, washing with deionized water for 3 times, drying at 40 ℃ for 72h to obtain a lithium titanate precursor, and calcining at 300 ℃ for 5h in an air atmosphere to obtain lithium titanate;
the preparation method of the carbon-coated lithium titanate is as follows:
grinding and mixing the lithium titanate with the mass ratio of 1:2 and 2-hydroxypropyl- β -cyclodextrin, and calcining at 500 ℃ for 20min in an argon atmosphere to obtain the carbon-coated lithium titanate.
In order to better illustrate the technical solution of the present invention, further comparison is made below by means of a comparative example and an example of the present invention.
Comparative example 1
On the basis of the embodiment 1, 4-dimethylamino pyridine serving as an accelerator is not added, and other components and preparation methods are the same as those of the embodiment 1, so that the corresponding Ti-MOF metal organic framework material, lithium titanate and carbon-coated lithium titanate are obtained.
Comparative example 2
The titanium dioxide precursor in example 1 was replaced with commercially available titanium dioxide, and the other components and preparation methods were the same as in example 1, to obtain corresponding lithium titanate and carbon-coated lithium titanate.
In order to better illustrate the characteristics of the Ti-MOF metal organic framework material, the lithium titanate and the carbon-coated lithium titanate provided by the embodiment of the invention, the Ti-MOF metal organic framework material and the lithium titanate prepared in the embodiment 1 and the comparative example 1 are subjected to electron microscope characterization, the lithium titanate prepared in the embodiment 1 and the comparative example 2 is subjected to BET and nitrogen adsorption tests, and the carbon-coated lithium titanate obtained in the embodiment 1 and the comparative example 2 is assembled into a button cell to test the electrochemical performance.
The SEM images of the Ti-MOF metal organic framework materials corresponding to comparative example 1 and example 1 are respectively shown in fig. 2 and 3, and compared with comparative example 1, the Ti-MOF metal organic framework material obtained in example 1 has a more complete and uniform morphology, which shows that the addition of 4-dimethylaminopyridine as a promoter can promote the formation of the morphology of the Ti-MOF metal organic framework material, and is more beneficial to the preparation of a subsequent porous cake-like structure titanium dioxide precursor (shown in fig. 1). The SEM images of the lithium titanate corresponding to comparative example 1 and example 1 are shown in fig. 4 and 5, respectively, and the lithium titanate obtained in comparative example 1 has disordered and irregular morphology, while the morphology obtained in example 1 is complete and uniform, further illustrating that 4-dimethylaminopyridine has an accelerating effect on the formation of Ti-MOF metal organic framework material morphology.
Titanium prepared in comparative example 2 and example 1The BET and nitrogen adsorption test results of lithium titanate are shown in FIGS. 6 and 7, respectively, and the BET of the lithium titanate obtained in comparative example 2 is 4.3686m2·g-1The BET of the lithium titanate obtained in example 1 is 35.0911m2·g-1It is demonstrated that the lithium titanate provided by the embodiment of the invention has more porous structures, so that the lithium titanate has larger specific surface area.
The carbon-coated lithium titanate obtained in example 1 and comparative example 2 was assembled into a button cell in a glove box and tested for electrochemical performance using a blue testing system and a Princeton electrochemical workstation. The result shows that, under a large current multiplying power of 10C, the specific discharge capacity of the carbon-coated lithium titanate of example 1 is 50% higher than that of the carbon-coated lithium titanate of comparative example 2, and under a high temperature condition of 60 ℃, the capacity of the carbon-coated lithium titanate of comparative example 2 is sharply reduced after 300 cycles, while the carbon-coated lithium titanate of example 1 still has a cycle retention rate of 99.1% after 200 cycles. In addition, alternating current impedance testing (EIS) showed that the ionic conductivity of the carbon-coated lithium titanate of example 1 was significantly improved over comparative example 2 after 500 cycles.
From the data, the carbon-coated lithium titanate provided by the embodiment of the invention has a porous structure and a large specific surface area, is used in an ion battery, obtains more active sites, obtains higher specific discharge capacity, and improves the conductivity of an electrode. The carbon-coated lithium titanate obtained in examples 2 and 3 of the present invention has an effect equivalent to that of the carbon-coated lithium titanate in example 1.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents or improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A preparation method of a Ti-MOF metal organic framework material is characterized by comprising the following steps:
mixing a titanium source and polybasic aromatic carboxylic acid, taking 4-dimethylamino pyridine as an accelerant, and preparing the Ti-MOF metal organic framework material by adopting a hydrothermal method.
2. A process for the preparation of a Ti-MOF metal organic framework material according to claim 1, wherein: the titanium source is titanium tetrachloride, titanium sulfate, tetrabutyl titanate or isopropyl titanate; the polybasic aromatic carboxylic acid is terephthalic acid, isophthalic acid, hemimellitic acid or trimesic acid.
3. A process for the preparation of a Ti-MOF metal organic framework material according to claim 1, wherein: the mass ratio of the titanium source to the benzene polycarboxylic acid to the 4-dimethylamino pyridine is (1-10): (0.5-50): (0.1-5); the reaction solvent is a mixed solvent of anhydrous methanol and anhydrous N, N-dimethylformamide with the volume ratio of 3: 10-50.
4. A process for the preparation of a Ti-MOF metal organic framework material according to claim 1, wherein: the reaction temperature of the hydrothermal method is 100-200 ℃, and the reaction time is 12-72 hours.
5. A preparation method of lithium titanate is characterized by comprising the following steps:
s1: subjecting the Ti-MOF metal organic framework material obtained in any one of claims 1 to 4 to calcination treatment in an air atmosphere to obtain a titanium dioxide precursor;
s2: and mixing the titanium dioxide precursor with a lithium salt solution to obtain a lithium titanate precursor, and calcining to obtain the lithium titanate.
6. The method for producing lithium titanate according to claim 5, wherein: the lithium salt is one of lithium hydroxide, lithium carbonate or lithium acetate.
7. The method for producing lithium titanate according to claim 5, wherein: in the step S1, the calcining temperature is 200-400 ℃, and the time is 2-4 h; in the step S2, the calcining temperature is 300-600 ℃, and the time is 1-5 h.
8. A preparation method of carbon-coated lithium titanate is characterized by comprising the following steps: grinding and mixing the lithium titanate obtained in any one of claims 5 to 7 and a carbon source in a mass ratio of 1: 0.5-2, and calcining at 300-500 ℃ for 10-30 min to obtain the carbon-coated lithium titanate.
9. A carbon-coated lithium titanate is characterized in that: the method for producing carbon-coated lithium titanate as claimed in claim 8.
10. Use of the carbon-coated lithium titanate of claim 9 in a lithium ion battery.
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| CN113083280A (en) * | 2021-04-22 | 2021-07-09 | 中国科学院过程工程研究所 | High-load vanadium-titanium oxide catalyst for catalytic oxidation of VOCs (volatile organic compounds), and preparation method and application thereof |
| CN113083280B (en) * | 2021-04-22 | 2022-05-13 | 中国科学院过程工程研究所 | High-load vanadium-titanium oxide catalyst for catalytic oxidation of VOCs (volatile organic compounds), and preparation method and application thereof |
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