CN110534720B - Preparation method and application of nano-carbon and titanium dioxide co-modified sepiolite composite material - Google Patents
Preparation method and application of nano-carbon and titanium dioxide co-modified sepiolite composite material Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 239000004113 Sepiolite Substances 0.000 title claims abstract description 68
- 229910052624 sepiolite Inorganic materials 0.000 title claims abstract description 68
- 235000019355 sepiolite Nutrition 0.000 title claims abstract description 68
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 53
- 239000002131 composite material Substances 0.000 title claims abstract description 49
- 229910021392 nanocarbon Inorganic materials 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 8
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 7
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000002244 precipitate Substances 0.000 claims description 44
- 238000006243 chemical reaction Methods 0.000 claims description 42
- 238000001035 drying Methods 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000002243 precursor Substances 0.000 claims description 17
- 238000001354 calcination Methods 0.000 claims description 14
- 229910052593 corundum Inorganic materials 0.000 claims description 12
- 239000010431 corundum Substances 0.000 claims description 12
- 229910052573 porcelain Inorganic materials 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 9
- 229910001416 lithium ion Inorganic materials 0.000 claims description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000010406 cathode material Substances 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 238000004729 solvothermal method Methods 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims 1
- 239000011941 photocatalyst Substances 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 239000002105 nanoparticle Substances 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000002121 nanofiber Substances 0.000 abstract 1
- 239000007773 negative electrode material Substances 0.000 abstract 1
- 239000002957 persistent organic pollutant Substances 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000002734 clay mineral Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229960000907 methylthioninium chloride Drugs 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000002717 carbon nanostructure Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 238000007709 nanocrystallization Methods 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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Abstract
The invention discloses a preparation method and application of a nano-carbon and titanium dioxide co-modified sepiolite composite material. The invention has the advantages that: firstly, the nano-fiber sepiolite is rich in raw materials; secondly, the cost of citric acid used as a carbon-coated carbon source and tetrabutyl titanate used for growing titanium dioxide nano particles is low; thirdly, the preparation method has low synthesis temperature and good repeatability, and the whole process flow is environment-friendly and suitable for industrial production; fourthly, the sepiolite composite material co-modified by the nano carbon and the titanium dioxide obtained by the preparation method has high charge and discharge capacity and excellent cycle performance when being used as a negative electrode material. And when the photocatalyst is used as a photocatalyst, the photocatalyst can effectively degrade organic pollutants in water, and is an environment-friendly high-performance photocatalyst material.
Description
Technical Field
The invention relates to a preparation method and application of a nano-carbon and titanium dioxide co-modified sepiolite composite material, belonging to the technical field of new energy materials.
Background
Nowadays, lithium ion batteries have been widely used in daily life of people, and play more and more important roles in electric vehicles, stationary energy storage systems, and portable electronic devices, and thus, people have been increasingly aware of these factorsThe requirements on the lithium ion battery are continuously improved, and the development of efficient electrode materials also becomes the key for improving the performance of the lithium ion battery. Graphite is one of the most common lithium ion battery cathode materials, but the low theoretical specific capacity (372 mAh/g) is low, and the cycle performance is poor. Metal oxides are considered ideal lithium ion battery anode material candidates, particularly TiO 2 The material has low cost, environmental protection, high safety and good cycle stability. But TiO 2 2 The ion diffusion energy barrier is high, the band gap is large, and the ion diffusion performance and the electron conductivity are low. The nano-size and the carbon coating are used for improving TiO 2 An effective way of performance.
Sepiolite is a fibrous natural clay mineral, the main component of which is hydrous magnesium silicate, has very high specific surface area and unique pore channel structure, and is a recognized clay mineral with strongest adsorption capacity. Sepiolite is commonly used as a carrier for the preparation of catalysts and functional materials and has wide application in the nanocrystallization of material dimensions. The particular structure of sepiolite dictates that it possess channels, including channels throughout the structure, which can theoretically be used for the storage of lithium ions. However, so far, no report on the application of sepiolite to the anode material of the lithium ion battery is found.
Disclosure of Invention
The invention aims to provide a preparation method and application of a nano-carbon and titanium dioxide co-modified sepiolite composite material.
A preparation method of a nano-carbon and titanium dioxide co-modified sepiolite composite material comprises the following steps:
the method comprises the following steps: ultrasonically dispersing sepiolite in deionized water, adding citric acid into the dispersion liquid, and stirring on a magnetic stirrer;
step two: transferring the dispersion liquid obtained in the step one into a micro reaction kettle for hydrothermal reaction, taking the precipitate after the reaction is finished, cleaning the precipitate with deionized water and absolute ethyl alcohol, and then putting the precipitate into a drying oven for drying;
step three: ultrasonically dispersing the dried precipitate in absolute ethyl alcohol, adding tetrabutyl titanate, and fully stirring on a magnetic stirrer to obtain a suspension solution;
step four: putting the suspension solution into a micro reaction kettle for solvothermal reaction, taking a precipitate after the reaction is finished, cleaning the precipitate with deionized water and absolute ethyl alcohol, and then putting the precipitate into a drying oven for drying to obtain a precursor;
step five: and flatly paving the precursor in a corundum porcelain boat, calcining the precursor in a tubular furnace protected by inert gas, cooling the precursor to room temperature, and taking the calcined precursor out to obtain the sepiolite composite material co-modified by the nano carbon and the titanium dioxide.
The carbon content of the composite material is 0-10%, the titanium dioxide content is 0-30%, and the sepiolite content is 60-100%.
In the first step, the mass ratio of the sepiolite to the citric acid is 1:4-1:6, and the mass ratio of the sepiolite to the deionized water is 1.
In the second step, the hydrothermal reaction temperature of the micro reaction kettle is 160-200 ℃, and the reaction time is 4-8 h.
In the second step, the drying temperature is 60-80 ℃, and the drying time is 18-24h.
In the third step, the mass percentage of the precipitate and the tetrabutyl titanate is 1:2-1:5.
In the fourth step, the solvent thermal reaction temperature of the micro reaction kettle is 160-200 ℃, and the reaction time is 6-10 h.
In the fourth step, the drying temperature is 60-80 ℃, and the drying time is 18-24h.
And in the fifth step, before calcination, the corundum porcelain boat filled with the precursor is placed in a tube furnace, vacuum pumping is carried out, and inert protective gas is introduced for protection until calcination is finished. The calcining temperature is set to be 400-600 ℃, and the calcining time is 4-6 h.
The application of the nano-carbon and titanium dioxide co-modified sepiolite composite material comprises the following steps: the catalyst is used for the lithium ion battery cathode material or catalyst.
The invention has the following technical effects: the invention prepares a nano-carbon and titanium dioxide co-modified sepiolite composite material, which fully utilizes the lithium storage capacity of titanium dioxide and sepiolite and is modified by a nano-carbon modification methodThe sepiolite and the titanium dioxide have the defect of low conductivity. Moreover, the sepiolite is used as a carrier in the preparation process to effectively control the particle size of the titanium dioxide, ultrafine titanium dioxide particles with the average particle size of about 5nm are obtained, and the particles are uniformly distributed on the surface of the sepiolite. The composite material is at 0.3 A.g -1 After circulating for 300 times under the current, the high specific capacity of 614mAh/g is kept, and the specific capacity is 1 A.g -1 After the current is circulated for 800 times, the high specific capacity of 513mAh/g is kept, and the rate capability is excellent. In addition, carbon doping can accelerate the effective separation of hole and electron pairs and improve the photocatalytic capacity of anatase titanium dioxide, so that the sepiolite composite material co-modified by nano carbon and titanium dioxide can also be used as a catalyst.
Drawings
FIG. 1 is a XED scan of a nano-carbon and titanium dioxide co-modified sepiolite composite material in example 1 of the present invention.
Fig. 2 is an XED scan of a nano-carbon and titanium dioxide co-modified sepiolite composite material in example 2 of the present invention.
FIG. 3 is a XED scan of a sepiolite composite material co-modified with nanocarbon and titanium dioxide in example 3 of the invention.
FIG. 4 is a Raman curve diagram of a sepiolite composite material co-modified by nanocarbon and titanium dioxide.
FIG. 5 is an SEM image of a sepiolite composite material co-modified by nanocarbon and titanium dioxide.
FIG. 6 is a TEM image of a sepiolite composite material co-modified by nanocarbon and titanium dioxide.
FIG. 7 is a cycle performance diagram of a nano-carbon and titanium dioxide co-modified sepiolite composite material.
Detailed Description
The invention is further illustrated with reference to the specific example .
Example 1
The method comprises the following steps: ultrasonically dispersing 0.588g of sepiolite in 40ml of deionized water, adding 2.94g of citric acid, placing on a magnetic stirrer, stirring at 500r/min for 2 hours;
step two: putting the stirred solution into a micro reaction kettle with the capacity of 100ml for hydrothermal reaction, setting the reaction temperature at 180 ℃ and the reaction time at 6h, taking the precipitate after the reaction is finished, respectively washing the precipitate with 80ml of deionized water and absolute ethyl alcohol for 5 times, and then drying the precipitate for 20h at the temperature of 65 ℃;
step three: ultrasonically dispersing 0.2g of the dried precipitate in 40ml of absolute ethyl alcohol, adding 0.8g of tetra-n-butyl titanate, placing on a magnetic stirrer, and fully stirring for 2 hours at 500r/min to obtain a suspension solution;
step four: putting the suspension into a micro reaction kettle with the capacity of 100ml for carrying out solvent thermal reaction, setting the reaction temperature to be 180 ℃ and the reaction time to be 6h, after the reaction is finished, taking the precipitate, respectively washing the precipitate with 80ml of deionized water and absolute ethyl alcohol for 5 times, and then drying the precipitate for 20h at the temperature of 65 ℃ to obtain a precursor;
step five: and paving the precursor in a corundum porcelain boat, putting the corundum porcelain boat into a quartz tube of a tube furnace, vacuumizing, introducing inert gas argon for protection, heating to 400 ℃ at the heating rate of 5 ℃/min, carrying out heat preservation calcination at the temperature of 400 ℃ for 4h, and taking out after cooling to room temperature to obtain the sepiolite composite material co-modified by nano carbon and titanium dioxide.
XRD test is carried out on the sepiolite composite material co-modified by the nanocarbon and the titanium dioxide, as shown in figure 1, the composite material is composed of a sepiolite and titanium dioxide mixed structure, and the crystal structure of the titanium dioxide is anatase.
The sepiolite composite material co-modified by the nanocarbon and the titanium dioxide is subjected to Raman test, and as shown in figure 4, a characteristic peak of a carbon nanostructure can be seen in Raman spectrum, which indicates that carbon exists in the composite material.
Example 2
The method comprises the following steps: ultrasonically dispersing 1.0g of sepiolite in 50ml of deionized water, adding 5.0g of citric acid, placing on a magnetic stirrer, stirring at 500r/min for 3 hours;
step two: putting the stirred solution into a micro reaction kettle with the capacity of 100ml for hydrothermal reaction, setting the reaction temperature to be 190 ℃ and the reaction time to be 5 hours, taking the precipitate after the reaction is finished, respectively washing the precipitate for 5 times by using 100ml of deionized water and absolute ethyl alcohol, and then drying the precipitate for 20 hours at the temperature of 70 ℃;
step three: ultrasonically dispersing 0.2g of the dried precipitate in 40ml of absolute ethyl alcohol, adding 0.6g of tetra-n-butyl titanate, placing on a magnetic stirrer, and fully stirring for 2 hours at 500r/min to obtain a suspension solution;
step four: putting the suspension into a micro reaction kettle with the capacity of 100ml for carrying out solvent thermal reaction, setting the reaction temperature to be 180 ℃ and the reaction time to be 6h, after the reaction is finished, taking the precipitate, respectively washing the precipitate with 80ml of deionized water and absolute ethyl alcohol for 5 times, and then drying the precipitate for 20h at the temperature of 70 ℃ to obtain a precursor;
step five: and paving the precursor in a corundum porcelain boat, putting the corundum porcelain boat into a quartz tube of a tube furnace, vacuumizing, introducing inert gas argon for protection, heating to 500 ℃ at the heating rate of 5 ℃/min, carrying out heat preservation calcination at the temperature of 500 ℃ for 4h, and taking out after cooling to room temperature to obtain the sepiolite composite material co-modified by nano carbon and titanium dioxide.
The results of XRD tests on the sepiolite composite material co-modified with nanocarbon and titania are shown in fig. 2. The characteristic diffraction peaks of sepiolite and anatase titanium dioxide can be seen in the figure, indicating that the composite material is composed mainly of two components.
Example 3
The method comprises the following steps: ultrasonically dispersing 1.0g of sepiolite in 50ml of deionized water, adding 6.0g of citric acid, placing on a magnetic stirrer, stirring at 500r/min for 3 hours;
step two: putting the stirred solution into a micro reaction kettle with the capacity of 100ml for hydrothermal reaction, setting the reaction temperature at 200 ℃, the reaction time at 5h, taking the precipitate after the reaction is finished, respectively washing the precipitate for 5 times by 100ml of deionized water and absolute ethyl alcohol, and then drying the precipitate for 20h at the temperature of 70 ℃;
step three: ultrasonically dispersing 0.2g of the dried precipitate in 40ml of absolute ethyl alcohol, adding 0.6g of tetra-n-butyl titanate, placing on a magnetic stirrer, and fully stirring for 2 hours at a speed of 500r/min to obtain a suspension solution;
step four: putting the suspension into a micro reaction kettle with the capacity of 100ml for carrying out solvent thermal reaction, setting the reaction temperature at 200 ℃ and the reaction time at 6h, taking the precipitate after the reaction is finished, respectively washing the precipitate with 80ml of deionized water and absolute ethyl alcohol for 5 times, and then drying the precipitate for 20h at the temperature of 70 ℃ to obtain a precursor;
step five: and paving the precursor in a corundum porcelain boat, putting the corundum porcelain boat into a quartz tube of a tube furnace, vacuumizing, introducing inert gas argon for protection, heating to 500 ℃ at the heating rate of 5 ℃/min, carrying out heat preservation calcination at the temperature of 500 ℃ for 4h, and taking out after cooling to room temperature to obtain the sepiolite composite material co-modified by nano carbon and titanium dioxide.
XRD tests are carried out on the sepiolite composite material co-modified by the nanocarbon and the titanium dioxide, and the results are shown in figure 3, the XRD spectrum of the composite material mainly comprises sepiolite and anatase type titanium dioxide, which shows that the sepiolite and the titanium dioxide are the main components. The shape of the sepiolite composite material co-modified by the nanocarbon and the titanium dioxide is shown in fig. 5, and the nano-sized titanium dioxide can be uniformly distributed on the surface of the sepiolite fiber.
Example 4
The method comprises the following steps: ultrasonically dispersing 1.0g of sepiolite in 50ml of deionized water, adding 5.0g of citric acid, placing on a magnetic stirrer, stirring at 500r/min for 3 hours;
step two: putting the stirred solution into a micro reaction kettle with the capacity of 100ml for hydrothermal reaction, setting the reaction temperature to be 190 ℃ and the reaction time to be 5 hours, taking the precipitate after the reaction is finished, respectively washing the precipitate for 5 times by using 100ml of deionized water and absolute ethyl alcohol, and then drying the precipitate for 20 hours at the temperature of 70 ℃;
step three: ultrasonically dispersing 0.2g of the dried precipitate in 40ml of absolute ethyl alcohol, adding 0.6g of tetra-n-butyl titanate, placing on a magnetic stirrer, and fully stirring for 2 hours at 500r/min to obtain a suspension solution;
step four: putting the suspension into a micro reaction kettle with the capacity of 100ml for carrying out solvent thermal reaction, setting the reaction temperature to be 190 ℃ and the reaction time to be 6h, after the reaction is finished, taking the precipitate, respectively washing the precipitate with 80ml of deionized water and absolute ethyl alcohol for 5 times, and then drying the precipitate for 20h at the temperature of 70 ℃ to obtain a precursor;
step five: and paving the precursor in a corundum porcelain boat, putting the corundum porcelain boat into a quartz tube of a tube furnace, vacuumizing, introducing inert gas argon for protection, heating to 400 ℃ at the heating rate of 5 ℃/min, carrying out heat preservation calcination at the temperature of 400 ℃ for 4h, and taking out after cooling to room temperature to obtain the sepiolite composite material co-modified by nano carbon and titanium dioxide.
TEM test is carried out on the sepiolite composite material co-modified by the nano-carbon and the titanium dioxide, and the result is shown in figure 6, wherein the titanium dioxide nanocrystals are uniformly distributed on the surface of the sepiolite fibers, and the nano-carbon sheets are uniformly distributed among the fibers. The grain size of the nano titanium dioxide is about 5 nanometers.
The application of the nano-carbon and titanium dioxide co-modified sepiolite composite material comprises the following steps:
example 6
The metal lithium, the nano carbon and the titanium dioxide co-modified sepiolite composite material prepared by the invention are used as a positive electrode and a negative electrode, and the battery diaphragm is a commercial diaphragm produced by Karlerd (Celgard) company, 1M LiPF 6 The EC/EMC/DMC solution (mass ratio 1 -1 The current is used for charging and discharging tests, the cycle performance is shown in fig. 7, the capacity of the composite material is higher under a larger current density, and the capacity is greatly improved along with the increase of the cycle times along with the activation process. After 800 times of circulation, the capacity exceeds 500mAh g -1 。
Example 7
The nano-carbon and titanium dioxide co-modified sepiolite composite material prepared in example 1 is used as a photocatalyst to degrade methylene blue under the condition of simulating sunlight, wherein the initial concentration of the methylene blue is 5 multiplied by 10 -5 mol/L, the dosage of the catalyst is 0.2g/L, and the degradation rate reaches more than 80 percent after 1 hour.
The above description is only a preferred embodiment of the present invention, and a person skilled in the art may make several modifications without departing from the technical principle of the present invention, and these modifications should also be regarded as the protection scope of the present invention.
Claims (8)
1. A preparation method of a nano-carbon and titanium dioxide co-modified sepiolite composite material is characterized by comprising the following steps: the method comprises the following steps:
the method comprises the following steps: ultrasonically dispersing sepiolite in deionized water, adding citric acid into the dispersion liquid, and stirring on a magnetic stirrer;
step two: transferring the dispersion liquid obtained in the step one into a micro reaction kettle for hydrothermal reaction, precipitating after the reaction is finished, taking a precipitate, cleaning the precipitate with deionized water and absolute ethyl alcohol, and then putting the precipitate into a drying box for drying;
step three: ultrasonically dispersing the dried precipitate in absolute ethyl alcohol, adding tetrabutyl titanate, and fully stirring on a magnetic stirrer to obtain a suspension solution;
step four: putting the suspension solution into a micro reaction kettle for solvothermal reaction, taking a precipitate after the reaction is finished, cleaning the precipitate with deionized water and absolute ethyl alcohol, and then putting the precipitate into a drying oven for drying to obtain a precursor;
step five: the precursor is spread in a corundum porcelain boat, put into a tube furnace protected by inert gas for calcination, and taken out after being cooled to room temperature, so as to obtain the sepiolite composite material co-modified by nano carbon and titanium dioxide;
in the third step, the mass percentage of the precipitate and the tetra-n-butyl titanate is 1:2-1:5;
the sepiolite composite material co-modified by the nano carbon and the titanium dioxide is applied to a lithium ion battery cathode material.
2. The preparation method of the sepiolite composite material co-modified by the nanocarbon and the titanium dioxide, according to the claim 1, is characterized in that: the carbon content of the composite material is less than or equal to 10 percent, the titanium dioxide content is less than or equal to 30 percent, and the sepiolite content is more than or equal to 60 percent.
3. The preparation method of the sepiolite composite material co-modified by the nanocarbon and the titanium dioxide, according to the claim 1, is characterized in that: in the first step, the mass ratio of the sepiolite to the citric acid is 1:4-1:6, and the mass ratio of the sepiolite to the deionized water is 1.
4. The preparation method of the sepiolite composite material co-modified by the nanocarbon and the titanium dioxide, according to the claim 1, is characterized in that: in the second step, the hydrothermal reaction temperature of the micro reaction kettle is 160-200 ℃, and the reaction time is 4-8 h.
5. The preparation method of the sepiolite composite material co-modified by the nanocarbon and the titanium dioxide, according to the claim 1, is characterized in that: in the second step, the drying temperature is 60-80 ℃, and the drying time is 18-24h.
6. The preparation method of the sepiolite composite material co-modified by the nanocarbon and the titanium dioxide, according to the claim 1, is characterized in that: in the fourth step, the solvent thermal reaction temperature of the micro reaction kettle is 160-200 ℃, and the reaction time is 6-10 h.
7. The preparation method of the sepiolite composite material co-modified by the nanocarbon and the titanium dioxide, according to the claim 1, is characterized in that: in the fourth step, the drying temperature is 60-80 ℃, and the drying time is 18-24h.
8. The preparation method of the sepiolite composite material co-modified by the nanocarbon and the titanium dioxide, according to the claim 1, is characterized in that: putting the corundum porcelain boat filled with the precursor into a tube furnace before calcination, vacuumizing, and introducing inert protective gas for protection until the calcination is finished; the calcining temperature is set to be 400-600 ℃, and the calcining time is 4-6 h.
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| CN110090657A (en) * | 2019-06-04 | 2019-08-06 | 中南大学 | A kind of sepiolite composite catalyst and preparation method thereof, novel Fenton-like and its application |
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