WO2023165041A1 - Preparation method for porous tio2-based nanomaterial, and porous tio2-based nanomaterial and sodium-ion battery - Google Patents

Preparation method for porous tio2-based nanomaterial, and porous tio2-based nanomaterial and sodium-ion battery Download PDF

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WO2023165041A1
WO2023165041A1 PCT/CN2022/097270 CN2022097270W WO2023165041A1 WO 2023165041 A1 WO2023165041 A1 WO 2023165041A1 CN 2022097270 W CN2022097270 W CN 2022097270W WO 2023165041 A1 WO2023165041 A1 WO 2023165041A1
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mil
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任玉荣
赵宏顺
戚燕俐
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常州大学
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    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention belongs to the field of sodium batteries, and in particular relates to a preparation method of a porous TiO2- based nanometer material, a porous TiO2- based nanometer material, and a sodium ion battery.
  • sodium-ion batteries have attracted much attention due to their abundant raw materials, low cost, good cycle stability, and good rate performance.
  • the radius of the sodium ion and atomic mass much larger than Li-ion
  • the energy density is low and the ion migration rate is slow, which seriously hinders the kinetics of sodium ions in the electrochemical reaction, which makes the commercial graphite anode of lithium battery unsuitable as the anode material of sodium ion battery. Therefore, the development of high-performance anode materials has a profound impact on promoting the development and application of sodium-ion batteries.
  • anatase titanium dioxide (TiO 2 ) has the characteristics of low self-discharge, high safety, long cycle life, and low cost. And it has a higher working voltage than the deposition voltage of sodium metal, which inhibits the generation of sodium dendrites, so it has attracted extensive attention from researchers.
  • TiO 2 is a semiconductor material, it has the inevitable slow ion diffusion rate (10 -15 ⁇ 10 -9 cm 2 s -1 ) and poor electrical conductivity ( ⁇ : 10 -12 ⁇ 10 -7 s cm -1 ).
  • the electrochemical sodium storage capacity is relatively weak, which limits the further development space.
  • the surface energies of (001), (100) and (101) planes are 0.90, 0.53 and 0.44 J m -2 , respectively, while the band gap of (001) plane of TiO 2 is much lower than ( 101), (010) and (111) crystal planes, indicating that the (001) crystal plane has higher activity.
  • the exposed high-energy crystal faces are fragile and easily lose their activity after continuous cycling.
  • the object of the present invention is to provide a method for preparing porous TiO2- based nanomaterials with high-rate sodium storage properties with exposed (001) crystal planes, porous TiO2- based nanomaterials, and sodium-ion batteries.
  • First object of the present invention is to provide a kind of porous TiO2
  • the preparation method of base nano material comprises the steps:
  • the titanium ester solution is one selected from tetrabutyl titanate, tetraethyl titanate, and tetrapropyl titanate dissolved in methanol, acetic acid, isopropanol, n-butanol, acetylacetone A solution obtained in one of the solvents.
  • the solvent is selected from N,N dimethylformamide, N-methylpyrrolidone, dimethylacetamide, 1,3-dimethyl-2-imidazolinone, dimethyl One or more of the group sulfoxides.
  • step S1 the feeding molar ratio of the terephthalic acid, the titanium ester solution and the 4-dimethylaminopyridine is (13-15):(160-180):1.
  • the buffer solution is at least one selected from Tris buffer, Tris-HCl buffer, and Tris-phosphate buffer, and the concentration of the buffer solution is 5-20 mM.
  • step S2 the molar ratio of the MIL-125 disc-shaped metal-organic framework precursor to the dopamine hydrochloride is (3-6):1.
  • step S3 the gas flow rate of the inert gas is 50-150mL min -1 , the temperature of the high-temperature carbonization treatment is 350-420°C, and the holding time is 4-6h;
  • the inert gas is one selected from argon, nitrogen, and argon-hydrogen mixed gas.
  • step S1 and step S2 the post-treatments are independently centrifuging the solution obtained after the reaction with anhydrous methanol as a solvent, collecting the precipitate, and drying at 60-90° C. for 6-10 hours.
  • the second object of the present invention is to provide a porous TiO 2 -based nanomaterial obtained by the above-mentioned preparation method.
  • the third object of the present invention is to provide a sodium-ion battery, including the negative electrode material, which includes the porous TiO 2 -based nanomaterial obtained by the preparation method described above and the porous TiO 2 -based nanomaterial as described above.
  • the present invention uses a metal-organic framework (MIL-125) as a precursor to coat polydopamine (Polydopamine, PDA) on the surface of TiO by in - situ polymerization, and undergoes high-temperature carbonization heat treatment to obtain porous TiO 2- based nanomaterials ( p-TiO 2 @NC material), the preparation method is simple and easy to operate, the energy consumption is relatively low, and the pollution is small;
  • MIL-125 metal-organic framework
  • PDA polydopamine
  • the p-TiO 2 @NC material prepared by the present invention has the following advantages when used as an anode material for a sodium ion battery: the p-TiO 2 @NC material retains the unique round cake shape of MIL-125 , the nitrogen-doped carbon skeleton reduces the band gap of TiO 2 and lowers the Na + deintercalation barrier; the porous structure accelerates the diffusion of Na + ; the highly exposed (001) crystal plane can provide higher reactivity , to speed up the reaction kinetics; the pseudocapacitive storage process can provide additional storage sites for sodium ions, which is conducive to the improvement of electronic conductivity, thereby improving the sodium storage performance of porous TiO 2 -based nanomaterials at high rates.
  • the present invention considers that the combination of high-energy active crystal faces and carbon coating can significantly improve the sodium storage performance of TiO 2 .
  • dopamine (DA) is oxidized and self-polymerized into polydopamine (PDA), which can be used for coating on the surface of various materials.
  • PDA polydopamine
  • the nitrogen-rich carbon-based material can be heat-treated to form a conductive network, which improves the material's conductivity.
  • the invention provides a kind of porous TiO
  • the preparation method of base nano material comprises the following steps:
  • MIL-125 disc-shaped metal-organic framework precursor Disperse the MIL-125 disc-shaped metal-organic framework precursor in a solution (at least one selected from Tris buffer, Tris-HCl buffer, Tris-phosphate buffer, the concentration of the buffer solution is 5-20mM ), add dopamine hydrochloride, stir for 15-20h, and obtain dry MIL-125@PDA discs after post-treatment; wherein, the molar ratio of MIL-125 disc-shaped metal-organic framework precursor to dopamine hydrochloride is ( 3-6): 1;
  • step S1 and step S2 the post-treatment is independently centrifuging the solution obtained after the reaction with anhydrous methanol as a solvent, collecting the precipitate, and drying at 60-90° C. for 6-10 hours.
  • the addition of 4-dimethylaminopyridine in the present invention can improve the porosity of the metal-organic framework (MIL-125); in the inert gas, argon-hydrogen mixed gas, the volume ratio of argon and hydrogen is 95:5.
  • the invention also provides a sodium ion battery, including the negative electrode material.
  • the negative electrode material includes the porous TiO2- based nanomaterial obtained by the above preparation method and the above porous TiO2 - based nanomaterial.
  • the preparation method of the negative electrode material comprises the following steps: dispersing the silicon-based composite material, the conductive agent and the binder in the water solvent according to the mass ratio of (7-9):1:1 to obtain a mixed dispersion liquid, and coating the mixed dispersion liquid Coated on copper foil, dried to obtain electrode sheet, that is, negative electrode material.
  • the preparation method and type of the sodium ion battery are prepared by methods known in the art, and are not specifically limited in this application. The following is an example to illustrate:
  • the preparation method of negative electrode material comprises the steps: the porous TiO2 base nano material that above-mentioned preparation obtains, superconducting carbon and sodium carboxymethyl cellulose are dispersed in water solvent according to mass ratio according to 8:1:1, The mixed dispersion is obtained, and then the mixed dispersion is coated on the copper foil, and dried to obtain the electrode sheet, that is, the negative electrode material;
  • the above-mentioned negative electrode material is used as the working electrode, the high-purity sodium sheet is used as the counter electrode, the glass fiber (Whatman, GF/D) is used as the separator, and the electrolyte is 1M NaClO 4 dissolved in ethylene carbonate (EC)/dicarbonate Methyl ester (DMC) (1:1v/v) and 5wt% fluoroethylene carbonate (FEC) were added in a glove box (H 2 O ⁇ 0.01ppm, O 2 ⁇ 0.01ppm) into a 2032-type button battery, that is, a sodium-ion battery.
  • EC ethylene carbonate
  • DMC dicarbonate Methyl ester
  • FEC fluoroethylene carbonate
  • the present embodiment provides a kind of porous TiO 2 preparation method of base nanomaterial, comprises the following steps:
  • MIL-125 disc-shaped metal-organic framework precursor Disperse 0.3g of MIL-125 disc-shaped metal-organic framework precursor in 250mL of 10mM Tris-HCl buffer solution, add 50mg of dopamine hydrochloride, stir vigorously for 24h, and after post-treatment (using anhydrous methanol as solvent centrifugation Collect the precipitate and dry it at 70°C for 8h) to obtain a dried MIL-125@PDA disc;
  • the gas flow rate of the argon gas is 100mL min -1 , perform high-temperature carbonization treatment, the temperature is 380°C, and the holding time is 4h, and the black powder with (001 ) porous TiO 2 -based nanomaterials with exposed facets (p-TiO 2 @NC).
  • This embodiment also provides a sodium-ion battery.
  • the preparation method and type of the sodium-ion battery are prepared by methods known in the art, and are not specifically limited in this application. The following is an example to illustrate:
  • the preparation method of negative electrode material comprises the steps: the porous TiO2 base nano material that above-mentioned preparation obtains, superconducting carbon and sodium carboxymethyl cellulose are dispersed in water solvent according to mass ratio according to 8:1:1, The mixed dispersion is obtained, and then the mixed dispersion is coated on the copper foil, and dried to obtain the electrode sheet, that is, the negative electrode material;
  • the above-mentioned negative electrode material is used as the working electrode, the high-purity sodium sheet is used as the counter electrode, the glass fiber (Whatman, GF/D) is used as the separator, and the electrolyte is 1M NaClO 4 dissolved in ethylene carbonate (EC)/dicarbonate Methyl ester (DMC) (1:1v/v) and 5wt% fluoroethylene carbonate (FEC) were added in a glove box (H 2 O ⁇ 0.01ppm, O 2 ⁇ 0.01ppm) into a 2032-type button battery, that is, a sodium-ion battery.
  • EC ethylene carbonate
  • DMC dicarbonate Methyl ester
  • FEC fluoroethylene carbonate
  • This embodiment provides a method for preparing porous TiO2 - based nanomaterials, which is basically the same as in Embodiment 1, except that, in step S2, 75 mg of dopamine hydrochloride is added.
  • This embodiment provides a sodium ion battery, except that the porous TiO2- based nanomaterial prepared in embodiment 2 is used, the rest is the same as that of embodiment 1.
  • This example provides a method for preparing porous TiO2 - based nanomaterials, which is basically the same as Example 1, except that, in step S2, 100 mg of dopamine hydrochloride is added.
  • This embodiment provides a sodium ion battery, except that the porous TiO2- based nanomaterial prepared in embodiment 3 is used, the rest is the same as that of embodiment 1.
  • This example provides a method for preparing porous TiO2- based nanomaterials, which is basically the same as Example 2, except that in step S3, high-temperature carbonization treatment is performed at a temperature of 350°C.
  • This embodiment provides a sodium ion battery, except that the porous TiO2- based nanomaterial prepared in embodiment 4 is used, the rest is the same as that of embodiment 2.
  • This example provides a method for preparing porous TiO2- based nanomaterials, which is basically the same as Example 2, except that in step S3, high-temperature carbonization treatment is performed at a temperature of 420°C.
  • This embodiment provides a sodium ion battery, except that the porous TiO 2 -based nanomaterial prepared in embodiment 5 is used, the rest is the same as that of embodiment 2.
  • this comparative example provides a kind of porous TiO
  • the preparation method of base nano material comprises the steps:
  • the MIL-125 disc-shaped metal-organic framework precursor prepared in S1 is subjected to high-temperature carbonization treatment in an argon atmosphere at a gas flow rate of 100mL min -1 at a temperature of 380°C and a holding time of 4h , to obtain porous TiO 2 -based nanomaterials (p-TiO 2 ).
  • This comparative example provides a sodium ion battery, except that the porous TiO 2 -based nanomaterial prepared in comparative example 5 is used, and the rest is the same as that of embodiment 2.
  • This comparative example provides a preparation method of a porous TiO2 - based nanomaterial, which includes the following steps: It is basically the same as Example 1, except that in step S2, 30 mg of dopamine hydrochloride is added.
  • This comparative example provides a preparation method of a porous TiO2 - based nanomaterial, which includes the following steps: It is basically the same as Example 1, except that in step S2, 150 mg of dopamine hydrochloride is added.
  • This comparative example provides a method for preparing porous TiO2- based nanomaterials, which includes the following steps: It is basically the same as in Example 1, except that in step S3, high-temperature carbonization treatment is carried out at a temperature of 300°C.
  • This comparative example provides a kind of preparation method of porous TiO2 - based nanomaterials, comprising the following steps: It is basically the same as Example 1, the difference is: in the S2 step, in the S3 step, high-temperature carbonization treatment, the temperature is 450 ° C .
  • the sodium-ion battery prepared by the above-mentioned Examples 1-5 and Comparative Examples 1-5 was subjected to a charge-discharge experiment on the Xinwei battery test system using a constant current charge-discharge test standard, and the results obtained were as follows:
  • p-TiO 2 @NC still maintains the disk-like appearance of the MIL-125 precursor after self-polymerized PDA coating and calcination.
  • the surface is covered with nitrogen-doped carbon coating , which makes it appear rougher, which proves that a nitrogen-doped carbon layer is formed after PDA is carbonized at high temperature.
  • Fig. 2 Under the low magnification transmission electron microscope (Fig. 2), it is shown that the p-TiO 2 @NC composite has a disc-like structure with a diameter of about 500 nm, which is consistent with the SEM results.
  • the lattice fringe distances are 0.351 and 0.235nm, respectively, which match the (101) and (001) crystal planes of anatase TiO 2 , and also prove the highly exposed (001) crystal planes from the side. surface formation.
  • the N 2 adsorption-desorption isotherms in Fig. 3 show that the specific surface areas of p-TiO 2 and p-TiO 2 @NC are 98 and 333 m 2 g -1 , respectively.
  • Tests show that the increase in BET provides additional intercalation sites for Na + and enhances the pseudocapacitive contribution, resulting in better Na + /electron conduction.
  • the charge-discharge test results shown in Figure 4 show that the specific capacity of p-TiO 2 @NC is stable at 313.2mAh g -1 after 200 cycles, and the capacity retention rate is 91.82% calculated from the 4th cycle.
  • the present invention uses a metal-organic framework (MIL-125) as a precursor, coats polydopamine (Polydopamine, PDA) on the surface of TiO2 through in-situ polymerization, and undergoes high-temperature carbonization heat treatment to obtain porous TiO2- based nanomaterials (p-TiO 2 @NC material), the preparation method is simple and easy to operate, the energy consumption is relatively low, and the pollution is small;
  • MIL-125 metal-organic framework
  • the p-TiO 2 @NC material prepared by the present invention has the following advantages when used as a negative electrode material for a sodium ion battery: the p-TiO 2 @NC material retains the unique round cake shape of MIL-125, The heterogeneous carbon skeleton reduces the band gap of TiO 2 and lowers the Na + deintercalation barrier; the porous structure accelerates the diffusion of Na + ; the highly exposed (001) crystal plane can provide higher reactivity and accelerate the Reaction kinetics; the pseudocapacitive storage process can provide additional storage sites for sodium ions, which is conducive to the improvement of electronic conductivity, thereby improving the sodium storage performance of porous TiO 2 -based nanomaterials at high rates.

Abstract

A preparation method for a porous TiO2-based nanomaterial, and a porous TiO2-based nanomaterial and a sodium-ion battery. The preparation method comprises the following steps: S1, adding terephthalic acid, a titanium ester solution and 4-dimethylaminopyridine to a solvent, dispersing same to obtain a mixed solution, then adding same to an aqueous hydrofluoric acid solution, stirring same, maintaining the temperature at 140-160ºC and reacting same, and then subjecting same to a post-treatment to obtain an MIL-125 metal organic framework precursor; S2, dispersing the MIL-125 metal organic framework precursor in a buffer solution, then adding dopamine hydrochloride, and stirring same to then obtain MIL-125@PDA; and S3, subjecting the MIL-125@PDA to a high-temperature carbonization treatment in the presence of an inert gas, so as to obtain a porous TiO2-based nanomaterial with an exposed (001) crystal plane. When the porous TiO2-based nanomaterial is used as a negative electrode material of a sodium ion-battery, the potential barrier during deintercalation of Na+ is reduced; the pore structure accelerates the diffusion of Na+; and multiple highly exposed (001) crystal planes can provide a higher reaction activity and accelerate reaction kinetics.

Description

一种多孔TiO 2基纳米材料的制备方法及多孔TiO 2基纳米材料、钠离子电池 A kind of porous TiO Preparation method of 2-based nanomaterials and porous TiO 2-based nanomaterials, sodium-ion batteries 技术领域technical field
本发明属于钠电池领域，具体涉及一种多孔TiO 2基纳米材料的制备方法及多孔TiO 2基纳米材料、钠离子电池。 The invention belongs to the field of sodium batteries, and in particular relates to a preparation method of a porous TiO2- based nanometer material, a porous TiO2- based nanometer material, and a sodium ion battery.
背景技术Background technique
近年来，钠离子电池以其原材料丰富、成本低、循环稳定性好、倍率性能好等优点备受关注。但是与锂离子电池中脱嵌锂情况不同，钠离子的半径
Figure PCTCN2022097270-appb-000001
Figure PCTCN2022097270-appb-000002
和原子质量远大于锂离子
Figure PCTCN2022097270-appb-000003
因此导致能量密度较低和离子迁移速率较慢，严重阻碍了钠离子在电化学反应中的动力学，这使得锂电商业化的石墨负极不适合作为钠离子电池的负极材料。因此高性能负极材料的开发对于推动钠离子电池的发展及应用有着深远的影响。 In recent years, sodium-ion batteries have attracted much attention due to their abundant raw materials, low cost, good cycle stability, and good rate performance. However, unlike the lithium-ion battery, the radius of the sodium ion
Figure PCTCN2022097270-appb-000001
Figure PCTCN2022097270-appb-000002
and atomic mass much larger than Li-ion
Figure PCTCN2022097270-appb-000003
As a result, the energy density is low and the ion migration rate is slow, which seriously hinders the kinetics of sodium ions in the electrochemical reaction, which makes the commercial graphite anode of lithium battery unsuitable as the anode material of sodium ion battery. Therefore, the development of high-performance anode materials has a profound impact on promoting the development and application of sodium-ion batteries.
在种类繁多的负极材料中，锐钛矿型二氧化钛(TiO 2)具有自放电低、安全性高、循环寿命长、成本低廉等特性。且有相对于钠金属的沉积电压具有较高的工作电压，抑制了钠枝晶的产生，因此引起了研究者们广泛的关注。然则，由于TiO 2属于半导体材料，有离子扩散速率缓慢(10 -15～10 -9cm 2s -1)和导电性差(σ:10 -12～10 -7s cm -1)等不可避免的问题，使得其电化学储钠能力偏弱，限制了进一步的发展空间。 Among various negative electrode materials, anatase titanium dioxide (TiO 2 ) has the characteristics of low self-discharge, high safety, long cycle life, and low cost. And it has a higher working voltage than the deposition voltage of sodium metal, which inhibits the generation of sodium dendrites, so it has attracted extensive attention from researchers. However, since TiO 2 is a semiconductor material, it has the inevitable slow ion diffusion rate (10 -15 ～10 -9 cm 2 s -1 ) and poor electrical conductivity (σ: 10 -12 ～10 -7 s cm -1 ). However, the electrochemical sodium storage capacity is relatively weak, which limits the further development space.
表面氧化还原赝电容能实现较短的充电时间和较高的功率输送，具有广阔的应用前景。为了实现最大的比容量，开发纳米级或多孔电极材料是增强赝电容反应的最常见和通用的策略之一。通过合理的纳米结构制备结构，可以缩短Na +扩散和电子传输的路径，以此达到改善电极材料的反应动力学的目的。此外， 金属有机框架衍生的方法对于构建多孔结构是简单有效的；自模板法极大地简化了合成程序，使实现量产成为可能。另外，纳米粒子的高能面取向是实现快速脱嵌钠的关键因素。对于锐钛矿型TiO 2，(001)、(100)和(101)面的表面能分别为0.90、0.53和0.44J m -2，而TiO 2的(001)晶面带隙远低于(101)、(010)和(111)晶面，说明(001)晶面的活性较高。但值得注意的是，暴露在外的高能晶面很脆弱，连续循环后也容易失去活性。 Surface redox pseudocapacitance can achieve short charging time and high power delivery, which has broad application prospects. To achieve the maximum specific capacity, developing nanoscale or porous electrode materials is one of the most common and versatile strategies to enhance the pseudocapacitive response. Fabrication of structures through rational nanostructures can shorten the paths of Na + diffusion and electron transport, thereby achieving the purpose of improving the reaction kinetics of electrode materials. In addition, the metal-organic framework-derived method is simple and effective for constructing porous structures; the self-template method greatly simplifies the synthesis procedure and makes mass production possible. In addition, the high-energy plane orientation of nanoparticles is the key factor to achieve fast sodium intercalation. For anatase TiO 2 , the surface energies of (001), (100) and (101) planes are 0.90, 0.53 and 0.44 J m -2 , respectively, while the band gap of (001) plane of TiO 2 is much lower than ( 101), (010) and (111) crystal planes, indicating that the (001) crystal plane has higher activity. However, it is worth noting that the exposed high-energy crystal faces are fragile and easily lose their activity after continuous cycling.
为了解决以上问题，需要研发出一种多孔TiO 2基纳米材料的制备方法，以提升材料的储钠特性。 In order to solve the above problems, it is necessary to develop a preparation method of porous TiO2- based nanomaterials to improve the sodium storage properties of the materials.
发明内容Contents of the invention
鉴于此，本发明的目的是提供一种具有高倍率的储钠性能的具有(001)晶面暴露的多孔TiO 2基纳米材料的制备方法及多孔TiO 2基纳米材料、钠离子电池。本发明的第一个目的在于提供一种多孔TiO 2基纳米材料的制备方法，包括如下步骤： In view of this, the object of the present invention is to provide a method for preparing porous TiO2- based nanomaterials with high-rate sodium storage properties with exposed (001) crystal planes, porous TiO2- based nanomaterials, and sodium-ion batteries. First object of the present invention is to provide a kind of porous TiO2 The preparation method of base nano material, comprises the steps:
S1、将对苯二甲酸、钛酯溶液、4-二甲基氨基吡啶加入到溶剂中，超声分散得到混合溶液，再将所述混合溶液加入氢氟酸水溶液中搅拌，在140-160℃下保温反应，再进行后处理得到MIL-125圆饼状金属有机骨架前驱体；S1. Add terephthalic acid, titanium ester solution, and 4-dimethylaminopyridine into the solvent, and disperse it ultrasonically to obtain a mixed solution, then add the mixed solution into hydrofluoric acid aqueous solution and stir, and heat at 140-160°C Insulation reaction, and then post-treatment to obtain the MIL-125 round cake-shaped metal-organic framework precursor;
S2、将所述MIL-125圆饼状金属有机骨架前驱体分散在缓冲溶液中，再添加盐酸多巴胺，搅拌15-20h后，经后处理得到干燥的MIL-125@PDA圆盘；S2. Dispersing the MIL-125 disc-shaped metal-organic framework precursor in a buffer solution, then adding dopamine hydrochloride, stirring for 15-20 hours, and post-processing to obtain a dry MIL-125@PDA disc;
S3、将所述MIL-125@PDA圆盘在惰性气体氛围下进行高温碳化处理，得到粉末即具有(001)晶面暴露的多孔TiO 2基纳米材料。 S3, subjecting the MIL-125@PDA disk to high-temperature carbonization treatment in an inert gas atmosphere to obtain a powder, that is, a porous TiO 2 -based nanomaterial with exposed (001) crystal planes.
具体的，所述钛酯溶液为选自钛酸四丁酯、钛酸四乙酯、钛酸四丙酯中的一种溶解在选自甲醇、乙酸、异丙醇、正丁醇、乙酰丙酮中的一种的溶剂中得到的溶液。Specifically, the titanium ester solution is one selected from tetrabutyl titanate, tetraethyl titanate, and tetrapropyl titanate dissolved in methanol, acetic acid, isopropanol, n-butanol, acetylacetone A solution obtained in one of the solvents.
具体的，步骤S1中，所述溶剂为选自N，N二甲基甲酰胺、N-甲基吡咯烷酮、二甲基乙酰胺、1,3-二甲基-2-咪唑啉酮、二甲基亚砜中的一种或多种。Specifically, in step S1, the solvent is selected from N,N dimethylformamide, N-methylpyrrolidone, dimethylacetamide, 1,3-dimethyl-2-imidazolinone, dimethyl One or more of the group sulfoxides.
具体的，步骤S1中，所述对苯二甲酸、所述钛酯溶液和所述4-二甲基氨基吡啶的投料摩尔比为(13-15)：(160-180)：1。Specifically, in step S1, the feeding molar ratio of the terephthalic acid, the titanium ester solution and the 4-dimethylaminopyridine is (13-15):(160-180):1.
具体的，步骤S2中，所述缓冲溶液为选自Tris缓冲液、Tris-HCl缓冲液、Tris-磷酸盐缓冲液中的至少一种，所述缓冲溶液的浓度为5-20mM。Specifically, in step S2, the buffer solution is at least one selected from Tris buffer, Tris-HCl buffer, and Tris-phosphate buffer, and the concentration of the buffer solution is 5-20 mM.
具体的，步骤S2中，所述MIL-125圆饼状金属有机骨架前驱体与所述盐酸多巴胺的投料摩尔比为(3-6):1。Specifically, in step S2, the molar ratio of the MIL-125 disc-shaped metal-organic framework precursor to the dopamine hydrochloride is (3-6):1.
具体的，步骤S3中，所述惰性气体的气体流通速率为50～150mL min -1，所述高温碳化处理的温度为350-420℃，保温时间为4-6h； Specifically, in step S3, the gas flow rate of the inert gas is 50-150mL min -1 , the temperature of the high-temperature carbonization treatment is 350-420°C, and the holding time is 4-6h;
优选地，所述惰性气体为选自氩气、氮气、氩氢混合气中的一种。Preferably, the inert gas is one selected from argon, nitrogen, and argon-hydrogen mixed gas.
具体的，步骤S1和步骤S2中，所述后处理各自独立地为将反应后得到的溶液用无水甲醇为溶剂离心，收集沉淀，并在60-90℃下烘干6-10h。Specifically, in step S1 and step S2, the post-treatments are independently centrifuging the solution obtained after the reaction with anhydrous methanol as a solvent, collecting the precipitate, and drying at 60-90° C. for 6-10 hours.
本发明的第二个目的在于提供一种多孔TiO 2基纳米材料，采用如上所述制备方法得到。 The second object of the present invention is to provide a porous TiO 2 -based nanomaterial obtained by the above-mentioned preparation method.
本发明的第三个目的在于提供一种钠离子电池，包括负极材料，所述负极材料包括如上一所述制备方法得到的多孔TiO 2基纳米材料和如上所述多孔TiO 2基纳米材料。 The third object of the present invention is to provide a sodium-ion battery, including the negative electrode material, which includes the porous TiO 2 -based nanomaterial obtained by the preparation method described above and the porous TiO 2 -based nanomaterial as described above.
本发明克服了现有技术中，具有如下优点：The present invention overcomes the prior art and has the following advantages:
(1)本发明以金属有机骨架(MIL-125)作为前驱体，通过原位聚合在TiO 2表面包覆聚多巴胺(Polydopamine,PDA)，并经过高温碳化热处理，得到多孔TiO 2基纳米材料(p-TiO 2@NC材料)，制备方法简单易操作，能耗相对较低，且污染小； (1) The present invention uses a metal-organic framework (MIL-125) as a precursor to coat polydopamine (Polydopamine, PDA) on the surface of TiO by in - situ polymerization, and undergoes high-temperature carbonization heat treatment to obtain porous TiO 2- based nanomaterials ( p-TiO 2 @NC material), the preparation method is simple and easy to operate, the energy consumption is relatively low, and the pollution is small;
(2)本发明制备得到的的p-TiO 2@NC材料，当用于钠离子电池负极材料时，有如下优点：p-TiO 2@NC材料保留了MIL-125特有的圆饼状形貌，氮掺杂的碳骨架减小了TiO 2的带隙，降低了Na +脱嵌势垒；多孔结构加速了Na +的扩散；高度暴露的(001)晶面，能提供更高的反应活性，加快了反应动力学；赝电容存储过程，能为钠离子提供了额外的存储位点，有利于电子电导率的提高，从而提升了多孔TiO 2基纳米材料在高倍率下的储钠性能。 (2) The p-TiO 2 @NC material prepared by the present invention has the following advantages when used as an anode material for a sodium ion battery: the p-TiO 2 @NC material retains the unique round cake shape of MIL-125 , the nitrogen-doped carbon skeleton reduces the band gap of TiO 2 and lowers the Na + deintercalation barrier; the porous structure accelerates the diffusion of Na + ; the highly exposed (001) crystal plane can provide higher reactivity , to speed up the reaction kinetics; the pseudocapacitive storage process can provide additional storage sites for sodium ions, which is conducive to the improvement of electronic conductivity, thereby improving the sodium storage performance of porous TiO 2 -based nanomaterials at high rates.
附图说明：Description of drawings:
附图1为实施例2中制得的多孔TiO 2基纳米材料的SEM图； Accompanying drawing 1 is the porous TiO that makes in embodiment 2 The SEM figure of base nanomaterial;
附图2为实施例2中制得的多孔TiO 2基纳米材料的TEM图； Accompanying drawing 2 is the porous TiO that makes in embodiment 2 The TEM figure of base nano material;
附图3为实施例2和对比例1中的多孔TiO 2基纳米材料的BET对比图； Accompanying drawing 3 is the BET contrast figure of porous TiO in the embodiment 2 and comparative example 1 base nanomaterial;
附图4为实施例2和对比例1中的多孔TiO 2基纳米材料的充放电循环性能图。 Accompanying drawing 4 is the charge-discharge cycle performance diagram of the porous TiO2- based nanomaterial in Example 2 and Comparative Example 1.
具体实施方式Detailed ways
鉴于现有技术中的各种不足，本发明考虑结合高能活性晶面和碳涂层，可以显著提高TiO 2的钠储存性能。同时，多巴胺(DA)被氧化并自聚合成聚多巴胺(PDA)，可用于各种材料表面的涂层。而这种富含氮的碳基材料经过热处理后可以形成导电网络，从而提高材料的导电性。 In view of various deficiencies in the prior art, the present invention considers that the combination of high-energy active crystal faces and carbon coating can significantly improve the sodium storage performance of TiO 2 . At the same time, dopamine (DA) is oxidized and self-polymerized into polydopamine (PDA), which can be used for coating on the surface of various materials. The nitrogen-rich carbon-based material can be heat-treated to form a conductive network, which improves the material's conductivity.
本发明提供一种多孔TiO 2基纳米材料的制备方法，包括如下步骤： The invention provides a kind of porous TiO The preparation method of base nano material comprises the following steps:
S1、将对苯二甲酸、钛酯溶液(选自钛酸四丁酯、钛酸四乙酯、钛酸四丙酯中的一种溶解在选自甲醇、乙酸、异丙醇、正丁醇、乙酰丙酮中的一种的溶剂中得到的溶液)、4-二甲基氨基吡啶加入到溶剂(N，N二甲基甲酰胺、N-甲基吡咯烷酮、二甲基乙酰胺、1,3-二甲基-2-咪唑啉酮、二甲基亚砜中的一种或多种)中，超声分散得到混合溶液，再将混合溶液加入氢氟酸水溶液中搅拌，在 140-160℃下保温反应，再进行后处理得到MIL-125圆饼状金属有机骨架前驱体；其中，对苯二甲酸、钛酯溶液和4-二甲基氨基吡啶的投料摩尔比为(13-15)：(160-180)：1；S1, dissolving terephthalic acid, titanium ester solution (one selected from tetrabutyl titanate, tetraethyl titanate, tetrapropyl titanate) in methanol, acetic acid, isopropanol, n-butanol , a solution obtained in a solvent of acetylacetone), 4-dimethylaminopyridine is added to the solvent (N, N dimethylformamide, N-methylpyrrolidone, dimethylacetamide, 1,3 -one or more of dimethyl-2-imidazolidinone, dimethyl sulfoxide), ultrasonic dispersion to obtain a mixed solution, then add the mixed solution to hydrofluoric acid aqueous solution and stir, at 140-160 ° C Insulation reaction, and then post-treatment to obtain the MIL-125 round cake-shaped metal organic framework precursor; wherein, the molar ratio of terephthalic acid, titanium ester solution and 4-dimethylaminopyridine is (13-15):( 160-180): 1;
S2、将MIL-125圆饼状金属有机骨架前驱体分散在溶液(选自Tris缓冲液、Tris-HCl缓冲液、Tris-磷酸盐缓冲液中的至少一种，缓冲溶液的浓度为5-20mM)中，再添加盐酸多巴胺，搅拌15-20h后，经后处理得到干燥的MIL-125@PDA圆盘；其中，MIL-125圆饼状金属有机骨架前驱体与盐酸多巴胺的投料摩尔比为(3-6):1；S2. Disperse the MIL-125 disc-shaped metal-organic framework precursor in a solution (at least one selected from Tris buffer, Tris-HCl buffer, Tris-phosphate buffer, the concentration of the buffer solution is 5-20mM ), add dopamine hydrochloride, stir for 15-20h, and obtain dry MIL-125@PDA discs after post-treatment; wherein, the molar ratio of MIL-125 disc-shaped metal-organic framework precursor to dopamine hydrochloride is ( 3-6): 1;
S3、将MIL-125@PDA圆盘在惰性气体(为选自氩气、氮气、氩氢混合气中的一种，惰性气体的气体流通速率为50～150mL min -1)氛围下进行高温碳化处理(温度为350-420℃，保温时间为4-6h)，得到粉末即具有(001)晶面暴露的多孔TiO 2基纳米材料。 S3. Carry out high-temperature carbonization of the MIL-125@PDA disc in an atmosphere of an inert gas (one selected from argon, nitrogen, and argon-hydrogen mixed gas, and the gas flow rate of the inert gas is 50-150mL min -1 ) After treatment (at a temperature of 350-420° C. and a holding time of 4-6 h), a powder is obtained, that is, a porous TiO 2 -based nanomaterial with exposed (001) crystal faces.
步骤S1和步骤S2中，后处理各自独立地为将反应后得到的溶液用无水甲醇为溶剂离心，收集沉淀，并在60-90℃下烘干6-10h。In step S1 and step S2, the post-treatment is independently centrifuging the solution obtained after the reaction with anhydrous methanol as a solvent, collecting the precipitate, and drying at 60-90° C. for 6-10 hours.
本发明中4-二甲基氨基吡啶的加入，能够提高金属有机骨架(MIL-125)的多孔性；惰性气体中，氩氢混合气，氩气和氢气的体积比为95:5。The addition of 4-dimethylaminopyridine in the present invention can improve the porosity of the metal-organic framework (MIL-125); in the inert gas, argon-hydrogen mixed gas, the volume ratio of argon and hydrogen is 95:5.
本发明还提供一种钠离子电池，包括负极材料。负极材料包括如上制备方法得到的多孔TiO 2基纳米材料和如上多孔TiO 2基纳米材料。负极材料的制备方法，包括如下步骤：将硅基复合材料、导电剂和粘结剂按照质量比为(7-9):1:1分散在水溶剂中得到混合分散液，将混合分散液涂覆在铜箔上，干燥得到电极片，即负极材料。 The invention also provides a sodium ion battery, including the negative electrode material. The negative electrode material includes the porous TiO2- based nanomaterial obtained by the above preparation method and the above porous TiO2 - based nanomaterial. The preparation method of the negative electrode material comprises the following steps: dispersing the silicon-based composite material, the conductive agent and the binder in the water solvent according to the mass ratio of (7-9):1:1 to obtain a mixed dispersion liquid, and coating the mixed dispersion liquid Coated on copper foil, dried to obtain electrode sheet, that is, negative electrode material.
钠离子电池的制备方法及类型采用本领域的公知方法进行制备，本申请中并不做具体限定。以下以一种举例进行说明：The preparation method and type of the sodium ion battery are prepared by methods known in the art, and are not specifically limited in this application. The following is an example to illustrate:
(1)负极材料的制备方法，包括如下步骤：将上述制备得到的多孔TiO 2基纳米材料、超导炭和羧甲基纤维素钠按照质量比为8:1:1分散在水溶剂中，得到混合分散液，再将混合分散液涂覆在铜箔上，干燥得到电极片，即负极材料； (1) the preparation method of negative electrode material, comprises the steps: the porous TiO2 base nano material that above-mentioned preparation obtains, superconducting carbon and sodium carboxymethyl cellulose are dispersed in water solvent according to mass ratio according to 8:1:1, The mixed dispersion is obtained, and then the mixed dispersion is coated on the copper foil, and dried to obtain the electrode sheet, that is, the negative electrode material;
(2)将上述负极材料用作工作电极，高纯钠片用作对电极，以玻璃纤维(Whatman，GF/D)作为隔膜，电解液为1M NaClO 4溶解在碳酸乙烯酯(EC)/碳酸二甲酯(DMC)(1:1v/v)以及添加了5wt％氟代碳酸乙烯酯(FEC)，在装有高纯氩气(99.999％)的手套箱(H 2O<0.01ppm，O 2<0.01ppm)中的组装成2032型纽扣电池，即得到钠离子电池。 (2) The above-mentioned negative electrode material is used as the working electrode, the high-purity sodium sheet is used as the counter electrode, the glass fiber (Whatman, GF/D) is used as the separator, and the electrolyte is 1M NaClO 4 dissolved in ethylene carbonate (EC)/dicarbonate Methyl ester (DMC) (1:1v/v) and 5wt% fluoroethylene carbonate (FEC) were added in a glove box (H 2 O<0.01ppm, O 2 <0.01ppm) into a 2032-type button battery, that is, a sodium-ion battery.
本申请中钠离子电池的充放电实验在新威电池测试***上进行。The charge and discharge experiment of the sodium ion battery in this application is carried out on the Xinwei battery test system.
下面结合具体实施例对本发明做进一步详细的说明，但本发明并不限于以下实施例。实施例中采用的实施条件可以根据具体使用的不同要求做进一步调整，未注明的实施条件为本行业中的常规条件。The present invention will be described in further detail below in conjunction with specific examples, but the present invention is not limited to the following examples. The implementation conditions adopted in the examples can be further adjusted according to the different requirements of specific use, and the implementation conditions not indicated are the conventional conditions in this industry.
实施例1Example 1
1、本实施例提供一种多孔TiO 2基纳米材料的制备方法，包括如下步骤： 1, the present embodiment provides a kind of porous TiO 2 preparation method of base nanomaterial, comprises the following steps:
S1、将3.0g对苯二甲酸、钛酯溶液(1.56mL钛酸四丁酯溶解在选自6mL无水甲醇中得到的溶液)、0.2g 4-二甲基氨基吡啶加入到60mL N，N二甲基甲酰胺中，超声分散得到混合溶液，30min后，再将混合溶液加入10％的氢氟酸水溶液中剧烈搅拌3h，在150℃下保温反应24h，再进行后处理(使用无水甲醇为溶剂离心收集沉淀，70℃下烘干8h)得到大小均匀、形状规则的MIL-125圆饼状金属有机骨架前驱体；S1. Add 3.0g terephthalic acid, titanium ester solution (1.56mL tetrabutyl titanate dissolved in 6mL anhydrous methanol) and 0.2g 4-dimethylaminopyridine to 60mL N, N In dimethylformamide, ultrasonically disperse to obtain a mixed solution. After 30 minutes, add the mixed solution to 10% hydrofluoric acid aqueous solution and stir vigorously for 3 hours, and keep it warm at 150°C for 24 hours, and then carry out post-treatment (using anhydrous methanol Collect the precipitate by centrifuging the solvent, and dry it at 70°C for 8h) to obtain a MIL-125 disc-shaped metal-organic framework precursor with uniform size and regular shape;
S2、将0.3g MIL-125圆饼状金属有机骨架前驱体分散在250mL 10mM的Tris-HCl缓冲溶液中，再添加50mg盐酸多巴胺，剧烈搅拌24h后，经后处理 (使用无水甲醇为溶剂离心收集沉淀，70℃下烘干8h)得到干燥的MIL-125@PDA圆盘；S2. Disperse 0.3g of MIL-125 disc-shaped metal-organic framework precursor in 250mL of 10mM Tris-HCl buffer solution, add 50mg of dopamine hydrochloride, stir vigorously for 24h, and after post-treatment (using anhydrous methanol as solvent centrifugation Collect the precipitate and dry it at 70°C for 8h) to obtain a dried MIL-125@PDA disc;
S3、将MIL-125@PDA圆盘在氩气氛围中，氩气的气体流通速率为100mL min -1，进行高温碳化处理，温度为380℃，保温时间为4h，得到黑粉末即具有(001)晶面暴露的多孔TiO 2基纳米材料(p-TiO 2@NC)。 S3. Put the MIL-125@PDA disc in the argon atmosphere, the gas flow rate of the argon gas is 100mL min -1 , perform high-temperature carbonization treatment, the temperature is 380°C, and the holding time is 4h, and the black powder with (001 ) porous TiO 2 -based nanomaterials with exposed facets (p-TiO 2 @NC).
2、本实施例还提供一种钠离子电池，钠离子电池的制备方法及类型采用本领域的公知方法进行制备，本申请中并不做具体限定。以下以一种举例进行说明：2. This embodiment also provides a sodium-ion battery. The preparation method and type of the sodium-ion battery are prepared by methods known in the art, and are not specifically limited in this application. The following is an example to illustrate:
(1)负极材料的制备方法，包括如下步骤：将上述制备得到的多孔TiO 2基纳米材料、超导炭和羧甲基纤维素钠按照质量比为8:1:1分散在水溶剂中，得到混合分散液，再将混合分散液涂覆在铜箔上，干燥得到电极片，即负极材料； (1) the preparation method of negative electrode material, comprises the steps: the porous TiO2 base nano material that above-mentioned preparation obtains, superconducting carbon and sodium carboxymethyl cellulose are dispersed in water solvent according to mass ratio according to 8:1:1, The mixed dispersion is obtained, and then the mixed dispersion is coated on the copper foil, and dried to obtain the electrode sheet, that is, the negative electrode material;
(2)将上述负极材料用作工作电极，高纯钠片用作对电极，以玻璃纤维(Whatman，GF/D)作为隔膜，电解液为1M NaClO 4溶解在碳酸乙烯酯(EC)/碳酸二甲酯(DMC)(1:1v/v)以及添加了5wt％氟代碳酸乙烯酯(FEC)，在装有高纯氩气(99.999％)的手套箱(H 2O<0.01ppm，O 2<0.01ppm)中的组装成2032型纽扣电池，即得到钠离子电池。 (2) The above-mentioned negative electrode material is used as the working electrode, the high-purity sodium sheet is used as the counter electrode, the glass fiber (Whatman, GF/D) is used as the separator, and the electrolyte is 1M NaClO 4 dissolved in ethylene carbonate (EC)/dicarbonate Methyl ester (DMC) (1:1v/v) and 5wt% fluoroethylene carbonate (FEC) were added in a glove box (H 2 O<0.01ppm, O 2 <0.01ppm) into a 2032-type button battery, that is, a sodium-ion battery.
钠离子电池的充放电实验在新威电池测试***上进行。The charge and discharge experiments of sodium-ion batteries are carried out on Xinwei battery test system.
实施例2Example 2
1、本实施例提供一种多孔TiO 2基纳米材料的制备方法，其与实施例1基本相同，不同之处在于，S2步骤中，加入75mg盐酸多巴胺。 1. This embodiment provides a method for preparing porous TiO2 - based nanomaterials, which is basically the same as in Embodiment 1, except that, in step S2, 75 mg of dopamine hydrochloride is added.
2、本实施例提供一种钠离子电池，除了采用实施例2制备得到的多孔TiO 2基纳米材料，其余与实施例1相同。 2. This embodiment provides a sodium ion battery, except that the porous TiO2- based nanomaterial prepared in embodiment 2 is used, the rest is the same as that of embodiment 1.
实施例3Example 3
1、本实施例提供一种多孔TiO 2基纳米材料的制备方法，其与实施例1基本相同，不同之处在于，S2步骤中，加入100mg盐酸多巴胺。 1. This example provides a method for preparing porous TiO2 - based nanomaterials, which is basically the same as Example 1, except that, in step S2, 100 mg of dopamine hydrochloride is added.
2、本实施例提供一种钠离子电池，除了采用实施例3制备得到的多孔TiO 2基纳米材料，其余与实施例1相同。 2. This embodiment provides a sodium ion battery, except that the porous TiO2- based nanomaterial prepared in embodiment 3 is used, the rest is the same as that of embodiment 1.
实施例4Example 4
1、本实施例提供一种多孔TiO 2基纳米材料的制备方法，其与实施例2基本相同，不同之处在于，S3步骤中，高温碳化处理，温度为350℃。 1. This example provides a method for preparing porous TiO2- based nanomaterials, which is basically the same as Example 2, except that in step S3, high-temperature carbonization treatment is performed at a temperature of 350°C.
2、本实施例提供一种钠离子电池，除了采用实施例4制备得到的多孔TiO 2基纳米材料，其余与实施例2相同。 2. This embodiment provides a sodium ion battery, except that the porous TiO2- based nanomaterial prepared in embodiment 4 is used, the rest is the same as that of embodiment 2.
实施例5Example 5
1、本实施例提供一种多孔TiO 2基纳米材料的制备方法，其与实施例2基本相同，不同之处在于，S3步骤中，高温碳化处理，温度为420℃。 1. This example provides a method for preparing porous TiO2- based nanomaterials, which is basically the same as Example 2, except that in step S3, high-temperature carbonization treatment is performed at a temperature of 420°C.
2、本实施例提供一种钠离子电池，除了采用实施例5制备得到的多孔TiO 2基纳米材料，其余与实施例2相同。 2. This embodiment provides a sodium ion battery, except that the porous TiO 2 -based nanomaterial prepared in embodiment 5 is used, the rest is the same as that of embodiment 2.
对比例1Comparative example 1
1、本对比例提供一种多孔TiO 2基纳米材料的制备方法，包括如下步骤： 1, this comparative example provides a kind of porous TiO The preparation method of base nano material comprises the steps:
S1、将3.0g对苯二甲酸、钛酯溶液(1.56mL钛酸四丁酯溶解在选自6mL无水甲醇中得到的溶液)、0.2g 4-二甲基氨基吡啶加入到60mL N，N二甲基甲酰胺中，超声分散得到混合溶液，30min后，再将混合溶液加入10％的氢氟酸水溶液中剧烈搅拌3h，在150℃下保温反应24h，再进行后处理(使用无水甲醇为溶剂离心收集沉淀，70℃下烘干8h)得到大小均匀、形状规则的MIL-125圆饼 状金属有机骨架前驱体；S1. Add 3.0g terephthalic acid, titanium ester solution (1.56mL tetrabutyl titanate dissolved in 6mL anhydrous methanol) and 0.2g 4-dimethylaminopyridine to 60mL N, N In dimethylformamide, ultrasonically disperse to obtain a mixed solution. After 30 minutes, add the mixed solution to 10% hydrofluoric acid aqueous solution and stir vigorously for 3 hours, and keep it warm at 150°C for 24 hours, and then carry out post-treatment (using anhydrous methanol Collect the precipitate by centrifuging the solvent, and dry it at 70°C for 8h) to obtain a MIL-125 disc-shaped metal-organic framework precursor with uniform size and regular shape;
S2、将S1制备得到的MIL-125圆饼状金属有机骨架前驱体在氩气氛围中，氩气的气体流通速率为100mL min -1，进行高温碳化处理，温度为380℃，保温时间为4h，得到多孔TiO 2基纳米材料(p-TiO 2)。 S2. The MIL-125 disc-shaped metal-organic framework precursor prepared in S1 is subjected to high-temperature carbonization treatment in an argon atmosphere at a gas flow rate of 100mL min -1 at a temperature of 380°C and a holding time of 4h , to obtain porous TiO 2 -based nanomaterials (p-TiO 2 ).
2、本对比例提供一种钠离子电池，除了采用对比例5制备得到的多孔TiO 2基纳米材料，其余与实施例2相同。 2. This comparative example provides a sodium ion battery, except that the porous TiO 2 -based nanomaterial prepared in comparative example 5 is used, and the rest is the same as that of embodiment 2.
对比例2Comparative example 2
本对比例提供一种多孔TiO 2基纳米材料的制备方法，包括如下步骤：，其与实施例1基本相同，不同之处在于：S2步骤中，加入30mg盐酸多巴胺。 This comparative example provides a preparation method of a porous TiO2 - based nanomaterial, which includes the following steps: It is basically the same as Example 1, except that in step S2, 30 mg of dopamine hydrochloride is added.
对比例3Comparative example 3
本对比例提供一种多孔TiO 2基纳米材料的制备方法，包括如下步骤：，其与实施例1基本相同，不同之处在于：S2步骤中，加入150mg盐酸多巴胺。 This comparative example provides a preparation method of a porous TiO2 - based nanomaterial, which includes the following steps: It is basically the same as Example 1, except that in step S2, 150 mg of dopamine hydrochloride is added.
对比例4Comparative example 4
本对比例提供一种多孔TiO 2基纳米材料的制备方法，包括如下步骤：，其与实施例1基本相同，不同之处在于：S3步骤中，高温碳化处理，温度为300℃。 This comparative example provides a method for preparing porous TiO2- based nanomaterials, which includes the following steps: It is basically the same as in Example 1, except that in step S3, high-temperature carbonization treatment is carried out at a temperature of 300°C.
对比例5Comparative example 5
本对比例提供一种多孔TiO 2基纳米材料的制备方法，包括如下步骤：，其与实施例1基本相同，不同之处在于：S2步骤中，S3步骤中，高温碳化处理，温度为450℃。 This comparative example provides a kind of preparation method of porous TiO2 - based nanomaterials, comprising the following steps: It is basically the same as Example 1, the difference is: in the S2 step, in the S3 step, high-temperature carbonization treatment, the temperature is 450 ° C .
将上述实施例1-5及对比例1-5制备得到的钠离子电池采用恒电流充放电的测试标准在新威电池测试***上进行充放电实验，得到的结果如下：The sodium-ion battery prepared by the above-mentioned Examples 1-5 and Comparative Examples 1-5 was subjected to a charge-discharge experiment on the Xinwei battery test system using a constant current charge-discharge test standard, and the results obtained were as follows:
Figure PCTCN2022097270-appb-000004
Figure PCTCN2022097270-appb-000004
如图1的SEM所示，p-TiO 2@NC在自聚合PDA涂层和煅烧后仍然保持MIL-125前驱体的圆盘状外观，另外，表面随着氮掺杂碳涂层的包覆，使得其表观上变得更加粗糙，证明了PDA在高温碳化后形成了氮掺杂碳层。在低倍透射电镜下(图2)，表明p-TiO 2@NC复合材料具有圆盘状结构形态，直径约为500nm，与SEM结果一致。另外，利用Digital Micrograph计算可得，晶格条纹距离分别为0.351和0.235nm，与锐钛矿型TiO 2的(101)和(001)晶面相匹配，也从侧面证明了高暴露(001)晶面的形成。图3中的N 2吸脱附等温线显示p-TiO 2和p-TiO 2@NC的比表面积分别为98和333m 2g -1。测试表明BET的提高为Na +提供了额外的嵌入位点并增强赝电容贡献，从而获得更好的Na +/电子传导能力。如图4充放电测试结果显示，p-TiO 2@NC在循环200次比容量稳定在313.2mAh g -1，从第4次循环计算，其容量保持率为91.82％。 As shown in the SEM of Fig. 1, p-TiO 2 @NC still maintains the disk-like appearance of the MIL-125 precursor after self-polymerized PDA coating and calcination. In addition, the surface is covered with nitrogen-doped carbon coating , which makes it appear rougher, which proves that a nitrogen-doped carbon layer is formed after PDA is carbonized at high temperature. Under the low magnification transmission electron microscope (Fig. 2), it is shown that the p-TiO 2 @NC composite has a disc-like structure with a diameter of about 500 nm, which is consistent with the SEM results. In addition, using Digital Micrograph calculations, the lattice fringe distances are 0.351 and 0.235nm, respectively, which match the (101) and (001) crystal planes of anatase TiO 2 , and also prove the highly exposed (001) crystal planes from the side. surface formation. The N 2 adsorption-desorption isotherms in Fig. 3 show that the specific surface areas of p-TiO 2 and p-TiO 2 @NC are 98 and 333 m 2 g -1 , respectively. Tests show that the increase in BET provides additional intercalation sites for Na + and enhances the pseudocapacitive contribution, resulting in better Na + /electron conduction. The charge-discharge test results shown in Figure 4 show that the specific capacity of p-TiO 2 @NC is stable at 313.2mAh g -1 after 200 cycles, and the capacity retention rate is 91.82% calculated from the 4th cycle.
本发明以金属有机骨架(MIL-125)作为前驱体，通过原位聚合在TiO 2表面包覆聚多巴胺(Polydopamine,PDA)，并经过高温碳化热处理，得到多孔TiO 2基纳米材料(p-TiO 2@NC材料)，制备方法简单易操作，能耗相对较低，且污染 小； The present invention uses a metal-organic framework (MIL-125) as a precursor, coats polydopamine (Polydopamine, PDA) on the surface of TiO2 through in-situ polymerization, and undergoes high-temperature carbonization heat treatment to obtain porous TiO2- based nanomaterials (p-TiO 2 @NC material), the preparation method is simple and easy to operate, the energy consumption is relatively low, and the pollution is small;
本发明制备得到的的p-TiO 2@NC材料，当用于钠离子电池负极材料时，有如下优点：p-TiO 2@NC材料保留了MIL-125特有的圆饼状形貌，氮掺杂的碳骨架减小了TiO 2的带隙，降低了Na +脱嵌势垒；多孔结构加速了Na +的扩散；高度暴露的(001)晶面，能提供更高的反应活性，加快了反应动力学；赝电容存储过程，能为钠离子提供了额外的存储位点，有利于电子电导率的提高，从而提升了多孔TiO 2基纳米材料在高倍率下的储钠性能。 The p-TiO 2 @NC material prepared by the present invention has the following advantages when used as a negative electrode material for a sodium ion battery: the p-TiO 2 @NC material retains the unique round cake shape of MIL-125, The heterogeneous carbon skeleton reduces the band gap of TiO 2 and lowers the Na + deintercalation barrier; the porous structure accelerates the diffusion of Na + ; the highly exposed (001) crystal plane can provide higher reactivity and accelerate the Reaction kinetics; the pseudocapacitive storage process can provide additional storage sites for sodium ions, which is conducive to the improvement of electronic conductivity, thereby improving the sodium storage performance of porous TiO 2 -based nanomaterials at high rates.
显然，本领域的技术人员可以对本发明进行各种改动和变型而不脱离本发明的精神和范围。这样，倘若本发明的这些修改和变型属于本发明权利要求及其等同技术的范围之内，则本发明也意图包含这些改动和变型在内Obviously, those skilled in the art can make various changes and modifications to the present invention without departing from the spirit and scope of the present invention. In this way, if these modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalent technologies, the present invention is also intended to include these modifications and variations.

Claims (10)

  1. 一种多孔TiO 2基纳米材料的制备方法，其特征在于，包括如下步骤： A method for preparing porous TiO2 - based nanomaterials, comprising the steps of:
    S1、将对苯二甲酸、钛酯溶液、4-二甲基氨基吡啶加入到溶剂中，超声分散得到混合溶液，再将所述混合溶液加入氢氟酸水溶液中搅拌，在140-160℃下保温反应，再进行后处理得到MIL-125圆饼状金属有机骨架前驱体；S1. Add terephthalic acid, titanium ester solution, and 4-dimethylaminopyridine into the solvent, and disperse it ultrasonically to obtain a mixed solution, then add the mixed solution into hydrofluoric acid aqueous solution and stir, and heat at 140-160°C Insulation reaction, and then post-treatment to obtain the MIL-125 round cake-shaped metal-organic framework precursor;
    S2、将所述MIL-125圆饼状金属有机骨架前驱体分散在缓冲溶液中，再添加盐酸多巴胺，搅拌15-20h后，经后处理得到干燥的MIL-125@PDA圆盘；S2. Dispersing the MIL-125 disc-shaped metal-organic framework precursor in a buffer solution, then adding dopamine hydrochloride, stirring for 15-20 hours, and post-processing to obtain a dry MIL-125@PDA disc;
    S3、将所述MIL-125@PDA圆盘在惰性气体氛围下进行高温碳化处理，得到粉末即具有(001)晶面暴露的多孔TiO 2基纳米材料。 S3, subjecting the MIL-125@PDA disk to high-temperature carbonization treatment in an inert gas atmosphere to obtain a powder, that is, a porous TiO 2 -based nanomaterial with exposed (001) crystal planes.
  2. 根据权利要求1所述制备方法，其特征在于：所述钛酯溶液为选自钛酸四丁酯、钛酸四乙酯、钛酸四丙酯中的一种溶解在选自甲醇、乙酸、异丙醇、正丁醇、乙酰丙酮中的一种的溶剂中得到的溶液。According to the described preparation method of claim 1, it is characterized in that: the titanium ester solution is a kind of solution selected from tetrabutyl titanate, tetraethyl titanate, tetrapropyl titanate dissolved in methanol, acetic acid, A solution obtained in a solvent of isopropanol, n-butanol, and acetylacetone.
  3. 根据权利要求1所述制备方法，其特征在于：步骤S1中，所述溶剂为选自N，N二甲基甲酰胺、N-甲基吡咯烷酮、二甲基乙酰胺、1,3-二甲基-2-咪唑啉酮、二甲基亚砜中的一种或多种。The preparation method according to claim 1, characterized in that: in step S1, the solvent is selected from N,N dimethylformamide, N-methylpyrrolidone, dimethylacetamide, 1,3-dimethyl One or more of base-2-imidazolinone, dimethyl sulfoxide.
  4. 根据权利要求1所述制备方法，其特征在于：步骤S1中，所述对苯二甲酸、所述钛酯溶液和所述4-二甲基氨基吡啶的投料摩尔比为(13-15)：(160-180)：1。The preparation method according to claim 1, characterized in that: in step S1, the molar ratio of the terephthalic acid, the titanium ester solution and the 4-dimethylaminopyridine is (13-15): (160-180):1.
  5. 根据权利要求1所述制备方法，其特征在于：步骤S2中，所述缓冲溶液为选自Tris缓冲液、Tris-HCl缓冲液、Tris-磷酸盐缓冲液中的至少一种，所述缓冲溶液的浓度为5-20mM。The preparation method according to claim 1, characterized in that: in step S2, the buffer solution is at least one selected from Tris buffer, Tris-HCl buffer, and Tris-phosphate buffer, and the buffer solution The concentration is 5-20mM.
  6. 根据权利要求1所述制备方法，其特征在于：步骤S2中，所述MIL-125圆饼状金属有机骨架前驱体与所述盐酸多巴胺的投料摩尔比为(3-6):1。The preparation method according to claim 1, characterized in that: in step S2, the molar ratio of the MIL-125 disc-shaped metal-organic framework precursor to the dopamine hydrochloride is (3-6):1.
  7. 根据权利要求1所述制备方法，其特征在于：步骤S3中，所述惰性气 体的气体流通速率为50～150mL min -1，所述高温碳化处理的温度为350-420℃，保温时间为4-6h； The preparation method according to claim 1, characterized in that: in step S3, the gas flow rate of the inert gas is 50-150mL min -1 , the temperature of the high-temperature carbonization treatment is 350-420°C, and the holding time is 4 -6h;
    优选地，所述惰性气体为选自氩气、氮气、氩氢混合气中的一种。Preferably, the inert gas is one selected from argon, nitrogen, and argon-hydrogen mixed gas.
  8. 根据权利要求1所述制备方法，其特征在于：步骤S1和步骤S2中，所述后处理各自独立地为将反应后得到的溶液用无水甲醇为溶剂离心，收集沉淀，并在60-90℃下烘干6-10h。The preparation method according to claim 1, characterized in that: in step S1 and step S2, the post-treatments are independently centrifuging the solution obtained after the reaction with anhydrous methanol as a solvent, collecting the precipitate, and Dry at ℃ for 6-10h.
  9. 一种多孔TiO 2基纳米材料，其特征在于：采用如权利要求1-8任一所述制备方法得到。 A porous TiO2 - based nanomaterial, characterized in that it is obtained by the preparation method as described in any one of claims 1-8.
  10. 一种钠离子电池，其特征在于，包括负极材料，所述负极材料包括如权利要求1-8任一所述制备方法得到的多孔TiO 2基纳米材料和如权利要求9所述多孔TiO 2基纳米材料。 A kind of sodium ion battery, it is characterized in that, comprises negative pole material, and described negative pole material comprises porous TiO as described in any one of claim 8 2 based nanomaterials and as claimed in claim 9 porous TiO 2 based nanomaterials nanomaterials.
PCT/CN2022/097270 2022-05-07 2022-06-07 Preparation method for porous tio2-based nanomaterial, and porous tio2-based nanomaterial and sodium-ion battery WO2023165041A1 (en)

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