WO2023165041A1 - Procédé de préparation de nanomatériau à base de tio2 poreux, nanomatériau à base de tio2 poreux et batterie au sodium-ion - Google Patents

Procédé de préparation de nanomatériau à base de tio2 poreux, nanomatériau à base de tio2 poreux et batterie au sodium-ion 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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preparation
mil
solution
porous
sodium
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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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    • 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
    • H01M4/04—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
    • 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
    • H01M4/48—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
    • H01M4/02—Electrodes composed of, or comprising, active material
    • 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

L'invention concerne un procédé de préparation d'un nanomatériau à base de TiO2 poreux, et un nanomatériau à base de TiO2 poreux et une batterie sodium-ion. Le procédé de préparation comprend les étapes suivantes consistant à : S1, ajouter de l'acide téréphtalique, une solution d'ester de titane et de la 4-diméthylaminopyridine à un solvant, les disperser pour obtenir une solution mixte, puis l'ajouter à une solution aqueuse d'acide fluorhydrique, l'agiter, maintenir la température à 140-160 °C et la faire réagir, puis la soumettre à un post-traitement pour obtenir un précurseur de structure organométallique MIL -125 ; S2, disperser le précurseur de structure organométallique MIL -125 dans une solution tampon, puis ajouter du chlorhydrate de dopamine, et l'agiter pour obtenir ensuite MIL-125@PDA ; et S3, soumettre le MIL-125 @ PDA à un traitement de carbonisation à haute température en présence d'un gaz inerte, de façon à obtenir un nanomatériau à base de TiO2 poreux ayant un plan cristallin exposé (001). Lorsque le nanomatériau à base de TiO2 poreux est utilisé en tant que matériau d'électrode négative d'une batterie au sodium-ion, la barrière de potentiel pendant la désintercalation de Na+ est réduite ; la structure de pore accélère la diffusion de Na+ ; et de multiples plans cristallins hautement exposés (001) peuvent fournir une activité de réaction plus élevée et accélérer la cinétique de réaction.
PCT/CN2022/097270 2022-05-07 2022-06-07 Procédé de préparation de nanomatériau à base de tio2 poreux, nanomatériau à base de tio2 poreux et batterie au sodium-ion WO2023165041A1 (fr)

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CN112582609A (zh) * 2020-12-14 2021-03-30 浙江倪阮新材料有限公司 一种钠离子电池负极材料的制备方法
CN112919533A (zh) * 2021-01-14 2021-06-08 华南理工大学 一种氮掺杂碳包覆的磷掺杂二氧化钛材料及其制备方法与应用
CN114204028A (zh) * 2021-11-26 2022-03-18 南通金通储能动力新材料有限公司 一种聚多巴胺包覆的钠离子电池正极材料的制备方法

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