WO2023165040A1 - Titanium dioxide-coated cose2-based nanomaterial, preparation method therefor, and application thereof - Google Patents

Titanium dioxide-coated cose2-based nanomaterial, preparation method therefor, and application thereof Download PDF

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WO2023165040A1
WO2023165040A1 PCT/CN2022/097262 CN2022097262W WO2023165040A1 WO 2023165040 A1 WO2023165040 A1 WO 2023165040A1 CN 2022097262 W CN2022097262 W CN 2022097262W WO 2023165040 A1 WO2023165040 A1 WO 2023165040A1
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cose2
pba
preparation
titanium dioxide
coated
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French (fr)
Chinese (zh)
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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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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • 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
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    • 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
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
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    • H01M4/00—Electrodes
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    • 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
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    • 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
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    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
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    • 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
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention relates to a method for preparing a nanometer material, in particular to a method for preparing a titanium dioxide-coated CoSe2 - based nanometer material, and belongs to the technical field of sodium ion materials.
  • Sodium-ion batteries have similar structural features and electrochemical principles to lithium-ion batteries (LIBs), and have attracted extensive attention from researchers due to the abundance and low cost of sodium raw materials.
  • LIBs lithium-ion batteries
  • Lithium-ion batteries are mainly made of graphite anodes. These materials have good lithium intercalation properties, but for sodium-ion batteries, the sodium intercalation efficiency is low, and the specific capacity is only 31mAh g -1 . Therefore, scientists have focused on developing anode materials with high specific capacity for Na-ion batteries.
  • CoSe 2 has been favored by many research groups at home and abroad because of its advantages such as abundant reserves, environmental friendliness, small band gap, easy control of morphology, and high theoretical specific capacity.
  • its practical application is limited by the disadvantages of poor conductivity, slow reaction kinetics, obvious volume effect and unstable electrode-electrolyte interface. Even at low rates, the charge-discharge specific capacity may still decay rapidly, so that the battery fail.
  • Prussian blue analogue is a nitrogen-rich carbon-based material that can form a conductive network after heat treatment, which can significantly improve the electrical conductivity of the material, thereby effectively improving the electrochemical performance of the composite material.
  • TiO2 is a promising anode material with many properties worthy of investigation: low cost, good structural robustness, and negligible volume change due to its layered crystal structure. Compared with traditional conductive coatings, it also has redox activity, which can further enhance the stability of structure and interface without losing capacity.
  • TiO2 As a coating to alleviate the volume change of TMDs and provide a reasonable channel for charge transfer.
  • the purpose of the present invention is to provide a method for preparing titanium dioxide-coated CoSe 2 -based nanomaterials (TNC-CoSe 2 ) based on Prussian blue analogue templates for optimizing the performance of CoSe 2 -based materials in sodium-ion batteries.
  • the present invention at first provides a kind of CoSe2 preparation method of titanium dioxide coating base nano material, and this preparation method comprises the following steps:
  • Co-Co PBA@TiO 2 and selenium powder were uniformly ground, and high-temperature selenization and carbonization were carried out under the protection of inert gas to obtain CoSe 2- based nanomaterials coated with titanium dioxide (the prepared black powder was the one with TiO 2 coating on the outside.
  • Protected nitrogen-doped carbon CoSe 2 composite (TNC-CoSe 2 )), wherein the mixing mass ratio of Co-Co PBA@TiO 2 and selenium powder is 1:3-6.
  • the present invention uses the Prussian blue analogue (Co 3 [Co(CN) 6 ] 2 , Co-Co PBA) as a precursor, coats a layer of TiO 2 coating by sol-gel method, and then synthesizes the outer layer with Nitrogen-doped carbon CoSe 2 composite (TNC-CoSe 2 ) protected by TiO 2 coating, which retains the original cubic morphology, and the nitrogen-doped carbon skeleton can facilitate interfacial electron transport, thereby facilitating the reaction kinetics Secondly, due to its superior structural stability, the TiO 2 protective layer can effectively alleviate the volume expansion of CoSe 2 during cycling, and can also prevent it from falling off and pulverizing; finally, this heterostructure promotes the pseudocapacitive charge storage , resulting in excellent cycling stability at ultrahigh magnifications.
  • Prussian blue analogue Co 3 [Co(CN) 6 ] 2 , Co-Co PBA
  • the titanium ester used is one selected from tetrabutyl titanate, tetraethyl titanate, and tetrapropyl titanate.
  • the organic solution is selected from one of acetic acid, isopropanol, n-butanol, and acetylacetone.
  • the amount of titanium ester added in every 60-100 mL of organic solution is 100 ⁇ L-300 ⁇ L.
  • the concentration of the concentrated ammonia solution is 20-28wt%.
  • the inert gas is selected from one of argon, nitrogen, and argon-hydrogen mixed gas; wherein, the volume ratio of argon to hydrogen in the argon-hydrogen mixed gas is 95%:5%.
  • the flow rate of the inert gas is 50-150 mL min -1 .
  • the temperature of high-temperature selenization and carbonization is 300°C-450°C, and the holding time is 3-6h.
  • the present invention also provides a titanium dioxide-coated CoSe 2 -based nanometer material, which is prepared by the preparation method of the titanium dioxide-coated CoSe 2 -based nanometer material of the present invention.
  • the CoSe2 - based nanomaterial coated with titanium dioxide is used for the negative electrode material of a sodium-ion battery.
  • TNC-CoSe 2 particles are coated on a copper foil to make a negative electrode of a sodium-ion battery.
  • TNC-CoSe 2 particles, conductive agent (superconducting carbon (Super P)) and binder (sodium carboxymethylcellulose (CMC)) were dispersed in water solvent at a mass ratio of 8:1:1, and then uniformly Coated on copper foil and dried to make a circular electrode sheet with a diameter of 12mm.
  • the electrochemical performance test of the CoSe2- based negative electrode material adopts a sodium ion battery system composed of two electrodes. Among them, CoSe2- based materials are used as the working electrode, and high-purity sodium flakes are used as the counter electrode.
  • a 2032-type button cell was assembled in a glove box (H2O ⁇ 0.01ppm, O2 ⁇ 0.01ppm) filled with high-purity argon (99.999%).
  • the preparation method of the titanium dioxide-coated CoSe2 - based nanomaterial of the present invention is based on a self-sacrificing template method using a Prussian blue analogue as a precursor, and the titanium dioxide-coated CoSe2 - based nanomaterial can be synthesized.
  • Co-Co PBA microcubes were prepared by co-precipitation method, Co-Co PBA@TiO 2 was prepared by sol-gel method, and the composite material was finally synthesized by solid-phase method. It is carried out in a container with little pollution.
  • the advantage when used for the negative electrode material of sodium-ion battery, the advantage has: this product has kept the characteristic cube shape of Prussian blue analogue, small-sized CoSe2 microcube and nitrogen
  • the doped carbon skeleton can promote interfacial electron transport, resulting in fast reaction kinetics; while the outer coated TiO2 coating can be used as a buffer layer to adapt to the volume effect of CoSe2 ; in addition, the material also has a large specific surface area , so that the contact resistance between the electrode material and the electrolyte is small, thereby improving the cycle performance and rate performance of the battery.
  • Fig. 1 is the CoSe2 - based nanomaterial (TNC- CoSe2-200 ) SEM figure of the titanium dioxide coating that makes in embodiment 2;
  • Fig. 2 is the CoSe2 - based nanomaterial (TNC- CoSe2-200 ) TEM figure of the titanium dioxide coating that makes in embodiment 2;
  • Fig. 3 is the CoSe 2- based nanomaterial (NC-CoSe 2 -200) and the CoSe 2- based nanomaterial (TNC-CoSe 2 -200) coated with titanium dioxide that are not prepared in Experimental Example 1 and Example 2 BET chart;
  • Fig. 4 is the CoSe 2- based nanomaterial (NC-CoSe 2 -200) and the CoSe 2- based nanomaterial (TNC-CoSe 2 -200) coated with titanium dioxide that are not prepared in Experimental Example 1 and Example 2 Charge-discharge cycle performance graph;
  • Fig. 5 is the CoSe2 - based nanomaterial (NC- CoSe2-200 ) and the CoSe2 - based nanomaterial (TNC- CoSe2-200 ) coated with titanium dioxide that are not prepared in Experimental Example 1 and Example 2 SEM image.
  • the present invention is based on the preparation method of CoSe2 - based nanomaterials coated with titanium dioxide based on the Prussian blue analogue template, which also includes the following steps:
  • step (b) Uniformly ultrasonically disperse the Co-Co PBA microcubes synthesized in step (a) in a mixed solution of absolute ethanol and concentrated ammonia solution (28 wt%), and then use a pipette gun at a rate of 1 mL min The organic solution of titanium ester was added dropwise into the mixed solution. After heating in an oil bath for 5 hours, it was left to stand at room temperature for 24 hours. After the reaction, the product was washed with a solvent and collected by centrifugation to obtain the Co-Co PBA@TiO 2 product.
  • step (c) First, the Co-Co PBA@ TiO2 and selenium powder synthesized in step (b) were uniformly ground and dispersed in a ceramic boat. Subsequently, the mixture is subjected to high-temperature heat treatment under the protection of an inert gas.
  • the prepared black powder is a nitrogen-doped carbon CoSe 2 composite material (TNC-CoSe 2 ) with a TiO 2 coating on the outside.
  • TNC-CoSe 2 particles TNC-CoSe 2 particles, conductive agent (Superconducting carbon (Super P)) and binder (sodium carboxymethyl cellulose (CMC)) were dispersed in water solvent according to the mass ratio of 8:1:1, and then uniformly coated on copper foil, dried and prepared Form a circular electrode sheet with a diameter of 12mm, and use it as a working electrode, and a high-purity sodium sheet as a counter electrode, in a glove box (H 2 O ⁇ 0.01ppm, O 2 ⁇ 0.01ppm) assembled into a 2032-type button cell.
  • conductive agent Superconducting carbon (Super P)
  • binder sodium carboxymethyl cellulose (CMC)
  • the present embodiment provides a kind of preparation method of TNC- CoSe2-100 composite electrode material, and it comprises the following steps:
  • step (b) Uniformly ultrasonically disperse 0.2 g of the Co-Co PBA synthesized in step (a) in a mixed solution of 60 mL of absolute ethanol and 0.15 mL of concentrated ammonia solution (28 wt%), and after ultrasonically dispersing for 30 minutes, dissolve in 1 mL min - Add 100 ⁇ L tetrabutyl titanate (TBOT) dropwise to the mixed solution at a rate of 1 . After heating in an oil bath at 80°C for 5h, stand at 25°C for 24h. Centrifuge four times using absolute ethanol as a solvent, and dry in an oven at 70°C for 8 hours.
  • TBOT tetrabutyl titanate
  • step (c) 0.2 g of Co-Co PBA@ TiO2 synthesized in step (b) and 0.8 g of selenium powder were uniformly ground and dispersed in a ceramic boat. Subsequently, the mixture was heated and kept at 350° C. for 4 hours in an Ar/H 2 (volume ratio of 95:5) atmosphere.
  • the prepared black powder is TNC-CoSe 2 .
  • Assemble 2032 button cells in a glove box H 2 O ⁇ 0.01ppm, O 2 ⁇ 0.01ppm).
  • the present embodiment provides a kind of preparation method of TNC- CoSe2-200 composite electrode material, and it comprises the following steps:
  • step (b) Uniformly ultrasonically disperse 0.2 g of the Co-Co PBA synthesized in step (a) in a mixed solution of 60 mL of absolute ethanol and 0.15 mL of concentrated ammonia solution (28 wt%), and after ultrasonically dispersing for 30 minutes, dissolve in 1 mL min - Add 200 ⁇ L tetrabutyl titanate (TBOT) dropwise to the mixed solution at a rate of 1 . After heating in an oil bath at 80°C for 5h, stand at 25°C for 24h. Centrifuge four times using absolute ethanol as a solvent, and dry in an oven at 70°C for 8 hours.
  • TBOT tetrabutyl titanate
  • step (c) 0.2 g of Co-Co PBA@ TiO2 synthesized in step (b) and 0.8 g of selenium powder were uniformly ground and dispersed in a ceramic boat. Subsequently, the mixture was heated and kept at 350° C. for 4 hours in an Ar/H 2 (volume ratio of 95:5) atmosphere.
  • the prepared black powder is TNC-CoSe 2 .
  • Assemble 2032 button cells in a glove box H 2 O ⁇ 0.01ppm, O 2 ⁇ 0.01ppm).
  • the present embodiment provides a kind of preparation method of TNC-CoSe 2 -300 composite electrode material, and it comprises the following steps:
  • step (b) Uniformly ultrasonically disperse 0.2 g of the Co-Co PBA synthesized in step (a) in a mixed solution of 60 mL of absolute ethanol and 0.15 mL of concentrated ammonia solution (28 wt%), and after ultrasonically dispersing for 30 minutes, dissolve in 1 mL min - Add 300 ⁇ L tetrabutyl titanate (TBOT) dropwise to the mixed solution at a rate of 1 . After heating in an oil bath at 80°C for 5h, stand at 25°C for 24h. Centrifuge four times using absolute ethanol as a solvent, and dry in an oven at 70°C for 8 hours.
  • TBOT tetrabutyl titanate
  • step (c) 0.2 g of Co-Co PBA@ TiO2 synthesized in step (b) and 0.8 g of selenium powder were uniformly ground and dispersed in a ceramic boat. Subsequently, the mixture was heated and kept at 350° C. for 4 hours in an Ar/H 2 (volume ratio of 95:5) atmosphere.
  • the prepared black powder is TNC-CoSe 2 .
  • Assemble 2032 button cells in a glove box H 2 O ⁇ 0.01ppm, O 2 ⁇ 0.01ppm).
  • This embodiment provides a method for preparing a TNC-CoSe 2 -300°C composite electrode material, which includes the following steps:
  • step (b) Uniformly ultrasonically disperse 0.2 g of the Co-Co PBA synthesized in step (a) in a mixed solution of 60 mL of absolute ethanol and 0.15 mL of concentrated ammonia solution (28 wt%), and after ultrasonically dispersing for 30 minutes, dissolve in 1 mL min - Add 200 ⁇ L tetrabutyl titanate (TBOT) dropwise to the mixed solution at a rate of 1 . After heating in an oil bath at 80°C for 5h, stand at 25°C for 24h. Centrifuge four times using absolute ethanol as a solvent, and dry in an oven at 70°C for 8 hours.
  • TBOT tetrabutyl titanate
  • step (c) 0.2 g of Co-Co PBA@ TiO2 synthesized in step (b) and 0.8 g of selenium powder were uniformly ground and dispersed in a ceramic boat. Subsequently, the mixture was heated and kept at 300° C. for 4 hours in an Ar/H 2 (volume ratio of 95:5) atmosphere.
  • the prepared black powder is TNC-CoSe 2 .
  • a 2032-type button cell was assembled in a glove box (H 2 O ⁇ 0.01ppm, O 2 ⁇ 0.01ppm).
  • This embodiment provides a method for preparing a TNC-CoSe 2 -400°C composite electrode material, which includes the following steps:
  • step (b) Uniformly ultrasonically disperse 0.2 g of the Co-Co PBA synthesized in step (a) in a mixed solution of 60 mL of absolute ethanol and 0.15 mL of concentrated ammonia solution (28 wt%), and after ultrasonically dispersing for 30 minutes, dissolve in 1 mL min - Add 200 ⁇ L tetrabutyl titanate (TBOT) dropwise to the mixed solution at a rate of 1 . After heating in an oil bath at 80°C for 5h, stand at 25°C for 24h. Centrifuge four times using absolute ethanol as a solvent, and dry in an oven at 70°C for 8 hours.
  • TBOT tetrabutyl titanate
  • step (c) 0.2 g of Co-Co PBA@ TiO2 synthesized in step (b) and 0.8 g of selenium powder were uniformly ground and dispersed in a ceramic boat. Subsequently, the mixture was heated and kept at 400° C. for 4 hours in an Ar/H 2 (volume ratio of 95:5) atmosphere.
  • the prepared black powder is TNC-CoSe 2 .
  • TNC-CoSe 2 -400°C particles Disperse TNC-CoSe 2 -400°C particles, conductive agent (superconducting carbon (Super P)) and binder (sodium carboxymethylcellulose (CMC)) in water solvent at a mass ratio of 8:1:1 , and then uniformly coated on the copper foil, dried to make a circular electrode sheet with a diameter of 12mm, and use it as a working electrode, and a high-purity sodium sheet as a counter electrode.
  • a 2032-type button cell was assembled in a glove box (H 2 O ⁇ 0.01ppm, O 2 ⁇ 0.01ppm).
  • This embodiment provides a method for preparing a TNC-CoSe 2 -450°C composite electrode material, which includes the following steps:
  • step (b) Uniformly ultrasonically disperse 0.2 g of the Co-Co PBA synthesized in step (a) in a mixed solution of 60 mL of absolute ethanol and 0.15 mL of concentrated ammonia solution (28 wt%), and after ultrasonically dispersing for 30 minutes, dissolve in 1 mL min - Add 200 ⁇ L tetrabutyl titanate (TBOT) dropwise to the mixed solution at a rate of 1 . After heating in an oil bath at 80°C for 5h, stand at 25°C for 24h. Centrifuge four times using absolute ethanol as a solvent, and dry in an oven at 70°C for 8 hours.
  • TBOT tetrabutyl titanate
  • step (c) 0.2 g of Co-Co PBA@ TiO2 synthesized in step (b) and 0.8 g of selenium powder were uniformly ground and dispersed in a ceramic boat. Subsequently, the mixture was heated and kept at 450° C. for 4 hours in an Ar/H 2 (volume ratio of 95:5) atmosphere.
  • the prepared black powder is TNC-CoSe 2 .
  • TNC-CoSe 2 -450°C particles Disperse TNC-CoSe 2 -450°C particles, conductive agent (superconducting carbon (Super P)) and binder (sodium carboxymethylcellulose (CMC)) in water solvent at a mass ratio of 8:1:1 , and then uniformly coated on the copper foil, dried to make a circular electrode sheet with a diameter of 12mm, and use it as a working electrode, and a high-purity sodium sheet as a counter electrode.
  • a 2032-type button cell was assembled in a glove box (H 2 O ⁇ 0.01ppm, O 2 ⁇ 0.01ppm).
  • step (b) 0.2 g of Co-Co PBA synthesized in step (a) and 0.8 g of selenium powder were uniformly ground and dispersed in a ceramic boat. Subsequently, the mixture was heated and kept at 350° C. for 4 hours in an Ar/H 2 (volume ratio of 95:5) atmosphere.
  • the prepared black powder is NC-CoSe 2 .
  • NC-CoSe 2 particles, conductive agent (superconducting carbon (Super P)) and binder (sodium carboxymethylcellulose (CMC)) were dispersed in water solvent at a mass ratio of 8:1:1, and then uniformly Coated on copper foil, after drying, make a circular electrode sheet with a diameter of 12mm, and use it as a working electrode, and a high-purity sodium sheet as a counter electrode. (H 2 O ⁇ 0.01ppm, O 2 ⁇ 0.01ppm) assembled into a 2032-type button battery.

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Abstract

A titanium dioxide-coated CoSe2-based nanomaterial, a preparation method therefor, and an application thereof. The preparation method comprises: preparing nanoscale Co-Co PBA microcubes; ultrasonically dispersing the Co-Co PBA microcubes in a mixed solution of absolute ethyl alcohol and a concentrated ammonia solution, and performing dropwise addition of an organic solution of a titanium ester into the mixed solution at a rate of 0.5-1 mL/min; heating for 5-8 hours at a temperature of 70-100 °C in an oil bath, allowing to sit at room temperature for 20-24 hours, cleaning the product with a solvent after the completion of a reaction, and carrying out centrifugal collection to obtain Co-Co PBA@TiO2; uniformly grinding the Co-Co PBA@TiO2 and a selenium powder, and carrying out high-temperature selenization and carbonization under the protection of inert gas to obtain the titanium dioxide-coated CoSe2-based nanomaterial TNC-CoSe2. The titanium dioxide-coated CoSe2-based nanomaterial is used as a negative electrode material of a sodium-ion battery and has both an ultrahigh rate and cycling stability.

Description

一种二氧化钛包覆的CoSe 2基纳米材料及其制备方法和应用 A TiO-coated CoSe 2-based nanomaterials and their preparation methods and applications 技术领域technical field
本发明涉及一种纳米材料的制备方法，尤其涉及一种二氧化钛包覆的CoSe 2基纳米材料的制备方法，属于钠离子材料技术领域。 The invention relates to a method for preparing a nanometer material, in particular to a method for preparing a titanium dioxide-coated CoSe2 - based nanometer material, and belongs to the technical field of sodium ion materials.
背景技术Background technique
钠离子电池(SIBs)具有与锂离子电池(LIBs)相似的结构特征和电化学原理，由于钠原材料丰富且成本低廉，因此引起了研究者们广泛的关注。然而，Na+的半径较大且扩散动力学缓慢，限制了钠离子电池的实际应用。锂离子电池以石墨负极为主，这些材料具有良好的嵌锂特性，但是对于钠离子电池来说，其嵌钠效率较低，比容量仅有31mAh g -1。因此，科学家们致力于为钠离子电池开发具有高比容量的负极材料。其中，CoSe 2因为储量丰富、环境友好、带隙小、形态易于调控且理论比容量高等优点，进而受到了国内外很多课题组的青睐。但是，其实际应用却受制于导电性差、反应动力学缓慢和体积效应明显和不稳定的电极-电解质界面等缺点，即使在低倍率下，充放电比容量仍然可能会快速衰减，以至于使得电池失效。 Sodium-ion batteries (SIBs) have similar structural features and electrochemical principles to lithium-ion batteries (LIBs), and have attracted extensive attention from researchers due to the abundance and low cost of sodium raw materials. However, the large radius and slow diffusion kinetics of Na+ limit the practical application of Na-ion batteries. Lithium-ion batteries are mainly made of graphite anodes. These materials have good lithium intercalation properties, but for sodium-ion batteries, the sodium intercalation efficiency is low, and the specific capacity is only 31mAh g -1 . Therefore, scientists have focused on developing anode materials with high specific capacity for Na-ion batteries. Among them, CoSe 2 has been favored by many research groups at home and abroad because of its advantages such as abundant reserves, environmental friendliness, small band gap, easy control of morphology, and high theoretical specific capacity. However, its practical application is limited by the disadvantages of poor conductivity, slow reaction kinetics, obvious volume effect and unstable electrode-electrolyte interface. Even at low rates, the charge-discharge specific capacity may still decay rapidly, so that the battery fail.
目前据报道，通过合理构建纳米结构，不仅可以改善电极材料的反应动力学，还可以缓解大体积膨胀带来的材料粉碎。此外，与导电基体复合也是研究者们常用的改性方法。其中，掺杂了杂原子的碳层表现出优异的导电性。特别是氮掺杂碳层可以有效地产生缺陷并提高材料的导电性，从而提高复合电极材料的储钠性能。普鲁士蓝类似物(PBA)是一种富氮碳基材料，经热处理后可构成导电网络，可明显改善材料的电导率，从而可以有效改善复合材料的电化学性能。另一方面，众所周知，TiO 2是一种很有前途的负极材料，具有很多值得研究的特性：成本低廉、结构坚固性好以及由于其层状晶体结构而导致的体积变化可忽略不计。与传统的导电涂料相比，它还有氧化还原活性，可以在不损失容量的前提下，进一步增强了结构和界面的稳定性。 It has been reported that the rational construction of nanostructures can not only improve the reaction kinetics of electrode materials, but also alleviate the material crushing caused by large volume expansion. In addition, compounding with a conductive matrix is also a commonly used modification method for researchers. Among them, the carbon layer doped with heteroatoms exhibits excellent electrical conductivity. In particular, the nitrogen-doped carbon layer can effectively generate defects and improve the conductivity of the material, thereby improving the sodium storage performance of the composite electrode material. Prussian blue analogue (PBA) is a nitrogen-rich carbon-based material that can form a conductive network after heat treatment, which can significantly improve the electrical conductivity of the material, thereby effectively improving the electrochemical performance of the composite material. On the other hand, it is well known that TiO2 is a promising anode material with many properties worthy of investigation: low cost, good structural robustness, and negligible volume change due to its layered crystal structure. Compared with traditional conductive coatings, it also has redox activity, which can further enhance the stability of structure and interface without losing capacity.
因此，有必要利用TiO 2作为涂层来缓解TMDs的体积变化，并为电荷转移提供合理通道。 Therefore, it is necessary to utilize TiO2 as a coating to alleviate the volume change of TMDs and provide a reasonable channel for charge transfer.
发明内容Contents of the invention
本发明的目的在于提供一种优化CoSe 2基材料在钠离子电池中的性能而提供的一种基于普鲁士蓝类似物模板制备二氧化钛包覆的CoSe 2基纳米材料(TNC-CoSe 2)的方法。 The purpose of the present invention is to provide a method for preparing titanium dioxide-coated CoSe 2 -based nanomaterials (TNC-CoSe 2 ) based on Prussian blue analogue templates for optimizing the performance of CoSe 2 -based materials in sodium-ion batteries.
为了实现上述技术目的，本发明首先提供了一种二氧化钛包覆的CoSe 2基纳米材料的制备方法，该制备方法包括以下步骤： In order to achieve the above-mentioned technical purpose, the present invention at first provides a kind of CoSe2 preparation method of titanium dioxide coating base nano material, and this preparation method comprises the following steps:
制备纳米尺寸的Co-Co PBA微立方体；将乙酸钴、六氰基羧酸钾和十二烷基硫酸钠加入到水中，超声分散均匀，经过1-3h的剧烈磁力搅拌，25℃静置20-24h，用无水乙醇为溶剂离心收集沉淀，60-80℃下干燥8-12小时，制备出纳米尺寸的Co-Co PBA微立方体；其中，乙酸钴、六氰基羧酸钾和十二烷基硫酸钠的混合比为1：(1-2)：(90-120)；Prepare nano-sized Co-Co PBA microcubes; add cobalt acetate, potassium hexacyanocarboxylate and sodium lauryl sulfate into water, disperse evenly by ultrasonic, and after 1-3h of vigorous magnetic stirring, stand at 25°C for 20 -24h, use ethanol as a solvent to collect the precipitate by centrifugation, dry at 60-80°C for 8-12 hours, and prepare nano-sized Co-Co PBA microcubes; wherein, cobalt acetate, potassium hexacyanocarboxylate and dodeca The mixing ratio of sodium alkyl sulfate is 1: (1-2): (90-120);
将Co-Co PBA微立方体超声分散在无水乙醇与浓氨溶液的混合溶液中，以0.5-1mL min -1的速率向混合溶液中滴加钛酯的有机溶液，油浴70℃-100℃加热5-8h，室温下静置20-24h，反应结束后用溶剂清洗产品并离心收集，得到Co-Co PBA@TiO 2；；其中，Co-Co PBA微立方体与无水乙醇为(0.1-0.3)g：(60-100)mL； Ultrasonic disperse the Co-Co PBA microcubes in the mixed solution of absolute ethanol and concentrated ammonia solution, add the organic solution of titanium ester dropwise to the mixed solution at a rate of 0.5-1mL min -1 , and oil bath at 70°C-100°C Heating for 5-8h, standing at room temperature for 20-24h, washing the product with a solvent after the reaction and collecting it by centrifugation to obtain Co-Co PBA@TiO 2 ; wherein, Co-Co PBA microcubes and absolute ethanol are (0.1- 0.3) g: (60-100) mL;
将Co-Co PBA@TiO 2和硒粉均匀研磨，在惰性气体保护下进行高温硒化和碳化，得到二氧化钛包覆的CoSe 2基纳米材料(所制备的黑色粉末即是外部具有TiO 2涂层保护的氮掺杂碳的CoSe 2复合材料(TNC-CoSe 2))，其中，Co-Co PBA@TiO 2和硒粉的混合质量比为1：3-6。 Co-Co PBA@TiO 2 and selenium powder were uniformly ground, and high-temperature selenization and carbonization were carried out under the protection of inert gas to obtain CoSe 2- based nanomaterials coated with titanium dioxide (the prepared black powder was the one with TiO 2 coating on the outside. Protected nitrogen-doped carbon CoSe 2 composite (TNC-CoSe 2 )), wherein the mixing mass ratio of Co-Co PBA@TiO 2 and selenium powder is 1:3-6.
本发明以普鲁士蓝类似物(Co 3[Co(CN) 6] 2，Co-Co PBA)为前驱体，通过溶胶凝胶法包覆一层TiO 2涂层，再通过高温热处理合成了外部具有TiO 2涂层保护的氮掺杂碳的CoSe 2复合材料(TNC-CoSe 2)，该材料保留了原有的立方体形貌，氮掺杂的碳骨架可以促进界面电子传输，从而促进反应动力学的提升；其次，TiO 2保护层由于其优越的结构稳定性，有效缓解了CoSe 2在循环过程的体积膨胀，也可以防止其脱落粉化；最后，这种异质结构促进了赝电容电荷存储，从而产生了超高倍率下出色的循环稳定性能。 The present invention uses the Prussian blue analogue (Co 3 [Co(CN) 6 ] 2 , Co-Co PBA) as a precursor, coats a layer of TiO 2 coating by sol-gel method, and then synthesizes the outer layer with Nitrogen-doped carbon CoSe 2 composite (TNC-CoSe 2 ) protected by TiO 2 coating, which retains the original cubic morphology, and the nitrogen-doped carbon skeleton can facilitate interfacial electron transport, thereby facilitating the reaction kinetics Secondly, due to its superior structural stability, the TiO 2 protective layer can effectively alleviate the volume expansion of CoSe 2 during cycling, and can also prevent it from falling off and pulverizing; finally, this heterostructure promotes the pseudocapacitive charge storage , resulting in excellent cycling stability at ultrahigh magnifications.
在本发明的一具体实施方式中，采用的钛酯选自钛酸四丁酯、钛酸四乙酯、钛酸四丙酯中的一种。In a specific embodiment of the present invention, the titanium ester used is one selected from tetrabutyl titanate, tetraethyl titanate, and tetrapropyl titanate.
在本发明的一具体实施方式中，有机溶液选自乙酸、异丙醇、正丁醇、乙酰丙酮中的一种。In a specific embodiment of the present invention, the organic solution is selected from one of acetic acid, isopropanol, n-butanol, and acetylacetone.
在本发明的一具体实施方式中，钛酯的有机溶液中，每60-100mL有机溶液中钛酯的添加量为100μL-300μL。In a specific embodiment of the present invention, in the organic solution of titanium ester, the amount of titanium ester added in every 60-100 mL of organic solution is 100 μL-300 μL.
在本发明的一具体实施方式中，无水乙醇与浓氨溶液的混合溶液中，浓氨溶液的浓度为20-28wt％。In a specific embodiment of the present invention, in the mixed solution of absolute ethanol and concentrated ammonia solution, the concentration of the concentrated ammonia solution is 20-28wt%.
在本发明的一具体实施方式中，惰性气体选自氩气、氮气、氩氢混合气中的一种；其中，氩氢混合气中氩气与氢气的体积比为95％:5％。In a specific embodiment of the present invention, the inert gas is selected from one of argon, nitrogen, and argon-hydrogen mixed gas; wherein, the volume ratio of argon to hydrogen in the argon-hydrogen mixed gas is 95%:5%.
在本发明的一具体实施方式中，惰性气体的流通速率为50-150mL min -1。 In a specific embodiment of the present invention, the flow rate of the inert gas is 50-150 mL min -1 .
在本发明的一具体实施方式中，高温硒化和碳化的温度为300℃-450℃，保温时间为3-6h。In a specific embodiment of the present invention, the temperature of high-temperature selenization and carbonization is 300°C-450°C, and the holding time is 3-6h.
本发明还提供了一种二氧化钛包覆的CoSe 2基纳米材料，该二氧化钛包覆的CoSe 2基纳米材料时通过本发明的二氧化钛包覆的CoSe 2基纳米材料的制备方法制备得到的。 The present invention also provides a titanium dioxide-coated CoSe 2 -based nanometer material, which is prepared by the preparation method of the titanium dioxide-coated CoSe 2 -based nanometer material of the present invention.
本发明的上述二氧化钛包覆的CoSe 2基纳米材料的应用，该二氧化钛包覆的CoSe 2基纳米材料用于钠离子电池的负极材料。 The application of the above-mentioned CoSe2 - based nanomaterial coated with titanium dioxide in the present invention, the CoSe2 - based nanomaterial coated with titanium dioxide is used for the negative electrode material of a sodium-ion battery.
在本发明的一具体实施方式中，将TNC-CoSe 2颗粒涂覆在铜箔上制成钠离子电池的负极。将TNC-CoSe 2颗粒、导电剂(超导炭(Super P))和粘结剂(羧甲基纤维素钠(CMC))按照8:1:1的质量比分散在水溶剂里，随后均匀涂覆在铜箔上，干燥后制成直径为12mm的圆形电极片。 In a specific embodiment of the present invention, TNC-CoSe 2 particles are coated on a copper foil to make a negative electrode of a sodium-ion battery. TNC-CoSe 2 particles, conductive agent (superconducting carbon (Super P)) and binder (sodium carboxymethylcellulose (CMC)) were dispersed in water solvent at a mass ratio of 8:1:1, and then uniformly Coated on copper foil and dried to make a circular electrode sheet with a diameter of 12mm.
本发明中，CoSe 2基负极材料的电化学性能测试采用由双电极组成的钠离子电池系统。其中，CoSe 2基材料用作工作电极，高纯钠片用作对电极。在装有高纯氩气(99.999％)的手套箱(H2O<0.01ppm，O2<0.01ppm)中的组装成2032型纽扣电池。在纽扣电池中，使用玻璃纤维(Whatman，GF/D)作为隔膜，1M NaClO4溶解在碳酸乙烯酯(EC)/碳酸二甲酯(DMC)(1:1v/v)以及添加了5wt％的氟代碳酸乙烯酯(FEC)作为电解液。钠离子电池的充放电实验在新威电池测试系统上进行。 In the present invention, the electrochemical performance test of the CoSe2- based negative electrode material adopts a sodium ion battery system composed of two electrodes. Among them, CoSe2- based materials are used as the working electrode, and high-purity sodium flakes are used as the counter electrode. A 2032-type button cell was assembled in a glove box (H2O<0.01ppm, O2<0.01ppm) filled with high-purity argon (99.999%). In a button cell, glass fiber (Whatman, GF/D) was used as a separator, 1M NaClO4 was dissolved in ethylene carbonate (EC)/dimethyl carbonate (DMC) (1:1 v/v) and 5 wt% fluorine was added Ethylene carbonate (FEC) was used as the electrolyte. The charge and discharge experiments of sodium-ion batteries are carried out on Xinwei battery test system.
本发明的二氧化钛包覆的CoSe 2基纳米材料的制备方法，基于以普鲁士蓝类似物为前驱体的自牺牲模板法，可合成得到二氧化钛包覆的CoSe 2基纳米材料。通过共沉淀法制备Co-Co PBA微立方体，溶胶凝胶法制备Co-Co PBA@TiO 2，最终通过固相法合成复合材料，制备方法简单易操作，能耗相对较低，且在密闭的容器中进行，污染小。 The preparation method of the titanium dioxide-coated CoSe2 - based nanomaterial of the present invention is based on a self-sacrificing template method using a Prussian blue analogue as a precursor, and the titanium dioxide-coated CoSe2 - based nanomaterial can be synthesized. Co-Co PBA microcubes were prepared by co-precipitation method, Co-Co PBA@TiO 2 was prepared by sol-gel method, and the composite material was finally synthesized by solid-phase method. It is carried out in a container with little pollution.
利用本发明所提供的方法制备的TNC-CoSe 2，当用于钠离子电池负极材料时，优点有：该产物保留了普鲁士蓝类似物特有的立方体形貌，小尺寸的CoSe 2微立方体和氮掺杂的碳骨架可以促进界面电子传输，从而产生快速的反应动力学；而外部包覆的TiO 2涂层可以作为缓冲层适应CoSe 2的体积效应；另外，该材料还具有较大的比表面积，使得电极材料与电解液的接触电阻小，从而提高了电池的循环性能和倍率性能。 Utilize the TNC- CoSe2 prepared by the method provided by the present invention, when used for the negative electrode material of sodium-ion battery, the advantage has: this product has kept the characteristic cube shape of Prussian blue analogue, small-sized CoSe2 microcube and nitrogen The doped carbon skeleton can promote interfacial electron transport, resulting in fast reaction kinetics; while the outer coated TiO2 coating can be used as a buffer layer to adapt to the volume effect of CoSe2 ; in addition, the material also has a large specific surface area , so that the contact resistance between the electrode material and the electrolyte is small, thereby improving the cycle performance and rate performance of the battery.
附图说明Description of drawings
图1为实施例2中制得的二氧化钛包覆的CoSe 2基纳米材料(TNC-CoSe 2-200)SEM图； Fig. 1 is the CoSe2 - based nanomaterial (TNC- CoSe2-200 ) SEM figure of the titanium dioxide coating that makes in embodiment 2;
图2为实施例2中制得的二氧化钛包覆的CoSe 2基纳米材料(TNC-CoSe 2-200)TEM图； Fig. 2 is the CoSe2 - based nanomaterial (TNC- CoSe2-200 ) TEM figure of the titanium dioxide coating that makes in embodiment 2;
图3为实验例1、实施例2中制得的没有二氧化钛包覆的CoSe 2基纳米材料(NC-CoSe 2-200)和二氧化钛包覆的CoSe 2基纳米材料(TNC-CoSe 2-200)BET图； Fig. 3 is the CoSe 2- based nanomaterial (NC-CoSe 2 -200) and the CoSe 2- based nanomaterial (TNC-CoSe 2 -200) coated with titanium dioxide that are not prepared in Experimental Example 1 and Example 2 BET chart;
图4为实验例1、实施例2中制得的没有二氧化钛包覆的CoSe 2基纳米材料(NC-CoSe 2-200)和二氧化钛包覆的CoSe 2基纳米材料(TNC-CoSe 2-200)充放电循环性能图； Fig. 4 is the CoSe 2- based nanomaterial (NC-CoSe 2 -200) and the CoSe 2- based nanomaterial (TNC-CoSe 2 -200) coated with titanium dioxide that are not prepared in Experimental Example 1 and Example 2 Charge-discharge cycle performance graph;
图5为实验例1、实施例2中制得的没有二氧化钛包覆的CoSe 2基纳米材料(NC-CoSe 2-200)和二氧化钛包覆的CoSe 2基纳米材料(TNC-CoSe 2-200)SEM图。 Fig. 5 is the CoSe2 - based nanomaterial (NC- CoSe2-200 ) and the CoSe2 - based nanomaterial (TNC- CoSe2-200 ) coated with titanium dioxide that are not prepared in Experimental Example 1 and Example 2 SEM image.
具体实施方式Detailed ways
本发明基于以普鲁士蓝类似物模板制备二氧化钛包覆的CoSe 2基纳米材料的制备方法，它还包括以下步骤： The present invention is based on the preparation method of CoSe2 - based nanomaterials coated with titanium dioxide based on the Prussian blue analogue template, which also includes the following steps:
(a)称取乙酸钴、六氰基羧酸钾和十二烷基硫酸钠加入到一定量的去离子水中，超声分散均匀，经过约1h的剧烈磁力搅拌，25℃静置24h。使用无水乙醇为溶剂离心收集沉淀，60℃下干燥12小时。(a) Weigh cobalt acetate, potassium hexacyanocarboxylate and sodium lauryl sulfate and add them into a certain amount of deionized water, disperse them evenly by ultrasonic, stir vigorously for about 1 hour, and let stand at 25°C for 24 hours. The precipitate was collected by centrifugation using absolute ethanol as a solvent, and dried at 60° C. for 12 hours.
(b)将步骤(a)中合成的Co-Co PBA微立方体均匀超声分散在无水乙醇和浓氨溶液(28wt％)的混合溶液中，随后用移液枪以1mL min -1的速率向混合溶液中滴加钛酯的有机溶液。油浴加热5h后，室温环境下静置24h。反应结束后用溶剂清洗产品并离心收集，得到Co-Co PBA@TiO 2产物。 (b) Uniformly ultrasonically disperse the Co-Co PBA microcubes synthesized in step (a) in a mixed solution of absolute ethanol and concentrated ammonia solution (28 wt%), and then use a pipette gun at a rate of 1 mL min The organic solution of titanium ester was added dropwise into the mixed solution. After heating in an oil bath for 5 hours, it was left to stand at room temperature for 24 hours. After the reaction, the product was washed with a solvent and collected by centrifugation to obtain the Co-Co PBA@TiO 2 product.
(c)首先，将步骤(b)中合成的Co-Co PBA@TiO 2和硒粉均匀研磨并分散在陶瓷舟中。随后，将该混合物在惰性气体保护下进行高温热处理。所制备的黑色粉末即是外部具有TiO 2涂层保护的氮掺杂碳的CoSe 2复合材料(TNC-CoSe 2)。 (c) First, the Co-Co PBA@ TiO2 and selenium powder synthesized in step (b) were uniformly ground and dispersed in a ceramic boat. Subsequently, the mixture is subjected to high-temperature heat treatment under the protection of an inert gas. The prepared black powder is a nitrogen-doped carbon CoSe 2 composite material (TNC-CoSe 2 ) with a TiO 2 coating on the outside.
上述制得的具有TiO 2涂层保护的氮掺杂碳的CoSe 2复合材料(TNC-CoSe 2)的应用，它用于组装扣式电池，具体为：将TNC-CoSe 2颗粒、导电剂(超导炭(Super P))和粘结剂(羧甲基纤维素钠(CMC))按照8:1:1的质量比分散在水溶剂里，随后均匀涂覆在铜箔上，干燥后制成直径为12mm的圆形电极片，并将其用作工作电极，高纯钠片用作对电极，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。在纽扣电池中，使用玻璃纤维(Whatman，GF/D)作为隔膜，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％的氟代碳酸乙烯酯(FEC)作为电解液。钠离子电池的充放电实验在新威电池测试系统上进行。 The application of the above-mentioned CoSe 2 composite material (TNC-CoSe 2 ) with TiO 2 coating protection nitrogen-doped carbon, which is used for assembling button cells, is specifically: TNC-CoSe 2 particles, conductive agent ( Superconducting carbon (Super P)) and binder (sodium carboxymethyl cellulose (CMC)) were dispersed in water solvent according to the mass ratio of 8:1:1, and then uniformly coated on copper foil, dried and prepared Form a circular electrode sheet with a diameter of 12mm, and use it as a working electrode, and a high-purity sodium sheet as a counter electrode, in a glove box (H 2 O<0.01ppm, O 2 <0.01ppm) assembled into a 2032-type button cell. In a button cell, glass fiber (Whatman, GF/D) was used as a separator, 1M NaClO 4 was dissolved in ethylene carbonate (EC)/dimethyl carbonate (DMC) (1:1 v/v) and 5 wt% of Fluoroethylene carbonate (FEC) was used as the electrolyte. The charge and discharge experiments of sodium-ion batteries are carried out on Xinwei battery test system.
实施例1Example 1
本实施例提供一种TNC-CoSe 2-100复合电极材料的制备方法，它包括以下步骤： The present embodiment provides a kind of preparation method of TNC- CoSe2-100 composite electrode material, and it comprises the following steps:
(a)将0.2g乙酸钴、0.265g六氰基羧酸钾和5.4g十二烷基硫酸钠加入到400mL去离子水中，超声分散均匀，经过约1h的剧烈磁力搅拌，25℃静置24h。使用无水乙醇为溶剂离心收集沉淀，60℃下干燥12小时。(a) Add 0.2g of cobalt acetate, 0.265g of potassium hexacyanocarboxylate and 5.4g of sodium lauryl sulfate into 400mL of deionized water, and disperse evenly by ultrasonic waves. After about 1h of vigorous magnetic stirring, stand at 25°C for 24h . The precipitate was collected by centrifugation using absolute ethanol as a solvent, and dried at 60° C. for 12 hours.
(b)将0.2g步骤(a)中合成的Co-Co PBA均匀超声分散在60mL无水乙醇和0.15mL浓氨溶液(28wt％)的混合溶液中，超声分散30分钟后，以1mL min -1的速率向混合溶液中滴加100μL钛酸四丁酯(TBOT)。80℃油浴加热5h后，25℃静置24h。使用无水乙醇为溶剂离心四次，70℃烘箱干燥8h。 (b) Uniformly ultrasonically disperse 0.2 g of the Co-Co PBA synthesized in step (a) in a mixed solution of 60 mL of absolute ethanol and 0.15 mL of concentrated ammonia solution (28 wt%), and after ultrasonically dispersing for 30 minutes, dissolve in 1 mL min - Add 100 μL tetrabutyl titanate (TBOT) dropwise to the mixed solution at a rate of 1 . After heating in an oil bath at 80°C for 5h, stand at 25°C for 24h. Centrifuge four times using absolute ethanol as a solvent, and dry in an oven at 70°C for 8 hours.
(c)将0.2g步骤(b)中合成的Co-Co PBA@TiO 2和0.8g硒粉均匀研磨并分散在陶瓷舟中。随后，将混合物在Ar/H 2(体积比为95:5)气氛中于350℃下加热并保温4小时。所制备的黑色粉末是TNC-CoSe 2。 (c) 0.2 g of Co-Co PBA@ TiO2 synthesized in step (b) and 0.8 g of selenium powder were uniformly ground and dispersed in a ceramic boat. Subsequently, the mixture was heated and kept at 350° C. for 4 hours in an Ar/H 2 (volume ratio of 95:5) atmosphere. The prepared black powder is TNC-CoSe 2 .
将TNC-CoSe 2-100颗粒、导电剂(超导炭(Super P))和粘结剂(羧甲基纤维素钠(CMC))按照8:1:1的质量比分散在水溶剂里，随后均匀涂覆在铜箔上，干燥后制成直径为12mm的圆形电极片，并将其用作工作电极，高纯钠片用作对电极，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。在纽扣电池中，使用玻璃纤维(Whatman，GF/D)作为隔膜，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％的氟代碳酸乙烯酯(FEC)作为电解液。钠离子电池的充放电实验在新威电池测试系统上进行。 Disperse TNC-CoSe 2 -100 particles, conductive agent (superconducting carbon (Super P)) and binder (sodium carboxymethylcellulose (CMC)) in water solvent at a mass ratio of 8:1:1, Then it is evenly coated on the copper foil, and after drying, it is made into a circular electrode sheet with a diameter of 12mm, and it is used as a working electrode, and the high-purity sodium sheet is used as a counter electrode. Assemble 2032 button cells in a glove box (H 2 O<0.01ppm, O 2 <0.01ppm). In a button cell, glass fiber (Whatman, GF/D) was used as a separator, 1M NaClO 4 was dissolved in ethylene carbonate (EC)/dimethyl carbonate (DMC) (1:1 v/v) and 5 wt% of Fluoroethylene carbonate (FEC) was used as the electrolyte. The charge and discharge experiments of sodium-ion batteries are carried out on Xinwei battery test system.
实施例2Example 2
本实施例提供一种TNC-CoSe 2-200复合电极材料的制备方法，它包括以下步骤： The present embodiment provides a kind of preparation method of TNC- CoSe2-200 composite electrode material, and it comprises the following steps:
(a)将0.2g乙酸钴、0.265g六氰基羧酸钾和5.4g十二烷基硫酸钠加入到400mL去离子水中，超声分散均匀，经过约1h的剧烈磁力搅拌，25℃静置24h。使用无水乙醇为溶剂离心收集沉淀，60℃下干燥12小时。(a) Add 0.2g of cobalt acetate, 0.265g of potassium hexacyanocarboxylate and 5.4g of sodium lauryl sulfate into 400mL of deionized water, and disperse evenly by ultrasonic waves. After about 1h of vigorous magnetic stirring, stand at 25°C for 24h . The precipitate was collected by centrifugation using absolute ethanol as a solvent, and dried at 60° C. for 12 hours.
(b)将0.2g步骤(a)中合成的Co-Co PBA均匀超声分散在60mL无水乙醇和0.15mL浓氨溶液(28wt％)的混合溶液中，超声分散30分钟后，以1mL min -1的速率向混合溶液中滴加200μL钛酸四丁酯(TBOT)。80℃油浴加热5h后，25℃静置24h。使用无水乙醇为溶剂离心四次，70℃烘箱干燥8h。 (b) Uniformly ultrasonically disperse 0.2 g of the Co-Co PBA synthesized in step (a) in a mixed solution of 60 mL of absolute ethanol and 0.15 mL of concentrated ammonia solution (28 wt%), and after ultrasonically dispersing for 30 minutes, dissolve in 1 mL min - Add 200 μL tetrabutyl titanate (TBOT) dropwise to the mixed solution at a rate of 1 . After heating in an oil bath at 80°C for 5h, stand at 25°C for 24h. Centrifuge four times using absolute ethanol as a solvent, and dry in an oven at 70°C for 8 hours.
(c)将0.2g步骤(b)中合成的Co-Co PBA@TiO 2和0.8g硒粉均匀研磨并分散在陶瓷舟中。随后，将混合物在Ar/H 2(体积比为95:5)气氛中于350℃下加热并保温4小时。所制备的黑色粉末是TNC-CoSe 2。 (c) 0.2 g of Co-Co PBA@ TiO2 synthesized in step (b) and 0.8 g of selenium powder were uniformly ground and dispersed in a ceramic boat. Subsequently, the mixture was heated and kept at 350° C. for 4 hours in an Ar/H 2 (volume ratio of 95:5) atmosphere. The prepared black powder is TNC-CoSe 2 .
将TNC-CoSe 2-200颗粒、导电剂(超导炭(Super P))和粘结剂(羧甲基纤维素钠(CMC))按照8:1:1的质量比分散在水溶剂里，随后均匀涂覆在铜箔上，干燥后制成直径为12mm的圆形电极片，并将其用作工作电极，高纯钠片用作对电极，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。在纽扣电池中，使用玻璃纤维(Whatman，GF/D)作为隔膜，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％的氟代碳酸乙烯酯(FEC)作为电解液。钠离子电池的充放电实验在新威电池测试系统上进行。如图1的SEM所示，溶胶凝胶法包覆二氧化钛后材料表面变得更粗糙，证明了TiO 2涂层包覆在CoSe 2表面。此外，该立方体颗粒的凹陷表面归因于前前驱体的热解和硒化过程，导致局部收缩。如图2所示，在低倍透射电镜下观察到TNC-CoSe 2的整体形貌，表明立方CoSe 2表面涂有一层均匀且连续的TiO 2。显然，TiO 2保留了NC-CoSe 2的高度立方结构，并成功地建立了以立方NC-CoSe 2为核、一层TiO 2为壳的核壳结构。图3中的N 2吸脱附等温线显示NC-CoSe 2和TNC-CoSe 2的Brunauer-Emmett-Teller(BET)表面积分别为14.18和23.52m 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，从而改善其电化学性能。如图4充放电测试结果显示，TNC-CoSe 2复合电极材料在循环200次比容量稳定在511.2mAh g -1，从第4次循环计算，其容量保持率为81.95％，表明该种精心设计的材料在反复充放电循环中没有发生较大体积效应。对比发现，NC-CoSe 2复合电极材料循环时容量损失较快，循环200圈后电池已经完全失效。根据图5所示的二者循环后的SEM图像所示，TNC-CoSe 2复合电极材料循环后样品仍保持相对完整的立方体结构，而NC-CoSe 2电极材料的立方结构经过充放电循环已经坍塌，一些纳米颗粒已经聚集在一起。 Disperse TNC-CoSe 2 -200 particles, conductive agent (superconducting carbon (Super P)) and binder (sodium carboxymethylcellulose (CMC)) in water solvent at a mass ratio of 8:1:1, Then it is evenly coated on the copper foil, and after drying, it is made into a circular electrode sheet with a diameter of 12mm, and it is used as a working electrode, and the high-purity sodium sheet is used as a counter electrode. Assemble 2032 button cells in a glove box (H 2 O<0.01ppm, O 2 <0.01ppm). In a button cell, glass fiber (Whatman, GF/D) was used as a separator, 1M NaClO 4 was dissolved in ethylene carbonate (EC)/dimethyl carbonate (DMC) (1:1 v/v) and 5 wt% of Fluoroethylene carbonate (FEC) was used as the electrolyte. The charge and discharge experiments of sodium-ion batteries are carried out on Xinwei battery test system. As shown in the SEM of Figure 1, the surface of the material becomes rougher after the sol-gel coating of titanium dioxide, which proves that the TiO 2 coating is coated on the CoSe 2 surface. Furthermore, the concave surface of this cubic particle is attributed to the pyrolysis and selenization process of the former precursor, leading to local shrinkage. As shown in Figure 2, the overall morphology of TNC-CoSe 2 was observed under a low-magnification transmission electron microscope, indicating that the surface of cubic CoSe 2 was coated with a uniform and continuous layer of TiO 2 . Apparently, TiO2 retained the highly cubic structure of NC- CoSe2 and successfully established a core-shell structure with cubic NC- CoSe2 as the core and a layer of TiO2 as the shell. The N 2 adsorption-desorption isotherms in Fig. 3 show that the Brunauer-Emmett-Teller (BET) surface areas of NC-CoSe 2 and TNC-CoSe 2 are 14.18 and 23.52 m 2 g -1 , respectively. Tests show that the increase in BET provides additional intercalation sites for Na + and enhances the pseudocapacitive contribution, thereby improving its electrochemical performance. As shown in Figure 4, the charge and discharge test results show that the specific capacity of the TNC-CoSe 2 composite electrode material is stable at 511.2mAh g -1 after 200 cycles, and its capacity retention rate is 81.95% calculated from the 4th cycle, indicating that this kind of well-designed The material does not have a large volume effect during repeated charge-discharge cycles. By comparison, it was found that the capacity loss of the NC-CoSe 2 composite electrode material was rapid when it was cycled, and the battery had completely failed after 200 cycles. According to the SEM images of the two after cycling shown in Figure 5, the sample of the TNC-CoSe 2 composite electrode material still maintains a relatively complete cubic structure after cycling, while the cubic structure of the NC-CoSe 2 electrode material has collapsed after charging and discharging cycles. , some nanoparticles have aggregated together.
实施例3Example 3
本实施例提供一种TNC-CoSe 2-300复合电极材料的制备方法，它包括以下步骤： The present embodiment provides a kind of preparation method of TNC-CoSe 2 -300 composite electrode material, and it comprises the following steps:
(a)将0.2g乙酸钴、0.265g六氰基羧酸钾和5.4g十二烷基硫酸钠加入到400mL去离子水中，超声分散均匀，经过约1h的剧烈磁力搅拌，25℃静置24h。使用无水乙醇为溶剂离心收集沉淀，60℃下干燥12小时。(a) Add 0.2g of cobalt acetate, 0.265g of potassium hexacyanocarboxylate and 5.4g of sodium lauryl sulfate into 400mL of deionized water, and disperse evenly by ultrasonic waves. After about 1h of vigorous magnetic stirring, stand at 25°C for 24h . The precipitate was collected by centrifugation using absolute ethanol as a solvent, and dried at 60° C. for 12 hours.
(b)将0.2g步骤(a)中合成的Co-Co PBA均匀超声分散在60mL无水乙醇和0.15mL浓氨溶液(28wt％)的混合溶液中，超声分散30分钟后，以1mL min -1的速率向混合溶液中滴加300μL钛酸四丁酯(TBOT)。80℃油浴加热5h后，25℃静置24h。使用无水乙醇为溶剂离心四次，70℃烘箱干燥8h。 (b) Uniformly ultrasonically disperse 0.2 g of the Co-Co PBA synthesized in step (a) in a mixed solution of 60 mL of absolute ethanol and 0.15 mL of concentrated ammonia solution (28 wt%), and after ultrasonically dispersing for 30 minutes, dissolve in 1 mL min - Add 300 μL tetrabutyl titanate (TBOT) dropwise to the mixed solution at a rate of 1 . After heating in an oil bath at 80°C for 5h, stand at 25°C for 24h. Centrifuge four times using absolute ethanol as a solvent, and dry in an oven at 70°C for 8 hours.
(c)将0.2g步骤(b)中合成的Co-Co PBA@TiO 2和0.8g硒粉均匀研磨并分散在陶瓷舟中。随后，将混合物在Ar/H 2(体积比为95:5)气氛中于350℃下加热并保温4小时。所制备的黑色粉末是TNC-CoSe 2。 (c) 0.2 g of Co-Co PBA@ TiO2 synthesized in step (b) and 0.8 g of selenium powder were uniformly ground and dispersed in a ceramic boat. Subsequently, the mixture was heated and kept at 350° C. for 4 hours in an Ar/H 2 (volume ratio of 95:5) atmosphere. The prepared black powder is TNC-CoSe 2 .
将TNC-CoSe 2-300颗粒、导电剂(超导炭(Super P))和粘结剂(羧甲基纤维素钠(CMC))按照8:1:1的质量比分散在水溶剂里，随后均匀涂覆在铜箔上，干燥后制成直径为12mm的圆形电极片，并将其用作工作电极，高纯钠片用作对电极，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。在纽扣电池中，使用玻璃纤维(Whatman，GF/D)作为隔膜，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％的氟代碳酸乙烯酯(FEC)作为电解液。钠离子电池的充放电实验在新威电池测试系统上进行。 Disperse TNC-CoSe 2 -300 particles, conductive agent (superconducting carbon (Super P)) and binder (sodium carboxymethylcellulose (CMC)) in an aqueous solvent at a mass ratio of 8:1:1, Then it is evenly coated on the copper foil, and after drying, it is made into a circular electrode sheet with a diameter of 12mm, and it is used as a working electrode, and the high-purity sodium sheet is used as a counter electrode. Assemble 2032 button cells in a glove box (H 2 O<0.01ppm, O 2 <0.01ppm). In a button cell, glass fiber (Whatman, GF/D) was used as a separator, 1M NaClO 4 was dissolved in ethylene carbonate (EC)/dimethyl carbonate (DMC) (1:1 v/v) and 5 wt% of Fluoroethylene carbonate (FEC) was used as the electrolyte. The charge and discharge experiments of sodium-ion batteries are carried out on Xinwei battery test system.
实施例4Example 4
本实施例提供一种TNC-CoSe 2-300℃复合电极材料的制备方法，它包括以下步骤： This embodiment provides a method for preparing a TNC-CoSe 2 -300°C composite electrode material, which includes the following steps:
(a)将0.2g乙酸钴、0.265g六氰基羧酸钾和5.4g十二烷基硫酸钠加入到400mL去离子水中，超声分散均匀，经过约1h的剧烈磁力搅拌，25℃静置24h。使用无水乙醇为溶剂离心收集沉淀，60℃下干燥12小时。(a) Add 0.2g of cobalt acetate, 0.265g of potassium hexacyanocarboxylate, and 5.4g of sodium lauryl sulfate into 400mL of deionized water, and disperse evenly with ultrasonic waves. After about 1h of vigorous magnetic stirring, stand at 25°C for 24h . The precipitate was collected by centrifugation using absolute ethanol as a solvent, and dried at 60° C. for 12 hours.
(b)将0.2g步骤(a)中合成的Co-Co PBA均匀超声分散在60mL无水乙醇和0.15mL浓氨溶液(28wt％)的混合溶液中，超声分散30分钟后，以1mL min -1的速率向混合溶液中滴加200μL钛酸四丁酯(TBOT)。80℃油浴加热5h后，25℃静置24h。使用无水乙醇为溶剂离心四次，70℃烘箱干燥8h。 (b) Uniformly ultrasonically disperse 0.2 g of the Co-Co PBA synthesized in step (a) in a mixed solution of 60 mL of absolute ethanol and 0.15 mL of concentrated ammonia solution (28 wt%), and after ultrasonically dispersing for 30 minutes, dissolve in 1 mL min - Add 200 μL tetrabutyl titanate (TBOT) dropwise to the mixed solution at a rate of 1 . After heating in an oil bath at 80°C for 5h, stand at 25°C for 24h. Centrifuge four times using absolute ethanol as a solvent, and dry in an oven at 70°C for 8 hours.
(c)将0.2g步骤(b)中合成的Co-Co PBA@TiO 2和0.8g硒粉均匀研磨并分散在陶瓷舟中。随后，将混合物在Ar/H 2(体积比为95:5)气氛中于300℃下加热并保温4小时。所制备的黑色粉末是TNC-CoSe 2。 (c) 0.2 g of Co-Co PBA@ TiO2 synthesized in step (b) and 0.8 g of selenium powder were uniformly ground and dispersed in a ceramic boat. Subsequently, the mixture was heated and kept at 300° C. for 4 hours in an Ar/H 2 (volume ratio of 95:5) atmosphere. The prepared black powder is TNC-CoSe 2 .
将TNC-CoSe 2-300℃颗粒、导电剂(超导炭(Super P))和粘结剂(羧甲基纤维素钠(CMC))按照8:1:1的质量比分散在水溶剂里，随后均匀涂覆在铜箔上，干燥后制成直径为12mm的圆形电极片，并将其用作工作电极，高纯钠片用作对电极，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。在纽扣电池中，使用玻璃纤维(Whatman，GF/D)作为隔膜，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％的氟代碳酸乙烯酯(FEC)作为电解液。钠离子电池的充放电实验在新威电池测试系统上进行。 Disperse TNC-CoSe 2 -300℃ particles, conductive agent (superconducting carbon (Super P)) and binder (sodium carboxymethylcellulose (CMC)) in water solvent at a mass ratio of 8:1:1 , and then uniformly coated on the copper foil, dried to make a circular electrode sheet with a diameter of 12mm, and use it as a working electrode, and a high-purity sodium sheet as a counter electrode. A 2032-type button cell was assembled in a glove box (H 2 O<0.01ppm, O 2 <0.01ppm). In a button cell, glass fiber (Whatman, GF/D) was used as a separator, 1M NaClO 4 was dissolved in ethylene carbonate (EC)/dimethyl carbonate (DMC) (1:1 v/v) and 5 wt% of Fluoroethylene carbonate (FEC) was used as the electrolyte. The charge and discharge experiments of sodium-ion batteries are carried out on Xinwei battery test system.
实施例5Example 5
本实施例提供一种TNC-CoSe 2-400℃复合电极材料的制备方法，它包括以下步骤： This embodiment provides a method for preparing a TNC-CoSe 2 -400°C composite electrode material, which includes the following steps:
(a)将0.2g乙酸钴、0.265g六氰基羧酸钾和5.4g十二烷基硫酸钠加入到400mL去离子水中，超声分散均匀，经过约1h的剧烈磁力搅拌，25℃静置24h。使用无水乙醇为溶剂离心收集沉淀，60℃下干燥12小时。(a) Add 0.2g of cobalt acetate, 0.265g of potassium hexacyanocarboxylate, and 5.4g of sodium lauryl sulfate into 400mL of deionized water, and disperse evenly with ultrasonic waves. After about 1h of vigorous magnetic stirring, stand at 25°C for 24h . The precipitate was collected by centrifugation using absolute ethanol as a solvent, and dried at 60° C. for 12 hours.
(b)将0.2g步骤(a)中合成的Co-Co PBA均匀超声分散在60mL无水乙醇和0.15mL浓氨溶液(28wt％)的混合溶液中，超声分散30分钟后，以1mL min -1的速率向混合溶液中滴加200μL钛酸四丁酯(TBOT)。80℃油浴加热5h后，25℃静置24h。使用无水乙醇为溶剂离心四次，70℃烘箱干燥8h。 (b) Uniformly ultrasonically disperse 0.2 g of the Co-Co PBA synthesized in step (a) in a mixed solution of 60 mL of absolute ethanol and 0.15 mL of concentrated ammonia solution (28 wt%), and after ultrasonically dispersing for 30 minutes, dissolve in 1 mL min - Add 200 μL tetrabutyl titanate (TBOT) dropwise to the mixed solution at a rate of 1 . After heating in an oil bath at 80°C for 5h, stand at 25°C for 24h. Centrifuge four times using absolute ethanol as a solvent, and dry in an oven at 70°C for 8 hours.
(c)将0.2g步骤(b)中合成的Co-Co PBA@TiO 2和0.8g硒粉均匀研磨并分散在陶瓷舟中。随后，将混合物在Ar/H 2(体积比为95:5)气氛中于400℃下加热并保温4小时。所制备的黑色粉末是TNC-CoSe 2。 (c) 0.2 g of Co-Co PBA@ TiO2 synthesized in step (b) and 0.8 g of selenium powder were uniformly ground and dispersed in a ceramic boat. Subsequently, the mixture was heated and kept at 400° C. for 4 hours in an Ar/H 2 (volume ratio of 95:5) atmosphere. The prepared black powder is TNC-CoSe 2 .
将TNC-CoSe 2-400℃颗粒、导电剂(超导炭(Super P))和粘结剂(羧甲基纤维素钠(CMC))按照8:1:1的质量比分散在水溶剂里，随后均匀涂覆在铜箔上，干燥后制成直径为12mm的圆形电极片，并将其用作工作电极，高纯钠片用作对电极，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。在纽扣电池中，使用玻璃纤维(Whatman，GF/D)作为隔膜，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％的氟代碳酸乙烯酯(FEC)作为电解液。钠离子电池的充放电实验在新威电池测试系统上进行。 Disperse TNC-CoSe 2 -400℃ particles, conductive agent (superconducting carbon (Super P)) and binder (sodium carboxymethylcellulose (CMC)) in water solvent at a mass ratio of 8:1:1 , and then uniformly coated on the copper foil, dried to make a circular electrode sheet with a diameter of 12mm, and use it as a working electrode, and a high-purity sodium sheet as a counter electrode. A 2032-type button cell was assembled in a glove box (H 2 O<0.01ppm, O 2 <0.01ppm). In a button cell, glass fiber (Whatman, GF/D) was used as a separator, 1M NaClO 4 was dissolved in ethylene carbonate (EC)/dimethyl carbonate (DMC) (1:1 v/v) and 5 wt% of Fluoroethylene carbonate (FEC) was used as the electrolyte. The charge and discharge experiments of sodium-ion batteries are carried out on Xinwei battery test system.
实施例6Example 6
本实施例提供一种TNC-CoSe 2-450℃复合电极材料的制备方法，它包括以下步骤： This embodiment provides a method for preparing a TNC-CoSe 2 -450°C composite electrode material, which includes the following steps:
(a)将0.2g乙酸钴、0.265g六氰基羧酸钾和5.4g十二烷基硫酸钠加入到400mL去离子水中，超声分散均匀，经过约1h的剧烈磁力搅拌，25℃静置24h。使用无水乙醇为溶剂离心收集沉淀，60℃下干燥12小时。(a) Add 0.2g of cobalt acetate, 0.265g of potassium hexacyanocarboxylate and 5.4g of sodium lauryl sulfate into 400mL of deionized water, and disperse evenly by ultrasonic waves. After about 1h of vigorous magnetic stirring, stand at 25°C for 24h . The precipitate was collected by centrifugation using absolute ethanol as a solvent, and dried at 60° C. for 12 hours.
(b)将0.2g步骤(a)中合成的Co-Co PBA均匀超声分散在60mL无水乙醇和0.15mL浓氨溶液(28wt％)的混合溶液中，超声分散30分钟后，以1mL min -1的速率向混合溶液中滴加200μL钛酸四丁酯(TBOT)。80℃油浴加热5h后，25℃静置24h。使用无水乙醇为溶剂离心四次，70℃烘箱干燥8h。 (b) Uniformly ultrasonically disperse 0.2 g of the Co-Co PBA synthesized in step (a) in a mixed solution of 60 mL of absolute ethanol and 0.15 mL of concentrated ammonia solution (28 wt%), and after ultrasonically dispersing for 30 minutes, dissolve in 1 mL min - Add 200 μL tetrabutyl titanate (TBOT) dropwise to the mixed solution at a rate of 1 . After heating in an oil bath at 80°C for 5h, stand at 25°C for 24h. Centrifuge four times using absolute ethanol as a solvent, and dry in an oven at 70°C for 8 hours.
(c)将0.2g步骤(b)中合成的Co-Co PBA@TiO 2和0.8g硒粉均匀研磨并分散在陶瓷舟中。随后，将混合物在Ar/H 2(体积比为95:5)气氛中于450℃下加热并保温4小时。所制备的黑色粉末是TNC-CoSe 2。 (c) 0.2 g of Co-Co PBA@ TiO2 synthesized in step (b) and 0.8 g of selenium powder were uniformly ground and dispersed in a ceramic boat. Subsequently, the mixture was heated and kept at 450° C. for 4 hours in an Ar/H 2 (volume ratio of 95:5) atmosphere. The prepared black powder is TNC-CoSe 2 .
将TNC-CoSe 2-450℃颗粒、导电剂(超导炭(Super P))和粘结剂(羧甲基纤维素钠(CMC))按照8:1:1的质量比分散在水溶剂里，随后均匀涂覆在铜箔上，干燥后制成直径为12mm的圆形电极片，并将其用作工作电极，高纯钠片用作对电极，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。在纽扣电池中，使用玻璃纤维(Whatman，GF/D)作为隔膜，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％的氟代碳酸乙烯酯(FEC)作为电解液。钠离子电池的充放电实验在新威电池测试系统上进行。 Disperse TNC-CoSe 2 -450℃ particles, conductive agent (superconducting carbon (Super P)) and binder (sodium carboxymethylcellulose (CMC)) in water solvent at a mass ratio of 8:1:1 , and then uniformly coated on the copper foil, dried to make a circular electrode sheet with a diameter of 12mm, and use it as a working electrode, and a high-purity sodium sheet as a counter electrode. A 2032-type button cell was assembled in a glove box (H 2 O<0.01ppm, O 2 <0.01ppm). In a button cell, using glass fiber (Whatman, GF/D) as a separator, 1M NaClO 4 was dissolved in ethylene carbonate (EC)/dimethyl carbonate (DMC) (1:1 v/v) and 5 wt% of Fluoroethylene carbonate (FEC) was used as the electrolyte. The charge and discharge experiments of sodium-ion batteries are carried out on Xinwei battery test system.
对比例1Comparative example 1
(a)将0.2g乙酸钴、0.265g六氰基羧酸钾和5.4g十二烷基硫酸钠加入到400mL去离子水中，超声分散均匀，经过约1h的剧烈磁力搅拌，25℃静置24h。使用无水乙醇为溶剂离心收集沉淀，60℃下干燥12小时。(a) Add 0.2g of cobalt acetate, 0.265g of potassium hexacyanocarboxylate, and 5.4g of sodium lauryl sulfate into 400mL of deionized water, and disperse evenly with ultrasonic waves. After about 1h of vigorous magnetic stirring, stand at 25°C for 24h . The precipitate was collected by centrifugation using absolute ethanol as a solvent, and dried at 60° C. for 12 hours.
(b)将0.2g步骤(a)中合成的Co-Co PBA和0.8g硒粉均匀研磨并分散在陶瓷舟中。随后，将混合物在Ar/H 2(体积比为95:5)气氛中于350℃下加热并保温4小时。所制备的黑色粉末是NC-CoSe 2。 (b) 0.2 g of Co-Co PBA synthesized in step (a) and 0.8 g of selenium powder were uniformly ground and dispersed in a ceramic boat. Subsequently, the mixture was heated and kept at 350° C. for 4 hours in an Ar/H 2 (volume ratio of 95:5) atmosphere. The prepared black powder is NC-CoSe 2 .
将NC-CoSe 2颗粒、导电剂(超导炭(Super P))和粘结剂(羧甲基纤维素钠(CMC))按照8:1:1的质量比分散在水溶剂里，随后均匀涂覆在铜箔上，干燥后制成直径为12mm的圆形电极片，并将其用作工作电极，高纯钠片用作对电极，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。在纽扣电池中，使用玻璃纤维(Whatman，GF/D)作为隔膜，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％的氟代碳酸乙烯酯(FEC)作为电解液。钠离子电池的充放电实验在新威电池测试系统上进行。 NC-CoSe 2 particles, conductive agent (superconducting carbon (Super P)) and binder (sodium carboxymethylcellulose (CMC)) were dispersed in water solvent at a mass ratio of 8:1:1, and then uniformly Coated on copper foil, after drying, make a circular electrode sheet with a diameter of 12mm, and use it as a working electrode, and a high-purity sodium sheet as a counter electrode. (H 2 O<0.01ppm, O 2 <0.01ppm) assembled into a 2032-type button battery. In a button cell, glass fiber (Whatman, GF/D) was used as a separator, 1M NaClO 4 was dissolved in ethylene carbonate (EC)/dimethyl carbonate (DMC) (1:1 v/v) and 5 wt% of Fluoroethylene carbonate (FEC) was used as the electrolyte. The charge and discharge experiments of sodium-ion batteries are carried out on Xinwei battery test system.
上述实施例和对比例的电池进行循环测试，结果如表1所示。The batteries of the above examples and comparative examples were subjected to cycle tests, and the results are shown in Table 1.
表1Table 1
Figure PCTCN2022097262-appb-000001
Figure PCTCN2022097262-appb-000001
上述实施例只为说明本发明的技术构思及特点，其目的在于让熟悉此项技术的人士能够了解本发明的内容并据以实施，并不能以此限制本发明的保护范围。凡根据本发明精神实质所作的等效变化或修饰，都应涵盖在本发明的保护范围之内。The above-mentioned embodiments are only to illustrate the technical concept and characteristics of the present invention, and the purpose is to enable those skilled in the art to understand the content of the present invention and implement it accordingly, and not to limit the protection scope of the present invention. All equivalent changes or modifications made according to the spirit of the present invention shall fall within the protection scope of the present invention.

Claims (10)

  1. 一种二氧化钛包覆的CoSe 2基纳米材料的制备方法，该制备方法包括以下步骤： A preparation method of CoSe2 - based nanomaterial coated with titanium dioxide, the preparation method may further comprise the steps:
    将乙酸钴、六氰基羧酸钾和十二烷基硫酸钠加入到水中，超声分散均匀，经过1-3h的剧烈磁力搅拌，25℃静置20-24h，用无水乙醇为溶剂离心收集沉淀，60-80℃下干燥8-12小时，制备出纳米尺寸的Co-Co PBA微立方体；其中，乙酸钴、六氰基羧酸钾和十二烷基硫酸钠的混合质量比为1：(1-2)：(25-30)；Add cobalt acetate, potassium hexacyanocarboxylate and sodium lauryl sulfate into water, ultrasonically disperse evenly, after 1-3 hours of vigorous magnetic stirring, let stand at 25°C for 20-24 hours, and use absolute ethanol as solvent to collect by centrifugation Precipitate, dry at 60-80°C for 8-12 hours, and prepare nano-sized Co-Co PBA microcubes; wherein, the mixing mass ratio of cobalt acetate, potassium hexacyanocarboxylate and sodium lauryl sulfate is 1: (1-2): (25-30);
    将所述Co-Co PBA微立方体超声分散在无水乙醇与浓氨溶液的混合溶液中，以0.5-1mL min -1的速率向混合溶液中滴加钛酯的有机溶液，油浴70℃-100℃加热5-8h，室温下静置20-24h，反应结束后用溶剂清洗产品并离心收集，得到Co-Co PBA@TiO 2；其中，Co-Co PBA微立方体与无水乙醇为(0.1-0.3)g：(60-100)mL； The Co-Co PBA microcubes were ultrasonically dispersed in a mixed solution of absolute ethanol and concentrated ammonia solution, and an organic solution of titanium ester was added dropwise to the mixed solution at a rate of 0.5-1mL min -1 , and the oil bath was 70°C- Heating at 100°C for 5-8h, standing at room temperature for 20-24h, washing the product with a solvent after the reaction and centrifuging to obtain Co-Co PBA@TiO 2 ; wherein, Co-Co PBA microcubes and absolute ethanol are (0.1 -0.3) g: (60-100) mL;
    将所述Co-Co PBA@TiO 2和硒粉均匀研磨，在惰性气体保护下进行高温硒化和碳化，得到二氧化钛包覆的CoSe 2基纳米材料TNC-CoSe 2；其中，Co-Co PBA@TiO 2和硒粉的混合质量比为1：3-6。 The Co-Co PBA@TiO 2 and selenium powder are uniformly ground, and high-temperature selenization and carbonization are carried out under the protection of an inert gas to obtain a CoSe 2- based nanomaterial TNC-CoSe 2 coated with titanium dioxide; wherein, Co-Co PBA@ The mixing mass ratio of TiO 2 and selenium powder is 1:3-6.
  2. 根据权利要求1所述的制备方法，其中，所述钛酯选自钛酸四丁酯、钛酸四乙酯、钛酸四丙酯中的一种。The preparation method according to claim 1, wherein the titanium ester is selected from one of tetrabutyl titanate, tetraethyl titanate and tetrapropyl titanate.
  3. 根据权利要求1所述的制备方法，其中，所述有机溶液选自乙酸、异丙醇、正丁醇、乙酰丙酮中的一种。The preparation method according to claim 1, wherein the organic solution is selected from one of acetic acid, Virahol, n-butanol, and acetylacetone.
  4. 根据权利要求1所述的制备方法，其中，所述钛酯的有机溶液中，每60-100mL有机溶液中，钛酯的添加量为100μL-300μL。The preparation method according to claim 1, wherein, in the organic solution of the titanium ester, the addition amount of the titanium ester is 100 μL-300 μL per 60-100 mL of the organic solution.
  5. 根据权利要求1所述的制备方法，其中，所述无水乙醇与浓氨溶液的混合溶液中，浓氨溶液的浓度为20-28wt％。The preparation method according to claim 1, wherein, in the mixed solution of absolute ethanol and concentrated ammonia solution, the concentration of the concentrated ammonia solution is 20-28wt%.
  6. 根据权利要求1所述的制备方法，其中，所述惰性气体选自氩气、氮气、氩氢混合气中的一种；The preparation method according to claim 1, wherein the inert gas is selected from one of argon, nitrogen, and argon-hydrogen mixed gas;
    优选地，所述氩氢混合气中氩气与氢气的体积比为95％:5％。Preferably, the volume ratio of argon to hydrogen in the argon-hydrogen mixture is 95%:5%.
  7. 根据权利要求1或6所述的制备方法，其中，所述惰性气体的流通速率为50-150mL min -1。 The preparation method according to claim 1 or 6, wherein the flow rate of the inert gas is 50-150mL min -1 .
  8. 根据权利要求1所述的制备方法，其中，所述高温硒化和碳化的温度为300℃-450℃，保温时间为3-6h。The preparation method according to claim 1, wherein the temperature of the high-temperature selenization and carbonization is 300°C-450°C, and the holding time is 3-6h.
  9. 一种二氧化钛包覆的CoSe 2基纳米材料，该二氧化钛包覆的CoSe 2基纳米材料时通过权利要求1-8任一项所述的二氧化钛包覆的CoSe 2基纳米材料的制备方法制备得到的。 A kind of CoSe2 - based nanomaterial coated with titanium dioxide, which is prepared by the CoSe2 - based nanomaterial coated with titanium dioxide according to any one of claims 1-8 . .
  10. 权利要求9所述的二氧化钛包覆的CoSe 2基纳米材料的应用，该二氧化钛包覆的CoSe 2基纳米材料用于钠离子电池的负极材料。 The application of the CoSe2 - based nanomaterial coated with titanium dioxide according to claim 9, the CoSe2 - based nanomaterial coated with titanium dioxide is used for the negative electrode material of a sodium-ion battery.
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