CN113511674A - Multifunctional ultralong TiO2-B nanotube material, preparation method and application thereof - Google Patents

Multifunctional ultralong TiO2-B nanotube material, preparation method and application thereof Download PDF

Info

Publication number
CN113511674A
CN113511674A CN202110737395.3A CN202110737395A CN113511674A CN 113511674 A CN113511674 A CN 113511674A CN 202110737395 A CN202110737395 A CN 202110737395A CN 113511674 A CN113511674 A CN 113511674A
Authority
CN
China
Prior art keywords
tio
multifunctional
ultralong
nanotube
lithium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202110737395.3A
Other languages
Chinese (zh)
Other versions
CN113511674B (en
Inventor
甄蒙蒙
李虎振
沈伯雄
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hebei University of Technology
Original Assignee
Hebei University of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hebei University of Technology filed Critical Hebei University of Technology
Priority to CN202110737395.3A priority Critical patent/CN113511674B/en
Publication of CN113511674A publication Critical patent/CN113511674A/en
Application granted granted Critical
Publication of CN113511674B publication Critical patent/CN113511674B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • C01G23/08—Drying; Calcining ; After treatment of titanium oxide
    • 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
    • H01M10/052—Li-accumulators
    • 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
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
    • C01P2004/13—Nanotubes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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

Abstract

The invention relates to the technical field of battery materials, in particular to multifunctional ultralong TiO2-B nanotube material, method of preparation and use thereof; the invention is prepared by mixing anatase phase TiO2Dispersing nano particles and hexamethylene tetramine in 10mol/L NaOH solution, stirring, reacting at 140-160 ℃ for 36-48 h, cooling, centrifuging and calcining to obtain TiO2the-B-NTs material has simple preparation process, easy operation, low energy consumption and obvious effectThe nanotube structure and the hollow cavity of (A) and (B) is prepared by mixing TiO with2the-B-NTs material is applied to a lithium ion battery cathode material and a lithium sulfur battery anode material, and can simultaneously realize high specific capacity, excellent rate capability and strong cycling stability of the lithium ion battery and the lithium sulfur battery.

Description

Multifunctional ultralong TiO2-B nanotube material, preparation method and application thereof
Technical Field
The invention relates to the technical field of battery materials, in particular to multifunctional ultralong TiO2-B sodiumA rice tube material, a preparation method and application thereof.
Background
The current rapid development of economy makes its demand for energy increasing, and the burning of large quantities of fossil fuels makes the problem of environmental pollution even more serious. In order to meet the increasing demand for energy and reduce the dependence on fossil fuels, there is an urgent need for clean new energy sources to replace the conventional energy sources. However, most new energy sources are intermittent and cannot provide energy stably and continuously. Therefore, a reliable and efficient energy storage system is needed. Lithium ion batteries and lithium sulfur batteries play a key role in energy storage systems due to their advantages of low cost, high energy density, environmental friendliness, and the like. However, as the demand for high-energy and long-life energy storage batteries increases, a series of problems such as capacity, safety, cycling stability and reaction kinetics are accompanied by the demand. For example, the large volume changes produced in the electrodes during lithiation/delithiation of lithium ion batteries can cause the active material to flake off of the current collector; shuttling of soluble polysulfides between the positive and negative electrodes can cause rapid decay in the capacity of lithium sulfur batteries. Therefore, designing an advanced electrode material with high specific capacity, long cycle life and high energy density is a key for meeting the requirements of lithium ion batteries and lithium sulfur batteries.
In electrode materials for lithium ion batteries, titanium dioxide (TiO)2) It is of great interest because of its higher rate capability, higher safety and lower cost than ordinary graphite. Furthermore, TiO2It also has a strong chemisorption capacity and is considered to be an effective adsorbent for capturing soluble polysulfides. In TiO2In various crystal forms, TiO2-Bronze(TiO2-B) has an open channel, capable of providing a diffusion channel for lithium ions and providing a plurality of active sites in pseudocapacitive properties. This makes TiO2Theoretical capacity of-B up to 335mAhg-1Is anatase phase TiO2(167.5mAhg-1) 2 times the theoretical capacity of (a). In addition, the lithium ion is in TiO2The rapid diffusion of the-B surface can also effectively improve the specific capacity of the lithium-sulfur battery, inhibit the shuttle effect and improve the performance of the lithium-sulfur battery. However, TiO2B is circulating throughThe practical application of the material as an energy storage electrode material is hindered by factors such as large volume change, poor conductivity, serious particle agglomeration and the like in the process.
In general, TiO is controlled2The morphology, microstructure and pore size of the-B plays an important role in improving the electrochemical storage performance of the-B. Compared with the low porosity of a rod-shaped, block-shaped or spherical structure, the nanotube structure combines the advantages of a tubular structure and a one-dimensional structure, so that the porosity and the surface area of the electrode material can be effectively improved, and the permeability of the electrolyte is enhanced. In addition, the hollow nanotube structure can not only shorten the diffusion path of lithium ions, but also provide enough space to relieve the volume change of lithium ions during insertion/extraction in the lithium ion battery, and effectively encapsulate polysulfide to inhibit the shuttling effect of the lithium sulfur battery, while TiO can be improved by increasing the aspect ratio2-material properties of B nanotubes. Thus, ultra-long multifunctional TiO2The construction of the-B nanotube has great potential for solving the bottleneck problem of lithium ion batteries and lithium sulfur batteries and improving the energy storage performance of the lithium ion batteries and the lithium sulfur batteries. At present, although some anatase phase TiO is available2Nanotube and B phase TiO2The preparation method of nanobelts and the like is reported, but the ultralong TiO with high length-diameter ratio is prepared due to the factors of low yield, harsh reaction conditions and the like2B nanotubes still face significant research challenges; in addition to this, the TiO obtainable by these preparation processes2Due to the structural defects, the nano material is difficult to form an excellent lithium storage unit when being used as an electrode material of a lithium ion battery, cannot carry sulfur with high load and capture liquid-phase lithium polysulfide strongly when being used as the electrode material of the lithium sulfur battery, and cannot effectively improve the performances of the lithium ion battery and the lithium sulfur battery.
In view of the above-mentioned drawbacks, the inventors of the present invention have finally obtained the present invention through a long period of research and practice.
Disclosure of Invention
The invention aims to solve the problem that the ultralong TiO with high length-diameter ratio can not be prepared due to the factors of low yield, harsh reaction conditions and the like2Problem of-B nanotube, providing a multifunctional ultralong TiO2-B nanotube material, method of preparation and use thereof.
In order to achieve the purpose, the invention discloses multifunctional ultralong TiO2-a method of preparing a nanotube material comprising the steps of:
s1: adding TiO into the mixture2Dispersing the nano particles and the hexamethylene tetramine in 10mol/L NaOH solution, magnetically stirring for 0.5-1 h by using a magnetic stirrer, and uniformly mixing;
s2: reacting the mixed solution obtained in the step S1 at 140-160 ℃ for 36-48 h, cooling to room temperature, and centrifuging;
s3: pouring out the supernatant of the solution centrifuged in the step S2, filtering the obtained precursor material, washing the precursor material with hydrochloric acid and deionized water until the pH is 7, and drying the precursor material at 60 ℃ for 8 hours;
s4: calcining the dried precursor material in the step S3 for 2h in Ar atmosphere at the calcining temperature of 350 ℃ and the heating rate of 2 ℃/min to obtain TiO2-B-NTs。
The invention also discloses the multifunctional ultralong TiO prepared by the preparation method2-B nanotube material.
The invention also discloses a multifunctional ultralong TiO adopting the above2-B a method for preparing a lithium ion battery anode material by using a nanotube material, comprising the following steps:
1) adding TiO into the mixture2Mixing the-B-NTs material, the carbon nano tube, the polyvinylidene fluoride and the N-methyl pyrrolidone to obtain first slurry;
2) coating the first slurry in the step 1) on a copper foil with the thickness of 0.25-0.5 mm, and drying for 12-16 h at the temperature of 60-80 ℃ in vacuum to obtain the multifunctional ultralong TiO2-B nanotube lithium ion battery negative electrode.
The ratio of the mass parts of the polyvinylidene fluoride to the volume parts of the N-methylpyrrolidone in the step 1) is 1:5 to 6.
The invention also discloses the multifunctional ultralong TiO prepared by the preparation method2-B nanotube lithium ion battery negative electrode material, wherein the multifunctional ultralong TiO in the lithium ion battery negative electrode material2The content of the-B nano tube is 1.5-2.0 mg/cm2。
The invention also disclosesAdopt above-mentioned multi-functional overlength TiO2-a method for preparing a lithium-sulfur battery positive electrode material from a B nanotube material, comprising the steps of:
(1) under high power ultrasonic wave, TiO is mixed2-B-NTs material, carbon nanotubes and sulphur in a weight ratio of 2.5:0.5:1 to CS2In solution until CS2Completely evaporating to form a mixture;
(2) transferring the mixture obtained in the step (1) into a high-pressure reaction kettle, heating at 155 ℃ and standing for 24 hours to obtain the lithium-sulfur battery active material;
(3) and (3) mixing the lithium-sulfur battery active material obtained in the step (2), a carbon black conductive agent, polyvinylidene fluoride and N-methylpyrrolidone in a mass ratio of 8-7: 1-2: 1, obtaining a second slurry, coating the second slurry on an aluminum foil, and drying for 12-16 h at the temperature of 60-80 ℃ in vacuum to obtain the multifunctional ultralong TiO2-B nanotube lithium-sulfur battery positive electrode material.
In the step (3), the ratio of the mass part of the polyvinylidene fluoride to the volume part of the N-methylpyrrolidone is 1: 5-6, the thickness of the aluminum foil is 0.25-0.5 mm.
The invention also discloses the multifunctional ultralong TiO prepared by the preparation method2-B nanotube lithium-sulfur battery positive electrode material, the multifunctional ultralong TiO2The sulfur content in the cathode material of the-B nanotube lithium-sulfur battery is 1.5mg/cm2。
The invention adopts anatase phase TiO2The nano particles are used as a precursor of titanium, and are hydrothermally reacted with a strong alkali solution to form a two-dimensional sheet layered product, and then the two-dimensional sheet layered product is further peeled off along a crystal face to form a sheet; along with the hydrothermal reaction, the number of unsaturated dangling bonds is increased, so that the surface activity of the sheet is enhanced, and the sheet is curled to form a tubular structure to reduce the number of dangling bonds and reduce the energy of a system; the added hexamethylene tetramine is used as a structure guiding agent to control the growth rate of different surfaces, and the longitudinal growth of the nano tube is further induced to obtain the ultra-long sodium carbonate nano tube; finally, the porous multifunctional ultralong TiO with large specific surface area is obtained through ion exchange treatment and calcination process2-B nanotubes.
Compared with the prior art, the invention has the beneficial effects that: the invention discloses a multifunctional ultralong TiO2the-B nanotube material can be applied to lithium ion batteries and lithium sulfur batteries, and the multifunctional ultralong TiO2The B nanotube material has the advantages of simple preparation process, easy operation and low energy consumption, has an obvious nanotube structure and a hollow cavity, can provide enough space to relieve volume expansion in the lithium ion embedding/separating process, accelerate diffusion of lithium ions, improve the performance of the lithium ion battery, effectively load sulfur and capture lithium polysulfide, effectively inhibit shuttle effect of the sulfur-loaded lithium ion battery, and improve the cycle performance of the lithium-sulfur battery. The invention overcomes the defects of the traditional method for improving the performance of the lithium ion battery and the lithium sulfur battery, namely the problems of complex preparation operation, low material yield, poor performance stability and the like of the produced electrode material. Using multifunctional ultralong TiO2When the-B nanotube material is used as a lithium ion battery cathode material and a lithium sulfur battery anode material, high specific capacity, excellent rate capability and strong cycle stability of the lithium ion battery and the lithium sulfur battery can be realized simultaneously.
Drawings
FIG. 1 shows the ultralong TiO obtained in example 12-B scanning electron micrographs of nanotube material;
FIG. 2 shows TiO obtained in comparative example 12-scanning electron micrographs of B nanorod material;
FIG. 3 shows the ultralong TiO obtained in example 12-transmission electron microscopy of B nanotube material;
FIG. 4 shows TiO obtained in comparative example 12-transmission electron microscopy of B nanorod material;
FIG. 5 shows the ultralong TiO particles obtained in examples 1 to 32The negative electrode material of the-B nanotube as a lithium ion battery is 0.2C (1C ═ 335 mAg)-1) A plot of the cycling performance of the test at current density;
FIG. 6 shows the ultralong TiO obtained in example 12The circulation performance graph of the negative electrode material of the lithium ion battery tested under the current density of 2.0C by using the B nano tube and the TiO2-B nano rod obtained in the comparative example 1;
FIG. 7 shows the ultralong TiO obtained in example 12B nanotubes and TiO from comparative example 12-B sodiumThe rice bar is used as a multiplying power performance diagram of the lithium ion battery cathode material under different current densities;
FIG. 8 shows an ultralong TiO obtained in example 12B nanotubes and TiO from comparative example 12the-B nano rod as the positive electrode material of the lithium-sulfur battery is 1.0C (1C: 1675 mAg)-1) A plot of the cycling performance of the test at current density;
FIG. 9 shows an ultralong TiO obtained in example 12B nanotubes and TiO from comparative example 12And the-B nanorod is used as a rate performance graph of the lithium-sulfur battery cathode material under different current densities.
Detailed Description
The above and further features and advantages of the present invention are described in more detail below with reference to the accompanying drawings.
The chemicals and instruments used in the experiment are shown in tables 1 and 2
TABLE 1 chemicals used in the experiments
Name of reagent Molecular formula Purity of Manufacturer of the product
Sodium hydroxide NaOH 96.0％ SINOPHARM CHEMICAL REAGENT Co.,Ltd.
Hexamethylene tetramine C6H12N4 95.0％ SINOPHARM CHEMICAL REAGENT Co.,Ltd.
Titanium dioxide nanoparticles TiO2 99.0％ SINOPHARM CHEMICAL REAGENT Co.,Ltd.
Carbon nanotube CNTs 95％ SINOPHARM CHEMICAL REAGENT Co.,Ltd.
Carbon disulfide CS2 99.9％ SINOPHARM CHEMICAL REAGENT Co.,Ltd.
TABLE 2 Instrument and Equipment for experiments
Figure BDA0003142084180000041
Figure BDA0003142084180000051
Example 1
Multifunctional ultralong TiO2-B nanotube material (TiO)2-B-NTs) according to the following experimental procedure:
1) a50 mL beaker was charged with 40mL of a NaOH solution (10mol/L), followed by addition of 1.0g of TiO2Nanoparticles and 0.3g of hexamethylene tetramine were dispersed in NaOH solution and magnetically stirredThe stirrer magnetically stirs for 0.5 hour to mix the solution evenly.
2) After magnetic stirring, the mixed solution was transferred to a stainless steel autoclave having a volume of 50mL and lined with Teflon, and maintained at 140 ℃ for 48 hours. After cooling at room temperature, the reaction was transferred to a centrifuge tube and centrifuged.
3) After centrifugation, the supernatant was decanted and the resulting precursor material was filtered and washed with hydrochloric acid solution (0.1mol/L) and deionized water to a pH of about 7, followed by drying at 60 ℃ for 8 hours.
4) After drying, the obtained precursor material is placed in a tube furnace and calcined for 2 hours at 350 ℃ under Ar atmosphere, and the heating rate is 2 ℃ for min-1Finally forming TiO2-B-NTs。
Example 2
Multifunctional ultralong TiO2-B nanotube material (TiO)2-B-NTs) according to the following experimental procedure:
1) a50 mL beaker was charged with 40mL of a NaOH solution (10mol/L), followed by addition of 1.0g of TiO2The nanoparticles and 0.3g of hexamethylene tetramine were dispersed in the NaOH solution and magnetically stirred by a magnetic stirrer for 0.5 hour to uniformly mix the solution.
2) After magnetic stirring, the mixed solution was transferred to a stainless steel autoclave having a volume of 50mL and lined with Teflon, and maintained at 150 ℃ for 48 hours. After cooling at room temperature, the reaction was transferred to a centrifuge tube and centrifuged.
3) After centrifugation, the supernatant was decanted and the resulting precursor material was filtered and washed with hydrochloric acid solution (0.1mol/L) and deionized water to a pH of about 7, followed by drying at 60 ℃ for 8 hours.
4) After drying, the obtained precursor material is placed in a tube furnace and calcined for 2 hours at 350 ℃ under Ar atmosphere, and the heating rate is 2 ℃ for min-1Finally forming TiO2-B-NTs。
Example 3
Multifunctional ultralong TiO2-B nanotube material (TiO)2Preparation method of (E) -B-NTs), experimentThe method comprises the following steps:
1) a50 mL beaker was charged with 40mL of a NaOH solution (10mol/L), followed by addition of 1.0g of TiO2The nanoparticles and 0.3g of hexamethylene tetramine were dispersed in the NaOH solution and magnetically stirred by a magnetic stirrer for 0.5 hour to uniformly mix the solution.
2) After magnetic stirring, the mixed solution was transferred to a stainless steel autoclave having a volume of 50mL and lined with Teflon, and maintained at 160 ℃ for 48 hours. After cooling at room temperature, the reaction was transferred to a centrifuge tube and centrifuged.
3) After centrifugation, the supernatant was decanted and the resulting precursor material was filtered and washed with hydrochloric acid solution (0.1mol/L) and deionized water to a pH of about 7, followed by drying at 60 ℃ for 8 hours.
4) After drying, placing the obtained precursor material in a tube furnace, calcining for 2 hours at 350 ℃ under Ar atmosphere at the heating rate of 2 ℃/min, and finally forming TiO2-B-NTs。
Multifunctional ultralong TiO2The preparation method of the negative electrode material of the B nanotube lithium ion battery comprises the following steps:
TiO obtained in any one of examples 1 to 32Mixing the-B-NTs material with carbon nanotubes, polyvinylidene fluoride (PVDF) and N-methylpyrrolidone (NMP) to obtain a first slurry, coating the first slurry on a copper foil with a thickness of 0.3mm by using a wet film maker and drying at 60 ℃ for 16 hours in a vacuum environment to obtain the multifunctional ultralong TiO2-B nanotube lithium ion battery cathode material, wherein, in parts by mass, TiO2-the ratio of B-NTs material to carbon nanotubes, polyvinylidene fluoride (binder) is 8:1: 1; in the first slurry, the ratio of the mass part of polyvinylidene fluoride to the volume part of N-methylpyrrolidone is 1: 5. parts by mass are in milligrams, parts by volume are in milliliters.
The multifunctional ultralong TiO obtained in example 1 was determined2Multifunctional ultralong TiO contained in negative electrode material of-B nanotube lithium ion battery2The amount of-B nanotubes was 1.8mg/cm2。
Multifunctional ultralong TiO2The preparation method of the-B nanotube lithium-sulfur battery positive electrode material comprises the following steps:
1) the multifunctional ultralong TiO obtained in any one of embodiments 1 to 32-dissolving B nanotubes to Carbon Nanotubes (CNTs) and sulfur in a weight ratio of 2.5:0.5:1 to CS2In solution (30mL) until CS2Completely evaporating to form a mixture;
2) transferring the mixture into a 10mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, heating at 155 ℃, and standing for 24 hours to obtain the active material of the lithium-sulfur battery;
3) mixing an active material, SuperP, polyvinylidene fluoride (PVDF) and N-methylpyrrolidone (NMP) to obtain a second slurry, coating the second slurry on an aluminum foil with the thickness of 0.3mm by using a wet film preparation device, and drying for 16 hours at 60 ℃ in a vacuum environment to obtain the multifunctional ultralong TiO2-B nanotube lithium-sulfur battery positive electrode material (S-TiO)2-B-NTs), wherein the ratio of active material, SuperP and polyvinylidene fluoride (binder) is 8:1: 1; in the second slurry, the ratio of the mass part of the polyvinylidene fluoride to the volume part of the N-methylpyrrolidone is 1: 5. Parts by mass are in milligrams, parts by volume are in milliliters.
The multifunctional ultralong TiO obtained in example 1 was determined2The sulfur content of the cathode material of the B nanotube lithium-sulfur battery is 1.5mg/cm2。
Comparative example 1
TiO22-B nanorod (TiO)2-B-NWs) comprising the steps of:
1) a40 mL of a LKOH solution (10mol/L) was added to a 50mL beaker, and then 3mL of tetrabutyl titanate (TBT) was dispersed in the KOH solution and magnetically stirred for 0.5 hour by a magnetic stirrer to uniformly mix the solution.
2) After magnetic stirring, the mixed solution was transferred to a stainless steel autoclave having a capacity of 50ml and lined with polytetrafluoroethylene, and maintained at 180 ℃ for 48 hours. After cooling at room temperature, the reaction was transferred to a centrifuge tube and centrifuged.
3) After centrifugation, the supernatant was decanted and the resulting precursor material was filtered and washed with hydrochloric acid solution (0.1mol/L) and deionized water to a pH of about 7, followed by drying at 60 ℃ for 8 hours.
4) After drying, placing the obtained precursor material in a tube furnace, calcining for 2 hours at 350 ℃ under Ar atmosphere at the heating rate of 2 ℃/min, and finally forming TiO2-B-NWs。
TiO2The preparation method of the-B nanorod lithium ion battery negative electrode material comprises the following steps:
the TiO obtained in comparative example 1 was added2Mixing the-B-NWs material with carbon nanotubes, polyvinylidene fluoride (PVDF) and N-methylpyrrolidone (NMP) to obtain a first slurry, coating the first slurry on a copper foil having a thickness of 0.3mm using a wet film maker and drying at 60 ℃ for 16 hours in a vacuum environment to obtain TiO2The negative electrode material of the-B nanorod lithium ion battery is characterized in that the negative electrode material is TiO in parts by mass2-the ratio of B-NWs material to carbon nanotubes, polyvinylidene fluoride (binder) is 8:1: 1; in the first slurry, the ratio of the mass part of polyvinylidene fluoride to the volume part of N-methylpyrrolidone is 1: 5. Parts by mass are in milligrams, parts by volume are in milliliters.
The TiO obtained in comparative example 1 was measured2TiO contained in negative electrode material of-B nanorod lithium ion battery2The amount of the-B nano rod is 1.8mg/cm2。
TiO2The preparation method of the-B nanorod lithium-sulfur battery cathode material comprises the following steps:
1) the TiO obtained in comparative example 1 was added2-dissolving B-NWs material in a weight ratio of 2.5:0.5:1 to CS with Carbon Nanotubes (CNTs) and sulfur2In solution (30mL) until CS2Completely evaporating to form a mixture;
2) transferring the mixture into a 10mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, heating at 155 ℃, and standing for 24 hours to obtain the active material of the lithium-sulfur battery;
3) mixing the active material, SuperP, polyvinylidene fluoride (PVDF) and N-methylpyrrolidone (NMP) to obtain a second slurry, and coating the second slurry by using a wet film makerDrying on an aluminium foil with a thickness of 0.3mm at 60 ℃ for 16 hours in a vacuum atmosphere to give TiO2-B nanorod positive electrode material (S-TiO) of lithium-sulfur battery2-B-NWs), wherein the ratio of active material, SuperP and polyvinylidene fluoride (binder) is 8:1:1 in parts by weight; in the second slurry, the ratio of the mass part of the polyvinylidene fluoride to the volume part of the N-methylpyrrolidone is 1: 5. Parts by mass are in milligrams, parts by volume are in milliliters.
The TiO obtained in comparative example 1 was measured2The sulfur content of the-B nanorod lithium-sulfur battery cathode material is 1.5mg/cm2。
Performance testing
Through testing, the multifunctional ultralong TiO obtained in example 12The specific surface area of the-B nanotubes was 168.5m2g-1Comparative example 1 TiO2The specific surface area of the-B nanorod is 82.3m2g-1。
Test example 1 multifunctional ultralong TiO2B nanotubes and TiO from comparative example 12-morphology of B nanorods. FIG. 1 is a multi-functional ultra-long TiO2-scanning electron micrograph of B nanotubes, FIG. 2 is TiO2Scanning electron micrographs of the B nanorods, it can be seen from fig. 1 and 2 that both the resulting materials are long, above about 1 micron; FIG. 3 is a multi-functional ultra-long TiO2-transmission electron micrograph of B nanotubes, FIG. 4 is TiO2The transmission electron microscope image of the-B nano rod shows that the multifunctional ultralong TiO2-B nano tube has an obvious tubular cavity structure with the diameter of about 7nm as shown in FIG. 3, and the TiO 4 is shown in FIG. 42the-B nanorod is of a solid structure.
The multifunctional ultralong TiO obtained in examples 1 to 32B nanotubes and TiO from comparative example 12And (4) carrying out electrochemical performance test on the lithium ion battery cathode material prepared from the B nanorod. The results are shown in FIGS. 5 and 6.
As can be seen from FIG. 5, the multifunctional ultralong TiO obtained in examples 1 to 32As can be seen from the cycle performance diagram of the B nanotube at a current density of 0.2C, the functional ultralong TiO obtained in example 12-B nanotube as lithium ion battery cathode materialCan provide higher specific capacity and stronger cycling stability.
As can be seen from FIG. 6, the multifunctional ultralong TiO obtained in example 12B nanotubes and TiO from comparative example 12The cyclic performance diagram of the-B nano rod under the current density of 2.0C shows that the multifunctional ultralong TiO2-B nanotube to TiO2the-B nanorod has more excellent cycling stability, and the specific capacity is still kept at about 260mAh/g after the cycling for 100 weeks.
As can be seen from FIG. 7, the multifunctional ultralong TiO obtained in example 12B nanotubes and TiO from comparative example 12The multiplying power performance diagram of the-B nano rod under different current densities can show that the multifunctional ultralong TiO is applied under the current densities of 0.5, 1.0, 2.0, 3.0 and 5.0C2The specific capacity of the-B nano tube serving as the negative electrode material of the lithium ion battery is respectively kept at about 325, 290, 245, 220 and 170 mAh/g. In contrast, TiO2The specific capacity of the-B nano rod is low, and particularly, the specific capacity is only 100mAh/g under the current density of 5.0C.
For the multifunctional ultralong TiO obtained in example 12B nanotubes and TiO from comparative example 12And (4) carrying out electrochemical performance test on the lithium-sulfur battery cathode material prepared from the-B nanorod. The results are shown in FIGS. 8 and 9.
As can be seen from FIG. 8, the multifunctional ultralong TiO obtained in example 12B nanotubes and TiO from comparative example 12The cycle performance diagram of the-B nano rod under the current density of 1.0C shows that the multifunctional ultralong TiO2-B nanotube to TiO2the-B nanorod as a lithium-sulfur battery positive electrode material has more excellent cycling stability, and the specific capacity is still kept at about 800mAh/g after 100 cycles of cycling.
As can be seen from FIG. 9, the multifunctional ultralong TiO obtained in example 12The multiplying power performance graphs of the-B nano tube and the TiO2-B nano rod obtained in the comparative example 1 under different current densities can show that the multifunctional ultralong TiO has the current densities of 0.1, 0.2, 0.5, 1.0, 2.0C and 5.0C2The specific capacity of the-B nanotube serving as the positive electrode material of the lithium-sulfur battery is obviously higher than that of TiO obtained in comparative example 12-B nanorods.
As can be seen from the above data, TiO2When the-B nanorod is used as a lithium ion battery cathode material and a lithium sulfur battery anode material, the specific capacity is attenuated too fast, the cycle life is short, and the multifunctional ultralong TiO is2The specific capacity, the cycle life and the cycle stability of the-B nano tube are obviously superior to those of TiO no matter the-B nano tube is used as a lithium ion battery cathode material or a lithium sulfur battery anode material2-B nanorods, especially at high current densities. In addition, multifunctional ultralong TiO2the-B nanotube can effectively inhibit the diffusion of lithium polysulfide and can remarkably promote the catalytic conversion of the lithium polysulfide, and the multifunctional effect effectively improves the cycle performance of the lithium-sulfur battery.
The foregoing is merely a preferred embodiment of the invention, which is intended to be illustrative and not limiting. It will be understood by those skilled in the art that various changes, modifications and equivalents may be made therein without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (10)

1. Multifunctional ultralong TiO2-B nanotube material production method, characterized in that it comprises the following steps:
s1: adding TiO into the mixture2Dispersing the nano particles and the hexamethylene tetramine in 10mol/L NaOH solution, magnetically stirring for 0.5-1 h by using a magnetic stirrer, and uniformly mixing;
s2: reacting the mixed solution obtained in the step S1 at 140-160 ℃ for 36-48 h, cooling to room temperature, and centrifuging;
s3: pouring out the supernatant of the solution centrifuged in the step S2, filtering the obtained precursor material, washing the precursor material with hydrochloric acid and deionized water until the pH is 7, and drying the precursor material at 60 ℃ for 8 hours;
s4: calcining the dried precursor material in the step S3 for 2h in Ar atmosphere at the calcining temperature of 350 ℃ and the heating rate of 2 ℃/min to obtain TiO2-B-NTs。
2. A process according to claim 1The obtained multifunctional ultralong TiO2-B nanotube material.
3. The multifunctional ultra-long TiO of claim 22-B nanotube material preparation lithium ion battery negative electrode material method, characterized by, including the following steps:
1) adding TiO into the mixture2Mixing the-B-NTs material, the carbon nano tube, the polyvinylidene fluoride and the N-methyl pyrrolidone to obtain first slurry;
2) coating the first slurry in the step 1) on a copper foil with the thickness of 0.25-0.5 mm, and drying for 12-16 h at the temperature of 60-80 ℃ in vacuum to obtain the multifunctional ultralong TiO2-B nanotube lithium ion battery negative electrode.
4. The multifunctional ultralong TiO of claim 32The method for preparing the lithium ion battery cathode material by using the-B nanotube material is characterized in that the ratio of the mass part of polyvinylidene fluoride to the volume part of N-methylpyrrolidone in the step 1) is 1:5 to 6.
5. Multifunctional ultralong TiO prepared by the preparation method of claim 3 or 42-B nanotube lithium ion battery negative electrode material.
6. The multifunctional ultralong TiO of claim 52-B nanotube lithium ion battery cathode material, characterized in that multifunctional ultralong TiO in the lithium ion battery cathode material2The content of the-B nano tube is 1.5-2.0 mg/cm2。
7. The multifunctional ultra-long TiO of claim 22-B nanotube material method for the preparation of a lithium sulphur battery positive electrode material, characterized in that it comprises the following steps:
(1) under high power ultrasonic wave, TiO is mixed2-B-NTs material, carbon nanotubes and sulphur in a weight ratio of 2.5:0.5:1 to CS2In solution until CS2Completely evaporating to form a mixture;
(2) transferring the mixture obtained in the step (1) into a high-pressure reaction kettle, heating at 155 ℃ and standing for 24 hours to obtain the lithium-sulfur battery active material;
(3) and (3) mixing the lithium-sulfur battery active material obtained in the step (2), a carbon black conductive agent, polyvinylidene fluoride and N-methylpyrrolidone in a mass ratio of 8-7: 1-2: 1, obtaining a second slurry, coating the second slurry on an aluminum foil, and drying for 12-16 h at the temperature of 60-80 ℃ in vacuum to obtain the multifunctional ultralong TiO2-B nanotube lithium-sulfur battery positive electrode material.
8. The multifunctional ultralong TiO of claim 72The method for preparing the lithium-sulfur battery cathode material from the B nanotube material is characterized in that in the step (3), the ratio of the mass part of polyvinylidene fluoride to the volume part of N-methylpyrrolidone is 1: 5-6, the thickness of the aluminum foil is 0.25-0.5 mm.
9. Multifunctional ultralong TiO prepared by the preparation method of claim 7 or 82-B nanotube lithium-sulfur battery positive electrode material.
10. The multifunctional ultralong TiO of claim 92-B nanotube lithium-sulfur battery positive electrode material, characterized in that said multifunctional ultralong TiO2The sulfur content in the cathode material of the-B nanotube lithium-sulfur battery is 1.5mg/cm2。
CN202110737395.3A 2021-06-30 2021-06-30 Multifunctional ultralong TiO2-B nanotube material, preparation method and application thereof Active CN113511674B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110737395.3A CN113511674B (en) 2021-06-30 2021-06-30 Multifunctional ultralong TiO2-B nanotube material, preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110737395.3A CN113511674B (en) 2021-06-30 2021-06-30 Multifunctional ultralong TiO2-B nanotube material, preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN113511674A true CN113511674A (en) 2021-10-19
CN113511674B CN113511674B (en) 2022-04-19

Family

ID=78066457

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110737395.3A Active CN113511674B (en) 2021-06-30 2021-06-30 Multifunctional ultralong TiO2-B nanotube material, preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN113511674B (en)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103693681A (en) * 2013-12-11 2014-04-02 贵州中烟工业有限责任公司 Method for preparing super-long titanate micro/nanotubes
CN105271388A (en) * 2015-10-10 2016-01-27 同济大学 Preparation method of high specific surface area ultralong TiO2 nanotube
CN105406042A (en) * 2015-11-16 2016-03-16 中国海洋大学 Preparation method for carbon-coated super-long titanium dioxide nanotube negative electrode material of lithium ion battery
CN106207112A (en) * 2016-07-15 2016-12-07 湖北工业大学 Graphene/overlength TiO2(B) nanometer tube composite materials and preparation method thereof
CN108993470A (en) * 2018-08-02 2018-12-14 福州大学 A kind of preparation and application of the double array structure catalysis materials of titanium dioxide/graphene/zinc oxide
CN109546095A (en) * 2017-09-22 2019-03-29 银隆新能源股份有限公司 A kind of preparation method of lithium ion battery negative material
CN112510170A (en) * 2019-09-16 2021-03-16 河北工业大学 Nitrogen and sulfur double-doped porous carbon lithium sulfur battery positive electrode material and preparation method and application thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103693681A (en) * 2013-12-11 2014-04-02 贵州中烟工业有限责任公司 Method for preparing super-long titanate micro/nanotubes
CN105271388A (en) * 2015-10-10 2016-01-27 同济大学 Preparation method of high specific surface area ultralong TiO2 nanotube
CN105406042A (en) * 2015-11-16 2016-03-16 中国海洋大学 Preparation method for carbon-coated super-long titanium dioxide nanotube negative electrode material of lithium ion battery
CN106207112A (en) * 2016-07-15 2016-12-07 湖北工业大学 Graphene/overlength TiO2(B) nanometer tube composite materials and preparation method thereof
CN109546095A (en) * 2017-09-22 2019-03-29 银隆新能源股份有限公司 A kind of preparation method of lithium ion battery negative material
CN108993470A (en) * 2018-08-02 2018-12-14 福州大学 A kind of preparation and application of the double array structure catalysis materials of titanium dioxide/graphene/zinc oxide
CN112510170A (en) * 2019-09-16 2021-03-16 河北工业大学 Nitrogen and sulfur double-doped porous carbon lithium sulfur battery positive electrode material and preparation method and application thereof

Also Published As

Publication number Publication date
CN113511674B (en) 2022-04-19

Similar Documents

Publication Publication Date Title
Chu et al. NiO nanocrystals encapsulated into a nitrogen-doped porous carbon matrix as highly stable Li-ion battery anodes
CN108695495B (en) Reduced graphene oxide modified antimony trisulfide battery cathode material
US8685550B2 (en) Bacteria/transition metal oxides organic-inorganic composite and method for manufacturing the same
CN108493425B (en) Preparation method of Sn4P3 nanoparticle sodium ion battery cathode material coated by mesoporous carbon nanotube
Li et al. Facile synthesis of nanocrystalline-assembled nest-like NiO hollow microspheres with superior lithium storage performance
Barqi et al. Nanoribbon-like NiCo2O4/reduced graphene oxide nanocomposite for high-performance hybrid supercapacitor
CN110880589B (en) Carbon nanotube @ titanium dioxide nanocrystal @ carbon composite material and preparation method and application thereof
CN110838583B (en) Carbon nanotube/M-phase vanadium dioxide composite structure, preparation method thereof and application thereof in water-based zinc ion battery
Sun et al. Construction of KCu7S4@ NiMoO4 three-dimensional core-shell hollow structure with high hole mobility and fast ion transport for high-performance hybrid supercapacitors
CN112736235B (en) Biomass/carbon nanotube induced Fe 3 O 4 Nanocomposite and application thereof as lithium ion battery anode material
CN109473643B (en) CoSe2Preparation method and application of graphene composite material
CN110350170A (en) A kind of preparation method of lithium titanate/graphene composite material
CN108091868B (en) Multi-dimensional composite high-performance lithium ion battery cathode material and preparation method thereof
CN114242983A (en) V-shaped groove3S4@ C composite material and preparation method and application thereof
CN109767925A (en) T-Nb for lithium ion super capacitor2O5/ egg white carbon composite and preparation method thereof
Majeed et al. Metal–organic framework mediated nickel doped copper ferrite for superior lithium storage
CN110482604B (en) Cu2V2O7Nanorod potassium ion battery positive electrode material, potassium ion battery and preparation method thereof
CN113571681B (en) Hollow titanium dioxide/nickel/carbon composite material and preparation method and application thereof
Wu et al. Fe2O3/carbon derived from peanut shell hybrid as an advanced anode for high performance lithium ion batteries
CN113410459B (en) Embedded MoS x Three-dimensional ordered macroporous graphene carbon material of nanosheet, preparation and application
CN113782713B (en) MoS 2 Nano-sheet vertically embedded biological carbon nano composite material and preparation method and application thereof
CN112736234B (en) Novel lithium ion battery anode material based on biomass/carbon nanotube composite modified lithium titanate and application thereof
Li et al. Fe-functionalized mesoporous carbonaceous microsphere with high sulfur loading as cathode for lithium-sulfur batteries
Tong et al. Mn3O4 nanocrystalline@ carbon nanotube-carbon nanotube for long-lifetime and excellent rate-capability zinc-ion storage
CN109786709B (en) Ferroferric oxide/carbon composite negative electrode material and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant