CN112768681A - Hollow Ti4O7Positive electrode material of lithium-sulfur battery - Google Patents

Hollow Ti4O7Positive electrode material of lithium-sulfur battery Download PDF

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CN112768681A
CN112768681A CN202110248922.4A CN202110248922A CN112768681A CN 112768681 A CN112768681 A CN 112768681A CN 202110248922 A CN202110248922 A CN 202110248922A CN 112768681 A CN112768681 A CN 112768681A
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hollow
nanospheres
sulfur
lithium
electrode material
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雷毅敏
武德凯
胡启航
杨成哲
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Xidian University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • 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

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  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Electrochemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
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Abstract

The invention discloses a hollow Ti4O7The positive electrode material of the lithium-sulfur battery is hollow Ti loaded with sulfur4O7Nanospheres of said hollow Ti4O7The nanosphere has an outer diameter of 400-700 nm, an inner diameter of 330-650 nm, and a specific surface area of 160-190 m2The load of the sulfur is 60 to 80 percent; it is in hollow TiO2Coating a layer of dopamine hydrochloride (PDA) on the surface of the nanosphere to form TiO2And annealing the @ PDA nanospheres in an inert atmosphere at 850-1000 ℃. Hollow Ti of the invention4O7The preparation method of the nanosphere is simple, low in cost and environment-friendly, and the nanosphere is used as a carrier loaded with sulfurThe lithium-sulfur battery cathode material has excellent electrochemical performance.

Description

Hollow Ti4O7Positive electrode material of lithium-sulfur battery
Technical Field
The invention belongs to the technical field of lithium-sulfur battery anode materials, and particularly relates to Ti with good cycle stability and excellent rate performance4O7Nanosphere lithium-sulfur batteryAnd (3) a positive electrode material.
Background
The energy problem always puzzles human beings, and the demand of people for energy is increasing day by day. The lithium-sulfur battery is a new high-efficiency and clean technology, and has become a hot spot for developing new energy in the world nowadays. However, lithium sulfur batteries still have many problems: (1) elemental sulfur of the cathode has very poor conductivity, which is not beneficial to improving the rate capability of the lithium-sulfur battery; (2) lithium polysulfide generated in the charging and discharging process is easily dissolved in the organic electrolyte, and the ionic conductivity is reduced. Meanwhile, the shuttle effect enables the capacity of the lithium-sulfur battery to be quickly attenuated, so that the cycling stability of the battery is poor; (3) volume expansion is easy to occur in sulfur in the charging and discharging processes, and the expansion causes changes of the appearance and the structure of a cathode material, so that the sulfur is separated from a conductive framework, and the attenuation of the battery capacity is caused. Therefore, the development of new cathode materials has become a key to improving the performance of lithium sulfur batteries.
Titanium oxide, Ti, as a non-stoichiometric proportion4O7Has higher conductivity (1995S/m) and excellent chemical and electrochemical stability, so that the method has a plurality of researches and applications in the fields of fuel cells, lithium-sulfur cells, photocatalysis, electrocatalysis and the like. The titanium oxide has two abrupt change modes of conductivity at different temperatures, one mode is semiconductor-semiconductor transition occurring at the temperature of 130-140K, and the other mode is semiconductor-metal transition occurring at the temperature of 150K, so that the titanium oxide with high conductivity has potential application value in the field of lithium-sulfur batteries. Mei et al (Nature Communications,2016,7:13065.) with PS-P2Preparing cross-linked porous Ti by using VP as template and PDA as reducing agent4O7@ PDA nanoparticles, which provide a polar surface for their encapsulated sulfur, and also enable chemisorption of lithium polysulfides to inhibit their dissolution. Thus, Ti4O7Is a novel lithium-sulfur battery anode material with great popularization potential. However, the above reduction method has harsh conditions, and the prepared Ti4O7Generally, the Ti alloy has large grain diameter, uneven appearance and small specific surface area, and can generate serious grain coarsening phenomenon, which are unfavorable for improving the sulfur content in Ti4O7The loading capacity of the material is further not beneficial to improving the specific capacity, rate capability and cycling stability of the lithium-sulfur battery, which seriously influences Ti4O7The material is applied to the field of lithium-sulfur batteries. Therefore, a hollow Ti having a large specific surface area was developed4O7The lithium-sulfur battery positive electrode material can expand the application of non-stoichiometric titanium oxide materials and has important theoretical and practical significance.
Disclosure of Invention
The invention aims to provide a hollow Ti with good cycle stability and excellent rate capability aiming at the defects of the prior materials and the prior art4O7A positive electrode material for a lithium-sulfur battery,
to achieve the above object, the present invention adopts hollow Ti4O7The positive electrode material of the lithium-sulfur battery is hollow Ti loaded with sulfur4O7Nanospheres of said hollow Ti4O7The nanosphere has an outer diameter of 400-700 nm, an inner diameter of 330-650 nm, and a specific surface area of 160-190 m2The mass content of sulfur in the positive electrode material is 60-80%.
The above hollow Ti4O7The lithium-sulfur battery positive electrode material is prepared by the following method:
1. mixing hollow TiO2Uniformly dispersing the nanospheres in Tris-HCl buffer solution with the pH value of 8.0-9.0, adding dopamine hydrochloride, stirring at room temperature for 20-30 hours, centrifugally washing, and drying to obtain hollow TiO2@ PDA nanosphere.
2. Mixing hollow TiO2Annealing the @ PDA nanosphere for 10-40 minutes at 850-1000 ℃ in inert atmosphere to obtain hollow Ti4O7Nanospheres.
3. With hollow Ti4O7The nanospheres are used as carriers, and sulfur is carried by adopting a melting-diffusion method.
In the step 1, the dopamine hydrochloride and the hollow TiO are mixed2The mass ratio of the nanospheres is 1: 0.5-7. Wherein the hollow TiO2The nanosphere has an outer diameter of 400-700 nm, an inner diameter of 300-600 nm, and a specific surface area of 100-130 m2/g。
In the step 2, preferably, the hollow TiO is used2@ PDA nanospheres were annealed at 950 ℃ for 15 minutes under an argon atmosphere. The flow rate of the argon is 90-120 mL/min.
In the step 2, the temperature rise rate of annealing is more preferably 20 to 25 ℃/min.
The invention has the following beneficial effects:
1. hollow Ti of the invention4O7The preparation method of the nanosphere is simple, the used reactant solvent and reaction product are environment-friendly, and the obtained Ti is4O7The nanosphere has small particle size, uniform appearance, large specific surface area, high sulfur loading and obviously improved oxygen reduction activity.
2. Hollow Ti loaded with sulfur of the invention4O7The nanosphere is used as the anode material of the lithium-sulfur battery, and is hollow Ti4O7The nanosphere can effectively accelerate the transmission speed of electrons in the electrode and increase the effective contact area of the electrode material and the electrolyte, thereby accelerating the reaction rate of the battery, and meanwhile, the nanosphere is hollow Ti4O7The cavity inside the nanosphere can trap or confine polysulfide and other intermediates, thereby reducing the loss of electrode capacity caused by the shuttle effect. Further, hollow Ti4O7The nanospheres can absorb stress caused by volume change of the active material during battery cycling, so that the battery has good cycling stability and excellent rate performance. The positive electrode material solves the problem of poor stability of the lithium-sulfur battery, realizes effective adsorption of lithium polysulfide, and improves the specific capacity and the cycling stability of the battery.
Drawings
FIG. 1 is a hollow Ti prepared in example 14O7XRD pictures of nanospheres.
FIG. 2 is a hollow Ti prepared in example 14O7SEM photograph of nanospheres.
FIG. 3 is a hollow Ti prepared in example 14O7TEM photograph of nanospheres.
FIG. 4 is a hollow Ti prepared in example 14O7BET of nanospheresFigure (a).
FIG. 5 shows hollow Ti loaded with sulfur in example 14O7TG profile of nanospheres.
FIG. 6 shows a sulfur-supporting hollow Ti in example 14O7CV graph of nanospheres.
FIG. 7 shows a sulfur-supporting hollow Ti in example 14O70.2C cycle plot of nanospheres.
FIG. 8 shows a sulfur-supporting hollow Ti in example 14O7Constant current charge and discharge diagrams of different current densities of the nanospheres.
Detailed Description
The invention will be further described in detail with reference to the following figures and examples, but the scope of the invention is not limited to these examples.
Hollow TiO in the following examples2The nanosphere is prepared by the following method:
1. preparation of SiO2Nanosphere
10g of deionized water, 58.5g of absolute ethyl alcohol and 4.25mL of 25% ammonia water are uniformly mixed and then placed in a constant-temperature water bath kettle at the temperature of 30 ℃ and stirred for 30min at the rotating speed of 300 rpm. Then 5.6mL tetraethyl silicate is added drop by drop, stirred vigorously for 1h, washed by deionized water and absolute ethyl alcohol, and dried for 24h at 60 ℃ to obtain SiO2Nanospheres.
2. Preparation of TiO2@SiO2Nanosphere
0.2g of SiO are weighed2And ultrasonically dispersing the nanospheres in 150mL of absolute ethyl alcohol, dropwise adding 0.9mL of 25% ammonia water into the mixed solution, and stirring for 1 h. Then dropwise adding 2mL of tetrabutyl titanate within 10min, stirring for 24h at 45 ℃, washing with deionized water and absolute ethyl alcohol, and drying for 24h at 60 ℃ to obtain amorphous TiO2@SiO2Nanospheres; adding amorphous TiO2@SiO2Placing the nanospheres in a muffle furnace, heating to 500 ℃ at the heating rate of 2 ℃/min, and keeping the temperature for 5h to obtain crystalline TiO2@SiO2Nanospheres.
3. Preparation of hollow TiO2Nanosphere
Adding 4g NaOH into 200mL deionized water, stirring for 30min, and adding crystalline TiO2@SiO2Carrying out ultrasonic stirring on the nanospheres for 5 min; then placing the mixture into a constant-temperature water bath kettle with the temperature of 80 ℃, stirring for 2h, washing with deionized water and absolute ethyl alcohol, and drying at 60 ℃ for 24h to obtain hollow TiO2Nanospheres having an outer diameter of 400nm, an inner diameter of 370nm and a specific surface area of 140m2/g。
Example 1
1. 0.30g of hollow TiO2Nanosphere (400 nm outer diameter, 370nm inner diameter, 140m specific surface area)2/g) is evenly dispersed in 50mL Tris-HCl buffer solution with pH value of 8.5, 0.15g dopamine hydrochloride is added after stirring for 15min, stirring is continued for 24h at room temperature, centrifugal washing is sequentially carried out by deionized water and absolute ethyl alcohol, drying is carried out for 24h at 60 ℃, and hollow TiO is obtained2@ PDA nanosphere.
2. Mixing hollow TiO2Heating up the @ PDA nanosphere to 950 ℃ at the heating rate of 21.23 ℃/min under the argon atmosphere with the flow rate of 500mL/min, and annealing at constant temperature for 15min to obtain hollow Ti4O7Nanospheres.
Prepared hollow Ti by X-ray diffractometer4O7The nanospheres were subjected to phase characterization, and the results are shown in fig. 1; hollow Ti prepared by adopting scanning electron microscope and transmission electron microscope4O7Performing morphology characterization on the nanospheres, wherein the results are shown in the figure 2-3; adopting physical adsorption instrument to prepare hollow Ti4O7The nanospheres were characterized for specific surface area and the results are shown in figure 4. XRD characterization phase of figure 1 is Ti4O7(ii) a As can be seen from FIGS. 2 to 3, the hollow Ti is obtained by annealing and reduction in an argon atmosphere4O7The nanosphere retains hollow TiO2The precursor has regular shape, the outer diameter is 450nm, and the inner diameter is 360 nm. The results of FIGS. 1 to 3 are combined to show that hollow Ti is obtained4O7Nanospheres. According to the hollow Ti in FIG. 44O7N of nanospheres2The absorption and desorption curves are calculated to obtain the specific surface area of 186.479m2/g。
3. Mixing the above hollow Ti4O7The nanosphere adopts a melting-diffusion methodCarrying sulfur, mixing sulfur and hollow Ti4O7Mixing and grinding the nanospheres according to the mass ratio of 7:3, then filling the nanospheres into a 10mL reaction kettle, transferring the nanospheres into a glove box, filling nitrogen into the glove box, and reacting the nanospheres in a vacuum drying box at the temperature of 155 ℃ for 20 hours to obtain the sulfur-loaded hollow Ti4O7Nanospheres.
The hollow Ti loaded with sulfur is used4O7The nanospheres were TG characterized and the results are shown in figure 5. Hollow Ti loaded with sulfur4O7The nanospheres are used as the anode material to assemble the lithium-sulfur battery, and the electrochemical performance test is carried out, and the result is shown in FIGS. 6-8. As can be seen from FIG. 5, the hollow Ti4O7The sulfur loading of the nanospheres is up to 77%. Analysis from the CV plot of FIG. 6 reveals that the reduction peak at 2.22V, for the low-order polysulfide, is further towards Li2Conversion of S, the oxidation peak at 2.43V corresponds to Li2The conversion of S to S, the first and third curves have better repeatability, which shows that the sulfur-loaded hollow Ti is4O7The electrochemical reversibility of the nanosphere is good. As can be seen from FIG. 7, the initial discharge capacity was 1355mAh/g at a current density of 0.2C, which remained 612.8mAh/g after 100 cycles, indicating sulfur-loaded hollow Ti4O7The capacity retention rate of the nanospheres is good. As can be seen from the results of constant current charge and discharge tests at different current densities in FIG. 8, the sulfur-loaded hollow Ti4O7The nanospheres still have two obvious discharge platforms under the current density of 2C, and the electrode material is shown to have excellent cycle performance.
Example 2
In the step 1 of this example, 0.05g of dopamine hydrochloride was added after stirring for 15min, and the other steps were the same as in example 1 to obtain sulfur-loaded hollow Ti4O7Nanospheres of hollow Ti4O7The nanosphere has an outer diameter of 600nm, an inner diameter of 520nm, and a specific surface area of 172.285m2G, hollow Ti4O7The sulfur loading of the nanospheres was 72%.
Example 3
In step 2 of this example, a hollow TiO is added2@ PDA nanosphere, heating to 1000 deg.C at a heating rate of 15 deg.C/min, annealing at constant temperature for 30min, and other stepsSulfur-supporting hollow Ti was obtained in the same manner as in example 14O7Nanospheres of hollow Ti4O7The nanosphere has an outer diameter of 700nm, an inner diameter of 620nm, and a specific surface area of 163.745m2G, hollow Ti4O7The sulfur loading of the nanospheres was 65%.

Claims (6)

1. Hollow Ti4O7The lithium-sulfur battery positive electrode material is characterized in that: the anode material is hollow Ti loaded with sulfur4O7Nanospheres of hollow Ti4O7The nanosphere has an outer diameter of 400-700 nm, an inner diameter of 330-650 nm, and a specific surface area of 160-190 m2The mass content of sulfur in the positive electrode material is 60-80%;
the positive electrode material is prepared by the following method:
(1) mixing hollow TiO2Uniformly dispersing the nanospheres in Tris-HCl buffer solution with the pH value of 8.0-9.0, adding dopamine hydrochloride, stirring at room temperature for 20-30 hours, centrifugally washing, and drying to obtain hollow TiO2@ PDA nanospheres;
(2) mixing hollow TiO2Annealing the @ PDA nanosphere for 10-40 minutes at 850-1000 ℃ in inert atmosphere to obtain hollow Ti4O7Nanospheres;
(3) with hollow Ti4O7The nanospheres are used as carriers, and sulfur is carried by adopting a melting-diffusion method.
2. The hollow Ti of claim 14O7The lithium-sulfur battery positive electrode material is characterized in that: in the step (1), the dopamine hydrochloride and the hollow TiO are mixed2The mass ratio of the nanospheres is 1: 0.5-7.
3. The hollow Ti of claim 1 or 24O7The lithium-sulfur battery positive electrode material is characterized in that: in the step (1), the hollow TiO2The nanosphere has an outer diameter of 400-700 nm, an inner diameter of 300-600 nm, and a specific surface area of 100-130 m2/g。
4. The hollow Ti of claim 14O7The lithium-sulfur battery positive electrode material is characterized in that: in the step (2), the hollow TiO is treated2@ PDA nanospheres were annealed at 950 ℃ for 15 minutes under an argon atmosphere.
5. The hollow Ti of claim 1 or 44O7The lithium-sulfur battery positive electrode material is characterized in that: in the step (2), the annealing temperature rise rate is 20-25 ℃/min.
6. The hollow Ti of claim 44O7The lithium-sulfur battery positive electrode material is characterized in that: in the step (2), the flow rate of the argon is 90-120 mL/min.
CN202110248922.4A 2021-03-08 2021-03-08 Hollow Ti4O7Positive electrode material of lithium-sulfur battery Pending CN112768681A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115911329A (en) * 2022-12-02 2023-04-04 中南民族大学 Titanium dioxide microsphere loaded by sulfur hollow sphere and preparation method and application thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108383154A (en) * 2018-04-03 2018-08-10 陕西师范大学 A kind of hollow mesoporous Ti with bigger serface4O7The preparation method of@C nano balls

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108383154A (en) * 2018-04-03 2018-08-10 陕西师范大学 A kind of hollow mesoporous Ti with bigger serface4O7The preparation method of@C nano balls

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115911329A (en) * 2022-12-02 2023-04-04 中南民族大学 Titanium dioxide microsphere loaded by sulfur hollow sphere and preparation method and application thereof
CN115911329B (en) * 2022-12-02 2024-06-07 中南民族大学 Sulfur hollow sphere-loaded titanium dioxide microsphere and preparation method and application thereof

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Application publication date: 20210507