CN108832098B - Lithium-sulfur battery positive electrode S @ TiO2Polypyrrole composite material and preparation method thereof - Google Patents
Lithium-sulfur battery positive electrode S @ TiO2Polypyrrole composite material and preparation method thereof Download PDFInfo
- Publication number
- CN108832098B CN108832098B CN201810614877.8A CN201810614877A CN108832098B CN 108832098 B CN108832098 B CN 108832098B CN 201810614877 A CN201810614877 A CN 201810614877A CN 108832098 B CN108832098 B CN 108832098B
- Authority
- CN
- China
- Prior art keywords
- tio
- polypyrrole
- sulfur
- lithium
- preparation
- 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.)
- Active
Links
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- 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
-
- 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
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
-
- 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 provides S @ TiO with a core-shell structure for a lithium-sulfur battery positive electrode2The preparation method of the/polypyrrole composite material specifically comprises the following steps: firstly, resorcinol-formaldehyde resin spheres are taken as a sacrificial template, and then butyl titanate is taken as a raw material to uniformly cover a layer of Ti (OH) on the resorcinol-formaldehyde resin spheres4By high temperature calcination to obtain TiO2Filling sulfur into hollow spheres by a hot melting method to obtain S @ TiO2The composite structure is prepared by preparing polypyrrole nano-wires by a chemical oxidation method and finally stirring S @ TiO by ultrasonic2Uniformly compounded with polypyrrole nano-wires to form S @ TiO2The hollow sphere is externally wound with a composite structure of polypyrrole nano wires. The structure can effectively inhibit the diffusion of polysulfide and the volume expansion in the charge-discharge process, and the polypyrrole nanowire with high conductivity can perform effective electron conduction, so that the electrochemical performance of the lithium-sulfur battery is improved by the synergistic effect of the polypyrrole nanowire and the polypyrrole.
Description
Technical Field
The invention relates to S @ TiO with a core-shell structure for a lithium-sulfur battery positive electrode2A polypyrrole composite material and a preparation method thereof, belonging to the field of battery materials.
Background
With the increasingly prominent energy and environmental problems and the rapid development of electronic and electric equipment, the conventional lithium ion battery has low energy density and is difficult to meet the requirements of people on high-power batteries and high-energy storage. Therefore, how to develop a novel energy storage component with high specific capacity, long cycle life and high safety performance is a problem to be solved urgently at present.
The lithium-sulfur battery using elemental sulfur as the anode material has higher theoretical specific capacity (1675 mAh/g) and theoretical specific energy (2600 Wh/kg), which is 3-5 times of the lithium ion batteries of lithium cobaltate, lithium iron phosphate and the like. In addition, the elemental sulfur also has the advantages of low toxicity, large reserves, low price and the like. Therefore, the lithium-sulfur battery using elemental sulfur as a positive electrode material and metal lithium as a negative electrode material is a new energy device with great prospect. Has extremely high research value and application prospect.
However, lithium sulfur batteries also currently present a number of challenges: (1) the low conductivity of the elemental sulfur reduces the electrochemical utilization rate of the active substance and seriously influences the transmission of electrons on the anode; (2) the change of the volume appearance of the sulfur anode in the circulation affects the stability of the anode structure and the electron transmission, thereby causing capacity attenuation; (3) the formation, dissolution and migration of lithium polysulfide in electrolyte can seriously affect the electrochemical utilization rate, rate capability and cycle life of active substances in the lithium-sulfur battery; (4) lithium dendrite generated on the surface of the lithium negative electrode during the cycle may damage the separator to cause a safety problem.
The core-shell structure of coating the surface of sulfur with a layer of conductive polymer/polar metal oxide is considered to be an effective way for solving the problems of low conductivity of elemental sulfur, volume expansion of a sulfur positive electrode in circulation and the like. The resorcinol-formaldehyde resin spheres prepared by the hydrothermal method of ZHOU Wencui et al are sacrificial templates with wide application prospect. (Controllable preparation and application of carbon spheres based on regenerative-regenerative resin in. Journal of Zhejiang Sci-Tech University (Natural Sciences), Vol.39, No.2, Mar.2018) the precursor of the metal oxide is uniformly coated on the surface of the resorcinol-formaldehyde resin spheres, and the metal oxide nanospheres with hollow structure can be obtained by calcining.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides S @ TiO with a core-shell structure2A preparation method of a polypyrrole composite material. The material isThe structure can accommodate volume change of sulfur in the charging and discharging process, and can adsorb polysulfide to relieve shuttle effect, thereby improving the cycle stability of the lithium-sulfur battery.
In order to achieve the purpose, the invention adopts the technical scheme that:
s @ TiO with core-shell structure for positive electrode of lithium-sulfur battery2The preparation method of the/polypyrrole composite material comprises the following steps:
(1) dispersing resorcinol-formaldehyde resin spheres as a template and cetyl trimethyl ammonium bromide as a surfactant into absolute ethyl alcohol, uniformly mixing, slowly adding tetrabutyl titanate into the mixed solution, stirring at room temperature for 8-12 hours, centrifugally separating, and calcining the product at high temperature to obtain TiO2A hollow ball.
(2) Dissolving sublimed sulfur in carbon disulfide solution, stirring until sulfur is completely dissolved, and adding the sulfur into the TiO obtained in the step (1)2The hollow ball is ultrasonically treated to form uniform mixed suspension, the suspension is stirred at room temperature until the suspension is volatilized and dried, then the suspension is transferred into a polytetrafluoroethylene stainless steel reaction kettle under the argon atmosphere, and the temperature is maintained at 120 ℃ and 180 ℃ for 12 to 16 hours to obtain S @ TiO2A hollow ball.
(3) Dispersing cetyl trimethyl ammonium bromide and pyrrole into deionized water, uniformly mixing, slowly adding an ammonium persulfate aqueous solution into the mixed solution, stirring in an ice water bath for 1-4 hours, centrifugally washing, and then drying the product in vacuum to obtain the polypyrrole nano wire.
(4) The S @ TiO obtained in the step (2)2Ultrasonically dispersing the hollow spheres and the polypyrrole nanowires obtained in the step (3) in absolute ethyl alcohol uniformly, and stirring at 50-90 ℃ until the mixture is dried to obtain S @ TiO with the core-shell structure2A/polypyrrole composite material.
In the scheme, the diameter of the resorcinol-formaldehyde resin spheres in the step (1) is 200nm-600 nm.
In the scheme, the concentration of the hexadecyl trimethyl ammonium bromide in the step (1) is 0.2 mmol/L-1.5 mmol/L.
In the scheme, the molar ratio of the resorcinol-formaldehyde resin spheres to the tetrabutyl titanate in the step (1) is 1: (0.1-1.0).
In the scheme, the high-temperature calcination in the step (1) has the temperature rise rate of 2-5 ℃/min, the heat preservation temperature of 400-.
In the above scheme, the TiO in the step (1)2The diameter of the hollow sphere is 100nm-500 nm.
In the above scheme, the TiO in the step (2)2The mass ratio of the hollow ball to the sublimed sulfur is 1: (1-10).
In the scheme, the concentration of the carbon disulfide solution of sublimed sulfur in the step (2) is 1-5 mg/ml.
In the scheme, the mole ratio of the hexadecyl trimethyl ammonium bromide to the pyrrole to the ammonium persulfate in the step (3) is 16: (4-64): (4-64) wherein the concentration of cetyltrimethylammonium bromide is 1.6X 10-2mol/L, and the molar ratio of pyrrole to ammonium persulfate is 1: 1.
In the scheme, the diameter of the polypyrrole nanowire in the step (3) is 20-80nm, and the length of the polypyrrole nanowire is 1-5 μm.
The principle of the invention is as follows: the invention adopts a hard template method, uses resorcinol-formaldehyde resin spheres as a hard template and tetrabutyl titanate as a precursor, and removes the template through high-temperature calcination to obtain TiO with uniform particle size2A hollow ball; filling sulfur by a hot melting method to obtain S @ TiO2A composite structure; the method adopts a soft template method, uses cetyl trimethyl ammonium bromide as a soft template, uses ammonium persulfate as an oxidant, and dries the product in vacuum to obtain the polypyrrole nano-wire; the invention adopts ultrasonic dispersion to disperse S @ TiO2Uniformly compounding with polypyrrole to obtain S @ TiO2A/polypyrrole composite structure.
The invention has the beneficial effects that: the S @ TiO with the core-shell structure is synthesized for the first time2/polypyrrole composite structures, TiO2The hollow ball effectively accommodates volume expansion of sulfur in the charging and discharging processes of the lithium-sulfur battery, and meanwhile, the polar material TiO2Has certain inhibiting effect on the dissolution of polysulfide. The conductive network formed by polypyrrole effectively improves the conductivity of the anode material, and improvesCycling stability of lithium sulfur batteries.
Drawings
FIG. 1 shows TiO prepared in example 12SEM image of hollow spheres.
Fig. 2 is an SEM image of polypyrrole nanowires prepared in example 1.
FIG. 3 is S @ TiO prepared in example 12SEM image of/polypyrrole nanowire recombination.
FIG. 4 is S @ TiO prepared in example 12And the cycle performance diagram of the lithium-sulfur battery taking the/polypyrrole composite material as the cathode material is that the lithium-sulfur battery is charged and discharged for 200 times at 1C.
Detailed Description
The following examples further illustrate the present invention but do not limit the scope of the invention.
S @ TiO of the invention2The polypyrrole composite material is applied to the lithium-sulfur battery, and the specific test process is as follows: prepared S @ TiO in an argon-protected glove box2Polypyrrole as a positive electrode, Celgard 2300 as a separator, a lithium metal plate as a negative electrode, and LiTFSI (DOL/DME 1:1) of 1.0mol/L to which LiNO of 0.1mol/L was added3The battery was assembled as an electrolyte. In the charge and discharge test system, the charge and discharge test voltage is 1.5V-3.0V.
Example 1
Dispersing 300mg resorcinol-formaldehyde resin spheres with the particle size of 500nm in 40ml absolute ethyl alcohol, taking 0.5 mmol/L cetyl trimethyl ammonium bromide as a surfactant, stirring for 2 hours, and then centrifugally washing with the absolute ethyl alcohol.
Dispersing the modified resorcinol-formaldehyde resin spheres in 40ml of absolute ethyl alcohol, measuring 240 mu L of tetrabutyl titanate to be dissolved in 20ml of absolute ethyl alcohol, dripping the ethanol solution of the tetrabutyl titanate into the resorcinol-formaldehyde resin sphere dispersion liquid at the dripping speed of 5ml/min, and stirring for 12 hours at room temperature.
And centrifugally washing the stirred mixed solution, drying at 60 ℃, transferring into a muffle furnace, and carrying out temperature rise at the rate of 2 ℃/min, heat preservation at the temperature of 550 ℃, heat preservation for 3 hours and temperature reduction at the rate of 5 ℃/min. To obtain TiO2A hollow ball.
70mg ofDissolving sublimed sulfur in CS2To the solution, 20mg of TiO was added2Hollow spheres were stirred at room temperature to dryness. Sulfur and TiO2Transferring the mixture of the hollow spheres into a polytetrafluoroethylene stainless steel reaction kettle under the protection of argon atmosphere, and preserving the heat at 155 ℃ for 12 hours to obtain S @ TiO2And (c) a complex.
A500 ml three-neck flask is taken, 200ml deionized water, 0.0032mol hexadecyl trimethyl ammonium bromide and 0.0032mol pyrrole are sequentially added, the mixture is stirred for 2 hours at 0 ℃, ammonium persulfate aqueous solution with the same molar ratio with the pyrrole is added, and the mixture is stirred for 2 hours at 0 ℃. And centrifuging and filtering the reacted mixed solution, and performing vacuum drying at 60 ℃ for 12h to obtain the polypyrrole nano wire.
Adding S @ TiO2Dispersing the compound and 10mg of polypyrrole nano wire in an absolute ethyl alcohol solution, and stirring at 60 ℃ until the mixture is dried to obtain S @ TiO2A/polypyrrole composite material.
Adding S @ TiO2Uniformly mixing the polypyrrole composite material, the ketjen black and the PVDF according to the mass ratio of 7:2:1, adjusting the concentration by using N-methyl pyrrolidone, and stirring for 4 hours to prepare slurry. Coating the prepared slurry on a current collector by a blade coating method, and drying for 12 hours at 60 ℃ in a vacuum environment. Circular pole pieces 16mm in diameter were cut and assembled for battery testing.
FIG. 1 shows TiO prepared in this example2SEM image of hollow sphere, from which we can see that we succeeded in preparing TiO with a diameter of 200nm2A hollow ball. Fig. 2 is an SEM image of the polypyrrole nanowires prepared in this example, and it can be seen from this figure that the polypyrrole nanowires have a diameter of 40nm and a length of 2 μm. FIG. 3 is the S @ TiO in this example2SEM image of/polypyrrole composite, from which it can be seen that polypyrrole nano-wire is uniformly wound on S @ TiO2And forming a core-shell structure on the surface. FIG. 4 shows sulfur @ TiO produced in this example2The specific charge-discharge capacity and the coulombic efficiency curve of the lithium-sulfur battery taking polypyrrole as a positive electrode material are measured by charging and discharging 200 times at 1C.
The electrochemical performance test results show that S @ TiO prepared in the example2The first discharge specific capacity of the polypyrrole composite material under 1C reaches 1014.6mAh/g, and the polypyrrole composite material still keeps 516.3mAh/g after circulation for 200 times. Effectively improve lithiumCycling stability of the sulfur cell.
Example 2
300mg of resorcinol-formaldehyde resin spheres with a particle size of 250nm were dispersed in 40ml of absolute ethanol, and 0.5 mmol/L of cetyltrimethylammonium bromide was taken as a surfactant, stirred for 2 hours, and then centrifuged and washed with absolute ethanol.
Dispersing the modified resorcinol-formaldehyde resin spheres in 40ml of absolute ethyl alcohol, measuring 400 mu L of tetrabutyl titanate to be dissolved in 20ml of absolute ethyl alcohol, dripping the ethanol solution of the tetrabutyl titanate into the resorcinol-formaldehyde resin sphere dispersion liquid at the dripping speed of 5ml/min, and stirring for 12 hours at room temperature.
And centrifugally washing the stirred mixed solution, drying at 60 ℃, transferring into a muffle furnace, and carrying out temperature rise at the rate of 2 ℃/min, heat preservation at the temperature of 550 ℃, heat preservation for 3 hours and temperature reduction at the rate of 5 ℃/min. To obtain TiO2A hollow ball.
70mg of sublimed sulphur was dissolved in CS2To the solution, 20mg of TiO was added2Hollow spheres were stirred at room temperature to dryness. Sulfur and TiO2Transferring the mixture of the hollow spheres into a polytetrafluoroethylene stainless steel reaction kettle under the protection of argon atmosphere, and preserving the heat at 155 ℃ for 12 hours to obtain S @ TiO2And (c) a complex.
A500 ml three-neck flask is taken, 200ml deionized water, 0.0032mol hexadecyl trimethyl ammonium bromide and 0.0032mol pyrrole are sequentially added, the mixture is stirred for 2 hours at 0 ℃, ammonium persulfate aqueous solution with the same molar ratio with the pyrrole is added, and the mixture is stirred for 2 hours at 0 ℃. And centrifuging and filtering the reacted mixed solution to obtain the polypyrrole nano-wire.
Adding S @ TiO2Dispersing the compound and 10mg of polypyrrole nano wire in an absolute ethyl alcohol solution, and stirring at 60 ℃ until the mixture is dried to obtain S @ TiO2A/polypyrrole composite material.
Adding S @ TiO2Uniformly mixing the polypyrrole composite material, the ketjen black and the PVDF according to the mass ratio of 7:2:1, adjusting the concentration by using N-methyl pyrrolidone, and stirring for 4 hours to prepare slurry. Coating the prepared slurry on a current collector by a blade coating method, and drying for 12 hours at 60 ℃ in a vacuum environment. Circular pole pieces 16mm in diameter were cut and assembled for battery testing.
Comparative example 1
A500 ml three-neck flask is taken, 200ml deionized water, 0.0032mol hexadecyl trimethyl ammonium bromide and 0.0032mol pyrrole are sequentially added, the mixture is stirred for 2 hours at 0 ℃, ammonium persulfate aqueous solution with the same molar ratio with the pyrrole is added, and the mixture is stirred for 2 hours at 0 ℃. And centrifuging and filtering the reacted mixed solution to obtain the polypyrrole nano-wire.
70mg of sublimed sulphur was dissolved in CS2To the solution, 20mg of polypyrrole nanowires were added, and the mixture was stirred at room temperature until dried. And (3) transferring the mixture of the sulfur and the polypyrrole nanowires into a polytetrafluoroethylene stainless steel reaction kettle under the protection of argon atmosphere, and preserving heat at 155 ℃ for 12 hours to obtain the S/polypyrrole nanowire compound.
Uniformly mixing the S/polypyrrole nanowire composite material, the Ketjen black and the PVDF according to the mass ratio of 7:2:1, adjusting the concentration by using N-methyl pyrrolidone, and stirring for 4 hours to prepare slurry. Coating the prepared slurry on a current collector by a blade coating method, and drying for 12 hours at 60 ℃ in a vacuum environment. Circular pole pieces 16mm in diameter were cut and assembled for battery testing.
Comparative example 2
Dispersing 300mg resorcinol-formaldehyde resin spheres with the particle size of 500nm in 40ml absolute ethyl alcohol, taking 0.5 mmol/L cetyl trimethyl ammonium bromide as a surfactant, stirring for 2 hours, and then centrifugally washing with the absolute ethyl alcohol.
Dispersing the modified resorcinol-formaldehyde resin spheres in 40ml of absolute ethyl alcohol, measuring 240 mu L of tetrabutyl titanate to be dissolved in 20ml of absolute ethyl alcohol, dripping the ethanol solution of the tetrabutyl titanate into the resorcinol-formaldehyde resin sphere dispersion liquid at the dripping speed of 5ml/min, and stirring for 12 hours at room temperature.
And centrifugally washing the stirred mixed solution, drying at 60 ℃, transferring into a muffle furnace, and carrying out temperature rise at the rate of 2 ℃/min, heat preservation at the temperature of 550 ℃, heat preservation for 3 hours and temperature reduction at the rate of 5 ℃/min. To obtain TiO2A hollow ball.
70mg of sublimed sulphur was dissolved in CS2To the solution, 20mg of TiO was added2Hollow spheres were stirred at room temperature to dryness. Sulfur and TiO2The mixture of the hollow spheres is transferred into polytetrafluoroethylene under the protection of argon atmosphereKeeping the temperature of a stainless steel reaction kettle at 155 ℃ for 12 hours to obtain S @ TiO2And (c) a complex.
Adding S @ TiO2Uniformly mixing the composite material, the Ketjen black and the PVDF according to the mass ratio of 7:2:1, adjusting the concentration by using N-methyl pyrrolidone, and stirring for 4 hours to prepare slurry. Coating the prepared slurry on a current collector by a blade coating method, and drying for 12 hours at 60 ℃ in a vacuum environment. Circular pole pieces 16mm in diameter were cut and assembled for battery testing.
Claims (9)
1. S @ TiO with core-shell structure for positive electrode of lithium-sulfur battery2The preparation method of the/polypyrrole composite material is characterized by comprising the following steps:
(1) dispersing resorcinol-formaldehyde resin spheres as a template and cetyl trimethyl ammonium bromide as a surfactant into absolute ethyl alcohol, uniformly mixing, slowly adding tetrabutyl titanate into the mixed solution, stirring at room temperature for 8-12 hours, centrifugally separating, and calcining the product at high temperature to obtain TiO2A hollow ball;
(2) dissolving sublimed sulfur in carbon disulfide solution, stirring until sulfur is completely dissolved, and adding the sulfur into the TiO obtained in the step (1)2The hollow ball is ultrasonically treated to form uniform mixed suspension, the suspension is stirred at room temperature until the suspension is volatilized and dried, then the suspension is transferred into a polytetrafluoroethylene stainless steel reaction kettle under the argon atmosphere, and the temperature is maintained at 120 ℃ and 180 ℃ for 12 to 16 hours to obtain S @ TiO2A hollow ball;
(3) dispersing cetyl trimethyl ammonium bromide and pyrrole into deionized water, uniformly mixing, slowly adding an ammonium persulfate aqueous solution into the mixed solution, stirring in an ice water bath for 1-4 hours, centrifugally washing, and then drying the product in vacuum to obtain a polypyrrole nanowire;
(4) the S @ TiO obtained in the step (2)2Ultrasonically dispersing the hollow spheres and the polypyrrole nanowires obtained in the step (3) in absolute ethyl alcohol uniformly, and stirring at 50-90 ℃ until the mixture is dried to obtain S @ TiO with the core-shell structure2A/polypyrrole composite;
the diameter of the resorcinol-formaldehyde resin sphere in the step (1) is 200nm-600 nm.
2. The method according to claim 1, wherein the concentration of cetyltrimethylammonium bromide in step (1) is 0.2 mmol/l to 1.5 mmol/l.
3. The method according to claim 1, wherein the molar ratio of the resorcinol-formaldehyde resin beads to the tetrabutyl titanate in the step (1) is 1: (0.1-1.0).
4. The preparation method according to claim 1, wherein the temperature rise rate of the high-temperature calcination in the step (1) is 2-5 ℃/min, the heat preservation temperature is 400-.
5. The process according to claim 1, wherein the TiO obtained in step (1) is used as a catalyst2The diameter of the hollow sphere is 100nm-500 nm.
6. The method according to claim 1, wherein the TiO in the step (2)2The mass ratio of the hollow spheres to the sublimed sulfur is 1: 1-10; the concentration of the carbon disulfide solution of sublimed sulfur is 1-5 mg/ml.
7. The preparation method according to claim 1, wherein the mole ratio of cetyl trimethyl ammonium bromide, pyrrole and ammonium persulfate in the step (3) is 16: (4-64): (4-64) wherein the concentration of cetyltrimethylammonium bromide is 1.6X 10-2mol/l, the molar ratio of pyrrole to ammonium persulfate is 1: 1.
8. The preparation method according to claim 1, wherein the polypyrrole nanowires obtained in the step (3) have a diameter of 20 to 80nm and a length of 1 to 5 μm.
9. The preparation method of claim 1, the prepared S @ Ti having a core-shell structureO2The application of the/polypyrrole composite material in the positive electrode of the lithium-sulfur battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810614877.8A CN108832098B (en) | 2018-06-14 | 2018-06-14 | Lithium-sulfur battery positive electrode S @ TiO2Polypyrrole composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810614877.8A CN108832098B (en) | 2018-06-14 | 2018-06-14 | Lithium-sulfur battery positive electrode S @ TiO2Polypyrrole composite material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108832098A CN108832098A (en) | 2018-11-16 |
| CN108832098B true CN108832098B (en) | 2020-12-08 |
Family
ID=64141999
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810614877.8A Active CN108832098B (en) | 2018-06-14 | 2018-06-14 | Lithium-sulfur battery positive electrode S @ TiO2Polypyrrole composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108832098B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109473659B (en) * | 2018-12-07 | 2020-09-25 | 杭州电子科技大学 | Polypyrrole nanotube/Co3O4Particle composite material and preparation method thereof |
| CN109698333B (en) * | 2018-12-17 | 2020-08-14 | 中国空间技术研究院 | Lithium-sulfur battery positive electrode material and preparation method and application thereof |
| CN110620235B (en) * | 2019-09-16 | 2021-04-13 | 安徽师范大学 | Polypyrrole-coated hollow porous cobalt manganate-loaded sulfur composite material, preparation method thereof, lithium-sulfur battery positive electrode and lithium-sulfur battery |
| CN110752355A (en) * | 2019-10-09 | 2020-02-04 | 天津大学 | Method for preparing high-sulfur-content electrode material sulfur-titanium dioxide-polypyrrole |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103247788A (en) * | 2012-02-13 | 2013-08-14 | 苏州宝时得电动工具有限公司 | Preparation method of electrode composite material |
-
2018
- 2018-06-14 CN CN201810614877.8A patent/CN108832098B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103247788A (en) * | 2012-02-13 | 2013-08-14 | 苏州宝时得电动工具有限公司 | Preparation method of electrode composite material |
Non-Patent Citations (2)
| Title |
|---|
| Hollow polypyrrole@MnO2 spheres as nano-sulfur hosts for improved lithium-sulfur batteries;Yong Li et al.;《Electrochimica Acta》;20171212;第260卷;第912-920页 * |
| Template-assisted hydrothermal synthesis and photocatalytic activity of novel TiO2 hollow nanostructures;Guogang Tang et al.;《Ceramics International》;20121205;第39卷;第4969-4974页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108832098A (en) | 2018-11-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3128585B1 (en) | Composite cathode material and preparation method thereof, cathode pole piece of lithium ion secondary battery, and lithium ion secondary battery | |
| CN108832098B (en) | Lithium-sulfur battery positive electrode S @ TiO2Polypyrrole composite material and preparation method thereof | |
| CN109103399B (en) | Functional diaphragm for lithium-sulfur battery, preparation method of functional diaphragm and application of functional diaphragm in lithium-sulfur battery | |
| CN102324511B (en) | Preparation method for lithium ion battery composite cathode material | |
| CN110247047B (en) | Lithium-sulfur battery positive electrode material and preparation method thereof | |
| CN111362254A (en) | Preparation method and application of nitrogen-doped carbon nanotube-loaded phosphorus-doped cobaltosic oxide composite material | |
| CN109473659B (en) | Polypyrrole nanotube/Co3O4Particle composite material and preparation method thereof | |
| CN105470481A (en) | Nitrogen-doped carbon-coated manganese monoxide composite material with one-dimensional porous core-shell structure and preparation method of nitrogen-doped carbon-coated manganese monoxide composite material | |
| WO2017000219A1 (en) | Doped conductive oxide and improved electrochemical energy storage device polar plate based on same | |
| CN108199014B (en) | Porous nitrogen-doped carbon/Fe2O3Graphene foam flexible composite material, preparation method and application thereof | |
| CN105355877A (en) | Graphene-metal oxide composite negative electrode material and preparation method therefor | |
| CN106960954A (en) | A kind of preparation method and application of Prussian blue/graphene/sulphur composite | |
| CN112174220B (en) | Titanium dioxide coated cobaltosic oxide honeycomb pore nanowire material and preparation and application thereof | |
| CN107331839A (en) | A kind of preparation method of carbon nanotube loaded nano titanium oxide | |
| CN106410153A (en) | Titanium nitride-cladded nickel titanate composite material as well as preparation method and application thereof | |
| CN105742593A (en) | Cathode material for lithium-sulfur battery and preparation method of cathode material | |
| CN108400320B (en) | Method for vulcanizing surface of spinel lithium nickel manganese oxide positive electrode material | |
| CN111777065A (en) | Graphite modified material for lithium ion battery and preparation method thereof | |
| CN110336035B (en) | Tin dioxide/aluminum oxide doped carbon composite material and preparation method thereof | |
| CN114023957B (en) | Selenium-containing compound/carbon fiber energy storage material and preparation method and application thereof | |
| CN113937261B (en) | Lithium-sulfur battery positive electrode material, preparation method thereof and lithium-sulfur battery positive electrode plate | |
| CN109786769B (en) | Carbon-supported noble metal oxide bifunctional catalyst and preparation method and application thereof | |
| CN108598417B (en) | Conductive carbon black modified silica aerogel sulfur-loaded composite cathode material and preparation method thereof | |
| CN113488629A (en) | Spherical carbon-coated tungsten oxide/sulfur positive electrode material of core-shell structure loaded with multiple rare earth oxides and preparation method thereof | |
| CN113571702A (en) | Positive electrode matrix material of quasi-solid-state lithium-sulfur battery 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 | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20181116 Assignee: LEO GROUP PUMP (ZHEJIANG) Co.,Ltd. Assignor: HANGZHOU DIANZI University Contract record no.: X2022980024262 Denomination of invention: Lithium sulfur battery cathode S@TiO2/polypyrrole composite and its preparation method Granted publication date: 20201208 License type: Common License Record date: 20221202 |
|
| EE01 | Entry into force of recordation of patent licensing contract |