WO2021151138A1 - A lithium-sulfur battery cathode material synthesized by using silica hollow spheres - Google Patents

A lithium-sulfur battery cathode material synthesized by using silica hollow spheres Download PDF

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Publication number
WO2021151138A1
WO2021151138A1 PCT/AU2020/051294 AU2020051294W WO2021151138A1 WO 2021151138 A1 WO2021151138 A1 WO 2021151138A1 AU 2020051294 W AU2020051294 W AU 2020051294W WO 2021151138 A1 WO2021151138 A1 WO 2021151138A1
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Prior art keywords
sulfur
lithium
solution
silica
hollow spheres
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PCT/AU2020/051294
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French (fr)
Inventor
Jinwei Cao
Kejun HUANG
Brighsun Huang
Charles Brent
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Brighsun New Energy Pty Ltd
Brighsun New Energy (Cyprus) Ltd
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Priority claimed from AU2020900246A external-priority patent/AU2020900246A0/en
Application filed by Brighsun New Energy Pty Ltd, Brighsun New Energy (Cyprus) Ltd filed Critical Brighsun New Energy Pty Ltd
Publication of WO2021151138A1 publication Critical patent/WO2021151138A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B01J13/14—Polymerisation; cross-linking
    • B01J13/18—In situ polymerisation with all reactants being present in the same phase
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/20—After-treatment of capsule walls, e.g. hardening
    • B01J13/203—Exchange of core-forming material by diffusion through the capsule wall
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/02—Preparation of sulfur; Purification
    • C01B17/10—Finely divided sulfur, e.g. sublimed sulfur, flowers of sulfur
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C01P2004/34—Spheres hollow
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention belongs to the technical field of cathode materials for lithium- sulfur batteries and relates to the preparation and application of hollow silica spheres.
  • Li-S batteries have high theoretical specific capacity and theoretical specific energy, reaching 1672mAh/g and 2600 Wh/kg, re spectively. It is a lithium secondary battery system of highest research and application values.
  • lithium- sulfur batteries have advantages such as high capacity and high specific energy, currently they have problems such as low utilization of active materials, low cycle life, and poor safety, which severely restrict the development of lithium- sulfur batteries. The main reasons are as follows:
  • Elemental sulfur is an electronic and ionic insulator with low room temperature conductivity. Since there is no ionic sulfur, activation as a cathode material is difficult, leading to low-rate performance of lithium- sulfur batteries;
  • the object of the present invention is to provide a preparation and application method of silica hollow spheres in order to overcome the defects existing in the prior art.
  • One aspect of the present invention is to provide one kind of silica hollow spheres preparation method, comprising the steps of:
  • step (1) The SiO 2 /PS composite microspheres obtained in step (1) are placed in a muffle furnace for calcination. After calcination, silica hollow spheres can be obtained.
  • the mass fraction of the polystyrene pellets is between 1 to 10 wt%.
  • the pH value of the ammonia ranges from 7- 10.
  • step (1) the mass fraction ratio of tetraethyl silicate and polystyrene pellets is 1 to 3:1.
  • SiO 2 /PS composite microspheres are calcined in a muffle furnace, wherein the calcination temperature is 600-1500 °C, the calcination time is 2- 10 h.
  • the sulfur-loading treatment is as following: Sulfur and silica hollow spheres are mixed and grinded and are subsequently dissolved in carbon disulfide. Apply continuous grinding and heat for reaction to complete.
  • the mass ratio of sulfur to silica hollow spheres is 1 to 4:1.
  • the condition of the heating is: 155 - 180 °C heating for 1-10 h.
  • the second aspect of the present invention is to provide a silica hollow spheres, which employs a preparation method as described in any of the method above.
  • the third aspect of the present invention is to provide an application of the silica hollow spheres as carbon-sulfur cathode materials applied in lithium-sulfur battery.
  • a method of a silica hollow spheres as a positive electrode material for a lithium- sulfur battery in presented in this invention aiming to solve the low battery positive electrode material utilization and poor cycle performance in the conventional lithium- sulfur batteries.
  • Uses its own structural characteristics of hollow silica spheres lithium sulfide battery cathode materials were obtained by infiltrating elemental sulfur into the hollow silica spheres.
  • the method is simple and effective, and the obtained battery materials have excellent energy storage performance.
  • the hollow structured silica can well store and absorb sulfur, and prevent the polysulfide generated by the lithium- sulfur battery during the charge and discharge process from being lost to the negative electrode. Therefore, the obtained positive electrode material has excellent energy storage performance (at a charge and discharge rate of 1C, the specific capacity can be maintained at 610 mAh/g after 600 cycles).
  • the present invention has the following advantages: [0023] 1.
  • the hollow structure of the silica beads provides a good sulfur storage space, and solves the problem of poor conductivity of elemental sulfur;
  • FIG.l][Fig.l] is SEM photograph of silica hollow spheres Synthesized in Example 1;
  • FIG.2 is TEM photograph of silica hollow spheres Synthesized in Example 1;
  • FIG.3 is XRD pattern of silica hollow spheres synthesized in Example 1;
  • FIG.4 is lithium- sulfur battery cycle performance where silica hollow spheres synthesized in Example 1 is used as cathode.
  • a lithium-sulfur battery cathode material is prepared by a preparation method including the following steps:
  • SiO 2 /PS composite microspheres Prepare PS (polystyrene) micro beads with a mass fraction of 3% through ultrasonic dispersion, and then sequentially add water and isopropyl alcohol solution; pH value of the solution was then adjusted with concentrated aqueous ammonia to 7.5, then add a certain amount of TEOS (tetraethylorthosilicate), wherein tetraethylorthosilicate and polystyrene beads follow mass fraction ratio of 1:1 , keep stirring during the reaction. Then SiO 2 /PS composite microspheres are obtained after filtration and drying.
  • PS polystyrene
  • TEOS tetraethylorthosilicate
  • step (1) Treatment of silica hollow spheres :
  • the SiO 2 /PS composite microspheres obtained in step (1) are placed in a muffle furnace for calcination , wherein the heating rate is 1 to 10 °C/min (Heating rate of 5 °C/ min is preferred in this embodiment) , the reaction temperature is 600 °C, and the isothermal time is 2 h ;
  • FIG.l is a scanning electron microscope photograph of the obtained hollow silica sphere, and the external morphology of the hollow silica sphere material can be clearly seen.
  • FIG.2 is a transmission electron microscope photograph of the obtained hollow silica sphere material, and the hollow structure of the hollow silica sphere can be clearly seen.
  • FIG.3 is an XRD spectrum of the hollow silica sphere, and the material of the hollow silica sphere is a silicon-carbon material containing silicon dioxide as a main component and a carbon component.
  • FIG.4 is a plot of cycle performance of lithium- sulfur battery, where resulting sulfur/hollow silica sphere are used as lithium- sulfur battery positive electrode material, the battery in the data still maintained 610 mAh/g specific capacity after being charged and discharged for 600 cycles.
  • a lithium-sulfur battery cathode material is prepared by a preparation method including the following steps:
  • SiO 2 /PS composite microspheres Prepare PS (polystyrene) micro beads with a mass fraction of 5% through ultrasonic dispersion, and then sequentially add water and isopropyl alcohol solution; pH value of the solution was then adjusted with concentrated aqueous ammonia to 7.5, then add a certain amount of TEOS (tetraethylorthosilicate), wherein tetraethylorthosilicate and polystyrene beads follow mass fraction ratio of 1:1 , keep stirring during the reaction. Then SiO 2 /PS composite microspheres are obtained after filtration and drying.
  • PS polystyrene
  • TEOS tetraethylorthosilicate
  • step (1) Treatment of silica hollow spheres :
  • the SiO 2 /PS composite microspheres obtained in step (1) are placed in a muffle furnace for calcination , wherein the heating rate is 1 to 10 °C/min (Heating rate of 5 °C/ min is preferred in this embodiment) , the reaction temperature is 600 °C, and the isothermal time is 2 h ;
  • a lithium-sulfur battery cathode material is prepared by a preparation method including the following steps:
  • Si02/PS composite microspheres Prepare PS (polystyrene) micro beads with a mass fraction of 10% through ultrasonic dispersion, and then sequentially add water and isopropyl alcohol solution; pH value of the solution was then adjusted with concentrated aqueous ammonia to 7.5, then add a certain amount of TEOS (tetraethylorthosilicate), wherein tetraethylorthosilicate and polystyrene beads follow mass fraction ratio of 1:1 , keep stirring during the reaction. Then SiO 2 /PS composite microspheres are obtained after filtration and drying.
  • PS polystyrene
  • TEOS tetraethylorthosilicate
  • step (1) Treatment of silica hollow spheres :
  • the SiO 2 /PS composite microspheres obtained in step (1) are placed in a muffle furnace for calcination , wherein the heating rate is 1 to 10°C/min (Heating rate of 5°C/ min is preferred in this embodiment) , the reaction temperature is 600°C, and the isothermal time is 2 h ;
  • Example 9 Most of the procedure is kept the same as compared with Example 1, except that in this embodiment, during the high-temperature carbonization process, the reaction tem perature is 600 °C, the isothermal time is 10 h. [0057] Example 9

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The present invention relates to a method where hollow spheres of silica is the host material for lithium-sulfur battery cathode active materials. The method comprising following steps: 1) Prepare a solution where certain mass fraction of PS (polystyrene) small balls are dispersed through sonication, and subsequently add isopropanol water solution; then the pH value of the solution was adjusted with concentrated ammonia water, and subsequently a certain amount of TEOS (tetraethyl silicate). After stirring, filtration and drying of the solution, SiO 2 / PS composite microsphere can be obtained. 2) The SiO 2 / PS composite microspheres obtained in step (1) are placed in a muffle furnace for calcination. After calcination, lithium-sulfur battery cathode material, which synthesized by using silica hollow spheres as a raw material, can be collected. The preparation method is simple, low in cost, excellent in performance, and is suitable for the large-scale production of commercial batteries

Description

Description
Title of Invention: A lithium-sulfur battery cathode material synthesized by using silica hollow spheres Technical Field
[0001] The invention belongs to the technical field of cathode materials for lithium- sulfur batteries and relates to the preparation and application of hollow silica spheres.
Background Art
[0002] The energy storage mechanism of lithium- sulfur batteries is the rupture and re generation of sulfur-sulfur bonds, and the active material is sulfur. Elemental sulfur exists mainly in the form of S 8 at room temperature, which is abundant in the earth, low price and environmentally friendly. Lithium- sulfur batteries utilize elemental sulfur as the cathode active material. Li-S batteries have high theoretical specific capacity and theoretical specific energy, reaching 1672mAh/g and 2600 Wh/kg, re spectively. It is a lithium secondary battery system of highest research and application values. Although lithium- sulfur batteries have advantages such as high capacity and high specific energy, currently they have problems such as low utilization of active materials, low cycle life, and poor safety, which severely restrict the development of lithium- sulfur batteries. The main reasons are as follows:
[0003] 1. Elemental sulfur is an electronic and ionic insulator with low room temperature conductivity. Since there is no ionic sulfur, activation as a cathode material is difficult, leading to low-rate performance of lithium- sulfur batteries;
[0004] 2. Highly polymerized lithium polysulfide Li 2S n (8> n> 4) formed during the electrode reaction is easily soluble in the electrolyte, resulting in a concentration difference between the positive and negative electrodes, and migrates to the negative electrode under the concentration gradient, the polymeric lithium polysulfide is reduced to the oligo state by the metal lithium. As the progress of the such reaction, oligomeric lithium polysulfide aggregates on the negative electrode, and finally a con centration difference is formed between the two electrodes, and then it migrates to the positive electrode to be oxidized to high-polymer lithium polysulfide. This phenomenon is called the shuttling effect, which reduces the utilization of sulfur-active substances. At the same time, insoluble Li 2S and Li 2S 2 are deposited on the surface of the lithium negative electrode, which further deteriorates the performance of the lithium- sulfur battery, leading to the problem of low cycle performance of the lithium- sulfur battery;
[0005] 3. Sulfur and the final product Li 2S have distinct density. When sulfur is lithiated, the volume expands by about 79%, which easily leads to pulverization of Li 2S and causes safety problems of lithium-sulfur batteries.
Summary of Invention
[0006] The object of the present invention is to provide a preparation and application method of silica hollow spheres in order to overcome the defects existing in the prior art.
[0007] The object of the present invention can be achieved by the following technical solutions:
[0008] One aspect of the present invention is to provide one kind of silica hollow spheres preparation method, comprising the steps of:
[0009] 1. Prepare a solution where certain mass fraction of PS (polystyrene) small balls are dispersed through sonication, and subsequently add isopropanol water solution; then the pH value of the solution was adjusted with concentrated ammonia water, and sub sequently a certain amount of TEOS (tetraethyl silicate). After stirring, filtration and drying of the solution, SiO 2 / PS composite microsphere can be obtained.
[0010] 2. The SiO 2/PS composite microspheres obtained in step (1) are placed in a muffle furnace for calcination. After calcination, silica hollow spheres can be obtained.
[0011] 3. Finally, a sulfur-loading treatment is applied to the silica hollow spheres obtained in step (2) to obtain the target product.
[0012] Further, in step (1), the mass fraction of the polystyrene pellets is between 1 to 10 wt%.
[0013] Further, in the step (1), the pH value of the ammonia ranges from 7- 10.
[0014] Furthermore, in step (1), the mass fraction ratio of tetraethyl silicate and polystyrene pellets is 1 to 3:1.
[0015] Further, in the step (2), SiO 2/PS composite microspheres are calcined in a muffle furnace, wherein the calcination temperature is 600-1500 °C, the calcination time is 2- 10 h.
[0016] Further, in the step (3) the sulfur-loading treatment is as following: Sulfur and silica hollow spheres are mixed and grinded and are subsequently dissolved in carbon disulfide. Apply continuous grinding and heat for reaction to complete.
[0017] Furthermore, the mass ratio of sulfur to silica hollow spheres is 1 to 4:1.
[0018] Further, the condition of the heating is: 155 - 180 °C heating for 1-10 h.
[0019] The second aspect of the present invention is to provide a silica hollow spheres, which employs a preparation method as described in any of the method above.
[0020] The third aspect of the present invention is to provide an application of the silica hollow spheres as carbon-sulfur cathode materials applied in lithium-sulfur battery.
[0021] A method of a silica hollow spheres as a positive electrode material for a lithium- sulfur battery in presented in this invention, aiming to solve the low battery positive electrode material utilization and poor cycle performance in the conventional lithium- sulfur batteries. Uses its own structural characteristics of hollow silica spheres, lithium sulfide battery cathode materials were obtained by infiltrating elemental sulfur into the hollow silica spheres. The method is simple and effective, and the obtained battery materials have excellent energy storage performance. Specifically, the hollow structured silica can well store and absorb sulfur, and prevent the polysulfide generated by the lithium- sulfur battery during the charge and discharge process from being lost to the negative electrode. Therefore, the obtained positive electrode material has excellent energy storage performance (at a charge and discharge rate of 1C, the specific capacity can be maintained at 610 mAh/g after 600 cycles).
[0022] Compared with the prior art, the present invention has the following advantages: [0023] 1. The hollow structure of the silica beads provides a good sulfur storage space, and solves the problem of poor conductivity of elemental sulfur;
[0024] 2. There are many micropores, mesopores, and macropores with a diameter of 1-500 nanometers in the hollow silica spheres. The existence of these pore structures is conducive to the infiltration of elemental sulfur, and it can prevent the shuttling of the sulfides, which improves the cycling performance of the battery (under a charge and discharge rate of 1C, the specific capacity can be maintained at 610 mAh/g after 600 cycles);
Brief Description of Drawings Fig·!
[0025] [Fig.l][Fig.l] is SEM photograph of silica hollow spheres Synthesized in Example 1;
Fig.2
[0026] [Fig.2] [Fig.2] is TEM photograph of silica hollow spheres Synthesized in Example 1;
Fig.3
[0027] [Fig.3] [Fig.3] is XRD pattern of silica hollow spheres synthesized in Example 1;
Fig.4
[0028] [Fig.4] [Fig.4] is lithium- sulfur battery cycle performance where silica hollow spheres synthesized in Example 1 is used as cathode.
Description of Embodiments
[0029] The present invention is described in detail below with reference to the drawings and specific embodiments. This embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the protection scope of the present invention is not limited to the following embodiments.
[0030] In the following embodiments, if there is no special description of raw materials or processing technologies, it means that they are all conventional commercially available raw materials or conventional processing technologies in the art
Examples
[0031] Example 1
[0032] A lithium-sulfur battery cathode material is prepared by a preparation method including the following steps:
[0033] 1. Preparation of SiO 2/PS composite microspheres: Prepare PS (polystyrene) micro beads with a mass fraction of 3% through ultrasonic dispersion, and then sequentially add water and isopropyl alcohol solution; pH value of the solution was then adjusted with concentrated aqueous ammonia to 7.5, then add a certain amount of TEOS (tetraethylorthosilicate), wherein tetraethylorthosilicate and polystyrene beads follow mass fraction ratio of 1:1 , keep stirring during the reaction. Then SiO 2/PS composite microspheres are obtained after filtration and drying.
[0034] 2. Treatment of silica hollow spheres : The SiO 2 /PS composite microspheres obtained in step (1) are placed in a muffle furnace for calcination , wherein the heating rate is 1 to 10 °C/min (Heating rate of 5 °C/ min is preferred in this embodiment) , the reaction temperature is 600 °C, and the isothermal time is 2 h ;
[0035] [Fig.l] is a scanning electron microscope photograph of the obtained hollow silica sphere, and the external morphology of the hollow silica sphere material can be clearly seen.
[0036] [Fig.2] is a transmission electron microscope photograph of the obtained hollow silica sphere material, and the hollow structure of the hollow silica sphere can be clearly seen.
[0037] [Fig.3] is an XRD spectrum of the hollow silica sphere, and the material of the hollow silica sphere is a silicon-carbon material containing silicon dioxide as a main component and a carbon component.
[0038] [Fig.4] is a plot of cycle performance of lithium- sulfur battery, where resulting sulfur/hollow silica sphere are used as lithium- sulfur battery positive electrode material, the battery in the data still maintained 610 mAh/g specific capacity after being charged and discharged for 600 cycles.
[0039] Example 2
[0040] A lithium-sulfur battery cathode material is prepared by a preparation method including the following steps:
[0041] 1. Preparation of SiO 2/PS composite microspheres: Prepare PS (polystyrene) micro beads with a mass fraction of 5% through ultrasonic dispersion, and then sequentially add water and isopropyl alcohol solution; pH value of the solution was then adjusted with concentrated aqueous ammonia to 7.5, then add a certain amount of TEOS (tetraethylorthosilicate), wherein tetraethylorthosilicate and polystyrene beads follow mass fraction ratio of 1:1 , keep stirring during the reaction. Then SiO 2/PS composite microspheres are obtained after filtration and drying.
[0042] 2. Treatment of silica hollow spheres : The SiO 2 /PS composite microspheres obtained in step (1) are placed in a muffle furnace for calcination , wherein the heating rate is 1 to 10 °C/min (Heating rate of 5 °C/ min is preferred in this embodiment) , the reaction temperature is 600 °C, and the isothermal time is 2 h ;
[0043] Example 3
[0044] A lithium-sulfur battery cathode material is prepared by a preparation method including the following steps:
[0045] 1. Preparation of Si02/PS composite microspheres: Prepare PS (polystyrene) micro beads with a mass fraction of 10% through ultrasonic dispersion, and then sequentially add water and isopropyl alcohol solution; pH value of the solution was then adjusted with concentrated aqueous ammonia to 7.5, then add a certain amount of TEOS (tetraethylorthosilicate), wherein tetraethylorthosilicate and polystyrene beads follow mass fraction ratio of 1:1 , keep stirring during the reaction. Then SiO 2/PS composite microspheres are obtained after filtration and drying.
[0046] 2. Treatment of silica hollow spheres : The SiO 2 /PS composite microspheres obtained in step (1) are placed in a muffle furnace for calcination , wherein the heating rate is 1 to 10°C/min (Heating rate of 5°C/ min is preferred in this embodiment) , the reaction temperature is 600°C, and the isothermal time is 2 h ;
[0047] Example 4
[0048] Most of the procedure is kept the same as compared with Example 1, except that in this embodiment, the pH value is adjusted to 8.5 with concentrated ammonia solution.
[0049] Example 5
[0050] Most of the procedure is kept the same as compared with Example 1, except that in this embodiment, the pH value is adjusted to 10 with concentrated ammonia solution.
[0051] Example 6
[0052] Most of the procedure is kept the same as compared with Example 1, except that in this embodiment, the mass fraction ratio of tetraethyl silicate to polystyrene pellets is 2:1.
[0053] Example 7
[0054] Most of the procedure is kept the same as compared with Example 1, except that in this embodiment, the mass fraction ratio of tetraethyl silicate to polystyrene pellets is 3:1.
[0055] Example 8
[0056] Most of the procedure is kept the same as compared with Example 1, except that in this embodiment, during the high-temperature carbonization process, the reaction tem perature is 600 °C, the isothermal time is 10 h. [0057] Example 9
[0058] Most of the procedure is kept the same as compared with Example 1, except that in this embodiment, during the high-temperature carbonization process, the reaction tem perature is 1000 °C, the isothermal time is 2 h.
[0059] Example 10
[0060] Most of the procedure is kept the same as compared with Example 1, except that in this embodiment, during the high-temperature carbonization process, the reaction tem perature is 1500 °C, the isothermal time is 2 h.
[0061] Example 11
[0062] Most of the procedure is kept the same as compared with Example 1, except that in this embodiment, the mass ratio of sulfur and silica hollow spheres is 2:1.
[0063] The foregoing description of the embodiments is to facilitate understanding and use of the invention by those skilled in the art. It will be apparent to those skilled in the art that various modifications can be easily made to these embodiments and the general principles described herein can be applied to other embodiments without creative effort. Accordingly, the present invention is not limited to the above embodiments, those skilled in the art according to the present invention disclosed, without departing from the present invention, improvements and modifications should be made visible in the present invention within the scope of protection.

Claims

Claims [Claim 1] A method for preparing a silica hollow sphere as a sulfur host material, which comprises the following steps:
1. Prepare a solution where certain mass fraction of PS (polystyrene) small balls are dispersed through sonication, and subsequently add isopropanol water solution; then the pH value of the solution was adjusted with concentrated ammonia water, and subsequently a certain amount of TEOS (tetraethyl silicate). After stirring, filtration and drying of the solution, SiO 2 / PS composite microsphere can be obtained.
2. The SiO 2/PS composite microspheres obtained in step (1) are placed in a muffle furnace for calcination. After calcination, silica hollow spheres can be obtained.
3. Finally, a sulfur-loading treatment is applied to the silica hollow spheres obtained in step (2) to obtain the target product.
[Claim 2] The method in claim 1, wherein polystyrene beads mass fraction in step (1) is 1-10 wt%. [Claim 3] The method in claim 1, wherein the pH value of the ammonia in step (1) is in the range of 7-10.
[Claim 4] The method in claim 1, wherein said mass fraction of the tetraethy- lorthosilicate beads and polystyrene beads is 1: 1-3:1.
[Claim 5] The method in claim 1, wherein the SiO 2/PS composite microspheres are calcined in a muffle furnace, wherein the calcination temperature is 600-1500 °C, the calcination time is 2- 10 h .
[Claim 6] The method in claim 1, wherein the sulfur-loading treatment in step (3) is as following: Sulfur and silica hollow spheres are mixed and grinded and are subsequently dissolved in carbon disulfide. Apply continuous grinding and heat for reaction to complete.
[Claim 7] The method in claim 6, wherein the mass ratio of sulfur to C@Fe 304 nanospheres coated with porous carbon nanotubes is 1 to 4: 1. [Claim 8] The method in claim 7, wherein the condition of the heating is: 155 - 180 °C heating for 1-10 h. [Claim 9] A hollow silica sphere that is prepared by using the preparation method according to any said claim from claims 1 to 7. [Claim 10] The use of the silica hollow sphere in claim 8 as a carbon-sulfur cathode material in a lithium- sulfur battery.
PCT/AU2020/051294 2020-01-30 2020-11-29 A lithium-sulfur battery cathode material synthesized by using silica hollow spheres WO2021151138A1 (en)

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