CN108793083B - Three-dimensional porous sulfur particle nano material, preparation method thereof, lithium-sulfur battery positive electrode and lithium-sulfur battery - Google Patents
Three-dimensional porous sulfur particle nano material, preparation method thereof, lithium-sulfur battery positive electrode and lithium-sulfur battery Download PDFInfo
- Publication number
- CN108793083B CN108793083B CN201810379452.3A CN201810379452A CN108793083B CN 108793083 B CN108793083 B CN 108793083B CN 201810379452 A CN201810379452 A CN 201810379452A CN 108793083 B CN108793083 B CN 108793083B
- Authority
- CN
- China
- Prior art keywords
- sulfur
- preparation
- dimensional porous
- pore
- 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.)
- Active
Links
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000011593 sulfur Substances 0.000 title claims abstract description 63
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 63
- 239000002245 particle Substances 0.000 title claims abstract description 59
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 32
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 14
- 239000004793 Polystyrene Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- 239000012153 distilled water Substances 0.000 claims description 9
- 238000002791 soaking Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 239000004005 microsphere Substances 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 238000007599 discharging Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 description 14
- 239000000047 product Substances 0.000 description 12
- 238000001291 vacuum drying Methods 0.000 description 12
- 239000011148 porous material Substances 0.000 description 10
- 239000002244 precipitate Substances 0.000 description 10
- 239000008188 pellet Substances 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 238000009210 therapy by ultrasound Methods 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- FGRVOLIFQGXPCT-UHFFFAOYSA-L dipotassium;dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [K+].[K+].[O-]S([O-])(=O)=S FGRVOLIFQGXPCT-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Images
Classifications
-
- 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
- C01B17/0253—Preparation of sulfur; Purification from non-gaseous sulfur compounds other than sulfides or materials containing such sulfides
-
- 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
-
- 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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
-
- 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
-
- 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
- C01P2004/41—Particle morphology extending in three dimensions octahedron-like
-
- 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
- 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
- H01M2004/028—Positive 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a three-dimensional porous sulfur particle nano material and a preparation method thereof, a lithium sulfur battery anode and a lithium sulfur battery. Compared with the prior art, the sulfur particles prepared by the chemical synthesis method have high yield and good controllability; the pore-forming template is easy to remove, and has no influence on sulfur particles; the three-dimensional porous structure can buffer the volume expansion in the charging and discharging process; and the experimental process is simple, the yield is high, the raw materials are cheap and easy to obtain, and the cost is low.
Description
Technical Field
The invention belongs to the field of new energy science and technology, and particularly relates to a three-dimensional porous sulfur particle nano material, a preparation method thereof, a lithium-sulfur battery anode and a lithium-sulfur battery.
Background
The development and utilization of new energy is an important subject of continuous research of human beings, and in the research process of the development of the new energy, a lithium ion battery is excellent in energy storage aspect and widely applied to the fields of portable electronic equipment, electric automobiles, energy storage systems and the like. However, the energy density of the traditional lithium ion battery is close to the theoretical limit, the lithium-sulfur battery has higher energy density and specific capacity than the traditional lithium ion battery, and the theoretical energy density of the lithium-sulfur battery is about 2600Wh kg-110 times that of the currently commercialized battery. And the theoretical specific capacity of the lithium-sulfur battery can reach 1673mAh g-1And is far higher than the traditional lithium ion battery. In addition, the sulfur is widely distributed in nature, the cost of raw materials is extremely low, no harmful substances are generated in the charging and discharging process, and the material is non-toxic and pollution-free and is an environment-friendly material. Aspects of the aboveThe great advantage of the lithium-sulfur battery enables the lithium-sulfur battery to become a new generation of lithium secondary battery with great development prospect.
Lithium-sulfur batteries also have a number of problems that limit their practical application, mainly the poor conductivity of elemental sulfur and discharge products; the shuttling effect results in lower coulombic efficiency and reversible capacity; the volume change causes the active material to be exfoliated, and these problems combine to result in a rapid decrease in the capacity of the lithium-sulfur battery.
Disclosure of Invention
In order to solve the technical problems, the invention provides a three-dimensional porous sulfur particle nano material and a preparation method thereof.
The invention also provides a lithium-sulfur battery anode which is made of the three-dimensional porous sulfur particle nano material.
The invention also provides a lithium-sulfur battery which is manufactured by using the positive electrode made of the three-dimensional porous sulfur particle nano material.
The specific technical scheme of the invention is as follows:
the invention provides a preparation method of a three-dimensional porous sulfur particle nano material, which comprises the following steps:
1) mixing the pore-forming template with distilled water, and performing ultrasonic dispersion at room temperature to obtain a mixed solution;
2) adding thiosulfate into the mixed solution obtained in the step 1), stirring until the thiosulfate is completely dissolved, adding a surfactant and acid, stirring at room temperature for reaction, standing after the reaction is finished, centrifuging, washing and drying to obtain sulfur particles coated with the pore-forming template;
3) soaking the sulfur particles coated with the pore-forming template prepared in the step 2) in a fixed solvent, dissolving the pore-forming template, centrifugally washing, and drying to obtain the three-dimensional porous sulfur particle nano material.
The pore-forming template in the step 1) is selected from carboxyl polystyrene microspheres (PS beads); the dosage ratio of the pore-forming template to the distilled water is 0.1-2.0 mg/mL, preferably 0.5-1.6 mg/mL.
Further, in the step 2), thiosulfate is added into the mixed solution obtained in the step 1), and the concentration of the thiosulfate is 0.01-0.2 mol/L, preferably 0.02-0.1 mol/L.
The thiosulfate in the step 2) is selected from one or two of sodium thiosulfate and potassium thiosulfate.
The concentration of the surfactant added in the step 2) in the system is 0.001-0.1 mol/L, preferably 0.002-0.006 mol/L.
The surfactant in the step 2) is selected from one or two of polyvinylpyrrolidone (PVP) or Sodium Dodecyl Sulfate (SDS). The average molecular weight of polyvinylpyrrolidone is 8000.
The concentration of the acid added in the step 2) in the system is 0.01-0.2 mol/L, preferably 0.05-0.15 mol/L.
Further, the acid in the step 2) is selected from one or two of hydrochloric acid or sulfuric acid. The concentration is 8-12 mol/L.
Further, the stirring reaction time at room temperature in the step 2) is 1-10 hours, preferably 3-6 hours. The stirring speed was 500 rpm.
The drying in the step 2) is vacuum drying, the temperature is 30-80 ℃, and the preferable temperature is 40-60 ℃; the time is 2 to 18 hours, preferably 6 to 10 hours.
The fixed solvent in the step 3) is selected from Tetrahydrofuran (THF), the dosage ratio of the sulfur particles wrapping the pore-forming template to the fixed solvent is less than 1:20-200g/mL, and the volume of the THF is 2-20 mL, preferably 5-12 mL; the soaking time is 5-90min, preferably 15-60 min at room temperature.
The drying in the step 3) is vacuum drying, the temperature is 30-80 ℃, and the preferable temperature is 40-60 ℃; the drying time is 2 to 18 hours, preferably 2 to 6 hours.
The three-dimensional porous sulfur particle nano material provided by the invention is prepared by adopting the method, wherein the porous sulfur particles are spherical or octahedral and have the size of 2-3 mu m.
The invention provides a lithium-sulfur battery anode which is prepared from the prepared three-dimensional porous sulfur particle nano material.
The invention provides a lithium-sulfur battery which is manufactured by using a positive electrode made of the three-dimensional porous sulfur particle nano material.
The method comprises the steps of firstly obtaining sulfur particles wrapped with PS pellets by a chemical synthesis method and a template method, taking the PS pellets as a pore-forming template, enabling the PS pellets to be stable in chemical property, easy to compound with a host material and easy to remove, and being an excellent pore-forming template, and then removing the PS pellets by dissolving with a fixed solvent to finally obtain the porous sulfur particle nano material. The porous structure can well accommodate the volume change of sulfur in the charging and discharging process, greatly improves the structural integrity of sulfur, and has the characteristics of high capacity and stable cycle performance when the material is used as the anode of a lithium-sulfur battery. Compared with the prior art, the sulfur particles prepared by the chemical synthesis method have high yield and good controllability; the pore-forming template is easy to remove, and has no influence on sulfur particles; the three-dimensional porous structure can effectively buffer the volume expansion in the charging and discharging process; and the experimental process is simple, the yield is high, the raw materials are cheap and easy to obtain, and the cost is low.
Drawings
FIG. 1 is an SEM image of a three-dimensional porous sulfur particle nanomaterial prepared in example 1;
FIG. 2 is an SEM image of a three-dimensional porous sulfur particle nanomaterial prepared in example 2;
FIG. 3 is an SEM image of a three-dimensional porous sulfur particle nanomaterial prepared in example 3;
FIG. 4 is an SEM image of a three-dimensional porous sulfur particle nanomaterial prepared in example 4;
FIG. 5 is an SEM image of a three-dimensional porous sulfur particle nanomaterial prepared in example 5;
FIG. 6 is an XRD pattern of the three-dimensional porous sulfur particle nanomaterial prepared in example 3;
FIG. 7 is a graph of the cycling stability test of the three-dimensional porous sulfur particle nanomaterial prepared in example 3 as a lithium sulfur battery at a current density of 200 mA/g;
FIG. 8 is a test chart of a charge and discharge curve of the three-dimensional porous sulfur particle nano material prepared in example 3 as a lithium sulfur battery at a current density of 200 mA/g.
Detailed Description
Example 1
A preparation method of a three-dimensional porous sulfur particle nano material comprises the following steps:
1) mixing 0.02g of PS pellets with 100mL of distilled water, and performing ultrasonic treatment at room temperature for 20min to obtain a mixed solution;
2) adding 0.18g of Na into the mixed solution in the step 1)2S2O3Stirring until the mixture is completely dissolved, adding 2.0g of PVP into the mixture, then dropwise adding 0.002mol of 8mol/L hydrochloric acid into the mixture, stirring for 2 hours at room temperature, standing to obtain light yellow precipitate, centrifugally washing, and drying in vacuum at 30 ℃ for 10 hours to obtain sulfur particles coated with the pore-forming template.
3) Soaking 0.1g of the product obtained in the step 2) in 3mL of THF for 10min, centrifuging to obtain a precipitate, washing, vacuum-drying at 30 ℃ for 10 hours, and collecting the product to obtain the three-dimensional porous sulfur particles.
The obtained three-dimensional porous sulfur particles are spherical, the size is about 2 mu m, the diameter of the pores is about 80nm, and the pores are uniformly distributed.
Example 2
A preparation method of a three-dimensional porous sulfur particle nano material comprises the following steps:
1) mixing 0.08g of PS pellets with 100mL of distilled water, and performing ultrasonic treatment at room temperature for 20min to obtain a mixed solution;
2) adding 0.8g K of the mixed solution in the step 1)2S2O3Stirring until the mixture is completely dissolved, adding 5.0g of PVP into the mixture, then dropwise adding 0.005mol of 9mol/L sulfuric acid into the mixture, stirring for 5 hours at room temperature, standing to obtain light yellow precipitate, centrifugally washing, and drying for 16 hours in vacuum at 40 ℃ to obtain sulfur particles coated with the pore-forming template.
3) Soaking 0.1g of the product obtained in the step 2) in 6mL of THF for 20min, centrifuging to obtain a precipitate, washing, vacuum-drying at 40 ℃ for 16 h, and collecting the product to obtain the three-dimensional porous sulfur particles.
The obtained three-dimensional porous sulfur particles are spherical, the size is about 2 mu m, the diameter of the pores is about 80nm, and the pores are uniformly distributed.
Example 3
A preparation method of a three-dimensional porous sulfur particle nano material comprises the following steps:
1) mixing 0.1g of PS pellets with 100mL of distilled water, and performing ultrasonic treatment at room temperature for 20min to obtain a mixed solution;
2) adding 1.27g of Na into the mixed solution in the step 1)2S2O3Stirring until the mixture is completely dissolved, adding 0.18g of SDS, dropwise adding 0.01mol of 10mol/L hydrochloric acid into the mixture, stirring for 6 hours at room temperature, standing to obtain light yellow precipitate, centrifuging, washing, and vacuum-drying at 45 ℃ for 12 hours to obtain the sulfur particles coated with the pore-forming template.
3) Soaking 0.1g of the product obtained in the step 2) in 10mL of THF for 40min, centrifuging to obtain a precipitate, washing, vacuum-drying at 45 ℃ for 12 hours, and collecting the product to obtain the three-dimensional porous sulfur particles.
The obtained three-dimensional porous sulfur particles are octahedral, the size is about 3 mu m, the diameter of the pores is about 80nm, and the pores are uniformly distributed.
A lithium-sulfur battery positive electrode is prepared from the prepared three-dimensional porous sulfur particle nano material:
a lithium-sulfur battery, made using a positive electrode made of the three-dimensional porous sulfur particle nanomaterial comprising the above-prepared:
the method specifically comprises the following steps:
the final product three-dimensional porous sulfur material obtained in example 3 was used as a positive electrode active material of a lithium sulfur battery, and the obtained active material was mixed with superconducting carbon, PVDF in a ratio of 7: 2: 1, preparing the mixture into uniform slurry by using an N-methyl pyrrolidone (NMP) solvent, coating the uniform slurry on an aluminum foil, uniformly coating the uniform slurry into a film sheet by using a scraper, and uniformly adhering the film sheet to the surface of the aluminum foil. Then the prepared coating is put in a drying oven and dried for 12 hours at the temperature of 60 ℃; after drying, moving the mixture into a vacuum drying oven, and carrying out vacuum drying for 10 hours at the temperature of 60 ℃; then tabletting the dried composite material coating by a roller machine or a tablet press and the like; a mechanical cutting machine is adopted to cut an electrode plate, a lithium plate is used as a counter electrode, electrolyte is a commercially available 1mol/L LiTFSI/DME + DOL solution, a battery tester is used for carrying out charge and discharge performance tests, and the obtained product is used as a lithium sulfur battery anode material, and the cycle stability test result under the current density of 200mA/g is shown in figure 7. As can be seen from the attached figure 7, the cycling stability of the battery is good, and the battery capacity is still stabilized at 600mAh/g after 30 times of cycling.
Example 4
A preparation method of a three-dimensional porous sulfur particle nano material comprises the following steps:
1) mixing 0.17g of PS pellets with 100mL of distilled water, and performing ultrasonic treatment at room temperature for 20min to obtain a mixed solution;
2) adding 2.2g of Na into the mixed solution in the step 1)2S2O3Stirring until the mixture is completely dissolved, adding 0.10g SDS, dropwise adding 0.017mol 10mol/L hydrochloric acid into the mixture, stirring for 8 hours at room temperature, standing to obtain light yellow precipitate, centrifuging, washing, and vacuum drying for 5 hours at 60 ℃ to obtain sulfur particles coated with the pore-forming template.
3) Soaking 0.1g of the product obtained in the step 2) in 15mL of THF for 80min, centrifuging to obtain a precipitate, washing, vacuum-drying at 60 ℃ for 5 hours, and collecting the product to obtain the three-dimensional porous sulfur particles.
The obtained three-dimensional porous sulfur particles are octahedral, the size is about 3 mu m, the diameter of the pores is about 80nm, and the pores are uniformly distributed.
Example 5
A preparation method of a three-dimensional porous sulfur particle nano material comprises the following steps:
1) mixing 0.13g of PS pellets with 100mL of distilled water, and performing ultrasonic treatment at room temperature for 20min to obtain a mixed solution;
2) adding 2.8g K of the mixed solution in the step 1)2S2O3Stirring until the mixture is completely dissolved, adding 0.28g of SDS, dropwise adding 0.02mol of 10mol/L sulfuric acid into the mixture, stirring for 10 hours at room temperature, standing to obtain light yellow precipitate, centrifuging, washing, and vacuum drying for 8 hours at 50 ℃ to obtain the sulfur particles coated with the pore-forming template.
3) Soaking 0.1g of the product obtained in the step 2) in 20mL of THF for 60min, centrifuging to obtain a precipitate, washing, vacuum-drying at 50 ℃ for 8 hours, and collecting the product to obtain the three-dimensional porous sulfur particles.
The obtained three-dimensional porous sulfur particles are octahedral, the size is about 3 mu m, the diameter of the pores is about 80nm, and the pores are uniformly distributed.
Claims (13)
1. A preparation method of a three-dimensional porous sulfur particle nano material is characterized by comprising the following steps:
1) mixing the pore-forming template with distilled water, and performing ultrasonic dispersion at room temperature to obtain a mixed solution;
2) adding thiosulfate into the mixed solution obtained in the step 1), stirring until the thiosulfate is completely dissolved, adding a surfactant and acid, stirring at room temperature for reaction, standing after the reaction is finished, centrifuging, washing and drying to obtain sulfur particles coated with the pore-forming template;
3) soaking the sulfur particles coated with the pore-forming template prepared in the step 2) in a fixed solvent, dissolving the pore-forming template, centrifugally washing, and drying to obtain the three-dimensional porous sulfur particle nano material;
the pore-forming template is selected from carboxyl polystyrene microspheres; the fixing solvent is selected from tetrahydrofuran.
2. The preparation method according to claim 1, wherein the pore-forming template in step 1) is selected from carboxyl polystyrene microspheres; the dosage ratio of the pore-forming template to the distilled water is 0.1-2.0 mg/mL.
3. The preparation method according to claim 1 or 2, characterized in that thiosulfate is added to the mixed system obtained in step 1) in step 2), and the concentration of thiosulfate is 0.01-0.2 mol/L.
4. The preparation method according to claim 1, wherein the concentration of the surfactant added in the step 2) in the system is 0.001-0.1 mol/L.
5. The preparation method according to claim 3, wherein the concentration of the surfactant added in the step 2) in the system is 0.001-0.1 mol/L.
6. The preparation method according to claim 1, wherein the concentration of the acid added in the step 2) in the system is 0.01 to 0.2 mol/L.
7. The preparation method according to claim 3, wherein the concentration of the acid added in the step 2) in the system is 0.01 to 0.2 mol/L.
8. The method according to any one of claims 1, 2, 4, 5, 6 or 7, wherein the reaction time with stirring at room temperature in step 2) is 1 to 10 hours.
9. The preparation method according to claim 3, wherein the reaction time of stirring at room temperature in the step 2) is 1 to 10 hours.
10. The method according to claim 1, wherein the fixing solvent in step 3) is selected from tetrahydrofuran, and the soaking time is 5-90 min; the dosage ratio of the sulfur particles wrapping the pore-forming template to the fixed solvent is less than 1:20-200 g/ml.
11. A three-dimensional porous sulfur particle nano-material prepared by the preparation method of any one of claims 1 to 10.
12. A lithium-sulfur battery positive electrode, characterized by being made of the three-dimensional porous sulfur particle nanomaterial prepared by the method of any one of claims 1 to 10.
13. A lithium-sulfur battery, characterized by being produced using the positive electrode according to claim 12.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810379452.3A CN108793083B (en) | 2018-04-25 | 2018-04-25 | Three-dimensional porous sulfur particle nano material, preparation method thereof, lithium-sulfur battery positive electrode and lithium-sulfur battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810379452.3A CN108793083B (en) | 2018-04-25 | 2018-04-25 | Three-dimensional porous sulfur particle nano material, preparation method thereof, lithium-sulfur battery positive electrode and lithium-sulfur battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108793083A CN108793083A (en) | 2018-11-13 |
| CN108793083B true CN108793083B (en) | 2020-01-10 |
Family
ID=64093887
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810379452.3A Active CN108793083B (en) | 2018-04-25 | 2018-04-25 | Three-dimensional porous sulfur particle nano material, preparation method thereof, lithium-sulfur battery positive electrode and lithium-sulfur battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108793083B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4340071A4 (en) * | 2021-12-28 | 2024-10-23 | Renaisis Co Ltd | Positive electrode active material, positive electrode mixture, and secondary battery |
| JP7246789B1 (en) | 2021-12-28 | 2023-03-28 | 株式会社ルネシス | Positive electrode active material, positive electrode mixture and secondary battery |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101382869B1 (en) * | 2012-06-04 | 2014-04-08 | 현대자동차주식회사 | Solid high-ionic conductor for battery and Litium-Sulfur battery using the same |
| CN103606646B (en) * | 2013-11-14 | 2016-05-04 | 湘潭大学 | Nickel sulphur positive pole of a kind of lithium-sulfur cell and preparation method thereof |
| CN104183834A (en) * | 2014-08-15 | 2014-12-03 | 南京师范大学 | Preparation method of sulphur/silicon dioxide core-shell nanostructure for lithium sulphur battery anode |
| CN105038317A (en) * | 2015-06-06 | 2015-11-11 | 青岛科技大学 | Preparation method of polystyrene coated sulfur microcapsule |
| CN107195868B (en) * | 2017-01-06 | 2019-08-13 | 中国计量大学 | A kind of sulphur anode composite material preparation facilities and control method based on sodium thiosulfate and acid reaction |
-
2018
- 2018-04-25 CN CN201810379452.3A patent/CN108793083B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN108793083A (en) | 2018-11-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103579590B (en) | A kind of preparation method of clad anode material of lithium battery | |
| CN105742611B (en) | A kind of lithium ion battery negative material, preparation method and lithium ion battery | |
| CN109449374A (en) | A kind of lithium-sulphur cell positive electrode, battery and preparation method using nitride/carbon nanotube as interlayer | |
| CN114665065B (en) | Positive electrode plate and preparation method and application thereof | |
| CN111362254A (en) | Preparation method and application of nitrogen-doped carbon nanotube-loaded phosphorus-doped cobaltosic oxide composite material | |
| CN103682327B (en) | Based on the lithium ion battery and preparation method thereof of the hollow porous nickel oxide composite material of N doping carbon-coating parcel | |
| CN103474620A (en) | Solid-state lithium ion electrode, solid-state lithium ion battery and preparation method of solid-state lithium ion electrode | |
| CN113594415B (en) | Sandwich independent positive electrode for inhibiting shuttle effect of lithium-sulfur battery and preparation method thereof | |
| CN108183213B (en) | Preparation method of ferric oxide/carbon nanotube lithium ion battery cathode material | |
| CN105514378A (en) | Lithium-sulfur battery positive-pole composite material with imitated cellular structure and preparation method thereof | |
| CN111370675B (en) | Carbon nanosheet sodium ion battery cathode material inlaid with metal phosphide and preparation method thereof | |
| CN106654193A (en) | Preparation method of porous CoO@ nitrogen-doped carbon coaxial nanorod | |
| CN101867061A (en) | Lithium-ion battery with long service life and high power and preparation method thereof | |
| CN108793083B (en) | Three-dimensional porous sulfur particle nano material, preparation method thereof, lithium-sulfur battery positive electrode and lithium-sulfur battery | |
| CN115207263B (en) | Secondary battery | |
| CN103531789A (en) | Iron oxide-carbon nanotube ternary composite material and preparation method thereof | |
| CN107507958A (en) | A kind of powder in situ cladding for lithium-sulfur cell prepares integral method with pole plate | |
| CN102544507B (en) | Lithium ion power battery positive plate and lithium ion power battery | |
| CN104852042A (en) | Preparation method and application of cobalt-iron composite oxide nanorods for lithium ion battery anode material | |
| CN116632249B (en) | Lithium ion battery | |
| CN106602032B (en) | A kind of preparation method of lithium-sulfur cell electrode material | |
| CN114751395A (en) | Nitrogen-doped porous carbon sphere/S composite material, preparation method thereof and application thereof in lithium-sulfur battery | |
| CN106784759A (en) | A kind of silicon/activated carbon composite negative pole material and preparation method thereof | |
| CN113809282A (en) | High-capacity nitrogen-doped carbon-coated SiOxPreparation method of nano-beam lithium ion battery cathode material | |
| CN107887580B (en) | A kind of flower-shaped cobalt oxide/graphene hollow microsphere lithium ion battery negative material and preparation method 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 |