CN112864375A - Method for preparing lithium-sulfur battery positive electrode material by taking smelting slag as raw material - Google Patents
Method for preparing lithium-sulfur battery positive electrode material by taking smelting slag as raw material Download PDFInfo
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- CN112864375A CN112864375A CN202110024422.2A CN202110024422A CN112864375A CN 112864375 A CN112864375 A CN 112864375A CN 202110024422 A CN202110024422 A CN 202110024422A CN 112864375 A CN112864375 A CN 112864375A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- 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
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- H—ELECTRICITY
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- 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 a method for preparing a lithium-sulfur battery anode material by taking smelting slag as a raw material, which comprises the following steps: s1: calcining, dealkalizing and drying the smelting slag to obtain slag powder; s2: adding the slag powder and the sulfur powder obtained in the step S1 into the carbon-containing dispersion liquid, heating and stirring, drying and grinding the obtained block-shaped sample after the aqueous solution is evaporated to dryness to obtain the lithium-sulfur battery positive electrode composite material; s3: and mixing and grinding the composite material obtained in the step S2, acetylene black and PVDF according to a proportion to obtain the cathode material. The invention carries out physical processing and chemical processing on the waste smelting slag in the metallurgical industry to construct the lithium-sulfur battery anode composite material. The electrochemical performance of the lithium-sulfur battery is improved, high-value utilization and reduction of smelting waste residues are realized, and the environmental pollution caused by the smelting waste residues is relieved.
Description
Technical Field
The invention relates to the field of comprehensive utilization of solid waste resources, in particular to a method for preparing a lithium-sulfur battery anode material by taking smelting slag as a raw material.
Background
As a large industrial country, China develops rapidly in various smelting industries and is accompanied by the discharge of a large amount of smelting slag every year. According to the national industry management classification, the smelting slag can be divided into steel slag, non-ferrous slag and iron alloy slag, wherein the non-ferrous slag refers to various metal slag formed in the smelting process. Among iron-based smelting slags, red mud is waste slag generated in aluminum industry for extracting aluminum oxide from aluminide ores, and is famous for being red and brown. Due to different ore grades, production methods and technical levels, about 1.0-1.8 tons of red mud is discharged when 1 ton of alumina is produced. As a large country for alumina production in China, the red mud discharged each year is up to millions of tons. A large amount of piled red mud not only occupies scarce land resources, but also causes a series of environmental problems such as soil and underground water pollution and the like due to alkaline waste liquid and heavy metal ions in the red mud. Therefore, resource treatment is required to reduce the harm of red mud to the environment. The existing red mud treatment methods are mainly applied to building materials, ceramic production, metal recovery and the like, but the methods have the defects of high cost, large environmental pollution and the like.
The elemental sulfur is used as a light and multi-electron reaction positive electrode material and has large specific capacity (1675mAh g)-1) Environment-friendly, abundant and cheap reserves and the like. However, lithium sulfur batteries as next generation high specific energy batteries, the dissolution loss and shuttle effect of the intermediate polysulfide severely worsen the positive and negative electrode transport interface and cycle stability. In addition, improving the kinetics of the lithium-sulfur conversion reaction and realizing rapid phase inversion among polysulfides is an effective means for improving the utilization rate of sulfur and reducing the shuttle effect.
Disclosure of Invention
The invention provides a method for preparing a lithium-sulfur battery anode material by taking smelting slag as a raw material, and aims to realize high-value utilization and reduction of smelting waste slag and relieve environmental pollution caused by the smelting waste slag; and meanwhile, the electrochemical performance of the lithium-sulfur battery is improved.
In order to achieve the above object, the present invention provides a method for preparing a positive electrode material for a lithium-sulfur battery from smelting slag as a raw material, comprising the steps of:
s1: calcining, dealkalizing and drying the smelting slag to obtain slag powder;
s2: adding the slag powder and the sulfur powder obtained in the step S1 into the carbon-containing dispersion liquid, heating and stirring, drying and grinding the obtained block-shaped sample after the aqueous solution is evaporated to dryness to obtain the lithium-sulfur battery positive electrode composite material;
s3: and mixing and grinding the composite material obtained in the step S2, acetylene black and PVDF according to a proportion to obtain the cathode material.
Preferably, in S1, the smelting slag includes one or more of red mud, steel slag, fly ash, and lead-zinc smelting slag.
Preferably, in S1, the calcining temperature is 300-800 ℃ and the calcining time is 120-300 min.
Preferably, in the S1, the calcining temperature is 450 ℃ and the calcining time is 280 min.
Preferably, in S1, the alkali removing method is one or more of acid alkali removing and suction filtration alkali removing, and more preferably, the alkali removing method is acid alkali removing.
Preferably, in S1, the acid is one or more of nitric acid, sulfuric acid, hydrochloric acid, acetic acid, and oxalic acid. More preferably, the acid is nitric acid.
Preferably, in the S1, the mass concentration of the acid is 0.1-1 mol/L, and more preferably, the mass concentration of the pickling acid is 0.5 mol/L.
Preferably, in the step S1, the drying temperature is 40-80 ℃, and the drying time is 15-24 h.
Preferably, in S1, the drying temperature is 70 ℃ and the drying time is 20 h.
Preferably, in the step S2, the mass ratio of carbon to sulfur powder to slag powder is 20-25: 75-70: 5, more preferably, the optimal ratio is 25: 70: 5.
preferably, in S2, the carbon includes one or more of graphene, carbon nanotubes, carbon black, acetylene black, and ketjen black; the sulfur powder comprises micro-scale and nano-scale sublimed sulfur powder; the mass percentage concentration of the carbon-containing dispersion liquid is 1-50%.
Preferably, in S2, the heating temperature is set to 60 to 100 ℃, and more preferably, the heating temperature is 90 ℃.
Preferably, in the step S3, the composite material, the acetylene black and the PVDF are mixed in a mass ratio of 8-7: 1-2: 1, more preferably, the mass ratio is 8: 1: 1.
the scheme of the invention has the following beneficial effects:
the invention carries out physical processing and chemical processing on the waste smelting slag in the metallurgical industry to construct the lithium-sulfur battery anode composite material. Therefore, the electrochemical performance of the lithium-sulfur battery can be improved, high-value utilization and reduction of smelting waste can be realized, and the environmental pollution caused by the smelting waste is relieved.
The method has the advantages of simple process flow, high efficiency and environment-friendly treatment process, and the prepared lithium-sulfur cathode composite material is used for large-scale industrial production.
The invention has the advantages of reducing the cost of the anode material of the lithium-sulfur battery, thereby reducing the cost of the lithium-sulfur battery, and opening up a new way for high-value utilization of smelting waste residues.
Drawings
FIG. 1 is a process flow diagram of example 1 of the present invention.
Fig. 2 is an electrochemical cycle diagram of the positive electrode material obtained in example 1 of the present invention.
Fig. 3 is an electrochemical cycle diagram of the positive electrode material obtained in example 2 of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantages of the present invention more apparent, the following detailed description is given with reference to the accompanying drawings and specific embodiments.
Example 1
As shown in fig. 1, a method for preparing a lithium-sulfur battery cathode material by using red mud as a raw material comprises the following steps:
s1: taking 2g of red mud raw ore, grinding the red mud raw ore into fine particle powder in a mortar, then placing the red mud in a muffle furnace, calcining for 280min at 450 ℃, setting the heating rate to be 3 ℃/min, and cooling to room temperature to obtain the calcined red mud;
adding 200ml of pure water into the calcined red mud, adjusting the solid-to-liquid ratio to be 10g/L, carrying out ultrasonic treatment on the aqueous solution for 4h, then setting magneton stirring, rotating the speed to 600rpm, and stirring for 8h to prepare suspension;
dropwise adding a nitric acid solution into the obtained suspension under the action of a magnetic stirrer, wherein the concentration of the nitric acid solution is 0.5mol/L, monitoring the change of the pH of the solution in real time by using a pH meter, taking the pH as 7 +/-0.2 as a titration end point, stirring for 12 hours under the magnetic stirrer, and then aging the solution for 24 hours at room temperature;
performing suction filtration on the aged solution by using suction filtration equipment, and removing supernatant to obtain a red mud block;
drying the obtained blocky red mud for 20 hours at 70 ℃ to obtain dry red mud powder, and grinding the powder;
placing the obtained red mud fine particles in a muffle furnace for high-temperature calcination, calcining for 4h at 600 ℃, and setting the heating rate to be 10 ℃/min;
grinding the calcined powder again to finally obtain neutral red mud powder;
s2: taking 0.1g of neutral red mud powder and 1.4g of sublimed sulfur, mixing and adding into a graphene aqueous solution (10g) with the mass fraction of 5%;
placing the solution on a hot bench, heating and stirring the solution, setting the temperature of the hot bench at 90 ℃ and the rotating speed at 600rpm until viscous slurry is obtained;
drying the obtained viscous slurry in an oven at 60 ℃ for 24h to obtain a block sample, and grinding to obtain fine composite material powder;
s3: the composite material powder, acetylene black and PVDF are mixed according to the mass ratio of 8: 1: 1, grinding and mixing to obtain the sulfur cathode material.
FIG. 2 is a charge-discharge cycle chart of the lithium-sulfur battery cathode material prepared from the smelting waste residue in example 1 of the present invention. As can be seen from FIG. 2, the specific discharge capacity is maintained above 530mAh g-1 after 100 cycles of charge and discharge at a rate of 0.2C, and the capacity is attenuated to 0.32% per cycle, which indicates that the material has good cycle stability; in addition, the coulombic efficiency of the material is always stably kept above 95%. Therefore, the material prepared by using the acid-washed red mud as a raw material in example 1 can be used as a positive electrode material for a lithium sulfur battery.
Example 2
S1: taking 10g of red mud raw ore, grinding the red mud raw ore into fine particle powder in a mortar, then placing the red mud in a muffle furnace to calcine for 280min at 800 ℃, setting the heating rate to be 3 ℃/min, and cooling to room temperature to obtain the calcined red mud;
adding 200ml of pure water into the calcined red mud, adjusting the solid-to-liquid ratio to be 10g/L, carrying out ultrasonic treatment on the aqueous solution for 4h, then setting magneton stirring, rotating the speed to 600rpm, and stirring for 8h to prepare suspension;
carrying out suction filtration treatment on the suspension, and carrying out suction filtration for four times by using pure water to obtain neutral red mud slurry;
drying the red mud slurry for 24 hours at 80 ℃ to obtain dry red mud blocks, and grinding the red mud blocks to obtain red mud powder;
s2: placing 0.1g of red mud powder, 10g of graphene aqueous solution (mass fraction is 5%) and 1.4g of sublimed sulfur in a beaker, and adding a proper amount of deionized water and ethanol;
placing the solution on a hot bench, wherein the temperature of the hot bench is 90 ℃, the rotating speed is 600rpm, and stirring is carried out for 12 hours;
carrying out ultrasonic treatment on the solution for 4h, then placing the solution on a hot table, heating and stirring the solution at the temperature of 90 ℃ and the rotating speed of 600rpm, and finally obtaining viscous slurry;
drying the obtained viscous slurry in an oven at 60 ℃ for 24h to obtain a block sample, and grinding to obtain fine powder;
s3: the obtained dry powder was mixed with acetylene black and PVDF in a mass ratio of 8: 1: 1, grinding and mixing to obtain a sulfur anode material;
FIG. 3 is a charge-discharge cycle chart of the lithium-sulfur battery cathode material prepared from the smelting waste residue in example 2 of the present invention. As can be seen from FIG. 3, the initial capacity is 807.9mAh g-1 after 100 cycles of the cycle under the charge-discharge rate of 0.2C, the capacity is 469.6mAh g-1 after 100 cycles of the cycle, and the capacity is attenuated to 0.42% per cycle; in addition, the coulombic efficiency of the material fluctuates greatly during 100 cycles, but is kept above 95%. Therefore, the material prepared by using the suction filtration dealkalized red mud as a raw material in example 2 can be used as a positive electrode material of a lithium-sulfur battery.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A method for preparing a lithium-sulfur battery positive electrode material by taking smelting slag as a raw material is characterized by comprising the following steps:
s1: calcining, dealkalizing and drying the frozen slag to obtain slag powder;
s2: adding the slag powder and the sulfur powder obtained in the step S1 into the carbon-containing dispersion liquid, heating and stirring, drying and grinding the obtained block-shaped sample after the aqueous solution is evaporated to dryness to obtain the lithium-sulfur battery positive electrode composite material;
s3: and mixing and grinding the composite material obtained in the step S2, acetylene black and PVDF according to a proportion to obtain the cathode material.
2. The method for preparing the lithium-sulfur battery cathode material from smelting slag as the raw material according to claim 1, wherein in S1, the smelting slag comprises one or more of red mud, steel slag, fly ash and lead-zinc smelting slag.
3. The method for preparing the positive electrode material of the lithium-sulfur battery from the smelting slag as the raw material according to claim 2, wherein in the step S1, the calcining temperature is 300-800 ℃ and the calcining time is 120-300 min.
4. The method for preparing the positive electrode material of the lithium-sulfur battery by using the smelting slag as the raw material according to claim 3, wherein in the step S1, the alkali removing method is one or more of acid alkali removing and suction filtration alkali removing.
5. The method for preparing the positive electrode material of the lithium-sulfur battery by using the smelting slag as the raw material according to claim 4, wherein in the step S1, the acid is one or more of nitric acid, sulfuric acid, hydrochloric acid, acetic acid and oxalic acid; the mass concentration of the acid is 0.1-1 mol/L.
6. The method for preparing the positive electrode material of the lithium-sulfur battery from the smelting slag as the raw material according to claim 5, wherein in the step S1, the drying temperature is 40-80 ℃ and the drying time is 15-24 hours.
7. The method for preparing the lithium-sulfur battery cathode material from the smelting slag as the raw material according to claim 6, wherein in S2, the mass ratio of carbon to sulfur powder to slag powder is 20-25: 75-70: 5.
8. the method for preparing the positive electrode material of the lithium-sulfur battery from the smelting slag as the raw material according to claim 7, wherein in the step S2, the carbon comprises one or more of graphene, carbon nanotubes, carbon black, acetylene black and Ketjen black; the sulfur powder comprises micro-scale and nano-scale sublimed sulfur powder; the mass percentage concentration of the carbon-containing dispersion liquid is 1-50%.
9. The method for preparing the positive electrode material of the lithium-sulfur battery from the smelting slag as the raw material according to claim 8, wherein in the step S2, the heating temperature is set to be 60-100 ℃.
10. The method for preparing the lithium-sulfur battery cathode material from the smelting slag as the raw material according to claim 9, wherein in S3, the composite material, the acetylene black and the PVDF are mixed in a mass ratio of 8-7: 1-2: 1.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017139990A1 (en) * | 2016-02-21 | 2017-08-24 | 肖丽芳 | Method for preparing alumina-hollow-sphere cathode material for lithium-sulfur battery |
| CN108878829A (en) * | 2018-06-26 | 2018-11-23 | 广西师范大学 | A kind of lithium sulfur battery anode material and preparation method thereof of discarded diatomite preparation |
| CN109119613A (en) * | 2018-08-27 | 2019-01-01 | 上海电力学院 | Using rejected fly ash as the method for the lithium sulfur battery anode material of Material synthesis |
| CN111342026A (en) * | 2020-03-16 | 2020-06-26 | 桂林理工大学 | Method for using red mud as lithium ion battery cathode active material |
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- 2021-01-08 CN CN202110024422.2A patent/CN112864375A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017139990A1 (en) * | 2016-02-21 | 2017-08-24 | 肖丽芳 | Method for preparing alumina-hollow-sphere cathode material for lithium-sulfur battery |
| CN108878829A (en) * | 2018-06-26 | 2018-11-23 | 广西师范大学 | A kind of lithium sulfur battery anode material and preparation method thereof of discarded diatomite preparation |
| CN109119613A (en) * | 2018-08-27 | 2019-01-01 | 上海电力学院 | Using rejected fly ash as the method for the lithium sulfur battery anode material of Material synthesis |
| CN111342026A (en) * | 2020-03-16 | 2020-06-26 | 桂林理工大学 | Method for using red mud as lithium ion battery cathode active material |
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Application publication date: 20210528 |