CN107785554A - The preparation method of lithium-sulfur cell graphene nano sulphur composite positive pole - Google Patents
The preparation method of lithium-sulfur cell graphene nano sulphur composite positive pole Download PDFInfo
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- CN107785554A CN107785554A CN201711021017.5A CN201711021017A CN107785554A CN 107785554 A CN107785554 A CN 107785554A CN 201711021017 A CN201711021017 A CN 201711021017A CN 107785554 A CN107785554 A CN 107785554A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- 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
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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
- 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
- H01M4/36—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
- 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
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention discloses a kind of preparation method of lithium-sulfur cell graphene nano sulphur composite positive pole, comprises the following steps：（1）The preparation of graphite oxide；（2）The preparation of graphene：Graphite oxide is calcined under an argon atmosphere, after naturally cooling to room temperature, obtains graphene；（3）The preparation of graphene nano sulphur composite：By graphene ultrasonic disperse in deionized water, sodium thiosulfate is added in the graphene aqueous solution that ultrasonic disperse obtains, then adds hydrochloric acid solution, stirred, filtering, after precipitation is washed with ethanol, dry drying.The present invention, by nano-sulfur uniform load to graphene sheet layer, obtains graphene nano sulphur composite, good cycling stability, also with good multiplying power discharging property by chemical precipitation method.
Description
Technical field
The invention belongs to the preparation field of electrode material, and in particular to a kind of lithium-sulfur cell graphene-nano-sulfur is compound just
The preparation method of pole material.
Background technology
The arriving of Internet era, the fast development of electric automobile, large-scale energy-accumulating power station, all to lithium rechargeable battery
Performance proposes higher requirement, but existing secondary lithium battery is limited by own material properties and has been insufficient for needing
Ask.Lithium-sulfur cell is due to up toTheoretical specific capacity and 2600Theoretical energy density,
And active material sulphur is cheap, aboundresources and outstanding advantages of hypotoxicity, it is considered to be it is a kind of very there is application before
The secondary cell system of scape.At present, lithium-sulfur cell still suffers from the problem of obvious, it is necessary to be modified to sulfur electrode from practical,
Non-conductive elemental sulfur and the carrier with special construction and excellent conductive capability is compound, prepare high performance sulfur-based composite anode
Material.The carrier material used should have the characteristics that：（1）Ion and electronic conductivity are excellent；（2）Active material sulphur can be uniformly
Disperse on a support material, the utilization rate of active material can be improved；（3）With suppression sulphur and more sulphions in the molten of electrolyte
Solution, alleviate the shuttle effect of more sulphions.
Graphene（graphene）Be have sp2 hybridized orbits carbon atom form two-dimensional material, this special construction
Make grapheme material that there is unique mechanics, calorifics and electric property.The electron mobility of graphene is up to 200000 cm2/
(Vs), electrical conductivity reaches 106S/m.Meanwhile graphene is a kind of high-absorption material, its theoretical specific surface area is up to 2630 m2/
G, it is widely used in recent years in the anode composite material of lithium-sulfur cell.Elemental sulfur is mostly particle diameter in micron order and granularity at present
The relatively scattered sublimed sulfur product of distribution, directly do the performance that positive pole is unfavorable for battery performance with this material.Research shows, nanometer
Sulphur has the advantages that size is small, specific surface area is big, surface pore is abundant, can improve the chemical property of battery, therefore, more suitable
Close and be applied in lithium-sulfur cell.
But at present, the positive electrode of graphene and nano-sulfur laminating production, cyclical stability is poor, multiplying power discharging property
Difference.
The content of the invention
The defects of for prior art, the present invention provide a kind of lithium-sulfur cell graphene-nano-sulfur composite positive pole
Preparation method.
The preparation method of lithium-sulfur cell graphene-nano-sulfur composite positive pole, comprises the following steps：
（1）The preparation of graphite oxide：Graphite powder is added in the concentrated sulfuric acid, then adds KMnO under ice bath state4, Ran Hou
2h is reacted at 35 DEG C, adds deionized water terminating reaction, the hydrogen peroxide that mass concentration is 30% is then added, 2h is stirred, by institute
Solution centrifugal, washing are obtained to pH=7 for centrifuging upper liquid, obtained centrifugation is graphite oxide；
（2）The preparation of graphene：By step（1）Obtained graphite oxide under an argon atmosphere, 30s is calcined at 800-900 DEG C,
After naturally cooling to room temperature, graphene is obtained；
（3）The preparation of graphene-nano-sulfur composite：By graphene ultrasonic disperse in deionized water, by sodium thiosulfate
It is added in the graphene aqueous solution that ultrasonic disperse obtains, then adds hydrochloric acid solution, stirs 30min, filtering, precipitation ethanol
After washing, drying is dried, wherein, graphene, sodium thiosulfate, the adding proportion of hydrochloric acid solution are 4g:7g:50mL.
Preferably, step（1）In, graphite powder, the concentrated sulfuric acid, KMnO4, deionized water, the adding proportion of hydrogen peroxide be 2g:
90mL:6g:600mL:25mL。
Preferably, step（3）The condition of middle ultrasonic disperse is ultrasonic power 300-500W, supersonic frequency 50Hz.
Preferably, step（3）The concentration of middle hydrochloric acid solution is 1mol/L.
Preferably, step（3）The dry condition of middle drying is：3-5h is first dried at 55 DEG C, then under nitrogen protection,
10h is dried at 160 DEG C.
Advantages of the present invention：The present invention, by nano-sulfur uniform load to graphene sheet layer, is obtained by chemical precipitation method
Graphene-nano-sulfur composite, after the circulation of 55 times, specific capacity is still higher, good cycling stability, also has good
Multiplying power discharging property.
Embodiment
Embodiment 1
The preparation method of lithium-sulfur cell graphene-nano-sulfur composite positive pole, comprises the following steps：
（1）The preparation of graphite oxide：Graphite powder is added in the concentrated sulfuric acid, then adds KMnO under ice bath state4, Ran Hou
2h is reacted at 35 DEG C, adds deionized water terminating reaction, the hydrogen peroxide that mass concentration is 30% is then added, 2h is stirred, by institute
Solution centrifugal, washing are obtained to pH=7 for centrifuging upper liquid, obtained centrifugation is graphite oxide；Wherein, graphite powder, dense sulphur
Acid, KMnO4, deionized water, the adding proportion of hydrogen peroxide be 2g:90mL:6g:600mL:25mL；
（2）The preparation of graphene：By step（1）Obtained graphite oxide under an argon atmosphere, is calcined 30s at 800 DEG C, natural
After being cooled to room temperature, graphene is obtained；
（3）The preparation of graphene-nano-sulfur composite：Under conditions of ultrasonic power 300W, supersonic frequency 50Hz, by graphite
Alkene ultrasonic disperse in deionized water, sodium thiosulfate is added in the graphene aqueous solution that ultrasonic disperse obtains, Ran Houjia
It is 1mol/L hydrochloric acid solutions to enter concentration, stirs 30min, filtering, after precipitation is washed with ethanol, dries drying；Wherein, drying is dried
3h is specially first dried at 55 DEG C, then under nitrogen protection, 10h is dried at 160 DEG C,；Wherein, graphene, thio sulphur
Sour sodium, the adding proportion of hydrochloric acid solution are 4g:7g:50mL.
Embodiment 2
The preparation method of lithium-sulfur cell graphene-nano-sulfur composite positive pole, comprises the following steps：
（1）The preparation of graphite oxide：Graphite powder is added in the concentrated sulfuric acid, then adds KMnO under ice bath state4, Ran Hou
2h is reacted at 35 DEG C, adds deionized water terminating reaction, the hydrogen peroxide that mass concentration is 30% is then added, 2h is stirred, by institute
Solution centrifugal, washing are obtained to pH=7 for centrifuging upper liquid, obtained centrifugation is graphite oxide；Wherein, graphite powder, dense sulphur
Acid, KMnO4, deionized water, the adding proportion of hydrogen peroxide be 2g:90mL:6g:600mL:25mL；
（2）The preparation of graphene：By step（1）Obtained graphite oxide under an argon atmosphere, is calcined 30s at 900 DEG C, natural
After being cooled to room temperature, graphene is obtained；
（3）The preparation of graphene-nano-sulfur composite：Under conditions of ultrasonic power 500W, supersonic frequency 50Hz, by graphite
Alkene ultrasonic disperse in deionized water, sodium thiosulfate is added in the graphene aqueous solution that ultrasonic disperse obtains, Ran Houjia
It is 1mol/L hydrochloric acid solutions to enter concentration, stirs 30min, filtering, after precipitation is washed with ethanol, dries drying；Wherein, drying is dried
5h is specially first dried at 55 DEG C, then under nitrogen protection, 10h is dried at 160 DEG C,；Wherein, graphene, thio sulphur
Sour sodium, the adding proportion of hydrochloric acid solution are 4g:7g:50mL.
Embodiment 3
The preparation method of lithium-sulfur cell graphene-nano-sulfur composite positive pole, comprises the following steps：
（1）The preparation of graphite oxide：Graphite powder is added in the concentrated sulfuric acid, then adds KMnO under ice bath state4, Ran Hou
2h is reacted at 35 DEG C, adds deionized water terminating reaction, the hydrogen peroxide that mass concentration is 30% is then added, 2h is stirred, by institute
Solution centrifugal, washing are obtained to pH=7 for centrifuging upper liquid, obtained centrifugation is graphite oxide；Wherein, graphite powder, dense sulphur
Acid, KMnO4, deionized water, the adding proportion of hydrogen peroxide be 2g:90mL:6g:600mL:25mL；
（2）The preparation of graphene：By step（1）Obtained graphite oxide under an argon atmosphere, is calcined 30s at 800 DEG C, natural
After being cooled to room temperature, graphene is obtained；
（3）The preparation of graphene-nano-sulfur composite：Under conditions of ultrasonic power 400W, supersonic frequency 50Hz, by graphite
Alkene ultrasonic disperse in deionized water, sodium thiosulfate is added in the graphene aqueous solution that ultrasonic disperse obtains, Ran Houjia
It is 1mol/L hydrochloric acid solutions to enter concentration, stirs 30min, filtering, after precipitation is washed with ethanol, dries drying；Wherein, drying is dried
4h is specially first dried at 55 DEG C, then under nitrogen protection, 10h is dried at 160 DEG C,；Wherein, graphene, thio sulphur
Sour sodium, the adding proportion of hydrochloric acid solution are 4g:7g:50mL.
Claims (5)
1. the preparation method of lithium-sulfur cell graphene-nano-sulfur composite positive pole, it is characterised in that：Comprise the following steps：
（1）The preparation of graphite oxide：Graphite powder is added in the concentrated sulfuric acid, then adds KMnO under ice bath state4, Ran Hou
2h is reacted at 35 DEG C, adds deionized water terminating reaction, the hydrogen peroxide that mass concentration is 30% is then added, 2h is stirred, by institute
Solution centrifugal, washing are obtained to pH=7 for centrifuging upper liquid, obtained centrifugation is graphite oxide；
（2）The preparation of graphene：By step（1）Obtained graphite oxide under an argon atmosphere, 30s is calcined at 800-900 DEG C,
After naturally cooling to room temperature, graphene is obtained；
（3）The preparation of graphene-nano-sulfur composite：By graphene ultrasonic disperse in deionized water, by sodium thiosulfate
It is added in the graphene aqueous solution that ultrasonic disperse obtains, then adds hydrochloric acid solution, stirs 30min, filtering, precipitation ethanol
After washing, drying is dried, wherein, graphene, sodium thiosulfate, the adding proportion of hydrochloric acid solution are 4g:7g:50mL.
2. the preparation method of lithium-sulfur cell graphene-nano-sulfur composite positive pole according to claim 1, its feature exist
In：Step（1）In, graphite powder, the concentrated sulfuric acid, KMnO4, deionized water, the adding proportion of hydrogen peroxide be 2g:90mL:6g:600mL:
25mL。
3. the preparation method of lithium-sulfur cell graphene-nano-sulfur composite positive pole according to claim 1, its feature exist
In：Step（3）The condition of middle ultrasonic disperse is ultrasonic power 300-500W, supersonic frequency 50Hz.
4. the preparation method of lithium-sulfur cell graphene-nano-sulfur composite positive pole according to claim 1, its feature exist
In：Step（3）The concentration of middle hydrochloric acid solution is 1mol/L.
5. the preparation method of lithium-sulfur cell graphene-nano-sulfur composite positive pole according to claim 1, its feature exist
In：Step（3）The dry condition of middle drying is：3-5h is first dried at 55 DEG C, then under nitrogen protection, is done at 160 DEG C
Dry 10h.
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| CN201711021017.5A CN107785554A (en) | 2017-10-26 | 2017-10-26 | The preparation method of lithium-sulfur cell graphene nano sulphur composite positive pole |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108666531A (en) * | 2018-04-27 | 2018-10-16 | 西安理工大学 | A kind of electrochemical preparation method of graphene/sulphur positive plate |
| CN109817941A (en) * | 2019-02-18 | 2019-05-28 | 山东星火科学技术研究院 | A kind of high capacity high efficiency sulphur/graphene composite material and preparation method thereof |
| CN116072877A (en) * | 2023-03-13 | 2023-05-05 | 中国铁塔股份有限公司 | Battery and battery preparation method |
-
2017
- 2017-10-26 CN CN201711021017.5A patent/CN107785554A/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108666531A (en) * | 2018-04-27 | 2018-10-16 | 西安理工大学 | A kind of electrochemical preparation method of graphene/sulphur positive plate |
| CN108666531B (en) * | 2018-04-27 | 2021-04-06 | 西安理工大学 | Electrochemical preparation method of graphene/sulfur positive plate |
| CN109817941A (en) * | 2019-02-18 | 2019-05-28 | 山东星火科学技术研究院 | A kind of high capacity high efficiency sulphur/graphene composite material and preparation method thereof |
| CN116072877A (en) * | 2023-03-13 | 2023-05-05 | 中国铁塔股份有限公司 | Battery and battery preparation method |
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Application publication date: 20180309 |