CN103066254B - Sulfur/carbon composite material and application thereof - Google Patents
Sulfur/carbon composite material and application thereof Download PDFInfo
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- CN103066254B CN103066254B CN201210575488.1A CN201210575488A CN103066254B CN 103066254 B CN103066254 B CN 103066254B CN 201210575488 A CN201210575488 A CN 201210575488A CN 103066254 B CN103066254 B CN 103066254B
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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 invention discloses a sulfur/carbon composite material and application thereof. The sulfur/carbon composite material is prepared through the following steps: 1) dissolving sulfur powder in carbon disulfide to prepare a sulfur-containing carbon disulfide solvent; 2) dispersing carbon powder in the sulfur-containing carbon disulfide solvent prepared in step 1) so as to obtain turbid liquid, placing the turbid liquid in an enclosed reaction vessel and carrying out insulation at a temperature of 100 to 180 DEG C for 6 to 48 h; and 3) carrying out natural cooling, separating a black precipitate from the solvent and drying the black precipitate so as to obtain the sulfur/carbon composite material. The sulfur/carbon composite material prepared in the invention has good cycling stability and rate capability and can be extensively applied as a positive electrode material of a lithium-sulfur cell in fields like a high performance chemical energy storage device.
Description
(1) technical field
The present invention relates to a kind of sulphur/carbon composite and the application as Lithium-sulphur battery anode material thereof.
(2) background technology
The valence state of element sulphur enriches, and can change, utilize Li from-2 to+7
2reversible change between S and S, using lithium metal as negative pole, elemental sulfur or sulfenyl composite material, as the lithium-sulfur rechargeable battery of positive pole, have higher theoretical energy density (2600Wh/kg).In addition, elemental sulfur wide material sources, cheap and environmental friendliness, therefore lithium-sulfur rechargeable battery is considered to the novel high-capacity energy-storage battery system most with development potentiality.
However, still there is following problem in the sulfur-based positive electrode material as lithium-sulfur rechargeable battery critical material: (1) elemental sulfur at room temperature poorly conductive, need add a large amount of conductive agent, thus cause maximum system energy density to reduce; (2) elemental sulfur can be reduced into the polysulfide being soluble in electrolyte in discharge process, causes active material to run off, and makes sulfur electrode material morphology that huge change occur; (3) polysulfide being dissolved in electrolyte can be that electrolyte viscosity increases, and also can shuttle back and forth to electrode metal lithium sheet simultaneously, self discharge reaction occurs.These problems seriously constrain the practical application of lithium-sulfur rechargeable battery.
At present, the main method that domestic and international researcher synthesizes sulfur-based positive electrode material is by heating sulphur powder, utilizes porous carbon materials for matrix, is spread, is adsorbed onto in the hole of porous carbon materials by elemental sulfur, obtain sulphur/carbon composite.As the people such as Canadian Nazar (X.L. Ji, K.T. Lee, L.F. Nazar, A highly ordered nanostructured carbon-sulphur cathode for lithium-sulphur batteries, Nat.Mater., 2009,8:500-505) elemental sulfur is filled in mesoporous carbon, obtain high-performance sulfenyl material; People (the N. Jayaprakash such as the Lynden A. Archer of the U.S., J. Shen, Surya S. Moganty, A. Corona, and L.A. Archer, Porous Hollow CarbonSulfur Composites for High-Power Lithium-Sulfur Batteries, Angew. Chem. Int. Ed., 2011, mode 50:1-6) utilizing repeatedly vapour deposition to inject sulphur prepares a kind of hollow ball-shape sulphur/carbon composite, and it has higher cyclical stability and multiplying power property.The present invention adopts a kind of easy solvent-thermal method first, with the carbon disulfide solution of sulfur-bearing for solvent, carbon dust is carrier material, is reacted by continuous high-pressure in closed reactor, elemental sulfur and the even compound of carbon support material can be made, obtain a kind of sulphur/carbon composite.
(3) summary of the invention
First object of the present invention is to provide a kind of sulphur/carbon composite with good cyclical stability and high rate performance, and preparation method's low cost of this material, is suitable for suitability for industrialized production.
Second object of the present invention is the application providing described sulphur/carbon composite as Lithium-sulphur battery anode material.
Below technical scheme of the present invention is illustrated.
The invention provides a kind of sulphur/carbon composite, it is prepared as follows:
1) sulphur powder is dissolved in carbon disulfide, is mixed with the carbon disulfide solvent of sulfur-bearing;
2) carbon dust is scattered in the carbon disulfide solvent of sulfur-bearing prepared by step (1) and obtains suspension-turbid liquid, then gained suspension-turbid liquid is placed in closed reactor, at 100-180
o6-48 hour is incubated under C condition;
3), after naturally cooling, by black precipitate and separated from solvent, sulphur/carbon composite is drying to obtain.
Sulphur powder of the present invention is sublimed sulfur powder, and purity is not less than chemical pure.
Solvent of the present invention is carbon disulfide, and purity is not less than chemical pure.
Carbon dust of the present invention is natural graphite powder, graphous graphite powder, activated carbon, carbon fiber, carbonaceous mesophase spherules, carbon nano-tube, carbon black or organic resin carbon dust, and purity is not less than chemical pure.
Autoclave of the present invention refers to and can keep reacting the container carried out under enclosed high pressure condition.
As preferably, in step 1), the feed intake quality of sulphur powder in carbon disulfide is 0.05 ~ 0.5g/mL.
As preferably, step 2) in, the mass ratio of the sulphur powder contained in the carbon disulfide solvent of feed intake quality and the sulfur-bearing of carbon dust is 0.1 ~ 1:1.
The present invention specifically recommends described sulphur/carbon composite to be prepared in accordance with the following steps: sublimed sulfur powder is dissolved in carbon disulfide by 0.05 ~ 0.5g/mL, be that carbon dust to add in the carbon disulfide solvent of above-mentioned sulfur-bearing and is mixed with suspension-turbid liquid by 0.1 ~ 1:1 by carbon dust and sulphur powder mass ratio again, then this suspension-turbid liquid being transferred in autoclave, is 100-180 in temperature
obe incubated 6-48 hour under C condition, after naturally cooling with stove, by black precipitate and separated from solvent, namely obtain described sulphur/carbon composite after drying.
The form of sulphur/carbon composite of the present invention is powder, fragment, particle or fiber.
Present invention also offers the application of described sulphur/carbon composite as Lithium-sulphur battery anode material.Described lithium-sulfur cell adopts conventional method preparation.
Compared with prior art, the inventive method is simple in the present invention, is easy to control, with low cost, easily realizes industrialization; Sulphur/the carbon composite of gained has good cyclical stability and high rate performance, and the positive electrode that can be used as lithium-sulfur cell is widely used in the fields such as high-performance chemical energy storage device.
(4) accompanying drawing explanation
Fig. 1 is TEM and the Mapping collection of illustrative plates of sulphur/carbon composite prepared by embodiment 1.
Fig. 2 is the charging and discharging curve figure of simulated battery prepared by embodiment 1.
Fig. 3 is the high rate performance curve chart of simulated battery prepared by embodiment 1.
(5) embodiment
With specific embodiment, technical scheme of the present invention is described further below, but protection scope of the present invention is not limited thereto.
Embodiment 1
First be dissolved in 40mL carbon disulfide by 4g sublimed sulfur powder, then add 1g activated carbon, obtain black suspension after fully stirring, then transferring in autoclave by black suspension, is 140 in temperature
obe incubated 24 hours in C baking oven, after stove cooling, by black precipitate and separated from solvent, after drying, namely obtain described sulphur/carbon composite.Fig. 1 is the TEM-Mapping photo before and after active carbon material and sulphur compound, and can see after solvent thermal reaction, element sulphur is evenly distributed in sulphur/carbon composite.
Electrode is made as follows with the sulphur/carbon composite of embodiment 1 gained.
Sulphur/carbon composite is taken respectively: acetylene black: polyvinylidene fluoride with the mass ratio of 70:15:15, be coated on aluminium foil after grinding evenly and make electrode, employing metal lithium sheet is negative pole, electrolyte is 1 mol/L LiTFSI/DOL-DME(volume ratio is 1:1), polypropylene microporous film is barrier film (Celgard 2300), is assembled into simulated battery.Fig. 2 is that respective battery is at 0.1 A g
-1current density under charging and discharging curve in 1.5-3.0V voltage range, can find that this combination electrode material has excellent cyclical stability, after 50 circulations, specific capacity is still higher than 700 mAhg
-1.Fig. 3 is the high rate performance curve of respective battery under different discharge-rate, can find that this sulphur/carbon composite has excellent high rate performance, at 2 A g
-1current density under, reversible capacity is higher than 400 mAh g
-1.
Embodiment 2
First be dissolved in 45mL carbon disulfide by 8g sublimed sulfur powder, then add 5g carbon fiber, obtain black suspension after fully stirring, then transferring in autoclave by black suspension, is 160 in temperature
obe incubated 48 hours in C baking oven, after stove cooling, by black precipitate and separated from solvent, after drying, namely obtain described sulphur/carbon composite.
Electrode is made as follows with the sulphur/carbon composite of embodiment 2 gained.
Sulphur/carbon composite is taken respectively: acetylene black: polyvinylidene fluoride with the mass ratio of 70:20:10, be coated on aluminium foil after grinding evenly and make electrode, employing metal lithium sheet is negative pole, electrolyte is 1 mol/L LiTFSI/DOL-DME(volume ratio is 1:1), polypropylene microporous film is barrier film (Celgard 2300), is assembled into simulated battery.Simulated battery is at 0.1 A g
-1current density under in 1.5-3.0V voltage range, after 50 circulations, specific capacity is still higher than 610 mAhg
-1, at 2 A g
-1current density under, reversible capacity is higher than 320 mAh g
-1.
Embodiment 3
First be dissolved in 30mL carbon disulfide by 10g sublimed sulfur powder, then add 6g carbon nano-tube, obtain black suspension after fully stirring, then transferring in autoclave by black suspension, is 180 in temperature
obe incubated 16 hours in C baking oven, after stove cooling, by black precipitate and separated from solvent, after drying, namely obtain described sulphur/carbon composite.
Electrode is made as follows with the sulphur/carbon composite of embodiment 3 gained.
Sulphur/carbon composite is taken respectively: acetylene black: polyvinylidene fluoride with the mass ratio of 80:10:10, be coated on aluminium foil after grinding evenly and make electrode, employing metal lithium sheet is negative pole, electrolyte is 1 mol/L LiTFSI/DOL-DME(volume ratio is 1:1), polypropylene microporous film is barrier film (Celgard 2300), is assembled into simulated battery.Simulated battery is at 0.1 A g
-1current density under in 1.5-3.0V voltage range, after 50 circulations, specific capacity is still higher than 760 mAhg
-1, at 2 A g
-1current density under, reversible capacity is higher than 420 mAh g
-1.
Embodiment 4
First be dissolved in 25mL carbon disulfide by 2g sublimed sulfur powder, then add 0.5g carbon black, obtain black suspension after fully stirring, then transferring in autoclave by black suspension, is 120 in temperature
obe incubated 20 hours in C baking oven, after stove cooling, by black precipitate and separated from solvent, after drying, namely obtain described sulphur/carbon composite.
Electrode is made as follows with the sulphur/carbon composite of embodiment 4 gained.
Sulphur/carbon composite is taken respectively: acetylene black: polyvinylidene fluoride with the mass ratio of 80:5:15, be coated on aluminium foil after grinding evenly and make electrode, employing metal lithium sheet is negative pole, electrolyte is 1 mol/L LiTFSI/DOL-DME(volume ratio is 1:1), polypropylene microporous film is barrier film (Celgard 2300), is assembled into simulated battery.Simulated battery is at 0.1 A g
-1current density under in 1.5-3.0V voltage range, after 50 circulations, specific capacity is still higher than 580 mAhg
-1, at 2 A g
-1current density under, reversible capacity is higher than 230 mAh g
-1.
Claims (6)
1. a preparation method for sulphur/carbon composite, its preparation process is as follows:
1) sulphur powder is dissolved in carbon disulfide, is mixed with the carbon disulfide solvent of sulfur-bearing;
2) carbon dust is scattered in step 1) obtain suspension-turbid liquid in the carbon disulfide solvent of sulfur-bearing prepared, then gained suspension-turbid liquid is placed in closed reactor, under 100-180 DEG C of condition, is incubated 6-48 hour;
3), after naturally cooling, by black precipitate and separated from solvent, sulphur/carbon composite is drying to obtain.
2. the preparation method of sulphur/carbon composite as claimed in claim 1, is characterized in that: step 1) in, the quality consumption of sulphur powder counts 0.05 ~ 0.5g/mL with the volume of carbon disulfide.
3. the preparation method of sulphur/carbon composite as claimed in claim 1 or 2, is characterized in that: step 2) in, the mass ratio of the sulphur powder contained in the carbon disulfide solvent of feed intake quality and the sulfur-bearing of carbon dust is 0.1 ~ 1:1.
4. the preparation method of sulphur/carbon composite as claimed in claim 1 or 2, is characterized in that: described carbon dust is natural graphite powder, graphous graphite powder, activated carbon, carbon fiber, carbonaceous mesophase spherules, carbon nano-tube, carbon black or organic resin carbon dust.
5. the preparation method of sulphur/carbon composite as claimed in claim 3, is characterized in that: described carbon dust is natural graphite powder, graphous graphite powder, activated carbon, carbon fiber, carbonaceous mesophase spherules, carbon nano-tube, carbon black or organic resin carbon dust.
6. the preparation method of sulphur/carbon composite as claimed in claim 1, is characterized in that: the purity of raw material sulphur powder, carbon disulfide, carbon dust is all not less than chemical pure.
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| CN104659338B (en) * | 2015-03-17 | 2017-01-18 | 东莞市迈科科技有限公司 | Preparation method of positive electrode material of lithium sulfur battery |
| CN105375001B (en) * | 2015-10-16 | 2018-09-11 | 广东烛光新能源科技有限公司 | A kind of preparation method of sulfur-bearing electrode material |
| CN105374999B (en) * | 2015-10-16 | 2019-03-08 | 广东烛光新能源科技有限公司 | A kind of preparation method of sulfur-bearing electrode material |
| CN105655549A (en) * | 2015-12-17 | 2016-06-08 | 贵州梅岭电源有限公司 | Preparation method of sulfur-carbon composite for lithium sulfur battery positive electrode |
| CN106935841A (en) * | 2015-12-31 | 2017-07-07 | 深圳市比克动力电池有限公司 | A kind of preparation method of sulphur lithium battery anode sulphur/carbon nano tube compound material |
| CN113540420B (en) * | 2021-07-12 | 2022-08-23 | 成都博时捷科技有限公司 | Preparation method of lithium-sulfur battery positive electrode material and lithium-sulfur battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1613750A (en) * | 2004-09-24 | 2005-05-11 | 武汉大学 | Preparation for metal sulfide |
| CN101587951A (en) * | 2008-05-23 | 2009-11-25 | 中国人民解放军63971部队 | Novel carbon-sulfur compound for lithium-sulfur battery |
| CN102142554A (en) * | 2011-02-16 | 2011-08-03 | 中国人民解放军63971部队 | Nano carbon sulfur composite material with network structure and preparation method of nano carbon composite material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1613750A (en) * | 2004-09-24 | 2005-05-11 | 武汉大学 | Preparation for metal sulfide |
| CN101587951A (en) * | 2008-05-23 | 2009-11-25 | 中国人民解放军63971部队 | Novel carbon-sulfur compound for lithium-sulfur battery |
| CN102142554A (en) * | 2011-02-16 | 2011-08-03 | 中国人民解放军63971部队 | Nano carbon sulfur composite material with network structure and preparation method of nano carbon composite material |
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