CN101986443A - Lithium sulfur battery anode material and preparation method thereof - Google Patents
Lithium sulfur battery anode material and preparation method thereof Download PDFInfo
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- CN101986443A CN101986443A CN2010101813913A CN201010181391A CN101986443A CN 101986443 A CN101986443 A CN 101986443A CN 2010101813913 A CN2010101813913 A CN 2010101813913A CN 201010181391 A CN201010181391 A CN 201010181391A CN 101986443 A CN101986443 A CN 101986443A
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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
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- 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 relates to a lithium sulfur battery anode material and a preparation method thereof. In the anode material, nano sulfur particles are uniformly filled in hollow carbon nano-tubes of a nano mesoporous carbon material, so that sulfur is tightly contacted with carbon. The thickness of each carbon tube in the nano mesoporous carbon material is 5 to 200nm, the pore diameter is 2 to 100nm and the granularity of the sulfur nano particles is 2 to 100nm. The capacity of the prepared lithium sulfur battery anode material is more than 1,800mAh/g, and the capacity is kept over 80 percent after 500 cycles.
Description
Technical field
The present invention relates to a kind of lithium-sulphur cell positive electrode material and preparation method thereof, particularly relate to a kind of mesoporous nano material with carbon element that evenly is filled with sulfur nano particles and preparation method thereof.
Background technology
Along with the exhaustion gradually of main natural resources such as coal, oil, energy crisis has become one of human following key subjects that must solve.The novel high-energy chemical power source of green non-pollution has become competitively hot of research and development of countries in the world at present.
Lithium-sulfur cell has very wide application prospect, and chemists have carried out nearly 20 years research for this reason.Sulphur and lithium are considered to ideal a kind of battery material, the combination of these two kinds of chemical substances not only can provide highdensity energy, in stability, fail safe and also more outstanding on the life-span, and compare with the other materials that can be used in the lithium battery, the cost of sulphur is relatively low, and lithium-sulfur cell will become the energy of safety, longevity and low-carbon emission.
The theoretical specific capacity of elemental sulfur is 1675mAh/g, be assembled into battery with lithium, theoretical specific energy can reach 2600Wh/kg, meets the requirement of electric automobile (EV) to battery, also meet the requirement of portable type electronic product, will in lithium secondary battery, be used widely battery " light, thin, little ".Because sulphur has characteristics such as wide material sources (cost is low), theoretical specific capacity height, nontoxic (pollution-free), environmental friendliness, lithium-sulfur cell becomes the emphasis of people's research.
But the manufacturing of anode is puzzlement people's a a great problem always, this part is responsible for storing and discharging electronics in discharging and recharging, in this reversible electrochemical reaction in order to realize higher electric current, the such conductor of sulphur and similar carbon is wherein closely contacted, and there is no highly effective mode before this.
Summary of the invention
The present invention just is being based under the above-mentioned background, and a kind of lithium-sulphur cell positive electrode material is provided.In the described positive electrode, nanometer sulphur particle evenly is filled in the hollow Nano carbon pipe of mesoporous nano material with carbon element, makes sulphur closely contact with carbon.The hollow Nano carbon pipe of described mesoporous nano material with carbon element, every carbon tube thickness is the 5-200 nanometer, the aperture is the 2-100 nanometer.Described sulfur nano particles granularity is the 2-100 nanometer.
Correspondingly, the invention provides the lithium-sulphur cell positive electrode preparation methods that a kind of sulphur and carbon are combined closely, the steps include:
(1) preparation of mesoporous nano material with carbon element:
According to weight ratio 1: 0.01-0.1: 1-20: 0.1-2 takes by weighing sucrose, and the concentrated sulfuric acid and water and template silicon dioxide mix the back and evenly stirred 1～10 hour; Mixture is put into baking oven, and the baking oven heating rate is for per hour heating up 20 ℃, and temperature rises to 100～200 ℃, keeps 1～10 hour; After the solvent evaporation, mixture is put into the pyroreaction still roasting of inert gas shielding, pyroreaction still heating rate is for per hour heating up 100 ℃, and temperature rises to 500～1000 ℃, keeps 2～10 hours; Mixture after the roasting is put into sodium hydroxide solution or hydrofluoric acid stirred 1～20 hour, make the silica template dissolving, filter then, wash, drying, obtain the inner mesoporous nano material with carbon element of nano hollow carbon pipe that is.
(2) sulfur nano particles is filled in the nano hollow carbon pipe:
Mesoporous nano material with carbon element and sulfur nano particles are put into nanometer high pressure high temperature vapor mixer, the steam temperature scope is 100-600 ℃, with the high-temperature vapour is that carrier mixes both, nanometer high pressure high temperature vapor mixer heating rate is for per hour heating up 40 ℃, be warming up to 120～500 ℃, kept 2-20 hour behind the temperature stabilization, the sulphur of fusing evenly is filled in the hollow Nano carbon pipe of mesoporous nano material with carbon element.
The lithium-sulphur cell positive electrode material capacity of the present invention's preparation is greater than 1800mAh/g, and 500 times circulation volume keeps more than 80%.
Embodiment
Embodiment one:
Take by weighing 100g sucrose, the 1g concentrated sulfuric acid and 100g water and 10g silicon dioxide mix the back and evenly stirred 5 hours; Mixture is put into baking oven, and the baking oven heating rate is for per hour heating up 20 ℃, and temperature rises to 100 ℃, keeps 5 hours; After the solvent evaporation, mixture is put into the pyroreaction still roasting of inert gas shielding, pyroreaction still heating rate is for per hour heating up 100 ℃, and temperature rises to 1000 ℃, keeps 10 hours; Mixture after the roasting is put into sodium hydroxide solution or hydrofluoric acid stirred 10 hours, make the silica template dissolving, filter then, wash, drying, obtain the inner mesoporous nano material with carbon element of nano hollow carbon pipe that is.
Mesoporous nano material with carbon element and sulfur nano particles are put into nanometer high pressure high temperature vapor mixer, the steam temperature scope is 100-600 ℃, with the high-temperature vapour is that carrier mixes both, nanometer high pressure high temperature vapor mixer heating rate is for per hour heating up 40 ℃, be warming up to 200 ℃, kept 5 hours behind the temperature stabilization, the sulphur of fusing evenly is filled in the hollow Nano carbon pipe of mesoporous nano material with carbon element.
The lithium-sulphur cell positive electrode material capacity of preparation is 1850mAh/g, and 500 times circulation volume remains 81%.
Embodiment two:
Take by weighing 100g sucrose, the 10g concentrated sulfuric acid, 100g water and 20g silicon dioxide mix the back and evenly stirred 5 hours; Mixture is put into baking oven, and the baking oven heating rate is for per hour heating up 20 ℃, and temperature rises to 200 ℃, keeps 5 hours; After the solvent evaporation, mixture is put into the pyroreaction still roasting of inert gas shielding, pyroreaction still heating rate is for per hour heating up 100 ℃, and temperature rises to 1000 ℃, keeps 5 hours; Mixture after the roasting is put into sodium hydroxide solution or hydrofluoric acid stirred 10 hours, make the silica template dissolving, filter then, wash, drying, obtain the inner mesoporous nano material with carbon element of nano hollow carbon pipe that is.
Mesoporous nano material with carbon element and sulfur nano particles are put into nanometer high pressure high temperature vapor mixer, the steam temperature scope is 100-600 ℃, with the high-temperature vapour is that carrier mixes both, nanometer high pressure high temperature vapor mixer heating rate is for per hour heating up 40 ℃, be warming up to 200 ℃, kept 10 hours behind the temperature stabilization, the sulphur of fusing evenly is filled in the hollow Nano carbon pipe of mesoporous nano material with carbon element.
The lithium-sulphur cell positive electrode material capacity of preparation is 1820mAh/g, and 500 times circulation volume keeps 82%.
Embodiment three:
Take by weighing 100g sucrose, the 10g concentrated sulfuric acid, 200g water and 100g template silicon dioxide mix the back and evenly stirred 5 hours; Mixture is put into baking oven, and the baking oven heating rate is for per hour heating up 20 ℃, and temperature rises to 200 ℃, keeps 5 hours; After the solvent evaporation, mixture is put into the pyroreaction still roasting of inert gas shielding, pyroreaction still heating rate is for per hour heating up 100 ℃, and temperature rises to 800 ℃, keeps 10 hours; Mixture after the roasting is put into sodium hydroxide solution or hydrofluoric acid stirred 10 hours, make the silica template dissolving, filter then, wash, drying, obtain the inner mesoporous nano material with carbon element of nano hollow carbon pipe that is.
Mesoporous nano material with carbon element and sulfur nano particles are put into nanometer high pressure high temperature vapor mixer, the steam temperature scope is 100-600 ℃, with the high-temperature vapour is that carrier mixes both, nanometer high pressure high temperature vapor mixer heating rate is for per hour heating up 40 ℃, be warming up to 400 ℃, kept 10 hours behind the temperature stabilization, the sulphur of fusing evenly is filled in the hollow Nano carbon pipe of mesoporous nano material with carbon element.
The lithium-sulphur cell positive electrode material capacity of preparation is 1845mAh/g, and 500 times circulation volume remains 82.5%.
Claims (4)
1. a lithium-sulphur cell positive electrode material is characterized in that: in the described positive electrode, after the nanometer sulphur particle heat fused, evenly be filled in the hollow Nano carbon pipe of mesoporous nano material with carbon element, make sulphur closely contact with carbon.
2. a kind of lithium-sulphur cell positive electrode material as claimed in claim 1 is characterized in that: the hollow Nano carbon pipe of described mesoporous nano material with carbon element, and every carbon tube thickness is the 5-200 nanometer, the aperture is the 2-100 nanometer.
3. a kind of lithium-sulphur cell positive electrode material as claimed in claim 1 is characterized in that: described sulfur nano particles granularity is the 2-100 nanometer.
4. a kind of lithium-sulphur cell positive electrode preparation methods as claimed in claim 1 the steps include:
(1) preparation of mesoporous nano material with carbon element:
According to weight ratio 1: 0.01-0.1: 1-20: 0.1-2 takes by weighing sucrose, and the concentrated sulfuric acid and water and template silicon dioxide mix the back and evenly stirred 1～10 hour; Mixture is put into baking oven, and the baking oven heating rate is for per hour heating up 20 ℃, and temperature rises to 100～200 ℃, keeps 1～10 hour; After the solvent evaporation, mixture is put into the pyroreaction still roasting of inert gas shielding, pyroreaction still heating rate is for per hour heating up 100 ℃, and temperature rises to 500～1000 ℃, keeps 2～10 hours; Mixture after the roasting is put into sodium hydroxide solution or hydrofluoric acid stirred 1～20 hour, make the silica template dissolving, filter then, wash, drying, obtain the inner mesoporous nano material with carbon element of nano hollow carbon pipe that is.
(2) sulfur nano particles is filled in the nano hollow carbon pipe:
Mesoporous nano material with carbon element and sulfur nano particles are put into nanometer high pressure high temperature vapor mixer, the steam temperature scope is 100-600 ℃, with the high-temperature vapour is that carrier mixes both, nanometer high pressure high temperature vapor mixer heating rate is for per hour heating up 40 ℃, be warming up to 120～500 ℃, kept 2-20 hour behind the temperature stabilization, the sulphur of fusing evenly is filled in the hollow Nano carbon pipe of mesoporous nano material with carbon element.
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012131628A1 (en) * | 2011-03-31 | 2012-10-04 | Basf Se | Particulate porous carbon material and use thereof in lithium cells |
| CN102800865A (en) * | 2012-08-28 | 2012-11-28 | 吴永胜 | Lithium battery with total solid ions for conducting power |
| CN102891292A (en) * | 2012-09-24 | 2013-01-23 | 上海锦众信息科技有限公司 | Method for preparing composite anode material of lithium-sulfur battery |
| CN103560232A (en) * | 2013-09-30 | 2014-02-05 | 南京工业大学 | Preparation method of S-C positive pole composite material of high cycle performance lithium sulfur battery |
| CN103700859A (en) * | 2013-12-30 | 2014-04-02 | 温州大学 | Graphene-based nitrogen-doped hierachical-pore carbon nanosheet/sulfur composite material for cathode of lithium sulfur battery, as well as preparation method and application of graphene-based nitrogen-doped hierachical-pore carbon nanosheet/sulfur composite material |
| CN104157861A (en) * | 2013-05-14 | 2014-11-19 | 深圳华粤宝电池有限公司 | Mesoporous carbon material, elemental sulfur and preparation method for mesoporous carbon composite material |
| CN104157849A (en) * | 2013-05-14 | 2014-11-19 | 深圳华粤宝电池有限公司 | Method for preparing elemental sulfur and mesoporous carbon composite material |
| CN104254938A (en) * | 2011-12-22 | 2014-12-31 | 德州系统大学董事会 | Binder-free sulfur-carbon nanotube composite cathodes for rechargeable lithium-sulfur batteries and methods of making the same |
| CN104685672A (en) * | 2012-10-11 | 2015-06-03 | 赫罗伊斯石英玻璃股份有限两合公司 | Composite made of porous carbon and sulphur-containing active material as well as method for producing same |
| US9099744B2 (en) | 2011-03-31 | 2015-08-04 | Basf Se | Particulate porous carbon material and use thereof in lithium cells |
| CN105006557A (en) * | 2015-05-14 | 2015-10-28 | 中国矿业大学 | Method for preparing lithium sulfur battery cathode material sealed by nano metal valve |
| CN105374979A (en) * | 2015-10-16 | 2016-03-02 | 广东烛光新能源科技有限公司 | Preparation method of sulfur-containing electrode material |
| CN108400285A (en) * | 2018-03-09 | 2018-08-14 | 南京大学 | A kind of carbon-based no metal elctro-catalyst for promoting polysulfide conversion in lithium-sulfur cell |
| CN109360970A (en) * | 2018-11-20 | 2019-02-19 | 肇庆市华师大光电产业研究院 | A kind of lithium sulphur one-shot battery positive electrode and preparation method thereof |
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| 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 |
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Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012131628A1 (en) * | 2011-03-31 | 2012-10-04 | Basf Se | Particulate porous carbon material and use thereof in lithium cells |
| US9099744B2 (en) | 2011-03-31 | 2015-08-04 | Basf Se | Particulate porous carbon material and use thereof in lithium cells |
| CN104254938A (en) * | 2011-12-22 | 2014-12-31 | 德州系统大学董事会 | Binder-free sulfur-carbon nanotube composite cathodes for rechargeable lithium-sulfur batteries and methods of making the same |
| CN102800865A (en) * | 2012-08-28 | 2012-11-28 | 吴永胜 | Lithium battery with total solid ions for conducting power |
| CN102891292A (en) * | 2012-09-24 | 2013-01-23 | 上海锦众信息科技有限公司 | Method for preparing composite anode material of lithium-sulfur battery |
| CN104685672B (en) * | 2012-10-11 | 2018-04-27 | 赫罗伊斯石英玻璃股份有限两合公司 | The composite material and its manufacture method being made of porous carbon and sulfur-bearing active material |
| CN104685672A (en) * | 2012-10-11 | 2015-06-03 | 赫罗伊斯石英玻璃股份有限两合公司 | Composite made of porous carbon and sulphur-containing active material as well as method for producing same |
| US10340512B2 (en) | 2012-10-11 | 2019-07-02 | Heraeus Quarzglas Gmbh & Co. Kg | Composite made of porous carbon and sulfer-containing active material as well as method for producing same |
| CN104157861A (en) * | 2013-05-14 | 2014-11-19 | 深圳华粤宝电池有限公司 | Mesoporous carbon material, elemental sulfur and preparation method for mesoporous carbon composite material |
| CN104157849A (en) * | 2013-05-14 | 2014-11-19 | 深圳华粤宝电池有限公司 | Method for preparing elemental sulfur and mesoporous carbon composite material |
| CN103560232A (en) * | 2013-09-30 | 2014-02-05 | 南京工业大学 | Preparation method of S-C positive pole composite material of high cycle performance lithium sulfur battery |
| CN103700859A (en) * | 2013-12-30 | 2014-04-02 | 温州大学 | Graphene-based nitrogen-doped hierachical-pore carbon nanosheet/sulfur composite material for cathode of lithium sulfur battery, as well as preparation method and application of graphene-based nitrogen-doped hierachical-pore carbon nanosheet/sulfur composite material |
| CN105006557B (en) * | 2015-05-14 | 2017-02-22 | 中国矿业大学 | Method for preparing lithium sulfur battery cathode material sealed by nano metal valve |
| CN105006557A (en) * | 2015-05-14 | 2015-10-28 | 中国矿业大学 | Method for preparing lithium sulfur battery cathode material sealed by nano metal valve |
| CN105374979B (en) * | 2015-10-16 | 2018-01-19 | 广东烛光新能源科技有限公司 | A kind of preparation method of sulfur-bearing electrode material |
| CN105374979A (en) * | 2015-10-16 | 2016-03-02 | 广东烛光新能源科技有限公司 | Preparation method of sulfur-containing electrode material |
| CN108400285A (en) * | 2018-03-09 | 2018-08-14 | 南京大学 | A kind of carbon-based no metal elctro-catalyst for promoting polysulfide conversion in lithium-sulfur cell |
| CN109360970A (en) * | 2018-11-20 | 2019-02-19 | 肇庆市华师大光电产业研究院 | A kind of lithium sulphur one-shot battery positive electrode and preparation method thereof |
| CN109360970B (en) * | 2018-11-20 | 2022-04-08 | 肇庆市华师大光电产业研究院 | Positive electrode material of lithium-sulfur primary battery and preparation method of positive electrode material |
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Application publication date: 20110316 |