CN103187560B - A kind of sulphur carbon composite of imitative animal sclay texture and application thereof - Google Patents
A kind of sulphur carbon composite of imitative animal sclay texture and application thereof Download PDFInfo
- Publication number
- CN103187560B CN103187560B CN201310110000.2A CN201310110000A CN103187560B CN 103187560 B CN103187560 B CN 103187560B CN 201310110000 A CN201310110000 A CN 201310110000A CN 103187560 B CN103187560 B CN 103187560B
- Authority
- CN
- China
- Prior art keywords
- carbon composite
- sulphur
- sulphur carbon
- flakey
- carbon element
- 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
Classifications
-
- 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 kind of sulphur carbon composite and application thereof of imitative animal sclay texture, the preparation method of described sulphur carbon composite comprises the steps: that fibrous hollow biomaterial is risen to 400 ~ 1000 DEG C with the heating rate of 5 ~ 20 DEG C/min and carries out carbonization by (1) under nitrogen or argon, and cooling after carbonization, grinding obtain flakey material with carbon element; (2) by step (1) gained flakey material with carbon element and elemental sulfur 1:(2 ~ 10 in mass ratio) be scattered in solvent, magnetic agitation, to mixing, is then incubated 1 ~ 3 hour in 80 ~ 200 DEG C; (3) cooled and filtered be drying to obtain sulphur carbon composite.Sulphur carbon composite of the present invention can be used as anode material for lithium-ion batteries, has good conductivity, high sulfur content, high-volume and capacity ratio and good cycle performance and capability retention.
Description
(1) technical field
The present invention relates to a kind of sulphur carbon composite of imitative animal sclay texture and the application as anode material for lithium-ion batteries thereof.
(2) background technology
Lithium ion battery is the novel green high-energy secondary battery occurred early 1990s, has become the emphasis that countries in the world are are competitively researched and developed.Positive electrode is an important component part of lithium ion battery, current transition metal oxide (LiCoO
2) and phosphate (LiFePO
4) the highest theoretical specific capacity of positive electrode is only 300mAh/g, actual specific capacity is then lower, the lithium ion battery actual specific energy about 120 ~ 200Wh/Kg adopting these positive electrodes to build.For meeting the instructions for use of electrokinetic cell high-energy-density and high-specific-power, be that the new system of representative receives much concern in recent years with lithium-sulfur cell.The theoretical specific capacity of elemental sulfur is 1672mAh/g, and the theoretical specific energy of lithium-sulfur cell is up to 2600Wh/kg, and actual specific energy can reach 500 ~ 800Wh/Kg.Elemental sulfur has the advantages such as abundance, low price, environmental friendliness, battery security be good, therefore, lithium-sulfur cell is considered to green high-capacity secondary cell most with prospects, once succeed in developing, has good development prospect in new-energy automobile fields such as electric automobiles.
At present, the lithium-sulphur cell positive electrode structure of scientific research personnel's design is mainly mesoporous carbon, active carbon, hollow carbon balls, the coated sulphur of conducting polymer etc., is all with the coated sulphur of conducting base.Above conducting base synthesis cost is high, and the electrode material sulfur content obtained is low, can not meet the large-scale application demand of lithium-sulfur cell.
Nature has a lot of animal to have scale, and as fish, snake class and amphibian animal, its scale is taken layer by layer mutually, not only can prevent moisture from evaporating, also play the effect of isolated external substance and direct skin contact.Because the unique effect of scale, first this patent prepares flakey material with carbon element, is then packed into by sulphur in the gap of flakey material with carbon element formation.On the one hand, flakey material with carbon element gap can hold a large amount of sulphur, improves sulfur content, and volume and capacity ratio is increased greatly; On the other hand, the direct contact surface that flakey material with carbon element reduces sulphur and electrolyte amasss, and improves active material utilization.
(3) summary of the invention
The present invention's first object is to provide a kind of sulphur carbon composite, and this sulphur carbon composite has imitative animal sclay texture, has good conductivity, high sulfur content, high-volume and capacity ratio and good cycle performance and capability retention.
The present invention's second object is to provide the application of described sulphur carbon composite as anode material for lithium-ion batteries.
Illustrate technical scheme of the present invention below.
The invention provides a kind of sulphur carbon composite, the preparation method of described sulphur carbon composite comprises the steps:
(1) fibrous hollow biomaterial is risen to 400 ~ 1000 DEG C with the heating rate of 5 ~ 20 DEG C/min under nitrogen or argon and carry out carbonization, cooling after carbonization, grinding obtain flakey material with carbon element;
(2) by step (1) gained flakey material with carbon element and elemental sulfur 1:(2 ~ 10 in mass ratio) be scattered in solvent, magnetic agitation, to mixing, is then incubated 1 ~ 3 hour in 80 ~ 200 DEG C;
(3) cooled and filtered be drying to obtain sulphur carbon composite.The sulphur carbon composite that the present invention obtains has imitative animal sclay texture.
In described step (1), described biomaterial is fibrous hollow biomaterial, preferred cotton.Heating rate is preferably 5 ~ 18 DEG C/min, is more preferably 5 ~ 10 DEG C/min, most preferably is 10 DEG C/min; Carburizing temperature is preferably 400 ~ 800 DEG C, is more preferably 400 ~ 600 DEG C, most preferably is 600 DEG C; Carbonization time is preferably 1 ~ 2 hour.
In described step (2), described solvent can disperse flakey material with carbon element and elemental sulfur simultaneously, preferred Macrogol 200.The mass ratio of flakey material with carbon element and elemental sulfur is preferably 1:2 ~ 8, is more preferably 1:4 ~ 6, most preferably is 1:4.Holding temperature is preferably 80 ~ 150 DEG C, and temperature retention time is preferably 1 ~ 2 hour.
The present invention specifically recommends described sulphur carbon composite to carry out in accordance with the following steps:
(1) cotton risen to 400 ~ 600 DEG C of carbonizations 1 ~ 2 hour with the heating rate of 5 ~ 10 DEG C/min under nitrogen or argon, then cool, grind and obtain flakey material with carbon element;
(2) be scattered in Macrogol 200 in 1:4 ~ 6 in mass ratio by step (1) gained flakey material with carbon element and elemental sulfur, magnetic agitation, to mixing, is then incubated 1 ~ 2 hour in 80 ~ 150 DEG C;
(3) cooled and filtered be drying to obtain sulphur carbon composite.
Present invention also offers the application of described sulphur carbon composite as anode material for lithium-ion batteries, wherein the preparation of lithium ion battery adopts conventional method.
Compared with prior art, its beneficial effect is mainly reflected in the present invention:
(1) the present invention adopts cheap fibrous hollow biomaterial (cotton etc.) to be carbon source, its filamentary structure becomes fragile and caves in carbonisation, through grinding after can obtain flakey material with carbon element, raw materials wide material sources, be easy to get, cheap, be easy to industrializing implementation; Preparation technology is simple, without waste water and gas discharge, thus environmentally friendly.
(2) the sulphur carbon composite that prepared by the present invention has imitative animal sclay texture, and sulphur is closely filled in the gap of flakey material with carbon element formation, adds the touch opportunity of sulphur and electronics, therefore has good conductivity; Because flakey material with carbon element can form a large amount of gap to fill sulphur, therefore material has high sulfur content; During given volume, the higher then volume and capacity ratio of sulfur content is larger, and therefore material has high-volume and capacity ratio; In addition, sulphur is tightly bound in the gap of flakey material with carbon element formation, this structure effectively prevent intermediate product-many lithium sulfides of sulphur to the dissolving in electrolyte, inhibit effect of shuttling back and forth, improve the utilance of sulphur, therefore material has good capability retention, can be used as anode material for lithium-ion batteries and is widely used in the fields such as energy type lithium ion battery.
(4) accompanying drawing explanation
Fig. 1 is the scale figure of fish;
Fig. 2 is the XRD diffraction pattern of the imitative animal flakey sulphur carbon composite prepared by embodiment 1;
Fig. 3 is transmission electron microscope (TEM) photo of the imitative animal flakey sulphur carbon composite prepared by embodiment 1;
Fig. 4 is the cycle performance figure of the simulation lithium ion battery prepared by embodiment 1;
Fig. 5 is the cyclic voltammogram of the simulation lithium ion battery prepared by embodiment 1.
(5) specific implementation method
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
3g cotton is put into tube furnace, under the atmosphere of nitrogen or argon gas, 600 DEG C are risen to and constant temperature 1 hour with the heating rate of 10 DEG C/min, naturally after cooling, grinding obtains flakey material with carbon element, then by gained flakey material with carbon element and elemental sulfur in mass ratio 1:4 to be dissolved in Macrogol 200 and to be stirred to evenly, at 100 DEG C, be incubated 2 hours, cooling removes desolventizing and is drying to obtain product.Fig. 2 is the XRD diffraction pattern of this material, and reference standard card is crystallization sulphur, does not observe the diffraction maximum of carbon.Fig. 3 is the transmission electron microscope photo of this material, and product is imitative animal sclay texture as seen from the figure.
Electrode is made as follows with the imitative animal flakey sulphur carbon composite obtained by embodiment 1.
Imitative animal flakey sulphur carbon composite is taken respectively: acetylene black: poly-inclined tetrafluoroethene with the mass ratio of 80:10:10, electrode is made after grinding evenly, metal lithium sheet is negative pole, electrolyte is 1mol/LLiTFSI/DOL – DME (1:1), polypropylene microporous film is barrier film, is assembled into simulation lithium ion battery.Fig. 4 is the cycle performance curve of respective battery in 0.25C, 1.5 – 3.0V voltage ranges, show that surveyed battery has good cycle performance and capability retention at 0.25C, can find out that the imitative animal flakey sulphur carbon composite that obtained by embodiment 1 circulates the discharge capacity after 100 times close to 550mAh/g at 0.25C, capability retention is up to 93%(Fig. 3), cycle performance is excellent.See from Fig. 5 (cyclic voltammogram of lithium ion battery), prepared imitative animal flakey sulphur carbon composite invertibity is very good.
Embodiment 2
3g cotton is put into tube furnace, under the atmosphere of nitrogen or argon gas, 400 DEG C are risen to and constant temperature 1 hour with the heating rate of 10 DEG C/min, naturally after cooling, grinding obtains flakey material with carbon element, then gained flakey material with carbon element and elemental sulfur to be dissolved in Macrogol 200 by 1:4 and to be stirred to evenly, at 100 DEG C, be incubated 2 hours, cooled and filtered is also drying to obtain product.
Make electrode with obtained imitative animal flakey sulphur carbon composite by the method for embodiment 1, be assembled into simulation lithium ion battery, 0.25C circulates the discharge capacity after 100 times close to 495mAh/g, and capability retention reaches 80%, and cycle performance, reversibility are good.
Embodiment 3
3g cotton is put into tube furnace, under the atmosphere of nitrogen or argon gas, 600 DEG C are risen to and constant temperature 1 hour with the heating rate of 10 DEG C/min, naturally after cooling, grinding obtains flakey material with carbon element, then by gained flakey material with carbon element and elemental sulfur in mass ratio 1:6 to be dissolved in Macrogol 200 and to be stirred to evenly, at 100 DEG C, be incubated 2 hours, cooled and filtered is also drying to obtain product.
Make electrode with obtained imitative animal flakey sulphur carbon composite by the method for embodiment 1, be assembled into simulation lithium ion battery, 0.25C circulates the discharge capacity after 100 times close to 472mAh/g, and capability retention reaches 73%, and cycle performance, reversibility are good.
Embodiment 4
3g cotton is put into tube furnace, under the atmosphere of nitrogen or argon gas, 600 DEG C are risen to and constant temperature 1 hour with the heating rate of 5 DEG C/min, naturally after cooling, grinding obtains flakey material with carbon element, then by gained flakey material with carbon element and elemental sulfur in mass ratio 1:6 to be dissolved in Macrogol 200 and to be stirred to evenly, at 100 DEG C, be incubated 2 hours, cooled and filtered is also drying to obtain product.
Make electrode with obtained imitative animal flakey sulphur carbon composite by the method for embodiment 1, be assembled into simulation lithium ion battery, 0.25C circulates the discharge capacity after 100 times close to 403mAh/g, and capability retention reaches 62%.
Claims (8)
1. a sulphur carbon composite, is characterized in that: the preparation method of described sulphur carbon composite comprises the steps:
(1) fibrous hollow biomaterial is risen to 400 ~ 1000 DEG C with the heating rate of 5 ~ 20 DEG C/min under nitrogen or argon and carry out carbonization, cooling after carbonization, grinding obtain flakey material with carbon element; Described fibrous hollow biomaterial is cotton;
(2) by step (1) gained flakey material with carbon element and elemental sulfur 1:(2 ~ 10 in mass ratio) be scattered in solvent, described solvent is Macrogol 200, magnetic agitation, to mixing, is then incubated 1 ~ 3 hour in 80 ~ 200 DEG C;
(3) cooled and filtered be drying to obtain sulphur carbon composite.
2. sulphur carbon composite as claimed in claim 1, is characterized in that: in described step (1), heating rate is 5 ~ 18 DEG C/min, and carburizing temperature is 400 ~ 800 DEG C.
3. sulphur carbon composite as claimed in claim 2, is characterized in that: carbonization time is 1 ~ 2 hour.
4. sulphur carbon composite as claimed in claim 3, is characterized in that: in described step (1), heating rate is 5 ~ 10 DEG C/min, and carburizing temperature is 400 ~ 600 DEG C.
5. sulphur carbon composite as claimed in claim 1, it is characterized in that: in described step (2), the mass ratio of flakey material with carbon element and elemental sulfur is 1:2 ~ 1:8.
6. sulphur carbon composite as claimed in claim 5, it is characterized in that: in described step (2), the mass ratio of flakey material with carbon element and elemental sulfur is 1:4 ~ 1:6.
7. sulphur carbon composite as claimed in claim 1, it is characterized in that: in described step (2), holding temperature is 80 ~ 150 DEG C, and temperature retention time is 1 ~ 2 hour.
8. sulphur carbon composite as claimed in claim 1 is as the application of anode material for lithium-ion batteries.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310110000.2A CN103187560B (en) | 2013-03-30 | 2013-03-30 | A kind of sulphur carbon composite of imitative animal sclay texture and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310110000.2A CN103187560B (en) | 2013-03-30 | 2013-03-30 | A kind of sulphur carbon composite of imitative animal sclay texture and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103187560A CN103187560A (en) | 2013-07-03 |
| CN103187560B true CN103187560B (en) | 2016-02-24 |
Family
ID=48678625
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310110000.2A Active CN103187560B (en) | 2013-03-30 | 2013-03-30 | A kind of sulphur carbon composite of imitative animal sclay texture and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103187560B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106629665B (en) * | 2017-01-22 | 2019-03-12 | 福建师范大学 | Molten-salt growth method prepares sulfur doping hard carbon nanometer sheet and its application in sodium-ion battery |
| CN108666569B (en) * | 2018-03-28 | 2020-09-29 | 天能帅福得能源股份有限公司 | Preparation method of spongy carbon material |
| CN112701266B (en) * | 2020-12-30 | 2022-04-01 | 江西昌河汽车有限责任公司 | Preparation method and application of porous carbon and sulfur composite material |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1393334A (en) * | 2001-06-21 | 2003-01-29 | 王宽飞 | Activated carbon wadding structure for quilt and its productive technology |
| CN101700884A (en) * | 2009-12-02 | 2010-05-05 | 太原嘉能动力科技有限公司 | Method for producing activated carbon from straws |
| CN101728530A (en) * | 2008-11-03 | 2010-06-09 | 埃玛拉公司 | Lithium secondary batteries with positive electrode compositions and their methods of manufacturing |
| CN102246343A (en) * | 2010-03-01 | 2011-11-16 | 新神户电机株式会社 | Lead storage battery |
| CN102280630A (en) * | 2011-07-04 | 2011-12-14 | 中国科学院过程工程研究所 | Sulphur-graphene composite cathode material and manufacturing method thereof |
| CN102324507A (en) * | 2011-09-10 | 2012-01-18 | 中南大学 | Preparation method for lithium-sulfur battery composite anode material |
| CN102467990A (en) * | 2010-11-05 | 2012-05-23 | 海洋王照明科技股份有限公司 | Positive electrode as well as preparation method and application thereof |
| CN102576911A (en) * | 2010-09-30 | 2012-07-11 | 新神户电机株式会社 | Lead storage battery |
| WO2012096358A1 (en) * | 2011-01-14 | 2012-07-19 | 帝人化成株式会社 | Aromatic polycarbonate resin composition and molded article thereof |
| CN102820456A (en) * | 2012-08-20 | 2012-12-12 | 中国科学院化学研究所 | Porous carbon/sulfur composite material, its preparation method and application |
| CN102832379A (en) * | 2012-09-29 | 2012-12-19 | 上海空间电源研究所 | Preparation method of positive material for lithium-sulfur battery |
| CN102881869A (en) * | 2012-09-26 | 2013-01-16 | 东莞市翔丰华电池材料有限公司 | Modified hard carbon negative electrode material for lithium ion battery and preparation method for modified hard carbon negative electrode material |
-
2013
- 2013-03-30 CN CN201310110000.2A patent/CN103187560B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1393334A (en) * | 2001-06-21 | 2003-01-29 | 王宽飞 | Activated carbon wadding structure for quilt and its productive technology |
| CN101728530A (en) * | 2008-11-03 | 2010-06-09 | 埃玛拉公司 | Lithium secondary batteries with positive electrode compositions and their methods of manufacturing |
| CN101700884A (en) * | 2009-12-02 | 2010-05-05 | 太原嘉能动力科技有限公司 | Method for producing activated carbon from straws |
| CN102246343A (en) * | 2010-03-01 | 2011-11-16 | 新神户电机株式会社 | Lead storage battery |
| CN102576911A (en) * | 2010-09-30 | 2012-07-11 | 新神户电机株式会社 | Lead storage battery |
| CN102467990A (en) * | 2010-11-05 | 2012-05-23 | 海洋王照明科技股份有限公司 | Positive electrode as well as preparation method and application thereof |
| WO2012096358A1 (en) * | 2011-01-14 | 2012-07-19 | 帝人化成株式会社 | Aromatic polycarbonate resin composition and molded article thereof |
| CN102280630A (en) * | 2011-07-04 | 2011-12-14 | 中国科学院过程工程研究所 | Sulphur-graphene composite cathode material and manufacturing method thereof |
| CN102324507A (en) * | 2011-09-10 | 2012-01-18 | 中南大学 | Preparation method for lithium-sulfur battery composite anode material |
| CN102820456A (en) * | 2012-08-20 | 2012-12-12 | 中国科学院化学研究所 | Porous carbon/sulfur composite material, its preparation method and application |
| CN102881869A (en) * | 2012-09-26 | 2013-01-16 | 东莞市翔丰华电池材料有限公司 | Modified hard carbon negative electrode material for lithium ion battery and preparation method for modified hard carbon negative electrode material |
| CN102832379A (en) * | 2012-09-29 | 2012-12-19 | 上海空间电源研究所 | Preparation method of positive material for lithium-sulfur battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103187560A (en) | 2013-07-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | A novel zinc-ion hybrid supercapacitor for long-life and low-cost energy storage applications | |
| Yan et al. | Process optimization for producing hierarchical porous bamboo-derived carbon materials with ultrahigh specific surface area for lithium-sulfur batteries | |
| CN103779564B (en) | High-performance vanadium phosphate sodium symmetric form sodium-ion battery material and its preparation method and application | |
| CN101572305B (en) | Preparation method of LiFePO*/C cathode material with high rate performance | |
| CN103219493B (en) | A kind of sulphur conductive oxide composite material and the application as lithium sulfur battery anode material thereof | |
| CN102104144B (en) | Method for preparing lithium iron phosphate compound anode material | |
| CN102610803B (en) | Composite positive pole material for lithium ion battery and preparation method of composite material | |
| CN101794874A (en) | Electrode with grapheme as conductive additive and application thereof in lithium ion battery | |
| CN104882607A (en) | Anima bone base type graphene lithium ion battery negative electrode material and preparation method thereof | |
| CN103647043A (en) | Method for preparing negative electrode material of lithium ion secondary battery | |
| CN103606672A (en) | Rod-shaped nano iron oxide electrode material, and preparation method and application thereof | |
| CN102800858A (en) | Preparation method and purpose for iron oxide-based anode material for lithium ion battery | |
| CN103400988A (en) | Preparation method of lithium ion secondary battery anode material | |
| Zhang et al. | Yttrium substituting in Mn site to improve electrochemical kinetics activity of sol-gel synthesized LiMnPO 4/C as cathode for lithium ion battery | |
| CN104779379A (en) | Novel sulfur and carbon composite material for lithium secondary battery, and preparation method thereof | |
| CN103427068A (en) | Anode material for lithium-sulfur batteries and preparation method of anode material | |
| CN107492635B (en) | Composite positive electrode material Na of sodium-ion battery3V2(PO4)3/C and preparation method thereof | |
| CN104183836B (en) | A kind of lithium-sulfur cell anode composite material | |
| CN103187560B (en) | A kind of sulphur carbon composite of imitative animal sclay texture and application thereof | |
| CN105304866B (en) | A kind of lithium-sulphur cell positive electrode containing metal magnesium powder and preparation method thereof | |
| CN104979534B (en) | A kind of iodine sulphur/carbon composite and preparation method and application | |
| Gao et al. | Na3TiV (PO4) 3/C nanoparticles for sodium‐ion symmetrical and full batteries | |
| CN103545492A (en) | Preparation method of multiple composite anode material of lithium ion battery | |
| CN110556537B (en) | Method for improving electrochemical performance of anion-embedded electrode material | |
| CN104600260A (en) | C/Ni/S composite material prepared from absorbent cotton and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |