CN103219493B - A kind of sulphur conductive oxide composite material and the application as lithium sulfur battery anode material thereof - Google Patents
A kind of sulphur conductive oxide composite material and the application as lithium sulfur battery anode material thereof Download PDFInfo
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- CN103219493B CN103219493B CN201310110840.9A CN201310110840A CN103219493B CN 103219493 B CN103219493 B CN 103219493B CN 201310110840 A CN201310110840 A CN 201310110840A CN 103219493 B CN103219493 B CN 103219493B
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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 discloses a kind of sulphur conductive oxide composite material and the application as lithium sulfur battery anode material thereof, the preparation method of described sulphur conductive oxide composite material comprises the steps: that (1) gets a certain amount of titanium dioxide, in reducing atmosphere, be warming up to 800 ~ 1100 DEG C of sintering 1 ~ 4 hour, prepare conductive oxide; (2) being dissolved in solvent by sublimed sulfur, is (2 ~ 1) in the mass ratio of sulphur and conductive oxide: the ratio of 1 adds conductive oxide, ultrasonic mixing, obtains composite material precursor after removing solvent; (3) by abundant for composite material precursor ball milling, sulphur conductive oxide composite material is obtained.Preparation technology of the present invention is simple, is beneficial to and realizes industrialization, non-pollutant discharge, environmentally friendly; The composite material volume specific capacity of preparation is high, good conductivity, and cyclical stability is strong, can be used as anode material for lithium-ion batteries and is widely used in the fields such as lithium-sulfur cell.
Description
(1) technical field
The present invention relates to a kind of sulphur conductive oxide composite material and the application as lithium sulfur battery anode material thereof.
(2) background technology
With LiFePO 4, cobalt acid lithium, LiMn2O4 is the lithium ion battery of representative, its stable electrochemical property, be easy to synthesis, laboratory specific energy reaches 250Wh/kg, but by the restriction that positive electrode specific capacity improves further, its specific energy is difficult to improve a lot again, and by improving charging voltage to increase the approach of specific energy by the generation of aggravation safety problem.In new energy storage system, take lithium metal as negative pole, the theoretical specific energy of the elemental sulfur lithium-sulfur cell that is positive pole can reach 2600Wh/kg, the theoretical specific capacity of sulphur reaches 1675mAh/g, much larger than commercialization secondary cell.And sulphur is probably 0.048wt% in the abundance of occurring in nature, belongs to the natural resources underused, elemental sulfur has the features such as the large and low-density of hypotoxicity, cheap, storage, makes this system great commercial value.
The research of lithium sulfur battery anode material is conceived to carbon sulphur composite material substantially both at home and abroad at present, and this material volume specific energy is low, and complicated process of preparation, and cost is higher.The present invention adopts conductive oxide as the carrier of sulphur, prepare the lithium-sulfur cell composite material based on conductive oxide,, there is Lacking oxygen defect in this material and ordinary oxide material ratio, this Lacking oxygen defect has stronger suction-operated to polysulfide, the dissolving of polysulfide can be suppressed preferably in lithium-sulfur cell, meanwhile, it is strong that this material has conductivity, and volumetric specific energy is high, circulating battery stability is strong, and preparation technology is simple.
(3) summary of the invention
The present invention's first object is to provide a kind ofly has good conductivity, good battery cyclical stability and the low sulphur conductive oxide composite material of preparation cost.
The present invention's second object is applied in lithium-sulfur cell as positive electrode by described sulphur conductive oxide composite material.
Illustrate technical scheme of the present invention below.
A kind of sulphur conductive oxide composite material, its preparation method comprises the steps:
(1) get a certain amount of titanium dioxide, in reducing atmosphere, be warming up to 800 ~ 1100 DEG C of sintering 1 ~ 4 hour, prepare conductive oxide;
(2) being dissolved in solvent by sublimed sulfur, is (2 ~ 1) in the mass ratio of sulphur and conductive oxide: the ratio of 1 adds conductive oxide, ultrasonic mixing, obtains composite material precursor after removing solvent;
(3) by abundant for composite material precursor ball milling, sulphur conductive oxide composite material is obtained.
In described step (1), the P25 type titanium dioxide that titanium dioxide used is preferably commercial, reducing atmosphere is preferably hydrogen.
In described step (1), preferably with the ramp of 5 ~ 10 DEG C/min to sintering temperature; Sintering temperature is preferably 900 ~ 1100 DEG C, is more preferably 950 ~ 1050 DEG C, most preferably 1050 DEG C; Sintering temperature preferably 4 hours.
In described step (2), the solvent dissolving sublimed sulfur selects to dissolve at normal temperatures the solvent of sulphur, preferred carbon disulfide, and this process need be carried out in fume hood, leaves standstill at normal temperatures and carbon disulfide can be made to volatilize completely.
In described step (2), sulphur compares preferably (2 ~ 1.5) with the mixing quality of conductive oxide: 1, is more preferably 1.5 ~ 1.7:1, most preferably is 1.5:1.
In described step (2), by ultrasonic wave, sulphur and conductive oxide are mixed, ultrasonic incorporation time is preferably 10 ~ 30 minutes.
In described step (3), composite material precursor can be placed in ball mill (such as star ball mill) and carry out ball milling, and Ball-milling Time is preferably 12 ~ 24 hours.
The present invention specifically recommends described sulphur conductive oxide composite material to carry out in accordance with the following steps:
(1) P25 type titanium dioxide is placed in high temperature process furnances, under the atmosphere of pure hydrogen, tube furnace is warming up to 800 ~ 1100 DEG C, sinter 1 ~ 4 hour, cooling obtains conductive oxide;
(2) sublimed sulfur is dissolved in carbon disulfide, then be (2 ~ 1) in the mass ratio of sulphur and conductive oxide: the ratio of 1 adds conductive oxide, then ultrasonic vibration 10 ~ 30 minutes, conductive oxide and sulphur are mixed, leaving standstill at normal temperatures makes carbon disulfide volatilize again, and obtains composite material precursor;
(3) composite material precursor obtained in step (2) is positioned in ball mill, ball milling 12 ~ 24 hours, takes out and obtain sulphur conductive oxide composite material.
Present invention also offers the application of described sulphur conductive oxide composite material as lithium sulfur battery anode material, wherein lithium-sulfur cell is prepared by conventional method.
Compared with prior art, its beneficial effect is mainly reflected in the present invention:
(1) titanium dioxide that the present invention adopts is business-like P25 type titanium dioxide, abundance; Sulphur recombination process used is mechanical ball milling, and technique is simple, is beneficial to and realizes industrialization, non-pollutant discharge, environmentally friendly.
(2) the composite material volume specific capacity prepared of the present invention is high, good conductivity, and cyclical stability is strong, can be used as anode material for lithium-ion batteries and is widely used in the fields such as lithium-sulfur cell.
(4) accompanying drawing explanation
Fig. 1 is the XRD diffraction pattern of the conductive oxide prepared by embodiment 1.
Fig. 2 is the conductive oxide electron scanning micrograph prepared by embodiment 1.
Fig. 3 is the simulation lithium ion battery charging and discharging curve figure prepared by embodiment 1, voltage range 1.5 – 3.0V, electrolyte is 1mol/LLiTFSI/DOL – DME (1:1), and charge-discharge magnification is 0.1C, measuring tempeature is 25 ± 5 DEG C, and cycle-index is 50 times.
Fig. 4 is the AC impedance figure 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
1g commercialization P25 is positioned in high temperature process furnances, in a hydrogen atmosphere, is warming up to 1050 DEG C with 10 DEG C/min, sinter 4 hours, obtain conductive oxide.Fig. 1 is the XRD diffraction pattern of this material, and reference standard card is Ti
4o
7, Fig. 2 is the stereoscan photograph of this material, even particle size, and average grain diameter is 500 nanometers.
Be dissolved in by sublimed sulfur in carbon disulfide, the ratio being then 1.5:1 in sulphur and conductive oxide mass ratio adds conductive oxide, and rear ultrasonic vibration 30 minutes makes conductive oxide and sulphur mix.After at normal temperatures leave standstill carbon disulfide is volatilized.Then by resulting materials ball milling 24 hours, sulphur/Ti is obtained
4o
7composite material.
Sulphur/Ti is taken respectively with the mass ratio of 80:10:10
4o
7composite material: acetylene black: polytetrafluoroethylene, make electrode after grinding evenly, metal lithium sheet is negative pole, and electrolyte is 1mol/LLiTFSI/DOL – DME (1:1), and polypropylene microporous film is barrier film, is assembled into simulation lithium ion battery.Fig. 3 be respective battery at 0.1C multiplying power 50 cycle charge-discharge curves, show surveyed battery capacity stablizes in 50 cyclic processes, composite material capacity remains on about 500mAh/g.See from Fig. 4 (the AC impedance figure of lithium ion battery), prepared sulphur/Ti
4o
7composite material electrochemical charge transfger impedance only has 52.2 Ω, and the electric conductivity of material is very good.
Embodiment 2
1g commercialization P25 is positioned in high temperature process furnances, in a hydrogen atmosphere, is warming up to 950 DEG C with 10 DEG C/min, sinter 4 hours, obtain conductive oxide.Reference standard card is Ti
4o
7.
Be dissolved in by sublimed sulfur in carbon disulfide, the ratio being then 1.7:1 in sulphur conductive oxide mass ratio adds conductive oxide, and rear ultrasonic vibration 20 minutes makes conductive oxide and sulphur mix.After at normal temperatures leave standstill carbon disulfide is volatilized.Then by resulting materials ball milling 18 hours, sulphur/Ti is obtained
4o
7composite material.
Sulphur/Ti is taken respectively with the mass ratio of 80:10:10
4o
7composite material: acetylene black: polytetrafluoroethylene, make electrode after grinding evenly, metal lithium sheet is negative pole, and electrolyte is 1mol/LLiTFSI/DOL – DME (1:1), and polypropylene microporous film is barrier film, is assembled into simulation lithium ion battery.
Battery testing method is with embodiment 1, and gained battery is at 0.1C multiplying power 50 cycle charge-discharges, and capacity stablizes in cyclic process, capacity remains on about 450mAh/g.Prepared sulphur/Ti
4o
7composite material electrochemical charge transfger impedance has 63 Ω.
Embodiment 3
1g commercialization P25 is positioned in high temperature process furnances, in a hydrogen atmosphere, is warming up to 850 DEG C with 10 DEG C/min, sinter 1 hour, obtain conductive oxide.Reference standard card is Ti
5o
9.
Be dissolved in by sublimed sulfur in carbon disulfide, the ratio being then 2:1 in sulphur conductive oxide mass ratio adds conductive oxide, and rear ultrasonic vibration 15 minutes makes conductive oxide and sulphur mix.After at normal temperatures leave standstill carbon disulfide is volatilized.Then by resulting materials ball milling 12 hours, sulphur/Ti is obtained
5o
9composite material.
Sulphur/Ti is taken respectively with the mass ratio of 80:10:10
5o
9composite material: acetylene black: polytetrafluoroethylene, make electrode after grinding evenly, metal lithium sheet is negative pole, and electrolyte is 1mol/LLiTFSI/DOL – DME (1:1), and polypropylene microporous film is barrier film, is assembled into simulation lithium ion battery.
Battery testing method is with embodiment 1, and gained battery is at 0.1C multiplying power 50 cycle charge-discharges, and capacity stablizes in cyclic process, capacity remains on about 400mAh/g.Prepared sulphur/Ti
5o
9composite material electrochemical charge transfger impedance only has 76 Ω.
Claims (9)
1. a sulphur conductive oxide composite material, is characterized in that: its preparation method comprises the steps:
(1) get a certain amount of titanium dioxide, described titanium dioxide adopts P25 type titanium dioxide, is warming up to 850 ~ 1050 DEG C of sintering 1 ~ 4 hour, prepares conductive oxide in reducing atmosphere;
(2) being dissolved in solvent by sublimed sulfur, is (2 ~ 1.5) in the mass ratio of sulphur and conductive oxide: the ratio of 1 adds conductive oxide, ultrasonic mixing, obtains composite material precursor after removing solvent;
(3) by abundant for composite material precursor ball milling, sulphur conductive oxide composite material is obtained.
2. sulphur conductive oxide composite material as claimed in claim 1, is characterized in that: the reducing atmosphere in step (1) is nitrogen atmosphere.
3. sulphur conductive oxide composite material as claimed in claim 1, it is characterized in that: in described step (2), solvent is carbon disulfide.
4. the sulphur conductive oxide composite material as described in one of claims 1 to 3, is characterized in that: in described step (1), in reducing atmosphere with the ramp of 10 DEG C/min to sintering temperature.
5. sulphur conductive oxide composite material as claimed in claim 4, is characterized in that: sintering temperature is 900 ~ 1050 DEG C.
6. sulphur conductive oxide composite material as claimed in claim 5, is characterized in that: sintering temperature is 950 ~ 1050 DEG C.
7. the sulphur conductive oxide composite material as described in one of claims 1 to 3, is characterized in that: in described step (2), and sulphur is 1.5 ~ 1.7:1 with the mixing quality ratio of conductive oxide.
8. sulphur conductive oxide composite material as claimed in claim 1, it is characterized in that: in described step (2), ultrasonic incorporation time is 15 ~ 30 minutes; In described step (3), Ball-milling Time is 12 ~ 24 hours.
9. sulphur conductive oxide composite material as claimed in claim 1 is as the application of lithium sulfur battery anode material.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104201392B (en) * | 2014-08-20 | 2016-06-15 | 中南大学 | The preparation method of a kind of lithium sulphur battery electrode |
| CN104269544B (en) * | 2014-10-15 | 2016-08-17 | 南京中储新能源有限公司 | Graphene array anode composite and its preparation method and application |
| CN105006553B (en) * | 2015-07-11 | 2017-06-23 | 中国计量学院 | A kind of preparation method of sulphur/carbon/oxide combination 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 |
| CN105489863B (en) * | 2015-12-31 | 2017-11-17 | 长沙矿冶研究院有限责任公司 | One kind is based on C/Ti4O7Lithium sulfur battery anode material of composite nano fiber and preparation method thereof |
| CN105489864B (en) * | 2016-01-13 | 2018-08-14 | 李震祺 | A kind of Asia titanium-oxide-coated modified phosphate iron lithium composite material and preparation method thereof |
| CN105845916B (en) * | 2016-06-01 | 2019-04-16 | 中国计量大学 | A kind of ferroelectric oxide base sulphur composite material and its application in lithium-sulfur cell |
| CN107359321B (en) * | 2017-06-09 | 2018-07-27 | 深圳启辰新能源科技有限公司 | The lithium sulfur battery anode material and preparation method thereof of the nitrogen-doped carbon of spherical structure/titanium oxide bivalve cladding titanium oxide/sulphur |
| CN107492639B (en) * | 2017-07-28 | 2020-05-15 | 清华大学 | Lithium-sulfur battery composite positive electrode material and preparation method thereof |
| CN109546092B (en) * | 2017-09-22 | 2022-05-20 | 哈尔滨理工大学 | Lithium-sulfur thin film battery |
| CN110380052B (en) * | 2019-07-19 | 2022-05-17 | 东营昆宇电源科技有限公司 | High-conductivity sulfur-based composite material for lithium-sulfur battery positive electrode |
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| CN102945966A (en) * | 2012-12-07 | 2013-02-27 | 中国科学院上海硅酸盐研究所 | Positive pole composite system of lithium sulphur battery containing catalytic additive |
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| CN102945966A (en) * | 2012-12-07 | 2013-02-27 | 中国科学院上海硅酸盐研究所 | Positive pole composite system of lithium sulphur battery containing catalytic additive |
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| Sulphur–TiO2 yolk–shell nanoarchitecture with internal void space for long-cycle lithium–sulphur batteries;Seh Z W,etal;《nature communications》;20130108;第4卷;1331-1336 * |
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