CN103219493A - Sulfur conductive oxide composite material and application thereof as lithium-sulfur battery anode material - Google Patents
Sulfur conductive oxide composite material and application thereof as lithium-sulfur battery anode material Download PDFInfo
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- CN103219493A CN103219493A CN2013101108409A CN201310110840A CN103219493A CN 103219493 A CN103219493 A CN 103219493A CN 2013101108409 A CN2013101108409 A CN 2013101108409A CN 201310110840 A CN201310110840 A CN 201310110840A CN 103219493 A CN103219493 A CN 103219493A
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Abstract
The invention discloses a sulfur conductive oxide composite material and an application thereof as a lithium-sulfur battery anode material. The preparation method of the sulfur conductive oxide composite material comprises the following steps of: (1) taking a certain amount of titanium dioxide, increasing the temperature to 800-1,100 DEG C in a reducing atmosphere, and sintering for 1-4 hours so as to prepare a conductive oxide; (2) dissolving sublimed sulfur into a solvent, adding the conductive oxide, wherein the mass ratio of sulfur to the conductive oxide is (2-1):1; ultrasonically mixing, and removing the solvent so as to obtain a composite material precursor; and (3) sufficiently ball-milling the composite material precursor so as to obtain the sulfur conductive oxide composite material. The preparation process of the sulfur conductive oxide composite material is simple, beneficial to industrialization, free of pollutant discharge and environmental-friendly; the prepared composite material is high in volume ratio capacity, good in conductivity and high in circulation stability, and can be widely applied to fields of lithium-sulfur batteries and the like as the lithium-sulfur battery anode material.
Description
(1) technical field
The present invention relates to a kind of sulphur conductive oxide composite material and as the application of lithium-sulphur cell positive electrode material.
(2) background technology
With LiFePO 4, cobalt acid lithium, LiMn2O4 is the lithium ion battery of representative, its stable electrochemical property, be easy to synthesize, the laboratory specific energy has reached 250Wh/kg, but the restriction that further improved by the positive electrode specific capacity, its specific energy is difficult to improve a lot again, and will aggravate the generation of safety problem with the approach that increases specific energy by improving charging voltage.In new energy storage system, be that negative pole, elemental sulfur are that the theoretical specific energy of anodal lithium-sulfur cell can reach 2600Wh/kg with the lithium metal, the theoretical specific capacity of sulphur reaches 1675mAh/g, much larger than the commercialization secondary cell.And sulphur is 0.048wt% probably in the abundance of occurring in nature, belongs to the natural resources of underusing, elemental sulfur have hypotoxicity, cheap, storage big and characteristics such as low-density, makes this system great commercial value.
The research of lithium-sulphur cell positive electrode 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 the carrier of conductive oxide as sulphur, prepared lithium-sulfur cell composite material based on conductive oxide, there are the oxygen vacancy defect in this material and ordinary oxide material ratio, and this oxygen vacancy defect has stronger suction-operated to polysulfide, in lithium-sulfur cell, can suppress the dissolving of polysulfide preferably, simultaneously, it is strong that this material has conductivity, the volumetric specific energy height, the battery cyclical stability is strong, and preparation technology is simple.
(3) summary of the invention
First purpose of the present invention provides a kind of have good electrical conductivity, good battery cyclical stability and the low sulphur conductive oxide composite material of preparation cost.
Second purpose of the present invention is that described sulphur conductive oxide composite material is applied in the lithium-sulfur cell as positive electrode.
Specify technical scheme of the present invention below.
A kind of sulphur conductive oxide composite material, its preparation method comprises the steps:
(1) gets a certain amount of titanium dioxide, in reducing atmosphere, be warming up to 800～1100 ℃ of sintering 1～4 hour, prepare conductive oxide;
(2) sublimed sulfur being dissolved in the solvent, is (2～1) in the mass ratio of sulphur and conductive oxide: 1 ratio adds conductive oxide, and ultrasonic mixing obtains composite material precursor after removing solvent;
(3), obtain sulphur conductive oxide composite material with the abundant ball milling of composite material precursor.
In the described step (1), the preferred commercial P25 type titanium dioxide of used titanium dioxide, reducing atmosphere is preferably hydrogen.
In the described step (1), preferably the speed with 5～10 ℃/min is warming up to sintering temperature; Sintering temperature is preferably 900～1100 ℃, and more preferably 950～1050 ℃, most preferably 1050 ℃; Preferred 4 hours of sintering temperature.
In the described step (2), the solvent of dissolving sublimed sulfur is selected the solvent of dissolve sulfur at normal temperatures, preferred carbon disulfide, and this process needs to carry out in fume hood, leaves standstill at normal temperatures carbon disulfide is volatilized fully.
In the described step (2), sulphur compares preferred (2～1.5) with the mixing quality of conductive oxide: 1, and more preferably 1.5～1.7:1 most preferably is 1.5:1.
In the described step (2), make sulphur and conductive oxide mix by ultrasonic wave, ultrasonic incorporation time is preferred 10～30 minutes.
In the described step (3), composite material precursor can place ball mill (for example star ball mill) to carry out ball milling, and the ball milling time is preferably 12～24 hours.
The present invention is concrete to recommend described sulphur conductive oxide composite material to carry out according to following steps:
(1) P25 type titanium dioxide is placed high temperature process furnances, under the atmosphere of pure hydrogen, tube furnace is warming up to 800～1100 ℃, sintering 1～4 hour, cooling obtains conductive oxide;
(2) sublimed sulfur is dissolved in the carbon disulfide, mass ratio in sulphur and conductive oxide is (2～1) then: 1 ratio adds conductive oxide, ultrasonic then concussion 10～30 minutes, conductive oxide and sulphur are mixed, leave standstill at normal temperatures again and make the carbon disulfide volatilization, obtain composite material precursor;
(3) composite material precursor that obtains in the step (2) is positioned in the ball mill, ball milling 12～24 hours takes out and obtains sulphur conductive oxide composite material.
The present invention also provides the application of described sulphur conductive oxide composite material as the lithium-sulphur cell positive electrode material, and wherein lithium-sulfur cell prepares by conventional method.
The present invention compared with prior art, its beneficial effect is mainly reflected in:
(1) titanium dioxide of the present invention's employing is business-like P25 type titanium dioxide, and the source is abundant; Used sulphur recombination process is a mechanical ball milling, and technology is simple, is beneficial to the realization industrialization, and non-pollutant discharge is environmentally friendly.
(2) the composite material volume specific capacity height of the present invention's preparation, good conductivity, cyclical stability is strong, can be used as anode material for lithium-ion batteries and is widely used in fields such as lithium-sulfur cell.
(4) description of drawings
Fig. 1 is the XRD diffraction pattern of the prepared conductive oxide of embodiment 1.
Fig. 2 is the prepared conductive oxide electron scanning micrograph of embodiment 1.
Fig. 3 is the prepared simulation lithium ion battery charging and discharging curve figure of embodiment 1, and voltage range 1.5 – 3.0V, electrolyte are 1mol/L LiTFSI/DOL – DME (1:1), and charge-discharge magnification is 0.1C, and measuring temperature is 25 ± 5 ℃, and cycle-index is 50 times.
Fig. 4 is the AC impedance figure of the prepared simulation lithium ion battery of 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
P25 is positioned in the high temperature process furnances with the 1g commercialization, under hydrogen atmosphere, is warming up to 1050 ℃ with 10 ℃/min, and sintering 4 hours obtains conductive oxide.Fig. 1 is the XRD diffraction pattern of this material, and the reference standard card is Ti
4O
7, Fig. 2 is the stereoscan photograph of this material, even particle size, average grain diameter are 500 nanometers.
Sublimed sulfur is dissolved in the carbon disulfide, is the ratio adding conductive oxide of 1.5:1 in sulphur and conductive oxide mass ratio then, and the ultrasonic concussion in back 30 minutes mixes conductive oxide and sulphur.After leave standstill at normal temperatures and make carbon disulfide volatilization.With gained material ball milling 24 hours, obtain sulphur/Ti then
4O
7Composite material.
Mass ratio with 80:10:10 takes by weighing sulphur/Ti respectively
4O
7Composite material: acetylene black: polytetrafluoroethylene, make electrode after the grinding evenly, metal lithium sheet is a negative pole, and electrolyte is 1mol/L LiTFSI/DOL – DME (1:1), and polypropylene microporous film is a barrier film, is assembled into the simulation lithium ion battery.Fig. 3 be respective battery at 50 cycle charge-discharge curves of 0.1C multiplying power, show the battery of surveying capacity in 50 cyclic processes stable, the composite material capacity remains on about 500mAh/g.See prepared sulphur/Ti from Fig. 4 (the AC impedance figure of lithium ion battery)
4O
7Composite material electrochemical charge transfger impedance has only 52.2 Ω, and the electric conductivity of material is very good.
Embodiment 2
P25 is positioned in the high temperature process furnances with the 1g commercialization, under hydrogen atmosphere, is warming up to 950 ℃ with 10 ℃/min, and sintering 4 hours obtains conductive oxide.The reference standard card is Ti
4O
7
Sublimed sulfur is dissolved in the carbon disulfide, is the ratio adding conductive oxide of 1.7:1 in sulphur conductive oxide mass ratio then, and the ultrasonic concussion in back 20 minutes mixes conductive oxide and sulphur.After leave standstill at normal temperatures and make carbon disulfide volatilization.With gained material ball milling 18 hours, obtain sulphur/Ti then
4O
7Composite material.
Mass ratio with 80:10:10 takes by weighing sulphur/Ti respectively
4O
7Composite material: acetylene black: polytetrafluoroethylene, make electrode after the grinding evenly, metal lithium sheet is a negative pole, and electrolyte is 1mol/L LiTFSI/DOL – DME (1:1), and polypropylene microporous film is a barrier film, is assembled into the simulation lithium ion battery.
The battery testing method is with embodiment 1, and the gained battery is at 50 cycle charge-discharges of 0.1C multiplying power, and capacity is stable in the cyclic process, and capacity remains on about 450mAh/g.Prepared sulphur/Ti
4O
7Composite material electrochemical charge transfger impedance has 63 Ω.
Embodiment 3
P25 is positioned in the high temperature process furnances with the 1g commercialization, under hydrogen atmosphere, is warming up to 850 ℃ with 10 ℃/min, and sintering 1 hour obtains conductive oxide.The reference standard card is Ti
5O
9
Sublimed sulfur is dissolved in the carbon disulfide, is the ratio adding conductive oxide of 2:1 in sulphur conductive oxide mass ratio then, and the ultrasonic concussion in back 15 minutes mixes conductive oxide and sulphur.After leave standstill at normal temperatures and make carbon disulfide volatilization.With gained material ball milling 12 hours, obtain sulphur/Ti then
5O
9Composite material.
Mass ratio with 80:10:10 takes by weighing sulphur/Ti respectively
5O
9Composite material: acetylene black: polytetrafluoroethylene, make electrode after the grinding evenly, metal lithium sheet is a negative pole, and electrolyte is 1mol/L LiTFSI/DOL – DME (1:1), and polypropylene microporous film is a barrier film, is assembled into the simulation lithium ion battery.
The battery testing method is with embodiment 1, and the gained battery is at 50 cycle charge-discharges of 0.1C multiplying power, and capacity is stable in the cyclic process, and capacity remains on about 400mAh/g.Prepared sulphur/Ti
5O
9Composite material electrochemical charge transfger impedance has only 76 Ω.
Claims (10)
1. sulphur conductive oxide composite material, it is characterized in that: its preparation method comprises the steps:
(1) gets a certain amount of titanium dioxide, in reducing atmosphere, be warming up to 800～1100 ℃ of sintering 1～4 hour, prepare conductive oxide;
(2) sublimed sulfur being dissolved in the solvent, is (2～1) in the mass ratio of sulphur and conductive oxide: 1 ratio adds conductive oxide, and ultrasonic mixing obtains composite material precursor after removing solvent;
(3), obtain sulphur conductive oxide composite material with the abundant ball milling of composite material precursor.
2. sulphur conductive oxide composite material as claimed in claim 1 is characterized in that: the described titanium dioxide of step (1) adopts P25 type titanium dioxide, and reducing atmosphere is a nitrogen atmosphere.
3. sulphur conductive oxide composite material as claimed in claim 1 is characterized in that based on the lithium-sulfur cell composite material of conductive oxide: in the described step (2), solvent is a carbon disulfide.
4. as the described sulphur conductive oxide of one of claim 1～3 composite material, it is characterized in that: in the described step (1), the speed with 5～10 ℃/min in reducing atmosphere is warming up to sintering temperature.
5. sulphur conductive oxide composite material as claimed in claim 4 is characterized in that: sintering temperature is 900～1100 ℃.
6. sulphur conductive oxide composite material as claimed in claim 5 is characterized in that: sintering temperature is 950～1050 ℃.
7. as the described sulphur conductive oxide of one of claim 1～3 composite material, it is characterized in that: in the described step (2), sulphur is (2～1.5) with the mixing quality ratio of conductive oxide: 1.
8. sulphur conductive oxide composite material as claimed in claim 7 is characterized in that: in the described step (2), sulphur is 1.5～1.7:1 with the mixing quality ratio of conductive oxide.
9. sulphur conductive oxide composite material as claimed in claim 1 is characterized in that: in the described step (2), ultrasonic incorporation time is 10～30 minutes; In the described step (3), the ball milling time is 12～24 hours.
10. sulphur conductive oxide composite material as claimed in claim 1 is as the application of lithium-sulphur cell positive electrode material.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104201392A (en) * | 2014-08-20 | 2014-12-10 | 中南大学 | Preparation method of lithium-sulphur battery electrode |
| CN104269544A (en) * | 2014-10-15 | 2015-01-07 | 南京中储新能源有限公司 | Graphene array composited anode as well as preparation method and application thereof |
| CN105006553A (en) * | 2015-07-11 | 2015-10-28 | 中国计量学院 | Preparation method of sulfur/carbon/oxide combined electrode material |
| CN105374999A (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 |
| CN105489863A (en) * | 2015-12-31 | 2016-04-13 | 长沙矿冶研究院有限责任公司 | C/Ti4O7 composite nanofiber based lithium-sulfur battery positive electrode material and preparation method therefor |
| CN105489864A (en) * | 2016-01-13 | 2016-04-13 | 李震祺 | Titanium sub-oxide coated and modified lithium iron phosphate composite material and preparation method thereof |
| CN105845916A (en) * | 2016-06-01 | 2016-08-10 | 中国计量大学 | Composite material based on ferroelectric oxide and sulfur and application thereof in lithium sulfur batteries |
| CN107359321A (en) * | 2017-06-09 | 2017-11-17 | 深圳启辰新能源科技有限公司 | Lithium sulfur battery anode material of the nitrogen-doped carbon of spherical structure/titanium oxide bivalve cladding titanium oxide/sulphur and preparation method thereof |
| CN107492639A (en) * | 2017-07-28 | 2017-12-19 | 清华大学 | A kind of lithium-sulfur battery composite anode material and preparation method |
| CN109546092A (en) * | 2017-09-22 | 2019-03-29 | 哈尔滨理工大学 | The preparation method of lithium sulphur hull cell nano composite anode material |
| CN110380052A (en) * | 2019-07-19 | 2019-10-25 | 田韬 | One kind being based on the highly conductive sulfenyl composite material of lithium-sulphur cell positive electrode |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2013
- 2013-03-30 CN CN201310110840.9A patent/CN103219493B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| SEH Z W,ETAL: "Sulphur–TiO2 yolk–shell nanoarchitecture with internal void space for long-cycle lithium–sulphur batteries", 《NATURE COMMUNICATIONS》 * |
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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 |
| CN104201392A (en) * | 2014-08-20 | 2014-12-10 | 中南大学 | Preparation method of lithium-sulphur battery electrode |
| CN104269544A (en) * | 2014-10-15 | 2015-01-07 | 南京中储新能源有限公司 | Graphene array composited anode as well as preparation method and application thereof |
| 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 |
| CN105006553A (en) * | 2015-07-11 | 2015-10-28 | 中国计量学院 | Preparation method of sulfur/carbon/oxide combined electrode material |
| CN105374999A (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 |
| 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 |
| CN105489863A (en) * | 2015-12-31 | 2016-04-13 | 长沙矿冶研究院有限责任公司 | C/Ti4O7 composite nanofiber based lithium-sulfur battery positive electrode material and preparation method therefor |
| CN105489864A (en) * | 2016-01-13 | 2016-04-13 | 李震祺 | Titanium sub-oxide coated and modified lithium iron phosphate composite material 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 |
| CN105845916A (en) * | 2016-06-01 | 2016-08-10 | 中国计量大学 | Composite material based on ferroelectric oxide and sulfur and application thereof in lithium sulfur batteries |
| 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 |
| CN107359321A (en) * | 2017-06-09 | 2017-11-17 | 深圳启辰新能源科技有限公司 | Lithium sulfur battery anode material of the nitrogen-doped carbon of spherical structure/titanium oxide bivalve cladding titanium oxide/sulphur and preparation method thereof |
| 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 |
| CN107492639A (en) * | 2017-07-28 | 2017-12-19 | 清华大学 | A kind of lithium-sulfur battery composite anode material and preparation method |
| CN109546092A (en) * | 2017-09-22 | 2019-03-29 | 哈尔滨理工大学 | The preparation method of lithium sulphur hull cell nano composite anode material |
| CN109546092B (en) * | 2017-09-22 | 2022-05-20 | 哈尔滨理工大学 | Lithium-sulfur thin film battery |
| CN110380052A (en) * | 2019-07-19 | 2019-10-25 | 田韬 | One kind being based on the highly conductive sulfenyl composite material of lithium-sulphur cell positive electrode |
| 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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