CN106450245B - A kind of flexibility can charge and discharge lithium sulfur battery anode material and preparation method thereof - Google Patents
A kind of flexibility can charge and discharge lithium sulfur battery anode material and preparation method thereof Download PDFInfo
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Abstract
It can charge and discharge lithium sulfur battery anode material and preparation method thereof the invention discloses a kind of flexibility, it is characterised in that：First using ammonium persulfate and pyrroles as Material synthesis polypyrrole nanofibers (PPy)；Then positive active material sulphur simple substance is loaded into polypyrrole nanofibers, is prepared into composite material (PPy/S)；It is filtered according still further to graphene oxide-polypyrrole/sulphur-graphene oxide sequence, obtains the GO-PPy/S-GO composite material of sandwich structure；Finally the material is immersed in hydrofluoric acid, graphene oxide is reduced to graphene, obtains graphene-polypyrrole/sulphur-graphene (G-PPy/S-G) composite material, as positive electrode.The present invention uses conventional medication, obtains composite material by filtering method layer by layer, and preparation method is simple, and products therefrom has excellent battery performance as anode.
Description
Technical field
The present invention relates to a kind of flexibility can charge and discharge lithium sulfur battery anode material, belong to porous nanometer material field.
Background technique
Lithium-sulfur cell be using sulphur as positive active material, using lithium as the secondary cell of cathode, wherein positive active material sulphur
Theoretical specific capacity be up to 1672mAh g-1.But the complicated electrochemical reaction process of sulfur-bearing anode and its non-conductive etc. physical
Matter determines the research and development difficult point of lithium-sulfur cell mainly in positive electrode.For the application for realizing lithium-sulfur cell, on the one hand to improve just
The conductivity of pole material improves the high rate performance of battery to improve the utilization rate of positive active material；On the other hand also to inhibit
The irreversible loss of capacity, to improve the cycle performance of battery.Currently, the research work of lithium-sulfur cell is concentrated mainly on organic sulfur
Two kinds of positive electrodes of compound material and sulphur/carbon composite.Therefore, sulphur/carbon anode composite material is further designed and prepared, is changed
The kind charge-discharge performances such as lithium-sulfur cell cyclic specific capacity and cyclical stability are of great significance.
Summary of the invention
The present invention is intended to provide a kind of preparation method is simple, structure novel and have lithium sulfur battery anode material flexible and
Preparation method, to improve the cyclic specific capacity of battery.
The present invention solves technical problem, adopts the following technical scheme that：
It is of the invention it is flexible can charge and discharge lithium sulfur battery anode material preparation method, include the following steps：
(1) preparation of polypyrrole nanofibers
After Surfactant CTAB in deionized water ultrasonic dissolution, pyrroles is added, is subsequently placed into low temperature well, adjusts
Then temperature is slowly added to oxidant ammonium persulfate (APS) while stirring, continues stirring 10~14 hours, gained to 0~4 DEG C
Reaction solution deionized water and ethyl alcohol centrifuge washing, vacuum drying, obtain polypyrrole nanofibers；
(2) polypyrrole nanofibers/sulphur composite material preparation
After mixing by the polypyrrole nanofibers and crystal sulphur, Low Temperature Heat Treatment under an inert atmosphere, is made poly-
Pyrroles's nanofiber/sulphur composite material, is denoted as PPy/S composite material；
(3) preparation of GO-PPy/S-GO composite material
By the PPy/S composite material dispersion in deionized water, be added neopelex, ultrasonic dissolution it
Afterwards, middle layer dispersion liquid is obtained；
Using graphene oxide dispersion as first layer dispersion liquid and third layer dispersion liquid；
First layer dispersion liquid is drawn, carries out first layer suction filtration with pvdf membrane；It forms film and then draws middle layer dispersion
Liquid carries out second layer suction filtration；Third layer dispersion liquid is finally drawn again, carries out third layer suction filtration；It is completed wait filter, after drying at room temperature
Pvdf membrane is removed, i.e. acquisition GO-PPy/S-GO composite material；
(4) preparation of G-PPy/S-G composite material
The GO-PPy/S-GO composite material is immersed in hydrofluoric acid and is restored, deionized water and ethanol washing, room are then used
Temperature is dry, obtains G-PPy/S-G composite material, as flexibility can charge and discharge lithium sulfur battery anode material.
Pyrroles will be protected from light processing during addition in step (1), and CTAB and APS dissolve later again at room temperature
It is put into low temperature well.
CTAB in step (1), pyrroles, ammonium persulfate and deionized water mass volume ratio be：0.5~0.6g：550~
560μL：1.8~1.9g：380~420mL.
Vacuum drying temperature is 60~80 DEG C in step (1), and drying time is 10~14h.
The mass ratio of polypyrrole nanofibers and crystal sulphur is 1 in step (2):1.5~2.5.
Step (2) inert atmosphere is argon gas, nitrogen, one of protective gas such as helium；The journey of Low Temperature Heat Treatment
Sequence is：With 0.5 DEG C~10 DEG C min-1Heating rate rise to 140 DEG C~170 DEG C, keep the temperature 3h~6h, be then down to room temperature naturally.
The specific method of acquisition middle layer dispersion liquid is in step (3)：PPy/S 60~80mg of composite material is weighed, is dispersed
In the deionized water of 30~50mL, the neopelex of 6~8mg is added, then ultrasound 20-40min is obtained；
The concentration of step (3) described graphene oxide dispersion is 0.2~0.4mg/mL.
The aperture of pvdf membrane used is 0.2-0.3 μm in step (3), diameter 40-50mm.
The mass concentration of hydrofluoric acid is 40% in step (4), soaking time 50-70min.
By flexibility obtained by above-mentioned preparation method can charge and discharge lithium sulfur battery anode material be sandwich structure, be
Two layers of grapheme material is sandwiched between polypyrrole nanofibers/sulphur composite material.
The beneficial effects of the present invention are embodied in：
It is of the invention can charge and discharge lithium sulfur battery anode material, obtained using conventional raw material by filtering method preparation layer by layer
, method is simple, and products therefrom has sandwich-like structure, and compared with conventional material, polypyrrole nano material is with higher
Good, the reversible electrochemical redox characteristic of conductivity, environmental stability and stronger charge storage ability, and can effectively press down
Sulphur processed makes material have flexibility in the volume expansion of charge and discharge process, and can improve the cyclic specific capacity of battery.
Detailed description of the invention
Fig. 1 is the scanned photograph of polypyrrole nanofibers；
Fig. 2 is the scanned photograph of G-PPy/S-G composite material；
Fig. 3 is the cycle performance of battery test pair of tri- kinds of anode composite materials of PPy/S, GO-PPy/S-GO, G-PPy/S-G
Than；
Fig. 4 is the multiplying power figure that two kinds of anode composite materials of GO-PPy/S-GO, G-PPy/S-G recycle under different multiplying powers；
Fig. 5 is the coulombic efficiency figure of tri- kinds of anode composite materials of PPy/S, GO-PPy/S-GO, G-PPy/S-G.
Specific embodiment
Experimental method used in following embodiments is conventional method unless otherwise specified.
Agents useful for same, material etc. unless otherwise specified, commercially obtain in the following example.
Battery performance test is all made of blue electric battery test system in following embodiments, by sulphur anode material in following embodiments
Material tablet press machine extrude it is round after directly as working electrode, polypropylene screen is diaphragm, electrolyte be DOL and DME by volume
1:1 mixed solution (nitric acid containing 0.1M, 1M LiTFSI) constituted, is assembled into 2032 button cells in being full of argon gas glove box,
Test voltage range is 1.5V-3.0V vs Li+/Li.
Embodiment 1
The present embodiment prepares flexibility as follows can charge and discharge lithium sulfur battery anode material：
(1) preparation of polypyrrole nanofibers
It weighs 0.506g CTAB to be put into 400mL deionized water, after ultrasonic dissolution, 554 μ L pyrroles is added under the conditions of being protected from light
It coughs up, then the container for putting the mixed solution is put into low temperature well, temperature is adjusted to 0-4 DEG C, and 1.82g oxidation is added while stirring
Agent ammonium persulfate continues after stirring 12h, obtains dark solution, with deionized water and ethyl alcohol centrifuge washing, and in 70 DEG C of conditions
Lower vacuum drying 12h, obtains polypyrrole nanofibers；
(2) polypyrrole nanofibers/sulphur composite material preparation
By above-mentioned polypyrrole nanofibers and crystal sulphur according to mass ratio 1:2 ratio is ground uniformly in the agate mortar,
With 1 DEG C of min under argon atmosphere-1Heating rate rise to 155 DEG C, keep the temperature 4h, be then down to room temperature naturally, that is, obtain PPy/S
Composite material；
(3) preparation of GO-PPy/S-GO composite material
It takes 70mg PPy/S composite material to be dispersed in 40mL deionized water, the neopelex of 7mg is added, surpass
After sound 30min, the dispersion liquid of black is obtained, the middle layer dispersion liquid as suction filtration.
It draws 4mL the graphene oxide demarcated (3.57mg/mL) is dispersed in the deionized water of 40mL, stirring is equal
Even, as suction filtration first layer and third layer dispersion liquid.
10mL first layer dispersion liquid is drawn, carries out first layer suction filtration with pvdf membrane；It is pumped into first layer graphene oxide dry
Dry film and then absorption 7.5mLPPy/S middle layer dispersion liquid, carries out second layer suction filtration；After the completion of the second layer filters, then
10mL third layer dispersion liquid is drawn, third layer suction filtration is carried out, until being pumped into the film of evenly drying；It completes, puts wait filter
Pvdf membrane is removed after the local drying at room temperature of ventilation, i.e. acquisition GO-PPy/S-GO composite material；
(4) by GO-PPy/S-GO composite material immerse 30mL mass concentration be 40% hydrofluoric acid in 1h, then spend from
Sub- water and ethanol washing 4 times, drying at room temperature, obtain G-PPy/S-G composite material, as flexibility can charge and discharge lithium-sulphur cell positive electrode
Material.
Fig. 1 is the scanned photograph of polypyrrole nanofibers obtained by step (1), and polypyrrole is a kind of common conducting polymer
Object, present invention gained polypyrrole nano material is in uniform nano tubular structure as can be seen from Figure 1, and volume is fluffy, is conducive to
Form material flexible.
Fig. 2 is the scanned photograph of G-PPy/S-G composite material obtained by step (4), it can be seen that gained composite material is three
Mingzhi's structure is to be sandwiched between polypyrrole nanofibers/sulphur composite material in two layers of grapheme material.
Respectively by PPy/S composite material, GO-PPy/S-GO composite material, G-PPy/S-G obtained by step (2), (3), (4)
Composite material is as positive electrode, after being pressed into sequin by tablet press machine, according to anode coat, lithium piece, diaphragm, electrolyte, just
The sequence assembled battery of pole, gasket, reed, is tested for the property.
Fig. 3 is the cycle performance of battery test pair of tri- kinds of anode composite materials of PPy/S, GO-PPy/S-GO, G-PPy/S-G
Than test multiplying power is 0.1C.It can find by contrast：Tri- kinds of anode composite materials of PPy/S, GO-PPy/S-GO, G-PPy/S-G
First circle specific discharge capacity be respectively 800mAh g-1、1150mAh g-1、1164mAh g-1, reversible specific volume after circulation 100 is enclosed
Amount is respectively maintained at 40mAh g-1、450mAh g-1、572mAh g-1, show that sandwich-like G-PPy/S-G anode composite material has
There is good cycle performance.
Fig. 4 is the multiplying power figure that two kinds of anode composite materials of GO-PPy/S-GO, G-PPy/S-G recycle under different multiplying powers,
It can find that the specific discharge capacity of G-PPy/S-G remains to be respectively maintained at even if under the big circulation in 1C and 2C by contrast
630mAh g-1、370mAh g-1。
Fig. 5 is the coulombic efficiency figure of tri- kinds of anode composite materials of PPy/S, GO-PPy/S-GO, G-PPy/S-G.By contrast may be used
It was found that the coulombic efficiency of G-PPy/S-G composite material is most stable, almost close to 100%.And PPy/S composite material is existed due to sulphur
Decomposition in electrolyte leads to the unstability of electron-transport, so that coulombic efficiency is higher than 100%；GO-PPy/S-GO composite wood
The coulombic efficiency of material is slightly less than 100% and unstable.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (9)
1. a kind of flexibility can charge and discharge lithium sulfur battery anode material preparation method, it is characterised in that include the following steps：
(1) preparation of polypyrrole nanofibers
After surfactant cetyl trimethylammonium bromide in deionized water ultrasonic dissolution, pyrroles is added, is subsequently placed into
In low temperature well, 0~4 DEG C is adjusted the temperature to, is then slowly added to oxidant ammonium persulfate while stirring, it is small to continue stirring 10~14
When, gained reaction solution deionized water and ethyl alcohol centrifuge washing are dried in vacuo, and obtain polypyrrole nanofibers；
(2) polypyrrole nanofibers/sulphur composite material preparation
After mixing by the polypyrrole nanofibers and crystal sulphur, Low Temperature Heat Treatment under an inert atmosphere, is made polypyrrole
Nanofiber/sulphur composite material, is denoted as PPy/S composite material；
The program of the Low Temperature Heat Treatment is：With 1 DEG C of min-1Heating rate rise to 155 DEG C, keep the temperature 4h, be then down to room naturally
Temperature；
(3) preparation of GO-PPy/S-GO composite material
The PPy/S composite material is dispersed in deionized water, addition neopelex, after ultrasonic dissolution, is obtained
Obtain middle layer dispersion liquid；
Using graphene oxide dispersion as first layer dispersion liquid and third layer dispersion liquid；
First layer dispersion liquid is drawn, carries out first layer suction filtration with pvdf membrane；It forms film and then draws middle layer dispersion liquid,
Carry out second layer suction filtration；Third layer dispersion liquid is finally drawn again, carries out third layer suction filtration；It completes wait filter, is taken after drying at room temperature
Lower pvdf membrane, i.e. acquisition GO-PPy/S-GO composite material；
(4) preparation of G-PPy/S-G composite material
The GO-PPy/S-GO composite material is immersed in hydrofluoric acid and is restored, it is then dry with deionized water and ethanol washing, room temperature
It is dry, G-PPy/S-G composite material is obtained, as flexibility can charge and discharge lithium sulfur battery anode material.
2. flexibility according to claim 1 can charge and discharge lithium sulfur battery anode material preparation method, it is characterised in that：Step
Suddenly the mass volume ratio of cetyl trimethylammonium bromide in (1), pyrroles, ammonium persulfate and deionized water is：0.5~0.6g：
550~560 μ L：1.8~1.9g：380~420mL.
3. flexibility according to claim 1 can charge and discharge lithium sulfur battery anode material preparation method, it is characterised in that：Step
Suddenly vacuum drying temperature is 60~80 DEG C in (1), and drying time is 10~14h.
4. flexibility according to claim 1 can charge and discharge lithium sulfur battery anode material preparation method, it is characterised in that：Step
Suddenly the mass ratio of polypyrrole nanofibers and crystal sulphur is 1 in (2):1.5~2.5.
5. flexibility according to claim 1 can charge and discharge lithium sulfur battery anode material preparation method, it is characterised in that：Step
Suddenly the specific method of acquisition middle layer dispersion liquid is in (3)：PPy/S 60~80mg of composite material is weighed, 30~50mL is dispersed in
Deionized water in, be added 6~8mg neopelex, then ultrasound 20-40min acquisition；
The concentration of step (3) described graphene oxide dispersion is 0.2~0.4mg/mL.
6. flexibility according to claim 1 can charge and discharge lithium sulfur battery anode material preparation method, it is characterised in that：Step
Suddenly in (3) aperture of pvdf membrane used be 0.2-0.3 μm, diameter 40-50mm.
7. flexibility according to claim 1 can charge and discharge lithium sulfur battery anode material preparation method, it is characterised in that：Step
Suddenly the mass concentration of hydrofluoric acid is 40% in (4), soaking time 50-70min.
8. flexibility prepared by preparation method described in a kind of any one of claim 1~7 can charge and discharge lithium-sulphur cell positive electrode
Material.
9. flexibility according to claim 8 can charge and discharge lithium sulfur battery anode material, it is characterised in that：The positive electrode
It is to be sandwiched between polypyrrole nanofibers/sulphur composite material in two layers of graphene film for sandwich structure.
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| CN107039646A (en) * | 2017-04-18 | 2017-08-11 | 合肥工业大学 | Flexible negative material of a kind of lithium ion battery and preparation method thereof |
| CN107863520A (en) * | 2017-11-12 | 2018-03-30 | 四川大学 | A kind of lithium sulfur battery anode material and preparation method thereof |
| CN109888183B (en) * | 2019-04-02 | 2022-12-02 | 上海理工大学 | Preparation method and application of organic-inorganic hybrid film |
| CN110783537A (en) * | 2019-09-19 | 2020-02-11 | 安徽清泉新能源科技集团有限责任公司 | Polypyrrole lithium-sulfur battery material |
| CN115000366B (en) * | 2022-05-19 | 2023-06-02 | 同济大学 | Flexible self-supporting lithium-sulfur battery positive electrode film with core-shell structure and preparation method thereof |
| CN114874439B (en) * | 2022-06-22 | 2023-11-28 | 武汉工程大学 | Three-dimensional conductive network polypyrrole material, sulfur positive electrode material and lithium sulfur battery |
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| WO2011019765A1 (en) * | 2009-08-10 | 2011-02-17 | Battelle Memorial Institute | Self assembled multi-layer nanocomposite of graphene and metal oxide materials |
| CN104810504A (en) * | 2014-01-24 | 2015-07-29 | 中国科学院金属研究所 | Flexible graphene current collector and active material integrated electrode pole piece and preparation method thereof |
| CN105140490A (en) * | 2015-09-28 | 2015-12-09 | 中南大学 | Preparation method of lithium-sulfur battery flexible positive electrode |
| CN105895382A (en) * | 2016-03-23 | 2016-08-24 | 中国航空工业集团公司北京航空材料研究院 | Self-supporting flexible composite electrode film, preparation method and application thereof |
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| US9373829B2 (en) * | 2013-10-11 | 2016-06-21 | GM Global Technology Operations LLC | Porous interlayer for a lithium-sulfur battery |
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| WO2011019765A1 (en) * | 2009-08-10 | 2011-02-17 | Battelle Memorial Institute | Self assembled multi-layer nanocomposite of graphene and metal oxide materials |
| CN104810504A (en) * | 2014-01-24 | 2015-07-29 | 中国科学院金属研究所 | Flexible graphene current collector and active material integrated electrode pole piece and preparation method thereof |
| CN105140490A (en) * | 2015-09-28 | 2015-12-09 | 中南大学 | Preparation method of lithium-sulfur battery flexible positive electrode |
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| CF01 | Termination of patent right due to non-payment of annual fee |