CN114400328A - Lithium-sulfur battery and preparation method thereof - Google Patents
Lithium-sulfur battery and preparation method thereof Download PDFInfo
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- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000002131 composite material Substances 0.000 claims description 22
- 239000002033 PVDF binder Substances 0.000 claims description 19
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 16
- 239000006229 carbon black Substances 0.000 claims description 15
- 238000000227 grinding Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 239000003792 electrolyte Substances 0.000 claims description 12
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 11
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 11
- 239000002041 carbon nanotube Substances 0.000 claims description 11
- 239000002002 slurry Substances 0.000 claims description 11
- 229910052717 sulfur Inorganic materials 0.000 claims description 11
- 239000011593 sulfur Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 8
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 7
- 239000006258 conductive agent Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 239000011888 foil Substances 0.000 claims description 6
- 239000007774 positive electrode material Substances 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000004743 Polypropylene Substances 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 claims description 4
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 12
- 239000000654 additive Substances 0.000 abstract description 10
- 230000000996 additive effect Effects 0.000 abstract description 9
- 239000005077 polysulfide Substances 0.000 abstract description 7
- 229920001021 polysulfide Polymers 0.000 abstract description 7
- 150000008117 polysulfides Polymers 0.000 abstract description 7
- 238000007599 discharging Methods 0.000 abstract description 6
- 230000002401 inhibitory effect Effects 0.000 abstract description 6
- 239000001257 hydrogen Chemical group 0.000 abstract description 4
- 229910052739 hydrogen Chemical group 0.000 abstract description 4
- 150000001450 anions Chemical class 0.000 abstract description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 2
- 239000003153 chemical reaction reagent Substances 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 6
- 210000004027 cell Anatomy 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000010277 constant-current charging Methods 0.000 description 3
- -1 mercapto compound Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007600 charging Methods 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
- H01M4/623—Binders being polymers fluorinated polymers
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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Abstract
The invention provides a lithium-sulfur battery and a preparation method thereof, and relates to the technical field of lithium-sulfur batteries. The invention takes the ethylene urea containing polar carbonyl and hydrogen bond donor as the additive, and the ethylene urea is added into the positive pole piece of the lithium-sulfur battery, during the discharging process, the polar carbonyl of the ethylene urea can generate electrostatic adsorption with polysulfide, and meanwhile, the amino can also form hydrogen bond with polysulfide anion, thereby inhibiting the shuttle effect of polysulfide compounds, and improving the specific capacity and the cycle performance of the lithium-sulfur battery. And the ethylene urea is used as a commercial reagent, is cheap and easy to obtain, and is suitable for large-scale application.
Description
Technical Field
The invention relates to the technical field of lithium-sulfur batteries, in particular to a lithium-sulfur battery and a preparation method thereof.
Background
Lithium-sulfur batteries, as the most promising secondary batteries, have many significant advantages, such as abundant electrode resources, low cost, environmental friendliness, and theoretical energy density as high as 2600Wh Kg-1. However, the existing lithium-sulfur battery generally has the problems of poor conductivity of sulfur materials, low cycle life and efficiency of the battery due to shuttle effect, growth of dendrite of a lithium negative electrode and the like. The short cycle life caused by the shuttle effect is the most troublesome problem for preventing the commercial application of the lithium-sulfur battery.
In order to solve the above problems, researchers have conducted a great deal of research. Among them, the most important research point is to develop a novel sulfur positive electrode host material and a battery separator material, and to suppress the shuttle effect by suppressing the dissolution and transfer of polysulfides through physical and chemical actions between substances. And the research for inhibiting the shuttling effect and prolonging the cycle life of the lithium-sulfur battery by the additive is relatively less.
Patents CN 111969249 and CN 111653826 disclose a method for improving the cycle stability of a lithium-sulfur battery by adding a mercapto compound to an electrolyte; patent CN 111916828 discloses a method for improving the performance of lithium-sulfur battery by adding fused ring imide compounds in electrolyte; patent CN 107623143 discloses a method for improving the cycling stability of a battery by adding an organic sulfur compound or an inorganic sulfur compound to the electrolyte to inhibit the shuttle effect; patent CN 110649316 discloses a method for inhibiting shuttle effect by adding fluorine-containing cyclic sulfone ester compounds into electrolyte. The additives used in the above methods have problems of poor air stability or great synthesis difficulty, respectively. In 2019, patent CN 110993902 discloses addition of [ H ] at positive electrode2PBD]2+·2[NO3]-The additive is simple and easy to obtain by using a method for inhibiting the shuttle effect by electrostatic adsorption, but the stable capacity of the lithium-sulfur battery is only 800mAhg-1And the content of the additive is higher (5-10 percent of the total weight of the anode material), so that the specific capacity of the anode is reduced.
Therefore, how to prepare an additive with good effect and low addition amount to overcome the problems in the prior art and significantly improve the performance of the lithium-sulfur battery is a technical problem to be solved in the field.
Disclosure of Invention
In order to solve the above problems, the present invention provides a novel lithium sulfur battery and a method for manufacturing the same. The special polar anode additive-ethylene urea is added into the lithium-sulfur battery, and the capacity and the cycling stability of the lithium-sulfur battery are improved by effectively inhibiting the shuttle effect of polysulfide through the electrostatic action and the hydrogen bond action between the additive and a battery system. The lithium-sulfur battery comprises the following raw materials in percentage by mass:
60 to 80 percent of positive active material,
5 to 15 percent of polyvinylidene fluoride,
10 to 25 percent of conductive agent,
0.1 to 1 percent of ethylene urea,
the sum of the mass percentages of the raw materials is 100 percent.
Further, the positive active material is an ethylene urea/S/C working electrode.
Further, the conductive agent is one or more of carbon black, carbon nanotubes, carbon fibers and graphene.
Another object of the present invention is to provide a method for preparing the lithium sulfur battery, comprising the steps of:
(1) preparing an S/C composite material:
mixing and grinding sulfur powder and commercial carbon nanotubes to uniformly mix sulfur and porous carbon, removing oxygen, drying the mixed material, and cooling to room temperature to obtain an S/C composite material;
(3) preparation of ethylene urea/S/C working electrode:
mixing the S/C composite material, carbon black and polyvinylidene fluoride, adding ethylene urea, grinding for 30min, adding N-methyl pyrrolidone, uniformly stirring to obtain black slurry, coating the slurry on a clean aluminum foil, drying in vacuum, cooling to room temperature, and cutting to obtain an ethylene urea/S/C working electrode;
(3) preparation of lithium-sulfur battery:
the ethylene urea/S/C working electrode is used as a positive electrode, a metal lithium sheet is used as a negative electrode, a polyethylene-polypropylene film is used as a diaphragm, 1, 3-dioxolane and ethylene glycol dimethyl ether are mixed according to the mass ratio of 1:1 to be used as a solution, and lithium trifluoromethanesulfonate and lithium nitrate are used as electrolytes to assemble the lithium-sulfur battery finished product.
Further, the mass ratio of the sulfur powder to the commercial carbon nano tubes in the step (1) is (3-5):1, the mixing and grinding time is 0.5-1h, the drying temperature is 150-.
Further, in the step (2), the mass ratio of the S/C composite material to the conductive carbon black to the polyvinylidene fluoride is 7:2 (0.9-1), the drying temperature is 50-60 ℃, and the drying time is 12 hours.
Further, the addition amount of the ethylene urea in the step (2) is 1% of the total mass of the S/C composite material, the carbon black and the polyvinylidene fluoride mixture.
Further, the adding amount of the N-methyl pyrrolidone in the step (2) is 25-35% of the total mass of the S/C composite material, the carbon black and the polyvinylidene fluoride mixture.
Further, the mass ratio of the 1, 3-dioxolane to the glycol dimethyl ether in the step (3) is 1: 1.
Further, the finished lithium-sulfur battery in the step (3) is a CR2032 button cell type battery, and the ratio of the electrolyte to the sulfur is 5-10 muL mg-1。
Compared with the prior art, the invention has the beneficial technical effects that:
(1) according to the invention, ethylene urea is uniformly dispersed in the positive slurry through a grinding process step, polysulfide anions generated in the battery charging and discharging process can generate electrostatic adsorption with polar carbonyl, and meanwhile, the polysulfide anions can also form a hydrogen bond with amino, so that the aim of inhibiting shuttle effect is achieved;
(2) the structural formula of the ethylene urea adopted by the invention is as follows:
compared with the existing additive, the ethylene urea provided by the invention is simple in preparation process and low in cost, is an environment-friendly chemical product, and can reduce the preparation cost and environmental pollution while improving the performance of the battery;
(3) according to the invention, ethylene urea is used as an additive, and a specific binder is combined with polyvinylidene fluoride and a conductive agent, so that the specific binder can exert a good synergistic effect, and compared with a lithium-sulfur battery without the additive, the capacity retention rate of the finished lithium-sulfur battery is increased by 5% -10%.
Drawings
The invention is further described in the following description with reference to the drawings.
FIG. 1 shows the results of constant current charging and discharging tests at 0.2C for the example 1 cell of the present invention and the comparative example lithium-sulfur cell;
FIG. 2 shows the results of constant current charging and discharging tests at 0.2C for the example 2 battery of the present invention and the comparative example lithium-sulfur battery.
Detailed Description
The invention provides a lithium-sulfur battery which comprises the following raw materials in percentage by mass:
60 to 80 percent of positive active material,
5 to 15 percent of polyvinylidene fluoride,
10 to 25 percent of conductive agent,
0.1 to 1 percent of ethylene urea,
the sum of the mass percentages of the raw materials is 100 percent.
In one embodiment, the positive active material is an ethylene urea/S/C working electrode.
In one embodiment, the conductive agent is one or more of carbon black, carbon nanotubes, carbon fibers and graphene.
Another object of the present invention is to provide a method for preparing the lithium sulfur battery, comprising the steps of:
(1) preparing an S/C composite material:
mixing and grinding sulfur powder and commercial carbon nanotubes to uniformly mix sulfur and porous carbon, removing oxygen, drying the mixed material, and cooling to room temperature to obtain an S/C composite material;
(4) preparation of ethylene urea/S/C working electrode:
mixing the S/C composite material, carbon black and polyvinylidene fluoride, adding ethylene urea, grinding for 30min, adding N-methyl pyrrolidone, uniformly stirring to obtain black slurry, coating the slurry on a clean aluminum foil, drying in vacuum, cooling to room temperature, and cutting to obtain an ethylene urea/S/C working electrode;
(3) preparation of lithium-sulfur battery:
the ethylene urea/S/C working electrode is used as a positive electrode, a metal lithium sheet is used as a negative electrode, a polyethylene-polypropylene film is used as a diaphragm, 1, 3-dioxolane and ethylene glycol dimethyl ether are mixed according to the mass ratio of 1:1 to be used as a solution, and lithium trifluoromethanesulfonate and lithium nitrate are used as electrolytes to assemble the lithium-sulfur battery finished product.
In one embodiment, the mass ratio of the sulfur powder to the commercial carbon nanotubes in the step (1) is (3-5):1, the mixing and grinding time is 0.5-1h, the drying temperature is 150-.
In one embodiment, the mass ratio of the S/C composite material, the conductive carbon black and the polyvinylidene fluoride in the step (2) is 7:2 (0.9-1), the drying temperature is 50-60 ℃, and the drying time is 12 h.
In one embodiment, the amount of ethylene urea added in step (2) is 1% of the total mass of the S/C composite, carbon black and polyvinylidene fluoride mixture.
In one embodiment, the amount of N-methyl pyrrolidone added in step (2) is 25-35% of the total mass of the S/C composite material, the carbon black and the polyvinylidene fluoride mixture.
In one embodiment, the mass ratio of 1, 3-dioxolane to glyme in step (3) is 1: 1.
In one embodiment, the finished lithium-sulfur battery in step (3) is a CR2032 button cell battery, and the ratio of electrolyte to sulfur is 5-10 μ L · mg-1。
The technical solution provided by the present invention is further illustrated by the following examples.
Example 1
The method comprises the following steps: preparing an S/C rechecking material:
1) mixing: putting the sublimed and purified sulfur powder and the carbon nano tubes into a ball mill according to the proportion of 3:1, and ball-milling for 1h at the rotating speed of 400r/min to uniformly mix the sulfur and the carbon nano tubes to prepare uniform black powder;
2) sulfur injection: transferring the powder into a glove box in an argon environment, keeping the temperature for 30min to remove air in the powder, transferring the powder into an oven, heating the powder at 155 ℃ for 12h, taking out the powder after cooling, and grinding the powder in the air environment for 30min by using an agate mortar to obtain S/C composite material powder;
step two: preparing positive electrode slurry:
mixing the S/C composite material prepared in the step one with carbon black, PVDF and ethylene urea according to the weight ratio of 7:2: 0.9: mixing according to the mass ratio of 0.1, grinding for 30min, adding a proper amount of N-methyl pyrrolidone solution, and stirring to obtain uniform slurry;
step three: preparing a working electrode of the lithium-sulfur battery:
coating the slurry prepared in the step two on an aluminum foil, coating the aluminum foil into an electrode plate with the thickness of 200-350 mu m, putting the coated electrode plate into an oven, drying the electrode plate in a vacuum oven at 60 ℃ for 12h, cooling the electrode plate to room temperature, and cutting the aluminum foil coated with the slurry into a working electrode with the diameter of 10 mm.
Step four: assembling a lithium-sulfur battery;
the CR2032 button cell is assembled by taking an ethylene urea/S/C working electrode as a positive electrode, a metal lithium sheet as a negative electrode, a polyethylene-polypropylene film as a diaphragm, 1, 3-dioxolane and ethylene glycol dimethyl ether which are mixed according to the weight ratio of 1:1 as a solution and lithium trifluoromethanesulfonate and lithium nitrate as electrolytes, wherein the ratio of the electrolyte to sulfur is 10 muL mg-1。
The test result of constant current charging and discharging under 0.2C shows that the first discharging specific capacity of the battery reaches 1427 mAh.g-1After 50 times of charge-discharge cycles, the concentration of the active carbon still remains 1224mAh g-1The capacity retention was 86%, and the results are shown in FIG. 1.
Example 2
The basic method is the same as example 1 except that
Step two: preparing positive electrode slurry;
mixing the S/C composite material prepared in the step one with carbon black, PVDF and ethylene urea according to the mass ratio of 7:2:0.99:0.01, grinding for 30min, adding a proper amount of N-methyl pyrrolidone solution, and stirring to obtain uniform slurry.
Constant current charge and discharge at 0.2CThe electric test result shows that the first discharge specific capacity of the battery reaches 1330 mAh.g-1After 50 charge-discharge cycles, the concentration of the compound remained 1207mAh g-1The capacity retention rate was 91%, and the results are shown in FIG. 2.
Comparative example:
the same as example 1, except that ethylene urea was not added, and the mass ratio of the S/C composite, carbon black and PVDF was 7:2: 1.
The constant current charge and discharge test result at 0.2C shows that the initial capacity of the comparative example is 1341 mAh.g-1After 50 charge-discharge cycles, the capacity dropped to 1092mAh g-1The capacity retention was only 81%, and the results are shown in FIG. 1.
From the above results, it can be seen that the specific capacity and the cycle performance of the lithium-sulfur battery are increased by adding ethylene urea. Therefore, the problems in the prior art are solved by adding the ethylene urea and combining the special raw material proportion and the preparation process, and the capacity retention rate of the finished lithium-sulfur battery is obviously improved.
The principles and embodiments of the present invention have been described herein using specific examples, which are provided only to help understand the method and the core concept of the present invention; meanwhile, for a person skilled in the art, according to the idea of the present invention, the specific embodiments and the application range may be changed. In view of the above, the present disclosure should not be construed as limiting the invention.
Claims (10)
1. The lithium-sulfur battery is characterized by comprising the following raw materials in percentage by mass:
60 to 80 percent of positive active material,
5 to 15 percent of polyvinylidene fluoride,
10 to 25 percent of conductive agent,
0.1 to 1 percent of ethylene urea,
the sum of the mass percentages of the raw materials is 100 percent.
2. The lithium sulfur battery of claim 1 wherein the positive active material is an ethylene urea/S/C working electrode.
3. The lithium sulfur battery of claim 1, wherein the conductive agent is one or more of carbon black, carbon nanotubes, carbon fibers, and graphene.
4. A method of manufacturing a lithium-sulphur cell according to any of claims 1 to 3, comprising the steps of:
(1) preparing an S/C composite material:
mixing and grinding sulfur powder and commercial carbon nanotubes to uniformly mix sulfur and porous carbon, removing oxygen, drying the mixed material, and cooling to room temperature to obtain an S/C composite material;
(2) preparation of ethylene urea/S/C working electrode:
mixing the S/C composite material, carbon black and polyvinylidene fluoride, adding ethylene urea, grinding for 30min, adding N-methyl pyrrolidone, uniformly stirring to obtain black slurry, coating the slurry on a clean aluminum foil, drying in vacuum, cooling to room temperature, and cutting to obtain an ethylene urea/S/C working electrode;
(3) preparation of lithium-sulfur battery:
the ethylene urea/S/C working electrode is used as a positive electrode, a metal lithium sheet is used as a negative electrode, a polyethylene-polypropylene film is used as a diaphragm, 1, 3-dioxolane and ethylene glycol dimethyl ether are mixed according to the mass ratio of 1:1 to be used as a solution, and lithium trifluoromethanesulfonate and lithium nitrate are used as electrolytes to assemble the lithium-sulfur battery finished product.
5. The method for preparing a lithium-sulfur battery as claimed in claim 4, wherein the mass ratio of the sulfur powder to the commercial carbon nanotubes in the step (1) is (3-5):1, the mixing and grinding time is 0.5-1h, the drying temperature is 150-.
6. The preparation method of the lithium-sulfur battery according to claim 4, wherein the mass ratio of the S/C composite material to the conductive carbon black to the polyvinylidene fluoride in the step (2) is 7:2 (0.9-1), the drying temperature is 50-60 ℃, and the drying time is 12 h.
7. The method of claim 4, wherein the amount of ethylene urea added in step (2) is 1% of the total mass of the S/C composite, the carbon black and the polyvinylidene fluoride mixture.
8. The method for preparing a lithium-sulfur battery according to claim 4, wherein the N-methylpyrrolidone is added in the step (2) in an amount of 25-35% by mass based on the total mass of the S/C composite material, the carbon black and the polyvinylidene fluoride mixture.
9. The method of claim 4, wherein the mass ratio of 1, 3-dioxolane to glyme in step (3) is 1: 1.
10. The method for preparing the lithium-sulfur battery according to claim 4, wherein the finished lithium-sulfur battery in the step (3) is a CR2032 button cell battery, and the ratio of the electrolyte to the sulfur is 5-10 μ L-mg-1。
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| CN102185127A (en) * | 2011-04-07 | 2011-09-14 | 武汉理工大学 | Lithium sulphur battery anode piece added with absorbent and lithium sulphur battery |
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| CN102185127A (en) * | 2011-04-07 | 2011-09-14 | 武汉理工大学 | Lithium sulphur battery anode piece added with absorbent and lithium sulphur battery |
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