CN113130892B - Sulfur-carbon composite emulsion and preparation method and application thereof - Google Patents
Sulfur-carbon composite emulsion and preparation method and application thereof Download PDFInfo
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- GJEAMHAFPYZYDE-UHFFFAOYSA-N [C].[S] Chemical compound [C].[S] GJEAMHAFPYZYDE-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000000839 emulsion Substances 0.000 title claims abstract description 47
- 239000002131 composite material Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000004945 emulsification Methods 0.000 title abstract description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 71
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 31
- 239000011593 sulfur Substances 0.000 claims abstract description 31
- 239000004020 conductor Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 239000000243 solution Substances 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 239000011259 mixed solution Substances 0.000 claims abstract description 16
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- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 claims description 15
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 12
- 229910002804 graphite Inorganic materials 0.000 claims description 10
- 239000010439 graphite Substances 0.000 claims description 10
- -1 alkyl glucoside Chemical class 0.000 claims description 9
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- 229930182478 glucoside Natural products 0.000 claims description 8
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- 239000002041 carbon nanotube Substances 0.000 claims description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 4
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 claims description 4
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 claims description 3
- ZGOWINRYWXPJQT-UHFFFAOYSA-N C[NH+](C)C.CCCCCCCCCCCCCCCC([O-])=O Chemical compound C[NH+](C)C.CCCCCCCCCCCCCCCC([O-])=O ZGOWINRYWXPJQT-UHFFFAOYSA-N 0.000 claims description 3
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- LQLQDKBJAIILIQ-UHFFFAOYSA-N Dibutyl terephthalate Chemical compound CCCCOC(=O)C1=CC=C(C(=O)OCCCC)C=C1 LQLQDKBJAIILIQ-UHFFFAOYSA-N 0.000 claims description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
- 229920001214 Polysorbate 60 Polymers 0.000 claims description 2
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 2
- 229920000136 polysorbate Polymers 0.000 claims description 2
- 229950008882 polysorbate Drugs 0.000 claims description 2
- 229920000053 polysorbate 80 Polymers 0.000 claims description 2
- 239000007774 positive electrode material Substances 0.000 claims description 2
- 229940057950 sodium laureth sulfate Drugs 0.000 claims description 2
- SXHLENDCVBIJFO-UHFFFAOYSA-M sodium;2-[2-(2-dodecoxyethoxy)ethoxy]ethyl sulfate Chemical compound [Na+].CCCCCCCCCCCCOCCOCCOCCOS([O-])(=O)=O SXHLENDCVBIJFO-UHFFFAOYSA-M 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims 1
- 239000003575 carbonaceous material Substances 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 6
- 238000013329 compounding Methods 0.000 abstract description 2
- 238000002844 melting Methods 0.000 abstract description 2
- 230000008018 melting Effects 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 238000009792 diffusion process Methods 0.000 description 8
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical group CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
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- 230000015572 biosynthetic process Effects 0.000 description 2
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- 239000006185 dispersion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003273 ketjen black Substances 0.000 description 2
- YQCIWBXEVYWRCW-UHFFFAOYSA-N methane;sulfane Chemical compound C.S YQCIWBXEVYWRCW-UHFFFAOYSA-N 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- IVHLCRXCNVBWTP-UHFFFAOYSA-N 1-chlorohexadecane N,N-dimethylmethanamine Chemical compound CN(C)C.CCCCCCCCCCCCCCCCCl IVHLCRXCNVBWTP-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000002388 carbon-based active material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000009828 non-uniform distribution Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
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- 238000012360 testing method Methods 0.000 description 1
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Images
Classifications
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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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
-
- 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
-
- 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
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides a sulfur-carbon composite emulsion, a preparation method and application thereof, wherein the preparation method specifically comprises the following steps: (1) melting to form a sulfur solution; (2) adding 1-30% by mass of emulsifier and 10-40% by mass of conductive material into the sulfur solution, and continuously stirring at 110-150 ℃ until a uniform mixed solution is formed; (3) adding 20-90% of solvent by mass into the uniformly mixed solution, and stirring for 10min-5h at the temperature of 100-180 ℃ and the rotating speed of 1000r-5000r to obtain the sulfur-carbon composite emulsion. The preparation method is a new method for realizing sulfur-carbon material compounding by utilizing a simple emulsification process, and has the application potential of commercial large-scale production.
Description
Technical Field
The invention belongs to the technical field of new materials, and particularly relates to a sulfur-carbon composite emulsion and a preparation method and application thereof.
Background
With the rapid development of scientific technologies such as communication and the like, portable electronic technologies such as wearable and the like urgently require energy storage materials with high energy density and long service life for energy storage systems. Among the various rechargeable batteries, lithium sulfur batteries are due to their theoretical energy density: (2600 wh kg-1) Specific capacity (1675 mAh g)-1) And received much attention. In addition, sulfur has the properties of non-toxicity, environmental protection and abundant reserves, and compared with the current commercial lithium ion batteries, the commercial competitiveness and sustainability of lithium-sulfur batteries are greatly improved.
However, lithium-sulfur batteries still face a great problem in practical applications, especially the poor electronic conductivity (5 × 10) of elemental sulfur -30 S cm -125 deg.C) and needs to add conductive material (such as carbon material) during the use process to obtain better electrochemical property. At present, elemental sulfur is usually prepared in pores of a carbon material or wrapped in the carbon material by a melt diffusion method and a chemical coprecipitation method, so that sulfur-carbon compounding is realized. For example, the melting diffusion method needs to uniformly mix sublimed sulfur and a carbon material, then perform heat treatment at a temperature of more than 155 ℃ or even diffuse sulfur in a low-pressure environment, extra heating and heat preservation are needed, and the diffusion process usually needs a long time (10-12 hours), which increases the cost of material synthesis. In addition, uncertainty in the diffusion process of the sublimed sulfur also easily causes the non-uniform distribution of the sublimed sulfur on the carbon material, thereby affecting the performance of the battery. In addition, during the melt diffusion process, heating and heat preservation processes are required, which is time-consuming and increases the cost. In a typical melt diffusion process, it typically takes 12 hours to produce a small amount of carbon-sulfur composite. Chemical coprecipitation also requires carbon-sulfur recombination at low concentrations and long processing times to achieve uniform and controlled thickness deposition, which often results in low product yields and difficult large-scale commercial applications. Therefore, the development of a sulfur-carbon material composite mode with high production efficiency, controllable process and low synthesis temperature is urgently needed.
Disclosure of Invention
The invention provides a sulfur-carbon composite emulsion, a preparation method and application thereof aiming at the problems faced by the sulfur-carbon composite material in the lithium sulfur battery.
The technical scheme adopted by the invention is as follows:
a preparation method of a sulfur-carbon composite emulsion specifically comprises the following steps:
(1) weighing certain mass of sublimed sulfur powder, and stirring the sublimed sulfur powder at 100-180 ℃ for 10-30 min to melt to form a sulfur solution;
(2) adding 1-30% by mass of emulsifier and 10-40% by mass of conductive material into the sulfur solution, and continuously stirring at 110-150 ℃ until a uniform mixed solution is formed;
(3) adding 20-90% of solvent by mass into the uniformly mixed solution based on the mass of the sublimed sulfur powder, and stirring for 10-5 h under the temperature condition of 100-180 ℃ and the rotating speed of 1000-5000 r/min to obtain the sulfur-carbon composite emulsion.
Generally, the sulfur content in a sulfur cathode is more than 70% of the total solid content, and the high sulfur content provides the possibility of preparing a high sulfur cathode, while the sublimed sulfur and the lithium sulfide which is the final reaction product have very poor conductivity, so that an additional conductive material needs to be added to increase the conductivity of the sulfur cathode. The final energy density of the battery is reduced due to the excessive content of the conductive material; the conductive material can not fully play a role when the content is too low, and tests show that the conductive material can play a better electrical property when the content is 10-40%. The emulsifier is an important material for stably storing the sublimed sulfur and the conductive material in the emulsion, and can effectively avoid the phenomenon of uneven dispersion of the material. The dosage of the solvent firstly needs to ensure the dispersion requirement of the sublimed sulfur and the conductive material, secondly, the solvent is excessive, and the required time is longer when the solvent is finally dried, so the dosage is controlled to be 20-90 percent. The mass ratio can ensure that the emulsion has higher sulfur content, and is beneficial to preparing the lithium-sulfur battery cathode material with high sulfur content.
In the above method for preparing a sulfur-carbon composite emulsion, preferably, the solvent is one or more of water, ethylene glycol, octanol, ethanolamine, N-butanol, cyclohexane, N-methylpyrrolidone and dibutyl terephthalate; the above solvent is preferably water, ethylene glycol, octanol or N-methylpyrrolidone.
The selected solvent has high boiling point and stable property, so that the sublimed sulfur does not react with the solvent at a high temperature, the solubility of the sublimed sulfur in the solvent is low, and the sublimed sulfur can be stably dispersed in the solvent under the action of the emulsifier.
Preferably, the emulsifier is one or more of diethylene glycol monobutyl ether, sodium laureth sulfate, tween-80, tween-60, span-60, amidopropyl trimethyl ammonium chloride palmitate, alkyl glucoside, sorbitan fatty acid-80, polysorbate, sorbitan fatty acid-80 and cetyl trimethyl ammonium bromide; the above emulsifier is preferably diethylene glycol butyl ether, amidopropyl trimethyl ammonium cetyl chloride and alkyl glucoside.
The emulsifier is an important material for stably storing the sublimed sulfur and the conductive material in the emulsion, and the sublimed sulfur and the conductive material can be uniformly dispersed in the solvent by a small content of the emulsifier.
In the preparation method of the sulfur-carbon composite emulsion, preferably, the conductive material is one or more of carbon nanotubes, graphene, conductive carbon fibers, acetylene black, conductive graphite and ketjen black, and is preferably carbon nanotubes, conductive graphite, graphene and ketjen black.
For the selection of the conductive material, the following factors need to be considered: firstly, the higher the conductivity of the conductive material is, the more the transfer of electrons in the reaction process can be accelerated; secondly, the smaller the density is, the larger the volume is, the larger the contact area with the sublimed sulfur is, and in addition, the larger the specific surface area can relieve the volume expansion of the sulfur battery in the prior charge and discharge processes under the same mass; thirdly, the raw materials are widely available and the cost is low, thereby reducing the production cost.
The sulfur-carbon composite emulsion prepared by the preparation method has the advantages of uniform distribution of sublimed sulfur and conductive carbon materials, simple preparation method and large-scale preparation.
The sulfur-carbon composite emulsion is applied to the lithium-sulfur battery, and the coated and dried sulfur-carbon composite emulsion is used as the positive electrode material of the lithium-sulfur battery, so that the rate capability of the lithium-sulfur battery can be effectively improved
Compared with the prior art, the technical scheme provided by the invention has the following beneficial effects:
the emulsification can uniformly disperse a substance in another liquid which is not mutually soluble in a particle mode, uniformly disperse an active substance sulfur in a solvent in a particle mode under the strong stirring action with the help of an emulsifier, directly coat the sulfur-carbon composite emulsion on an aluminum foil when in use, and dry the aluminum foil at a low temperature to obtain the sulfur-carbon active material.
Compared with the traditional methods such as a melt diffusion method and chemical coprecipitation, the method has the advantages of simple preparation process, short time, high production efficiency and the like. The sulfur-carbon composite emulsion prepared by the process can be directly plated on the surfaces of electrodes such as aluminum foil and the like in a simple coating mode and the like, can show excellent electrochemical performance after low-temperature drying treatment, and can be widely applied to fields such as lithium-sulfur batteries and the like related to energy storage.
Drawings
FIG. 1 is a photograph of a sulfur-carbon composite emulsion prepared in example 1 of the present invention;
FIG. 2 is a scanning electron micrograph of sublimed sulfur used in the present invention;
FIG. 3 is a scanning electron micrograph of a sulfur-carbon composite emulsion prepared in example 1 of the present invention;
fig. 4 is a graph showing rate capability of sulfur cathodes prepared from the sulfur-carbon composite emulsion according to example 1 of the present invention applied to lithium-sulfur batteries at current densities of 0.1, 0.2, 0.5, 1, 2, and 3C.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments that can be derived by one of ordinary skill in the art from the embodiments given herein are intended to be within the scope of the present invention.
Example 1
A sulfur-carbon composite emulsion is prepared by the following steps:
(1) 90 g of sublimed sulfur powder is weighed and stirred for 20 min at 160 ℃ to form a molten sulfur solution.
(2) Based on the mass of the sublimed sulfur powder, 4.5g of diethylene glycol butyl ether and cetylamidopropyl trimethyl ammonium chloride (wherein the dosage of the diethylene glycol butyl ether is 2.0g, and the dosage of the cetylamidopropyl trimethyl ammonium chloride is 2.5 g) and 18g of acetylene black and conductive graphite (the dosages of the acetylene black and the conductive graphite are respectively 9.0 g) are added into the sulfur solution, and the stirring is continued at the temperature of 150 ℃ until a uniform mixed solution is formed.
(3) And (3) adding 18g of octanol into the uniformly mixed solution according to the mass of the sublimed sulfur powder, and rapidly stirring at 150 ℃ and 5000 r/min for 30 min to obtain the sulfur-carbon composite emulsion.
Example 2
A sulfur-carbon composite emulsion is prepared by the following steps:
(1) 90 g of sublimed sulfur powder is weighed and stirred at 180 ℃ for 10min to be melted to form a sulfur solution.
(2) Based on the mass of the sublimed sulfur powder, 18g of amidopropyl trimethyl ammonium palmitate and alkyl glucoside (the dosage of the amidopropyl trimethyl ammonium palmitate and the dosage of the alkyl glucoside are respectively 9 g) and 27g of acetylene black and Kejing black (the dosage of the acetylene black is 12g and the dosage of the Kejing black is 15 g) are added into the sulfur solution, and the stirring is continued at 150 ℃ until a uniform mixed solution is formed.
(3) Adding 81g of ethylene glycol into the uniformly mixed solution according to the mass of the sublimed sulfur powder, and rapidly stirring for 1 h at 150 ℃ at 4000 r/min to obtain the sulfur-carbon composite emulsion.
Example 3
A sulfur-carbon composite emulsion is prepared by the following steps:
(1) 70 g of sublimed sulfur powder is weighed and stirred at 180 ℃ for 10min to be melted to form a sulfur solution.
(2) Based on the mass of the sublimed sulfur powder, 17.5g of diethylene glycol butyl ether and alkyl glucoside (the amount of diethylene glycol butyl ether is 10g, and the amount of alkyl glucoside is 7.5 g), 28g of acetylene black and conductive graphite (the amount of acetylene black is 10g, and the amount of conductive graphite is 18 g) were added to the sulfur solution, and stirring was continued at 120 ℃ until a uniform mixed solution was formed.
(3) Adding 14g of N-methyl pyrrolidone into the uniformly mixed solution according to the mass of the sublimed sulfur powder, and rapidly stirring at 170 ℃ and 5000 r/min for 20 min to obtain the sulfur-carbon composite emulsion.
Example 4
A sulfur-carbon composite emulsion is prepared by the following steps:
(1) 70 g of sublimed sulfur powder is weighed and stirred at 180 ℃ for 10min to be melted to form a sulfur solution.
(2) Based on the mass of the sublimed sulfur powder, 14g of diethylene glycol butyl ether and hexadecyl amidopropyl trimethyl ammonium chloride (the dosage of the diethylene glycol butyl ether is 10g, and the dosage of the hexadecyl amidopropyl trimethyl ammonium chloride is 4 g) and 14g of Kejing black and conductive graphite (each 7 g) are added into the sulfur solution, and the stirring is continued at the temperature of 110 ℃ until a uniform mixed solution is formed.
(3) Adding 35g of octanol into the uniformly mixed solution according to the mass of the sublimed sulfur powder, and rapidly stirring for 4 hours at 110 ℃ at 1000 r/min to obtain the sulfur-carbon composite emulsion.
Example 5
A sulfur-carbon composite emulsion is prepared by the following steps:
(1) 80 g of sublimed sulfur powder is weighed and stirred at 160 ℃ for 25 min to be melted to form a sulfur solution.
(2) Based on the mass of the sublimed sulfur powder, 8g of diethylene glycol monobutyl ether, 4g of each cetylamidopropyl trimethyl ammonium chloride and 8g of conductive graphite are added into the sulfur solution, and the mixture is continuously stirred at the temperature of 150 ℃ until a uniform mixed solution is formed.
(3) Adding 32g of N-methyl pyrrolidone into the uniformly mixed solution according to the mass of the sublimed sulfur powder, and rapidly stirring for 4 hours at 140 ℃ at 1000 r/min to obtain the sulfur-carbon composite emulsion.
As shown in FIG. 1, which is a photograph of the sulfur-carbon composite emulsion prepared in example 1 of the present invention, it can be seen that the prepared emulsion is uniformly distributed and the emulsion is not delaminated.
Comparing fig. 2 and fig. 3, it can be seen that after the sublimed sulfur and the conductive material used in the present invention are mixed and emulsified, the surface of the sublimed sulfur is coated with a layer of conductive material and emulsifier, and the diameter of the sublimed sulfur particles is significantly reduced.
The invention further applies the sulfur cathode prepared from the sulfur-carbon composite emulsion prepared in the example 1 to the lithium-sulfur battery, and the specific discharge capacity is 412.4 mAh g under the high current density of 3C-1Under the current density of 1C, the specific discharge capacity after high-rate circulation is 470.5 mAh g-1The recovery rate of the capacity was 95.2%.
Therefore, the preparation method of the sulfur-carbon composite emulsion provided by the invention can be applied to the field of lithium-sulfur battery cathode materials, and the sulfur-carbon composite emulsion is prepared by mixing a sulfur raw material, a solvent, an emulsifier and a conductive material according to a certain proportion and emulsifying the mixture. The method has the advantages of short time consumption, simple preparation process, low cost, realization of large-scale preparation and the like, is applied to the preparation of the sulfur anode composite material of the lithium-sulfur battery, avoids high-temperature treatment and complex process control brought by adopting methods such as melt diffusion or liquid phase deposition and the like, and has huge industrial application prospect.
The above description is only exemplary of the invention and should not be taken as limiting the invention, as any modification, equivalent replacement, or improvement made within the spirit and principle of the invention is intended to be covered by the appended claims.
Claims (8)
1. The preparation method of the sulfur-carbon composite emulsion is characterized by comprising the following steps of:
(1) weighing certain mass of sublimed sulfur powder, and stirring the sublimed sulfur powder at 100-180 ℃ for 10-30 min to melt to form a sulfur solution;
(2) adding 1-30% by mass of emulsifier and 10-40% by mass of conductive material into the sulfur solution, and continuously stirring at 110-150 ℃ until a uniform mixed solution is formed;
(3) adding 20-90% of solvent by mass into the uniformly mixed solution based on the mass of the sublimed sulfur powder, and stirring for 10min-5h under the temperature condition of 100-180 ℃ and the rotating speed of 1000-5000 r/min to obtain sulfur-carbon composite emulsion;
wherein the solvent is one or more of water, ethylene glycol, octanol, ethanolamine, N-butanol, cyclohexane, N-methylpyrrolidone and dibutyl terephthalate.
2. The method for preparing a sulfur-carbon composite emulsion according to claim 1, wherein: the solvent is preferably water, ethylene glycol, octanol or N-methylpyrrolidone.
3. The method for preparing a sulfur-carbon composite emulsion according to claim 1, wherein: the emulsifier is one or more of diethylene glycol monobutyl ether, sodium laureth sulfate, tween-80, tween-60, span-60, cetyl amidopropyl trimethyl ammonium chloride, alkyl glucoside, sorbitan fatty acid-80, polysorbate and cetyl trimethyl ammonium bromide.
4. The method for preparing a sulfur-carbon composite emulsion according to claim 3, wherein: the emulsifier is preferably diethylene glycol monobutyl ether, amidopropyl trimethyl ammonium palmitate or alkyl glucoside.
5. The method for preparing a sulfur-carbon composite emulsion according to claim 1, wherein: the conductive material is one or more of carbon nano tube, graphene, conductive carbon fiber, acetylene black, conductive graphite and Kejing black.
6. The method for preparing a sulfur-carbon composite emulsion according to claim 5, wherein: the conductive material is preferably carbon nanotubes, conductive graphite, graphene, and cocrystal black.
7. A sulfur-carbon composite emulsion produced by the production method according to any one of claims 1 to 6.
8. Use of the sulfur-carbon composite emulsion of claim 7 in a lithium sulfur battery, wherein: the sulfur-carbon composite emulsion is used as a lithium-sulfur battery positive electrode material after being coated and dried.
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| CN102509780A (en) * | 2011-10-26 | 2012-06-20 | 广州微宏电源科技有限公司 | Lithium battery anode composite material and preparing method thereof |
| CN103326001A (en) * | 2013-05-28 | 2013-09-25 | 中国科学院苏州纳米技术与纳米仿生研究所 | Method for preparing core-shell polymer-nano sulfur particle composite material |
| CN103500813A (en) * | 2013-09-24 | 2014-01-08 | 上海空间电源研究所 | Elemental sulfur anode of secondary lithium-sulfur battery and preparation method of elemental sulfur anode |
| KR20140086811A (en) * | 2012-12-28 | 2014-07-08 | 현대자동차주식회사 | Fabrication process of sulfur-infiltrated mesoporous conductive nanocomposites for cathode of lithium-sulfur secondary batteries |
| CN107887590A (en) * | 2017-11-10 | 2018-04-06 | 中山大学 | One kind carries sulphur composite positive pole and its preparation method and application |
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| CN102509780A (en) * | 2011-10-26 | 2012-06-20 | 广州微宏电源科技有限公司 | Lithium battery anode composite material and preparing method thereof |
| KR20140086811A (en) * | 2012-12-28 | 2014-07-08 | 현대자동차주식회사 | Fabrication process of sulfur-infiltrated mesoporous conductive nanocomposites for cathode of lithium-sulfur secondary batteries |
| CN103326001A (en) * | 2013-05-28 | 2013-09-25 | 中国科学院苏州纳米技术与纳米仿生研究所 | Method for preparing core-shell polymer-nano sulfur particle composite material |
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