CN110649251A - Porous carbon-sulfur composite positive electrode material for lithium-sulfur battery and preparation method thereof - Google Patents
Porous carbon-sulfur composite positive electrode material for lithium-sulfur battery and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a porous carbon-sulfur composite positive electrode material for a lithium-sulfur battery, which is prepared from the following raw materials in parts by weight: 35-50 parts of modified graphene porous carbon material, 230 parts of ethylene glycol, 10-15 parts of doping agent, 2-6 parts of carbon black, 15-25 parts of elemental sulfur and 250 parts of N-methylpyrrolidone through 225; the invention also discloses a preparation method of the porous carbon-sulfur composite positive electrode material for the lithium-sulfur battery; the modified graphene porous carbon material has a porous structure and a wrinkle appearance, cannot generate aggregation, has an ultrahigh specific surface area and porosity, and can load sulfur simple substances more.
Description
Technical Field
The invention belongs to the field of electrochemistry, and particularly relates to a porous carbon-sulfur composite positive electrode material for a lithium-sulfur battery and a preparation method thereof.
Background
The lithium sulfur battery takes elemental sulfur as a positive electrode reaction substance and elemental lithium or lithium alloy as a negative electrode material. During discharge, the negative electrode reacts to lose electrons of lithium and change the lithium into lithium ions, and the positive electrode reacts to generate sulfide through the reaction of sulfur, the lithium ions and the electrons. The potential difference of the reaction of the anode and the cathode is the discharge voltage of the lithium-sulfur battery. The theoretical discharge voltage of a lithium-sulfur battery is 2.287V, and lithium sulfide (Li) is generated when sulfur and lithium are completely reacted2S), the overall theoretical energy density of the lithium-sulfur battery reaches 2600 Wh/kg. Much larger than the commercial secondary batteries used at the present stage. In addition, elemental sulfur is used as a positive electrode material, the raw material source is rich, the cost is low, and therefore the elemental sulfur is hopeful to exceed that of a common lithium ion battery in the aspect of a large-capacity battery, and sulfur is an environmentally-friendly element, basically has no pollution to the environment, and is a battery electrode material with a very good prospect. However, since elemental sulfur is an insulator, it needs to be compounded with a conductive material to effectively transport ions and charges.
The Chinese invention patent CN105390665B discloses a water-based polyaniline lithium-sulfur battery anode material and a preparation method thereof, belonging to the field of electrochemistry. The problem that the existing lithium-sulfur battery electrode material cannot be dispersed in water is solved. Firstly, mixing graphene oxide and aqueous polyaniline to obtain a mixed solution A; then adding a sodium thiosulfate aqueous solution into the mixed solution A, and then adding hydrochloric acid for reaction to obtain a mixed solution B; and adding hydroiodic acid into the mixed solution B for reaction to obtain the water-based polyaniline lithium-sulfur battery cathode material.
Disclosure of Invention
The invention aims to provide a porous carbon-sulfur composite positive electrode material for a lithium-sulfur battery and a preparation method thereof.
The technical problems to be solved by the invention are as follows:
the graphene has super van der Waals force and conjugate acting force, a three-dimensional structure is easily formed, so that the graphene is poor in dispersibility in an organic phase and a water phase solvent and is easy to agglomerate; in the prior art, when carbon dioxide etches a graphene oxide sheet, the etching effect is incomplete due to the influence of the structure of graphene.
The purpose of the invention can be realized by the following technical scheme:
the porous carbon-sulfur composite cathode material for the lithium-sulfur battery is prepared from the following raw materials in parts by weight: 35-50 parts of modified graphene porous carbon material, 230 parts of ethylene glycol, 10-15 parts of doping agent, 2-6 parts of carbon black, 15-25 parts of elemental sulfur and 250 parts of N-methylpyrrolidone through 225;
the porous carbon-sulfur composite positive electrode material for the lithium-sulfur battery is prepared by the following method:
step S1, adding the modified graphene porous carbon material into ethylene glycol for ultrasonic treatment to form a suspension A, then adding a doping agent, transferring the suspension A into a hydrothermal kettle, heating in a water bath at 45 ℃, stirring for 15min at a rotating speed of 120r/min, then filtering, washing with absolute ethyl alcohol for three times, and drying to obtain the doped modified graphene porous carbon material;
step S2, adding carbon black and elemental sulfur into N-methyl pyrrolidone, heating in a water bath at 40 ℃, and performing ultrasonic treatment until the elemental sulfur is dissolved to obtain a suspension B;
and step S3, adding the suspension B into the suspension A, stirring for 30min at the rotating speed of 150r/min, adding deionized water, centrifuging, washing with the deionized water for three times, and drying to obtain the porous carbon-sulfur composite cathode material for the lithium-sulfur battery.
Further, the modified graphene porous carbon material is prepared from the following raw materials in parts by weight: 10-15 parts of graphene, 5-8 parts of sodium nitrate, 150 parts of 98% concentrated sulfuric acid with mass fraction, 1-1.5 parts of potassium chlorate, 40-60 parts of 20% aqueous hydrogen peroxide with volume fraction, 20-30 parts of xylene, 20-30 parts of absolute ethyl alcohol, 20-30 parts of deionized water, 2-3 parts of dodecylbenzene sulfonic acid, 25-40 parts of aniline, 5-8 parts of p-phenylenediamine and 3.5-6 parts of sodium persulfate.
Further, the modified graphene porous carbon material is prepared by the following method:
(1) adding graphene into a round-bottom flask, adding sodium nitrate and 98% concentrated sulfuric acid, stirring for 15min in an ice bath at 3 ℃, adding potassium chlorate, continuously stirring for 30min, then heating in a water bath at 40 ℃, reacting for 3h, adding deionized water, placing under an oil bath at 80 ℃, reacting for 30min, adding 20% aqueous hydrogen peroxide, continuously reacting for 10min, then performing suction filtration, washing and drying to obtain graphene oxide;
(2) adding dimethylbenzene, absolute ethyl alcohol and deionized water into a beaker, mixing, magnetically stirring for 15min, adding dodecylbenzene sulfonic acid, then adding the prepared graphene oxide, ultrasonically stirring for 30min, magnetically stirring, adding aniline and p-phenylenediamine, heating in a water bath at 55 ℃, continuously magnetically stirring for 30min, adding sodium persulfate, stirring for 5h at the rotating speed of 240r/min, filtering after the reaction is finished, and washing with the deionized water for three times to obtain the modified graphene;
(3) and putting the modified graphene into a tubular furnace, introducing nitrogen to discharge air, heating to 800 ℃ at the speed of 8 ℃/min, introducing carbon dioxide, reacting for 2.5 hours at the temperature, introducing nitrogen, and cooling to 30 ℃ to obtain the modified graphene porous carbon material.
The method comprises the following steps that (1) superstrong van der Waals force and conjugate acting force exist among graphene, a three-dimensional structure is easy to form, and the dispersibility of the graphene in an organic phase and an aqueous phase solvent is poor, graphene oxide is prepared from the graphene under the action of potassium chlorate, 20% hydrogen peroxide water solution and the like, the graphene oxide can be dispersed in water and can also be dispersed in the organic solvent, and rich oxygen-containing functional groups are added on the surface of the graphene oxide, so that the graphene oxide is not easy to agglomerate; in the step (2), aniline, p-phenylenediamine and graphene oxide are mixed in a solution, the aniline and the p-phenylenediamine can be polymerized in the solution to form a polymer, the polymer can shuttle between graphene oxide sheet layers, the graphene oxide sheet layers are wrapped, and in the step (3), the separated graphene oxide sheet layers are etched through carbon dioxide to obtain the modified graphene porous carbon material.
Further, the dopant is one or two of phosphate and sulfonate.
The preparation method of the porous carbon-sulfur composite cathode material for the lithium-sulfur battery comprises the following steps:
step S1, adding the modified graphene porous carbon material into ethylene glycol for ultrasonic treatment to form a suspension A, then adding a doping agent, transferring the suspension A into a hydrothermal kettle, heating in a water bath at 45 ℃, stirring for 15min at a rotating speed of 120r/min, then filtering, washing with absolute ethyl alcohol for three times, and drying to obtain the doped modified graphene porous carbon material;
step S2, adding carbon black and elemental sulfur into N-methyl pyrrolidone, heating in a water bath at 40 ℃, and performing ultrasonic treatment until the elemental sulfur is dissolved to obtain a suspension B;
and step S3, adding the suspension B into the suspension A, stirring for 30min at the rotating speed of 150r/min, adding deionized water, centrifuging, washing with the deionized water for three times, and drying to obtain the porous carbon-sulfur composite cathode material for the lithium-sulfur battery.
The invention has the beneficial effects that:
(1) according to the porous carbon-sulfur composite cathode material for the lithium-sulfur battery, a modified graphene porous carbon material, elemental sulfur and the like are used as raw materials, the modified graphene porous carbon material is used as a base material, graphene is prepared into graphene oxide under the action of potassium chlorate, 20% hydrogen peroxide water solution and the like in the step (1) in the preparation process of the modified graphene porous carbon material, the graphene oxide can be dispersed in water and can also be dispersed in an organic solvent, and rich oxygen-containing functional groups are added to the surface of the graphene oxide, so that the graphene oxide is not easy to agglomerate; mixing aniline, p-phenylenediamine and graphene oxide in a solution in the step (2), wherein the aniline and the p-phenylenediamine can be polymerized in the solution to form a polymer, the polymer can shuttle among graphene oxide lamella, the graphene oxide lamella is wrapped, the separated graphene oxide lamella is etched through carbon dioxide in the step (3), and the modified graphene porous carbon material is prepared, the porous carbon material has a porous structure and a wrinkle appearance, does not generate aggregation, has an ultra-high specific surface area and porosity, can load sulfur simple substances more, the utilization rate of sulfur in the electrochemical reaction can be improved, the problem that ultra-strong van der Waals force and conjugate acting force exist among the graphene is solved, a three-dimensional structure is easily formed, and the graphene is poor in dispersibility in organic phase and aqueous phase solvents and easy to agglomerate; in the prior art, when carbon dioxide etches a graphene oxide sheet, the graphene oxide sheet is influenced by the self structure of graphene, so that the technical problem of incomplete etching effect is solved;
(2) in the using process of the prepared cathode material, the ultrahigh specific surface area enables the modified graphene porous carbon material to be in full contact with electrolyte, a double-electron layer is formed, and the high porosity of the modified graphene porous carbon material can provide a channel for rapid transfer of electrons, so that charge transmission is facilitated, and further the modified graphene porous carbon material has more excellent conductivity.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described 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, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The porous carbon-sulfur composite cathode material for the lithium-sulfur battery is prepared from the following raw materials in parts by weight: 35 parts of modified graphene porous carbon material, 200 parts of ethylene glycol, 10 parts of phosphate, 2 parts of carbon black, 15 parts of elemental sulfur and 225 parts of N-methylpyrrolidone;
the porous carbon-sulfur composite positive electrode material for the lithium-sulfur battery is prepared by the following method:
step S1, adding the modified graphene porous carbon material into ethylene glycol for ultrasonic treatment to form a suspension A, then adding phosphate, transferring the suspension A into a hydrothermal kettle, heating in a water bath at 45 ℃, stirring for 15min at a rotating speed of 120r/min, then filtering, washing with absolute ethyl alcohol for three times, and drying to obtain the doped modified graphene porous carbon material;
step S2, adding carbon black and elemental sulfur into N-methyl pyrrolidone, heating in a water bath at 40 ℃, and performing ultrasonic treatment until the elemental sulfur is dissolved to obtain a suspension B;
and step S3, adding the suspension B into the suspension A, stirring for 30min at the rotating speed of 150r/min, adding deionized water, centrifuging, washing with the deionized water for three times, and drying to obtain the porous carbon-sulfur composite cathode material for the lithium-sulfur battery.
The modified graphene porous carbon material is prepared by the following method:
(1) adding graphene into a round-bottom flask, adding sodium nitrate and 98% concentrated sulfuric acid, stirring for 15min in an ice bath at 3 ℃, adding potassium chlorate, continuously stirring for 30min, then heating in a water bath at 40 ℃, reacting for 3h, adding deionized water, placing under an oil bath at 80 ℃, reacting for 30min, adding 20% aqueous hydrogen peroxide, continuously reacting for 10min, then performing suction filtration, washing and drying to obtain graphene oxide;
(2) adding dimethylbenzene, absolute ethyl alcohol and deionized water into a beaker, mixing, magnetically stirring for 15min, adding dodecylbenzene sulfonic acid, then adding the prepared graphene oxide, ultrasonically stirring for 30min, magnetically stirring, adding aniline and p-phenylenediamine, heating in a water bath at 55 ℃, continuously magnetically stirring for 30min, adding sodium persulfate, stirring for 5h at the rotating speed of 240r/min, filtering after the reaction is finished, and washing with the deionized water for three times to obtain the modified graphene;
(3) and putting the modified graphene into a tubular furnace, introducing nitrogen to discharge air, heating to 800 ℃ at the speed of 8 ℃/min, introducing carbon dioxide, reacting for 2.5 hours at the temperature, introducing nitrogen, and cooling to 30 ℃ to obtain the modified graphene porous carbon material.
Example 2
The porous carbon-sulfur composite cathode material for the lithium-sulfur battery is prepared from the following raw materials in parts by weight: 40 parts of a modified graphene porous carbon material, 210 parts of ethylene glycol, 12 parts of phosphate, 4 parts of carbon black, 18 parts of elemental sulfur and 230 parts of N-methylpyrrolidone;
the porous carbon-sulfur composite positive electrode material for the lithium-sulfur battery is prepared by the following method:
step S1, adding the modified graphene porous carbon material into ethylene glycol for ultrasonic treatment to form a suspension A, then adding phosphate, transferring the suspension A into a hydrothermal kettle, heating in a water bath at 45 ℃, stirring for 15min at a rotating speed of 120r/min, then filtering, washing with absolute ethyl alcohol for three times, and drying to obtain the doped modified graphene porous carbon material;
step S2, adding carbon black and elemental sulfur into N-methyl pyrrolidone, heating in a water bath at 40 ℃, and performing ultrasonic treatment until the elemental sulfur is dissolved to obtain a suspension B;
and step S3, adding the suspension B into the suspension A, stirring for 30min at the rotating speed of 150r/min, adding deionized water, centrifuging, washing with the deionized water for three times, and drying to obtain the porous carbon-sulfur composite cathode material for the lithium-sulfur battery.
Example 3
The porous carbon-sulfur composite cathode material for the lithium-sulfur battery is prepared from the following raw materials in parts by weight: 45 parts of modified graphene porous carbon material, 220 parts of ethylene glycol, 14 parts of phosphate, 5 parts of carbon black, 22 parts of elemental sulfur and 240 parts of N-methylpyrrolidone;
the porous carbon-sulfur composite positive electrode material for the lithium-sulfur battery is prepared by the following method:
step S1, adding the modified graphene porous carbon material into ethylene glycol for ultrasonic treatment to form a suspension A, then adding phosphate, transferring the suspension A into a hydrothermal kettle, heating in a water bath at 45 ℃, stirring for 15min at a rotating speed of 120r/min, then filtering, washing with absolute ethyl alcohol for three times, and drying to obtain the doped modified graphene porous carbon material;
step S2, adding carbon black and elemental sulfur into N-methyl pyrrolidone, heating in a water bath at 40 ℃, and performing ultrasonic treatment until the elemental sulfur is dissolved to obtain a suspension B;
and step S3, adding the suspension B into the suspension A, stirring for 30min at the rotating speed of 150r/min, adding deionized water, centrifuging, washing with the deionized water for three times, and drying to obtain the porous carbon-sulfur composite cathode material for the lithium-sulfur battery.
Example 4
The porous carbon-sulfur composite cathode material for the lithium-sulfur battery is prepared from the following raw materials in parts by weight: 50 parts of a modified graphene porous carbon material, 230 parts of ethylene glycol, 15 parts of phosphate, 6 parts of carbon black, 25 parts of elemental sulfur and 250 parts of N-methylpyrrolidone;
the porous carbon-sulfur composite positive electrode material for the lithium-sulfur battery is prepared by the following method:
step S1, adding the modified graphene porous carbon material into ethylene glycol for ultrasonic treatment to form a suspension A, then adding phosphate, transferring the suspension A into a hydrothermal kettle, heating in a water bath at 45 ℃, stirring for 15min at a rotating speed of 120r/min, then filtering, washing with absolute ethyl alcohol for three times, and drying to obtain the doped modified graphene porous carbon material;
step S2, adding carbon black and elemental sulfur into N-methyl pyrrolidone, heating in a water bath at 40 ℃, and performing ultrasonic treatment until the elemental sulfur is dissolved to obtain a suspension B;
and step S3, adding the suspension B into the suspension A, stirring for 30min at the rotating speed of 150r/min, adding deionized water, centrifuging, washing with the deionized water for three times, and drying to obtain the porous carbon-sulfur composite cathode material for the lithium-sulfur battery.
Comparative example 1
Compared with the example 1, the preparation method of the comparative example, which replaces the modified graphene porous carbon material with the graphene, is as follows:
s1, adding graphene into ethylene glycol, performing ultrasonic treatment to form a suspension A, adding phosphate, transferring the suspension A into a hydrothermal kettle, heating in a water bath at 45 ℃, stirring for 15min at a rotating speed of 120r/min, filtering, washing with absolute ethyl alcohol for three times, and drying to obtain the doped modified graphene porous carbon material;
step S2, adding carbon black and elemental sulfur into N-methyl pyrrolidone, heating in a water bath at 40 ℃, and performing ultrasonic treatment until the elemental sulfur is dissolved to obtain a suspension B;
and step S3, adding the suspension B into the suspension A, stirring for 30min at the rotating speed of 150r/min, adding deionized water, centrifuging, washing with the deionized water for three times, and drying to obtain the porous carbon-sulfur composite cathode material for the lithium-sulfur battery.
Comparative example 2
The comparative example is a positive electrode material for a lithium-sulfur battery in the market.
The specific surface area and the pore volume of the modified graphene porous carbon material prepared in example 1 were calculated, and the specific surface area of the modified graphene porous carbon material was 3350m2·g-1Pore volume of 1.98m3·g-1；
The results of the tests conducted on examples 1 to 4 and comparative examples 1 to 2 are shown in the following table;
from the above table, it can be seen that the first discharge specific capacity of the examples 1-4 is 756-plus 801mAh/g, the first efficiency is 78-81%, the discharge specific capacity after 100 cycles is 667-plus 682mAh/g, the ring capacity retention rate is 84.0-88.2%, the first discharge specific capacity of the comparative examples 1-2 is 496-plus 568mAh/g, the first efficiency is 60-65%, the discharge specific capacity after 100 cycles is 387-plus 422mAh/g, and the ring capacity retention rate is 74.3-78.0%; therefore, the prepared cathode material has an ultra-high specific surface area, so that the modified graphene porous carbon material can be in full contact with electrolyte to form a double-electron layer, and the high porosity of the modified graphene porous carbon material can provide a channel for rapid transfer of electrons, so that charge transmission is facilitated, and further the modified graphene porous carbon material has more excellent conductivity.
The foregoing is merely exemplary and illustrative of the present invention and various modifications, additions and substitutions may be made by those skilled in the art to the specific embodiments described without departing from the scope of the invention as defined in the following claims.
Claims (5)
1. The porous carbon-sulfur composite cathode material for the lithium-sulfur battery is characterized by being prepared from the following raw materials in parts by weight: 35-50 parts of modified graphene porous carbon material, 230 parts of ethylene glycol, 10-15 parts of doping agent, 2-6 parts of carbon black, 15-25 parts of elemental sulfur and 250 parts of N-methylpyrrolidone through 225;
the porous carbon-sulfur composite positive electrode material for the lithium-sulfur battery is prepared by the following method:
step S1, adding the modified graphene porous carbon material into ethylene glycol for ultrasonic treatment to form a suspension A, then adding a doping agent, transferring the suspension A into a hydrothermal kettle, heating in a water bath at 45 ℃, stirring for 15min at a rotating speed of 120r/min, then filtering, washing with absolute ethyl alcohol for three times, and drying to obtain the doped modified graphene porous carbon material;
step S2, adding carbon black and elemental sulfur into N-methyl pyrrolidone, heating in a water bath at 40 ℃, and performing ultrasonic treatment until the elemental sulfur is dissolved to obtain a suspension B;
and step S3, adding the suspension B into the suspension A, stirring for 30min at the rotating speed of 150r/min, adding deionized water, centrifuging, washing with the deionized water for three times, and drying to obtain the porous carbon-sulfur composite cathode material for the lithium-sulfur battery.
2. The porous carbon-sulfur composite positive electrode material for the lithium-sulfur battery according to claim 1, wherein the modified graphene porous carbon material is prepared from the following raw materials in parts by weight: 10-15 parts of graphene, 5-8 parts of sodium nitrate, 150-200 parts of 98% concentrated sulfuric acid, 1-1.5 parts of potassium chlorate, 40-60 parts of 20% aqueous hydrogen peroxide, 20-30 parts of xylene, 20-30 parts of absolute ethyl alcohol, 20-30 parts of deionized water, 2-3 parts of dodecylbenzenesulfonic acid, 25-40 parts of aniline, 5-8 parts of p-phenylenediamine and 3.5-6 parts of sodium persulfate.
3. The porous carbon-sulfur composite positive electrode material for a lithium-sulfur battery according to claim 2, wherein the modified graphene porous carbon material is prepared by a method comprising:
(1) adding graphene into a round-bottom flask, adding sodium nitrate and 98% concentrated sulfuric acid, stirring for 15min in an ice bath at 3 ℃, adding potassium chlorate, continuously stirring for 30min, then heating in a water bath at 40 ℃, reacting for 3h, adding deionized water, placing under an oil bath at 80 ℃, reacting for 30min, adding 20% aqueous hydrogen peroxide, continuously reacting for 10min, then performing suction filtration, washing and drying to obtain graphene oxide;
(2) adding dimethylbenzene, absolute ethyl alcohol and deionized water into a beaker, mixing, magnetically stirring for 15min, adding dodecylbenzene sulfonic acid, then adding the prepared graphene oxide, ultrasonically stirring for 30min, magnetically stirring, adding aniline and p-phenylenediamine, heating in a water bath at 55 ℃, continuously magnetically stirring for 30min, adding sodium persulfate, stirring for 5h at the rotating speed of 240r/min, filtering after the reaction is finished, and washing with the deionized water for three times to obtain the modified graphene;
(3) and putting the modified graphene into a tubular furnace, introducing nitrogen to discharge air, heating to 800 ℃ at the speed of 8 ℃/min, introducing carbon dioxide, reacting for 2.5 hours at the temperature, introducing nitrogen, and cooling to 30 ℃ to obtain the modified graphene porous carbon material.
4. The porous carbon-sulfur composite positive electrode material for a lithium-sulfur battery according to claim 1, wherein the dopant is one or both of phosphate and sulfonate.
5. The preparation method of the porous carbon-sulfur composite cathode material for the lithium-sulfur battery is characterized by comprising the following steps of:
step S1, adding the modified graphene porous carbon material into ethylene glycol for ultrasonic treatment to form a suspension A, then adding a doping agent, transferring the suspension A into a hydrothermal kettle, heating in a water bath at 45 ℃, stirring for 15min at a rotating speed of 120r/min, then filtering, washing with absolute ethyl alcohol for three times, and drying to obtain the doped modified graphene porous carbon material;
step S2, adding carbon black and elemental sulfur into N-methyl pyrrolidone, heating in a water bath at 40 ℃, and performing ultrasonic treatment until the elemental sulfur is dissolved to obtain a suspension B;
and step S3, adding the suspension B into the suspension A, stirring for 30min at the rotating speed of 150r/min, adding deionized water, centrifuging, washing with the deionized water for three times, and drying to obtain the porous carbon-sulfur composite cathode material for the lithium-sulfur battery.
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