CN113471416B - Nitrogen-sulfur-boron co-doped carbon aerogel-based sulfur composite material and preparation method and application thereof - Google Patents
Nitrogen-sulfur-boron co-doped carbon aerogel-based sulfur composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of a nitrogen-sulfur-boron co-doped carbon aerogel-based sulfur composite material, which comprises the following steps: s1, adding resorcinol, formaldehyde, a sulfur source, a nitrogen source, a boron source and a dispersing agent into water, heating and stirring to obtain a mixed solution; s2, filtering the mixed solution, and drying the obtained filter cake at high temperature to obtain precursor powder; s3, calcining the precursor powder in a high-purity nitrogen atmosphere to obtain nitrogen-sulfur-boron co-doped carbon aerogel; and S4, mixing and grinding the nitrogen-sulfur-boron co-doped carbon aerogel and sublimed sulfur uniformly, and sintering under an air atmosphere to obtain the carbon aerogel. The invention also discloses a nitrogen-sulfur-boron co-doped carbon aerogel-based sulfur composite material and application thereof as a lithium-sulfur battery positive electrode material. The preparation method is simple and convenient to regulate, and the prepared material can effectively solve the problems of shuttle effect, volume expansion and the like of the lithium-sulfur battery and improve the electrochemical performance of the lithium-sulfur battery.
Description
Technical Field
The invention relates to the technical field of battery materials, in particular to a nitrogen-sulfur-boron co-doped carbon aerogel-based sulfur composite material, and a preparation method and application thereof.
Background
With the importance of the country to the new energy direction, people in all communities develop high-energy-density and environment-friendly batteries. The lithium sulfur battery is used as a very potential battery, has a theoretical gram capacity of up to 1675mAh and enters the eye curtains of all people. And the elemental sulfur has the advantages of wide sources, no toxicity, no harm, low cost, environmental friendliness and the like. While lithium sulfur batteries have these advantages, their disadvantages are also not negligible. Simple substance sulfur has low conductivity and can not be directly used as a positive electrode material; the sulfur electrode has larger volume change in the circulation process, which affects the circulation life of the battery; polysulfide can be generated in the charge and discharge process, so that a shuttle effect is caused, the utilization rate of an active material is reduced, and the electrochemical characteristics of the lithium-sulfur battery are affected.
For the above-mentioned problems, the expert conducted intensive research analyses. At present, a plurality of scholars adopt a mode of compounding carbon materials and sulfur to form the anode material. The carbon material has high conductivity and a porous structure, and the interconnected porous structure can fix elemental sulfur and polysulfide, but the physical adsorption capacity is weak, so that the shuttle effect cannot be effectively reduced.
Disclosure of Invention
Based on the technical problems in the background technology, the invention provides a nitrogen-sulfur-boron co-doped carbon aerogel-based sulfur composite material, a preparation method thereof and application of the composite material as a positive electrode material of a lithium-sulfur battery. The carbon aerogel has a large specific surface area and a micropore interconnection structure, can physically adsorb polysulfide, and meanwhile, nitrogen-sulfur-boron co-doping can provide multiple functional groups for chemically adsorbing polysulfide, so that the shuttle effect is effectively reduced.
The invention provides a preparation method of a nitrogen-sulfur-boron co-doped carbon aerogel-based sulfur composite material, which comprises the following steps:
s1, adding resorcinol, formaldehyde, a sulfur source, a nitrogen source, a boron source and a dispersing agent into water, heating and stirring to obtain a mixed solution;
s2, filtering the mixed solution, and drying the obtained filter cake at high temperature to obtain precursor powder;
s3, calcining the precursor powder in a high-purity nitrogen atmosphere to obtain nitrogen-sulfur-boron co-doped carbon aerogel;
s4, mixing and grinding the nitrogen-sulfur-boron co-doped carbon aerogel and sublimed sulfur uniformly, and sintering under an air atmosphere to obtain the nitrogen-sulfur-boron co-doped carbon aerogel-based sulfur composite material.
Preferably, the resorcinol to formaldehyde molar ratio is 1:1.5 to 2.5; the mol ratio of the resorcinol to the sulfur source, the nitrogen source, the boron source and the dispersing agent is 1: (0.1-0.5): (0.1-0.4): (0.05-0.2): (0.005-0.01).
Preferably, the mass ratio of the nitrogen-sulfur-boron co-doped carbon aerogel to sublimed sulfur is 1: (1.5-2.5).
Preferably, in the step S1, the heating and stirring temperature is 60-90 ℃, and the heating and stirring time is 24-36 hours.
Preferably, in the step S2, the high-temperature drying temperature is 90-120 ℃, and the high-temperature drying time is 12-24 hours.
Preferably, in the step S3, the calcination temperature is 800-1000 ℃ and the calcination time is 2-3 hours.
Preferably, in the step S4, the sintering temperature is 160-180 ℃ and the sintering time is 10-16 h.
Preferably, the sulfur source is thiourea, dodecyl mercaptan, or a combination thereof; the nitrogen source is melamine, urea or a combination thereof; the boron source is boric acid, borax or a combination thereof; the dispersing agent is at least one of hexadecyl trimethyl ammonium bromide, sodium dodecyl benzene sulfonate and sodium dodecyl sulfate.
A nitrogen-sulfur-boron co-doped carbon aerogel-based sulfur composite material is prepared by the preparation method.
The nitrogen-sulfur-boron co-doped carbon aerogel-based sulfur composite material is applied to a lithium-sulfur battery positive electrode material.
The beneficial effects of the invention are as follows:
the nitrogen-sulfur-boron co-doped carbon aerogel is prepared by an in-situ method, and is combined with elemental sulfur by a fusion diffusion method to obtain the nitrogen-sulfur-boron co-doped carbon aerogel-based sulfur composite material. The method belongs to in-situ doping, is simple to operate and is suitable for large-scale practical production.
The nitrogen-sulfur-boron co-doped carbon aerogel-based sulfur composite material obtained by the method has high porosity and large specific surface area, the pore diameter is concentrated at 3-4 nm, and the pore diameter can be adjusted by changing the raw material ratio, the calcination temperature and the like. The material has rich pore structures, can effectively contain and adsorb elemental sulfur and polysulfide, and the doping of nitrogen, sulfur and boron nonmetallic elements chemically adsorbs polysulfide through nitrogen, sulfur and boron functional groups on the surface of the material, so that the shuttle effect is further reduced, and the cycle life and the multiplying power performance of the lithium-sulfur battery are improved; the material has small crystallization granularity, nitrogen, sulfur and boron are uniformly dispersed in the carbon aerogel material, the effect of co-doping elements can be fully exerted, the energy level of adjacent C atoms is changed due to the synergistic effect of the nitrogen, sulfur and boron, the activity of the material is increased, the conductivity of the material is improved, and the cycle life and the multiplying power performance of a lithium-sulfur battery are improved. The nitrogen-sulfur-boron co-doped carbon aerogel-based sulfur composite material prepared by the method is of a sphere-like structure, improves the mechanical property of the material, and maintains a stable structure after multiple charge and discharge processes when the material is applied to a lithium-sulfur battery, so that the cycle life of the lithium-sulfur battery is prolonged.
Drawings
FIG. 1 is an SEM image of a nitrogen-sulfur-boron co-doped carbon aerogel-based sulfur composite prepared in example 1 of the present invention.
FIG. 2 is a graph showing the results of a test of the cycle stability performance at 0.2C of a battery made of the nitrogen-sulfur-boron co-doped carbon aerogel-based sulfur composite material prepared in example 1 of the present invention.
Detailed Description
The technical scheme of the invention is described in detail through specific embodiments.
Example 1
The preparation method of the nitrogen-sulfur-boron co-doped carbon aerogel-based sulfur composite material comprises the following steps:
s1, adding resorcinol, formaldehyde, thiourea, melamine, boric acid and cetyltrimethylammonium bromide into deionized water, heating and stirring for 36 hours at 60 ℃ to obtain a mixed solution, wherein the mol ratio of resorcinol to formaldehyde is 1:2, the mol ratio of resorcinol to thiourea, melamine, boric acid and cetyltrimethylammonium bromide is 1:0.1:0.1:0.05:0.005, resorcinol to water mass ratio of 1:20, a step of;
s2, filtering the mixed solution, and placing the obtained filter cake in an oven, and drying at a high temperature of 90 ℃ for 24 hours to obtain reddish brown precursor powder;
s3, filling the precursor powder into a small porcelain boat, placing the small porcelain boat into a tube furnace, calcining for 3 hours at 800 ℃ under the atmosphere of high-purity nitrogen, and naturally cooling to obtain nitrogen-sulfur-boron co-doped carbon aerogel;
s4, mixing the nitrogen-sulfur-boron co-doped carbon aerogel with sublimed sulfur according to the mass ratio of 1:1.5, placing the materials in a mortar, mixing and grinding the materials uniformly, placing the materials in an autoclave, and sintering the materials for 16 hours at 160 ℃ in air atmosphere to obtain the nitrogen-sulfur-boron co-doped carbon aerogel-based sulfur composite material.
FIG. 1 is an SEM image of a nitrogen-sulfur-boron co-doped carbon aerogel-based sulfur composite prepared in example 1. As can be seen from fig. 1, the carbon aerogel has a rich pore structure, and is interconnected into a three-dimensional network system. The carbon aerogel material after nitrogen-sulfur-boron co-doping modification has a stable frame structure, has abundant micropores, can accommodate a large amount of electrolyte in the micropores, provides ion transmission channels, realizes rapid diffusion of ions, simultaneously relieves the problem of volume expansion caused by a charge-discharge process, and has a porous structure capable of physically adsorbing sulfur and polysulfide to inhibit a shuttle effect; the conductivity of the material is increased after the nitrogen-sulfur-boron co-doping modification, and simultaneously, nitrogen-sulfur-boron functional groups on the surface of the material can chemically adsorb sulfur and polysulfide, so that the shuttle effect is further improved, and the electrochemical performance and the cycling stability of the material are effectively improved.
The prepared nitrogen-sulfur-boron co-doped carbon aerogel-based sulfur composite material is used as a positive electrode material to prepare a lithium ion battery, and the specific steps are as follows: the nitrogen-sulfur-boron co-doped carbon aerogel-based sulfur composite material, acetylene black and polyvinylidene fluoride are weighed according to the weight ratio of 8:1:1 and mixed, and the mixture is put in a mortar for half an hour until being uniform. And then dropwise adding N-methyl-2-pyrrolidone into the mixture, continuously grinding to form uniform slurry, coating the slurry on an aluminum foil to prepare a positive plate, wherein the positive plate is a metal lithium plate, the electrolyte is 1mol/LLiTFSI/DOL-DME (1:1), and the diaphragm is polypropylene, so that the simulated lithium ion battery is assembled.
FIG. 2 is a graph showing the results of a test of the cyclic stability performance at 0.2C of a cell made of the nitrogen-sulfur-boron co-doped carbon aerogel-based sulfur composite prepared in example 1. As can be seen from fig. 2, the material shows advantages in both cycle life and specific capacity, and the prepared battery has a specific capacity of 1256mAh/g for initial discharge at 0.2C rate, and a specific capacity of 1134mAh/g for 100 cycles.
Example 2
The preparation method of the nitrogen-sulfur-boron co-doped carbon aerogel-based sulfur composite material comprises the following steps:
s1, adding resorcinol, formaldehyde, dodecyl mercaptan, melamine, borax and sodium dodecyl benzene sulfonate into deionized water, and heating and stirring at 70 ℃ for 32 hours to obtain a mixed solution, wherein the mol ratio of resorcinol to formaldehyde is 1:1.5, the mol ratio of resorcinol to dodecyl mercaptan, melamine, borax and sodium dodecyl benzene sulfonate is 1:0.2:0.2:0.1:0.006, resorcinol to water mass ratio of 1:20, a step of;
s2, filtering the mixed solution, and placing the obtained filter cake in an oven, and drying at a high temperature of 95 ℃ for 20 hours to obtain reddish brown precursor powder;
s3, filling the precursor powder into a small porcelain boat, placing the small porcelain boat into a tube furnace, calcining for 2.5 hours at 850 ℃ under the atmosphere of high-purity nitrogen, and naturally cooling to obtain nitrogen-sulfur-boron co-doped carbon aerogel;
s4, mixing the nitrogen-sulfur-boron co-doped carbon aerogel with sublimed sulfur according to the mass ratio of 1:1.8, placing the materials in a mortar, mixing and grinding the materials uniformly, placing the materials in an autoclave, and sintering the materials at 170 ℃ for 12 hours in an air atmosphere to obtain the nitrogen-sulfur-boron co-doped carbon aerogel-based sulfur composite material.
The specific procedure of example 1 was followed using the nitrogen-sulfur-boron co-doped carbon aerogel-based sulfur composite material prepared as described above as the positive electrode material to prepare a lithium ion battery.
Through tests, the battery prepared from the prepared material has the initial discharge specific capacity of 1225mAh/g at the rate of 0.2C, and the specific capacity of 100 cycles is kept at 1098mAh/g.
Example 3
The preparation method of the nitrogen-sulfur-boron co-doped carbon aerogel-based sulfur composite material comprises the following steps:
s1, adding resorcinol, formaldehyde, thiourea, urea, borax and sodium dodecyl sulfate into deionized water, heating and stirring for 28 hours at 80 ℃ to obtain a mixed solution, wherein the mol ratio of resorcinol to formaldehyde is 1:2, the mol ratio of resorcinol to thiourea, urea, borax and sodium dodecyl sulfate is 1:0.3:0.3:0.15:0.007, resorcinol to water mass ratio of 1:20, a step of;
s2, filtering the mixed solution, and then placing the obtained filter cake in an oven, and drying at a high temperature of 100 ℃ for 16 hours to obtain precursor powder;
s3, filling the precursor powder into a small porcelain boat, placing the small porcelain boat into a tube furnace, calcining for 2.5 hours at 900 ℃ under the atmosphere of high-purity nitrogen, and naturally cooling to obtain nitrogen-sulfur-boron co-doped carbon aerogel;
s4, mixing the nitrogen-sulfur-boron co-doped carbon aerogel with sublimed sulfur according to the mass ratio of 1:2, placing the mixture in a mortar, uniformly mixing and grinding, and sintering the mixture for 10 hours at 175 ℃ in an air atmosphere to obtain the nitrogen-sulfur-boron co-doped carbon aerogel-based sulfur composite material.
The specific procedure of example 1 was followed using the nitrogen-sulfur-boron co-doped carbon aerogel-based sulfur composite material prepared as described above as the positive electrode material to prepare a lithium ion battery.
Through tests, the battery prepared from the prepared material has the specific capacity of 1324mAh/g after first discharge at the rate of 0.2C, and the specific capacity of 1173mAh/g after 100 times of circulation.
Example 4
The preparation method of the nitrogen-sulfur-boron co-doped carbon aerogel-based sulfur composite material comprises the following steps:
s1, adding resorcinol, formaldehyde, thiourea, melamine, boric acid and cetyltrimethylammonium bromide into deionized water, heating and stirring for 24 hours at 90 ℃ to obtain a mixed solution, wherein the mol ratio of resorcinol to formaldehyde is 1:2, the mol ratio of resorcinol to thiourea, melamine, boric acid and cetyltrimethylammonium bromide is 1:0.4:0.3:0.15:0.008, resorcinol to water mass ratio of 1:20, a step of;
s2, filtering the mixed solution, and then placing the obtained filter cake in an oven, and drying at a high temperature of 110 ℃ for 14 hours to obtain precursor powder;
s3, filling the precursor powder into a small porcelain boat, placing the small porcelain boat into a tube furnace, calcining for 2.5 hours at 950 ℃ under the atmosphere of high-purity nitrogen, and naturally cooling to obtain nitrogen-sulfur-boron co-doped carbon aerogel;
s4, mixing the nitrogen-sulfur-boron co-doped carbon aerogel with sublimed sulfur according to the mass ratio of 1:2.2, placing the mixture in a mortar, uniformly mixing and grinding, and sintering the mixture for 12 hours at 180 ℃ in an air atmosphere to obtain the nitrogen-sulfur-boron co-doped carbon aerogel-based sulfur composite material.
The specific procedure of example 1 was followed using the nitrogen-sulfur-boron co-doped carbon aerogel-based sulfur composite material prepared as described above as the positive electrode material to prepare a lithium ion battery.
Through testing, the battery prepared from the material has the specific capacity of 1357mAh/g after first discharge at the rate of 0.2C, and the specific capacity of 1176mAh/g after 100 times of circulation.
Example 5
The preparation method of the nitrogen-sulfur-boron co-doped carbon aerogel-based sulfur composite material comprises the following steps:
s1, adding resorcinol, formaldehyde, dodecyl mercaptan, melamine, boric acid and sodium dodecyl benzene sulfonate into deionized water, heating and stirring for 24 hours at 90 ℃ to obtain a mixed solution, wherein the mol ratio of resorcinol to formaldehyde is 1:2.5, resorcinol to dodecyl mercaptan, melamine, boric acid and sodium dodecyl benzene sulfonate in a molar ratio of 1:0.5:0.4:0.2:0.01, resorcinol to water mass ratio of 1:20, a step of;
s2, filtering the mixed solution, and then placing the obtained filter cake in an oven, and drying at a high temperature of 120 ℃ for 12 hours to obtain precursor powder;
s3, filling the precursor powder into a small porcelain boat, placing the small porcelain boat into a tube furnace, calcining for 3 hours at 1000 ℃ under the atmosphere of high-purity nitrogen, and naturally cooling to obtain nitrogen-sulfur-boron co-doped carbon aerogel;
s4, mixing the nitrogen-sulfur-boron co-doped carbon aerogel with sublimed sulfur according to the mass ratio of 1:2.5, placing the mixture in a mortar, uniformly mixing and grinding, and sintering the mixture for 12 hours at 180 ℃ in an air atmosphere to obtain the nitrogen-sulfur-boron co-doped carbon aerogel-based sulfur composite material.
The specific procedure of example 1 was followed using the nitrogen-sulfur-boron co-doped carbon aerogel-based sulfur composite material prepared as described above as the positive electrode material to prepare a lithium ion battery.
Through tests, the battery prepared from the prepared material has the initial discharge specific capacity of 1338mAh/g at the rate of 0.2C, and the specific capacity of 100 times of circulation is kept at 1142mAh/g.
Example 6
The preparation method of the nitrogen-sulfur-boron co-doped carbon aerogel-based sulfur composite material comprises the following steps:
s1, adding resorcinol, formaldehyde, thiourea, urea, boric acid and sodium dodecyl benzene sulfonate into deionized water, heating and stirring for 30 hours at 85 ℃ to obtain a mixed solution, wherein the mol ratio of resorcinol to formaldehyde is 1:1.5, resorcinol to thiourea, urea, boric acid and sodium dodecylbenzenesulfonate in a molar ratio of 1:0.5:0.1:0.1:0.006, resorcinol to water mass ratio of 1:20, a step of;
s2, filtering the mixed solution, and then placing the obtained filter cake in an oven, and drying at a high temperature of 90 ℃ for 24 hours to obtain precursor powder;
s3, filling the precursor powder into a small porcelain boat, placing the small porcelain boat into a tube furnace, calcining for 3 hours at 900 ℃ under the atmosphere of high-purity nitrogen, and naturally cooling to obtain nitrogen-sulfur-boron co-doped carbon aerogel;
s4, mixing the nitrogen-sulfur-boron co-doped carbon aerogel with sublimed sulfur according to the mass ratio of 1:2, placing the mixture in a mortar, uniformly mixing and grinding, and sintering the mixture at 170 ℃ for 12 hours in an air atmosphere to obtain the nitrogen-sulfur-boron co-doped carbon aerogel-based sulfur composite material.
The specific procedure of example 1 was followed using the nitrogen-sulfur-boron co-doped carbon aerogel-based sulfur composite material prepared as described above as the positive electrode material to prepare a lithium ion battery.
Through tests, the battery prepared from the prepared material has a specific capacity of 1305mAh/g after first discharge at a rate of 0.2C, and a specific capacity of 1083mAh/g after 100 cycles.
Comparative example
The preparation method of the carbon aerogel-based sulfur composite material comprises the following steps:
s1, adding resorcinol, formaldehyde and hexadecyl trimethyl ammonium bromide into deionized water, heating and stirring for 36 hours at 60 ℃ to obtain a mixed solution, wherein the mol ratio of resorcinol to formaldehyde is 1:2, the molar ratio of resorcinol to cetyltrimethylammonium bromide is 1:0.005, resorcinol to water mass ratio of 1:20, a step of;
s2, filtering the mixed solution, and then placing the obtained filter cake in an oven, and drying at a high temperature of 90 ℃ for 24 hours to obtain precursor powder;
s3, filling the precursor powder into a small porcelain boat, placing the small porcelain boat into a tube furnace, calcining for 3 hours at 800 ℃ under the atmosphere of high-purity nitrogen, and naturally cooling to obtain carbon aerogel;
s4, mixing the carbon aerogel with sublimed sulfur according to the mass ratio of 1:1.5, placing the mixture in a mortar, uniformly mixing and grinding, and sintering the mixture for 16 hours at 160 ℃ in an air atmosphere to obtain the carbon aerogel-based sulfur composite material.
The specific procedure of example 1 was followed using the carbon aerogel-based sulfur composite prepared as described above as the positive electrode material to prepare a lithium ion battery.
Through tests, the battery prepared from the prepared material has a first discharge specific capacity of 1037mAh/g at a rate of 0.2C, and a specific capacity of 716mAh/g after 100 times of circulation.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (5)
1. The preparation method of the nitrogen-sulfur-boron co-doped carbon aerogel-based sulfur composite material is characterized by comprising the following steps of:
s1, adding resorcinol, formaldehyde, a sulfur source, a nitrogen source, a boron source and a dispersing agent into water, heating and stirring to obtain a mixed solution, wherein the heating and stirring temperature is 60-90 ℃, and the heating and stirring time is 24-36 h;
s2, filtering the mixed solution, and then drying the obtained filter cake at a high temperature to obtain precursor powder, wherein the high-temperature drying temperature is 90-120 ℃, and the high-temperature drying time is 12-24 hours;
s3, calcining the precursor powder in a high-purity nitrogen atmosphere to obtain nitrogen-sulfur-boron co-doped carbon aerogel, wherein the calcining temperature is 800-1000 ℃ and the calcining time is 2-3 hours;
s4, uniformly mixing and grinding the nitrogen-sulfur-boron co-doped carbon aerogel and sublimed sulfur, and sintering under an air atmosphere to obtain a nitrogen-sulfur-boron co-doped carbon aerogel-based sulfur composite material with the pore diameter concentrated at 3-4 nm;
the mol ratio of resorcinol to formaldehyde is 1: (1.5-2.5); the mol ratio of the resorcinol to the sulfur source, the nitrogen source, the boron source and the dispersing agent is 1: (0.1 to 0.5): (0.1 to 0.4): (0.05-0.2): (0.005-0.01);
the sulfur source is thiourea, dodecyl mercaptan or a combination thereof; the nitrogen source is melamine, urea or a combination thereof; the boron source is boric acid, borax or a combination thereof; the dispersing agent is at least one of hexadecyl trimethyl ammonium bromide, sodium dodecyl benzene sulfonate and sodium dodecyl sulfate.
2. The method for preparing the nitrogen-sulfur-boron co-doped carbon aerogel-based sulfur composite material according to claim 1, wherein the mass ratio of the nitrogen-sulfur-boron co-doped carbon aerogel to sublimed sulfur is 1: (1.5-2.5).
3. The method for preparing the nitrogen-sulfur-boron co-doped carbon aerogel-based sulfur composite material according to claim 1, wherein in the step S4, the sintering temperature is 160-180 ℃ and the sintering time is 10-16 h.
4. A nitrogen-sulfur-boron co-doped carbon aerogel-based sulfur composite material, characterized in that it is prepared by the preparation method of any one of claims 1 to 3.
5. The use of the nitrogen-sulfur-boron co-doped carbon aerogel-based sulfur composite material according to claim 4 as a positive electrode material of a lithium-sulfur battery.
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