CN114094081B - Crosslinked nano carbon sheet loaded boron nitride nanocrystalline/sulfur composite material, preparation method thereof, lithium sulfur battery positive electrode and lithium sulfur battery - Google Patents

Crosslinked nano carbon sheet loaded boron nitride nanocrystalline/sulfur composite material, preparation method thereof, lithium sulfur battery positive electrode and lithium sulfur battery Download PDF

Info

Publication number
CN114094081B
CN114094081B CN202111385586.4A CN202111385586A CN114094081B CN 114094081 B CN114094081 B CN 114094081B CN 202111385586 A CN202111385586 A CN 202111385586A CN 114094081 B CN114094081 B CN 114094081B
Authority
CN
China
Prior art keywords
nano carbon
sulfur
boron nitride
cross
lithium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202111385586.4A
Other languages
Chinese (zh)
Other versions
CN114094081A (en
Inventor
谷翠萍
曹雅娴
陶春明
高绿绿
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Anhui Normal University
Original Assignee
Anhui Normal University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Anhui Normal University filed Critical Anhui Normal University
Priority to CN202111385586.4A priority Critical patent/CN114094081B/en
Publication of CN114094081A publication Critical patent/CN114094081A/en
Application granted granted Critical
Publication of CN114094081B publication Critical patent/CN114094081B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • H01M4/362—Composites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • H01M4/36—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
    • 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
    • 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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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

Abstract

The invention discloses a crosslinked nano carbon sheet loaded boron nitride nanocrystalline/sulfur composite material, a preparation method thereof, a lithium sulfur battery anode and a lithium sulfur battery, wherein trisodium citrate is used as a raw material to prepare crosslinked nano carbon sheet powder by high-temperature carbonization in inert atmosphere; dispersing the boron oxide and boric acid into water, heating and stirring until the boron oxide and boric acid are dried, and then performing high-temperature treatment in an inert atmosphere to prepare a cross-linked nano carbon sheet loaded boron oxide material; then carrying out high-temperature nitridation reaction on the mixture in ammonia gas to obtain cross-linked nano carbon sheet-loaded boron nitride nanocrystalline; then mixing the mixture with sulfur powder uniformly, sealing and heating the mixture in inert atmosphere to carry out sulfur fumigation, thus obtaining the cross-linked nano carbon sheet loaded boron nitride nanocrystalline/sulfur composite material; the composite material has high specific surface area and good conductivity, and the cross-linked structure can relieve the volume expansion and shrinkage of the electrode caused in the charge and discharge processes of the lithium-sulfur battery to a certain extent. In addition, B, N atoms in the boron nitride can form Li-N and B-S bonds with lithium polysulfide, further limiting the dissolution and shuttling of lithium polysulfide, thereby improving the performance of lithium sulfur batteries.

Description

Crosslinked nano carbon sheet loaded boron nitride nanocrystalline/sulfur composite material, preparation method thereof, lithium sulfur battery positive electrode and lithium sulfur battery
Technical Field
The invention belongs to the technical field of lithium sulfur batteries, and particularly relates to a cross-linked nano carbon sheet loaded boron nitride nanocrystalline/sulfur composite material and a preparation method thereof, a lithium sulfur battery positive electrode and a lithium sulfur battery.
Background
With the development of economy and the growth of population, excessive consumption of fossil fuel is caused, energy and environmental crisis are caused, and particularly large-scale production and use of automobiles consume a large amount of fossil fuel to generate a large amount of SO 2 、NO 2 And nitrogen and oxygen gas, which threaten human safety, thus developing a secondary battery with high energy density, safety and environmental protection is of great significance. The lithium ion battery has dominant in the field of power storage with the advantages of long service life, small volume and the like, and along with the wide application of mobile portable electronic equipment and the rapid development of new energy electric vehicles, people have higher pursues on battery performances such as energy density, power density and the like, and the limited energy density of the traditional lithium ion battery is difficult to meet the demands. Lithium sulfur batteries can produce up to 1675mAh g due to the inherent two electron reaction system -1 Is 2600Wh kg -1 Is a novel secondary battery with great prospect. Sulfur is stored in nature and has the advantages of low price, no toxicity and the like, and completely meets the requirements of battery materials, but a lithium-sulfur battery has a plurality of problems which limit the practical application thereof and is mainly expressed by sulfur and a reduction product Li thereof 2 S 2 /Li 2 S is poor in conductivity; the volume of the positive electrode material expands in the charging process; the problems of polysulfide dissolution shuttling, lithium negative electrode corrosion, dendrite and the like result in low sulfur utilization rate and poor cycling stability, and simultaneously lead to a great reduction in coulomb efficiency, shortened service life and reduced energy density of the lithium-sulfur battery.
Disclosure of Invention
In order to solve the technical problems, the invention provides a cross-linked nano carbon plate loaded boron nitride nanocrystalline/sulfur composite material and a preparation method thereof. The conductive network is formed by using the crosslinked nano carbon sheets, so that the insulating defect of elemental sulfur can be overcome, sulfur is uniformly distributed in a material gap by using the crosslinked structure of the composite material, so that the sulfur loading capacity is improved, more active sites are provided by rich gaps, the electrode volume expansion and contraction caused in the charging and discharging processes of the lithium-sulfur battery can be relieved to a certain extent by using the crosslinked structure and excellent mechanical strength. In addition, B, N atoms in the boron nitride can form Li-N and B-S bonds with the lithium polysulfide, so that the dissolution and shuttling of the lithium polysulfide are further limited, and the capacity, the rate capability and the cycle stability of the lithium-sulfur battery are improved.
The invention also provides a lithium sulfur battery anode and a lithium sulfur battery, wherein the crosslinked nano carbon sheet loaded boron nitride nanocrystalline/sulfur composite material is used as an active material to prepare the lithium sulfur battery anode so as to assemble the lithium sulfur battery, and the lithium sulfur battery has good cycle stability and multiplying power performance.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a cross-linked nano carbon sheet loaded boron nitride nanocrystalline/sulfur composite material, which comprises the following steps:
(1) Preparing a cross-linked nano carbon sheet material by taking trisodium citrate as a raw material and carbonizing at a high temperature in an inert atmosphere;
(2) Dispersing the crosslinked nano carbon sheet material and boric acid into water, heating, stirring and evaporating to dryness, and then performing high-temperature treatment in an inert atmosphere to prepare a crosslinked nano carbon sheet loaded boron oxide material;
(3) Carrying out high-temperature nitridation reaction on the cross-linked nano carbon plate-loaded boron oxide material in ammonia gas to obtain a cross-linked nano carbon plate-loaded boron nitride nanocrystal;
(4) Uniformly mixing the cross-linked nano carbon plate-loaded boron nitride nanocrystalline with sulfur powder, and sealing and heating in an inert atmosphere to perform sulfur fumigation to obtain the cross-linked nano carbon plate-loaded boron nitride nanocrystalline/sulfur composite material.
In the step (1), the high-temperature carbonization condition is 400-1000 ℃ and the heating reaction is carried out for 0.5-6 h; preferably 600-800 deg.C, for 2-5 h.
In the step (2), the dosage ratio of boric acid, the crosslinked nano carbon sheet and water is (0.2-1.5) g:0.1g: (5-10) mL.
In the step (2), the heating condition is 50-99 ℃, preferably 60-70 ℃; the high temperature treatment condition is 600-1000 ℃ for 0.5-8 h, preferably 700-900 ℃ for 1-3 h.
In the step (3), the high-temperature nitriding reaction is carried out at 700-1000 ℃ for 0.5-6 h, preferably at 750-900 ℃ for 1-2 h.
In the step (4), the heating and sulfur fumigation conditions are 150-180 ℃, and the temperature is kept for 12-50 hours, preferably 155-165 ℃ and 18-30 hours.
In the step (4), the mass ratio of the crosslinked nano carbon sheet loaded boron nitride nanocrystalline to the sulfur powder is 1:1 to 4.
In the steps (1), (2) and (4), the inert atmosphere is argon or nitrogen.
The invention also provides the cross-linked nano carbon plate loaded boron nitride nanocrystalline/sulfur composite material prepared by the preparation method, which is a composite material formed by loading boron nitride nanocrystalline and sulfur particles on the cross-linked nano carbon plate.
The invention also provides a lithium-sulfur battery anode which is prepared by taking the crosslinked nano carbon sheet loaded boron nitride nanocrystalline/sulfur composite material as an active substance.
The invention also provides a lithium sulfur battery, which is assembled by taking the positive electrode of the lithium sulfur battery as the positive electrode, has good stability and is 0.2A g -1 The specific capacity of the positive electrode is still up to 589mAh g after 100 times of circulation under the current density -1 The above.
According to the preparation method of the crosslinked nano carbon plate loaded boron nitride nanocrystalline/sulfur composite material, trisodium citrate is used as a raw material to synthesize the crosslinked nano carbon plate material, then the crosslinked nano carbon plate and boric acid are dispersed in water, heated, stirred and dried, subjected to high-temperature treatment to prepare the crosslinked nano carbon plate loaded boron oxide material, nitrided in ammonia gas to obtain the crosslinked nano carbon plate loaded boron nitride nanocrystalline composite material, the crosslinked nano carbon plate loaded boron nitride nanocrystalline and sulfur powder are mixed in an inert atmosphere by a sulfur fumigation method, and the sulfur powder is sublimated into sulfur vapor to be loaded in and on the crosslinked nano carbon plate loaded boron nitride by sealing and heating, so that the carbon loaded boron nitride/sulfur composite material can be used as an active material of a positive electrode of a lithium sulfur battery, and further the lithium sulfur battery with excellent cycle stability and rate performance is obtained.
The synthesis method of the cross-linked nano carbon plate loaded boron nitride nanocrystalline/sulfur composite material provided by the invention is simple and environment-friendly, the cross-linked nano carbon plate has a high specific surface area, a larger reaction area can be provided, polarization is reduced, aggregation of sulfur is hindered, more adsorbed sulfur can be accommodated, sulfur loading is improved, and enough active substances in the electrode material are ensured. The metal nitride not only has high metal conductivity, but also shows strong chemical affinity to polysulfide, can effectively inhibit shuttle effect, and meanwhile, the adsorption performance of the cross-linked nano carbon sheet boron nitride nanocrystalline material can inhibit dissolution of polysulfide, has high conductivity, has more space to accommodate more sulfur and can relieve volume expansion, has strong interaction with sulfur, so that sulfur is highly dispersed and exists in a sample in the form of monoclinic sulfur, the utilization rate of sulfur is improved, and the cycle stability and rate performance of a lithium sulfur battery are enhanced.
Drawings
FIG. 1 is an SEM image of crosslinked nanocarbon tablets prepared in example 1;
FIG. 2 is an SEM image of a cross-linked nanocarbon sheet-supported boron nitride nanocrystal prepared in example 1;
FIG. 3 is an XRD pattern of the crosslinked nanocarbon sheet-supported boron nitride nanocrystal prepared in example 1;
FIG. 4 is an SEM image of a cross-linked nanocarbon flake-supported boron nitride nanocrystal/sulfur composite prepared in example 1;
FIG. 5 is an XRD pattern of the cross-linked nanocarbon sheet-supported boron nitride nanocrystal/sulfur composite material prepared in example 1;
FIG. 6 is an SEM image of a cross-linked nanocarbon flake-supported boron nitride nanocrystal/sulfur composite prepared in example 2;
FIG. 7 is an SEM image of a cross-linked nanocarbon flake-supported boron nitride nanocrystal/sulfur composite prepared in example 3;
FIG. 8 is an SEM image of a cross-linked nanocarbon flake-supported boron nitride nanocrystal/sulfur composite prepared in example 4;
FIG. 9 is an SEM image of a cross-linked nanocarbon flake-supported boron nitride nanocrystal/sulfur composite prepared in example 5;
FIG. 10 is a mapping graph of the cross-linked nanocarbon sheet-supported boron nitride nanocrystal/sulfur composite material prepared in example 5, (a) is an SEM graph, and (b), (c), (d), and (e) are in order of B, C, N, S;
FIG. 11 is a TEM image of the cross-linked nanocarbon flake-supported boron nitride nanocrystal/sulfur composite prepared in example 5;
FIG. 12 is a HRTEM image of the cross-linked nanocarbon sheet-supported boron nitride nanocrystal composite prepared in example 5;
FIG. 13 is an XRD pattern of the cross-linked nanocarbon sheet-supported boron nitride nanocrystal/sulfur composite prepared in example 5;
FIG. 14 shows that the cross-linked nanocarbon tablet-supported boron nitride nanocrystal/sulfur composite material prepared in example 5 was used as a positive electrode material to prepare a lithium-sulfur battery at 0.2A g -1 Cycling 100 times of test results under the current density;
fig. 15 shows that the cross-linked nano carbon sheet loaded boron nitride nanocrystalline/sulfur composite material prepared in example 5 is a lithium sulfur battery made of a positive electrode material in a range of 0.5. 0.5A g -1 The test results were cycled 300 times at current density.
Detailed Description
The present invention will be described in detail with reference to examples.
Example 1
The preparation method of the crosslinked nano carbon sheet loaded boron nitride nanocrystalline/sulfur composite material comprises the following steps:
(1) 5g, placing trisodium citrate in a high-temperature tube furnace, carbonizing at 400 ℃ in a nitrogen atmosphere for 6 hours, cooling, washing and drying the product to obtain a cross-linked nano carbon sheet material, wherein an SEM (scanning electron microscope) diagram is shown in figure 1, and the appearance of the cross-linked nano carbon sheet material is cross-linked nano sheet;
(2) Dispersing 0.1g of cross-linked nano carbon sheet material and 0.2g of boric acid in 5mL of water for 10 minutes in an ultrasonic manner, stirring at 50 ℃ in a water bath kettle, evaporating the solution to dryness, heating and reacting the mixture at 600 ℃ for 8 hours under nitrogen atmosphere to obtain cross-linked nano carbon sheet-loaded boron oxide black powder, and nitriding the cross-linked nano carbon sheet-loaded boron oxide black powder in ammonia gas at 700 ℃ for 6 hours to obtain cross-linked nano carbon sheet-loaded boron nitride black powder, wherein an SEM image is shown in FIG. 2, an XRD result is shown in FIG. 3, and the fact that boron nitride nanocrystals are uniformly loaded on the cross-linked nano carbon sheet can be seen from the image;
(3) Uniformly mixing 0.1g of cross-linked nano carbon plate-loaded boron nitride powder and 0.1g of sulfur powder, transferring into a polytetrafluoroethylene small bottle filled with argon, and fumigating sulfur at 150 ℃ for 50 hours under argon atmosphere to obtain the cross-linked nano carbon plate-loaded boron nitride nanocrystalline/sulfur composite material, wherein an SEM (scanning electron microscope) graph is shown in figure 4, an XRD (X-ray diffraction) result is shown in figure 5, and the fact that boron nitride nanocrystalline and sulfur are uniformly loaded on the cross-linked nano carbon plate can be seen from figure 4.
Example 2
The preparation method of the crosslinked nano carbon sheet loaded boron nitride nanocrystalline/sulfur composite material comprises the following steps:
(1) 15g of trisodium citrate is placed in a high-temperature tube furnace, carbonization reaction is carried out for 6 hours at 550 ℃ in a nitrogen atmosphere, and after cooling, the product is washed and dried, thus obtaining a crosslinked nano carbon sheet material;
(2) Dispersing 0.1g of cross-linked nano carbon sheet material and 0.5g of boric acid in 6mL of water for 10 minutes in an ultrasonic manner, stirring at 60 ℃ in a water bath kettle, evaporating the solution to dryness, heating and reacting the mixture at 750 ℃ for 6 hours under nitrogen atmosphere to obtain cross-linked nano carbon sheet-loaded boron oxide black powder, and nitriding the cross-linked nano carbon sheet-loaded boron oxide black powder in ammonia at 760 ℃ for 5 hours to obtain cross-linked nano carbon sheet-loaded boron nitride black powder;
(3) Uniformly mixing 0.1g of cross-linked nano carbon plate-loaded boron nitride powder and 0.2g of sulfur powder, transferring into a polytetrafluoroethylene small bottle filled with argon, and fumigating for 35h at 155 ℃ under the argon atmosphere to obtain a cross-linked nano carbon plate-loaded boron nitride nanocrystalline/sulfur composite material, wherein an SEM (scanning electron microscope) graph of the cross-linked nano carbon plate-loaded boron nitride nanocrystalline/sulfur composite material is shown in FIG. 6;
example 3
The preparation method of the crosslinked nano carbon sheet loaded boron nitride nanocrystalline/sulfur composite material comprises the following steps:
(1) Placing 30g of trisodium citrate in a high-temperature tube furnace, performing carbonization reaction for 3 hours at 750 ℃ in a nitrogen atmosphere, cooling, and washing and drying the product to obtain a crosslinked nano carbon sheet material;
(2) Dispersing 0.1g of cross-linked nano carbon sheet material and 0.8g of boric acid in 7mL of water for 10 minutes by ultrasonic, stirring in a water bath at 70 ℃, evaporating the solution to dryness, and then heating and reacting the mixture at 800 ℃ for 3 hours under nitrogen atmosphere to obtain cross-linked nano carbon sheet-loaded boron oxide black powder; then carrying out nitridation reaction for 3 hours at the high temperature of 720 ℃ in ammonia gas to obtain the crosslinked nano carbon sheet loaded boron nitride black powder;
(3) Uniformly mixing 0.1g of cross-linked nano carbon plate-loaded boron nitride black powder with 0.3g of sulfur powder, transferring into a polytetrafluoroethylene small bottle filled with argon, and fumigating and vulcanizing at 160 ℃ for 30 hours under an argon atmosphere to obtain a cross-linked nano carbon plate-loaded boron nitride/sulfur composite material, wherein an SEM (scanning electron microscope) graph of the cross-linked nano carbon plate-loaded boron nitride/sulfur composite material is shown in figure 7.
Example 4
The preparation method of the crosslinked nano carbon sheet loaded boron nitride nanocrystalline/sulfur composite material comprises the following steps:
(1) Placing 50g of trisodium citrate in a high-temperature tube furnace, performing carbonization reaction for 1.5 hours at 900 ℃ in a nitrogen atmosphere, cooling, and washing and drying the product to obtain a crosslinked nano carbon sheet material;
(2) Dispersing 0.1g of cross-linked nano carbon sheet material and 1.5g of boric acid in 9mL of water for 10 minutes in an ultrasonic manner, stirring at 80 ℃ in a water bath kettle, evaporating the solution to dryness, heating the mixture at 850 ℃ in a nitrogen atmosphere for reaction for 1 hour to obtain cross-linked nano carbon sheet-loaded boron oxide black powder, and carrying out high-temperature nitridation reaction for 1 hour at 850 ℃ in ammonia to obtain cross-linked nano carbon sheet-loaded boron nitride black powder;
(3) Uniformly mixing 0.1g of cross-linked nano carbon plate-loaded boron nitride black powder with 0.4g of sulfur powder, transferring into a polytetrafluoroethylene small bottle filled with argon, and fumigating and vulcanizing at 170 ℃ for 15 hours under an argon atmosphere to obtain a cross-linked nano carbon plate-loaded boron nitride nanocrystalline/sulfur composite material, wherein an SEM (scanning electron microscope) graph is shown in figure 8.
Example 5
The preparation method of the crosslinked nano carbon sheet loaded boron nitride nanocrystalline/sulfur composite material comprises the following steps:
(1) Placing 60g of trisodium citrate in a high-temperature tube furnace, performing carbonization reaction for 0.5 hour at 1000 ℃ in a nitrogen atmosphere, cooling, and washing and drying the product to obtain a crosslinked nano carbon sheet material;
(2) Dispersing 0.1g of cross-linked nano carbon sheet material and 1.1g of boric acid in 10mL of water for 10 minutes, stirring in a water bath at 99 ℃, evaporating the solution to dryness, heating the mixture at 1000 ℃ in a nitrogen atmosphere for reaction for 0.5h to obtain cross-linked nano carbon sheet-loaded boron oxide black powder, and carrying out high-temperature nitridation reaction for 0.5h at 1000 ℃ in ammonia to obtain cross-linked nano carbon sheet-loaded boron nitride black powder;
(3) Uniformly mixing 0.1g of cross-linked nano carbon plate-loaded boron nitride black powder with 0.32g of sulfur powder, transferring into a polytetrafluoroethylene small bottle filled with argon, and fumigating and vulcanizing for 12h at 180 ℃ under the argon atmosphere to obtain the cross-linked nano carbon plate-loaded boron nitride nanocrystalline/sulfur composite material, wherein an SEM (drawing and drawing) chart is shown in FIG. 9, a mapping chart is shown in FIG. 10, a TEM chart is shown in FIG. 11, an HRTEM chart is shown in FIG. 12, and XRD results are shown in FIG. 13.
Application example 1
Application of cross-linked nano carbon sheet loaded boron nitride nanocrystalline/sulfur composite material in lithium sulfur battery
The final product of the cross-linked nanocarbon plate-supported boron nitride nanocrystalline/sulfur composite material obtained in example 5 was used as a positive electrode active material of a lithium-sulfur battery, mixed with acetylene black and polyvinylidene fluoride (PVDF) in a ratio of 7:2:1, prepared into a uniform slurry with N-methylpyrrolidone (NMP) as a solvent, coated on an aluminum foil, and the prepared coating was transferred to an oven and dried at 60 ℃ for 6 hours. Then, transferring the sample into a vacuum drying oven, vacuum drying at 60 ℃ for 12 hours, rolling by a tablet press, and cutting into pieces; the lithium sheet is used as a counter electrode, the electrolyte is 1M mixed organic solvent containing lithium bis (trifluoromethanesulfonyl) imide (LITFSI), and the mixed organic solvent is used as a body1, 3-Dioxolane (DOL) and dimethyl ether (DME) mixed solvent with the product ratio of 1:1, and adding LiNO with the mass fraction of 2 percent 3 As an electrolyte additive, a lithium sulfur battery was assembled under an argon atmosphere with a polypropylene film (Celgard 240) as a battery separator.
The battery tester is used for testing the charge and discharge performance, and the obtained lithium-sulfur battery positive electrode material is prepared from 0.2Ag -1 The results of the cycle stability test at current density are shown in FIG. 14 at 0.5Ag -1 The results of the cycle stability test at current density are shown in fig. 15. From the graph, the lithium-sulfur battery has good cycle stability and is 0.2Ag -1 The specific capacity of the positive electrode after 100 times of circulation under the current density reaches 589mAh g -1 At 0.5. 0.5A g -1 The specific capacity of the positive electrode is still as high as 441mAh g after 300 times of circulation under the current density -1 。
The foregoing detailed description of a cross-linked nanocarbon supported boron nitride nanocrystal/sulfur composite material, a method for preparing the same, and a positive electrode of a lithium-sulfur battery and a lithium-sulfur battery, with reference to examples, is illustrative and not restrictive, and several examples can be listed according to the defined scope, so that variations and modifications without departing from the general inventive concept shall fall within the scope of protection of the present invention.

Claims (7)

1. The preparation method of the crosslinked carbon nano-sheet loaded boron nitride nanocrystalline/sulfur composite material is characterized by comprising the following steps:
(1) Preparing a cross-linked nano carbon sheet material by taking trisodium citrate as a raw material and carbonizing at a high temperature in an inert atmosphere;
(2) Dispersing the crosslinked nano carbon sheet material and boric acid into water, heating, stirring and evaporating to dryness, and then performing high-temperature treatment in an inert atmosphere to prepare a crosslinked nano carbon sheet loaded boron oxide material;
(3) Carrying out high-temperature nitridation reaction on the cross-linked nano carbon plate-loaded boron oxide material in ammonia gas to obtain a cross-linked nano carbon plate-loaded boron nitride nanocrystal;
(4) Uniformly mixing the cross-linked nano carbon plate-loaded boron nitride nanocrystalline with sulfur powder, and sealing and heating in an inert atmosphere to perform sulfur fumigation to obtain a cross-linked nano carbon plate-loaded boron nitride nanocrystalline/sulfur composite material;
in the step (2), the dosage ratio of the boric acid, the crosslinked nano carbon sheet and the water is (0.2-1.5) g:0.1g: (5-10) mL;
in the step (2), the heating condition is 50-99 ℃; the high-temperature treatment condition is 600-1000 ℃ for 0.5-8 hours;
in the step (3), the high-temperature nitriding reaction condition is 700-1000 ℃ for 0.5-6 h.
2. The method according to claim 1, wherein in the step (1), the high-temperature carbonization is performed at 400-1000 ℃ for 0.5-6 hours.
3. The method according to claim 1, wherein in the step (4), the heating is performed at 150 to 180 ℃ for 12 to 50 hours.
4. The method according to claim 1 or 3, wherein in the step (4), the mass ratio of the crosslinked nanocarbon sheet-supported boron nitride nanocrystals to the sulfur powder is 1: 1-4.
5. A crosslinked nanocarbon sheet-supported boron nitride nanocrystal/sulfur composite material prepared by the preparation method according to any one of claims 1 to 4.
6. The positive electrode of the lithium-sulfur battery is characterized in that the positive electrode is prepared by taking the cross-linked nano carbon sheet loaded boron nitride nanocrystalline/sulfur composite material as an active substance.
7. A lithium-sulfur battery, wherein the positive electrode of the lithium-sulfur battery of claim 6 is used as a positive electrode.
CN202111385586.4A 2021-11-22 2021-11-22 Crosslinked nano carbon sheet loaded boron nitride nanocrystalline/sulfur composite material, preparation method thereof, lithium sulfur battery positive electrode and lithium sulfur battery Active CN114094081B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111385586.4A CN114094081B (en) 2021-11-22 2021-11-22 Crosslinked nano carbon sheet loaded boron nitride nanocrystalline/sulfur composite material, preparation method thereof, lithium sulfur battery positive electrode and lithium sulfur battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111385586.4A CN114094081B (en) 2021-11-22 2021-11-22 Crosslinked nano carbon sheet loaded boron nitride nanocrystalline/sulfur composite material, preparation method thereof, lithium sulfur battery positive electrode and lithium sulfur battery

Publications (2)

Publication Number Publication Date
CN114094081A CN114094081A (en) 2022-02-25
CN114094081B true CN114094081B (en) 2024-04-09

Family

ID=80302661

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111385586.4A Active CN114094081B (en) 2021-11-22 2021-11-22 Crosslinked nano carbon sheet loaded boron nitride nanocrystalline/sulfur composite material, preparation method thereof, lithium sulfur battery positive electrode and lithium sulfur battery

Country Status (1)

Country Link
CN (1) CN114094081B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114735672B (en) * 2022-04-24 2023-08-25 深圳市科信通信技术股份有限公司 Boron-nitrogen co-doped hard carbon material and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110247043A (en) * 2019-07-11 2019-09-17 安徽师范大学 A kind of porous carbon/sulphur composite material, preparation method and applications
CN110336034A (en) * 2019-07-11 2019-10-15 安徽师范大学 A kind of N doping lithium sulfur battery anode material, preparation method and applications
CN112002889A (en) * 2020-09-09 2020-11-27 肇庆市华师大光电产业研究院 Lithium-sulfur battery positive electrode material and preparation method thereof
CN112289966A (en) * 2020-10-28 2021-01-29 中国科学院青海盐湖研究所 Lithium-sulfur battery positive electrode material, and preparation method and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110247043A (en) * 2019-07-11 2019-09-17 安徽师范大学 A kind of porous carbon/sulphur composite material, preparation method and applications
CN110336034A (en) * 2019-07-11 2019-10-15 安徽师范大学 A kind of N doping lithium sulfur battery anode material, preparation method and applications
CN112002889A (en) * 2020-09-09 2020-11-27 肇庆市华师大光电产业研究院 Lithium-sulfur battery positive electrode material and preparation method thereof
CN112289966A (en) * 2020-10-28 2021-01-29 中国科学院青海盐湖研究所 Lithium-sulfur battery positive electrode material, and preparation method and application thereof

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
A conductive sulfur-hosting material involving ultrafine vanadium nitride nanoparticles for high-performance lithium-sulfur battery;Wencheng Xu等;《Electrochimica Acta》;第257卷;第1-8页 *
Enhanced Adsorptions to Polysulfides on Graphene-Supported BN Nanosheets with Excellent Li−S Battery Performance in a Wide Temperature Range;Ding Rong Deng等;《ACS Nano》;第12卷(第11期);第11120-11129页 *
上海科学技术情报研究所.《材料技术参考资料》.上海科学技术情报研究所,1978,第46页. *
郭瑞松等.《工程结构陶瓷》.天津大学出版社,2002,第199-200页. *

Also Published As

Publication number Publication date
CN114094081A (en) 2022-02-25

Similar Documents

Publication Publication Date Title
CN108565446B (en) Preparation method of porous nitrogen-doped carbon-coated graphite material
CN109461902B (en) Preparation method and application of iron diselenide/honeycomb carbon composite material
CN112928388B (en) Iron nitride and monoatomic iron co-modified nitrogen-doped graphite composite material and preparation method and application thereof
CN114050265B (en) Nickel selenide/manganese selenide nanocomposite loaded by crosslinked nano carbon sheet, preparation method of nickel selenide/manganese selenide nanocomposite and sodium ion battery negative electrode
CN106252630A (en) A kind of lithium-sulfur cell rich nitrogen hollow carbon balls/sulfur composite positive pole and preparation method thereof
CN116332152A (en) Bagasse hard carbon-based anode material with sodium ion battery core-shell structure and preparation method thereof
Zhang et al. Synthesis of spherical Al-doping LiMn 2 O 4 via a high-pressure spray-drying method as cathode materials for lithium-ion batteries
CN112186162A (en) High-load high-surface-capacity lithium-sulfur battery positive electrode and preparation method and application thereof
CN114314673B (en) Preparation method of flaky FeOCl nano material
CN114094081B (en) Crosslinked nano carbon sheet loaded boron nitride nanocrystalline/sulfur composite material, preparation method thereof, lithium sulfur battery positive electrode and lithium sulfur battery
CN114388814A (en) Preparation method of Co0.85Se nanoparticle @3D carbon network composite material and application of composite material in lithium-sulfur battery
CN112838215B (en) Three-dimensional porous carbon nanosheet-sulfur material and preparation method and application thereof
CN112864362B (en) Lithium iron phosphate composite material and preparation method and application thereof
Huang et al. Electrochemical properties of hollow spherical Na3V2 (PO4) 3/C cathode materials for sodium-ion batteries
CN114751395A (en) Nitrogen-doped porous carbon sphere/S composite material, preparation method thereof and application thereof in lithium-sulfur battery
CN114162814A (en) Modification method of graphite
CN110061198B (en) Silicon-carbon composite negative electrode material and preparation method and application thereof
CN114094075B (en) Iron selenide-iron oxide nanotube/graphene aerogel composite anode material and preparation method and application thereof
CN115050938B (en) Preparation method of heteroatom doped hollow carbon material and application of heteroatom doped hollow carbon material in lithium sulfur battery
CN114873632B (en) Double-trifluoro lithium methanesulfonimide/zeolite imidazole ester skeleton composite material and preparation method and application thereof
CN114275776B (en) Molybdenum sulfide composite material with manganese element loaded on graphene, preparation method and application thereof
CN117219777B (en) Lithium supplementing agent, preparation method thereof, positive electrode plate and secondary battery
CN114551872B (en) Negative electrode material, preparation method thereof, battery negative electrode and battery
CN113517443B (en) Preparation method of polyacrylonitrile/iron disulfide composite positive electrode material for lithium secondary battery
Chen et al. Elevating the comprehensive performance of carbon-based hybrid electrode materials by incorporating nickel silicate for lithium-ion capacitors

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant