CN113410444A - Lithium-sulfur battery positive electrode material and preparation method thereof - Google Patents

Lithium-sulfur battery positive electrode material and preparation method thereof Download PDF

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CN113410444A
CN113410444A CN202110675401.7A CN202110675401A CN113410444A CN 113410444 A CN113410444 A CN 113410444A CN 202110675401 A CN202110675401 A CN 202110675401A CN 113410444 A CN113410444 A CN 113410444A
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lithium
positive electrode
sulfur battery
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刘大勇
包鑫龙
刘万强
郑传涛
王清爽
陈鹏
赵建勋
刘恒
王新伟
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Jilin University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • 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
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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

A lithium-sulfur battery anode material and a preparation method thereof belong to the technical field of lithium-sulfur batteries; wherein the positive electrode material of the lithium-sulfur battery comprises CoS2‑NC@Co‑FeS2Composite materials with sulfur, CoS2‑NC@Co‑FeS2The composite material comprises CoS2、FeS2And a nitrogen-doped cubic carbon material; the rate capability and the cycle performance of the lithium-sulfur battery prepared by the lithium-sulfur battery cathode material are obviously improved, and the lithium-sulfur battery cathode material has the advantages of low production cost, simple and convenient operation and the like, and can realize industrial mass productionAnd (4) producing.

Description

Lithium-sulfur battery positive electrode material and preparation method thereof
Technical Field
The invention belongs to the technical field of lithium-sulfur batteries, and particularly relates to a lithium-sulfur battery positive electrode material and a preparation method thereof.
Background
With the continuous progress of science and technology and society, various electronic devices and power automobiles develop at a high speed, so that the requirement of people on an energy storage system is continuously improved, and meanwhile, the development of a safe and efficient energy storage system is more and more urgent due to the increasingly exhausted non-renewable energy sources and the increasingly severe environmental problems. The energy density of conventional secondary batteries is close to the theoretical limit, but the demand of the human society for high energy density secondary batteries is still not met. Since the commercialization of lithium ion batteries, the advantages of good stability, long cycle life, portability and the like are favored by people. However, the theoretical capacity of the conventional lithium ion battery cathode material is low and the cost is high, so that the further development of the conventional lithium ion battery cathode material is limited.
In recent years, the lithium-sulfur battery has the characteristics of high theoretical capacity (1675mAh/g) and energy density (2600Wh/kg), environmental friendliness, low price, abundant storage in the earth crust, no toxicity and the like, and is widely concerned by people. And the characteristics can provide good basic conditions for the development of the lithium-sulfur battery.
However, many challenges remain in using it as a positive electrode material for lithium-sulfur batteries, e.g., sulfur as an active material and Li as a discharge end product2S/Li2S2Poor electrical conductivity; the apparent volume change of the material in the cyclic process caused by the density difference of the material; the "shuttle effect" caused by the migration of polysulfide in the middle discharge product of the electrode between the positive electrode and the negative electrode.The lithium-sulfur battery has the problems of poor cycle life, low utilization rate of active material sulfur, low charging and discharging efficiency and the like due to the characteristics of the lithium-sulfur battery.
In response to these problems, some electrode materials having high performance and low cost are required to improve the performance of lithium sulfur batteries. Spatial confinement of polysulfides using metal compounds with polar surfaces as additive materials has been considered as a viable solution to the deficiencies of lithium sulfur batteries in rate capability and cycling capability, with the strong interaction between transition metal compounds and polysulfides causing significant anchoring phenomena and resulting in higher energy density and long-term cycling stability.
The cobalt disulfide can have strong interaction with polysulfide, and is favorable for stable circulation of the electrode. Iron disulfide has excellent electron/ion conductivity and moderate voltage smoothness, and also interacts with polysulfides.
Therefore, it has been reported that cobalt disulfide and iron disulfide are respectively combined with carbon materials to form a composite material to be applied to a positive electrode and applied to a lithium sulfur battery, however, research on the co-application of cobalt disulfide and iron disulfide nanoparticles to the positive electrode of the lithium sulfur battery is blank.
Disclosure of Invention
In view of the above-mentioned technical problems, an object of the present invention is to provide a positive electrode material for a lithium-sulfur battery and a method for preparing the same, wherein the positive electrode material is applied to the lithium-sulfur battery, so that the battery rate capability and cycle performance of the lithium-sulfur battery are both significantly improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention firstly provides a lithium-sulfur battery anode material, which comprises CoS2-NC@Co-FeS2Composite materials with elemental sulfur, said CoS2-NC@Co-FeS2The composite material comprises CoS2、FeS2And nitrogen-doped cubic carbon material, said CoS2-NC@Co-FeS2The size of the composite material is 400-500 nm.
Preferably, the preparation method of the positive electrode material for the lithium-sulfur battery comprises the following steps:
the method comprises the following steps: 2-methylimidazole and Co (NO)3)2·6H2Dispersing O in absolute methanol respectively, and then mixing the two solutions uniformly; standing for 24h, performing centrifugal separation to collect purple substances, washing the collected purple substances with anhydrous methanol, and vacuum drying to obtain CoS2-NC@Co-FeS2Precursor of composite material ZIF-67, which is polyhedral structure;
step two: dissolving the ZIF-67 obtained in the step one in absolute ethyl alcohol to obtain solution A, K3[Fe(CN)6]Dissolving the powder in deionized water to obtain a solution B, dropwise adding the solution B into the solution A, and magnetically stirring at room temperature for 2-3h to obtain a purple solution; centrifuging, washing and drying the purple solution to obtain purple powder which is named as ZIF-67@ Co-Fe PBA;
step three: and (3) mixing the ZIF-67@ Co-Fe PBA obtained in the step (II) with sulfur powder in a mass ratio of 1: 2, mixing the mixture in N2Calcining at 350 deg.C for 2-3 hr in atmosphere, and calcining at 500 deg.C for 2-3 hr to obtain black powder named as CoS2-NC@Co-FeS2A composite material;
step four: the CoS obtained in the third step2-NC@Co-FeS2And mixing the composite material and sulfur powder according to a certain proportion, and fully melting to obtain the lithium-sulfur battery positive electrode material.
Preferably, the ZIF-67 and K are3[Fe(CN)6]The mass ratio of (A) to (B) is 5: 1.
Preferably, the CoS2-NC@Co-FeS2The mass ratio of the composite material to the sulfur powder is 3: 7.
The lithium-sulfur battery positive electrode material is used as a positive electrode active material.
The invention also provides a preparation method of the lithium-sulfur battery positive electrode, which comprises the following steps:
and uniformly mixing the lithium-sulfur battery positive electrode material, the conductive agent and the binder in a mass ratio of 7:2:1, dissolving the mixture in N-methylpyrrolidone to form slurry, uniformly coating the slurry on a carbon-coated aluminum foil, and drying the slurry in a vacuum oven at 60 ℃ for 12 hours to obtain the lithium-sulfur battery positive electrode.
Preferably, the conductive agent is acetylene black.
Preferably, the binder is polyvinylidene fluoride.
The invention has the advantages of
The invention provides a lithium-sulfur battery anode material and a preparation method thereof, wherein the anode material comprises CoS2-NC@Co-FeS2Composite materials with sulfur, CoS2-NC@Co-FeS2The composite material comprises CoS2、FeS2And nitrogen-doped cubic carbon materials. Due to CoS2Can have strong interaction with polysulfide, and is beneficial to the stable circulation of the electrode. FeS2Has excellent electron/ion conductivity and moderate voltage stability, and also has interaction with polysulfide. The presence of carbon favors the adsorption of polysulfides. The presence of nitrogen may increase the conductivity of the carbon. Therefore, the battery rate performance and the cycle performance of the lithium-sulfur battery adopting the cathode material are obviously improved. The experimental results show that: at constant temperature of 25 ℃, in the voltage range of 1.7-2.8V, the charge and discharge test is carried out with the current density of 0.5C, and the discharge capacity is kept very good after 200 cycles. Meanwhile, under the current density of 0.2C, the first discharge specific capacity of the battery using the lithium-sulfur battery cathode material reaches 938.9 mAh/g. Meanwhile, the lithium-sulfur battery cathode material has the advantages of low production cost, simplicity and convenience in operation and the like, and can be industrially produced in a large scale.
Drawings
FIG. 1 is CoS prepared in example2-NC@Co-FeS2Scanning electron micrographs of the composite.
FIG. 2 is CoS prepared in example2-NC@Co-FeS2The element distribution diagram of C, Co, Fe, N and S in the composite material.
FIG. 3 is the S/CoS prepared in the examples2-NC@Co-FeS2Photograph of positive electrode sheet.
FIG. 4 is CoS prepared by example2-NC@Co-FeS2Composite, CoS prepared in comparative example2-NC composite material and labelXRD pattern of quasicard.
FIG. 5 is the S/CoS prepared in example2-NC@Co-FeS2Comparative example prepared S/CoS2Discharge specific capacity cycling plot at current density of 0.2C for NC and S prepared in pure sulfur example as lithium sulfur battery cathode material.
FIG. 6 is S/CoS prepared in example2-NC@Co-FeS2And as a positive electrode material of a lithium-sulfur battery, a discharge specific capacity cycle chart under the current density of 0.5C.
Detailed Description
Principle of the invention
The invention aims at the problem of improving the capacity and the cycle performance of the lithium-sulfur battery and utilizes CoS2、FeS2The composite material formed by the nitrogen-doped cubic carbon material mainly improves the capacity and the cycle performance of the lithium-sulfur battery from four aspects, and specifically comprises the following components:
firstly, the method comprises the following steps: CoS2Can have strong interaction with polysulfide, and is beneficial to the stable circulation of the electrode.
Secondly, the method comprises the following steps: FeS2Has excellent electron/ion conductivity and moderate voltage stability, and also has interaction with polysulfide.
Thirdly, the method comprises the following steps: the presence of carbon favors the adsorption of polysulfides.
Fourthly: the presence of nitrogen may increase the conductivity of the carbon.
The invention firstly provides a lithium-sulfur battery anode material, which comprises CoS2-NC@Co-FeS2Composite materials with sulfur, said CoS2-NC@Co-FeS2The composite material comprises CoS2、FeS2And nitrogen-doped cubic carbon material, said CoS2-NC@Co-FeS2The size of the composite material is 400-500 nm.
According to the invention, the preparation method of the lithium-sulfur battery positive electrode material comprises the following steps:
the method comprises the following steps: 2-methylimidazole and Co (NO)3)2·6H2O is respectively dispersed in absolute methanol, and then the two solutions are uniformly mixed. Standing for 24h, centrifuging and collecting purpleThe collected purple material was washed with anhydrous methanol and dried under vacuum to give CoS2-NC@Co-FeS2Precursor of composite material ZIF-67, it is polyhedral structure;
step two: dissolving the ZIF-67 obtained in the step one in absolute ethyl alcohol to obtain solution A, K3[Fe(CN)6]Dissolving the powder in deionized water to obtain solution B, adding the solution B into the solution A dropwise, and magnetically stirring at room temperature for 2-3h to obtain purple solution. Centrifuging, washing and drying to obtain purple powder which is named as ZIF-67@ Co-Fe PBA;
step three: and (3) mixing the ZIF-67@ Co-Fe PBA obtained in the step (II) with sulfur powder in a mass ratio of 1: 2 and mixing. Mixture in N2Calcining at 350 deg.C for 2-3 hr in atmosphere, and calcining at 500 deg.C for 2-3 hr to obtain black powder named as CoS2-NC@Co-FeS2A composite material;
step four: the CoS obtained in the third step2-NC@Co-FeS2And mixing the composite material and sulfur powder according to a certain proportion, and fully melting to obtain the lithium-sulfur battery positive electrode material.
The invention also provides a preparation method of the lithium-sulfur battery positive electrode, which comprises the following steps:
and uniformly mixing the lithium-sulfur battery positive electrode material, the conductive agent and the binder in a mass ratio of 7:2:1, dissolving the mixture in N-methylpyrrolidone to form slurry, uniformly coating the slurry on an aluminum foil, and drying the aluminum foil in a vacuum oven at 60 ℃ for 12 hours to obtain the lithium-sulfur battery positive electrode.
According to the present invention, the coating is preferably performed by uniformly coating the mixed slurry on the aluminum foil using a coater.
According to the invention, the lithium-sulfur battery positive electrode obtained by the method is applied to a lithium-sulfur battery, and the method comprises the following steps:
and assembling the positive plate, the commercial PP diaphragm and the metal lithium plate into a button cell in a glove box in sequence for testing electrochemical performance.
The results show that: at constant temperature of 25 ℃, in the voltage range of 1.7-2.8V, the charge and discharge test is carried out with the current density of 0.5C, and the discharge capacity is kept very good after 200 cycles. Meanwhile, under the multiplying power of 0.2C, the first discharge specific capacity of the battery using the composite material anode reaches 938.9 mAh/g.
The invention is described in further detail below with reference to specific examples, comparative examples and pure sulfur examples, in which the starting materials are commercially available.
Examples
EXAMPLES preparation of S/CoS2-NC@Co-FeS2Positive electrode material
(1) Synthesis of ZIF-67 polyhedra
The ZIF-67 polyhedron is synthesized by a precipitation method. 5.24g (64mmol) of 2-methylimidazole and 4.64g (16mmol) of Co (NO)3)2·6H2O was dispersed in 400mL of anhydrous methanol. The two solutions were then mixed to a homogeneous purple solution. After aging for 24h, the purple ZIF-67 precursor is collected by centrifugal separation and washed with pure methanol. Finally, drying in a vacuum oven overnight yielded about 2g of ZIF-67 precursor.
(2) Synthesis of ZIF-67@ Co-Fe PBA nanocrystals
ZIF-67@ Co-Fe PBA nanocrystals were synthesized by an etching method. Dissolving 400mg of ZIF-67 precursor in 200ml of absolute ethanol to obtain solution A and 80mg of K3[Fe(CN)6]The powder was dissolved in 20ml of deionized water as solution B, and then solution B was added dropwise to solution A, followed by magnetic stirring at room temperature for 2 hours to form a purple solution. The resulting precipitate (named as ZIF-67@ Co-Fe PBA nanocrystals) was collected by centrifugation, washed with ethanol, and dried in a vacuum oven overnight.
(3) Synthesis of CoS2-NC@Co-FeS2
The ZIF-67@ Co-Fe PBA nanocrystals were mixed with sulfur powder and placed in a quartz boat. The mass ratio of the ZIF-67@ Co-Fe PBA nanocrystals to the sulfur powder is 1: 2. then, the mixture is in N2At 350 ℃ for 2h and then at 500 ℃ for 2h, with a heating rate of 5 ℃/min. Obtaining CoS2-NC@Co-FeS2。
(4) Synthesis of S/CoS2-NC@Co-FeS2
The CoS obtained above is subjected to2-NC@Co-FeS2Mixing with sublimed sulfur powder at a mass ratio of 3:7, placing the mixture into a Teflon high-pressure reaction kettle, heating at 155 deg.C for 12h to inject sulfur into CoS2-NC@Co-FeS2In the composite material, the obtained product is S/CoS2-NC@Co-FeS2。
The S/CoS prepared in the above way2-NC@Co-FeS2The positive electrode material is applied to a lithium-sulfur battery and comprises the following steps:
mixing S/CoS2-NC@Co-FeS2The positive electrode material, acetylene black and a binder (PVDF) are prepared into slurry according to the mass ratio of 7:2:1, and then the slurry is coated on an aluminum foil, dried in vacuum and then cut into a positive electrode sheet with the diameter of 12 mm.
According to S/CoS2-NC@Co-FeS2The positive plate, the commercial PP diaphragm and the metal lithium plate are sequentially assembled in a glove box to form the button cell for testing the electrochemical performance.
The experimental results show that: at constant temperature of 25 ℃, in the voltage range of 1.7-2.8V, the charge and discharge test is carried out with the current density of 0.5C, and the discharge capacity is kept very good after 200 cycles. At the same time, CoS is used under 0.2C multiplying power2-NC@Co-FeS2The first discharge specific capacity of the battery of the composite material anode reaches 938.9 mAh/g. The results are shown in Table 1.
FIG. 1 is CoS prepared in example2-NC@Co-FeS2Scanning electron micrographs of the composite. It can be clearly seen that a large number of larger nanoparticles are grown on the CoS2-NC@Co-FeS2On the concave surface of the polyhedron. The nanoparticles can increase the specific surface area and expose more active sites, which can strongly interact with polysulfides, thereby improving the rate capability and cycle performance of the battery.
FIG. 2 is CoS prepared in example2-NC@Co-FeS2The element distribution diagram of C, Co, Fe, N and S in the composite material. It can be seen that the elements are uniformly distributed.
FIG. 3 is the S/CoS prepared in the examples2-NC@Co-FeS2Photograph of positive electrode sheet. The macroscopic appearance of the positive plate can be seen.
FIG. 4 is CoS prepared by example2-NC@Co-FeS2Composite, CoS prepared in comparative example2XRD patterns of NC composite and standard card. It can be seen that CoS2-NC@Co-FeS2The diffraction peak of polyhedron is obviously higher than CoS2Diffraction peaks of NC polyhedrons, due to cubic CoS2And FeS2The diffraction peaks of (A) are very close in the adjacent regions, and the superposition of these peaks results in a CoS2-NC@Co-FeS2Polyhedral high intensity peaks.
Comparative example
Comparative example preparation of S/CoS2-NC positive electrode material
(1) Synthesis of CoS2-NC
The preparation method is the same as the example, except that ZIF-67 powder is mixed with sulfur powder. Obtaining CoS after calcination2-NC。
(2) Synthesis of S/CoS2-NC
The preparation method is the same as the example except that CoS is used2-NC instead of CoS2-NC@Co-FeS2. S/CoS prepared by comparative example2The results of the tests with the application of the NC positive electrode to the lithium sulfur battery are shown in table 1.
Example of pure sulfur
Preparation of pure Sulfur cathode Material
The preparation method is the same as the example except that sulfur powder is used to replace CoS2-NC@Co-FeS2Preparing slurry with acetylene black and a binder, coating the slurry on an aluminum foil, drying the aluminum foil in vacuum, and shearing the aluminum foil into a positive plate with the diameter of 12 mm. The S positive electrode prepared in the pure sulfur example was applied to a lithium sulfur battery and tested, and the results are shown in table 1.
The positive electrodes for lithium-sulfur batteries, which were prepared in the above examples, comparative examples, and pure sulfur example, respectively, were constructed with a commercially available PP separator and a lithium sheet as the negative electrode to prepare a 2032 type discharge, and were subjected to a charge-discharge test at a current density of 0.2C in a voltage range of 1.7 to 2.8V, and the results were shown in table 1 after 200 cycles.
TABLE 1
Figure BDA0003120778850000061
FIG. 5 is the S/CoS prepared in example2-NC@Co-FeS2Comparative example prepared S/CoS2Discharge specific capacity cycling plot at current density of 0.2C for NC and S prepared in pure sulfur example as lithium sulfur battery cathode material. As can be seen from the figure, the S/CoS prepared in the examples2-NC@Co-FeS2The positive electrode has the best effect, and is better than the comparative example and the pure sulfur example.
FIG. 6 is S/CoS prepared in example2-NC@Co-FeS2And as a positive electrode material of a lithium-sulfur battery, a discharge specific capacity cycle chart under the current density of 0.5C. It can be seen from the figure that after 200 cycles, a good discharge capacity was still maintained.

Claims (9)

1. The positive electrode material of the lithium-sulfur battery is characterized by comprising CoS2-NC@Co-FeS2Composite materials with sulfur, said CoS2-NC@Co-FeS2The composite material comprises CoS2、FeS2And nitrogen-doped cubic carbon material, said CoS2-NC@Co-FeS2The size of the composite material is 400-500 nm.
2. The positive electrode material for a lithium-sulfur battery according to claim 1, which is prepared by a method comprising:
the method comprises the following steps: 2-methylimidazole and Co (NO)3)2·6H2Dispersing O in absolute methanol respectively, and then mixing the two solutions uniformly; standing for 24h, performing centrifugal separation to collect purple substances, washing the collected purple substances with anhydrous methanol, and vacuum drying to obtain CoS2-NC@Co-FeS2Precursor of composite material ZIF-67, which is polyhedral structure;
step two: dissolving the ZIF-67 obtained in the step one in absolute ethyl alcohol to obtain solution A, K3[Fe(CN)6]Dissolving the powder in deionized water to obtain a solution B, dropwise adding the solution B into the solution A, and magnetically stirring at room temperature for 2-3h to obtain a purple solution; the purple solution is centrifuged,Washing and drying to obtain purple powder which is named as ZIF-67@ Co-Fe PBA;
step three: and (3) mixing the ZIF-67@ Co-Fe PBA obtained in the step (II) with sulfur powder in a mass ratio of 1: 2, mixing the mixture in N2Calcining at 350 deg.C for 2-3 hr in atmosphere, and calcining at 500 deg.C for 2-3 hr to obtain black powder named as CoS2-NC@Co-FeS2A composite material;
step four: the CoS obtained in the third step2-NC@Co-FeS2And mixing the composite material and sulfur powder according to a certain proportion, and fully melting to obtain the lithium-sulfur battery positive electrode material.
3. The positive electrode material of claim 2, wherein the ZIF-67 and K in step two3[Fe(CN)6]The mass ratio of the powders was 5: 1.
4. The positive electrode material for lithium-sulfur battery according to claim 2, wherein the CoS of step four2-NC@Co-FeS2The mass ratio of the composite material to the sulfur powder is 3: 7.
5. A positive electrode for a lithium-sulfur battery, characterized in that the positive electrode material for a lithium-sulfur battery according to claim 1 is used as a positive electrode active material.
6. The positive electrode for a lithium-sulfur battery according to claim 5, which is prepared by a method comprising:
and uniformly mixing the lithium-sulfur battery positive electrode material, the conductive agent and the binder in a mass ratio of 7:2:1, dissolving the mixture in N-methylpyrrolidone to form slurry, uniformly coating the slurry on a carbon-coated aluminum foil, and drying the carbon-coated aluminum foil in a vacuum oven at 60 ℃ for 12 hours to obtain the lithium-sulfur battery positive electrode.
7. The positive electrode for a lithium sulfur battery according to claim 6, wherein the conductive agent is acetylene black.
8. The positive electrode of claim 6, wherein the binder is polyvinylidene fluoride.
9. A lithium-sulfur battery comprising the positive electrode for a lithium-sulfur battery according to claim 5.
CN202110675401.7A 2021-06-18 2021-06-18 Lithium-sulfur battery positive electrode material and preparation method thereof Pending CN113410444A (en)

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CN115050938A (en) * 2022-06-18 2022-09-13 福州大学 Preparation method of heteroatom-doped hollow carbon material and application of heteroatom-doped hollow carbon material in lithium-sulfur battery
CN115050938B (en) * 2022-06-18 2024-03-08 福州大学 Preparation method of heteroatom doped hollow carbon material and application of heteroatom doped hollow carbon material in lithium sulfur battery
CN115043970A (en) * 2022-06-20 2022-09-13 吉林大学 Cross-linked porous polymer lithium-sulfur battery positive electrode carrier material containing maleimide structure, preparation method and application thereof

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Application publication date: 20210917