CN111211273A - Lithium-sulfur battery with iron nitride nanoparticles growing in situ on reduced graphene oxide as modified diaphragm material and preparation method thereof - Google Patents

Lithium-sulfur battery with iron nitride nanoparticles growing in situ on reduced graphene oxide as modified diaphragm material and preparation method thereof Download PDF

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CN111211273A
CN111211273A CN202010030175.2A CN202010030175A CN111211273A CN 111211273 A CN111211273 A CN 111211273A CN 202010030175 A CN202010030175 A CN 202010030175A CN 111211273 A CN111211273 A CN 111211273A
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lithium
diaphragm
sulfur battery
situ
rgo
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张冬
岳惠娟
王欣
马晨辉
陈岗
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Jilin University
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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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • 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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

A lithium-sulfur battery with iron nitride nanoparticles growing in situ on reduced graphene oxide as a modified diaphragm material and a preparation method thereof belong to the technical field of lithium ion batteries. The invention firstly adopts a hydrothermal method to prepare Fe2Dissolving the N/N-rGO composite material and a binder polyvinylidene fluoride in N-methyl pyrrolidone, uniformly mixing, coating the mixture on one side surface of a commercial diaphragm, drying the commercial diaphragm for 10 to 15 hours at the temperature of 40 to 60 ℃ in vacuum, and pressing the commercial diaphragm into a wafer by using a punch to obtain the Fe-coated diaphragm2A diaphragm made of N/N-rGO composite material is assembled with the lithium-sulfur battery to obtain the iron nitride nano-particles which grow in situ in the reduction oxidationAnd the graphene is used as a modified diaphragm material of the lithium-sulfur battery. The invention firstly converts Fe2The N/N-rGO composite material is used for modifying a diaphragm of a lithium-sulfur battery, so that the lithium-sulfur battery has excellent electrochemical performance, and the prepared lithium-sulfur battery has high specific capacity, stable cycle performance and good rate capability.

Description

Lithium-sulfur battery with iron nitride nanoparticles growing in situ on reduced graphene oxide as modified diaphragm material and preparation method thereof
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a lithium-sulfur battery taking iron nitride nanoparticles as a modified diaphragm material and growing in situ on reduced graphene oxide and a preparation method thereof.
Background
The development and utilization of environmental pollution caused by fossil energy and resource exhaustion caused by rapid consumption of fossil energy are problems to be solved urgently, and the search for novel energy has become a consensus of people. Lithium ion batteries are widely used in portable small-sized electrical appliances such as mobile phones and computers due to their advantages of high voltage, long charge-discharge life, small self-discharge, and the like. However, the lithium ion battery has high cost and is limited by an intercalation-deintercalation reaction mechanism, and the capacity and specific energy of the battery cannot be further improved. It is therefore necessary to construct a novel high energy density secondary battery system.
The theoretical energy density of the lithium-sulfur battery is as high as 2600Wh/kg, which is about 5 times that of the lithium-ion battery. And the crust of the sulfur has rich reserves, low cost and environmental protection. Therefore, lithium-sulfur batteries are considered as promising next-generation battery systems. However, during charging and discharging, polysulfide (Li) which is an intermediate product of lithium-sulfur batteries2SxAnd x is more than or equal to 4 and less than or equal to 8) is dissolved in the electrolyte and moves back and forth between the anode and the cathode to form a shuttle effect. At the same time, irreversible Li formation on the negative side2S deposition results in low utilization of active materials and poor cycle life of the battery. To overcome these problems, many measures have been taken, such as designing sulfur carriers, optimizing electrolytic liquids, and protecting lithium negative electrodes. In addition, the modification of the separator can also effectively inhibit polysulfide from diffusing to the negative electrode side, and improve the utilization rate of active substances.
The invention combines iron nitride nano-particles (Fe)2N) in-situ growth on reduced graphene oxide sheets (rGO) to prepare Fe2The N/N-rGO composite material is applied to the modification of a diaphragm of a lithium-sulfur battery for the first time, and excellent cycle and rate performance is obtained.
Disclosure of Invention
The invention aims to provide a lithium-sulfur battery taking iron nitride nanoparticles as a modified diaphragm material and growing in situ on reduced graphene oxide and a preparation method thereof, wherein the preparation method comprises the following steps:
1) preparation of Fe2N/N-rGO composite material
Dispersing 200-250 mg of graphene in 40-60 mL of deionized water, and marking as solution A; dissolving 180-220 mg of ferric nitrate nonahydrate and 100-140 mg of urea in 15-30 mL of deionized water, uniformly stirring, and dropwise adding into the solution A; then carrying out hydrothermal reaction on the obtained mixed solution at 180-220 ℃ for 10-15 hours, and washing and freeze-drying a product after cooling to room temperature; finally, heating to 700-800 ℃ at a heating rate of 1.5-3 ℃/min in an ammonia atmosphere, and carrying out heat treatment for 2-4 hours to obtain Fe2An N/N-rGO composite;
2)Fe2preparation of N/N-rGO diaphragm
Fe obtained in the step 1)2The N/N-rGO composite material and a binder polyvinylidene fluoride (PVDF) are mixed according to the mass ratio of 9-12: dissolving 1 in N-methyl pyrrolidone, uniformly mixing, coating on one side surface of a commercial diaphragm (Celgard 2320), drying at 40-60 ℃ in vacuum for 10-15 hours, and pressing into a wafer by using a punch to obtain the Fe-coated diaphragm2Diaphragms of N/N-rGO composites, Fe2The load capacity of N/N-rGO is 0.20-0.30 mg/cm2；
3) Containing Fe2Assembly of lithium-sulfur battery with N/N-rGO diaphragm
Elemental sulfur, a conductive additive (Super P) and a binder polyvinylidene fluoride (PVDF) are mixed according to a mass ratio of 7: 2: 1, dissolving the mixture in N-methyl pyrrolidone, uniformly grinding the mixture, coating the mixture on an aluminum foil, drying the aluminum foil for 10 to 15 hours at the temperature of between 40 and 60 ℃ in vacuum, pressing the dried aluminum foil into a wafer serving as a positive electrode by using a punching machine, and taking the wafer as the positive electrode for sulfur loading1.5 to 1.7mg/cm2(ii) a Lithium sheet as negative electrode, and Fe coated on the separator2One side of the N/N-rGO composite material faces the anode to assemble a half cell, so that the lithium-sulfur battery with the iron nitride nano-particles growing on the reduced graphene oxide in situ as a modified diaphragm material is obtained.
In the present invention, Fe is produced by hydrothermal method2The N/N-rGO composite material is applied to modifying a diaphragm of a lithium-sulfur battery for the first time, so that the lithium-sulfur battery has excellent electrochemical performance. Compared with the prior art, the invention has the following beneficial effects:
1) the preparation raw materials are low in price, low in cost and environment-friendly.
2) The preparation method has simple requirements on equipment and good reproducibility, and can be used for industrial large-scale production.
3) The product prepared by the invention has excellent conductivity, higher specific surface area and stable structure, and has great research and development values.
4) The lithium-sulfur battery prepared by the invention has high specific capacity, stable cycle performance and good rate capability.
Drawings
Fig. 1 is an X-ray diffraction (XRD) pattern of the materials prepared in example 1 and example 2. Wherein the vertical line is Fe2N Standard PDF card (No.89-3939), Curve 2 is the XRD spectrum of the N-rGO material prepared in example 2, and Curve 1 is Fe prepared in example 12XRD pattern of N/N-rGO composite material. Comparing to obtain the prepared Fe2The X-ray diffraction (XRD) pattern of the N/N-rGO composite material shows Fe2Diffraction peaks for both N and rGO species.
FIG. 2 shows Fe prepared in example 12The specific surface area of nitrogen absorption/desorption of the N/N-rGO composite material is shown in the figure, and the inset is the material pore size distribution. As can be seen, Fe2The specific surface area of the N/N-rGO composite material is 298.1m2(ii)/g, mesopores having a pore diameter of mainly 5.45 nm.
FIG. 3 is Fe prepared in example 12Scanning Electron Micrographs (SEM) of N/N-rGO composite at different magnifications. FIG. a shows a scanning electron microscope (SE) on a 2 μm scaleM) diagram. FIG. b is a (SEM) image on a scale of 1 μm, and an inset is an SEM image on a scale of 50 nm. The images (c-f) are scanning electron micrographs on a 2 μm scale and carbon, iron and nitrogen element distribution diagrams. FIG. g shows Fe2Cross-sectional SEM images of the N/N-rGO membrane on a 10 μm scale. From the scanning electron microscope picture, it can be seen that the Fe size is about 50nm2The N particles are uniformly distributed on the graphene nano-sheets and do not obviously agglomerate. Fe coated on separator2The N/N-rGO composite material has a thickness of about 10 μm.
FIG. 4 is a Fe-coated film prepared in example 12And a semi-cell front five-circle cyclic voltammogram (CV diagram) prepared by using a diaphragm Celgard 2320 of the N/N-rGO composite material as a diaphragm, using a sulfur sheet as a positive electrode and using a lithium sheet as a negative electrode. Two typical reduction peaks at 2.32V and 2.05V correspond to the initial conversion of elemental sulfur to mesophase long-chain polysulfides followed by insoluble Li formation2S/Li2S2. The oxidation peaks at subsequent 2.35V and 2.40V correspond to Li2S/Li2S2Returning to the sulfur. The sharp redox peak, small polarization voltage and good coincidence in the figure indicate that Fe is contained2The lithium sulfur battery with the N/N-rGO diaphragm has rapid reaction kinetics and stable electrochemical behavior.
FIG. 5 is a Fe-coated film prepared in example 12And the cycle performance diagram of the half-cell manufactured by using the diaphragm Celgard 2320 of the N/N-rGO composite material as the diaphragm, the sulfur sheet as the positive electrode and the lithium sheet as the negative electrode. As can be seen from the figure, after 3 cycles of activation at a current density of 0.2C (1C: 1675mAh/g), the first specific discharge capacity of the half-cell at the current density of 0.5C is 1100mAh/g, after 200 cycles, the specific discharge capacity can still reach 891mAh/g, the capacity retention rate is 81%, the average cycle attenuation per cycle is only 0.095%, and the coulomb efficiency is close to 100%. This is illustrated by Fe2The N/N-rGO diaphragm inhibits the shuttle effect, so that the battery has higher specific capacity and better cycling stability.
FIG. 6 is a Fe-coated film prepared in example 12And a long cycle performance diagram of a half cell manufactured by using a diaphragm Celgard 2320 of the N/N-rGO composite material as a diaphragm, a sulfur sheet as a positive electrode and a lithium sheet as a negative electrode. Can be seen from the figureIn the 1C high-current density charge-discharge test, the specific discharge capacity of the half-cell can still be kept at 734mAh/g after 300 cycles, which indicates that Fe passes through2The N/N-rGO diaphragm has physical obstruction and chemical adsorption effect on polysulfide, so that the battery has higher specific capacity and better cycling stability.
FIG. 7 is a Fe-coated film prepared in example 12And a specific capacity rate performance diagram of a half battery manufactured by using a diaphragm Celgard 2320 of the N/N-rGO composite material as a diaphragm, a sulfur sheet as a positive electrode and a lithium sheet as a negative electrode. As can be seen from the figure, the half-cell is stable in circulation under various current density tests, and the specific discharge capacity of the half-cell can still reach 755mAh/g and 640mAh/g respectively under high currents of 3C and 5C, which proves that the half-cell has excellent rate capability.
FIG. 8 is Fe prepared in example 12And the high-sulfur load specific capacity cycle performance diagram of the half-cell manufactured by taking the N/N-rGO diaphragm as the diaphragm, the sulfur sheet as the anode and the lithium sheet as the cathode. Wherein the sulfur loading of curve 1 is 3.08mg/cm2Under the current density of 1C, the specific capacity can still be maintained to 712mAh/g after 100 cycles. The sulfur loading of curve 2 was 5.04mg/cm2And under the current density of 1C, the battery obtains a high specific capacity of 513mAh/g after being cycled for 100 circles. This proves that Fe2The N/N-rGO diaphragm hinders polysulfide dissolution through physical hindrance and chemical adsorption catalysis synergistic effect, reaction kinetics is improved, and the battery still has excellent electrochemical performance even under high load.
FIG. 9 is a graph of the cycling performance of a half cell; curve 1 is Fe prepared in example 12A cycle performance diagram of a half-cell curve manufactured by taking an N/N-rGO diaphragm as a diaphragm, a sulfur sheet as a positive electrode and a lithium sheet as a negative electrode; curve 2 is a cycle performance plot for a half-cell made with the N-rGO separator prepared in example 2 as the separator, the sulfur sheet as the positive electrode, and the lithium sheet as the negative electrode. As can be seen, the cell corresponding to curve 2 is deficient in Fe2The chemical adsorption and catalysis of N on polysulfide can only intercept a small part of polysulfide through the physical barrier effect of N-rGO, so that the electrochemical reaction kinetics is low and the cycle stability is poor.
FIG. 10 is a graph of the cycling performance of a half cell; curve 1 is Fe prepared in example 12The cycle performance of half-cells made with N/N-rGO separator as separator, sulfur plate as positive electrode, and lithium plate as negative electrode, curve 2 is the cycle performance of half-cells made with the commercial separator prepared in example 3 as separator, sulfur plate as positive electrode, and lithium plate as negative electrode. It can be seen from the figure that curve 2 corresponds to a low utilization rate of the active material in the battery, a low specific capacity and a poor cycle performance due to a severe shuttle effect.
Detailed Description
Example 1:
dispersing 200mg of graphene in 50mL of deionized water, and carrying out ultrasonic treatment at room temperature for 5 hours to form a well-dispersed solution, wherein the well-dispersed solution is marked as solution A; next, 200mg of ferric nitrate nonahydrate and 120mg of urea were dissolved in 20mL of deionized water and stirred at room temperature for 10min, labeled as solution B. Subsequently, the solution B was added dropwise to the solution A, and after mixing well, the mixture was subjected to hydrothermal reaction at 180 ℃ for 10 hours. After the reaction solution was cooled to room temperature, the product was washed 3 times with deionized water and then lyophilized in a lyophilizer. Finally, the obtained product is transferred into a tubular furnace, is heated to 700 ℃ at the heating rate of 2 ℃/min under the atmosphere of ammonia gas, and is subjected to heat treatment for 3 hours to obtain the Fe2N/N-rGO composite materials.
10mg of Fe2Dissolving N/N-rGO composite material and a binder polyvinylidene fluoride (PVDF) in N-methylpyrrolidone according to the mass ratio of 10:1, uniformly mixing, coating the mixture on a commercial diaphragm (Celgard 2320), drying the mixture for 13 hours at 50 ℃ in vacuum, pressing the dried mixture into a wafer by using a punching machine, and forming Fe2N/N-rGO face load of about 0.25mg/cm2。
Elemental sulfur, a conductive additive (Super P) and a binding agent polyvinylidene fluoride are mixed according to a mass ratio of 7: 2: 1 is mixed in N-methyl pyrrolidone, evenly ground and coated on aluminum foil, dried for 13 hours at the temperature of 50 ℃ in vacuum and pressed into a wafer to be used as a positive electrode, and the sulfur loading capacity of the positive electrode is 1.5mg/cm2. Using pressed sulfur-containing wafer as positive electrode and coating Fe2The diaphragm Celgard 2320 of the N/N-rGO composite material is a diaphragm (coated with Fe)2One side of the N/N-rGO composite material faces to the positive electrode), the lithium sheet is used as a counter electrode, and the electrolyte is1mol/L of lithium bis (trichloromethane) sulfimide, 1, 2-dimethoxyethane and 1, 3-dioxolane in a volume ratio of 1: 1 in a glove box filled with argon gas to obtain the lithium-sulfur battery with the iron nitride nanoparticles growing in situ on the reduced graphene oxide as a modified diaphragm material.
The prepared battery CV curve and cycle performance curve are respectively shown in FIGS. 4 and 5, and the current density is 0.5C; as shown in fig. 6, the long cycle performance curve indicates that the charge/discharge current density is 1C (1C 1675mAh/g), and it can be seen that the cycle performance of the battery is good. The rate performance graph is shown in fig. 7, and the charge and discharge current densities are 0.2C, 0.5C, 1C, 2C, 3C, 5C, and 0.2C, which indicates that the battery has better rate performance. The high sulfur load cycle performance curve is shown in fig. 8, and the charge-discharge current density is 1C, indicating that the battery has better high load performance.
Example 2:
example 2 differs from example 1 in that no deionized water solution containing 200mg of ferric nitrate nonahydrate and 120mg of urea was added to synthesize the N-rGO material. The N-rGO diaphragm is prepared by dissolving 10mg of N-rGO and a binding agent polyvinylidene fluoride in N-methylpyrrolidone according to the mass ratio of 10:1, uniformly mixing, coating on a commercial diaphragm (Celgard 2320), drying at 50 ℃ in vacuum for 13h, and pressing into a wafer by using a punching machine, wherein the battery diaphragm is the N-rGO diaphragm. As shown in FIG. 9, curve 1 is Fe prepared in example 12The cycle performance of the half-cell made with the N/N-rGO separator as the separator, the sulfur sheet as the anode, and the lithium sheet as the cathode, and curve 2 is the cycle performance of the half-cell made with the N-rGO separator as the separator, the sulfur sheet as the anode, and the lithium sheet as the cathode, prepared in example 2. As can be seen from the figure, due to the lack of Fe2The chemical adsorption and catalysis of N on polysulfide can only intercept a small part of polysulfide through the physical barrier effect of N-rGO, so that the electrochemical reaction kinetics is low and the cycle stability is poor.
Example 3:
example 3 differs from example 1 in that a commercial separator (Celgard 2320) was used to package the cells in an argon filled glove box. As shown in FIG. 10, curve 1 is the same as that of example 1Prepared Fe2The cycle performance of half-cells made with N/N-rGO separator as separator, sulfur plate as positive electrode, and lithium plate as negative electrode, curve 2 is the cycle performance of half-cells made with the commercial separator prepared in example 3 as separator, sulfur plate as positive electrode, and lithium plate as negative electrode. As can be seen from the figure, due to the severe shuttle effect, the utilization rate of the active material in the battery is low, the specific capacity is low, and the cycle performance is poor.

Claims (7)

1. A preparation method of a lithium-sulfur battery with iron nitride nanoparticles growing in situ on reduced graphene oxide as a modified diaphragm material comprises the following steps:
1) preparation of Fe2N/N-rGO composite material
Dispersing 200-250 mg of graphene in 40-60 mL of deionized water, and marking as solution A; dissolving 180-220 mg of ferric nitrate nonahydrate and 100-140 mg of urea in 15-30 mL of deionized water, uniformly stirring, and dropwise adding into the solution A; then carrying out hydrothermal reaction on the obtained mixed solution, cooling to room temperature, washing and freeze-drying a product; finally, heat treatment is carried out for 2-4 hours at 700-800 ℃ in ammonia atmosphere to obtain Fe2An N/N-rGO composite;
2)Fe2preparation of N/N-rGO diaphragm
Fe obtained in the step 1)2The N/N-rGO composite material and a binder polyvinylidene fluoride are mixed according to a mass ratio of 9-12: dissolving 1 in N-methylpyrrolidone, uniformly mixing, coating on one side surface of a diaphragm Celgard 2320, vacuum drying, and pressing into a wafer by using a punching machine to obtain Fe2N/N-rGO membranes, Fe on membranes2The load capacity of N/N-rGO is 0.20-0.30 mg/cm2；
3) Containing Fe2Assembly of lithium-sulfur battery with N/N-rGO diaphragm
Mixing elemental sulfur, a conductive additive and a binder, namely polyvinylidene fluoride, dissolving the mixture in N-methyl pyrrolidone, uniformly grinding the mixture, coating the mixture on an aluminum foil, drying the aluminum foil in vacuum, pressing the dried aluminum foil into a wafer by using a punching machine to be used as a positive electrode, wherein the sulfur loading capacity of the positive electrode is 1.5-1.7 mg/cm2(ii) a A lithium sheet is used as a negative electrode, and then a diaphragm Celgard 2320 is coated with Fe2One side of N/N-rGO composite materialAnd assembling the half cell facing the positive electrode to obtain the lithium-sulfur cell with the iron nitride nanoparticles growing in situ on the reduced graphene oxide as a modified diaphragm material.
2. The method of claim 1, wherein the iron nitride nanoparticles are grown in situ on reduced graphene oxide to form a modified separator material for a lithium-sulfur battery, the method comprising: the step 1) is hydrothermal reaction for 10-15 hours at 180-220 ℃.
3. The method of claim 1, wherein the iron nitride nanoparticles are grown in situ on reduced graphene oxide to form a modified separator material for a lithium-sulfur battery, the method comprising: after freeze-drying, the temperature is raised to 700-800 ℃ at a temperature rise speed of 1.5-3 ℃/min.
4. The method of claim 1, wherein the iron nitride nanoparticles are grown in situ on reduced graphene oxide to form a modified separator material for a lithium-sulfur battery, the method comprising: the vacuum drying temperature of the step 2) is 40-60 ℃, and the drying time is 10-15 hours.
5. The method of claim 1, wherein the iron nitride nanoparticles are grown in situ on reduced graphene oxide to form a modified separator material for a lithium-sulfur battery, the method comprising: in the step 3), the mass ratio of the elemental sulfur to the conductive additive to the binder polyvinylidene fluoride is 7: 2: 1.
6. the method of claim 1, wherein the iron nitride nanoparticles are grown in situ on reduced graphene oxide to form a modified separator material for a lithium-sulfur battery, the method comprising: the vacuum drying temperature of the step 3) is 40-60 ℃, and the drying time is 10-15 hours.
7. A lithium sulfur battery with iron nitride nanoparticles growing in situ on reduced graphene oxide as a modified diaphragm material is characterized in that: is prepared by the method of any one of claims 1 to 6.
CN202010030175.2A 2020-01-13 2020-01-13 Lithium-sulfur battery with iron nitride nanoparticles growing in situ on reduced graphene oxide as modified diaphragm material and preparation method thereof Pending CN111211273A (en)

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于鹏: "改性过渡金属基锂电材料的制备及其电极过程机制", 《工程科技Ⅱ辑》 *
邸会芳: "《锂硫电池隔膜修饰与锂硒电池正极设计研究》", 《工程科技Ⅱ辑》 *

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CN112201904A (en) * 2020-10-30 2021-01-08 天目湖先进储能技术研究院有限公司 Diaphragm interlayer material of lithium-sulfur battery and preparation method and application thereof
CN112928388A (en) * 2021-02-22 2021-06-08 中南大学 Iron nitride and monoatomic iron co-modified nitrogen-doped graphite composite material and preparation method and application thereof
CN112864526A (en) * 2021-03-30 2021-05-28 吉林大学 Preparation method of room-temperature sodium-sulfur battery diaphragm
CN112864527A (en) * 2021-04-02 2021-05-28 衢州德联环保科技有限公司 Preparation method of Mxene/PVDF lithium-sulfur battery diaphragm
CN114156592A (en) * 2021-11-26 2022-03-08 电子科技大学 Diaphragm functional material for improving performance of lithium metal battery, preparation and application
CN114156592B (en) * 2021-11-26 2023-01-10 电子科技大学 Diaphragm functional material for improving performance of lithium metal battery, preparation and application
CN114497893A (en) * 2022-01-19 2022-05-13 广东工业大学 Diaphragm based on high-nitrogen-doped carbon composite graphene material and preparation method and application thereof
CN114725614A (en) * 2022-04-24 2022-07-08 扬州大学 Diaphragm coating material of lithium-sulfur battery and preparation method thereof

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