CN110739429A - Preparation method of functional interlayer of lithium-sulfur battery - Google Patents

Preparation method of functional interlayer of lithium-sulfur battery Download PDF

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Publication number
CN110739429A
CN110739429A CN201911035469.8A CN201911035469A CN110739429A CN 110739429 A CN110739429 A CN 110739429A CN 201911035469 A CN201911035469 A CN 201911035469A CN 110739429 A CN110739429 A CN 110739429A
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cobalt acetate
lithium
mxene
sulfur battery
temperature
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钊妍
王加义
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Zhaoqing South China Normal University Optoelectronics Industry Research Institute
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Zhaoqing South China Normal University Optoelectronics Industry Research Institute
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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
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
    • 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 relates to a preparation method of functional interlayers of lithium-sulfur batteries, which comprises the steps of firstly preparing a cobalt acetate-Mxene composite film, and then growing layers of carbon nanotube arrays on the surface of the cobalt acetate-Mxene composite film by using a vapor deposition method to texture the carbon nanotube arrays into the functional interlayers of self-supporting lithium-sulfur batteries.

Description

Preparation method of functional interlayer of lithium-sulfur battery
Technical Field
The invention relates to a preparation method of functional interlayers for lithium-sulfur batteries, in particular to a method for preparing cobalt acetate-Mxene composite films and growing layers of carbon nanotube arrays on the surfaces of the cobalt acetate-Mxene composite films by a vapor deposition method to texture the carbon nanotube arrays into self-supporting functional interlayers for lithium-sulfur batteries, and belongs to the field of material chemistry.
Background
The lithium ion battery has the advantages of high specific energy, environmental friendliness, no pollution, abundant resources, low price and the like, and becomes an ideal choice for energy storage devices such as mobile electronic products, electric automobiles and the like, elemental sulfur is used as a positive electrode material of the lithium sulfur battery, the theoretical capacity of the elemental sulfur battery reaches 1675mAh/g, the theoretical energy density can reach 2600Wh/kg, and the elemental sulfur is considered as a secondary battery positive electrode material with the greatest development prospect, however, the elemental sulfur has poor conductivity and intermediate product conductivity in the charging and discharging process, and polysulfide has the shuttle effect and the like in the reaction process, so that the utilization rate of of the positive electrode material is directly at a lower level, and the practical application of the polysulfide is influenced.
Disclosure of Invention
The invention aims to provide preparation methods of functional interlayers for lithium-sulfur batteries aiming at the defect of obvious shuttle effect of the current lithium-sulfur batteries, and the technical scheme adopted by the invention for solving the technical problem is as follows:
A method for preparing functional separator of lithium-sulfur battery, comprising the following steps:
step , MXene material preparation:
and (3) immersing the ground MAX-phase ceramic powder into HF solution, heating to 50-90 ℃, magnetically stirring at the temperature of 12-24 hours, centrifuging to obtain a product, washing to be neutral by using deionized water, and drying in an oven at the temperature of 60-80 ℃ for 12-24 hours to obtain the MXene material.
Further , the MAX phase ceramic of step can be Ti3AlC2、Ti2AlC、Cr2 or more kinds of AlC can be used to obtain MXene material (Ti)3C2Tx(TxIs a functional group such as-OH, -F), Ti2CTx(Tx is-OH, -F, etc.) and Cr2CTx(TxFunctional groups of-OH, -F, etc.) or more.
, the mass fraction of the HF solution in the step is 30-50%.
Secondly, preparing a cobalt acetate-Mxene composite film:
and (3) placing the MXene material prepared in the step and cobalt acetate in deionized water, stirring for 3-6h, performing ultrasonic treatment for 1-2h to uniformly disperse the MXene material, performing suction filtration to form a film, and naturally drying at room temperature to obtain the cobalt acetate-MXene composite film.
, the mass ratio of MXene material to cobalt acetate in the second step is 1-5:10-30, and the mass volume ratio of cobalt acetate to deionized water is 1-3 g/L.
Step three, preparing a functional interlayer for the lithium-sulfur battery:
and (3) placing 0.05-0.5g of the cobalt acetate-MXene composite film prepared in the second step into a tubular furnace for high-temperature calcination, introducing mixed gas of acetylene and hydrogen after the temperature is constant, and naturally cooling in an argon atmosphere to obtain the functional interlayer for the lithium-sulfur battery.
, the temperature rise rate of the high temperature calcination in the tubular furnace in the third step is 0.5-1, the temperature/m in at C is 500-.
The invention has the following beneficial effects:
according to the technical scheme, MXene materials are introduced into the functional interlayer for the lithium-sulfur battery and serve as lithium polysulfide adsorption layers, and MXene serves as novel two-dimensional metal carbide materials, so that the metal carbide has a strong anchoring effect on lithium polysulfide while having high conductivity, the polysulfide can be effectively adsorbed, the shuttle effect of the polysulfide is inhibited, the utilization rate of active substances in the positive electrode material is improved, and the cycle stability of the lithium-sulfur battery is improved.
In the technical scheme of the invention, layers of carbon nanotube arrays are successfully loaded on the surface of the MXene layer by using a vapor deposition method, cobalt is used as a catalyst for the growth of the carbon nanotubes, each carbon nanotube monomers forming the carbon nanotube array are loaded with metal cobalt particles, the carbon nanotube array has an obvious physical adsorption effect on lithium polysulfide, and the metal cobalt particles carried in the carbon nanotubes have an obvious chemical adsorption effect on the lithium polysulfide, so that the two synergistic effects jointly inhibit the shuttle effect of polysulfide and improve the electrochemical performance of the lithium-sulfur battery.
The functional interlayer for the lithium-sulfur battery prepared in the technical scheme of the invention is a self-supporting structure which is obtained by elaborate design, so that the complex coating process of the traditional functional interlayer is avoided, the preparation process is simplified, and meanwhile, the short place that the effective components are crushed and fall off from the diaphragm in the battery circulation process after coating in the traditional method is also avoided.
Drawings
The invention is further illustrated in with reference to the following figures and examples:
fig. 1 is a scanning electron microscope image of the functional separator for a lithium sulfur battery prepared in example 1.
FIG. 2 is a graph of the rate performance of the functional separator prepared in example 1 when applied to a lithium sulfur battery.
Detailed Description
Example 1:
step , MXene material preparation:
grinding MAX phase ceramic powder Ti3AlC2Immersing in HF solution with mass fraction of 40%, heating to 60 deg.C, magnetically stirring at deg.C for 12 hr, centrifuging to obtain product, and removing ionsWashing with water to neutrality, drying in oven at 70 deg.C for 12 hr to obtain MXene material Ti3C2。
Secondly, preparing a cobalt acetate-Mxene composite film:
taking 20mg of MAX phase ceramic powder Ti prepared in the step 3AlC2，0.2gAnd (3) placing the cobalt acetate into 100mL of deionized water, stirring for 3h, performing ultrasonic treatment for 1h to uniformly disperse the cobalt acetate, performing suction filtration to form a film, and naturally drying the film at room temperature to obtain the cobalt acetate-MXene composite film.
Step three, preparing a functional interlayer for the lithium-sulfur battery:
and (3) placing 0.3g of the cobalt acetate-MXene composite film prepared in the second step into a tubular furnace, heating to 600 ℃ at a heating rate of 1 ℃/min under the argon atmosphere, introducing acetylene and hydrogen mixed gas simultaneously after the temperature is constant, wherein the hydrogen flow rate is 200mL/min and the acetylene flow rate is 20mL/min, continuously introducing for 20min, closing the hydrogen and the acetylene after the completion, and naturally cooling under the argon atmosphere to obtain the functional interlayer for the lithium-sulfur battery.
Example 2:
step , MXene material preparation:
grinding MAX phase ceramic Ti3AlC2Immersing the powder into HF solution with the mass fraction of 30%, heating to 50 ℃, magnetically stirring at the temperature of 12 hours, centrifuging to obtain a product, washing the product to be neutral by using deionized water, and drying in a drying oven at the temperature of 60 ℃ for 12 hours to obtain the MXene material Ti3C2。
Secondly, preparing a cobalt acetate-Mxene composite film:
10mg of MXene material prepared in the th step and 0.1g of cobalt acetate are placed in 100mL of deionized water, stirred for 3 hours, ultrasonically treated for 1 hour to uniformly disperse the MXene material, and then the MXene material is subjected to suction filtration to form a film and naturally dried at room temperature to prepare a cobalt acetate-MXene composite film, and in the third step, a functional interlayer for a lithium-sulfur battery is prepared:
and (3) placing 0.05g of the cobalt acetate-MXene composite film prepared in the second step into a tubular furnace, heating to 500 ℃ at a heating rate of 0.5 ℃/min under the argon atmosphere, introducing acetylene and hydrogen mixed gas simultaneously after the temperature is constant, wherein the hydrogen flow rate is 100mL/min and the acetylene flow rate is 10mL/min, continuously introducing for 10min, closing hydrogen and acetylene after the completion, and naturally cooling under the argon atmosphere to obtain the functional interlayer for the lithium-sulfur battery.
Example 3:
step , MXene material preparation:
grinding MAX phase ceramic Ti3AlC2Immersing the powder into HF solution with the mass fraction of 50%, heating to 90 ℃, magnetically stirring at the temperature of 90 ℃ for 24 hours, centrifuging to obtain a product, washing the product to be neutral by using deionized water, and drying in a drying oven at the temperature of 80 ℃ for 24 hours to obtain the MXene material Ti3C2。
Secondly, preparing a cobalt acetate-Mxene composite film:
50mg of the MAX phase ceramic Ti prepared in step 3AlC2Putting 0.3g of powder and cobalt acetate into 100mL of deionized water, stirring for 6h, performing ultrasonic treatment for 2h to uniformly disperse the powder, performing suction filtration to form a film, and naturally drying the film at room temperature to obtain the cobalt acetate-MXene composite film.
Step three, preparing a functional interlayer for the lithium-sulfur battery:
and (3) placing 0.5g of the cobalt acetate-MXene composite film prepared in the second step into a tubular furnace, heating to 700 ℃ at a heating rate of 1 ℃/min under the argon atmosphere, introducing mixed gas of acetylene and hydrogen simultaneously after the temperature is constant, wherein the hydrogen flow rate is 300mL/min and the acetylene flow rate is 50mL/min, continuously introducing for 30min, closing the hydrogen and the acetylene after the completion, and naturally cooling under the argon atmosphere to obtain the functional interlayer for the lithium-sulfur battery.

Claims (5)

  1. The preparation method of the functional interlayer of the lithium-sulfur battery comprises the following steps:
    step , MXene material preparation:
    and (3) immersing the ground MAX-phase ceramic powder into an HF solution, heating to 50-90 ℃, magnetically stirring for 12-24 hours, centrifuging to obtain a product, washing to be neutral by using deionized water, and drying in an oven at 60-80 ℃ for 12-24 hours to obtain the MXene material.
    Secondly, preparing a cobalt acetate-Mxene composite film:
    and (3) placing the MXene material prepared in the step and cobalt acetate in deionized water, stirring for 3-6h, performing ultrasonic treatment for 1-2h to uniformly disperse the MXene material, performing suction filtration to form a film, and naturally drying at room temperature to obtain the cobalt acetate-MXene composite film.
    Step three, preparing a functional interlayer for the lithium-sulfur battery:
    and (3) placing 0.05-0.5 of the cobalt acetate-MXene composite film prepared in the second step into a tubular furnace for high-temperature calcination, introducing mixed gas of acetylene and hydrogen after the temperature is constant, and naturally cooling in an argon atmosphere to obtain the functional interlayer for the lithium-sulfur battery.
  2. 2. The method according to claim 1, wherein the MAX phase ceramic of step is Ti3AlC2、Ti2AlC、Cr2 or more kinds of AlC can be used to obtain MXene material (Ti)3C2Tx(TxIs a functional group such as-OH, -F), Ti2CTx(Tx is-OH, -F, etc.) and Cr2CTx(TxFunctional groups of-OH, -F, etc.) or more.
  3. 3. The method according to claim 1, wherein the HF solution in the step is 30-50 wt%.
  4. 4. The preparation method according to claim 1, wherein the mass ratio of MXene material to cobalt acetate in the second step is 1-5:10-30, and the mass volume ratio of cobalt acetate to deionized water is 1-3 g/L.
  5. 5. The method as claimed in claim 1, wherein the temperature rise rate of the high-temperature calcination in the tubular furnace in the third step is 0.5-1 ℃/min, the temperature is 500-.
CN201911035469.8A 2019-10-29 2019-10-29 Preparation method of functional interlayer of lithium-sulfur battery Pending CN110739429A (en)

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CN113173598A (en) * 2021-05-07 2021-07-27 青岛科技大学 Method for in-situ derivatization of sulfide by vanadium-based MXene
CN113571841A (en) * 2021-07-22 2021-10-29 哈尔滨师范大学 Lithium-sulfur battery composite diaphragm and preparation method thereof
CN114804883A (en) * 2021-01-27 2022-07-29 中国科学院金属研究所 Based on Ti 2 CT x Preparation method of mecamirene high-rate lithium ion battery cathode material

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111341973A (en) * 2020-03-10 2020-06-26 肇庆市华师大光电产业研究院 Preparation method of functional interlayer of lithium-sulfur battery
CN111341973B (en) * 2020-03-10 2022-03-15 肇庆市华师大光电产业研究院 Preparation method of functional interlayer of lithium-sulfur battery
CN114804883A (en) * 2021-01-27 2022-07-29 中国科学院金属研究所 Based on Ti 2 CT x Preparation method of mecamirene high-rate lithium ion battery cathode material
CN114804883B (en) * 2021-01-27 2023-11-10 中国科学院金属研究所 Ti-based 2 CT x Preparation method of Michael high-magnification lithium ion battery anode material
CN113173598A (en) * 2021-05-07 2021-07-27 青岛科技大学 Method for in-situ derivatization of sulfide by vanadium-based MXene
CN113173598B (en) * 2021-05-07 2022-07-29 青岛科技大学 Method for in-situ derivatization of sulfide from vanadium-based MXene
CN113571841A (en) * 2021-07-22 2021-10-29 哈尔滨师范大学 Lithium-sulfur battery composite diaphragm and preparation method thereof

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