CN110828753A - 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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CN110828753A
CN110828753A CN201911132361.0A CN201911132361A CN110828753A CN 110828753 A CN110828753 A CN 110828753A CN 201911132361 A CN201911132361 A CN 201911132361A CN 110828753 A CN110828753 A CN 110828753A
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sulfur
lithium
hydrogen sulfide
doped diamond
functional interlayer
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CN110828753B (en
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王新
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
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/54—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of unsaturated nitriles
    • 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
    • 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
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    • 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

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  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
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Abstract

The invention relates to a preparation method of a functional interlayer of a lithium-sulfur battery. The invention effectively relieves the defects of obvious shuttle effect of polysulfide in the lithium-sulfur battery prepared by the prior art and unstable electrochemical performance of the battery.

Description

Preparation method of functional interlayer of lithium-sulfur battery
Technical Field
The invention relates to a preparation method of a functional interlayer of a lithium-sulfur battery, in particular to a method for preparing sulfur-doped diamond and weaving the sulfur-doped diamond and carbon nano tubes together to form a self-supporting functional interlayer of the lithium-sulfur battery by utilizing electrostatic spinning, belonging to the field of material chemistry.
Background
With the rapid development of scientific technology and information industry, the demand of renewable energy and new energy in the world is urgent. The lithium ion battery has the advantages of high specific energy, environmental friendliness, no pollution, abundant resources, low price and the like, and becomes a choice for energy storage equipment such as mobile electronic products and electric vehicles. The sulfur is used as the positive electrode material of the lithium-sulfur battery, the theoretical capacity of the lithium-sulfur battery reaches 1675mAh/g, the theoretical energy density of the lithium-sulfur battery can reach 2600Wh/kg, and the lithium-sulfur battery is one of the secondary batteries which are considered to have the most development prospect. However, elemental sulfur has poor conductivity, and intermediate products of elemental sulfur in the charging and discharging processes have poor conductivity, so that problems such as shuttling effect of polysulfide in the reaction process exist, and the utilization rate of the positive electrode material is always in a low level, which affects the practical application of the positive electrode material. Therefore, the issues of improving the cycle life of the lithium-sulfur battery, improving the utilization of the positive active material, and improving the poor conductivity and polysulfide shuttling effect of the lithium-sulfur battery have been the focus of research on the lithium-sulfur battery. In the prior art, the scheme for improving the performance of the lithium-sulfur battery mainly includes optimization of a sulfur-based positive electrode structure and modification of a sulfur-based positive electrode material, and elemental sulfur and a porous material are mechanically compounded by a filling, mixing or coating method to form a composite positive electrode material, so that the lithium ion conductivity of the sulfur-based positive electrode and the cycle performance of the battery are improved. The functional interlayer is a simple and feasible method for directly solving the shuttle effect of the lithium-sulfur battery. The functional interlayer utilizes a common diaphragm, and the designed substances are coated on the surface of the diaphragm and exist between the pole piece and the lithium piece, so that the shuttle effect of fixing polysulfide physically or chemically can be achieved, the utilization rate of the active substances of the positive electrode is improved, and the overall performance of the lithium-sulfur battery is improved.
Disclosure of Invention
The invention aims to provide a preparation method of a functional interlayer for a lithium-sulfur battery, aiming at the obvious shuttle effect of the current lithium-sulfur battery. The technical scheme adopted by the invention for solving the technical problem is as follows:
a preparation method of a functional interlayer of a lithium-sulfur battery comprises the following steps:
the first step is as follows: preparing the sulfur-doped diamond:
heating diamond particles with the particle size of less than 100nm to 1500-2000 ℃ in argon atmosphere, preserving heat for 1-2h, cooling, soaking in concentrated sulfuric acid, washing, drying, placing in a tubular furnace, calcining at high temperature, introducing hydrogen sulfide gas into the tubular furnace after the temperature is raised, closing the hydrogen sulfide gas after the heat preservation is finished, and naturally cooling the hydrogen sulfide gas along with the furnace in the argon atmosphere to obtain the sulfur-doped diamond.
Further, concentrated sulfuric acid is added in the first step, the concentration is 1-10mol/L, the soaking time is 12-24h, the high-temperature calcination temperature is 1000-1500 ℃, the heating rate is 5-10 ℃/min, the ratio of hydrogen sulfide to argon introduced is 1:10-20, and the heat preservation time is 1-2 h.
The second step is that: preparing a functional interlayer:
and (3) placing a proper amount of polyacrylonitrile, the sulfur-doped diamond prepared in the first step and the multi-wall carbon nanotube powder into a certain amount of N, N-dimethylformamide, stirring for 12-24 hours, and then taking the uniform solution to prepare the required product through electrostatic spinning. The film is directly used as a functional interlayer of the lithium-sulfur battery after being torn off from the tin foil for electrostatic spinning, and is directly arranged between a lithium sheet and a diaphragm in the process of assembling the battery.
Further, in the second step, the mass-to-volume ratio of the polyacrylonitrile, the sulfur-doped diamond prepared in the first step, the multi-walled carbon nanotube powder, and the N, N-dimethylformamide is (1-2) g: (0.1-1) g: (0.05-0.1) g: (10-20) mL.
The invention has the following beneficial effects:
according to the invention, the sulfur-doped diamond, the carbon nano tube and the polyacrylonitrile are introduced, and the combined action of the three components inhibits the shuttle effect of the lithium-sulfur battery, so that the loss of active substances in the anode material is reduced, and the cycle stability of the lithium-sulfur battery is improved. The electrostatic spinning method is adopted in the preparation process of the invention, and the final product is a self-supporting structure, which is obviously different from the traditional diaphragm coating method, thereby not only simplifying the preparation process of the functional interlayer, but also avoiding 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.
Drawings
The invention is further illustrated with reference to the following figures and examples:
FIG. 1 is a graph showing the specific discharge capacity cycling of the functional separator prepared in example 1 when applied to a lithium-sulfur battery.
Detailed Description
Example 1:
first step preparation of sulfur-doped diamond:
heating diamond particles with the particle size of less than 100nm to 1800 ℃ in an argon atmosphere, preserving heat for 2 hours, cooling, soaking in concentrated sulfuric acid with the concentration of 5mol/L for 24 hours, then washing, drying, placing in a tubular furnace, heating to 1300 ℃ in the argon atmosphere, wherein the heating rate is 8 ℃/min, introducing hydrogen sulfide gas into the tubular furnace after the heating is finished, keeping the temperature for 2 hours, closing the hydrogen sulfide gas after the heat preservation is finished, and naturally cooling the hydrogen sulfide gas along with the furnace in the argon atmosphere to obtain the sulfur-doped diamond.
The second step is to prepare a functional interlayer:
1.5g of polyacrylonitrile, 0.5g of prepared sulfur-doped diamond and 0.08g of multi-walled carbon nanotube powder are put in 15ml of N-dimethylformamide and stirred for 18 hours, and then the uniform solution is taken to prepare the required product through electrostatic spinning. The film is directly used as a functional interlayer of the lithium-sulfur battery after being torn off from the tin foil for electrostatic spinning, and is directly arranged between a lithium sheet and a diaphragm in the process of assembling the battery.
Example 2:
the first step is as follows: preparing the sulfur-doped diamond:
heating diamond particles with the particle size of less than 100nm to 2000 ℃ in an argon atmosphere, preserving heat for 2 hours, cooling, soaking in concentrated sulfuric acid with the concentration of 10mol/L for 24 hours, then washing, drying, placing in a tubular furnace, heating to 1500 ℃ in the argon atmosphere, heating at the heating rate of 10 ℃/min, introducing hydrogen sulfide gas into the tubular furnace after the heating is completed, keeping the temperature for 2 hours, closing the hydrogen sulfide gas after the heat preservation is completed, and naturally cooling the hydrogen sulfide gas along with the furnace in the argon atmosphere to obtain the sulfur-doped diamond.
Second step of preparing functional interlayer
2g of polyacrylonitrile, 1g of prepared sulfur-doped diamond and 0.1g of multi-walled carbon nanotube powder are put into 20ml of N-dimethylformamide and stirred for 24 hours, and then the uniform solution is taken to prepare the required product through electrostatic spinning. The film is directly used as a functional interlayer of the lithium-sulfur battery after being torn off from the tin foil for electrostatic spinning, and is directly arranged between a lithium sheet and a diaphragm in the process of assembling the battery.
Example 3:
the first step is as follows: preparing the sulfur-doped diamond:
heating diamond particles with the particle size of less than 100nm to 1500 ℃ in an argon atmosphere, preserving heat for 1h, cooling, soaking in concentrated sulfuric acid with the concentration of 1mol/L for 12h, then washing, drying, placing in a tubular furnace, heating to 1000 ℃ in the argon atmosphere, heating at the rate of 5 ℃/min, introducing hydrogen sulfide gas into the tubular furnace after the temperature is raised, keeping the temperature for 1h, closing the hydrogen sulfide gas after the temperature is raised, and naturally cooling the hydrogen sulfide gas along with the furnace in the argon atmosphere to obtain the sulfur-doped diamond.
Second step of preparing functional interlayer
1g of polyacrylonitrile, 0.1g of prepared sulfur-doped diamond and 0.05g of multi-wall carbon nanotube powder are put into 10mLN, N-dimethylformamide and stirred for 12 hours, and then the uniform solution is taken to prepare the required product through electrostatic spinning. The film is directly used as a functional interlayer of the lithium-sulfur battery after being torn off from the tin foil for electrostatic spinning, and is directly arranged between a lithium sheet and a diaphragm in the process of assembling the battery.

Claims (3)

1. A preparation method of a functional interlayer of a lithium-sulfur battery comprises the following steps:
the first step is as follows: preparing the sulfur-doped diamond:
heating diamond particles with the particle size of less than 100nm to 1500-2000 ℃ in argon atmosphere, preserving heat for 1-2h, cooling, soaking in concentrated sulfuric acid, washing, drying, placing in a tubular furnace, calcining at high temperature, introducing hydrogen sulfide gas into the tubular furnace after the temperature is raised, closing the hydrogen sulfide gas after the heat preservation is finished, and naturally cooling the hydrogen sulfide gas along with the furnace in the argon atmosphere to obtain the sulfur-doped diamond;
the second step is that: preparing a functional interlayer:
and placing a proper amount of polyacrylonitrile, the sulfur-doped diamond prepared in the first step and the multi-wall carbon nanotube powder in a certain amount of N, N-dimethylformamide, stirring for 12-24 hours, taking the uniform solution, performing electrostatic spinning to obtain a required product, tearing the product off from the tin foil for electrostatic spinning, directly using the torn product as a functional interlayer of the lithium-sulfur battery, and directly placing the product between a lithium sheet and a diaphragm in the process of assembling the battery.
2. The method as claimed in claim 1, wherein the concentration of the concentrated sulfuric acid added in the first step is 1-10mol/L, the soaking time is 12-24h, the high-temperature calcination temperature is 1000-1500 ℃, the temperature rise rate is 5-10 ℃/min, the ratio of the introduced hydrogen sulfide to argon is 1:10-20, and the heat preservation time is 1-2 h.
3. The method according to claim 1, wherein in the second step, the mass-to-volume ratio of the polyacrylonitrile, the sulfur-doped diamond prepared in the first step, the multi-walled carbon nanotube powder, and the N, N-dimethylformamide is (1-2) g: (0.1-1) g: (0.05-0.1) g: (10-20) mL.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111900390A (en) * 2020-05-29 2020-11-06 湘潭大学 Metallic tin and carbon nanotube co-doped lithium-sulfur battery interlayer material and preparation method and application thereof
CN111900326A (en) * 2020-08-04 2020-11-06 大连理工大学 Preparation method and application of positive electrode-interlayer integrated membrane material for lithium-sulfur battery

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US5747118A (en) * 1994-04-06 1998-05-05 The Regents Of The University Of California Plasma enhanced chemical transport process for forming diamond films
WO2000058534A1 (en) * 1999-03-26 2000-10-05 Japan Science And Technology Corporation N-type semiconductor diamond and its fabrication method
WO2004075273A1 (en) * 2003-02-24 2004-09-02 Tokyo Gas Company Limited N-type diamond semiconductor and its manufacturing method
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CN108550764A (en) * 2018-03-16 2018-09-18 河南力旋科技股份有限公司 A kind of ultra-fine diamond coated insulation film and the lithium ion battery using this isolation film
CN109142313A (en) * 2018-08-03 2019-01-04 吉林大学 The diamond substrate and preparation method thereof of semiconductor surface enhancing Raman scattering
CN109881248A (en) * 2019-03-12 2019-06-14 吉林大学 Nitrogen sulphur codope n-type semiconductor diamond and preparation method thereof

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Publication number Priority date Publication date Assignee Title
US5075764A (en) * 1989-06-22 1991-12-24 Semiconductor Energy Laboratory Co., Ltd. Diamond electric device and manufacturing method for the same
US5747118A (en) * 1994-04-06 1998-05-05 The Regents Of The University Of California Plasma enhanced chemical transport process for forming diamond films
WO2000058534A1 (en) * 1999-03-26 2000-10-05 Japan Science And Technology Corporation N-type semiconductor diamond and its fabrication method
WO2004075273A1 (en) * 2003-02-24 2004-09-02 Tokyo Gas Company Limited N-type diamond semiconductor and its manufacturing method
CN104662705A (en) * 2012-09-14 2015-05-27 弗劳恩霍弗应用技术研究院 Alkali metal-chalcogen battery having low self-discharge and high cycle life and performance
US20160043370A1 (en) * 2013-03-19 2016-02-11 Sony Corporation Separator, battery, battery pack, electronic apparatus, electric vehicle, power storage device, and electric power system
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CN108550764A (en) * 2018-03-16 2018-09-18 河南力旋科技股份有限公司 A kind of ultra-fine diamond coated insulation film and the lithium ion battery using this isolation film
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CN109881248A (en) * 2019-03-12 2019-06-14 吉林大学 Nitrogen sulphur codope n-type semiconductor diamond and preparation method thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111900390A (en) * 2020-05-29 2020-11-06 湘潭大学 Metallic tin and carbon nanotube co-doped lithium-sulfur battery interlayer material and preparation method and application thereof
CN111900390B (en) * 2020-05-29 2022-04-01 湘潭大学 Metallic tin and carbon nanotube co-doped lithium-sulfur battery interlayer material and preparation method and application thereof
CN111900326A (en) * 2020-08-04 2020-11-06 大连理工大学 Preparation method and application of positive electrode-interlayer integrated membrane material for lithium-sulfur battery
CN111900326B (en) * 2020-08-04 2021-08-06 大连理工大学 Preparation method and application of positive electrode-interlayer integrated membrane material for lithium-sulfur battery

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