CN106299311A - A kind of preparation method and application of lithium-sulfur cell carbon/sulfur composite positive pole - Google Patents

A kind of preparation method and application of lithium-sulfur cell carbon/sulfur composite positive pole Download PDF

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Publication number
CN106299311A
CN106299311A CN201610882174.4A CN201610882174A CN106299311A CN 106299311 A CN106299311 A CN 106299311A CN 201610882174 A CN201610882174 A CN 201610882174A CN 106299311 A CN106299311 A CN 106299311A
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China
Prior art keywords
sulfur
carbon
lithium
porous
positive pole
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CN201610882174.4A
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Chinese (zh)
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翟文礼
赵永男
余建国
高海燕
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Tianjin Polytechnic University
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Tianjin Polytechnic 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses the preparation method and application of a kind of lithium-sulfur cell carbon/sulfur composite positive pole.Material with carbon element in the lithium-sulfur cell carbon/sulfur composite positive pole of the present invention is to prepare with porous aromatic skeleton material for carbon source, and using this porous carbon materials as skeleton, elemental sulfur, as active substance, is compounded to form lithium-sulfur cell carbon/sulfur composite positive pole.The composite positive pole electric conductivity obtained is good, and active material utilization is high, improves capacity and the cycle life of lithium-sulfur cell.The invention provides one utilizes suitable porous aromatic skeleton material (PAF X) to be carbon source, prepares the new method of lithium-sulfur cell carbon/sulfur positive electrode.

Description

A kind of preparation method and application of lithium-sulfur cell carbon/sulfur composite positive pole
Technical field
The invention belongs to electrochemical field, relate to lithium sulfur battery anode material, particularly to a kind of carbon/sulfur anode composite material Material and its preparation method and application.
Technical background
Along with the demand of electrochemical energy storage technology is increased by the development mankind of society and science and technology day by day, research worker is all being sought Look for the secondary cell of future generation with more high-energy-density.Lithium-sulfur cell is with sulfur as positive active material, based between sulfur and lithium Reversible electrochemical reaction realizes energy storage and release, and its theoretical specific energy, up to 2600Wh/kg, is current lithium ion battery 3-5 times, be expected to be applied to the field such as electrokinetic cell, portable type electronic product.But lithium-sulfur cell still can not commercialization Produce, this is owing to some defects of battery self are not the most well solved, and mainly has: 1) elemental sulfur and electric discharge produce Thing Li2S2/Li2S is typical electronics and ion insulator, and therefore the charge transfer within positive pole is obstructed, and causes utilization efficiency low Under, it is impossible to playing the advantage of its high theoretical specific capacity, load transfer inefficiency simultaneously also have impact on the power such as the high rate performance of battery Learn the lifting of performance；2) the many lithium sulfides of battery intermediate product can be dissolved in liquid electrolyte, causes the loss of active substance sulfur；3) During discharge and recharge, the great variety of sulfur volume can cause instability and the electrode loose contact of structure.
Therefore, research worker is developed various sulfenyl composites and is solved problem above, particularly by carbonaceous material The introducing of material can be greatly improved lithium-sulfur cell performance.Elemental sulfur and the porous carbon with high-specific surface area and high conductivity are received In carbon/sulfur composite positive pole that rice material high efficiency composition obtains, nanometer carbon material can form efficient positive conductive skeleton Structure, thus increase the electric conductivity of positive electrode, it is provided that electrochemical reaction active site, largely overcome sulfur, lithium sulfide low Electrical conductivity problems；Additionally unique pore structure of nanometer carbon material also can modulation polysulfide dissolving, migrate and shuttle back and forth, reduce The loss of active material, thus improve the capability retention of lithium-sulfur cell.The most conventional porous carbon materials mostly is activated carbon, carbon Nanotube, Graphene etc., although obtained composite positive pole has more stable chemical property, but its preparation is the most multiple Miscellaneous, preparation cost is higher, is unfavorable for large-scale commercial production.
Summary of the invention
An object of the present invention be to provide the preparation method of a kind of lithium-sulfur cell carbon/sulfur composite positive pole and Application in lithium-sulfur cell.
For achieving the above object, the technical scheme that the present invention provides is: a kind of lithium-sulfur cell carbon/sulfur anode composite material, It is characterized in that, this composite is made up of elemental sulfur and porous carbon nano material, and wherein porous carbon nano material is as skeleton, Elemental sulfur is as active substance.Described porous carbon materials is to be that carbon source prepares by porous aromatic skeleton.
Porous carbon nano material of the present invention is prepared with porous aromatic skeleton material for carbon source, and its feature exists In, preparation method can select the preparation method of the porous carbon materials having been known, it is also possible to designed, designed carbonization as required Program.
The present invention utilizes has high porosity, high-specific surface area, the porous aromatic skeleton material of high physical and chemical stability For presoma, use suitable carbonization method, while keeping porous aromatic skeleton material hole channel structure characteristic, make material carbon Change and obtain target porous carbon materials, then using this kind of porous carbon materials as the carrier of sulfur, prepare carbon/sulfur anode composite material Material.Owing to porous aromatic skeleton material can synthesize with rational design at present, therefore can be by porous aromatic skeleton material be selected Select design, it is achieved the controlled syntheses design of porous carbon materials.Namely: the present invention in fact provide a kind of lithium-sulfur cell carbon/ The new method of sulfur composite positive pole.
In the present invention, for preparing the presoma porous aromatic skeleton material of the porous carbon of carbon/sulfur composite positive pole, can To select porous aromatic skeleton material commonly known in the art, it is also possible to rational design synthesizes.Preferably those have high hole Degree, superhigh specific surface area, the porous aromatic skeleton material of high physical and chemical stability.
The present invention utilizes porous carbon that preferred porous aromatic skeleton material prepared for carbon source as the carrier of sulfur, prepares lithium Sulfur battery carbon/sulfur composite positive pole, the lithium-sulfur cell of follow-up preparation shows high coulombic efficiency and cyclical stability. As: selection PAF-45 (Li.L, Cai.K, Wang.P, et al, ACS applied materials & interfaces, 2014,7,201-208) as carbon source, prepare lithium-sulfur cell carbon/sulfur composite positive pole, and be applied to lithium-sulfur cell.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscopic picture of PAF-45
Fig. 2 is the scanning electron microscopic picture of the porous carbon materials that embodiment obtains；
Fig. 3 is the scanning electron microscopic picture of carbon/sulfur composite positive pole that embodiment obtains；
Fig. 4 is the carbon/sulfur composite positive pole chemical property figure as lithium sulfur battery anode material of embodiment acquisition.
Detailed description of the invention
In order to the technical solution adopted in the present invention and beneficial effect are expanded on further, below in conjunction with the preferred reality of the present invention Execute example and accompanying drawing is described in detail.Should be appreciated that described specific embodiment, and need not only in order to explain the present invention In limiting the present invention
Embodiments provide a kind of preferably porous aromatic skeleton material (PAF-45) to prepare as the presoma of carbon Porous carbon as the carrier of sulfur, the method preparing lithium-sulfur cell carbon/sulfur composite positive pole, comprise the following steps:
Step one: choose and there is the porous aromatic skeleton material PAF-45 of high-specific surface area and abundant microcellular structure as carbon Presoma prepare porous carbon.
1) weigh a certain amount of PAF-45 to be vacuum dried two hours at 100 DEG C,
2) dried PAF-45 is dispersed in porcelain boat, is placed in tube furnace, then tube furnace is led to continuously Argon 20 minutes, then flow down at argon, with 5 DEG C/heating rate per minute, from the slow temperature programming of room temperature to carburizing temperature 500 DEG C, carbonization 5 hours, obtain porous carbon at this temperature.
3) porous carbon obtained is flowed down at argon it is cooled to room temperature.
Step 2: carry out the porous carbon of gained and elemental sulfur compound preparing carbon/sulfur anode composite by melted diffusion method Material.The porous carbon materials of step one gained is mixed homogeneously with mass ratio 1: 3 with Sublimed Sulfur.It is sealed in reactor and is heated to 155 DEG C of insulation 15h, obtain carbon/sulfur composite.
The scanning electron microscope (SEM) photograph of porous carbon prepared by the present embodiment is as in figure 2 it is shown, pass through and the scanning electron microscopic picture of PAF-45 (Fig. 1) compare, it appeared that PAF-45 pattern after 500 DEG C of carbonizations is held essentially constant.After compound with sulfur, figure does not find The existence (Fig. 3) of bulky grain sulfur, illustrates that sulfur is evenly distributed in the porous carbon of preparation.Carbon/sulfur composite is at 0.5C (837.5mA/g) chemical property under electric current density is as shown in Figure 4, and first discharge specific capacity is up to 1211mAh/g, circulation After 1000 times, capacity remains on 310mAh/g, and coulombic efficiency is up to 97%.
The present embodiment is only presently preferred embodiments of the present invention, not in order to limit the present invention.General for this area For logical technical staff, can conceive according to technical scheme and technology and make other various corresponding changes and repair Decorations, and all these change and modification all should belong to the protection domain of the claims in the present invention.

Claims (3)

1. the preparation method of lithium-sulfur cell carbon/sulfur anode composite material, it is characterised in that this composite by elemental sulfur and Porous carbon materials forms, and wherein porous carbon materials is as skeleton, and elemental sulfur is as active substance.Described porous carbon materials be by Porous aromatic skeleton is that carbon source prepares.
The preparation method of lithium-sulfur cell carbon/sulfur composite positive pole the most according to claim 1, it is characterised in that institute State porous aromatic skeleton material for having high porosity, high-specific surface area, the porous aromatic skeleton material of high physical and chemical stability Material, can select porous aromatic skeleton material commonly known in the art, it is also possible to rational design synthesizes.
3. the carbon of the lithium-sulfur cell as described in claim 1-2/sulfur anode composite material application in lithium-sulfur cell.
CN201610882174.4A 2016-10-09 2016-10-09 A kind of preparation method and application of lithium-sulfur cell carbon/sulfur composite positive pole Pending CN106299311A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107591528A (en) * 2017-09-26 2018-01-16 珠海光宇电池有限公司 Carbon sulphur composite for lithium-sulphur cell positive electrode and preparation method thereof
CN108002362A (en) * 2017-12-22 2018-05-08 许昌学院 A kind of aromatic skeleton porous carbon materials, preparation method and application
CN110707327A (en) * 2019-10-13 2020-01-17 浙江大学 Preparation of modified porous carbon material based on cobaltocene and application of modified porous carbon material in lithium-sulfur battery
CN112317284A (en) * 2020-10-22 2021-02-05 常州润睿特种合金有限公司 Coating material for cutting tool and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104861154A (en) * 2015-04-13 2015-08-26 苏州纳埃净化科技有限公司 Preparation method of porous aromatic framework compound constructed with benzene ring base blocks
CN105921178A (en) * 2016-04-27 2016-09-07 吉林大学 Porous aromatic skeleton compound immobilized metal palladium catalyst PAF11-Pd, and preparation method and application thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104861154A (en) * 2015-04-13 2015-08-26 苏州纳埃净化科技有限公司 Preparation method of porous aromatic framework compound constructed with benzene ring base blocks
CN105921178A (en) * 2016-04-27 2016-09-07 吉林大学 Porous aromatic skeleton compound immobilized metal palladium catalyst PAF11-Pd, and preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
WENLI ZHAI ET AL.: ""Excellent Performance of Lithium-Sulfur batteries with Carbonized Porous Aromatic Framework Nanobeads as Support"", 《ELECTROCHIMICA ACTA》 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107591528A (en) * 2017-09-26 2018-01-16 珠海光宇电池有限公司 Carbon sulphur composite for lithium-sulphur cell positive electrode and preparation method thereof
CN108002362A (en) * 2017-12-22 2018-05-08 许昌学院 A kind of aromatic skeleton porous carbon materials, preparation method and application
CN110707327A (en) * 2019-10-13 2020-01-17 浙江大学 Preparation of modified porous carbon material based on cobaltocene and application of modified porous carbon material in lithium-sulfur battery
CN110707327B (en) * 2019-10-13 2020-10-23 浙江大学 Preparation of modified porous carbon material based on cobaltocene and application of modified porous carbon material in lithium-sulfur battery
CN112317284A (en) * 2020-10-22 2021-02-05 常州润睿特种合金有限公司 Coating material for cutting tool and preparation method thereof
CN112317284B (en) * 2020-10-22 2022-03-08 常州润睿特种合金有限公司 Coating material for cutting tool and preparation method thereof

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Application publication date: 20170104