CN103762345A - Preparation method of Li-S secondary cell composite positive pole material - Google Patents

Preparation method of Li-S secondary cell composite positive pole material Download PDF

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Publication number
CN103762345A
CN103762345A CN201310655174.7A CN201310655174A CN103762345A CN 103762345 A CN103762345 A CN 103762345A CN 201310655174 A CN201310655174 A CN 201310655174A CN 103762345 A CN103762345 A CN 103762345A
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China
Prior art keywords
clad
sulphur powder
positive pole
sulfur
porous
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CN201310655174.7A
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CN103762345B (en
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靳佳
杨晓亮
徐宁
吴孟涛
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Tianjin Bamo Technology Co., Ltd.
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Tianjin B & M Science And Technology Joint-Stock Co Ltd
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/362Composites
    • H01M4/366Composites as layered products
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention discloses a preparation method of a Li-S secondary cell composite positive pole material. The preparation method comprises the following steps of 1, in an inert atmosphere, adding elemental sulfur into a ball mill and carrying out ball milling for 0.5-2h to obtain dispersed sulfur powder having the particle size D50 <=100 micrometers, 2, orderly adding a coating material and the dispersed sulfur powder into a mechanical fusion machine and carrying out fusion to obtain a composite material precursor, and 3, putting the composite material precursor into a closed container filled with inert gas, carrying out melting at a temperature of 400 DEG C for 10-12h so that the sulfur powder is coated with the coating material, and carrying out melting volatilization at a temperature of 200 DEG C for 10-30min so that the sulfur powder adhering to the outer surface of the coating material is volatilized and the Li-S secondary cell composite positive pole material is obtained. The Li-S secondary cell composite positive pole material has high coating uniformity, inhibits sulfur active substance loss, improves an electronic transmission capability and improves electrical properties.

Description

The preparation method of lithium-sulfur rechargeable battery composite positive pole
Technical field
The present invention relates to electrode material of secondary lithium ion battery preparation field, particularly relate to a kind of preparation method of lithium-sulfur rechargeable battery composite positive pole.
Background technology
In the energy starved present age and future, the energy density of lithium-sulfur rechargeable battery Yin Qigao and obtain extensive concern and research, becomes a kind of energy form of alleviating shortage of resources.LiCoO in commercial lithium ion secondary battery anode material 2laboratory research and development and even scale production process are very ripe, and future studies concentrate on high voltage direction.LiFePO 4the bottleneck of positive electrode research never has breakthrough, although the application of existing mass production on electrokinetic cell also do not launch on a large scale.Tertiary cathode material and LiMn 2o 4the focus of power battery anode material research will be become within one period from now on.And lithium-sulfur rechargeable battery is because sulphur active substances in cathode materials losing issue is at present also in laboratory development.
Elemental sulfur due to poorly conductive often with together with the Material cladding of good conductivity as the positive electrode of lithium-sulfur rechargeable battery.Except increasing electric conductivity, another effect of electric conducting material is that restriction sulphur active material runs off in charge and discharge process.Electric conducting material has regular material with carbon element that oxide, carbon black, all kinds of template make, carbon nano-tube, Graphene etc.The people such as Ji [J.Am.Chem.Soc.133 (2011) 18522] are deposited on sulphur (S) on sheet graphene oxide by chemical reaction in microemulsion phase system, and improve its electro-chemical activity and suppress active material and run off by improving the contact area of active material S and ionic liquid-organic solvent mixed electrolytic solution.Because graphene oxide is expensive at present, so temporarily cannot drop into batch production.The people such as Guo [Angew.Chem., 124 (2012) 1] are with SnO 2hollow ball is that hard template has been prepared double-layer hollow carbon ball, after finally elemental sulfur being ground together with double-layer hollow carbon ball, at 400 ℃, fire and form the composite material that a kind of energy restricted activity material runs off, what the method that wherein S mixes with double-layer hollow carbon ball was used is the simplest laboratory polishing, the method just makes the two attach simply together, material after compound is inhomogeneous, easily occurs segregation phenomena.
Summary of the invention
The preparation method who the object of this invention is to provide a kind of lithium-sulfur rechargeable battery composite positive pole, its prepared composite positive pole coating layer is closely knit evenly, high as the conductive layer, the tap density that suppress outer wall layer that sulphur active material runs off and electric transmission, material fluidity good.
For this reason, technical scheme of the present invention is as follows:
A preparation method for lithium-sulfur rechargeable battery composite positive pole, comprises the following steps:
(1) in inert atmosphere, elemental sulfur is added in ball mill to ball milling 0.5~2 hour, obtain granularity D 50the dispersion sulphur powder of≤100 μ m;
(2) successively clad material, described dispersion sulphur powder are joined in mechanical fusion machine and merged, obtain composite material precursor.
(3) composite material precursor making is put into the closed container that is full of inert atmosphere, first 400 ℃ of meltings 10~12 hours, sulphur powder is incorporated in clad material, again 200 ℃ of melting volatilizations 10~30 minutes, the sulphur powder that clad material outer surface attaches is vapored away, obtain described lithium-sulfur rechargeable battery composite positive pole.
Preferably, in step (1), elemental sulfur is added together with solvent to ball milling in ball mill, described solvent is volatile non-polar solven, solvent adding amount is 2~3 times of elemental sulfur by mass, after ball milling, at 100 ℃, to dry 2~3 hours, described non-polar solven preferably adopts acetone or ether.
Described in step (2), clad material is porous conductive material, the aperture of clad material or D 50with dispersion sulphur powder D 50average grain diameter ratio be less than 1:10, clad material is 1:3~1:1 with disperseing the mass ratio of sulphur powder, and the specific area of clad material is greater than 10m 2/ g.Described porous conductive material is porous active carbon, regular porous template material with carbon element or porous SnO 2.
The mechanical time of fusion of described dispersion sulphur powder and clad material is 5 minutes~2 hours, and rotor speed is 400~4000rpm.Described inert atmosphere is Ar or N 2atmosphere.
The present invention prepares composite material by mechanical fusion method, compare with polishing, solvent-thermal method, the method is closely linked elemental sulfur and electric conducting material by mechanical stress in microcosmic particle rank, thereby elemental sulfur and electric conducting material contact area are significantly improved, inhomogeneous, the segregation phenomena of elemental sulfur and the compound rear appearance of electric conducting material have been avoided, thereby make the active raising of composite positive pole, after composition lithium-sulfur rechargeable battery, chemical property is improved.
Embodiment
Below in conjunction with specific embodiment, preparation method of the present invention is elaborated.
Embodiment 1:
A preparation method for lithium-sulfur rechargeable battery composite positive pole, comprises the following steps:
1) in inert atmosphere Ar, elemental sulfur is added in ball mill to ball milling 1 hour, it is tentatively dispersed into the elemental sulfur powder that particle is tiny, its granularity D 50be 80 μ m;
2) by aperture 100nm, specific area, be 400m successively 2the porous active material with carbon element of/g, disperse sulphur powder in mass ratio for 1:3 joins in mechanical fusion machine, with the rotating speed fusion of 1000rpm per minute, within 30 minutes, obtain composite material precursor;
3) described composite material precursor is put into the closed container that is full of Ar inert atmosphere, first 400 ℃ of meltings 10 hours, sulphur powder is incorporated in porous active material with carbon element, after 200 ℃ of meltings volatilization 10 minutes, the sulphur powder that porous active carbon outer surface attaches is vapored away.
Embodiment 2:
A preparation method for lithium-sulfur rechargeable battery composite positive pole, comprises the following steps:
1) at N 2in, elemental sulfur and acetone are counted to 1:2 in mass ratio and add in ball mill ball milling 2 hours, dry 2 hours, tentatively obtain the elemental sulfur powder that discrete particles is tiny, its granularity D for latter 100 ℃ 50be 30 μ m.
2) successively by D 50for 600nm, specific area are 20m 2the porous, electrically conductive SnO of/g 2material, disperse sulphur powder in mass ratio for 1:1 joins in mechanical fusion machine, with the rotating speed fusion of 1500rpm per minute, within 1 hour, obtain composite material precursor.
3 put into composite material precursor to be full of N 2closed container in, first 400 ℃ of meltings 12 hours, make sulphur powder incorporate porous, electrically conductive SnO 2in material, then, 200 ℃ of melting volatilizations 20 minutes, make porous, electrically conductive SnO 2the sulphur powder that outer surface attaches vapors away.
Comparative example 1
The first step is at inert atmosphere Ar or N 2in, elemental sulfur is added in ball mill to ball milling 1 hour, it is tentatively dispersed into the elemental sulfur powder that particle is tiny, its granularity D50 is 60~80 μ m.
Second step is 320~400m by aperture 100~150nm, specific area successively 2the porous active material with carbon element of/g, dispersion sulphur powder obtain composite material precursor for 30 minutes for 1:3 grinds in mass ratio.
The 3rd step is put into composite material precursor the closed container that is full of Ar, first 400 ℃ of meltings 10 hours, sulphur powder is incorporated in porous active material with carbon element, then 200 ℃ of melting volatilizations 10 minutes, the sulphur powder that porous active carbon outer surface attaches is vapored away.
The battery made from the material that method of the present invention makes, cut-ff voltage is 1.5-3.0V.Above embodiment, comparative example are made to material and be assembled into 2032 type lithium sulphur button cells and test, measured performance sees the following form:
As can be seen from the table, the battery made from the material that method of the present invention makes, discharge capacity is greater than 600mAh/g first, and within 50 weeks, circulating battery still can reach more than 80% capability retention, and electrical property compared by the battery making with comparative example and material fluidity all improves a lot.

Claims (7)

1. a preparation method for lithium-sulfur rechargeable battery composite positive pole, is characterized in that comprising the following steps:
(1) in inert atmosphere, elemental sulfur is added in ball mill to ball milling 0.5~2 hour, obtain granularity D 50the dispersion sulphur powder of≤100 μ m;
(2) successively clad material, described dispersion sulphur powder are joined in mechanical fusion machine and merged, obtain composite material precursor;
(3) composite material precursor making is put into the closed container that is full of inert atmosphere, first 400 ℃ of meltings 10~12 hours, sulphur powder is incorporated in clad material, again 200 ℃ of melting volatilizations 10~30 minutes, the sulphur powder that clad material outer surface attaches is vapored away, obtain described lithium-sulfur rechargeable battery composite positive pole.
2. preparation method according to claim 1, it is characterized in that: in step (1), elemental sulfur is added together with solvent to ball milling in ball mill, described solvent is volatile non-polar solven, solvent adding amount is 2~3 times of elemental sulfur by mass, after ball milling, at 100 ℃, dry 2~3 hours.
3. preparation method according to claim 2, is characterized in that: described non-polar solven is acetone or ether.
4. machinery according to claim 1 merges preparation method, it is characterized in that: described in step (2), clad material is porous conductive material, the aperture of clad material or D 50with dispersion sulphur powder D 50average grain diameter ratio be less than 1:10, clad material is 1:3~1:1 with disperseing the mass ratio of sulphur powder, and the specific area of clad material is greater than 10m 2/ g.
5. machinery according to claim 1 merges preparation method, it is characterized in that: described porous conductive material is porous active carbon, regular porous template material with carbon element or porous SnO 2.
6. preparation method according to claim 1, is characterized in that: the mechanical time of fusion of disperseing sulphur powder and clad material described in step (2) is 5 minutes~2 hours, and rotor speed is 400~4000rpm.
7. according to the preparation method described in any one in claim 1~6, it is characterized in that: described inert atmosphere is Ar or N 2atmosphere.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104993170A (en) * 2015-05-25 2015-10-21 天津巴莫科技股份有限公司 Preparation method of lithium sulfur secondary battery cathode material
CN110311113A (en) * 2019-07-02 2019-10-08 宁夏汉尧石墨烯储能材料科技有限公司 A kind of anode material for lithium-ion batteries of graphene coated
CN111192997A (en) * 2020-01-07 2020-05-22 北京理工大学 Diaphragm for activated carbon-loaded tin oxide lithium-sulfur battery and preparation method and application thereof

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CN101027803A (en) * 2004-09-22 2007-08-29 青井电子株式会社 Battery positive electrode material containing sulfur and/or sulfur compound having S-S bonding, and its manufacturing method
CN103247786A (en) * 2012-02-02 2013-08-14 中国人民解放军63971部队 Grafted carbon nanotube/sulfur composite positive electrode material having high specific capacity and long cycle life
CN103247799A (en) * 2012-02-02 2013-08-14 中国人民解放军63971部队 Carbon/sulfur composite positive material having long cycle life, and preparation method thereof

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CN101027803A (en) * 2004-09-22 2007-08-29 青井电子株式会社 Battery positive electrode material containing sulfur and/or sulfur compound having S-S bonding, and its manufacturing method
CN103247786A (en) * 2012-02-02 2013-08-14 中国人民解放军63971部队 Grafted carbon nanotube/sulfur composite positive electrode material having high specific capacity and long cycle life
CN103247799A (en) * 2012-02-02 2013-08-14 中国人民解放军63971部队 Carbon/sulfur composite positive material having long cycle life, and preparation method thereof

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104993170A (en) * 2015-05-25 2015-10-21 天津巴莫科技股份有限公司 Preparation method of lithium sulfur secondary battery cathode material
CN104993170B (en) * 2015-05-25 2017-03-15 天津巴莫科技股份有限公司 The preparation method of lithium-sulfur rechargeable battery anode material
CN110311113A (en) * 2019-07-02 2019-10-08 宁夏汉尧石墨烯储能材料科技有限公司 A kind of anode material for lithium-ion batteries of graphene coated
CN110311113B (en) * 2019-07-02 2021-04-13 宁夏汉尧石墨烯储能材料科技有限公司 Graphene-coated lithium ion battery cathode material
CN111192997A (en) * 2020-01-07 2020-05-22 北京理工大学 Diaphragm for activated carbon-loaded tin oxide lithium-sulfur battery and preparation method and application thereof

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Address before: 300384 in Tianjin Binhai Huayuan Industrial Park (outer ring) 8 Haitai Avenue

Patentee before: Tianjin B & M Science and Technology Joint-Stock Co., Ltd.