CN103515646A - Lithium-sulfur battery with conductive adsorption layer, and application of conductive polymer film - Google Patents

Lithium-sulfur battery with conductive adsorption layer, and application of conductive polymer film Download PDF

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Publication number
CN103515646A
CN103515646A CN201310405682.XA CN201310405682A CN103515646A CN 103515646 A CN103515646 A CN 103515646A CN 201310405682 A CN201310405682 A CN 201310405682A CN 103515646 A CN103515646 A CN 103515646A
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lithium
conducting polymer
sulfur
conductive
adsorption layer
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方静
李强
张凯
覃富荣
李劼
张治安
赖延清
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Central South University
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    • 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
    • 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
    • H01M4/64Carriers or collectors
    • H01M4/66Selection of materials
    • 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 lithium-sulfur battery with a conductive adsorption layer, and an application of a conductive polymer film. The lithium-sulfur battery comprises a sulfur-containing positive electrode sheet, a separation film, and a lithium negative-electrode sheet. A conductive absorption layer is arranged between the sulfur-containing positive electrode sheet and the separation film. The application comprises that the conductive polymer film prepared from a conductive polymer, a conductive agent, and an adhesive is arranged as a conductive absorption layer between the sulfur-containing positive electrode sheet and the separation film of the lithium-sulfur battery, such that the lithium-sulfur battery is prepared. The prepared lithium-sulfur battery has the characteristics of high specific capacity, high coulombic efficiency, and long service life. The conductive polymer film has the advantages of low raw material cost, simple preparation method, and suitability for industrialized productions.

Description

A kind of have the conduction lithium-sulfur cell of adsorption layer and an application of conducting polymer thin film
Technical field
The present invention relates to a kind of have the conduction lithium-sulfur cell of adsorption layer and the application of conducting polymer thin film, belong to lithium-sulfur cell system technical field.
Background technology
Sulphur was suggested and can, for cell positive material, have then occurred Li-S battery the earliest early than 1962.When being applied to serondary lithium battery, suppose to generate completely in discharge process Li 2s, the theoretical specific capacity of sulphur is 1672mAh g -1, theoretical discharge voltage is 2.287V, the electrode theory energy density of secondary lithium-sulfur cell is 2600Wh kg -1, be the current known serondary lithium battery system that energy density is the highest except lithia.
In typical secondary lithium-sulfur cell discharge process, there are two discharge platforms.First discharge platform is 2.4~2.1V, and in this process, elemental sulfur is converted into high valence state polysulfide ion S n 2-(5≤n≤8); Second discharge platform is 2.1~1.5V, and in this process, high valence state polysulfide ion continues to be reduced into lower valency polysulfide ion S n 2-(2≤n≤4) and Li 2s.Result of study shows, the intermediate product polysulfide ion producing in charge and discharge process particularly high valence state polysulfide ion is soluble in organic electrolyte, when it diffuses to the cycle performance that can have a strong impact on secondary lithium-sulfur cell after cathode of lithium generation side reaction generates irreversible lithium sulfide.If intermediate product polysulfide ion moves to negative pole, react with lithium metal self discharge occurs, and then move to positive pole, the interior circulation of secondary lithium-sulfur cell can occur, i.e. so-called " shuttling back and forth " phenomenon, this process can make the coulomb Efficiency Decreasing of battery.In addition, the insulating properties of elemental sulfur and discharging product thereof can cause in electrode active material utilization lower.Different from the density of many lithium sulfides due to sulphur, make in charge and discharge process electrode active material change in volume larger, easily cause the problems such as electrode structure deterioration.The performance that these problems have all restricted secondary lithium-sulfur cell improves.
In recent years, be to solve these problems of sulfur electrode, people from preparing carbon sulphur composite material, electrode structural designs is improved equal angles and has been carried out a lot of useful explorations to addressing these problems.
At present normally by elemental sulfur load (load, adhere to, mixing, epitaxial growth, coated etc.) in all kinds of carbon element class materials with high-specific surface area, high porosity and excellent conductive performance feature, form composite material, to limit the various negative effects that in cyclic process, polysulfide dissolves in electrolyte and causes thus.For example, composite material (the Angew.Chem.Int.Ed. of sulphur/hollow carbon balls, 2011,50,5904-5908.), the composite material of sulphur/carbon nano-tube (Nano Letter, 2011,11,4288-4294.), the composite material of sulphur/Mesoporous Spheres (Angew.Chem.Int.Ed.2012,51,3591 – 3595), composite material (the J.Am.Chem.Soc.2011 of sulphur/graphene oxide, 133,18522 – 18525.) the carbon sulphur composite material such as, these materials have improved the chemical property of lithium-sulfur cell to a great extent.But, being subject to the restriction of the conductivity of material with carbon element own, pore volume, specific area, ubiquity coulombic efficiency is low, side reaction is high causes the problems such as cycle life is short; And exist and make relative complex and the high problem of cost, make lithium-sulfur rechargeable battery be difficult to realize suitability for industrialized production.
Summary of the invention
The lithium-sulfur cell that the present invention is directed to sulfur-bearing positive pole in prior art exist coulombic efficiency low, cause the problems such as cycle life is short, use cost is high because of side reaction, object is to be to provide a kind of lithium-sulfur cell with features such as specific capacity are high, coulomb efficiency is high, have extended cycle life, cost is low, and that this battery is made is simple, with low cost, can large-scale industrial production.
Another object of the present invention is the application that is to provide conducting polymer thin film, conducting polymer thin film is arranged on to the feature that the lithium-sulfur cell making as conduction adsorption layer between the sulfur-bearing positive plate of lithium-sulfur cell and barrier film has height ratio capacity, high coulomb efficiency and has extended cycle life, and use cost is low.
The invention provides a kind of lithium-sulfur cell with conduction adsorption layer, comprise sulfur-bearing positive plate, barrier film, cathode of lithium sheet, between sulfur-bearing positive plate and barrier film, be provided with conduction adsorption layer; The conducting polymer thin film that described conduction adsorption layer is is 0.1~2.0mm by conducting polymer, conductive agent and the bonding agent thickness that make 5~8:1~4:1~4 in mass ratio.
Described conducting polymer thin film prepares by the following method: it is 20~80% slurry that conducting polymer, conductive agent and bonding agent are mixed to form to solid content in solvent, rolls after film forming, at 50~100 ℃ of vacuumize 10~20h, obtains.
Described conducting polymer is polyaniline, polypyrrole, polythiophene, coalescence benzene, p-phenylene vinylene, polyacetylene, gathers one or more during styrene is supportted.
Described conductive agent is one or more in conductive black, carbon nano-tube, carbon fiber, graphite, Graphene.
Described bonding agent is one or more in polytetrafluoroethylene, polyacrylic acid, polyvinylidene fluoride, sodium alginate.
The present invention also provides a kind of application of conducting electricity adsorpting polymerization thing film, and this application is that conducting polymer thin film that conducting polymer, conductive agent and bonding agent are made is arranged on the preparation that is applied to lithium-sulfur cell between the sulfur-bearing positive plate of lithium-sulfur cell and barrier film as conduction adsorption layer.
Described conducting polymer, conductive agent and bonding agent mass ratio are 5~8:1~4:1~4.
Described conducting polymer is polyaniline, polypyrrole, polythiophene, coalescence benzene, p-phenylene vinylene, polyacetylene, gathers one or more during styrene is supportted; Described conductive agent is one or more in conductive black, carbon nano-tube, carbon fiber, graphite, Graphene; Described bonding agent is one or more in polytetrafluoroethylene, polyacrylic acid, polyvinylidene fluoride, sodium alginate.
Described conducting polymer thin film thickness is 0.1~2.0mm.
Described conducting polymer thin film prepares by the following method: it is 20~80% slurry that conducting polymer, conductive agent and bonding agent are mixed to form to solid content in solvent, rolls after film forming, at 50~100 ℃ of vacuumize 10~20h, obtains.
Described solvent is one or more in deionized water, ethanol, NMP.
The electrolyte that lithium-sulfur cell of the present invention can adopt is nonaqueous electrolytic solution, electrolyte solvent is ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate mixed solvent, or be dioxolanes and tetraethyleneglycol dimethyl ether mixed solvent, electrolyte solute is lithium hexafluoro phosphate or trifluoromethyl sulfonic acid lithium.
Described barrier film is porous septum, for a kind of material in polytetrafluoroethylene, polypropylene, polyethylene, Kynoar is made.
In described sulfur-bearing anode pole piece, the quality percentage composition of active material sulphur is 10%~90%.
The preparation method with the lithium-sulfur cell of conduction adsorption layer of the present invention, comprises the following steps:
(1) prepare conducting polymer thin film: conducting polymer, conductive agent and bonding agent are mixed in solvent by the mass ratio of 5~8:1~4:1~4, add a small amount of deionized water and ethanol, by heating water bath, stir 1~5h, the slurry that formation solid content is 20~80%, then slurry is repeatedly rolled on twin rollers to the film that thickness is 0.1~2.0mm, be placed in vacuum drying chamber at 50~100 ℃ of dry 10~20h, obtain conducting polymer thin film;
(2) prepare lithium-sulfur cell: above sulfur-bearing anode pole piece, place successively conducting polymer thin film, barrier film, cathode of lithium sheet and the foam nickel screen of step (1) gained, inject electrolyte, then be pressed into one, after good seal, obtain lithium-sulfur cell.
Beneficial effect of the present invention: the conducting polymer thin film that the present invention is mixed and made into conducting polymer, conductive agent and bonding agent is first arranged between the sulfur-bearing positive plate and barrier film of lithium-sulfur cell as conduction adsorption layer, the lithium-sulfur cell that unexpected discovery makes has higher specific capacity and excellent coulomb efficiency and cyclical stability.The present invention is in the favorite outer discovery of research of lithium-sulfur cell: the conducting polymer thin film that conducting polymer, conductive agent and bonding agent are prepared by certain mass ratio is arranged between sulfur-bearing positive plate and barrier film, this conducting polymer thin film plays booster action to the conductivity of sulfur-bearing positive plate on the one hand, has greatly increased the electric action of sulphur positive pole; Can fine absorption be dissolved in the polysulfide in electrolyte on the other hand, suppress " effect of shuttling back and forth "; Meanwhile, conducting polymer thin film has good elasticity and pliability, can cushion the volumetric expansion that sulphur positive pole produces when discharging and recharging, thereby has effectively improved coulomb efficiency and the cycle performance of sulphur lithium battery.Research shows: lithium-sulfur cell of the present invention is at 0.2C(335mA/g) current density under, for the first time specific discharge capacity between 1350~1560mAh/g, after 100 circulations specific discharge capacity between 860~960mAh/g, and coulomb efficiency nearly 100%.In addition, conducting polymer thin film raw material is cheap, and preparation method is simple, can suitability for industrialized production.
Accompanying drawing explanation
The SEM figure of conducting polymer polyaniline (PANI) adsorption layer that [Fig. 1] obtains for embodiment 1.
The lithium-sulfur cell structural representation that [Fig. 2] obtains for embodiment 1.
The lithium-sulfur cell that [Fig. 3] obtains for embodiment 1 with the lithium-sulfur cell that conduction adsorption layer is not set at 0.2C(335mA/g) 100 circle cycle performance comparison diagrams under current density.
The high rate performance figure of the lithium-sulfur cell that [Fig. 4] obtains for embodiment 1.
Embodiment
Following examples are intended to further illustrate the present invention, rather than limit the scope of the invention.
Embodiment 1
The preparation of conducting polymer polyaniline (PANI) adsorption layer:
Conducting polymer PANI, conductive carbon black and polytetrafluoroethylene (PTFE) are mixed in deionized water by the mass ratio of 8:1:1, heating water bath stirs 2h, the slurry that formation solid content is 80%, then slurry is repeatedly rolled on twin rollers to the film that thickness is 0.5mm, 70 ℃ of dry 12h in vacuum drying chamber, be cut into again the sequin that diameter is 1.0cm, obtain conducting polymer PANI adsorption layer.The SEM figure of conducting polymer PANI adsorption layer as shown in Figure 1.
The preparation of lithium-sulfur cell:
By elemental sulfur, conductive black (SP), Kynoar (PVDF) in mass ratio 8:1:1 in 1-METHYLPYRROLIDONE (NMP) solvent, mix, the slurry that formation solid content is 30% is as positive electrode, be coated on aluminium foil plus plate current-collecting body, in vacuum drying chamber, at 60 ℃, be dried after 12h, be pressed into the anode pole piece that diameter is 1.0cm; Conducting polymer PANI adsorption layer is placed between anode pole piece and porous septum, porous septum another side is placed a slice as the lithium sheet of negative pole, be pressed into one, preparation is with the CR2025 type lithium sulphur secondary button cell of conduction adsorption layer, and its inside battery structural representation is shown in Fig. 2.After making battery, test, battery charging and discharging cut-ff voltage is 1.5~3.0V(vs.Li/Li +), charging and discharging specific capacity is calculated based on elemental sulfur active material, with 0.2C(335mA/g) current density do charge and discharge cycles test, specific discharge capacity is 1560mAh/g for the first time, after 100 circulations, specific capacity is 950mAh/g, and coulomb efficiency nearly 100%, has embodied extraordinary cycle performance, contrasted not containing the lithium-sulfur cell of conducting polymer PANI adsorption layer, its 100 circle cycle performance comparison diagram is shown in Fig. 3 simultaneously.Also it has been carried out to high rate performance test in addition, as shown in Figure 4, the high rate performance that can find it from figure is also very excellent.
Embodiment 2
The preparation of conducting polymer polypyrrole (PPy) adsorption layer:
Conducting polymer PPy, carbon nano-tube and PVDF are mixed in NMP by the mass ratio of 5:4:1, heating water bath stirs 1h, the slurry that formation solid content is 50%, then slurry is repeatedly rolled on twin rollers to the film that thickness is 0.1mm, 60 ℃ of dry 20h in vacuum drying chamber, be cut into again the sequin that diameter is 1.2cm, obtain conducting polymer PPy adsorption layer.
The preparation of lithium-sulfur cell:
By elemental sulfur, SP, PVDF in mass ratio 7:2:1 in nmp solvent, mix, the slurry that formation solid content is 30% is as positive electrode, be coated on aluminium foil plus plate current-collecting body, in vacuum drying chamber, at 60 ℃, be dried after 12h, be pressed into the anode pole piece that diameter is 1.0cm; Conducting polymer PPy adsorption layer is placed between anode pole piece and porous septum, and porous septum another side is placed a slice as the lithium sheet of negative pole, is pressed into one, and preparation is with the CR2025 type lithium sulphur secondary button cell of conduction adsorption layer.After making battery, test, battery charging and discharging cut-ff voltage is 1.5~3.0V(vs.Li/Li +), charging and discharging specific capacity is calculated based on elemental sulfur active material, with 0.2C(335mA/g) current density do charge and discharge cycles test, specific discharge capacity is 1450mAh/g for the first time, after 100 circulations, specific capacity is 900mAh/g, coulomb efficiency nearly 100%, has embodied extraordinary cycle performance.
Embodiment 3
The preparation of conductive polymer poly to styrene support (PEDOT) adsorption layer:
Conducting polymer PEDOT, carbon fiber and PAA are mixed in deionized water by the mass ratio of 5:1:4, heating water bath stirs 5h, the slurry that formation solid content is 60%, then slurry is repeatedly rolled on twin rollers to the film that thickness is 1.5mm, 100 ℃ of dry 10h in vacuum drying chamber, be cut into again the sequin that diameter is 1.5cm, obtain conducting polymer PEDOT adsorption layer.
The preparation of lithium-sulfur cell:
By elemental sulfur, SP, PVDF in mass ratio 6:2:2 in nmp solvent, mix, the slurry that formation solid content is 30% is as positive electrode, be coated on aluminium foil plus plate current-collecting body, in vacuum drying chamber, at 60 ℃, be dried after 12h, be pressed into the anode pole piece that diameter is 1.0cm; Conducting polymer PEDOT adsorption layer is placed between anode pole piece and porous septum, and porous septum another side is placed a slice as the lithium sheet of negative pole, is pressed into one, and preparation is with the CR2025 type lithium sulphur secondary button cell of conduction adsorption layer.After making battery, test, battery charging and discharging cut-ff voltage is 1.5~3.0V(vs.Li/Li +), charging and discharging specific capacity is calculated based on elemental sulfur active material, with 0.2C(335mA/g) current density do charge and discharge cycles test, specific discharge capacity is 1510mAh/g for the first time, after 100 circulations, specific capacity is 920mAh/g, coulomb efficiency nearly 100%, has embodied extraordinary cycle performance.
Embodiment 4
The preparation of conductive polymer poly to phenylacetylene (PPv) adsorption layer:
Conducting polymer PPv, graphite and sodium alginate are mixed in removing alcohol by the mass ratio of 7:2:1, heating water bath stirs 2h, the slurry that formation solid content is 70%, then slurry is repeatedly rolled on twin rollers to the film that thickness is 0.5mm, 50 ℃ of dry 15h in vacuum drying chamber, be cut into again the sequin that diameter is 1.3cm, obtain conducting polymer PPv adsorption layer.
The preparation of lithium-sulfur cell:
By elemental sulfur, SP, PVDF in mass ratio 5:3:2 in nmp solvent, mix, the slurry that formation solid content is 30% is as positive electrode, be coated on aluminium foil plus plate current-collecting body, in vacuum drying chamber, at 60 ℃, be dried after 12h, be pressed into the anode pole piece that diameter is 1.0cm; Conducting polymer PPv adsorption layer is placed between anode pole piece and porous septum, and porous septum another side is placed a slice as the lithium sheet of negative pole, is pressed into one, and preparation is with the CR2025 type lithium sulphur secondary button cell of conduction adsorption layer.After making battery, test, battery charging and discharging cut-ff voltage is 1.5~3.0V(vs.Li/Li +), charging and discharging specific capacity is calculated based on elemental sulfur active material, with 0.2C(335mA/g) current density do charge and discharge cycles test, specific discharge capacity is 1480mAh/g for the first time, after 100 circulations, specific capacity is 880mAh/g, coulomb efficiency nearly 100%, has embodied extraordinary cycle performance.
Embodiment 5
The preparation of conducting polymer polyacetylene (PAC) adsorption layer:
Conducting polymer PAC, Graphene and PAA are mixed in NMP by the mass ratio of 6:2:2, heating water bath stirs 3h, the slurry that formation solid content is 20%, then slurry is repeatedly rolled on twin rollers to the film that thickness is 1.0mm, 80 ℃ of dry 12h in vacuum drying chamber, be cut into again the sequin that diameter is 1.4cm, obtain conducting polymer PAC adsorption layer.
The preparation of lithium-sulfur cell:
By elemental sulfur, SP, PVDF in mass ratio 6:3:1 in nmp solvent, mix, the slurry that formation solid content is 30% is as positive electrode, be coated on aluminium foil plus plate current-collecting body, in vacuum drying chamber, at 60 ℃, be dried after 12h, be pressed into the anode pole piece that diameter is 1.0cm; Conducting polymer PAC adsorption layer is placed between anode pole piece and porous septum, and porous septum another side is placed a slice as the lithium sheet of negative pole, is pressed into one, and preparation is with the CR2025 type lithium sulphur secondary button cell of conduction adsorption layer.After making battery, test, battery charging and discharging cut-ff voltage is 1.5~3.0V(vs.Li/Li +), charging and discharging specific capacity is calculated based on elemental sulfur active material, with 0.2C(335mA/g) current density do charge and discharge cycles test, specific discharge capacity is 1350mAh/g for the first time, after 100 circulations, specific capacity is 860mAh/g, coulomb efficiency nearly 100%, has embodied extraordinary cycle performance.
Embodiment 6
The preparation of conducting polymer polythiophene (Pth) adsorption layer:
Conducting polymer Pth, Graphene and PTFE are mixed in deionized water by the mass ratio of 7:1:2, heating water bath stirs 4h, the slurry that formation solid content is 40%, then slurry is repeatedly rolled on twin rollers to the film that thickness is 0.8mm, 90 ℃ of dry 16h in vacuum drying chamber, be cut into again the sequin that diameter is 1.5cm, obtain conducting polymer Pth adsorption layer.
The preparation of lithium-sulfur cell:
By elemental sulfur, SP, PVDF in mass ratio 8:1:1 in nmp solvent, mix, the slurry that formation solid content is 30% is as positive electrode, be coated on aluminium foil plus plate current-collecting body, in vacuum drying chamber, at 60 ℃, be dried after 12h, be pressed into the anode pole piece that diameter is 1.0cm; Conducting polymer Pth adsorption layer is placed between anode pole piece and porous septum, and porous septum another side is placed a slice as the lithium sheet of negative pole, is pressed into one, and preparation is with the CR2025 type lithium sulphur secondary button cell of conduction adsorption layer.After making battery, test, battery charging and discharging cut-ff voltage is 1.5~3.0V(vs.Li/Li +), charging and discharging specific capacity is calculated based on elemental sulfur active material, with 0.2C(335mA/g) current density do charge and discharge cycles test, specific discharge capacity is 1510mAh/g for the first time, after 100 circulations, specific capacity is 920mAh/g, coulomb efficiency nearly 100%, has embodied extraordinary cycle performance.

Claims (10)

1. a lithium-sulfur cell with conduction adsorption layer, comprises sulfur-bearing positive plate, barrier film, cathode of lithium sheet, it is characterized in that, is provided with conduction adsorption layer between sulfur-bearing positive plate and barrier film; The conducting polymer thin film that described conduction adsorption layer is is 0.1~2.0mm by conducting polymer, conductive agent and the bonding agent thickness that make 5~8:1~4:1~4 in mass ratio.
2. lithium-sulfur cell as claimed in claim 1, it is characterized in that, described conducting polymer thin film prepares by the following method: it is 20~80% slurry that conducting polymer, conductive agent and bonding agent are mixed to form to solid content in solvent, roll after film forming, at 50~100 ℃ of vacuumize 10~20h, obtain.
3. lithium-sulfur cell as claimed in claim 2, is characterized in that, described conducting polymer is polyaniline, polypyrrole, polythiophene, coalescence benzene, p-phenylene vinylene, polyacetylene, gathers one or more during styrene is supportted.
4. lithium-sulfur cell as claimed in claim 2, is characterized in that, described conductive agent is one or more in conductive black, carbon nano-tube, carbon fiber, graphite, Graphene.
5. lithium-sulfur cell as claimed in claim 2, is characterized in that, described bonding agent is one or more in polytetrafluoroethylene, polyacrylic acid, polyvinylidene fluoride, sodium alginate.
6. an application for conducting polymer thin film, is characterized in that, the conducting polymer thin film that conducting polymer, conductive agent and bonding agent are made is arranged on the preparation that is applied to lithium-sulfur cell between the sulfur-bearing positive plate of lithium-sulfur cell and barrier film as conduction adsorption layer.
7. application as claimed in claim 6, is characterized in that, described conducting polymer, conductive agent and bonding agent mass ratio are 5~8:1~4:1~4.
8. application as claimed in claim 7, is characterized in that, described conducting polymer is polyaniline, polypyrrole, polythiophene, coalescence benzene, p-phenylene vinylene, polyacetylene, gathers one or more during styrene is supportted; Described conductive agent is one or more in conductive black, carbon nano-tube, carbon fiber, graphite, Graphene; Described bonding agent is one or more in polytetrafluoroethylene, polyacrylic acid, polyvinylidene fluoride, sodium alginate.
9. application as claimed in claim 6, is characterized in that, described conducting polymer thin film thickness is 0.1~2.0mm.
10. the application as described in claim 6~9 any one, it is characterized in that, described conducting polymer thin film prepares by the following method: it is 20~80% slurry that conducting polymer, conductive agent and bonding agent are mixed to form to solid content in solvent, roll after film forming, at 50~100 ℃ of vacuumize 10~20h, obtain.
CN201310405682.XA 2013-09-09 2013-09-09 Lithium-sulfur battery with conductive adsorption layer, and application of conductive polymer film Pending CN103515646A (en)

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CN103985840A (en) * 2014-06-04 2014-08-13 中国科学院上海硅酸盐研究所 Lithium negative electrode with functional protective layer and lithium sulfur battery
CN104577060A (en) * 2013-10-11 2015-04-29 通用汽车环球科技运作有限责任公司 Porous interlayer for a lithium-sulfur battery
CN104600251A (en) * 2014-12-26 2015-05-06 中南大学 Lithium-sulfur battery positive electrode and preparation method thereof
CN104716382A (en) * 2013-12-15 2015-06-17 中国科学院大连化学物理研究所 Lithium-sulfur battery structure
CN105280867A (en) * 2015-09-18 2016-01-27 长沙矿冶研究院有限责任公司 Modified diaphragm special for Li-S battery, preparation method of modified diaphragm and Li-S battery
CN105552281A (en) * 2014-11-04 2016-05-04 中国电子科技集团公司第十八研究所 Production method of carbon coated diaphragm used for lithium sulfur battery
CN105552282A (en) * 2015-11-13 2016-05-04 北京理工大学 Lithium-sulfur battery based on functional carbon fiber cloth as positive electrode barrier layer
CN105633471A (en) * 2014-11-04 2016-06-01 中国电子科技集团公司第十八研究所 Preparation method of carbon-coated membrane lithium-sulfur battery
CN105720231A (en) * 2014-12-05 2016-06-29 中国科学院大连化学物理研究所 Sulfonated graphene-modified sulfur-carbon electrode and preparation and application thereof
CN106356488A (en) * 2015-07-13 2017-01-25 中国科学院金属研究所 Composite diaphragm for lithium ion battery for lithium-sulfur battery and preparation method and application of composite diaphragm for lithium ion battery
CN106848319A (en) * 2016-12-29 2017-06-13 清华大学深圳研究生院 A kind of lithium-sulfur cell positive plate and the lithium-sulfur cell comprising the positive plate
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CN107394256A (en) * 2017-07-18 2017-11-24 天津工业大学 A kind of long-acting lithium-sulfur cell and preparation method thereof
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CN108774459A (en) * 2018-06-05 2018-11-09 桑德集团有限公司 A kind of coating and preparation method thereof, battery electrode
CN109698365A (en) * 2018-12-05 2019-04-30 上海空间电源研究所 A kind of lithium metal battery with elastic buffer structure
CN109742359A (en) * 2019-01-07 2019-05-10 清华大学深圳研究生院 Lithium sulfur battery anode material, preparation method, positive plate and lithium-sulfur cell
CN109923693A (en) * 2016-08-31 2019-06-21 威廉马歇莱思大学 For the anode of battery, cathode and diaphragm and its manufacturing method and purposes
CN111628208A (en) * 2019-02-27 2020-09-04 中国科学院宁波材料技术与工程研究所 Composite shielding layer of lithium-sulfur battery and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1495937A (en) * 2002-08-07 2004-05-12 三星Sdi株式会社 Positive pole for lithium-sulfur cell, its preparation method and lithium-sulfur cell
CN103050667A (en) * 2012-12-13 2013-04-17 中南大学 Composite anode of multi-layer structure for lithium-sulfur rechargeable battery and preparation method
CN103066255A (en) * 2012-12-26 2013-04-24 浙江工业大学 A nano-metal coated sulfur composite material and applications thereof
CN103208618A (en) * 2013-04-24 2013-07-17 中国科学院苏州纳米技术与纳米仿生研究所 Carbon-sulfur composite positive electrode material of lithium-ion battery and preparation method of material

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1495937A (en) * 2002-08-07 2004-05-12 三星Sdi株式会社 Positive pole for lithium-sulfur cell, its preparation method and lithium-sulfur cell
CN103050667A (en) * 2012-12-13 2013-04-17 中南大学 Composite anode of multi-layer structure for lithium-sulfur rechargeable battery and preparation method
CN103066255A (en) * 2012-12-26 2013-04-24 浙江工业大学 A nano-metal coated sulfur composite material and applications thereof
CN103208618A (en) * 2013-04-24 2013-07-17 中国科学院苏州纳米技术与纳米仿生研究所 Carbon-sulfur composite positive electrode material of lithium-ion battery and preparation method of material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
YU-SHENG SU,ET AL: "Lithium–sulphur batteries with a microporous carbon paper as a bifunctional interlayer", 《NATURE COMMUNICATIONS》 *

Cited By (25)

* Cited by examiner, † Cited by third party
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US10141559B2 (en) 2013-10-11 2018-11-27 GM Global Technology Operations LLC Porous interlayer for a lithium-sulfur battery
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CN104600251A (en) * 2014-12-26 2015-05-06 中南大学 Lithium-sulfur battery positive electrode and preparation method thereof
CN106356488A (en) * 2015-07-13 2017-01-25 中国科学院金属研究所 Composite diaphragm for lithium ion battery for lithium-sulfur battery and preparation method and application of composite diaphragm for lithium ion battery
CN105280867A (en) * 2015-09-18 2016-01-27 长沙矿冶研究院有限责任公司 Modified diaphragm special for Li-S battery, preparation method of modified diaphragm and Li-S battery
CN105552282A (en) * 2015-11-13 2016-05-04 北京理工大学 Lithium-sulfur battery based on functional carbon fiber cloth as positive electrode barrier layer
CN106935773A (en) * 2015-12-31 2017-07-07 中国人民解放军63971部队 A kind of interlayer for lithium-sulfur cell
CN109923693A (en) * 2016-08-31 2019-06-21 威廉马歇莱思大学 For the anode of battery, cathode and diaphragm and its manufacturing method and purposes
CN106848319A (en) * 2016-12-29 2017-06-13 清华大学深圳研究生院 A kind of lithium-sulfur cell positive plate and the lithium-sulfur cell comprising the positive plate
CN106848319B (en) * 2016-12-29 2019-04-26 清华大学深圳研究生院 A kind of lithium-sulfur cell positive plate and the lithium-sulfur cell comprising the positive plate
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CN107394256A (en) * 2017-07-18 2017-11-24 天津工业大学 A kind of long-acting lithium-sulfur cell and preparation method thereof
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CN109698365A (en) * 2018-12-05 2019-04-30 上海空间电源研究所 A kind of lithium metal battery with elastic buffer structure
CN109742359A (en) * 2019-01-07 2019-05-10 清华大学深圳研究生院 Lithium sulfur battery anode material, preparation method, positive plate and lithium-sulfur cell
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Application publication date: 20140115