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 PDFInfo
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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
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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
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.
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.
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