CN105322132A - Positive electrode of lithium-sulfur battery with multifunctional elastic protection layer - Google Patents
Positive electrode of lithium-sulfur battery with multifunctional elastic protection layer Download PDFInfo
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- CN105322132A CN105322132A CN201410371166.4A CN201410371166A CN105322132A CN 105322132 A CN105322132 A CN 105322132A CN 201410371166 A CN201410371166 A CN 201410371166A CN 105322132 A CN105322132 A CN 105322132A
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Abstract
The invention relates to a positive electrode of a lithium-sulfur battery with a multifunctional elastic protection layer. The positive electrode of the lithium-sulfur battery comprises a positive material layer and the multifunctional elastic protection layer, wherein the multifunctional elastic protection layer is formed on the surface of the positive material layer and comprises a polymer and/or a conductive carbon material; and the thickness of the multifunctional elastic protection layer is 0.1-50 microns. The multifunctional elastic protection layer is introduced to the surface of the positive material layer of the lithium-sulfur battery; the multifunctional elastic protection layer has elasticity and conductivity; and has no influence on charge and discharge processes of the positive electrode of the lithium-sulfur battery; compared with the positive electrode of the lithium-sulfur battery without protection from a multifunctional elastic layer structure, the prepared positive electrode of the lithium-sulfur battery with the protection of the multifunctional elastic layer structure has good stability; a structural damage to the positive electrode caused by the volume effect in a charge-discharge cycle process of the battery can be relieved; and meanwhile, the added multifunctional elastic layer structure can ensure that an active material in the positive electrode is not greatly dissolved into an electrolyte to cause the capacity loss.
Description
Technical field
The present invention relates to and a kind of there is lithium-sulphur cell positive electrode of Multifunctional elastic protective layer and preparation method thereof, belong to lithium-sulfur cell technical field.
Background technology
Since Sony in 1992 issues first commercial li-ion battery, lithium rechargeable battery because open circuit voltage is high, the advantage such as energy density is large, have extended cycle life, memory-less effect, portable mobile apparatus is used widely, is developed rapidly in hybrid vehicle and pure electric automobile simultaneously.Lithium ion battery negative material research and development were also achieving great breakthrough in recent years, and the specific capacity of the materials such as novel silica-based and tinbase all comparatively carbon-based material is improved largely, and can reach 2000 and 990mAhg respectively
-1.But the development of the positive electrode of lithium ion battery is but relatively slower, no matter is the ternary material of layer structure, the LiFePO of polyanionic
4or the LiMn of spinel structure
2o
4theoretical specific capacity is all less than 200mAhg
-1.Sulphur has high specific capacity in electrochemical reaction, and calculate according to 2 electron reactions of every mole of S atom, specific capacity is up to 1675mAhg
-1, be almost LiFePO
4ten times.The theoretical energy density of lithium-sulfur cell is up to 2600WhKg
-1, and elemental sulfur has, and cost is low, advantages of environment protection, and therefore lithium-sulfur rechargeable battery has great development potentiality and wide application prospect.
The sulphur of high-energy-density attracts the interest of cell researchers always, and as far back as 20 sixties in century, it is the thermal cell of positive electrode active materials that General Motors Corporation just proposes with sulphur, and this battery is used for their early stage electric motor car plan.Nearest 10 years, the lithium-sulfur cell research of a new round heated up gradually.Adopt the most successful story of lithium-sulfur cell, surely belong to 2010 07 month, the lithium-sulfur cell that SionPower company makes, as U.S.'s drone power source, its performance is noticeable, unmanned plane leans on rechargeable solar battery daytime, and evening, electric discharge provided power, created the non-stop flight record of 14 days.The immediate objective of its energy density and cycle performance is above 500Wh/kg and 500 circulation respectively.The said firm declares 2016, and its lithium-sulfur cell be allowed to reach 600Wh/kg and 1000 circulation.
Although lithium-sulfur cell has great advantage in raw material sources, cost, energy density and environmental friendliness etc., also there is the not good problem of cycle performance, high rate performance in lithium-sulfur cell.Lithium-sulfur cell Problems existing is, active material elemental sulfur and discharging product lithium sulfide, is all the insulator of electronics and ion, causes very large puzzlement to transmission electric charge; Intermediate product polysulfide is in the electrolyte soluble, and to negative pole migration, causes the rapid decay of active material loss and capacity; In addition, in course of reaction, because the density variation between active material sulphur and discharging product lithium sulfide, in discharge process, positive pole will expand, and huge bulk effect can destroy anode structure.
The physical property such as the electrochemical reaction process of sulfur-bearing positive pole complexity and non-conductive and bulk effect determines the research and development difficult point of lithium-sulfur cell mainly at positive electrode.In order to solve lithium-sulfur cell Problems existing, in cathode material structure, that the material with carbon element of elemental sulfur and loose structure is carried out compound to improve the conductivity of electrode, the polysulfide produced in the pore structure adsorption reaction process simultaneously utilizing material with carbon element to enrich, suppress polysulfide dissolving diffusion in the electrolytic solution, weaken shuttle back and forth effect and self-discharge phenomenon (J.Mater.Chem., 2010,20,9821 – 9826).But the porous carbon structure complicated process of preparation of complexity, aperture is difficult to regulation and control, and the loose structure of material with carbon element, to the limited sorption capacity of polysulfide, is difficult to prepare the high composite positive pole carrying sulfur content.In lithium anode, in order to suppress effect of shuttling back and forth, a small amount of additive can be added in the electrolytic solution, forming at metallic lithium surface the overreaction (patent No. US20040081894) that passivating film prevents many lithium sulfides and lithium metal.In addition, in the structure optimization of lithium-sulfur cell, between sulfur electrode and barrier film, add one deck conductive nano carbon fiber paper, utilize the middle discharging product (US20140050973) of high-specific surface area absorption of conductive nano carbon fiber.
Adopt said method to be merely able to suppress effect of shuttling back and forth to a certain extent, improve the cycle performance of battery, and the rapid decay of the structural deterioration that the enormousness effect that in charge and discharge process, positive pole produces causes and cycle performance not yet causes enough attention at present.
Summary of the invention
The object of the invention is to propose a kind ofly there is lithium-sulphur cell positive electrode of Multifunctional elastic protective layer and preparation method thereof, to solve the problems referred to above existed in existing lithium-sulfur cell.
At this; the invention provides a kind of lithium-sulphur cell positive electrode with Multifunctional elastic protective layer; described lithium-sulphur cell positive electrode comprises positive electrode material layer and is formed at the Multifunctional elastic protective layer comprising polymer and/or conductive carbon material on described positive electrode material layer surface, and the thickness of described Multifunctional elastic protective layer is 0.1 ~ 50 μm.
The present invention introduces Multifunctional elastic protective layer on the surface of lithium sulfur battery anode material layer, this Multifunctional elastic protective layer has elasticity and conductivity, and on the charge and discharge process of lithium-sulphur cell positive electrode without impact, compared with not increasing the lithium-sulphur cell positive electrode of multi-capable elastic structural defence, the lithium-sulphur cell positive electrode with multi-capable elastic structural defence prepared according to the present invention has good stability, positive pole can be alleviated in battery charging and discharging cyclic process because of structural deterioration that bulk effect causes, the Multifunctional elastic Rotating fields simultaneously increased can ensure that the active material in positive pole can not be dissolved in electrolyte in a large number and cause capacitance loss.
Preferably, the positive electrode in described positive electrode material layer select in bright sulfur positive electrode, sulphur/carbon composite, sulphur/conducting polymer composite material, sulphur/oxide composite, sulphur/sulfide polymer composite material any one.
Preferably, described polymer is at least one in polyacrylonitrile, Kynoar, polyoxyethylene, polymethyl methacrylate, Kynoar-hexafluoropropylene, polyvinyl butyral resin, polyvinylpyrrolidone, polypyrrole, polyaniline and polythiophene.
Preferably, polymer and conductive carbon material is contained in described Multifunctional elastic protective layer.Wherein, the mass ratio of described polymer and described conductive carbon material can be 100:(1 ~ 100).
Preferably, described conductive carbon material is at least one in carbon fiber, carbon nano-tube, Graphene, acetylene black, superconduction carbon black (Super-P) and Ketjen black.
Preferably, also filler is contained in described Multifunctional elastic protective layer.In described Multifunctional elastic protective layer, the mass ratio of described polymer and described filler can be 100:(1 ~ 50).
Preferably, SiO selected by described filler
2, Al
2o
3, Fe
2o
3, ZrO
2, MgO, ZnO
2, TiO
2, LiTaO
3, glass, γ-LiAlO
2, BaTiO
3, clay, imvite, zeolite, LiN
3, LiAg
4i
5, Li
0.5la
0.5tiO
3, NASICON type Li
(1+x)al
xti
(2-x)p
3o
12and Li
(1+x)al
xge
(2-x)p
3o
12pottery or glass ceramics, LISICON type lithium ceramic electrolyte, oxide type lead at least one in lithium glass, glassy state sulfide, the powder of Garnet structure electrolysis matter, butyl titanate, aluminium isopropoxide, tetraethoxysilane and zirconium iso-propoxide.
Preferably, described lithium-sulphur cell positive electrode also comprises the matrix supporting described positive electrode material layer, and described matrix is metal collector or conducting film.
Preferably, institute's metal collector comprises aluminium foil and plating carbon aluminium foil.
Preferably, described conducting film is any one in conduction carbon paper, conductive carbon fibre cloth, conductive porous metal film, conductive foam metal film, conductive porous oxidation film, conductive carbon nanotube periosteum, conductive graphene film, conductive polymer membrane.
Preferably; described Multifunctional elastic protective layer is formed at the surface of described positive electrode material layer by physical method or chemical method, described physical method or chemical method comprise in method of electrostatic spinning, spin-coating method, ink-jet printing process, the tape casting, dip-coating method, magnetron sputtering method, physical vapour deposition (PVD) and chemical vapour deposition (CVD) any one.
Accompanying drawing explanation
Fig. 1 is the lithium-sulphur cell positive electrode structural representation that the present invention has Multifunctional elastic protective layer;
Fig. 2 is that lithium-sulfur cell adopts the first charge-discharge curve without the lithium-sulphur cell positive electrode of Multifunctional elastic protective layer;
Fig. 3 is that in the present invention, lithium-sulfur cell adopts the first charge-discharge curve with the lithium-sulphur cell positive electrode of Multifunctional elastic protective layer;
Fig. 4 is the lithium-sulphur cell positive electrode without Multifunctional elastic protective layer at charge and discharge cycles electron scanning micrograph after 100 weeks;
Fig. 5 is the present invention's lithium-sulphur cell positive electrode with Multifunctional elastic protective layer of adopting method of electrostatic spinning to prepare at charge and discharge cycles electron scanning micrograph after 100 weeks;
Fig. 6 is the cross-sectional scanning electron microphotograph with the lithium-sulphur cell positive electrode of Multifunctional elastic protective layer that the present invention adopts the method for inkjet printing to prepare.
Embodiment
Further illustrate the present invention below in conjunction with accompanying drawing and following execution mode, should be understood that accompanying drawing and following execution mode are only for illustration of the present invention, and unrestricted the present invention.
The invention provides a kind of lithium-sulphur cell positive electrode with Multifunctional elastic protective layer, described lithium-sulphur cell positive electrode comprises positive electrode material layer and is formed at the Multifunctional elastic protective layer on described positive electrode material layer surface.
Positive electrode active materials in positive electrode material layer without particular limitation of, it can be known any lithium sulfur battery anode material, such as can be bright sulfur positive electrode, sulphur/electric conducting material composite material, particularly, can select in bright sulfur positive electrode, sulphur/carbon composite, sulphur/conducting polymer composite material, sulphur/oxide composite, sulphur/sulfide polymer composite material any one.
Also conductive agent and/or binding agent can be contained in positive electrode material layer.This conductive agent can be one in the conductive carbon materials such as carbon black, acetylene black, Ketjen black or mixture, also can be have excellent electric conductivity can the material with carbon element such as carbon fiber, carbon pipe, Graphene.This binding agent can be the organic system such as Kynoar or polytetrafluoroethylene binding agent, also can be CMC and the water-based binder such as butadiene-styrene rubber, sodium alginate.
The thickness of positive electrode material layer is not particularly limited, and can adopt the general thickness of lithium sulfur battery anode material layer, such as, can be 10 ~ 500 μm.
Positive electrode material layer can be formed at collector or conducting film surface and form positive plate, also can be formed as unsupported cathode film.As collector, conventional lithium-sulphur cell positive electrode collector can be selected, such as, can be aluminium foil, plating carbon aluminium foil etc.Conducting film can select in conductive carbon paper, conductive carbon fibre cloth, conductive porous metal film, conductive foam metal film, conductive porous oxidation film, conductive carbon nanotube periosteum, conductive graphene film, conductive polymer membrane any one.
The preparation method of positive electrode material layer does not limit, such as, the mode of coating can be adopted prefabricated.In one example, the positive electrode material layer being formed as positive plate obtains by the following method: sulphur and conductive black, binding agent are mixed into slurry, after coating collector or conducting film surface through drying, roll-in and cut and obtain electrode slice.In another example, be formed as positive plate positive electrode material layer to obtain by the following method: after the mixture of sulphur and electric conducting material is heat-treated, be mixed into slurry with conductive black, binding agent again, after coating collector or conducting film surface through drying, roll-in and cut and obtain electrode slice.In another example, the preparation method of unsupported cathode film comprises the steps: Graphene ultrasonic disperse in water, add sodium thiosulfate to stir, by dripping hydrochloric acid, sodium thiosulfate being hydrolyzed at graphenic surface generation nano-sulfur, obtaining unsupported Graphene/sulphur cell positive electrode film finally by suction filtration.
The Multifunctional elastic protective layer being arranged in positive electrode material layer surface comprises polymer and/or conductive carbon material.In addition, also filler can be contained.When the mixture containing polymer and conductive carbon material, the mass ratio of polymer and conductive carbon material can be 100:(1 ~ 100).When mixture (or also containing conductive carbon material) containing polymer and filler, the mass ratio of polymer and filler can be 100:(1 ~ 50).Multifunctional elastic protective layer is owing to having elasticity and conductivity containing these materials; positive pole can be alleviated in battery charging and discharging cyclic process because of structural deterioration that bulk effect causes; play shielding action again, the active material that can ensure in positive pole can not be dissolved in electrolyte in a large number and cause capacitance loss.
Wherein conductive carbon material includes but not limited at least one in carbon fiber, carbon nano-tube, Graphene, acetylene black, Super-p and Ketjen black.Polymer includes but not limited at least one in polyacrylonitrile, Kynoar, polyoxyethylene, polymethyl methacrylate, Kynoar-hexafluoropropylene, polyvinyl butyral resin, polyvinylpyrrolidone, polypyrrole, polyaniline and polythiophene.
The thickness of Multifunctional elastic protective layer is preferably 0.1 ~ 50 μm.
In Multifunctional elastic protective layer, filler includes but not limited to SiO
2, Al
2o
3, Fe
2o
3, ZrO
2, MgO, ZnO
2, TiO
2, LiTaO
3, glass, γ-LiAlO
2, BaTiO
3, clay, imvite, zeolite, LiN
3, LiAg
4i
5, Li
0.5la
0.5tiO
3, NASICON type Li
(1+x)al
xti
(2-x)p
3o
12and Li
(1+x)al
xge
(2-x)p
3o
12pottery or glass ceramics, LISICON type lithium ceramic electrolyte, oxide type lead at least one in lithium glass, glassy state sulfide, the powder of Garnet structure electrolysis matter, butyl titanate, aluminium isopropoxide, tetraethoxysilane and zirconium iso-propoxide.
When preparing containing Packed Multifunctional elastic protective layer; raw material also preferably includes appropriate plasticizer, and plasticizer includes but not limited to Polyethylene glycol dimethyl ether, repefral, phthalic acid diethyl, ester dibutyl phthalate, dioctyl phthalate.The consumption of plasticizer can be 0.5 ~ 5wt% of polymer.
Multifunctional elastic protective layer can be formed at the surface of positive electrode material layer by physical method or chemical method, such as, by method of electrostatic spinning, spin-coating method, ink-jet printing process, the tape casting, dip-coating method, magnetron sputtering method, physical vapour deposition (PVD) and chemical vapour deposition (CVD) etc.These method costs are low, technique is simple, environmental friendliness and can be easy to the thickness controlling Multifunctional elastic protective layer.
In one example, Multifunctional elastic protective layer is formed at the surface of positive electrode material layer by method of electrostatic spinning, can comprise the following steps:
I) mixture of polymer or polymer and material with carbon element is dissolved in solvent, is prepared into uniform solution;
Ii) solution is transferred in the syringe of electrostatic spinning machine, by the effect of electric field, at pre-lithium sulfur battery anode material layer surface coverage one deck nanofiber (Multifunctional elastic protective layer) obtained.
In another example, Multifunctional elastic protective layer is formed at the surface of positive electrode material layer by spin-coating method, can comprise the following steps:
I) mixture of polymer or polymer and filler and plasticizer is dissolved in solvent, is prepared into uniform solution;
Ii) lithium sulfur battery anode material layer is positioned on the working face of spin coating instrument; solution is dropped in described positive electrode material layer surface; the film that thickness is homogeneous is formed after spin coating; by naturally volatilizing and/or vacuum drying method removal solvent, the lithium-sulphur cell positive electrode of protective layer structure must be had.
Should be understood that the raw material in above-mentioned example is not limited to addressed raw material, such as, in the example of above-mentioned spin-coating method, also can also simultaneously containing conductive carbon material etc. in raw material.
Fig. 1 illustrates the lithium-sulphur cell positive electrode structural representation with Multifunctional elastic protective layer of the present invention's example, and in this example, lithium-sulphur cell positive electrode comprises the collector 1, positive electrode material layer 2 and the Multifunctional elastic protective layer 3 that stack gradually.Fig. 6 illustrates the cross-sectional scanning electron microphotograph with the lithium-sulphur cell positive electrode of Multifunctional elastic protective layer of the present invention's example; as shown in Figure 6; this lithium-sulphur cell positive electrode comprises the collector (aluminium foil), positive electrode material layer and the Multifunctional elastic protective layer that stack gradually, and wherein the thickness of Multifunctional elastic protective layer is 5.2 μm.But should be understood that lithium-sulphur cell positive electrode of the present invention also can not comprise collector.
Fig. 2 illustrates that lithium-sulfur cell adopts the first charge-discharge curve without the lithium-sulphur cell positive electrode of Multifunctional elastic protective layer, and Fig. 3 illustrates the first charge-discharge curve with the lithium-sulphur cell positive electrode of Multifunctional elastic protective layer (layers of nanofibers) of the present invention's example.As shown in Figure 2, due to the effect of shuttling back and forth not having protective layer to stop reaction intermediate many lithium sulfides, battery occurs certain overcharging phenomenon.As shown in Figure 3, this battery first discharge capacity more than 1100mAhg
-1, and because layers of nanofibers is to the barrier effect of many lithium sulfides, battery does not occur overcharging phenomenon.It can thus be appreciated that lithium-sulphur cell positive electrode of the present invention can suppress over-charging of battery phenomenon.
Fig. 4 illustrates that the lithium-sulphur cell positive electrode without Multifunctional elastic protective layer is at charge and discharge cycles 100 weeks rear electron scanning micrographs, and Fig. 5 illustrates the lithium-sulphur cell positive electrode with Multifunctional elastic protective layer of the present invention's example.At charge and discharge cycles 100 weeks rear electron scanning micrographs.As can be seen from Figure 4, owing to not having the bulk effect in protective layer buffering positive pole charge and discharge process, electrode structure has suffered certain destruction.As can be seen from Figure 5, the 100 weeks rear electrode structures that circulate still can keep complete.It can thus be appreciated that lithium-sulphur cell positive electrode of the present invention has good structural stability.
The present invention adopts physical method or chemical method to increase Multifunctional elastic protective layer at the pre-lithium sulphur positive electrode surface obtained, and obtains the lithium-sulphur cell positive electrode with surface enhanced, protected effect.And this sulphur positive pole is applied in lithium-sulfur cell, this novel lithium-sulphur cell positive electrode can keep the complete of sulphur anode structure in the cyclic process of battery, its structural damage can not be caused because of the bulk effect in charge and discharge process and effect of shuttling back and forth, obtain higher chemical property.Preparation method of the present invention has the advantages such as cost is low, technique simple, environmental friendliness, protective layer thickness are controlled.
Exemplify embodiment below further to describe the present invention in detail.Should understand equally; following examples are only used to further illustrate the present invention; can not be interpreted as limiting the scope of the invention, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjustment all belong to protection scope of the present invention.The technological parameter etc. that following example is concrete is also only an example in OK range, and namely those skilled in the art can be done in suitable scope by explanation herein and select, and do not really want the concrete numerical value being defined in Examples below.
Embodiment 1
One, conductive agent Ketjen black is mixed by ball milling in aqueous solvent with sublimed sulfur and binding agent butadiene-styrene rubber carboxylic & methylcellulose, in slurry, the mass ratio of conductive agent Ketjen black, sublimed sulfur and binding agent is 40:50:10, aluminium foil carries out be coated with post-drying and prepares the pre-lithium-sulphur cell positive electrode obtained;
Two, the ratio being 1:1 by acetylene black, polyacrylonitrile according to mass ratio is dissolved in nitrogen, in nitrogen-dimethyl formamide solution, obtains precursor solution after stirring;
Three, transfer in the syringe of electrostatic spinning machine by precursor solution, direct voltage is 15KV, and operating distance is 15cm, and collect nanofiber with the pre-lithium-sulphur cell positive electrode obtained, after dry, roll-in obtains the lithium-sulphur cell positive electrode with nanofiber protective layer structure.Adopt this electrode as positive pole using lithium metal as to electrode assembling CR2025 button cell, electrolyte adopts and adds 0.1mol/LLiNO
3the LiTFSIDME/DOL of 1mol/L.Battery first charge-discharge curve as shown in Figure 3, this battery first discharge capacity more than 1100mAhg
-1.And because layers of nanofibers is to the barrier effect of many lithium sulfides, battery does not occur overcharging phenomenon.Circulate 100 weeks rear electrode surfaces stereoscan photograph as shown in Figure 5, electrode structure still can keep complete.
Comparative example 1
Conductive agent Ketjen black is mixed (proportioning of each raw material and ball milling method are with embodiment 1) by ball milling with sublimed sulfur and binding agent butadiene-styrene rubber carboxylic & methylcellulose in aqueous solvent, aluminium foil carries out coating post-drying and prepares lithium-sulphur cell positive electrode.Adopt this electrode as positive pole using lithium metal as to electrode assembling CR2025 button cell, electrolyte adopts and adds 0.1mol/LLiNO
3the LiTFSIDME/DOL of 1mol/L.First charge-discharge curve as shown in Figure 2.Due to the effect of shuttling back and forth not having protective layer to stop reaction intermediate many lithium sulfides, battery occurs certain overcharging phenomenon.Circulate 100 weeks rear electrode surfaces stereoscan photograph as shown in Figure 4, owing to not having protective layer to cushion bulk effect in positive pole charge and discharge process, electrode structure has suffered certain destruction.
Embodiment 2
One, conductive agent Ketjen black is mixed by ball milling with sublimed sulfur and binding agent Kynoar in solvent N-methyl pyrilidone make slurry, in slurry, the mass ratio of conductive agent Ketjen black, sublimed sulfur and binding agent is 40:50:10, aluminium foil carries out coating post-drying, after solvent evaporates, carries out vacuumize prepare the pre-lithium-sulphur cell positive electrode obtained;
Two, conductive graphitized materials is selected; adopt nanometer printer in the pre-lithium-sulphur cell positive electrode surface preparation porous conductive layer obtained; after dry, roll-in obtains the lithium-sulphur cell positive electrode with elastic layer structural defence; the thickness of protective layer is about 5.2 μm, and the cross-sectional scanning electron microphotograph of this lithium-sulphur cell positive electrode as shown in Figure 6.Adopt this electrode as positive pole using lithium metal as to electrode assembling CR2025 button cell, Electrochemical Characterization result shows, and the effect of shuttling back and forth of lithium-sulfur cell obtains suppression to a great extent, and cycle performance also increases.
Embodiment 3
One, conductive agent Ketjen black is mixed by ball milling with sublimed sulfur and binding agent butadiene-styrene rubber carboxylic & methylcellulose in aqueous solvent make slurry, in slurry, the mass ratio of conductive agent Ketjen black, sublimed sulfur and binding agent is 40:50:10, aluminium foil carries out coating post-drying, after solvent evaporates, carries out vacuumize prepare the pre-lithium-sulphur cell positive electrode obtained;
Two, take acetonitrile as 100wt%, by 1wt% carbon nano-tube, 10wt% nanometer Al
2o
3be dispersed in middle acetonitrile, then add polyoxyethylene (PEO) and 5wt% plasticizer Polyethylene glycol dimethyl ether (PEGDME), after stirring 6-12h, obtain the precursor solution of thickness;
Three, adopt spin-coating method this precursor solution to be coated in the pre-lithium-sulphur cell positive electrode surface obtained, after solvent evaporates drying, roll-in obtains the lithium-sulphur cell positive electrode with elastic layer structural defence.The thickness of elastic layer is 1-5 μm.Adopt this electrode as positive pole using lithium metal as to electrode assembling CR2025 button cell, charge-discharge test result shows, the utilance of active material is about 75%, and after circulating 50 weeks, the capability retention of battery is 80%, shows good cycle performance.
Embodiment 4
One, sulphur is dissolved into CS
2in be prepared into homogeneous solution, then by polypyrrole nano line dispersion in the solution, in solution, the mass ratio of polypyrrole nano line and sulphur is 2:3, namely the polypyrrole nano line suction filtration film forming of Surface coating sulphur is prepared pre-must lithium-sulphur cell positive electrode;
Two, take acetone as 100wt%, by 10wt% acetylene black, 5wt%Li (1+x) Ti (2
-x) AlxP3O12 is scattered in acetone, then adds Kynoar-hexafluoropropylene (PVDF-HFP), prepares homogeneous precursor solution;
Three, adopt czochralski method precursor solution to be coated in the pre-lithium-sulphur cell positive electrode surface obtained, after drying, obtain the lithium-sulphur cell positive electrode with elastic layer structural defence.Charge-discharge test result shows, this lithium-sulphur cell positive electrode has higher discharge capacity first and good cycle performance.
Industrial applicability: the lithium-sulphur cell positive electrode with Multifunctional elastic protective layer of the present invention has surface enhanced, protected effect; lithium-sulfur cell can be applied to; this novel lithium-sulphur cell positive electrode can keep the complete of sulphur anode structure in the cyclic process of battery; its structural damage can not be caused because of the bulk effect in charge and discharge process and effect of shuttling back and forth, obtain higher chemical property.
Claims (9)
1. one kind has the lithium-sulphur cell positive electrode of Multifunctional elastic protective layer; it is characterized in that; comprise positive electrode material layer and be formed at the Multifunctional elastic protective layer comprising polymer and/or conductive carbon material on described positive electrode material layer surface, the thickness of described Multifunctional elastic protective layer is 0.1 ~ 50 μm.
2. the lithium-sulphur cell positive electrode with Multifunctional elastic protective layer according to claim 1; it is characterized in that, the positive electrode in described positive electrode material layer select in bright sulfur positive electrode, sulphur/carbon composite, sulphur/conducting polymer composite material, sulphur/oxide composite, sulphur/sulfide polymer composite material any one.
3. the lithium-sulphur cell positive electrode with Multifunctional elastic protective layer according to claim 1 and 2; it is characterized in that, described polymer is at least one in polyacrylonitrile, Kynoar, polyoxyethylene, polymethyl methacrylate, Kynoar-hexafluoropropylene, polyvinyl butyral resin, polyvinylpyrrolidone, polypyrrole, polyaniline and polythiophene.
4. the lithium-sulphur cell positive electrode with Multifunctional elastic protective layer according to any one of claim 1 to 3; it is characterized in that; containing polymer and conductive carbon material in described Multifunctional elastic protective layer, the mass ratio of wherein said polymer and conductive carbon material is 100:(1 ~ 100).
5. the lithium-sulphur cell positive electrode with Multifunctional elastic protective layer according to claim 4, is characterized in that, described conductive carbon material is at least one in carbon fiber, carbon nano-tube, Graphene, acetylene black, superconduction carbon black and Ketjen black.
6. the lithium-sulphur cell positive electrode with Multifunctional elastic protective layer according to any one of claim 1 to 5; it is characterized in that; also containing filler in described Multifunctional elastic protective layer; in described Multifunctional elastic protective layer, the mass ratio of described polymer and described filler is 100:(1 ~ 50).
7. want the lithium-sulphur cell positive electrode with Multifunctional elastic protective layer described in 6 according to right, it is characterized in that, SiO selected by described filler
2, Al
2o
3, Fe
2o
3, ZrO
2, MgO, ZnO
2, TiO
2, LiTaO
3, glass, γ-LiAlO
2, BaTiO
3, clay, imvite, zeolite, LiN
3, LiAg
4i
5, Li
0.5la
0.5tiO
3, NASICON type Li
(1+x)al
xti
(2-x)p
3o
12and Li
(1+x)al
xge
(2-x)p
3o
12pottery or glass ceramics, LISICON type lithium ceramic electrolyte, oxide type lead at least one in lithium glass, glassy state sulfide, the powder of Garnet structure electrolysis matter, butyl titanate, aluminium isopropoxide, tetraethoxysilane and zirconium iso-propoxide.
8. the lithium-sulphur cell positive electrode with Multifunctional elastic protective layer according to any one of claim 1 to 7; it is characterized in that; described lithium-sulphur cell positive electrode also comprises the matrix supporting described positive electrode material layer; described matrix is metal collector or conducting film; institute's metal collector comprises aluminium foil and plating carbon aluminium foil, and described conducting film is any one in conduction carbon paper, conductive carbon fibre cloth, conductive porous metal film, conductive porous oxidation film, conductive carbon nanotube periosteum, conductive graphene film, conductive polymer membrane.
9. the lithium-sulphur cell positive electrode with Multifunctional elastic protective layer according to any one of claim 1 to 8; it is characterized in that; described Multifunctional elastic protective layer is formed at the surface of described positive electrode material layer by physical method or chemical method, described physical method or chemical method comprise in method of electrostatic spinning, spin-coating method, ink-jet printing process, the tape casting, dip-coating method, magnetron sputtering method, physical vapour deposition (PVD) and chemical vapour deposition (CVD) any one.
Priority Applications (1)
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