CN104300128A - Integrated membrane electrode structure for lithium sulfur battery and preparation method thereof - Google Patents
Integrated membrane electrode structure for lithium sulfur battery and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an integrated membrane electrode structure for a lithium sulfur battery and a preparation method thereof. The structure is composed of two overlapped layers subjected to thermal compounding, one layer is a carbon material modified porous membrane, and the other layer is a sulfur composite material layer on a current collector. The integrated electrode not only effectively reduces the contact resistance of the lithium sulfur battery, and the modified porous membrane material can be more effective in adsorption of polysulfide dissolved from the sulfur compound layer, so as to reuse polysulfide in dissolving loss and improve the coulombic efficiency and cycle stability of the lithium sulfur battery.
Description
Technical field
The present invention relates to lithium-sulfur cell membrane electrode and preparation method thereof, particularly a kind of film electrode structure and preparation method thereof.
Background technology
In recent years, along with the continuous progress of science and technology, the fast development of various electronic product, requires that chemical power source used has the features such as quality is light, volume is little, capacity is large.Want the demand adapting to society, increase substantially the energy density of battery, the exploitation of new material and new system is necessary.
Lithium-sulfur cell adopts sulphur to be positive pole, and lithium is negative pole, and operating mechanism is that when being based upon electric discharge, sulfur molecule is reduced many lithium sulfides of synthetic time series finally form Li gradually
2s completes the non-topology conversion course of reaction of two electro transfer.Theoretical specific capacity is 1672mAh/g, and theoretical specific energy can reach 2600Wh/Kg.Sulphur rich reserves in addition, cost is low, environmental friendliness.These are all the speciality of this type of secondary cell most attraction.But study nearly 30 years, except the Applied D emonstration of fewer companies in high-end field in recent years, lithium-sulfur cell still can not be commercially produced.This is because intrinsic some major defects of battery self are not also well solved, mainly contain: it is much lower compared with theoretical value 1) to flow positive pole actual discharge specific capacity; 2) coulombic efficiency is low." the shuttle back and forth effect " of this two point defect all because occurring in inside battery: elemental sulfur reduction or sulfide-oxidation all can experience solubility polysulfide Li
2s
n(3≤n≤6) intermediate product, these polysulfides are diffused into cathode of lithium side through barrier film, are reduced and generate insoluble Li
2s/Li
2s
2.Once lithium surface is completely covered, follow-up diffusion and come S
n 2-be convenient to Li
2s/Li
2s
2there is disproportionated reaction and generate polysulfide S comparatively at a low price
n-x 2-, these S
n-x 2-get back to again positive pole check weighing through diffusion and be newly oxidized to S
n 2-.Above-mentioned effect of shuttling back and forth exists in cell operation always, shows as in discharge process the utilance reducing active material, and charging process reduces coulombic efficiency.3) circulating battery capacity attenuation is serious.Mainly deposited the insoluble Li of the insulation departed from completely with electronic conductor gradually because survey at positive pole
2s/Li
2s
2caking, causes the loss of active material sulphur.In addition, the stress that the change in volume that positive and negative pole material is huge is formed also can cause the destruction of electrode structure.4) reversibility of electrode and high rate capability poor.This is sulphur and reduzate Li thereof
2s/Li
2s
2insulating properties own causes.
Want these problems to improve, reach practical level, the loss by dissolution of suppression polysulfide of will trying every possible means, improves the cyclical stability of battery while improving battery coulombic efficiency.
At present, slurry normally by sulphurous materials, conductive additive and binding agent are made slurry in a solvent according to the dispersion of certain ratio, and to be directly coated in aluminum foil current collector and to dry and obtain by lithium-sulphur cell positive electrode.
Chinese patent (application number 201210032447.8) discloses a kind of preparation method of positive pole plate of lithium-sulfur cell.Chinese patent (application number 201010513866.4) discloses a kind of preparation method of positive pole plate of lithium-sulfur cell.Chinese patent (application number 200710122444.2) discloses a kind of preparation method of positive pole plate of lithium-sulfur cell.These methods provide different electrode preparation methods, but these methods ten thousand become not from wherein, are all structures of open type, effectively can not suppress the dissolving of polysulfide and the self-discharge processes of elemental sulfur, thus the object improving battery coulombic efficiency and cyclical stability can not be reached.
The present invention is directed to above-mentioned shortcoming, provide a kind of novel lithium-sulfur cell film electrode structure, the integrated electrode of this electrode structure, is composited by two layer materials, and one deck is the perforated membrane of material with carbon element modification, and one deck is the elemental sulfur composite material layer on collector.This integrated electrode not only efficiently reduces the contact resistance of lithium-sulfur cell, and the porous film material of modification can effectively adsorb the polysulfide dissolved from sulfur compound layer, and can electronics be provided well to the polysulfide dissolved, the polysulfide of generation loss by dissolution is recycled, improves coulombic efficiency and the cyclical stability of lithium-sulfur cell.When it is used as lithium-sulfur cell membrane electrode, discharge capacity 1400mAh/g-S first, circulate 50 times, discharge capacitance is greater than 96%.
Summary of the invention
The object of the present invention is to provide a kind of novel lithium-sulfur cell film electrode structure and preparation method thereof.
For achieving the above object, the technical solution used in the present invention is:
Prepare integrated film electrode, be composited by two layer materials, one deck is the perforated membrane of material with carbon element modification, and one deck is the elemental sulfur composite material layer on collector.Described sulfur compound layer is the mixture of the sulfur compound of sulfur content 10 ~ 95%, conductive agent and binding agent, and wherein the mass ratio of sulfur compound, conductive agent and binding agent is 1:(0 ~ 1): (0.01 ~ 0.5); The perforated membrane of described material with carbon element modification is the perforated membrane that the mixture of porous carbon and binding agent applies, and wherein the mass ratio of porous carbon and binding agent is 1:(0.01 ~ 0.5).
Sulphur composite layer thickness is 10 μm ~ 200 μm, preferably 20 ~ 100 μm;
In the perforated membrane of described porous carbon coating, the thickness of porous carbon layer is 50 μm ~ 200 μm, and pore-size distribution district is at 50nm ~ 500nm; The thickness of perforated membrane is 10 ~ 100 μm, and porosity is 30%-50%, and pore-size distribution district is at 5nm ~ 100nm.
In described porous carbon coat, porous carbon is one or more in carbon nano-tube, carbon nano-fiber, activated carbon, carbon gel, carbon black.
Described sulfur compound is one or two or more kinds in carbon sulphur composite material, sulphur-conducting polymer composite material and sulphur-metal oxide composite;
Described carbon sulphur composite material elemental sulfur is mixed material with carbon element to be formed, material with carbon element is wherein as filling the cathode material before sulphur, and it is one or two or more kinds mixture in active carbon, charcoal-aero gel, Graphene, graphite oxide, expanded graphite, carbon nano-tube, carbon nano-fiber, mesoporous carbon;
Described sulphur-conducting polymer composite material elemental sulfur is mixed conducting polymer to be formed, and conducting polymer is wherein as filling the cathode material before sulphur, and it is one or two or more kinds mixture in polyaniline, polypyrrole, polythiophene; Sulphur-metal oxide composite elemental sulfur is mixed metal oxide to be formed, and metal oxide is wherein as filling the cathode material before sulphur, and it is one or two or more kinds mixture of yittrium oxide, lanthana, cerium oxide, titanium oxide.
Described conductive agent is one or two or more kinds in acetylene black, carbon black, graphite, carbon nano-tube, carbon nano-fiber, mesoporous carbon;
Described binding agent be polytetrafluoroethylene, Kynoar, polyvinyl alcohol, sodium carboxymethylcellulose one or two or more kinds;
Described perforated membrane is with one or two or more kinds perforated membrane be prepared from for raw material of polytetrafluoroethylene, Kynoar, polyvinyl alcohol, sodium carboxymethylcellulose.
The preparation method of described sulfur compound is the one in mechanical mixing, solution composite approach, fusion method, reaction in-situ composite algorithm, gel precipitation composite algorithm, Charging sulphur method and decompression Charging sulphur method.
The preparation method of described lithium-sulfur cell integrated film electrode structure, its preparation process is:
(1) sulfur compound, conductive agent and binding agent are joined in proportion in dispersant, fully stir, wherein, solid content is 5 ~ 50%, obtains slurry A;
(2) slurry A is evenly applied on a current collector, be under 20 DEG C ~ 90 DEG C conditions after drying through temperature, obtain pole piece B;
(3) porous carbon and binding agent are joined in proportion in dispersant, fully stir, wherein, solid content is 5 ~ 50%, obtains slurry C;
(4) slurry C is evenly coated on the perforated membrane containing binding agent composition, is under 50 DEG C ~ 100 DEG C conditions after drying through temperature, obtains film D;
(5) by the vitrification point point of pole piece B and film D at binding agent used, use 2MPa pressure preheating 1min, 10MPa pressure hot pressing 1min, obtains integrated lithium-sulfur cell membrane electrode.
Described dispersant is the one in 1-METHYLPYRROLIDONE, water.
Described painting method is the one in knife coating, spraying process, silk screen print method, roll-in method, laser printing method;
Described collector is the one in foamy carbon, carbon paper, carbon cloth, nickel foam, aluminium foil;
Described drying mode is the one in forced air drying, vacuumize, the drying of heating platform open type.
Described binding agent be polytetrafluoroethylene, Kynoar, polyvinyl alcohol, sodium carboxymethylcellulose one or two or more kinds;
Described perforated membrane is with one or two or more kinds perforated membrane be prepared from for raw material of polytetrafluoroethylene, Kynoar, polyvinyl alcohol, sodium carboxymethylcellulose.
Compared with prior art, tool of the present invention has the following advantages:
(1). this integrated film electrode manufacturing cycle is short, and technique is simple, and cost is low;
(2). the film in this integrated film electrode contains the component of binding agent, makes film and sulfur compound layer close contact, greatly reduce the contact resistance between film and carbon-sulfur compound, improve the utilance of active material sulphur in hot pressing;
(3). the film in this integrated film electrode adopts porous carbon modification, effectively can adsorb the polysulfide of loss by dissolution from sulphur composite bed, and this coat has good electronic conduction ability, the polysulfide of loss by dissolution is recycled, effectively improves discharge capacity and the coulombic efficiency of lithium-sulfur cell;
(4). this integrated film electrode adopts to be prepared the mode of sulfur compound and the hot compound of porous carbon Modified Membrane, effectively can simplify the packaging technology of flexible package lithium-sulfur cell, reduce the use amount of electrolyte, improve the energy density of flexible-packed battery;
(5). integrated film electrode prepared by the present invention has higher utilization efficiency and good cyclical stability.More traditional electrode discharge capacity can reach 1400mAh/g-S, improves 100mAh/g-S, and after circulation 50 circle, discharge capacitance is greater than 96%, improves 30%.
Accompanying drawing explanation
Fig. 1. integrated film electrode structure schematic diagram prepared by the present invention.
(a)(b)
Fig. 2. integrated film electrode prepared by the present invention compares with the first circle discharge curve of the traditional electrode prepared under same condition (discharge-rate is 0.1C, by voltage 1.5-2.8V).
Fig. 3. integrated film electrode prepared by the present invention and the cyclical stability test curve (discharge-rate is 0.2C, by voltage 1.5-2.8V) with the traditional electrode prepared under condition.
Embodiment
Below by embodiment, the present invention is described in detail, but the present invention is not limited only to embodiment.
Embodiment 1
By elemental sulfur and ordered mesopore carbon, (aperture is 50nm, specific surface is 60) be prepared into carbon-sulfur compound A by hot melt compound, filling sulfur content is 70%, get A, electrically conductive graphite, Kynoar in mass ratio for 8:1:1 ball milling mix after be scattered in the aqueous solution, carry out stirring and obtain positive-active layer slurry, wherein in slurry, solid content is 15%, by even for slurry blade coating in aluminum foil current collector, after 80 DEG C of vacuumizes, compacting obtains carbon-sulfur compound layer B, and its thickness is 50 μm.By activated carbon (pore-size distribution district is 50nm), acetylene black, Kynoar in mass ratio for 9:0:1 ball milling mix after be scattered in 1-METHYLPYRROLIDONE, carry out stirring and obtain slurry, wherein in slurry, solid content is 8%, by even for slurry blade coating on the perforated membrane containing Kynoar composition, perforated membrane pore-size distribution district is 10nm, porosity is 40%, form film D, perforated membrane thickness is 10 μm, porous carbon layer thickness is 50 μm, after 90 DEG C of vacuumizes, by pole piece B and film D at 160 DEG C, use 2MPa pressure preheating 1min, 10MPa pressure hot pressing 1min, obtain integrated lithium-sulfur cell membrane electrode.
Electrochemical property test: membrane electrode is struck out the pole piece that diameter is 14mm.Take metal lithium sheet as negative pole, in the glove box being full of argon gas, be assembled into CR2016 button cell, at room temperature carry out constant current charge-discharge test with 0.2C.
Embodiment 2
Elemental sulfur and Graphene are prepared into carbon-sulfur compound A by hot melt compound, filling sulfur content is 95%, get A, electrically conductive graphite, sodium carboxymethylcellulose in mass ratio for 8:1:1 ball milling mix after be scattered in the aqueous solution, carry out stirring and obtain positive-active layer slurry, wherein in slurry, solid content is 10%, by even for slurry blade coating in aluminum foil current collector, after 20 DEG C of vacuumizes, obtain carbon-sulfur compound layer B, its thickness is 500 μm.
By carbon nano-tube, acetylene black, sodium carboxymethylcellulose in mass ratio for 9:0:1 ball milling mix after be scattered in 1-METHYLPYRROLIDONE, carry out stirring and obtain slurry, wherein in slurry, solid content is 10%, by even for slurry blade coating on the perforated membrane containing sodium carboxymethylcellulose composition, perforated membrane pore-size distribution district is 10nm, porosity is 40%, form film D, perforated membrane thickness is 100 μm, porous carbon layer thickness is 200 μm, after 50 DEG C of forced air dryings, by pole piece B and film D at 200 DEG C, use 2MPa pressure preheating 1min, 10MPa pressure hot pressing 1min, obtain integrated lithium-sulfur cell membrane electrode.
Electrochemical property test: take metal lithium sheet as negative pole, be assembled into flexible-packed battery in the glove box being full of argon gas, at room temperature carry out constant current charge-discharge test with 0.1C.
Embodiment 3
Elemental sulfur and conductive black are prepared into carbon-sulfur compound A by mechanical mixing, filling sulfur content is 10%, get A, electrically conductive graphite, Kynoar in mass ratio for 1:1:0.5 ball milling mix after be scattered in the aqueous solution, carry out stirring and obtain positive-active layer slurry, wherein in slurry, solid content is 5%, by even for slurry blade coating in aluminum foil current collector, after 50 DEG C of vacuumizes, obtain carbon-sulfur compound layer B, its thickness is 100 μm.
By carbon nano-fiber (pore-size distribution district is 500nm), acetylene black, Kynoar in mass ratio for 1:1:0.05 ball milling mix after be scattered in 1-METHYLPYRROLIDONE, carry out stirring and obtain positive-active layer slurry, wherein in slurry, solid content is 10%, by even for slurry blade coating on the perforated membrane containing Kynoar composition, perforated membrane pore-size distribution district is 100nm, porosity is 50%, form film D, perforated membrane thickness is 50 μm, porous carbon layer thickness is 100 μm, after 50 DEG C of vacuumizes, by pole piece B and film D at 160 DEG C, use 2MPa pressure preheating 1min, 10MPa pressure hot pressing 1min, obtain integrated lithium-sulfur cell membrane electrode.
Electrochemical property test: anode pole piece is struck out the pole piece that diameter is 14mm.Take metal lithium sheet as negative pole, in the glove box being full of argon gas, be assembled into CR2016 button cell, at room temperature carry out constant current charge-discharge test with 0.1C.
Embodiment 4
Elemental sulfur and carbon aerogels are prepared into carbon-sulfur compound A by solution composite approach, filling sulfur content is 50%, get A, electrically conductive graphite, polyvinyl alcohol in mass ratio for 1:0.5:0.01 ball milling mix after be scattered in the aqueous solution, carry out stirring and obtain positive-active layer slurry B, wherein in slurry, solid content is 50%, by even for slurry blade coating on nickel foam collector, after 50 DEG C of vacuumizes, compacting obtains wide-aperture carbon-sulfur compound layer, and its thickness is 200 μm.
By carbon nano-fiber, acetylene black, polyvinyl alcohol in mass ratio for 1:0.5:0.5 ball milling mix after be scattered in 1-METHYLPYRROLIDONE, carry out stirring and obtain positive-active layer slurry, wherein in slurry, solid content is 50%, by even for slurry blade coating on the perforated membrane containing polyvinyl alcohol composition, perforated membrane pore-size distribution district is 5nm, porosity is 30%, form film D, perforated membrane thickness is 50 μm, porous carbon layer thickness is 50 μm, after 120 DEG C of vacuumizes, by pole piece B and film D at 80 DEG C, use 2MPa pressure preheating 1min, 10MPa pressure hot pressing 1min, obtain integrated lithium-sulfur cell membrane electrode.
Electrochemical property test: anode pole piece is struck out the pole piece that diameter is 14mm.Take metal lithium sheet as negative pole, in the glove box being full of argon gas, be assembled into CR2016 button cell carry out constant current charge-discharge test.
Embodiment 5
Elemental sulfur and expanded graphite are prepared into carbon-sulfur compound A by Charging sulphur method, filling sulfur content is 75%, get A, acetylene black, Kynoar in mass ratio for 9:0.4:0.6 ball milling mix after be scattered in the aqueous solution, carry out stirring and obtain positive-active layer slurry B, wherein in slurry, solid content is 10%, by even for slurry blade coating on carbon foam current collector, after 60 DEG C of vacuumizes, obtain carbon-sulfur compound layer, its thickness is 100 μm.
By carbon nano-fiber, acetylene black, Kynoar in mass ratio for 8:1:1 ball milling mix after be scattered in 1-METHYLPYRROLIDONE, carry out stirring and obtain positive-active layer slurry, wherein in slurry, solid content is 8%, by slurry evenly containing on the perforated membrane of Kynoar composition, perforated membrane pore-size distribution district is 20nm, porosity is 30%, form film D, perforated membrane thickness is 20 μm, porous carbon layer thickness is 20 μm, after 120 DEG C of vacuumizes, by pole piece B and film D at 100 DEG C, use 2MPa pressure preheating 1min, 10MPa pressure hot pressing 1min, obtain integrated lithium-sulfur cell membrane electrode.
Electrochemical property test: anode pole piece is struck out the pole piece that diameter is 14mm.Take metal lithium sheet as negative pole, be assembled into CR2016 button cell in the glove box being full of argon gas, at room temperature carry out constant current charge-discharge test with 0.1C and 0.2C, circulate 50 times, capability retention is greater than 96% (as Fig. 2, Fig. 3).
Fig. 2. integrated film electrode prepared by the present invention and traditional electrode discharge capacity curve comparison first, 0.1C discharges.
Fig. 2 be the integrated film electrode prepared of the present invention and traditional electrode first discharge performance contrast.As can be seen from result, integrated film electrode first discharge capacity can reach 1400mAh/g-S, than traditional electrode discharge capacity height 100mAh/g-S, and discharge platform is also higher than traditional electrode, this integrated electrode illustrating prepared by the present invention significantly reduces the contact resistance of film and sulfur compound, reduce the charge transfer resistance of cell reaction, improve the utilance of elemental sulfur.
Fig. 3. the cycle life of integrated film electrode and traditional electrode contrasts, and 0.2C discharges.
The integrated membrane electrode of Fig. 3 and traditional electrode cyclical stability contrast.As can be seen from result, the integrated film electrode 0.2C capacity first that discharges reaches 1215mAh/g, nearly 100mAh/g high compared with traditional electrical, consistent with 0.1C result of discharging, 50 capability retentions that circulate reach more than 96%, and traditional electrode capability retention only has about 60%, this illustrates that integrated film electrode is while reduction contact resistance, the perforated membrane of modification effectively can adsorb the polysulfide of sulphur composite bed loss by dissolution, and good electron channel can be provided, thus the sulphur of loss is re-used, effectively improve cyclical stability and the coulombic efficiency of battery.
Embodiment 6
Elemental sulfur and polyaniline are prepared into carbon-sulfur compound A by Charging sulphur method, filling sulfur content is 50%, get A, polytetrafluoroethylene in mass ratio for 9:1 ball milling mix after be scattered in the aqueous solution, carry out stirring and obtain positive-active layer slurry B, wherein in slurry, solid content is 50%, by even for slurry blade coating on carbon foam current collector, after 90 DEG C of vacuumizes, compacting obtains wide-aperture carbon-sulfur compound layer, and its thickness is 50 μm.
By Graphene, acetylene black, polytetrafluoroethylene in mass ratio for 8:1:1 ball milling mix after be scattered in 1-METHYLPYRROLIDONE, carry out stirring and obtain positive-active layer slurry, wherein in slurry, solid content is 5%, by even for slurry blade coating on the perforated membrane containing polytetrafluoroethylene composition, perforated membrane pore-size distribution district is 10nm, porosity is 40%, form film D, perforated membrane thickness is 25 μm, porous carbon layer thickness is 25 μm, after 120 DEG C of vacuumizes, by pole piece B and film D at 100 DEG C, use 2MPa pressure preheating 1min, 10MPa pressure hot pressing 1min, obtain integrated lithium-sulfur cell membrane electrode.
Electrochemical property test: anode pole piece is struck out the pole piece that diameter is 14mm.Take metal lithium sheet as negative pole, in the glove box being full of argon gas, be assembled into CR2016 button cell, at room temperature carry out constant current charge-discharge test with 0.1C.
Embodiment 7
Elemental sulfur and yittrium oxide are prepared into carbon-sulfur compound A by mechanical mixing, filling sulfur content is 50%, get A, polytetrafluoroethylene in mass ratio for 9:1 ball milling mix after be scattered in the aqueous solution, carry out stirring and obtain positive-active layer slurry B, wherein in slurry, solid content is 50%, by slurry even application on carbon cloth collector, after 20 DEG C of dryings, obtain carbon-sulfur compound layer, its thickness is 300 μm.
By graphite oxide, acetylene black, polytetrafluoroethylene in mass ratio for 8:1:1 ball milling mix after be scattered in 1-METHYLPYRROLIDONE, carry out stirring and obtain positive-active layer slurry, wherein in slurry, solid content is 5%, by even for slurry silk screen printing on the perforated membrane containing polytetrafluoroethylene composition, perforated membrane pore-size distribution district is 5nm, porosity is 30%, form film D, perforated membrane thickness is 40 μm, porous carbon layer thickness is 40 μm, after 60 DEG C of vacuumizes, by pole piece B and film D at 100 DEG C, use 2MPa pressure preheating 1min, 10MPa pressure hot pressing 1min, obtain integrated lithium-sulfur cell membrane electrode.
Electrochemical property test: anode pole piece is struck out the pole piece that diameter is 14mm.Take metal lithium sheet as negative pole, in the glove box being full of argon gas, be assembled into CR2016 button cell, at room temperature carry out constant current charge-discharge test.
Embodiment 8
Elemental sulfur and polythiophene are prepared into carbon-sulfur compound A by mechanical mixing, filling sulfur content is 60%, get A, electrically conductive graphite, Kynoar in mass ratio for 96:0:4 ball milling mix after be scattered in the aqueous solution, carry out stirring and obtain positive-active layer slurry B, wherein in slurry, solid content is 15%, is pressed in aluminum foil current collector by slurry even roller, after 50 DEG C of vacuumizes, obtain carbon-sulfur compound layer, its thickness is 100 μm.
By conductive carbon black, acetylene black, Kynoar in mass ratio for 1:1:0.05 ball milling mix after be scattered in 1-METHYLPYRROLIDONE, carry out stirring and obtain positive-active layer slurry, wherein in slurry, solid content is 10%, slurry uniform laser is printed on the perforated membrane containing Kynoar composition, perforated membrane pore-size distribution district is 15nm, porosity is 40%, form film D, perforated membrane thickness is 40 μm, porous carbon layer thickness is 40 μm, after 60 DEG C of vacuumizes, by pole piece B and film D at 160 DEG C, use 2MPa pressure preheating 1min, 10MPa pressure hot pressing 1min, obtain integrated lithium-sulfur cell membrane electrode.
Electrochemical property test: anode pole piece is struck out the pole piece that diameter is 14mm.Take metal lithium sheet as negative pole, in the glove box being full of argon gas, be assembled into CR2016 button cell, at room temperature carry out constant current charge-discharge test with 1C.
Embodiment 9
Elemental sulfur and lanthana are prepared into carbon-sulfur compound A by hot melt compound, filling sulfur content is 60%, get A, electrically conductive graphite, sodium carboxymethylcellulose in mass ratio for 1:1:0.01 ball milling mix after be scattered in the aqueous solution, carry out stirring and obtain positive-active layer slurry B, wherein in slurry, solid content is 5%, by even for slurry blade coating in aluminum foil current collector, after 90 DEG C of vacuumizes, obtain carbon-sulfur compound layer, its thickness is 500 μm.
By ordered mesopore carbon, acetylene black, sodium carboxymethylcellulose in mass ratio for 1:0:0.5 ball milling mix after be scattered in 1-METHYLPYRROLIDONE, carry out stirring and obtain positive-active layer slurry, wherein in slurry, solid content is 50%, by even for slurry blade coating on the perforated membrane containing sodium carboxymethylcellulose composition, perforated membrane pore-size distribution district is 10nm, porosity is 35%, form film D, perforated membrane thickness is 80 μm, porous carbon layer thickness is 40 μm, after 60 DEG C of vacuumizes, by pole piece B and film D at 200 DEG C, use 2MPa pressure preheating 1min, 10MPa pressure hot pressing 1min, obtain integrated lithium-sulfur cell membrane electrode.
Electrochemical property test: anode pole piece is struck out the pole piece that diameter is 14mm.Take metal lithium sheet as negative pole, in the glove box being full of argon gas, be assembled into CR2016 button cell, at room temperature carry out constant current charge-discharge test.
Embodiment 10
Elemental sulfur and Graphene are prepared into carbon-sulfur compound A by mechanical mixing compound, filling sulfur content is 95%, get A, electrically conductive graphite, Kynoar in mass ratio for 8:1:1 ball milling mix after be scattered in the aqueous solution, carry out stirring and obtain positive-active layer slurry B, wherein in slurry, solid content is 50%, by even for slurry blade coating in aluminum foil current collector, after 50 DEG C of vacuumizes, obtain carbon-sulfur compound layer, its thickness is 300 μm.
By expanded graphite, acetylene black, Kynoar in mass ratio for 9:0:1 ball milling mix after be scattered in 1-METHYLPYRROLIDONE, carry out stirring and obtain positive-active layer slurry, wherein in slurry, solid content is 50%, by even for slurry blade coating on the perforated membrane containing Kynoar composition, perforated membrane pore-size distribution district is 100nm, porosity is 50%, form film D, perforated membrane thickness is 100 μm, porous carbon layer thickness is 50 μm, after 60 DEG C of vacuumizes, by pole piece B and film D at 160 DEG C, use 2MPa pressure preheating 1min, 10MPa pressure hot pressing 1min, obtain integrated lithium-sulfur cell membrane electrode.
Electrochemical property test: anode pole piece is struck out the pole piece that diameter is 14mm.Take metal lithium sheet as negative pole, in the glove box being full of argon gas, be assembled into CR2016 button cell, at room temperature carry out constant current charge-discharge test.
Embodiment 11
Elemental sulfur and polypyrrole are prepared into carbon-sulfur compound A by mechanical mixing, filling sulfur content is 50%, get A, Kynoar in mass ratio for 1:0:0.01 ball milling mix after be scattered in the aqueous solution, carry out stirring and obtain positive-active layer slurry B, wherein in slurry, solid content is 50%, is pressed in by slurry even roller on carbon cloth collector, after 90 DEG C of dryings, obtain carbon-sulfur compound layer, its thickness is 100 μm.
By graphite oxide, acetylene black, Kynoar in mass ratio for 8:1:1 ball milling mix after be scattered in 1-METHYLPYRROLIDONE, carry out stirring and obtain positive-active layer slurry, wherein in slurry, solid content is 50%, by even for slurry silk screen printing on the perforated membrane containing Kynoar composition, perforated membrane pore-size distribution district is 50nm, porosity is 50%, form film D, perforated membrane thickness is 90 μm, porous carbon layer thickness is 20 μm, after 60 DEG C of vacuumizes, by pole piece B and film D at 160 DEG C, use 2MPa pressure preheating 1min, 10MPa pressure hot pressing 1min, obtain integrated lithium-sulfur cell membrane electrode.
Electrochemical property test: anode pole piece is struck out the pole piece that diameter is 14mm.Take metal lithium sheet as negative pole, in the glove box being full of argon gas, be assembled into CR2016 button cell, at room temperature carry out constant current charge-discharge test.
Embodiment 12
Elemental sulfur and cerium oxide are prepared into carbon-sulfur compound A by hot melt compound, and filling sulfur content is 60%,
Get A, acetylene black, Kynoar in mass ratio for 9:0:1 ball milling mix after be scattered in 1-METHYLPYRROLIDONE, carry out stirring and obtain positive-active layer slurry B, wherein in slurry, solid content is 50%, slurry even roller is pressed on carbon cloth collector, after 90 DEG C of dryings, obtain carbon-sulfur compound layer, its thickness is 100 μm.
By carbon nano-tube, electrically conductive graphite, Kynoar in mass ratio for 8:1:1 ball milling mix after be scattered in the aqueous solution, carry out stirring and obtain positive-active layer slurry, wherein in slurry, solid content is 50%, by even for slurry silk screen printing on the perforated membrane containing Kynoar composition, perforated membrane pore-size distribution district is 10nm, porosity is 40%, form film D, perforated membrane thickness is 25 μm, porous carbon layer thickness is 10 μm, after 60 DEG C of vacuumizes, by pole piece B and film D at 160 DEG C, use 2MPa pressure preheating 1min, 10MPa pressure hot pressing 1min, obtain integrated lithium-sulfur cell membrane electrode.
Chemical property is tested: anode pole piece is struck out the pole piece that diameter is 14mm.Take metal lithium sheet as negative pole, in the glove box being full of argon gas, be assembled into CR2016 button cell, at room temperature carry out constant current charge-discharge test.
Claims (10)
1. a lithium-sulfur cell integrated film electrode structure, is characterized in that: be composited by the overlapping after heat of two layer materials, one deck is the perforated membrane of material with carbon element modification, and one deck is the sulphur composite layer on collector;
Described sulfur compound layer is the mixture of the sulfur compound of sulfur content 10 ~ 95%, conductive agent and binding agent, and wherein the mass ratio of sulfur compound, conductive agent and binding agent is 1:(0 ~ 1): (0.01 ~ 0.5); The perforated membrane of described material with carbon element modification is the perforated membrane that the mixture of porous carbon and binding agent applies, and wherein the mass ratio of porous carbon and binding agent is 1:(0.01 ~ 0.5).
2. lithium-sulfur cell film electrode structure according to claim 1, is characterized in that: sulphur composite layer thickness is 10mm ~ 200mm, preferably 20 ~ 100mm; In the perforated membrane of described porous carbon coating, the thickness of porous carbon layer is 50mm ~ 200mm, and pore-size distribution district is at 50nm ~ 500nm; The thickness of perforated membrane is 10 ~ 100mm, and porosity is 30%-50%, and pore-size distribution district is at 5nm ~ 100nm.
3. lithium-sulfur cell film electrode structure according to claim 2, is characterized in that: in described porous carbon coat, porous carbon is one or more in carbon nano-tube, carbon nano-fiber, activated carbon, carbon gel, carbon black.
4. lithium-sulfur cell film electrode structure according to claim 1, is characterized in that:
Described sulfur compound is one or two or more kinds in carbon sulphur composite material, sulphur-conducting polymer composite material and sulphur-metal oxide composite;
Described carbon sulphur composite material elemental sulfur is mixed material with carbon element to be formed, material with carbon element is wherein as filling the cathode material before sulphur, and it is one or two or more kinds mixture in active carbon, charcoal-aero gel, Graphene, graphite oxide, expanded graphite, carbon nano-tube, carbon nano-fiber, mesoporous carbon;
Described sulphur-conducting polymer composite material elemental sulfur is mixed conducting polymer to be formed, and conducting polymer is wherein as filling the cathode material before sulphur, and it is one or two or more kinds mixture in polyaniline, polypyrrole, polythiophene;
Sulphur-metal oxide composite elemental sulfur is mixed metal oxide to be formed, and metal oxide is wherein as filling the cathode material before sulphur, and it is one or two or more kinds mixture of yittrium oxide, lanthana, cerium oxide, titanium oxide.
5. lithium-sulfur cell film electrode structure according to claim 1, is characterized in that, described conductive agent is one or two or more kinds in acetylene black, carbon black, graphite, carbon nano-tube, carbon nano-fiber, mesoporous carbon; Described binding agent be polytetrafluoroethylene, Kynoar, polyvinyl alcohol, sodium carboxymethylcellulose one or two or more kinds;
Described perforated membrane is with one or two or more kinds perforated membrane be prepared from for raw material of polytetrafluoroethylene, Kynoar, polyvinyl alcohol, sodium carboxymethylcellulose.
6. the lithium-sulfur cell film electrode structure according to claim 1 or 4, is characterized in that: the preparation method of described sulfur compound is the one in mechanical mixing, solution composite approach, fusion method, reaction in-situ composite algorithm, gel precipitation composite algorithm, Charging sulphur method and decompression Charging sulphur method.
7. a preparation method for lithium-sulfur cell integrated film electrode structure according to claim 1, its preparation process is:
(1) sulfur compound, conductive agent and binding agent are joined in proportion in dispersant, fully stir, wherein, solid content is 5 ~ 50%, obtains slurry A;
(2) slurry A is evenly applied on a current collector, be under 20 DEG C ~ 90 DEG C conditions after drying through temperature, obtain pole piece B;
(3) porous carbon and binding agent are joined in proportion in dispersant, fully stir, wherein, solid content is 5 ~ 50%, obtains slurry C;
(4) slurry C is evenly coated on the perforated membrane containing binding agent composition, is under 50 DEG C ~ 100 DEG C conditions after drying through temperature, obtains film D;
(5) by the vitrification point point of pole piece B and film D at binding agent used, use 2MPa pressure preheating 1min, 10MPa pressure hot pressing 1min, obtains integrated lithium-sulfur cell membrane electrode.
8. lithium-sulfur cell method for preparing membrane electrode according to claim 7, is characterized in that, described dispersant is the one in 1-METHYLPYRROLIDONE, water.
9. lithium-sulfur cell method for preparing membrane electrode according to claim 7, is characterized in that, described painting method is the one in knife coating, spraying process, silk screen print method, roll-in method, laser printing method; Described collector is the one in foamy carbon, carbon paper, carbon cloth, nickel foam, aluminium foil; Described drying mode is the one in forced air drying, vacuumize, the drying of heating platform open type.
10. lithium-sulfur cell method for preparing membrane electrode according to claim 7, is characterized in that, described binding agent be polytetrafluoroethylene, Kynoar, polyvinyl alcohol, sodium carboxymethylcellulose one or two or more kinds;
Described perforated membrane is with one or two or more kinds perforated membrane be prepared from for raw material of polytetrafluoroethylene, Kynoar, polyvinyl alcohol, sodium carboxymethylcellulose.
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