CN105489818A - Preparation method for modified diaphragm for lithium-sulfur battery, modified diaphragm and lithium-sulfur battery adopting modified diaphragm - Google Patents
Preparation method for modified diaphragm for lithium-sulfur battery, modified diaphragm and lithium-sulfur battery adopting modified diaphragm Download PDFInfo
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- CN105489818A CN105489818A CN201511007459.5A CN201511007459A CN105489818A CN 105489818 A CN105489818 A CN 105489818A CN 201511007459 A CN201511007459 A CN 201511007459A CN 105489818 A CN105489818 A CN 105489818A
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a preparation method for a modified diaphragm for a lithium-sulfur battery, the modified diaphragm and the lithium-sulfur battery adopting the modified diaphragm. The preparation method for the modified diaphragm for the lithium-sulfur battery comprises the following steps of mixing a conductive agent with a nano-metal oxide at a mass ratio of 1:1-10:1 to obtain a uniformly-mixed coating material; uniformly mixing the coating material with a binder at a mass ratio of 1:1-5:1, and scattering the mixture into solvent; performing mechanical stirring or ultrasonic scattering to obtain uniformly-dispersed coating slurry; coating the surface of a diaphragm substrate with the obtained coating slurry, and performing vacuum drying to obtain the modified diaphragm for the lithium-sulfur battery. The modified diaphragm for the lithium-sulfur battery prepared by the method can effectively restrain a shuttle effect of polysulfide in a charge/discharge process of the lithium-sulfur battery and prolong the cycle life of the lithium-sulfur battery; and the lithium-sulfur battery adopting the modified diaphragm is high in capacity and good in cycling performance.
Description
Technical field
The invention belongs to technical field of lithium batteries, particularly relate to a kind of preparation method of lithium-sulfur cell modified diaphragm, modified diaphragm and there is the lithium-sulfur cell of this modified diaphragm.
Background technology
A kind of new chemical battery that lithium-sulfur cell take lithium metal as negative pole, be positive pole with elemental sulfur or organic sulfur compound is one of battery with high theoretical energy density, has aboundresources, nontoxic, environmental friendliness, the advantage such as cheap.But lithium-sulfur cell is still faced with many challenges in application process, wherein the severeest is that the polysulfide produced in battery charge and discharge process is dissolved in electrolyte, the loss that " effect of shuttling back and forth " causes active material occurs, causes lithium-sulfur cell capacity to be decayed rapidly.
In recent years, some scholars is on the basis not changing lithium-sulfur cell agent structure, and appropriate change lithium-sulfur cell structure makes chemical property improve, and new direction is opened up in the research and development for high-energy-density lithium-sulfur cell." advanced function material " magazine (AdvancedFunctionalMaterials.2015,25 (33): 5285-5291) describe JuanBalach and apply one deck porous carbon in diaphragms, effectively can improve the cycle life of lithium-sulfur cell.Patent (CN104393220A) discloses the lithium-sulfur cell of a kind of employing based on metal-organic framework material modified diaphragm, but metal-organic framework material is expensive, and cost is higher.Research shows, metal-organic framework material is only physical absorption to polysulfide, is difficult to " effect of shuttling back and forth " that fundamentally solve polysulfide.Meanwhile, above-mentioned lithium-sulfur cell of the prior art, sulphur, at the content of whole electrode slice lower (lower than 70%), is difficult to the utilance improving sulphur further.
Summary of the invention
Technical problem to be solved by this invention is, overcome the deficiency and defect mentioned in above background technology, there is provided a kind of " effect of shuttling back and forth " that can suppress polysulfide in lithium-sulfur cell charge and discharge process, improve preparation method, the modified diaphragm of the lithium-sulfur cell modified diaphragm of lithium-sulfur cell cycle life and adopt the lithium-sulfur cell that in the positive plate of this modified diaphragm, sulfur content is high.
For solving the problems of the technologies described above, the technical scheme that the present invention proposes is:
A preparation method for lithium-sulfur cell modified diaphragm, comprises the following steps: by conductive agent and nano-metal-oxide in mass ratio 1:1 ~ 10:1 mix, obtain the coating material mixed; By described coating material and binding agent in mass ratio 1:1 ~ 5:1 mix, be then distributed in solvent; Finely dispersed coating paste is obtained by mechanical agitation or ultrasonic disperse; Gained coating paste is coated on a diaphragm matrix surface, vacuumize, obtains lithium-sulfur cell modified diaphragm.
Conductive agent and nano-metal-oxide is adopted to mix obtained modified diaphragm in proportion, utilize the semipolar metal-oxygen key (M-O) of nano-metal-oxide, the polysulfide effectively adsorbing and produce in catalysis lithium-sulfur cell charge and discharge process, suppress " effect of shuttling back and forth " of polysulfide, improve battery capacity and the cycle life of lithium-sulfur cell; Meanwhile, avoid and adopt expensive metal-organic framework material, save battery cost, be conducive to suitability for industrialized production.The lithium-sulfur cell of the modified diaphragm prepared by the method is adopted to show good cycle performance under 0.5C multiplying power.
The preparation method of above-mentioned lithium-sulfur cell modified diaphragm, preferably, described nano-metal-oxide is nanometer Mg
0.6ni
0.4o, Mg
0.8cu
0.2o, TiO
2, Al
2o
3, SiO
2in one or more.
The preparation method of above-mentioned lithium-sulfur cell modified diaphragm, preferably, described conductive agent is one or more in conductive black, acetylene black, carbon fiber, carbon nano-tube, Ketjen black, nitrogen-doped carbon, Graphene, nitrogen-doped graphene.
The preparation method of above-mentioned lithium-sulfur cell modified diaphragm, preferably, described binding agent is one or more in polyvinylidene fluoride, polyvinyl alcohol, polytetrafluoroethylene, sodium carboxymethylcellulose, Polyurethane.
The preparation method of above-mentioned lithium-sulfur cell modified diaphragm, preferably, described solvent is one or more in ethanol, acetone, 1-METHYLPYRROLIDONE.
The preparation method of above-mentioned lithium-sulfur cell modified diaphragm, preferably, described vacuum drying temperature is 40 ~ 60 DEG C, and the vacuum drying time is 6 ~ 24 hours.
The present invention provides a kind of lithium-sulfur cell modified diaphragm on the other hand, this modified diaphragm is prepared by the preparation method of above-mentioned lithium-sulfur cell modified diaphragm, described modified diaphragm comprises the coating that diaphragm matrix and diaphragm matrix apply, described diaphragm matrix is one or more in polypropylene, polyethylene, polyimides, Kynoar, polytetrafluoroethylene, polyacrylonitrile, polyamide, glass ceramics, and the thickness of diaphragm matrix is 10 ~ 50 μm; The surface density of described coating is 0.1-10mg/cm
2; The integral thickness of described modified diaphragm is 15 ~ 100 μm.
Providing one has modified diaphragm lithium-sulfur cell on the other hand in the present invention, comprises sulphur positive plate, lithium sheet negative pole and electrolyte, is provided with above-mentioned lithium-sulfur cell modified diaphragm between described sulphur positive plate and lithium sheet negative pole.
The above-mentioned lithium-sulfur cell with modified diaphragm, preferably, described sulphur positive plate is made up of carbon/sulphur composite material, and its carbon/sulphur mass ratio is 1:4.
The above-mentioned lithium-sulfur cell with modified diaphragm, preferably, the described lithium-sulfur cell specific discharge capacity after 350 times that circulates under charging/discharging voltage scope is 1.5V-2.8V, 0.5C multiplying power is not less than 500mAh/g.
Compared with prior art, the invention has the advantages that:
(1) by nano-metal-oxide and conductive carbon, modification is carried out to barrier film, utilize the semipolar metal-oxygen key (M-O) of nano-metal-oxide to adsorb and catalysis the polysulfide produced in sulphur positive discharge process, improve capacity and the cyclical stability of lithium-sulfur cell.
(2) adopt nano-metal-oxide and conductive carbon to carry out modification to barrier film, avoid and use expensive metal-organic framework material, reduce battery cost, be conducive to large-scale production.
(3) adopt the carbon/sulphur anode composite of high sulfur content, improve the content of sulphur in electrode slice and utilance thereof, and then improve the battery capacity of lithium-sulfur cell.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art below, apparently, accompanying drawing in the following describes is some embodiments of the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
Fig. 1 is the operation chart be coated in by coating paste in lithium-sulfur cell barrier film preparation method of the present invention in diaphragm matrix.
Fig. 2 is the outward appearance comparison diagram of common diaphragm and modified diaphragm of the present invention.
The modified diaphragm cross-sectional scans Electronic Speculum figure of Fig. 3 prepared by the embodiment of the present invention 1.
Fig. 4 is the cycle performance correlation curve of lithium-sulfur cell under 0.5C multiplying power adopting prepared modified diaphragm in common diaphragm, porous carbon modified diaphragm and the embodiment of the present invention 1.
After the lithium-sulfur cell discharge and recharge of Fig. 5 modified diaphragm assembling prepared by the use embodiment of the present invention 1, the scanning electron microscope (SEM) photograph of its modified diaphragm and element Surface scan analysis chart.
Fig. 6 is for using the cycle performance curve of lithium-sulfur cell under 0.5C multiplying power of modified diaphragm assembling prepared by the embodiment of the present invention 2.
Fig. 7 is for using the cycle performance curve of lithium-sulfur cell under 0.5C multiplying power of modified diaphragm assembling prepared by the embodiment of the present invention 3.
Fig. 8 is for using the cycle performance curve of lithium-sulfur cell under 0.5C multiplying power of modified diaphragm assembling prepared by the embodiment of the present invention 4.
Fig. 9 is for using the cycle performance curve of lithium-sulfur cell under 0.5C multiplying power of modified diaphragm assembling prepared by the embodiment of the present invention 5.
Figure 10 is for using the cycle performance curve of lithium-sulfur cell under 0.5C multiplying power of modified diaphragm assembling prepared by the embodiment of the present invention 6.
Embodiment
For the ease of understanding the present invention, hereafter will do to describe more comprehensively, meticulously to the present invention in conjunction with Figure of description and preferred embodiment, but protection scope of the present invention is not limited to following specific embodiment.
Unless otherwise defined, hereinafter used all technical terms are identical with the implication that those skilled in the art understand usually.The object of technical term used herein just in order to describe specific embodiment is not be intended to limit the scope of the invention.
Unless otherwise specified, the various raw material, reagent, instrument and equipment etc. used in the present invention are all bought by market and are obtained or prepare by existing method.
Embodiment 1
A kind of preparation method of lithium-sulfur cell modified diaphragm of the present invention, modified diaphragm and there is the embodiment of lithium-sulfur cell of this modified diaphragm:
Prepared by modified diaphragm: by the Mg of preparation
0.6ni
0.4o nano particle mixes with the ratio of mass ratio 1.5:1 with Ketjen black (EC600JD), ball milling 12 hours, obtains the coating material mixed; Again by the coating material that mixes and polyvinylidene fluoride with mass ratio 1.5:1 Homogeneous phase mixing, and be distributed in 1-METHYLPYRROLIDONE solvent, mechanical agitation obtains finely dispersed coating material in 12 hours; The mode of scraper coating is adopted finely dispersed slurry to be coated on polypropylene diaphragm surface (coating operation as shown in Figure 1), the barrier film coated is put into vacuum drying chamber, drying 6 hours at 50 DEG C, obtained modified diaphragm (outward appearance of obtained modified diaphragm is as shown in Figure 2).
Battery is assembled: with carbon/sulphur, (carbon/sulphur mass ratio is for 1:4, sulfur content accounts for 80% of electrode slice quality) composite material prepares sulphur positive pole, metal lithium sheet is negative pole, the modified diaphragm adopting the present embodiment to prepare and common diaphragm, porous carbon modified diaphragm, be assembled into button cell respectively, and be filled with electrolyte.
Electrochemical property test: use the indigo plant of Wuhan Lan Bo Electronics Co., Ltd. electricity LANDCT2001A discharge and recharge instrument to carry out charge-discharge test to battery under room temperature (25 DEG C), charging/discharging voltage scope is 1.5V-2.8V.Under 0.5C multiplying power, its cycle performance is tested.
The Mg of Fig. 3 prepared by the present embodiment
0.6ni
0.4o/ Ketjen black (EC600JD) modified diaphragm cross-sectional scans Electronic Speculum figure.Find out by figure, coating is combined with polypropylene diaphragm intimate surface, and the integral thickness of this modified diaphragm is 32.5 μm, and the surface density of coating is 0.25mg/cm
2, the thickness of diaphragm matrix is 20.58 μm.Fig. 4 is common diaphragm, porous carbon modified diaphragm and Mg
0.6ni
0.4the cycle performance correlation curve of lithium-sulfur cell prepared by O/ Ketjen black (EC600JD) modified diaphragm under 0.5C multiplying power.Adopt the Mg of common diaphragm, porous carbon modified diaphragm and preparation
0.6ni
0.4the lithium-sulfur cell that O/ Ketjen black (EC600JD) modified diaphragm is assembled is under 0.5C multiplying power, and circulate 350 times, specific discharge capacity is respectively 75mAh/g, 410mAh/g and 530mAh/g.As can be seen here, compare with porous carbon modified diaphragm with common diaphragm, conductive carbon/metal oxide modified barrier film effectively can improve the cycle performance of lithium-sulfur cell.
Battery after lithium-sulfur cell prepared in this embodiment is carried out cycle performance test is taken apart in glove box, takes out modified diaphragm.By the anhydrous acetonitrile cleaning 3 ~ 5 times of this modified diaphragm, dry up, table analysis figure (as shown in Figure 5) is swept in the modified diaphragm scanning electron microscope (SEM) photograph after obtaining afterwards after tested discharging and face.Pass through Mg
0.6ni
0.4the barrier film that O/ Ketjen black (EC600JD) is modified, utilize the polar metal-oxygen key (M-O) in metal oxide, the polysulfide that effectively can adsorb and produce in catalysis charge and discharge process, effectively inhibit its " effect of shuttling back and forth ", explain the reason adopting the lithium-sulfur cell chemical property of this modified diaphragm to improve.
Embodiment 2
A kind of preparation method of lithium-sulfur cell modified diaphragm of the present invention, modified diaphragm and there is the embodiment of lithium-sulfur cell of this modified diaphragm:
Prepared by modified diaphragm: by the Mg of preparation
0.8cu
0.2o nano particle mixes with the ratio of mass ratio 2:1 with conductive black (BP2000), ball milling 12 hours, obtains the coating material mixed; Again by the coating material that mixes and sodium carboxymethylcellulose with mass ratio 3:1 Homogeneous phase mixing, and be distributed in 1-METHYLPYRROLIDONE solvent, ultrasonic disperse obtains finely dispersed coating material in 12 hours; Adopt the mode of scraper coating that finely dispersed slurry is coated on polyacrylonitrile membrane surface, the barrier film coated is put into vacuum drying chamber, drying 12 hours at 50 DEG C, obtained modified diaphragm.
Battery is assembled: prepare sulphur positive pole with carbon/sulphur (for 1:4, sulfur content accounts for 80% of electrode slice quality to carbon/sulphur mass ratio) composite material, metal lithium sheet is negative pole, and the modified diaphragm adopting the present embodiment to prepare is assembled into button cell, and is filled with electrolyte.
Electrochemical property test: use the indigo plant of Wuhan Lan Bo Electronics Co., Ltd. electricity LANDCT2001A discharge and recharge instrument to carry out charge-discharge test to battery in room temperature (25 DEG C), charging/discharging voltage scope is 1.5V-2.8V.Under 0.5C multiplying power, its cycle performance is tested.
Fig. 6 is for adopting the present embodiment Mg
0.8cu
0.2lithium-sulfur cell prepared by O/BP2000 modified diaphragm is cycle performance curve under 0.5C multiplying power.As seen from the figure, circulate 350 times under 0.5C multiplying power, specific discharge capacity is still 470mAh/g, illustrates and adopts the lithium-sulfur cell of this modified diaphragm to have good cycle performance under 0.5C multiplying power.
Embodiment 3
A kind of preparation method of lithium-sulfur cell modified diaphragm of the present invention, modified diaphragm and there is the embodiment of lithium-sulfur cell of this modified diaphragm:
Prepared by modified diaphragm: by the TiO of preparation
2nano particle mixes with the ratio of mass ratio 5:1 with acetylene black, ball milling 12 hours, obtain the coating material mixed, again by the coating material that mixes and polyvinyl alcohol with mass ratio 4:1 Homogeneous phase mixing, and being distributed in acetone solvent, mechanical agitation obtains finely dispersed coating material in 12 hours; Adopt the mode of scraper coating that finely dispersed slurry is coated on Teflon septum surface, the barrier film coated is put into vacuum drying chamber, drying 8 hours at 50 DEG C, obtained modified diaphragm.
Battery is assembled: prepare sulphur positive pole with carbon/sulphur (for 1:4, sulfur content accounts for 80% of electrode slice quality to carbon/sulphur mass ratio) composite material, metal lithium sheet is negative pole, and the modified diaphragm adopting the present embodiment to prepare is assembled into button cell, and is filled with electrolyte.
Electrochemical property test: use the indigo plant of Wuhan Lan Bo Electronics Co., Ltd. electricity LANDCT2001A discharge and recharge instrument to carry out charge-discharge test to battery in room temperature (25 DEG C), charging/discharging voltage scope is 1.5V-2.8V.Under 0.5C multiplying power, its cycle performance is tested.
Fig. 7 is for adopting the present embodiment TiO
2the cycle performance curve of lithium-sulfur cell prepared by/acetylene black modified diaphragm under 0.5C multiplying power.As seen from the figure, circulate 350 times under 0.5C multiplying power, specific discharge capacity is still 490mAh/g, illustrates and adopts the lithium-sulfur cell of this modified diaphragm to have good cycle performance under 0.5C multiplying power.
Embodiment 4
A kind of preparation method of lithium-sulfur cell modified diaphragm of the present invention, modified diaphragm and there is the embodiment of lithium-sulfur cell of this modified diaphragm:
Prepared by modified diaphragm: by the SiO of preparation
2nano particle mixes with the ratio of mass ratio 6:1 with carbon fiber, ball milling 12 hours, obtains the coating material mixed; Again by the coating material that mixes and Polyurethane with mass ratio 5:1 Homogeneous phase mixing, and be distributed in 1-METHYLPYRROLIDONE solvent, ultrasonic disperse obtains finely dispersed coating material in 12 hours; Adopt the mode of scraper coating that finely dispersed slurry is coated on Teflon septum surface, the barrier film coated is put into vacuum drying chamber, drying 6 hours at 50 DEG C, obtained modified diaphragm.
Battery is assembled: prepare sulphur positive pole with carbon/sulphur (for 1:4, sulfur content accounts for 80% of electrode slice quality to carbon/sulphur mass ratio) composite material, metal lithium sheet is negative pole, and the modified diaphragm adopting the present embodiment to prepare is assembled into button cell, and is filled with electrolyte.
Electrochemical property test: use the indigo plant of Wuhan Lan Bo Electronics Co., Ltd. electricity LANDCT2001A discharge and recharge instrument to carry out charge-discharge test to battery in room temperature (25 DEG C), charging/discharging voltage scope is 1.5V-2.8V.In 0.5C multiplying power, its cycle performance is tested.
Fig. 8 is for adopting the present embodiment SiO
2the cycle performance curve of lithium-sulfur cell prepared by/carbon fiber modifying barrier film under 0.5C multiplying power.As seen from the figure, circulate 350 times under 0.5C multiplying power, specific discharge capacity is still 450mAh/g, illustrates and adopts the lithium-sulfur cell of this modified diaphragm to have good cycle performance under 0.5C multiplying power.
Embodiment 5
A kind of preparation method of lithium-sulfur cell modified diaphragm of the present invention, modified diaphragm and there is the embodiment of lithium-sulfur cell of this modified diaphragm:
Prepared by modified diaphragm: by the Al of preparation
2o
3nano particle mixes with the ratio of mass ratio 3:1 with conductive black (SuperP), ball milling 12 hours, obtains the coating material mixed; Again by the coating material that mixes and polyvinyl alcohol with mass ratio 3:1 Homogeneous phase mixing, and be distributed in alcohol solvent, mechanical agitation obtains finely dispersed coating material in 12 hours; Adopt the mode of scraper coating that finely dispersed slurry is coated on polyacrylonitrile membrane surface, the barrier film coated is put into vacuum drying chamber, drying 6 hours at 50 DEG C, obtained modified diaphragm.
Battery is assembled: prepare sulphur positive pole with carbon/sulphur (for 1:4, sulfur content accounts for 80% of electrode slice quality to carbon/sulphur mass ratio) composite material, metal lithium sheet is negative pole, and the modified diaphragm adopting the present embodiment to prepare is assembled into button cell, and is filled with electrolyte.
Electrochemical property test: use the indigo plant of Wuhan Lan Bo Electronics Co., Ltd. electricity LANDCT2001A discharge and recharge instrument to carry out charge-discharge test to battery in room temperature (25 DEG C), charging/discharging voltage scope is 1.5V-2.8V.In 0.5C multiplying power, its cycle performance is tested.
Fig. 9 is for adopting the present embodiment Al
2o
3the cycle performance curve of lithium-sulfur cell prepared by/SuperP modified diaphragm under 0.5C multiplying power.As seen from the figure, circulate 350 times under 0.5C multiplying power, specific discharge capacity is still 405mAh/g, illustrates and adopts the lithium-sulfur cell of this modified diaphragm to have good cycle performance under 0.5C multiplying power.
Embodiment 6
A kind of preparation method of lithium-sulfur cell modified diaphragm of the present invention, modified diaphragm and there is the embodiment of lithium-sulfur cell of this modified diaphragm:
Prepared by modified diaphragm: by the Al of preparation
2o
3nano particle, SiO
2nano particle and nitrogen-doped carbon are with mass ratio 1:1:1, and ball milling 12 hours, obtains the coating material mixed; Again by the coating material that mixes and polyvinylidene fluoride with mass ratio 4:1 Homogeneous phase mixing, and be distributed in alcohol solvent, mechanical agitation obtains finely dispersed coating material in 12 hours; Adopt the mode of scraper coating that finely dispersed slurry is coated on polyimide diaphragm surface, the barrier film coated is put into vacuum drying chamber, drying 6 hours at 50 DEG C, obtained modified diaphragm.
Battery is assembled: prepare sulphur positive pole with carbon/sulphur (for 1:4, sulfur content accounts for 80% of electrode slice quality to carbon/sulphur mass ratio) composite material, metal lithium sheet is negative pole, and the modified diaphragm adopting the present embodiment to prepare is assembled into button cell, and is filled with electrolyte.
Electrochemical property test: use the indigo plant of Wuhan Lan Bo Electronics Co., Ltd. electricity LANDCT2001A discharge and recharge instrument to carry out charge-discharge test to battery in room temperature (25 DEG C), charging/discharging voltage scope is 1.5V-2.8V.In 0.5C multiplying power, its cycle performance is tested.
Figure 10 is for adopting the present embodiment (Al
2o
3+ SiO
2the cycle performance curve of lithium-sulfur cell prepared by)/nitrogen-doped carbon modified diaphragm under 0.5C multiplying power.As seen from the figure, circulate 350 times under 0.5C multiplying power, specific discharge capacity is still 405mAh/g, illustrates and adopts the lithium-sulfur cell of this modified diaphragm to have good cycle performance under 0.5C multiplying power.
Claims (10)
1. a preparation method for lithium-sulfur cell modified diaphragm, is characterized in that, comprises the following steps: by conductive agent and nano-metal-oxide in mass ratio 1:1 ~ 10:1 mix, obtain the coating material mixed; By described coating material and binding agent in mass ratio 1:1 ~ 5:1 mix, be then distributed in solvent; Finely dispersed coating paste is obtained by mechanical agitation or ultrasonic disperse; Gained coating paste is coated on a diaphragm matrix surface, vacuumize, obtains lithium-sulfur cell modified diaphragm.
2. the preparation method of lithium-sulfur cell modified diaphragm according to claim 1, is characterized in that: described nano-metal-oxide is nanometer Mg
0.6ni
0.4o, Mg
0.8cu
0.2o, TiO
2, Al
2o
3, SiO
2in one or more.
3. the preparation method of lithium-sulfur cell modified diaphragm according to claim 1, is characterized in that: described conductive agent is one or more in conductive black, acetylene black, carbon fiber, carbon nano-tube, Ketjen black, nitrogen-doped carbon, Graphene, nitrogen-doped graphene.
4. the preparation method of lithium-sulfur cell modified diaphragm according to claim 1, is characterized in that: described binding agent is one or more in polyvinylidene fluoride, polyvinyl alcohol, polytetrafluoroethylene, sodium carboxymethylcellulose, Polyurethane.
5. the preparation method of lithium-sulfur cell modified diaphragm according to claim 1, is characterized in that: described solvent is one or more in ethanol, acetone, 1-METHYLPYRROLIDONE.
6. the preparation method of lithium-sulfur cell modified diaphragm according to claim 1, is characterized in that: described vacuum drying temperature is 40 ~ 60 DEG C, and the vacuum drying time is 6 ~ 24 hours.
7. the lithium-sulfur cell modified diaphragm that preparation method obtains according to any one of claim 1-6, it is characterized in that: described modified diaphragm comprises the coating that diaphragm matrix and diaphragm matrix apply, described diaphragm matrix is one or more in polypropylene, polyethylene, polyimides, Kynoar, polytetrafluoroethylene, polyacrylonitrile, polyamide, glass ceramics, and the thickness of diaphragm matrix is 10 ~ 50 μm; The surface density of described coating is 0.1-10mg/cm
2; The integral thickness of described modified diaphragm is 15 ~ 100 μm.
8. one kind has the lithium-sulfur cell of modified diaphragm, comprise sulphur positive plate, metal lithium sheet negative pole and electrolyte, it is characterized in that: between described sulphur positive plate and metal lithium sheet negative pole, be provided with modified diaphragm that preparation method according to any one of claim 1-6 obtains or as claimed in claim 7.
9. the lithium-sulfur cell with modified diaphragm according to claim 8, is characterized in that: described sulphur positive plate is made up of carbon/sulphur composite material, and its carbon/sulphur mass ratio is 1:4.
10. the lithium-sulfur cell with modified diaphragm according to claim 8 or claim 9, is characterized in that: the described lithium-sulfur cell specific discharge capacity after 350 times that circulates under charging/discharging voltage scope is 1.5V-2.8V, 0.5C multiplying power is not less than 500mAh/g.
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|---|---|---|---|
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| CN106684290A (en) * | 2016-12-29 | 2017-05-17 | 宁波中科达新材料有限公司 | Lithium ion battery diaphragm and preparation method therefor |
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