CN105679983A - Modified diaphragm and preparation method and application therefor - Google Patents
Modified diaphragm and preparation method and application therefor Download PDFInfo
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- CN105679983A CN105679983A CN201610139128.5A CN201610139128A CN105679983A CN 105679983 A CN105679983 A CN 105679983A CN 201610139128 A CN201610139128 A CN 201610139128A CN 105679983 A CN105679983 A CN 105679983A
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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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- 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
- H01M10/052—Li-accumulators
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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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- 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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Abstract
The invention discloses a modified diaphragm. The modified diaphragm comprises a diaphragm substrate, and an electronic conductive coating layer and an inorganic hard coating layer positioned on the two surfaces of the diaphragm substrate respectively, wherein the electronic conductive coating layer is a mixed coating layer with graphene and a porous carbon material; and the inorganic hard coating layer is a nitrogen-carbon material coating layer, a nitrogen-silicon material coating layer, a carbon-boron material coating layer or a silicon-carbon material coating layer. The preparation method comprises the steps of uniformly coating the two surfaces of the diaphragm substrate with the electronic conductive coating layer and the inorganic hard coating layer respectively, and drying the two surfaces respectively obtain the modified diaphragm. The modified diaphragm has high diffusion and absorption capacity for an organic electrolyte, high ionic conductivity, and an obvious adsorption and blocking effect on poly-sulfur-lithium; in addition, the modified diaphragm can further restrain a shuttle effect, prevent battery short-circuit, effectively restrain the growth of negative electrode metal lithium dendrites in a cyclic process, prevent from punching the diaphragm, and protect the lithium negative electrode, so that the problem that the diaphragm is punched after dendrites formation is solved, and the safety performance of the battery is improved.
Description
Technical field
The present invention relates to lithium-sulfur cell technical field, modified diaphragm particularly relating to a kind of double measure and preparation method thereof and lithium-sulfur cell.
Background technology
Along with the fast development of the constantly progressive of science and technology and electronic product, people are in the urgent need to high-energy-density, eco-friendly battery system, thus lithium-sulfur cell comes into the visual field of researcher gradually.
With conventional lithium ion battery positive electrode LiCoO2、LiMn2O4、LiPFeO4Etc. comparing, lithium sulfur battery anode material sulfur positive pole has higher theoretical specific capacity (1675mAh/g), higher energy density (2600Wh/kg), is the secondary cell system that the energy density except lithium-air battery being currently known is the highest. In addition positive pole raw material Sulphur ressource enriches, and cheap, battery is less costly, and produces hardly to pollute in charging process, environmentally friendly, thus is paid close attention to widely and study.
But, compared with conventional lithium ion battery positive electrode, lithium-sulfur cell discharge voltage plateau is relatively low, and it has two discharge platforms, and first discharge platform, between 2.2～2.3V, is mainly the S of circulus8Molecule is converted into the S of long-chainn 2-(3≤n≤8) are combined the polysulfide lithium forming long-chain with lithium ion; Second discharge platform, mainly between 2.1V～2.2V, is mainly the S of long-chainn 2-(3≤n≤8) are converted into the S of short chainn 2-(1≤n≤2), this platform is main discharge platform. Long-chain polysulfide lithium owing to producing in charge and discharge process can dissolve in the electrolytic solution, causes the loss of active substance, and repeatedly move to cathode of lithium and react with it, cause " effect of shuttling back and forth ", so that capacity reduces, cause lithium-sulfur cell capacity rapid decay, thus cycle life is shorter. Additionally, the electrical conductivity of elemental sulfur is only 5 10 under room temperature-30S/cm, electro-chemical activity is poor, so that add substantial amounts of porous conductive material compound with it (such as Graphene, CNT etc.), so that the energy density of battery reduces. Further, electric discharge end-product Li2S、Li2S2Insoluble, conduct electricity hardly, be deposited on the surface of lithium metal, so that the internal resistance of battery increases, also can reduce specific discharge capacity and the cycle life of lithium-sulfur cell.In charge and discharge process, part lithium can lose activity, and becomes irreversible " dead lithium ". And the inhomogeneities due to electrode surface, it is possible to can form Li dendrite, puncture barrier film, cause short circuit, thus causing safety issue.
The shuttle back and forth reaction of effect and lithium anode and electrolyte of lithium-sulfur cell is restriction lithium-sulfur cell development business-like key factor. in order to solve the problems referred to above, research worker has carried out substantial amounts of research in anode, negative pole, electrolyte, barrier film etc. to on diagram modification, porous carbon nanotube/polyethyleneglycol modified barrier film [GuanchaoWang, RoyalSocietyofChemistryA, 2015, 3, 7139], carbon modifies barrier film [ShenghengChung, AdvFunctMater, 2014, 24, 5299-5306] etc. the application of functional barrier film, improve cycle life and the high rate performance of lithium-sulfur cell, but material with carbon element is coated on barrier film, electron conduction due to pore structure and the material with carbon element of barrier film, short circuit is easily caused after assembled battery, in addition feasible measure is not proposed in cathode of lithium protection, aluminium oxide modifies barrier film [ZhiyongZhang, ElectrochimicaActa, 129 (2014) 55-61] application, improve the performance of lithium-sulfur cell, but alumina adsorption ability is more weak, and feasible measure is not proposed in cathode of lithium protection. thus, not working out a kind of modified diaphragm at present can improve cycle life and the high rate performance of lithium-sulfur cell, moreover it is possible to cathode of lithium protection provides protective measure, the problem that especially Li dendrite pierces through barrier film after being formed.
Summary of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art, it is provided that modified diaphragm of a kind of double measure and preparation method thereof and lithium-sulfur cell.
For solving above-mentioned technical problem, the technical scheme that the present invention proposes is:
A kind of modified diaphragm, including diaphragm matrix and the electronic conductive coating and the inorganic hard coating that lay respectively at described diaphragm matrix two surface; Wherein said electronic conductive coating is the mixed coating of Graphene and porous carbon materials, and described inorganic hard coating is nitrogen material with carbon element coating, nitrogen silicon materials coating, carbon boron material coating or silicon carbon material coating. In the present invention, electronic conductive coating has high specific surface area and abundant functional group, and polysulfide lithium has significantly absorption barrier effect many for sulfur electrode intermediate product lithium sulfides can be limited in the side of sulfur electrode, and then the generation of the effect that suppresses to shuttle back and forth; Inorganic hard material, almost without electron conduction, is possible not only to prevent battery short circuit, moreover it is possible to effectively suppresses the growth of negative metal Li dendrite in cyclic process, improves the security performance of battery.
Above-mentioned modified diaphragm, it is preferred that in described electronic conductive coating, the mass content of Graphene is 10%～50%; The thickness of described electronic conductive coating is 100nm～100 μm; Described porous carbon materials at least one in conductive black, carbon fiber, acetylene black, CNT, nitrogen-doped carbon nanometer pipe, N doping porous carbon, nitrogen-doped carbon fiber.
Above-mentioned modified diaphragm, it is preferred that described inorganic hard coating at least one in carbon nitride coatings, boron carbide coating, silicon nitride coating, coat of silicon carbide, titanium carbide coating, the thickness of described inorganic hard coating is 100nm～100 μm.
Above-mentioned modified diaphragm, preferably, described diaphragm matrix is selected from any one in polyethylene diagrams, polypropylene diaphragm, polyethylene/polypropylene two-layer separator, polypropylene, polyethylene/polypropylene three-layer membrane, non-woven fabrics barrier film, polyacrylonitrile porous membrane, glass fibre membrane.
As a total inventive concept, the preparation method that the present invention also provides for a kind of above-mentioned modified diaphragm, comprise the following steps:
(1) by uniform to electronic conductive material, binding agent and dispersant grinding, electronic conduction slurry is obtained;
By uniform to inorganic hard material, binding agent and dispersant grinding, obtain inorganic hard material paste;
(2) electronic conduction slurry prepared by step (1) is coated uniformly on a surface of diaphragm matrix and dries;
(3) inorganic hard material paste it is coated uniformly on another surface of barrier film and dries, namely obtaining described modified diaphragm.
Above-mentioned preparation method, it is preferred that the preparation order exchange of described step (2) and described step (3).
Above-mentioned preparation method, preferably, one or more in Kynoar (PVDF), politef (PTFE), polyacrylic acid (PAA), acrylonitrile multiple copolymer (LA132), sodium carboxymethyl cellulose (CMC), gelatin of described binding agent; Described dispersant is one or more in water, N-Methyl pyrrolidone, methanol, ethanol, propanol, isopropanol.
Above-mentioned preparation method, it is preferred that described baking temperature is 30～60 DEG C, dry form is vacuum drying, and the vacuum drying time is 2～24h.
Above-mentioned preparation method, it is preferred that in described electronic conduction slurry, the addition of binding agent accounts for the 5%～20% of binding agent and electronic conductive material gross mass; In described inorganic hard material paste, the addition of binding agent accounts for the 5%～20% of binding agent and inorganic hard material gross mass.
As a total inventive concept, the present invention also provides for a kind of lithium-sulfur cell, including positive pole, negative pole and barrier film, and the modified diaphragm that wherein said barrier film is above-mentioned modified diaphragm or prepared by above-mentioned preparation method.
The present invention prepares functional decorative layer on battery diaphragm surface, this decorative layer respectively electronic conductive coating and inorganic hard coating, so that diffusion and the absorbability of organic electrolyte are strengthened by barrier film, makes the ionic conductivity of barrier film significantly improve simultaneously; Electronic conduction modifies the specific surface area of floor height and many lithium sulfides are had and significantly stop adsorption by abundant functional group, it is possible to many for sulfur electrode intermediate product lithium sulfides are limited in the side of sulfur electrode, and then the generation of the effect that suppresses to shuttle back and forth; Inorganic hard coating, almost without electron conduction, can not only prevent battery short circuit, moreover it is possible to effectively suppresses the growth of negative metal Li dendrite in cyclic process, improves the security performance of battery.
Compared with prior art, it is an advantage of the current invention that:
(1) modified diaphragm of the present invention, in electronic conductive coating and the inorganic hard coating on diaphragm matrix two surface so that diffusion and the absorbability of organic electrolyte are strengthened by barrier film, and the ionic conductivity of barrier film significantly improves simultaneously; Electronic conductive coating has high specific surface area and abundant functional group, and polysulfide lithium has significantly absorption barrier effect many for sulfur electrode intermediate product lithium sulfides can be limited in the side of sulfur electrode, and then the generation of the effect that suppresses to shuttle back and forth; And inorganic hard coating is almost without electron conduction; battery short circuit can not only be prevented; can also effectively suppress the growth of negative metal Li dendrite in cyclic process; prevent it from piercing through barrier film; cathode of lithium can be protected; solving the problem piercing through barrier film after Li dendrite is formed, improve the security performance of battery, this advantage makes the lithium-sulfur cell using the modified diaphragm of the present invention can be applicable to electrokinetic cell.
(2) the preparation method technological process of the present invention is simple, it is easy to accomplish industrial operation.
Accompanying drawing explanation
Fig. 1 is the lithium-sulfur cell structural representation of preparation in the embodiment of the present invention 1.
Marginal data: 1, diaphragm matrix; 2, electronic conductive coating; 3, inorganic hard coating.
Fig. 2 is the first charge-discharge curve of the lithium-sulfur cell of preparation in the embodiment of the present invention 1.
Fig. 3 is the cycle performance of lithium-sulfur cell of preparation in the embodiment of the present invention 1 and the coulombic efficiency variation diagram with cycle-index.
Fig. 4 is the first charge-discharge curve of the lithium-sulfur cell in comparative example 1.
Fig. 5 is the cycle performance of the lithium-sulfur cell in comparative example 1 and the coulombic efficiency variation diagram with cycle-index.
Fig. 6 is the high rate performance comparison diagram of the embodiment of the present invention 1 and the lithium-sulfur cell of comparative example 1.
Fig. 7 is the first charge-discharge curve chart of the lithium-sulfur cell of preparation in the embodiment of the present invention 2,3,4.
Fig. 8 is the cycle performance figure figure of the lithium-sulfur cell of preparation in the embodiment of the present invention 2,3,4.
Detailed description of the invention
For the ease of understanding the present invention, below in conjunction with Figure of description and preferred embodiment, the present invention is made more comprehensively, describes meticulously, but protection scope of the present invention is not limited to embodiment in detail below.
Unless otherwise defined, the implication that all technical term used hereinafter is generally understood that with those skilled in the art is identical. Technical term used herein is intended merely to the purpose describing specific embodiment, is not intended to limit the scope of the invention.
Except there being special instruction, the various reagent used in the present invention, raw material are can commodity commercially or can pass through the product that known method prepares.
Embodiment 1:
The modified diaphragm of a kind of present invention, including Celgard2325 diaphragm matrix (polypropylene, polyethylene/polypropylene three-layer membrane) and the electronic conductive coating (Graphene and CNT mixed coating) and the inorganic hard coating (carbon nitride coatings) that lay respectively at Celgard2325 barrier film two surface; In electronic conductive coating, the mass content of Graphene is 50%; The thickness of electronic conductive coating is 50 μm; The thickness of inorganic hard coating is 50 μm.
The preparation method of the modified diaphragm of the present embodiment, comprises the following steps:
(1) a Celgard2325 barrier film is taken, after using ethanol purge, drying for standby;
(2) 0.9mg carbonitride powder body and 0.1mg Kynoar (PVDF) are dispersed in N-Methyl pyrrolidone (NMP), prepare uniformly inorganic hard material paste;
0.5mg Graphene, 0.4mg CNT are dispersed in N-Methyl pyrrolidone (NMP) with 0.1mg Kynoar (PVDF), prepare uniformly electronic conduction slurry;
(3) adopting scraper coating method to be coated on a surface of Celgard2325 barrier film by inorganic hard material paste prepared by step (2), at 50 DEG C, vacuum drying 12h forms the inorganic hard coating of one layer of 50 μ m-thick; Then barrier film is overturn, adopt scraper semar technique to be coated on another surface of barrier film by electronic conduction slurry prepared by step (2), form the electronic conductive coating of one layer of 50 μ m-thick at 50 DEG C after vacuum drying 12h, obtain modified diaphragm.
Then conductive agent section qin white carbon black is dispersed in N-Methyl pyrrolidone (NMP) with Sublimed Sulfur and binding agent Kynoar (PVDF) according to mass ratio 6:3:1, aluminium foil is coated with drying and prepares sulfur electrode. The modified diaphragm prepared by the present embodiment again is as the barrier film of battery, sulfur electrode is as positive pole, lithium metal assembles CR2025 button cell as negative pole, as shown in Figure 1, electronic conductive coating 2 and inorganic hard coating 3 are positioned at two surfaces of diaphragm matrix 1 and form modified diaphragm, electronic conductive coating 2 faces toward sulfur electrode, the corresponding cathode of lithium of inorganic hard coating 3;Electrolyte adopts the LiTFSI/DME/DOL of 0.5 mol/L, and additive is the LiNO of 0.1 mol/L3. Testing this battery under 0.1C multiplying power, the first charge-discharge curve of battery is as in figure 2 it is shown, the discharge capacity first of this battery is more than 1247.5mAh/g; As it is shown on figure 3, circulating battery 100 times, specific discharge capacity keeps 802mAh/g, and the coulombic efficiency of battery is maintained at 99.9%, and the effect of shuttling back and forth of battery substantially weakens.
Comparative example 1:
This comparative example differs only in, with embodiment 1, the barrier film being battery with Celgard2325 barrier film, and other conditions are all identical with enforcement 1. Testing the chemical property of the battery of this comparative example, as shown in Figure 4, under 0.1C multiplying power, the discharge capacity first of this battery is more than 861mAh/g for the first charge-discharge curve of battery. As it is shown in figure 5, circulating battery 50 times, specific discharge capacity keeps 502mAh/g, and the coulombic efficiency of battery is maintained at 96%, and the effect of shuttling back and forth of battery strengthens relatively.
The high rate performance of the lithium-sulfur cell of embodiment 1 and this comparative example contrasts as shown in Figure 6, use the lithium-sulfur cell after modified diaphragm under the multiplying power of 0.1C, 0.2C, 0.5C, 1C, 2C, its specific discharge capacity respectively 1123.4mAh/g, 1005.6mAh/g, 894.2mAh/g, 797.6mAh/g, 698.6mAh/g, when returning to 0.1C electric discharge, its specific capacity also has 888mAh/g. And adopt the lithium-sulfur cell of unmodified barrier film, it is under the multiplying power of 0.1C, 0.2C, 0.5C, 1C, 2C, its specific discharge capacity respectively 923mAh/g, 602.2mAh/g, 431mAh/g, 301.6mAh/g, 198.1mAh/g, when returning to 0.1C electric discharge, its specific capacity only has 402.7mAh/g. It appeared that after use modified diaphragm, the high rate performance of battery improves, when particularly in big multiplying power discharging, can be applicable to electrokinetic cell.
Embodiment 2:
The modified diaphragm of a kind of present invention, including polyethylene diagrams and the electronic conductive coating (Graphene and carbon nano-fiber mixed coating) and the inorganic hard coating (boron carbide coating) that lay respectively at polyethylene diagrams two surface; In electronic conductive coating, the mass content of Graphene is 40%; The thickness of electronic conductive coating is 10 μm; The thickness of inorganic hard coating is 10 μm.
The preparation method of the modified diaphragm of the present embodiment, comprises the following steps:
(1) polyethylene diagrams is taken, after using ethanol purge, drying for standby;
(2) 0.9mg boron carbide powder and 0.1mg Kynoar (PVDF) are dispersed in N-Methyl pyrrolidone (NMP), prepare uniformly inorganic hard material paste;
0.4mg Graphene, 0.5mg carbon nano-fiber are dispersed in N-Methyl pyrrolidone (NMP) with 0.1mg Kynoar (PVDF), prepare uniformly electronic conduction slurry;
(3) adopting scraper coating method to be coated on polyethylene diagrams one surface by inorganic hard material paste prepared by step (2), at 60 DEG C, vacuum drying 10h forms the inorganic hard coating of one layer of 10 μ m-thick; Then being overturn by barrier film, adopt scraper semar technique to be coated on another surface of barrier film by electronic conduction slurry prepared by step (2), at 60 DEG C, vacuum drying 10h forms the electronic conductive coating of one layer of 10 μ m-thick, obtains modified diaphragm.
Then conductive agent section qin white carbon black is dispersed in N-Methyl pyrrolidone (NMP) with Sublimed Sulfur and binding agent Kynoar (PVDF) according to mass ratio 6:3:1, aluminium foil is coated with drying and prepares sulfur electrode. The modified diaphragm prepared by the present embodiment again is as the barrier film of battery, sulfur electrode is as positive pole, lithium metal assembles CR2025 button cell as negative pole, as shown in Figure 1, electronic conductive coating 2 and inorganic hard coating 3 are positioned at two surfaces of diaphragm matrix 1 and form modified diaphragm, electronic conductive coating 2 faces toward sulfur electrode, the corresponding cathode of lithium of inorganic hard coating 3;Electrolyte adopts the LiTFSI/DME/DOL of 0.5 mol/L, and additive is the LiNO of 0.1 mol/L3. Testing this battery under 0.1C multiplying power, the first charge-discharge curve of battery is as it is shown in fig. 7, the discharge capacity first of this battery is more than 1050.6mAh/g; As shown in Figure 8, circulating battery 50 times, specific discharge capacity keeps 761.6mAh/g, and cycle performance is better.
Embodiment 3:
The modified diaphragm of a kind of present invention, including polypropylene diaphragm matrix and the electronic conductive coating (Graphene and porous carbon mixed coating) and the inorganic hard coating (silicon nitride coating) that lay respectively at polypropylene diaphragm two surface; In electronic conductive coating, the mass content of Graphene is 20%; The thickness of electronic conductive coating is 50 μm; The thickness of inorganic hard coating is 50 μm.
The preparation method of the modified diaphragm of the present embodiment, comprises the following steps:
(1) polypropylene diaphragm is taken, after using ethanol purge, drying for standby;
(2) 0.8mg beta-silicon nitride powder and 0.2mg politef (PTFE) are dispersed in water, prepare uniformly inorganic hard material paste;
0.2mg Graphene, 0.6mg porous carbon are dispersed in N-Methyl pyrrolidone (NMP) with 0.2mg Kynoar (PVDF), prepare uniformly electronic conduction slurry;
(3) adopting scraper coating method to be coated on polypropylene diaphragm one surface by electronic conduction slurry prepared by step (2), at 40 DEG C, vacuum drying 12h forms the electronic conductive coating of one layer of 50 μ m-thick; Then being overturn by barrier film, adopt scraper semar technique to be coated on another surface of barrier film by inorganic hard material paste prepared by step (2), at 40 DEG C, vacuum drying 12h forms the inorganic hard coating of one layer of 50 μ m-thick, obtains modified diaphragm.
Then conductive agent section qin white carbon black is dispersed in N-Methyl pyrrolidone (NMP) with Sublimed Sulfur and binding agent Kynoar (PVDF) according to mass ratio 6:3:1, aluminium foil is coated with drying and prepares sulfur electrode. The modified diaphragm prepared by the present embodiment again is as the barrier film of battery, sulfur electrode is as positive pole, lithium metal assembles CR2025 button cell as negative pole, as shown in Figure 1, electronic conductive coating 2 and inorganic hard coating 3 are positioned at two surfaces of diaphragm matrix 1 and form modified diaphragm, electronic conductive coating 2 faces toward sulfur electrode, the corresponding cathode of lithium of inorganic hard coating 3; Electrolyte adopts the LiTFSI/DME/DOL of 0.5 mol/L, and additive is the LiNO of 0.1 mol/L3. Testing this battery under 0.1C multiplying power, the first charge-discharge curve of battery is as it is shown in fig. 7, the discharge capacity first of this battery is more than 1103.4mAh/g; As shown in Figure 8, circulating battery 50 times, specific discharge capacity keeps 814.1mAh/g, and cycle performance is better.
Embodiment 4:
The modified diaphragm of a kind of present invention, including polyethylene/polypropylene diaphragm matrix and the electronic conductive coating (Graphene and acetylene black mixed coating) and the inorganic hard coating (coat of silicon carbide) that lay respectively at polyethylene/polypropylene barrier film two surface; In electronic conductive coating, the mass content of Graphene is 33%; The thickness of electronic conductive coating is 100 μm; The thickness of inorganic hard coating is 100 μm.
The preparation method of the modified diaphragm of the present embodiment, comprises the following steps:
(1) a polyethylene/polypropylene barrier film is taken, after using ethanol purge, drying for standby;
(2) 0.8mg silicon carbide powder and 0.2mg politef (PTFE) are dispersed in water, prepare uniformly inorganic hard material paste;
0.3mg Graphene, 0.5mg acetylene black are dispersed in N-Methyl pyrrolidone (NMP) with 0.1mg Kynoar (PVDF), prepare uniformly electronic conduction slurry;
(3) adopting scraper coating method to be coated on polyethylene/polypropylene barrier film one surface by electronic conduction slurry prepared by step (2), at 50 DEG C, vacuum drying 12h forms the electronic conductive coating of one layer of 100 μ m-thick; Then being overturn by barrier film, adopt scraper semar technique to be coated on another surface of barrier film by inorganic hard material paste prepared by step (2), at 50 DEG C, vacuum drying 12h forms the inorganic hard coating of one layer of 100 μ m-thick, obtains modified diaphragm.
Then conductive agent section qin white carbon black is dispersed in N-Methyl pyrrolidone (NMP) with Sublimed Sulfur and binding agent Kynoar (PVDF) according to mass ratio 6:3:1, aluminium foil is coated with drying and prepares sulfur electrode. The modified diaphragm prepared by the present embodiment again is as the barrier film of battery, sulfur electrode is as positive pole, lithium metal assembles CR2025 button cell as negative pole, as shown in Figure 1, electronic conductive coating 2 and inorganic hard coating 3 are positioned at two surfaces of diaphragm matrix 1 and form modified diaphragm, electronic conductive coating 2 faces toward sulfur electrode, the corresponding cathode of lithium of inorganic hard coating 3; Electrolyte adopts the LiTFSI/DME/DOL of 0.5 mol/L, and additive is the LiNO of 0.1 mol/L3. Testing this battery under 0.1C multiplying power, the first charge-discharge curve of battery is as it is shown in fig. 7, the discharge capacity first of this battery is more than 1122.7mAh/g; As shown in Figure 8, circulating battery 50 times, specific discharge capacity keeps 875.9mAh/g, and cycle performance is better.
Claims (10)
1. a modified diaphragm, it is characterised in that described modified diaphragm includes diaphragm matrix and lays respectively at electronic conductive coating and the inorganic hard coating on described diaphragm matrix two surface; Wherein said electronic conductive coating is the mixed coating of Graphene and porous carbon materials, and described inorganic hard coating is nitrogen material with carbon element coating, nitrogen silicon materials coating, carbon boron material coating or silicon carbon material coating.
2. modified diaphragm as claimed in claim 1, it is characterised in that in described electronic conductive coating, the mass content of Graphene is 10%～50%; The thickness of described electronic conductive coating is 100nm～100 μm; Described porous carbon materials at least one in conductive black, carbon fiber, acetylene black, CNT, nitrogen-doped carbon nanometer pipe, N doping porous carbon, nitrogen-doped carbon fiber.
3. modified diaphragm as claimed in claim 1, it is characterized in that, described inorganic hard coating at least one in carbon nitride coatings, boron carbide coating, silicon nitride coating, coat of silicon carbide, titanium carbide coating, the thickness of described inorganic hard coating is 100nm～100 μm.
4. modified diaphragm as claimed in claim 1, it is characterized in that, described diaphragm matrix is selected from any one in polyethylene diagrams, polypropylene diaphragm, polyethylene/polypropylene two-layer separator, polypropylene, polyethylene/polypropylene three-layer membrane, non-woven fabrics barrier film, polyacrylonitrile porous membrane, glass fibre membrane.
5. the preparation method of the modified diaphragm as according to any one of Claims 1 to 4, it is characterised in that comprise the following steps:
(1) by uniform to electronic conductive material, binding agent and dispersant grinding, electronic conduction slurry is obtained;
By uniform to inorganic hard material, binding agent and dispersant grinding, obtain inorganic hard material paste;
(2) electronic conduction slurry prepared by step (1) is coated uniformly on a surface of diaphragm matrix and dries;
(3) inorganic hard material paste it is coated uniformly on another surface of barrier film and dries, namely obtaining described modified diaphragm.
6. preparation method as claimed in claim 5, it is characterised in that the preparation order exchange of described step (2) and described step (3).
7. the preparation method as described in claim 5 or 6, it is characterised in that one or more in Kynoar, politef, polyacrylic acid, acrylonitrile multiple copolymer, sodium carboxymethyl cellulose, gelatin of described binding agent; Described dispersant is one or more in water, N-Methyl pyrrolidone, methanol, ethanol, propanol, isopropanol.
8. the preparation method as described in claim 5 or 6, it is characterised in that described baking temperature is 30～60 DEG C, dry form is vacuum drying, and the vacuum drying time is 2～24h.
9. the preparation method as described in claim 5 or 6, it is characterised in that in described electronic conduction slurry, the addition of binding agent accounts for the 5%～20% of binding agent and electronic conductive material gross mass; In described inorganic hard material paste, the addition of binding agent accounts for the 5%～20% of binding agent and inorganic hard material gross mass.
10. a lithium-sulfur cell, including positive pole, negative pole and barrier film, it is characterised in that the modified diaphragm that described barrier film is the modified diaphragm described in any one of Claims 1 to 4 or prepared by the preparation method described in any one of claim 5～9.
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Cited By (44)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106450422A (en) * | 2016-09-30 | 2017-02-22 | 上海空间电源研究所 | Lithium-sulfur battery with multi-protection layer structure |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012124029A (en) * | 2010-12-08 | 2012-06-28 | Sony Corp | Layered microporous film, battery separator and nonaqueous electrolyte battery |
| CN105051941A (en) * | 2013-03-19 | 2015-11-11 | 索尼公司 | Separator, battery, battery pack, electronic apparatus, electric vehicle, power storage device, and power system |
| CN105140447A (en) * | 2015-07-23 | 2015-12-09 | 中国科学院上海硅酸盐研究所 | Functional composite membrane for lithium-sulfur battery and preparation method of functional composite membrane |
| CN105261721A (en) * | 2015-08-28 | 2016-01-20 | 清华大学 | Asymmetric diaphragm and application thereof in lithium-sulfur rechargeable battery |
-
2016
- 2016-03-11 CN CN201610139128.5A patent/CN105679983A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012124029A (en) * | 2010-12-08 | 2012-06-28 | Sony Corp | Layered microporous film, battery separator and nonaqueous electrolyte battery |
| CN105051941A (en) * | 2013-03-19 | 2015-11-11 | 索尼公司 | Separator, battery, battery pack, electronic apparatus, electric vehicle, power storage device, and power system |
| CN105140447A (en) * | 2015-07-23 | 2015-12-09 | 中国科学院上海硅酸盐研究所 | Functional composite membrane for lithium-sulfur battery and preparation method of functional composite membrane |
| CN105261721A (en) * | 2015-08-28 | 2016-01-20 | 清华大学 | Asymmetric diaphragm and application thereof in lithium-sulfur rechargeable battery |
Non-Patent Citations (2)
| Title |
|---|
| Q.XU，ET AL.: "A trilayer carbon nanotube/Al2O3/polypropylene separator for lithium-sulfur batteries", 《IONICS》 * |
| RENSHENG SONG，ET AL.: "A trilayer separator with dual function for high performance lithiumesulfur batteries", 《JOURNAL OF POWER SOURCES》 * |
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