CN104051695A - Polymer modified diaphragm for lithium sulphur battery, preparation method of polymer modified diaphragm and lithium sulphur battery - Google Patents
Polymer modified diaphragm for lithium sulphur battery, preparation method of polymer modified diaphragm and lithium sulphur battery Download PDFInfo
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- CN104051695A CN104051695A CN201410280367.3A CN201410280367A CN104051695A CN 104051695 A CN104051695 A CN 104051695A CN 201410280367 A CN201410280367 A CN 201410280367A CN 104051695 A CN104051695 A CN 104051695A
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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
- H01M50/411—Organic 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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
Abstract
The invention provides a polymer modified diaphragm for a lithium sulphur battery, a preparation method of the polymer modified diaphragm and the lithium sulphur battery. The polymer modified diaphragm for the lithium sulphur battery is composed of a battery diaphragm and a polymer modified layer attached on the battery diaphragm, wherein the polymer modified layer is a poly-dopamine modified layer; the poly-dopamine modified layer contains more organic functional groups, has a blocking and absorbing function on an intermediate product, namely lithium polysulfide, during circulation of a sulphur electrode, can effectively prevent solution loss of the lithium polysulfide in a reaction process so as to improve the circulating performance of the battery; the hydrophobic property of the diaphragm is changed into the hydrophilcity of the diaphragm, so that electrolyte can be easily infiltrated into the diaphragm, the ionic conductivity of the diaphragm is increased, and the cycling stability and the rate capability of the assembled lithium sulphur battery are greatly improved after the poly-dopamine modified diaphragm is adopted for the lithium sulphur battery.
Description
Technical field
The present invention relates to field of chemical power source, especially a kind of polymer-modified barrier film, its preparation method and the lithium-sulfur cell that has the polymer-modified barrier film of described lithium-sulfur cell to form for lithium-sulfur cell.
Background technology
Active electrode material based on light element, polyelectron " conversion reaction " is the basis that builds high-energy density secondary battery system.Using lithium metal as negative pole, there is can realize when complete conversion reaction the transfer of 2 electronics in the lithium-sulfur cell system that elemental sulfur or sulfenyl composite material are constructed as positive pole, its theoretical energy density up to 2600 watt-hours/kilogram.In addition, the lithium-sulfur cell production cost of raw material is lower, in use seldom produces environmentally harmful material, and can aerobic under overcharge condition separate out, with the obvious advantage aspect fail safe.Therefore, lithium-sulfur cell becomes the focus and emphasis of high specific energy secondary cell research field in recent years.
But, lithium-sulfur cell is still faced with many technical barriers that waits solution so far, these problems comprise: only 5 × 10-30 Siemens/cm of the conductivity of sulphur under (1) room temperature, electro-chemical activity is poor, while making electrode, need add a large amount of conductive additive (as acetylene black), cause the energy density of electrode system to reduce; (2) the many lithium sulfides of intermediate product that generate in charge and discharge process are soluble in organic electrolyte, cause the loss of active material, and cycle life decay is serious; (3) in charging process, be dissolved into that many lithium sulfides of high-order in electrolyte are easy to be diffused into negative pole and parasitic reduction reaction occurs lithium metal, the low order lithium sulfide that is reduced generation spreads back again anodal in oxidizing process subsequently, and then form the vicious circle mechanism that anodal oxidation-negative pole reduces, cause serious cathode of lithium corrosion and lower coulomb efficiency; (4) electric discharge end-product lithium sulfide can be deposited on electrode surface, and its insulating properties can hinder the transmission of electric charge and ion, changes electrode and electrolytical state of interface simultaneously, hinders the further generation of electrochemical reaction; (5) there is larger difference in the density of active material sulphur and electric discharge end-product lithium sulfide, cause sulfur electrode in cyclic process, to there will be obvious volumetric expansion and contraction, thereby the conductive network to electrode skeleton and overall structure causes destruction to a certain degree; (6) cycle performance and the security performance of cathode of lithium dendrite meeting to battery impacts.Above-mentioned many factors has limited the practical development of lithium-sulfur cell.
In order to solve above-mentioned these problems, the research work of recent domestic mainly concentrates on the following aspects: (1) prepares sulfenyl composite material, improves electronics and the ionic conduction ability of sulfur electrode; (2) optimize the composition of electrolyte or adopt novel electrolyte; (3) cathode of lithium modified and protected, stoping electrolyte and the corrosion of polysulfide to cathode of lithium.Such as, do positive pole with sulphur-activated carbon composite material, circulating battery after 25 weeks capacity can be stabilized in 400 MAhs/g (Electrochem.Commun., 2002,4,499); Make positive pole with sulphur-carbon nano tube compound material, 60 weeks rear capacity of circulating battery can remain on 500 MAhs/g (Electrochim Acta, 2006,51,1330); In Chinese patent ZL200810154151.7, use porous carbon and the elemental sulfur of high-ratio surface to prepare carbon/sulphur composite material, after circulating 50 weeks, capacity can be stabilized in 740 MAhs/g.Research paper (J.Power Sources., 2011,196,9839) pass through at LiCF3SO3 (DOL/TEGDME, v/v=1:1) in electrolyte, add LiNO3 and carry out modification electrolyte, the head week discharge capacity of battery in the electrolyte that is added with 0.4 mol/L LiNO3 is 1138.2 MAhs/g, it is 1079.6 MAhs/g in its first all discharge capacity of electrolyte of not adding LiNO3, and charging capacity is respectively 832 MAhs/g and 537 MAhs/g, coulomb efficiency obviously improves.Research paper (J.Power Sources., 2005,152,272) adds 5% or 10% imidazole salts EMIBeti in organic electrolyte, and discharge capacity of the cell also remains on more than 600 MAhs/g after circulation in 100 weeks.Research paper (J.Power Sources, 2003,119,964) method by light initiation polymerization monomer at the polymer film of cathode of lithium plated surface last layer 10 micron thick to avoid electrolyte to contact with the direct of lithium metal surface, thereby polysulfide and lithium metal generation side reaction in inhibition electrolyte, significantly improved the chemical property of lithium-sulfur cell.Other Patents also comprise CN101577323, ZL02111403.X, CN101986443A, CN102201567A, CN102208645A and CN102163712A etc.Generally, these technology can improve the utilance of sulphur to a certain extent, dissolve the problem of shuttling back and forth but fail fundamentally to solve many lithium sulfides, and the performance of lithium-sulfur cell still has much room for improvement.
Based on above-mentioned analysis, the present invention uses barrier film as research object using lithium-sulfur cell, by at commercialization battery diaphragm finishing one deck high molecular polymer, result of study shows, prepared polymer-modified barrier film has good wettability, barrier film after modification becomes hydrophily from hydrophobicity, and diffusion and the absorbability of barrier film to organic electrolyte strengthened, and the ionic conductivity of barrier film obviously improves simultaneously; In addition, the organo-functional group that polymer contains has and significantly stops suction-operated many lithium sulfides, many sulfur electrode intermediate product lithium sulfides can be limited in to a side of sulfur electrode, and then the generation of the effect that suppressed to shuttle back and forth, eliminated the surperficial passivity that cathode of lithium surface forms because of the deposition of insoluble sulfuration lithium simultaneously.High capacity characteristics, long circulation life and the high rate performance of polymer-modified barrier film to lithium-sulfur cell has obvious facilitation.
Summary of the invention
The deficiency existing in order to improve lithium-sulfur cell, the invention provides a kind of polymer-modified barrier film and preparation method thereof for lithium-sulfur cell, and a kind of lithium-sulfur cell being made up of with polymer-modified barrier film described lithium-sulfur cell is also provided simultaneously.
The present invention realizes above-mentioned technical purpose by following technological means.
The polymer-modified barrier film of lithium-sulfur cell, is made up of battery diaphragm and the polymer-modified layer being attached on described battery diaphragm, it is characterized in that, described polymer-modified layer is poly-dopamine decorative layer.
Preferably, the thickness of described poly-dopamine decorative layer is between 2-50nm.
Preferably, described battery diaphragm is membrane for polymer or nonwoven fabrics barrier film.
The preparation method of polymer-modified barrier film for lithium-sulfur cell, is characterized in that, comprises the following steps:
1) battery diaphragm of having reduced is first put into methyl alcohol and infiltrate 0.25～1h, the volume of described methyl alcohol is advisable with battery diaphragm described in energy complete wetting;
2) by step 1) in battery diaphragm take out, put into Tris-HCl (10 mMs) cushioning liquid that contains dopamine monomer, in air atmosphere, under normal temperature, infiltrate 6～36h.Wherein: dopamine monomer concentration is 2～10mg/ml; The PH of described Tris-HCl (10 mMs) cushioning liquid is in 8.5 left and right, its process for preparation is as follows: take solid trihydroxy methyl aminomethane 0.3028g and be dissolved in distilled water, then adding 7.3ml concentration is the HCl solution of 0.1mol/L, and constant volume is in the volumetric flask of 250ml.
3) by step 2) in battery diaphragm take out, repeatedly rinse 3～5 times with distilled water, then put into drying box, at 30 DEG C, dry 6～24h, makes the battery diaphragm with poly-dopamine decorative layer.
Lithium-sulfur cell, comprises for above-mentioned lithium-sulfur cell polymer-modified barrier film, sulfur electrode, lithium anode and contains anhydrous nitric acid lithium (LiNO
3) organic ethers electrolyte.
Preferably, the solvent of the described organic ethers electrolyte that contains additive is 1, the mixed solvent of one or more compositions of 3-dioxolanes (DOL), glyme (DEGDME), glycol dimethyl ether (DME), tetraethylene glycol dimethyl ether (TEGDME), electrolyte is two (trimethyl fluoride sulfonyl) imine lithium (C
2f
6liNO
4s
2), trifluoromethyl sulfonic acid lithium (LiCF
3sO
3), lithium hexafluoro phosphate (LiPF
6) or lithium perchlorate (LiClO
4).
Preferably, described sulfur electrode is that sulphur/carbon composite, conductive additive and binding agent are made through dispersion, film-making and dry technological process.
Preferably, described sulphur/carbon composite is that the content of elemental sulfur is placed on planetary ball mill first with 300r/min rotating speed ball milling 2h between the conductive carbon matrix of 50wt%～90wt% and elemental sulfur mixture, more above-mentioned sulphur/carbon complex is proceeded to heat treatment 12h in 155 DEG C of baking ovens makes; Described conductive carbon matrix is one or more mixtures in section's qin carbon black (Ketjenblack EC600JD), Cabot carbon black (BP2000), carbon nano-fiber (CNFs), ordered mesopore carbon (OMC), porous carbon (CMK-3), graphene oxide (GO), Graphene (Graphene), and sulphur is sublimed sulfur or Cosan.
Preferably, described conductive additive is one or more in acetylene black, Super-P, carbon nano-tube, section's qin carbon black, Cabot carbon black; Described binding agent is that the N-methyl of Kynoar (PVDF) adjoins one or more in pyrrolidone (NMP) solution, polytetrafluoroethylene (PTFE) aqueous solution, polyacrylic acid (PAA) aqueous solution, shuttle sodium carboxymethylcellulose pyce (CMC) aqueous solution, butadiene-styrene rubber/shuttle methylcellulose sodium water solution, sodium alginate (SA) aqueous solution, aqueous gelatin solution, the LA132 aqueous solution.
The polymer-modified barrier film of lithium-sulfur cell of the present invention, its poly-dopamine decorative layer is containing more organo-functional group, and the many lithium sulfides of intermediate product that functional group produces in cyclic process sulfur electrode have the suction-operated of stopping.Organo-functional group is the solution loss of many lithium sulfides in inhibitory reaction process effectively, thereby improves the cycle performance of battery; Make barrier film become hydrophily from hydrophobicity, be convenient to electrolyte and infiltrate barrier film, the ionic conductivity of barrier film increases, and the lithium-sulfur cell of assembling gathers the barrier film of dopamine modification for after lithium-sulfur cell by employing, and cyclical stability and high rate performance that it shows are greatly improved.Preparation method of the present invention is simply efficient, is suitable for large-scale application.
Brief description of the drawings
Fig. 1 adopts the first five week all charging and discharging curve of the made lithium-sulfur cell of embodiment 1 under 0.1C multiplying power.
Fig. 2 adopts the cycle performance of the made lithium-sulfur cell of embodiment 1 under 0.1C multiplying power.
Fig. 3 adopts the cycle performance of the made lithium-sulfur cell of embodiment 1 under 1C multiplying power.
Fig. 4 adopts the cycle performance of the made lithium-sulfur cell of embodiment 2 under 0.1C multiplying power.
Fig. 5 adopts the cycle performance of the made lithium-sulfur cell of embodiment 6 under 0.1C multiplying power.
Embodiment
Below in conjunction with accompanying drawing and specific embodiment, the present invention is further illustrated, but protection scope of the present invention is not limited to this.
Agents useful for same and material in described embodiment all can be buied on market below.
Embodiment 1
1) take 6.0g sublimed sulfur and 4.0g section qin conductive black (Ketjenblack EC600JD) and be placed in the rotating speed ball milling 2h with 300r/min on planetary ball mill, then gained mixture is transferred in the airtight container that is full of inert gas, in Muffle furnace, in 155 DEG C of heat treatment 12h, make sulphur/carbon composite.
2) sulphur/carbon composite of above-mentioned preparation, acetylene black and PTFE are mixed according to the mass ratio of 7:2:1, ethanol is dispersant, fully stirs and makes batch mixing even, then rolls and makes sulfur electrode sheet, for subsequent use in 55 DEG C of freeze-day with constant temperature 12h.
3) methanol solution that tri-layers of battery diaphragm of the PP/PE/PP that is 16mm by the diameter of having reduced are put into 50ml infiltrates 0.5h, then battery diaphragm is taken out, putting into concentration is Tris-HCl (10 mMs) cushioning liquid containing dopamine monomer of 2mg/ml again, in air atmosphere, under normal temperature, infiltrate 24h, after reaction finishes, battery diaphragm is taken out, repeatedly rinse 3-5 time with distilled water, then put into drying box, dry 12h at 30 DEG C, makes the battery diaphragm that poly-dopamine is modified.The PH of described Tris-HCl (10 mMs) cushioning liquid is in 8.5 left and right, its process for preparation is as follows: take solid trihydroxy methyl aminomethane 0.3028g and be dissolved in distilled water, then adding 7.3ml concentration is the HCl solution of 0.1mol/L, and constant volume is in the volumetric flask of 250ml.
4) taking above-mentioned prepare sulfur electrode sheet as battery diaphragm anodal, that the poly-dopamine of above-mentioned preparation is modified as barrier film, negative pole is dissolved in 1 of volume ratio 1:1 as lithium metal, electrolyte as two (trimethyl fluoride sulfonyl) imine lithium l.0mol/L, the mixed liquor that 3 dioxolanes and tetraethylene glycol dimethyl ether are joined, additive is the anhydrous nitric acid lithium of mass fraction 1wt%, in anhydrous anaerobism glove box, is assembled into battery.
The electrochemical property test of institute's assembled battery is as follows:
Assembled battery is carried out to constant current charge-discharge performance test at ambient temperature, and voltage range is: 1.5～3.0 volts, battery charging and discharging capacity and current density are all calculated with active material sulphur, and 1C multiplying power is equivalent to 1675 milliamperes of/gram of current densities.The charging and discharging curve in first three week as shown in Figure 1.Under 0.1C multiplying power, within first three week, discharge capacity is respectively 1271,837.6 and 1116.1 MAhs/g, and discharge curve is made up of two platforms, respectively at 2.3 volts and about 2.05 volts.As shown in Figure 2 and Figure 3, after lithium-sulfur cell circulates 50 weeks under 0.1C multiplying power, capacity is stabilized in 876.2 MAhs/g of left and right to cycle performance, and after circulating under 1C multiplying power 150 weeks, capacity is stabilized in 554.8 MAhs/g of left and right.
Embodiment 2
Change (3) step dopamine monomer concentration in embodiment 1 into 3mg/ml, other are identical with embodiment 1.As shown in Figure 4, the lithium-sulfur cell of assembling is under 0.1C multiplying power for cycle performance, and first all discharge capacities are 1283.6 MAhs/g, and after circulating 50 weeks, capacity can be stabilized in 915.3 MAhs/g of left and right.
Embodiment 3
Change (3) step dopamine monomer concentration in embodiment 1 into 5mg/ml, other are identical with embodiment 1.The lithium-sulfur cell of assembling is under 0.1C multiplying power, and first all discharge capacities are 1154.8 MAhs/g, and after circulating 50 weeks, capacity can be stabilized in 850.7 MAhs/g of left and right.
Embodiment 4
(3) step in embodiment 1 is infiltrated to 24h and change infiltration 12h into, other conditions are identical with embodiment 1.The lithium-sulfur cell of assembling is under 0.1C multiplying power, and first all discharge capacities are 1201.6 MAhs/g, and after circulating 100 weeks, capacity can be stabilized in 843 MAhs/g of left and right.
Embodiment 5
(3) step in embodiment 1 is infiltrated to 24h and change infiltration 36h into, other are identical with embodiment 1.The lithium-sulfur cell of assembling is under 0.1C multiplying power, and first all discharge capacities are 1184.2 MAhs/g, and after circulating 50 weeks, capacity can be stabilized in 937 MAhs/g of left and right.
Embodiment 6
Tri-layers of battery diaphragm of (3) step PP/PE/PP in embodiment 1 are changed to PE individual layer battery diaphragm, and other are identical with embodiment 1.As shown in Figure 5, the lithium-sulfur cell of assembling is under 0.1C multiplying power for cycle performance, and first all discharge capacities are 1246.1 MAhs/g, and after circulating 50 weeks, capacity can be stabilized in 1059.6 MAhs/g of left and right.
Embodiment 7
Tri-layers of battery diaphragm of (3) step PP/PE/PP in embodiment 1 are changed to PI battery diaphragm, and other are identical with embodiment 1.The lithium-sulfur cell of assembling is under 0.1C multiplying power, and first all discharge capacities are 1067.1 MAhs/g, and after circulating 50 weeks, capacity can be stabilized in 834.7 MAhs/g of left and right.
Embodiment 8
Tri-layers of barrier film of (3) step PP/PE/PP in embodiment 1 are changed to glass fibre non-woven battery diaphragm, and other are identical with embodiment 1.The lithium-sulfur cell of assembling is under 0.1C multiplying power, and first all discharge capacities are 1245 MAhs/g, and after circulating 50 weeks, capacity can be stabilized in 918.9 MAhs/g of left and right.
Embodiment 9
Make 6.0 grams of sublimed sulfurs of (1) step in embodiment 1 and 4.0 Ke Keqin conductive blacks (Ketjenblack EC600JD) into 8.0 grams of sublimed sulfurs and 2.0 Ke Keqin conductive blacks, other are identical with embodiment 1.The lithium-sulfur cell of assembling is under 0.1C multiplying power, and first all discharge capacities are 914 MAhs/g, and after circulating 50 weeks, capacity can be stabilized in 783.2 MAhs/g of left and right.
Embodiment 10
Change (1) step section qin conductive black (Ketjenblack EC600JD) in embodiment 1 into Cabot carbon black (BP2000), other are identical with embodiment 1.The lithium-sulfur cell of assembling is under 0.1C multiplying power, and first all discharge capacities are 1305.4 MAhs/g, and after circulating 50 weeks, capacity can be stabilized in 935.1 MAhs/g of left and right.
Embodiment 11
Change (1) step section qin conductive black (Ketjenblack EC600JD) in embodiment 1 into Graphene, other are identical with embodiment 1.The lithium-sulfur cell of assembling is under 0.1C multiplying power, and first all discharge capacities are 1402.8 MAhs/g, and after circulating 50 weeks, capacity can be stabilized in 1083.4 MAhs/g of left and right.
Embodiment 12
Change (2) step binding agent PTFE in embodiment 1 into PVDF, other are identical with embodiment 1.The lithium-sulfur cell of assembling is under 0.1C multiplying power, and first all discharge capacities are 1227 MAhs/g, and after circulating 50 weeks, capacity can be stabilized in 941.7 MAhs/g of left and right.
Embodiment 13
Change (2) step conductive additive acetylene black in embodiment 1 into Super-P, other are identical with embodiment 1.The lithium-sulfur cell of assembling is under 0.1C multiplying power, and first all discharge capacities are 1264.6 MAhs/g, and after circulating 50 weeks, capacity can be stabilized in 894.1 MAhs/g of left and right.
Embodiment 14
Be that to be dissolved in volume ratio be 1 of 1:1 for two (trimethyl fluoride sulfonyl) imine lithium lithium salts l.0mol/L by (4) one-step electrolysis liquid in embodiment 1, the mixed liquor that 3 dioxolanes and tetraethylene glycol dimethyl ether are joined, two (trimethyl fluoride sulfonyl) imine lithium lithium salts that changes electrolyte into and be is l.0mol/L dissolved in 1, the mixed liquor that 3 dioxolanes and glycol dimethyl ether (volume ratio 1:1) are joined, other conditions are identical with embodiment 1.The lithium-sulfur cell of assembling is under 0.1C multiplying power, and first all discharge capacities are 1363.4 MAhs/g, and after circulating 50 weeks, capacity can be stabilized in 851.2 MAhs/g of left and right.
Embodiment 15
Be that to be dissolved in volume ratio be 1 of 1:1 for two (trimethyl fluoride sulfonyl) imine lithium lithium salts l.0mol/L by (4) one-step electrolysis liquid in embodiment 1, the mixed liquor that 3 dioxolanes and tetraethylene glycol dimethyl ether are joined, change electrolyte into and be dissolved in the solution that tetraethylene glycol dimethyl ether is joined for two (trimethyl fluoride sulfonyl) imine lithium lithium salts l.0mol/L, other conditions are identical with embodiment 1.The lithium-sulfur cell of assembling is under 0.1C multiplying power, and first all discharge capacities are 1363.4 MAhs/g, and after circulating 50 weeks, capacity can be stabilized in 851.2 MAhs/g of left and right.
Described embodiment is preferred embodiment of the present invention; but the present invention is not limited to above-mentioned execution mode; in the situation that not deviating from flesh and blood of the present invention, any apparent improvement, replacement or modification that those skilled in the art can make all belong to protection scope of the present invention.
Claims (9)
1. the polymer-modified barrier film of lithium-sulfur cell, is made up of battery diaphragm and the polymer-modified layer being attached on described battery diaphragm, it is characterized in that, described polymer-modified layer is poly-dopamine decorative layer.
2. the polymer-modified barrier film of lithium-sulfur cell according to claim 1, is characterized in that, the thickness of described poly-dopamine decorative layer is between 2-50nm.
3. the polymer-modified barrier film of lithium-sulfur cell according to claim 1, is characterized in that, described battery diaphragm is membrane for polymer or nonwoven fabrics barrier film.
4. the preparation method of polymer-modified barrier film for lithium-sulfur cell, is characterized in that, comprises the following steps:
1) battery diaphragm of having reduced is first put into methyl alcohol and infiltrate 0.25～1h, the volume of described methyl alcohol is advisable with battery diaphragm described in energy complete wetting;
2) by step 1) in battery diaphragm take out, put into Tris-HCl (10 mMs) cushioning liquid that contains dopamine monomer, in air atmosphere, under normal temperature, infiltrate 6～36h.Wherein: dopamine monomer concentration is 2～10mg/ml; The PH of Tris-HCl (10 mMs) cushioning liquid is in 8.5 left and right, its process for preparation is as follows: take solid trihydroxy methyl aminomethane 0.3028g and be dissolved in distilled water, then adding 7.3ml concentration is the HCl solution of 0.1mol/L, and constant volume is in the volumetric flask of 250ml.
3) by step 2) in battery diaphragm take out, repeatedly rinse 3～5 times with distilled water, then put into drying box, at 30 DEG C, dry 6～24h, makes the battery diaphragm with poly-dopamine decorative layer.
5. the lithium-sulfur cell being made up of the polymer-modified barrier film of employing claimed in claim 1, comprises polymer-modified barrier film for above-mentioned lithium-sulfur cell, sulphur positive pole, lithium anode and contains anhydrous nitric acid lithium (LiNO
3) organic ethers electrolyte.
6. lithium-sulfur cell according to claim 5, it is characterized in that, the solvent of the described organic ethers electrolyte that contains additive is 1, the mixed solvent of one or more compositions of 3-dioxolanes (DOL), glyme (DEGDME), glycol dimethyl ether (DME), tetraethylene glycol dimethyl ether (TEGDME), electrolyte is two (trimethyl fluoride sulfonyl) imine lithium (C
2f
6liNO
4s
2), trifluoromethyl sulfonic acid lithium (LiCF
3sO
3), lithium hexafluoro phosphate (LiPF
6) or lithium perchlorate (LiClO
4).
7. lithium-sulfur cell according to claim 6, is characterized in that, described sulfur electrode is that sulphur/carbon composite, conductive additive and binding agent are made through dispersion, film-making and dry technological process.
8. lithium-sulfur cell according to claim 7, it is characterized in that, described sulphur/carbon composite is that the content of elemental sulfur is placed on planetary ball mill first with 300r/min rotating speed ball milling 2h between the conductive carbon matrix of 50wt%～90wt% and elemental sulfur mixture, more above-mentioned sulphur/carbon complex is proceeded to heat treatment 12h in 155 DEG C of baking ovens makes; Described conductive carbon matrix is one or more mixtures in section's qin carbon black (Ketjenblack EC600JD), Cabot carbon black (BP2000), carbon nano-fiber (CNFs), ordered mesopore carbon (OMC), porous carbon (CMK-3), graphene oxide (GO), Graphene (Graphene), and sulphur is sublimed sulfur or Cosan.
9. lithium-sulfur cell according to claim 8, is characterized in that, described conductive additive is one or more in acetylene black, Super-P, carbon nano-tube, section's qin carbon black, Cabot carbon black; Described binding agent is that the N-methyl of Kynoar (PVDF) adjoins one or more in pyrrolidone (NMP) solution, polytetrafluoroethylene (PTFE) aqueous solution, polyacrylic acid (PAA) aqueous solution, shuttle sodium carboxymethylcellulose pyce (CMC) aqueous solution, butadiene-styrene rubber/shuttle methylcellulose sodium water solution, sodium alginate (SA) aqueous solution, aqueous gelatin solution, the LA132 aqueous solution.
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| CN104617327A (en) * | 2014-12-31 | 2015-05-13 | 北京理工大学 | Anode material of lithium-sulfur battery, lithium-sulfur battery and method for preparing anode material |
| CN105551831A (en) * | 2016-01-11 | 2016-05-04 | 上海交通大学 | Preparation method and application of bowl-like nitrogen-doped carbon hollow particle |
| CN105655523A (en) * | 2016-03-31 | 2016-06-08 | 山东大学 | Deprotonated dopamine-coated film and preparation method and application thereof |
| 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 |
| CN107204414A (en) * | 2016-03-18 | 2017-09-26 | 东北师范大学 | It is a kind of that the method that barrier film prepares high-performance lithium-sulfur cell is modified based on rich nitrogen molecular |
| CN107732033A (en) * | 2017-07-14 | 2018-02-23 | 中国第汽车股份有限公司 | A kind of poly-dopamine modified lithium coating for being advantageous to battery radiating |
| CN107910584A (en) * | 2017-10-23 | 2018-04-13 | 西安理工大学 | A kind of production method of Soft Roll lithium-sulfur cell |
| CN107925042A (en) * | 2016-01-28 | 2018-04-17 | 株式会社Lg化学 | Lithium-sulfur cell membrane, its manufacture method with the composite coating comprising poly-dopamine and include its lithium-sulfur cell |
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