CN107546356A - A kind of application of molecular sieve composite porous film in lithium-sulfur cell - Google Patents
A kind of application of molecular sieve composite porous film in lithium-sulfur cell Download PDFInfo
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- CN107546356A CN107546356A CN201610490175.4A CN201610490175A CN107546356A CN 107546356 A CN107546356 A CN 107546356A CN 201610490175 A CN201610490175 A CN 201610490175A CN 107546356 A CN107546356 A CN 107546356A
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Abstract
The invention discloses a kind of application of molecular sieve composite porous film in lithium-sulfur cell, molecular sieve composite porous film be using by the one or two or more kinds in organic polymer resin be the perforated membrane that is prepared of raw material as matrix, in the composite porous film that the both side surface composite inorganic molecular sieve layer of this matrix is formed.The molecular sieve composite porous film of the present invention has high electrolyte absorbability and hold capacity in lithium-sulfur cell, while contributes to the transmission of lithium ion.The molecular sieve layer aperture of composite membrane is can be controlled between polysulfide size and lithium ion size, so as to effectively suppress " shuttle " effect of polysulfide on the premise of lithium ion conductivity is not influenceed, is reduced the loss of active material, is improved battery efficiency and stability.In addition the molecular sieve layer of the composite membrane has the preferable capacity of heat transmission, can suppress the generation of negative pole lithium piece dendrite, and dendrite puncture barrier film causes battery short circuit during preventing battery use.
Description
Technical field
The present invention relates to a kind of lithium-sulfur cell composite membrane, more particularly to lithium-sulfur cell composite porous film.
Background technology
As the improvement of people's living standards, automobile has come into huge numbers of families as the conventional vehicles, at present
Vehicle fuel causes environmental pollution and lack of energy essentially from non-renewable energy resources such as oil.A large amount of popularizations of fuel-engined vehicle
Caused environmental problem and energy crisis increasingly attract people's attention, and electric automobile is as a kind of environmentally friendly friendship
Logical instrument causes the concern of countries in the world, and countries in the world put into the exploitation that substantial amounts of manpower and materials are engaged in electric automobile.By
There is most negative potential in lithium metal, minimum density, best electronic conductivity, its electrochemistry capacitance reaches 3860mAh/g, with
Lithium metal is the lithium battery of negative pole, including lithium-air battery and lithium-sulfur cell have received people and greatly pay close attention to.Lithium-sulfur cell is made
There is very high specific energy density (1672mAh/g) for a kind of advanced lithium ion battery, and sulphur positive pole is cheap, environment
Close friend, thus lithium-sulfur cell is more and more paid attention to.
Although having above advantage, lithium-sulfur cell also has a longer segment distance, one of chief reason from practical
It is exactly " shuttle " effect of polysulfide.Polysulfide has very high dissolubility in common electrolyte, and dissolves more
(" shuttle " effect) is shuttled in diffusion to sulfide repeatedly between positive pole and negative pole." shuttle " effect can cause lithium-sulfur cell coulombic efficiency
Reduce, cycle life is deteriorated.Therefore shuttled by inhibiting polysulfide between positive pole and negative pole, the electricity of lithium-sulfur cell can be improved
Pond performance.
Many work have been done for " shuttle " effect, people caused by polysulfide dissolving migration.As added in the electrolytic solution
Entering additive lithium nitrate (Electrochimica Acta 70,2012,344-348) makes cathode of lithium surface form protective layer, from
And suppress the reaction of polysulfide and lithium metal, improve battery performance.But the addition of lithium nitrate also can cause shadow to anode
Ringing, the lithium sulfide of generation deposits in positive pole, hinders mass transfer and electronics conduction, and with the progress of electric discharge, the stability of diaphragm
Also need further to investigate.Research shows (Journal of Power Sources 212,2012,179-185) compound polymerization
Thing gel electrolyte separator can effectively solve " shuttle " effect of polysulfide.Gel electrolyte is by polymer, lithium salts and increasing
The gel polymeric network with appropriate microporous structure that agent is formed by certain method is moulded, using being fixed in microcellular structure
Liquid electrolyte molecule realize ionic conduction, due to electrolyte solution by " cladding " in polymer network structure, make more sulphur
The dissolving of compound is suppressed, so as to solve the problems, such as active material loss to a certain extent.But gel electrolyte separator electricity
Conductance and intensity are further applied all than relatively low so as to limit it.
Barrier film is one of important component of lithium-sulfur cell, and its main function is that the positive and negative electrode for making battery is physically separated from,
Prevent the two poles of the earth from directly contacting and short-circuit；Simultaneously passage is provided for lithium ion in the transmission of two interpolars.The performance of barrier film directly affects electricity
The security and chemical property in pond, the barrier film for researching and developing excellent performance are one of important means for improving battery combination property.
The lithium-sulfur cell barrier film developed and used at present, predominantly polyolefin based materials (polyethylene, polypropylene etc.), utilize
Lithium-sulfur cell (lithium nitrate additive is added without in electrolyte) coulombic efficiency of this kind of membrane material assembling is low, and polysulfide " flies
Shuttle " effect is serious, seriously constrains the battery performance of lithium-sulfur cell.
According to lithium ion and the difference of the size of polysulfide, if it is contemplated that can be realized by there is pore separation membrane
Separation to lithium ion and polysulfide, by controlling membrance casting condition, control the size of porous membrane aperture, realize to lithium ion and
The Selective Separation of polysulfide, pass freely through lithium ion in film, and polysulfide is trapped, it is possible to achieve suppress more
The function of sulfide " shuttle " effect.
But this perforated membrane when aperture it is small to a certain extent when, be further continued for reduce aperture can be relatively difficult, how to enter one
Step, which improves perforated membrane, turns into a major issue for solving this kind of film to the selective penetrated property of lithium ion and polysulfide.Due to nothing
Machine molecular sieve has specific aperture structure and controllable silica alumina ratio, has good interception capacity and ion-exchange capacity.Such as
These inorganic molecules are sieved and are combined with each other with perforated membrane by fruit, will greatly improve the ion selective ability of former perforated membrane.Have
Barrier of the pore membrane to polysulfide and selectivity to lithium ion pass through to be realized by the aperture control of film, but too small aperture will
The transmission of limiting lithium ion, therefore optimal value be present in the regulation and control in aperture.On the basis of aperture is optimized, its selection is further improved
Permeability, and then its performance in lithium-sulfur cell is improved, there is important Practical significance.
Inorganic molecule sieve composite porous film be it is a kind of using the specific pore size of molecular sieve and controllable silica alumina ratio, efficiently
Ground selection passes through lithium ion, obstructs other charged ions including polysulfide.As can be seen here, in the research and development of lithium sulphur barrier film
In, inorganic molecule sieve composite porous film is advantageous to the further raising of its ion selectivity, so as to obtain more excellent battery performance.
The content of the invention
Present invention aims at for current lithium-sulfur cell polysulfide shuttle problem, there is provided a kind of inorganic molecule sieve is compound
Application of the perforated membrane in lithium-sulfur cell.The inorganic molecule sieves composite porous film by one kind in organic polymer resin or two kinds
It is that the perforated membrane that raw material is prepared is matrix above, sieves to form composite porous film in the surface recombination inorganic molecule of this matrix.
To achieve the above object, the technical solution adopted by the present invention is as follows：
Using by the one or two or more kinds in organic polymer resin be the perforated membrane that is prepared of raw material as matrix, herein
The surface recombination inorganic molecule of matrix sieves to form composite porous film.
It is described be used to preparing the organic polymer resin of perforated membrane matrix for polyethylene, polypropylene, polysulfones, polyketone class,
One kind in polyacrylonitrile, polyimides, polytetrafluoroethylene (PTFE), Kynoar, polybenzimidazoles or polyvinyl pyridine or two kinds
More than.
The inorganic molecule sieve is ZSM-35, ZSM-5, USY, SAPO-34 or β zeolite.
The aperture size of the perforated membrane is 0.1~500nm, and porosity is 10~70%.
The composite membrane can be prepared according to the following procedure,
(1) by organic polymer resin dissolving in organic solvent, 0.5 is sufficiently stirred at being 20~100 DEG C in temperature~
Blend solution is made in 10h；Wherein organic polymer resin concentration is between 5~70wt.%；It can also add in above-mentioned solvent and easily wave
Hair property solvent, forms mixed solvent, effumability solvent is 0~50wt.% in the concentration of in the mixed solvent；
(2) blend solution prepared by step (1) is poured over nonwoven fabric base bottom or be poured directly on glass plate, volatilization is molten
Agent 0~60 second, then enters its mass-impregnation 5~600s in the poor solvent of resin, is prepared at a temperature of -20~100 DEG C
Perforated membrane；The thickness of film is between 5~150 μm；
(3) compound inorganic molecule screening will be prepared not being dissolved in methanol, ethanol, isopropanol, chloroform, dichloroethanes, water
One or two or more kinds of solvents in be made into concentration be 0.1~20wt.% solution, as inorganic molecule sieve solution；It is above-mentioned
It is 0~20wt.% in the concentration of in the mixed solvent that macromolecule organic resin can be also added in solution as binding agent, binding agent；
(4) obtained porous septum is cleaned up, 1h is soaked in isopropanol, displace water therein, placed naturally
Dry, until obtaining the more dry perforated membrane in surface；
(5) inorganic molecule sieve solution is coated uniformly on the surface that (4) prepare porous matrix, treats that solvent volatilizees naturally and dry in the air
It is dry, obtain composite porous film.
The perforated membrane matrix of the molecular sieve composite porous film can also pass through one kind in dry method, wet method or phase inversion
Or two kinds made above obtain.
The organic solvent is the one or two or more kinds in DMSO, DMAC, NMP, DMF；
The effumability non-solvent is one or two or more kinds of in methanol, ethanol, tetrahydrofuran or n-hexane；
The macromolecule organic resin as binding agent is polyimides, polybenzimidazoles or polyvinyl pyridine, gathered partially
One or two or more kinds in PVF, polytetrafluoroethylene (PTFE), sulfonated polyether-ether-ketone or Nafion resins；
The painting method of the molecular sieve solution be the tape casting, knife coating, spraying process, spin-coating method the methods of in one kind or
It is two or more.
The composite membrane can be used for lithium-sulfur cell, but be not limited to lithium-sulfur cell.
The beneficial outcomes of the present invention
(1) present invention in perforated membrane matrix surface composite inorganic molecular sieve, the matrix of composite membrane by having high electrolysis
Liquid absorbability and hold capacity, contribute to the transmission of lithium ion, while using the aperture sieve effect of molecular sieve, do not influenceing
" shuttle " effect of polysulfide is effectively obstructed in the case of lithium ion transport, reduces the loss of active material, improves battery effect
Rate and stability.
(2) composite membrane prepared by the present invention, its molecular sieve species is optional, and aperture is controllable., can be real by modulation above-mentioned parameter
The controllable adjustment of existing battery performance.
(3) molecular sieve layer of the composite membrane has the preferable capacity of heat transmission, can suppress the generation of negative pole lithium piece dendrite, prevent
Dendrite pierces through barrier film and causes battery short circuit during battery use.
(4) such compound membrane preparation method is simple, environmental friendly, has expanded species and the use of lithium-sulfur cell membrane material
Scope.
(5) compared with perforated membrane, molecular sieve composite porous film has preferable ionic selection abilities, the lithium sulphur assembled with this
Battery has higher combination property.
Brief description of the drawings
The inorganic molecule that Fig. 1 is the present invention sieves application principle schematic diagram of the composite porous film in lithium-sulfur cell；
TEM figures (a) and the HR-TEM figure (b) of Fig. 2 ZSM-35 molecular sieves, figure (c) is the compound polyethers of ZSM-35 molecular sieve
The surface SEM figures of acid imide film；Figure (d) is the section SEM figures of the compound polyetherimde films of ZSM-35 molecular sieve.
Fig. 3 is the coulombic efficiency of the composite membrane prepared by embodiment 1 and battery of the comparative example in lithium-sulfur cell under 0.2C
Contrast.
Embodiment
The following examples are the further explanations to the present invention, rather than limit the scope of the present invention.Embodiment 1
7.5 grams of PEIs are dissolved in 30mL NMP and 10mL THF, are stirred 48 hours, the polymer solution of formation,
Glass plate is laid in, thickness is 100 μm, then immerses in 5L water rapidly, solidification, forms pseudoseptum.
Obtained pseudoseptum is soaked into 2h in isopropanol, displaces water therein.
Compound concentration is the aqueous isopropanol of 80wt.% ZSM-35 molecular sieve, and adds 20wt.%'s wherein
Nafion resins, porous film surface is coated in spraying method.Composite porous film (A) is made.
Utilize the composite membrane assembling lithium-sulfur cell test of preparation.The negative pole of lithium-sulfur cell is the lithium paper tinsel that thickness is 20 μm, just
Pole is prepared using following methods：25wt.% Super P carbon, 65wt.% elemental sulfur, 10wt.% Kynoar is in N-
It is blended, is coated on aluminium foil in methyl pyrrolidone, the sulfur content after drying in positive-active layer is 1.2mg/cm2.Electrolyte
Using two (trifluoromethyl sulfonyl) imine lithiums, solvent is DOL/DME (volume ratio 1: 1), and the concentration of electrolyte is 1mol/L.
Said modules are fitted together with the layer structure of positive pole/barrier film/negative pole, and according to 20 μ L/cm2The addition electrolysis of positive pole area
Sealed after liquid.Stand 1 and discharge and recharge was as a child carried out with 0.2C relative to the quality of positive active material sulphur.Fig. 3 can be seen that assembling
Lithium-sulfur cell coulombic efficiency (CE) be 96.8%, the coulombic efficiency after continuous discharge and recharge 100 circulates is maintained at more than 96%.
It can be seen that the duct radius of ZSM-35 molecular sieve can effectively suppress more sulphur probably in 0.48nm or so from Fig. 2 b
The shuttle of compound.
Comparative example 1
Compared with Example 1, film is changed into pure PEI perforated film, other conditions are constant, and pure polyetherimide is made
Amine perforated film (B).Fig. 3 can be seen that the coulombic efficiency of battery is 73.5%, and the coulombic efficiency of battery is anxious after 30 circulations of discharge and recharge
Fall sharply low.
Compared with pure PEI perforated membrane, the coulombic efficiency and cycle life of inorganic molecule sieve composite porous film have
It is significant to improve.Illustrate the introducing of inorganic molecule sieve, be effectively improved the ion selectivity of film, obstructed polysulfide
" shuttle " effect, thus improve the coulombic efficiency and cycle life of battery.
Embodiment 2
With embodiment 1, organic polymer resin is changed into polysulfones, other conditions are constant.
Embodiment 3
With embodiment 1, organic polymer resin is changed into polybenzimidazoles, solvent changes NMP into, and other conditions are constant.
Embodiment 4
With embodiment 1 into, organic polymer resin is changed to the mixture of polyacrylonitrile and polysulfones, other conditions are constant.
Embodiment 5
With embodiment 1, organic polymer matrix is changed into polypropylene, other conditions are constant.
Embodiment 6
With embodiment 1, inorganic molecule sieve is changed into USY molecular sieve, other conditions are constant.
Embodiment 7
With embodiment 1 into, perforated film matrix is changed to the MIcroporous polyolefin film of commercialization, molecular sieve changes SAPO-34 molecules into
Sieve, other conditions are constant.
Claims (7)
- A kind of 1. application of molecular sieve composite porous film in lithium-sulfur cell, it is characterised in that：Molecular sieve composite porous film is more to be prepared by the one or two or more kinds in organic polymer resin as raw material Pore membrane is matrix, in the composite porous film that the both side surface composite inorganic molecular sieve layer of this matrix is formed.
- 2. application according to claim 1, it is characterised in that：The organic polymer resin for being used to prepare perforated membrane matrix is polyethylene, polypropylene, polysulfones, polyketone class, poly- third One or two or more kinds in alkene nitrile, polyimides, polytetrafluoroethylene (PTFE), Kynoar, polybenzimidazoles or polyvinyl pyridine.
- 3. application according to claim 1, it is characterised in that：The inorganic molecule sieve is the one or two or more kinds in ZSM-35, ZSM-5, USY, SAPO-34 or β zeolite.
- 4. according to the application described in claim 1,2 or 3, it is characterised in that：The aperture size of the perforated membrane matrix is 1~500nm, and porosity is 10~70%；Porous film thickness is 5~150 μm, and inorganic molecule screen layers thickness is 1~20 μm.
- 5. according to any described applications of claim 1-4, it is characterised in that：The composite porous film can be prepared according to the following procedure Form：(1) by organic polymer resin dissolving in organic solvent, 5~48h is sufficiently stirred in the case where temperature is by 20~100 DEG C to be made Blend solution；Wherein organic polymer resin concentration is between 5~70wt.%；It is added without or can be also added easily in above-mentioned solvent Volatile solvent, mixed solvent is formed, effumability solvent is 0~50wt.% in the concentration of in the mixed solvent；(2) blend solution prepared by step (1) is poured over nonwoven fabric base bottom or be poured directly on glass plate, solvent flashing 0 ~60 seconds, then its mass-impregnation is entered to 5~600s in the poor solvent of resin, be prepared at a temperature of 20~100 DEG C porous Film；The thickness of film is between 5~150 μm；(3) inorganic molecule is sieved into the one kind not being scattered in methanol, ethanol, isopropanol, chloroform, dichloroethanes, water or two kinds The dispersion liquid that concentration is 0.1~20wt.% is made into solvent above, solution is sieved as inorganic molecule；It is not added with above-mentioned solution It is 0~20wt.% in the concentration of in the mixed solvent to enter or can also add macromolecule organic resin as binding agent, binding agent；(4) perforated membrane prepared by step (2) is cleaned up with water, 2-24h is soaked in isopropanol, displaces water therein, Naturally place and dry, until obtaining the more dry perforated membrane in surface；(5) inorganic molecule sieve solution is coated uniformly on the both side surface that (4) prepare porous matrix, treats that solvent volatilizees naturally and dry in the air It is dry, obtain composite porous film.
- 6. application according to claim 5, it is characterised in that：The perforated membrane matrix of the molecular sieve composite porous film may be used also To be prepared by the one or two or more kinds in dry method, wet method or phase inversion.
- 7. application according to claim 5, it is characterised in that：The organic solvent is the one or two or more kinds in DMSO, DMAC, NMP, DMF；The effumability non-solvent is one or two or more kinds of in methanol, ethanol, tetrahydrofuran or n-hexane；The macromolecule organic resin as binding agent is polyimides, polybenzimidazoles or polyvinyl pyridine, polyvinylidene fluoride One or two or more kinds in alkene, polytetrafluoroethylene (PTFE), sulfonated polyether-ether-ketone or Nafion resins；Poor solvent is the one or two or more kinds in water, methanol, ethanol or isopropanol；One or both of the methods of painting method of the molecular sieve solution is the tape casting, knife coating, spraying process, spin-coating method More than.
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Cited By (8)
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| CN108666509A (en) * | 2018-05-18 | 2018-10-16 | 深圳市晶特智造科技有限公司 | A kind of lithium-sulfur cell diaphragm and preparation method thereof, application |
| CN110938228A (en) * | 2019-11-26 | 2020-03-31 | 武汉理工大学 | Preparation method and application of zeolite/polyimide composite membrane |
| CN112259914A (en) * | 2020-09-02 | 2021-01-22 | 江西师范大学 | Molecular sieve coated porous composite material and preparation method and application thereof |
| CN112713361A (en) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | Composite lithium-sulfur battery diaphragm and preparation method and application thereof |
| CN114649553A (en) * | 2022-02-11 | 2022-06-21 | 南京工业大学 | Porous membrane loaded by zeolite molecular sieve nanosheets, preparation method and application of porous membrane in zinc-based flow battery |
| CN115842214A (en) * | 2022-10-18 | 2023-03-24 | 福州大学 | High-voltage-resistant low-self-discharge diaphragm with screening effect, preparation method and application |
| WO2023051562A1 (en) | 2021-09-28 | 2023-04-06 | 中国石油化工股份有限公司 | Separator for lithium-sulfur battery, method for preparing same and lithium-sulfur battery containing same |
| CN116169434A (en) * | 2023-04-23 | 2023-05-26 | 宁德新能源科技有限公司 | Separator, electrochemical device and electronic device |
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| CN108666509A (en) * | 2018-05-18 | 2018-10-16 | 深圳市晶特智造科技有限公司 | A kind of lithium-sulfur cell diaphragm and preparation method thereof, application |
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| CN110938228A (en) * | 2019-11-26 | 2020-03-31 | 武汉理工大学 | Preparation method and application of zeolite/polyimide composite membrane |
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| CN112259914A (en) * | 2020-09-02 | 2021-01-22 | 江西师范大学 | Molecular sieve coated porous composite material and preparation method and application thereof |
| WO2023051562A1 (en) | 2021-09-28 | 2023-04-06 | 中国石油化工股份有限公司 | Separator for lithium-sulfur battery, method for preparing same and lithium-sulfur battery containing same |
| CN114649553A (en) * | 2022-02-11 | 2022-06-21 | 南京工业大学 | Porous membrane loaded by zeolite molecular sieve nanosheets, preparation method and application of porous membrane in zinc-based flow battery |
| CN115842214A (en) * | 2022-10-18 | 2023-03-24 | 福州大学 | High-voltage-resistant low-self-discharge diaphragm with screening effect, preparation method and application |
| CN116169434A (en) * | 2023-04-23 | 2023-05-26 | 宁德新能源科技有限公司 | Separator, electrochemical device and electronic device |
| CN116169434B (en) * | 2023-04-23 | 2023-12-22 | 宁德新能源科技有限公司 | Separator, electrochemical device and electronic device |
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Application publication date: 20180105 |