CN105322119A - Application of porous diaphragm in lithium sulfur secondary battery - Google Patents
Application of porous diaphragm in lithium sulfur secondary battery Download PDFInfo
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- CN105322119A CN105322119A CN201410363524.7A CN201410363524A CN105322119A CN 105322119 A CN105322119 A CN 105322119A CN 201410363524 A CN201410363524 A CN 201410363524A CN 105322119 A CN105322119 A CN 105322119A
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Abstract
The invention discloses an application of a porous diaphragm in a lithium sulfur secondary battery. The porous diaphragm is prepared by taking one or more than two kinds of organic polymer resins as the raw materials through gas phase-induced phase conversion. The diaphragm can effectively realize separation of poly-sulfur ions from lithium ions, keep the ion-permeability-selectivity, and can realize the ions transfer and the blocking of the poly-sulfur ions without depending on an ion exchange group and a special lattice structure; the diaphragm material is simple in preparation method, controllable in porous structure, low in cost, and easy to realize large-scale production, so that the manufacturing process and the select range of the lithium sulfur secondary battery diaphragm material are expanded.
Description
Technical field
The present invention relates to the application of a kind of porous septum in lithium-sulfur rechargeable battery, the particularly application of this type of film in lithium-sulfur rechargeable battery.
Background technology
Lithium-sulfur rechargeable battery is a kind of electrochemical energy storage new technology, compared with other energy storage technology, the advantage such as have that energy conversion efficiency is high, system is flexible, with low cost, specific energy is high (>400Wh/kg), safety and environmental protection, maintenance cost are low, can be widely used in the aspects such as electric automobile, unmanned aerial vehicle, emergency power system, stand-by station.Lithium-sulfur rechargeable battery (Lithiumsulfurbattery) is with low cost, be easy to processing, is considered to closest to industrialization and the secondary cell being hopeful replacement lithium ion battery most.
Battery diaphragm is the important component part in lithium-sulfur rechargeable battery, and it plays and intercepts positive and negative electrode short circuit, provides the effect of lithium ion transport passage.Lithium-ion-conducting, the chemical stability and ion selectivity etc. of film directly will affect chemical property and the useful life of battery; Therefore require that film has lower polysulfide ion permeability (namely having higher selectivity) and lower surface resistance (namely having higher lithium ion conductivity), also should have good chemical stability and lower cost simultaneously.The membrane material mainly PP/PE film used both at home and abroad now, this type of membrane material is for lithium ion battery exploitation, and aperture, more than 50 nanometers, effectively can not intercept polysulfide ion (size <10nm).Particularly be applied in lithium-sulfur cell shortcomings such as there is ion selectivity difference, thus limit the practical application of this film, limit the development of lithium-sulfur cell.Therefore, the battery diaphragm with high selectivity, high stability and low cost is developed most important.
The lithium-sulfur rechargeable battery barrier film with better resistance sulphur performance reported in current document, major part be perfluorinated sulfonic acid ion exchange membrane (
rSCAdvances3 (23): 8889), namely membrane material is made up of the polymer containing ion-exchange group, is mainly divided into perfluorinated ion-exchange membrane, half fluorine ion exchange membrane and non-fluorine ion exchange membrane.Because fluoropolymer membrane is expensive, and seriously swelling in the electrolytic solution, be difficult to meet Long-Time Service requirement, so the research work of current most of lithium-sulfur cell film concentrates in the coating modification of PP/PE barrier film.
Membrane separating process with selectivity through film for separating medium, when there are certain motive force (as pressure differential, concentration difference, potential difference etc.) in film both sides, feed side compositional selecting ground through film, with reach separations, purification object.The structure of diffusion barrier is generally porous membrane structure, and according to the size of membrane aperture, the molecule of different size optionally through film, thus can realize the object of separating-purifying.Porous septum used in industry is generally obtained by the method for inversion of phases.Basic skills is layered on by the solution of polymer dull and stereotyped upper (as glass plate), then as required, by solvent evaporates a period of time, immersed by flat board in the non-solvent bath of polymer and solidify, form the perforated membrane of polymer.In the methods of the invention, different preparation parameters will directly have influence on form and the performance of prepared film.Such as: the solvent evaporates time, the concentration of polymer solution and cosolvent etc.By controlling membrance casting condition, the size in perforated membrane aperture can be controlled, realizes the Selective Separation to different material.
For lithium-sulfur rechargeable battery, polysulfide ion and lithium ion all exist with the form of hydrated ion.Stokes radius (the R of pentavalent polysulfide ion
h) large between 2.5-3A °
[14].According to Stokes radius (R
h) computing formula (formula 1), the infiltration coefficient of ion stokes radius in the solution and ion is inversely.And the infiltration coefficient of lithium ion is far longer than polysulfide ion infiltration coefficient in the solution
[15], therefore, in solution, the Stokes radius of polysulfide ion is far longer than the Stokes radius of lithium ion.
Formula 1:
(k
bfor Boltzmann constant, T is kelvin degree, and D ion is infiltration coefficient, and η is the viscosity of solution)
According to the difference of polysulfide ion and lithium ion Stokes radius, if we can realize being separated polysulfide ion and lithium ion by diffusion barrier, lithium ion in film can freely be passed through, and polysulfide ion is trapped, and can realize the function of amberplex at VRB.Because this film does not need to introduce ion-exchange group, as long as just can be realized the function of film by simple aperture adjustment, greatly widen the range of choice of lithium-sulfur rechargeable battery membrane material.
The preparation method of perforated membrane is a lot, comprises track etching, template leaching, inversion of phases, cladding process etc.Wherein phase inversion is the most conventional, as vapor phase precipitation, controls evaporative precipitation, thermoprecipitation, immersion precipitation etc.The vapor phase precipitation method can make inversion of phases process carry out under close to the condition of stable state, and the perforated membrane aperture of preparation is homogeneous, and cortex is thinner.Be applied in lithium-sulfur cell by this type of film, what can increase film holds liquid ability and ion selectivity, and has widened the control measures of battery diaphragm pore structure.
Summary of the invention
The object of the invention is the deficiency existed in lithium-sulfur rechargeable battery for current amberplex, provides the application of a kind of porous septum in lithium-sulfur rechargeable battery, the particularly application of such film in lithium-sulfur rechargeable battery.
For achieving the above object, the technical solution used in the present invention is:
The application of porous septum in lithium-sulfur rechargeable battery, described porous septum, is prepared from by gas phase induction phase transformation for raw material is prepared from by one or more in organic polymer resin;
Described organic polymer resin is one or two or more kinds in polysulfones, polyketone, polyimides, polybenzimidazoles, polyphenylene quinoxaline, Kynoar, polyvinyl pyridine, polyacrylonitrile, polypropylene, polyethylene, polybutadiene or cellulose acetate.
Induction gas phase is one or more in steam, alcohol steam, ether, acid, alcohol is one or more in methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, ether is one or both in methyl ether, ether, and acid is one or more in formic acid, acetic acid.
Described porous septum aperture size is 0.05 ~ 10nm, and porosity is 5 ~ 50%, and thickness is 10 ~ 50 μm.Preferred aperture size is 0.05 ~ 2nm, and porosity is 20 ~ 50%.
Described porous septum adopts phase inversion to be prepared from.
(1) organic polymer resin is dissolved in organic solvent, at temperature is 20 ~ 200 DEG C, fully stirs 0.5 ~ 24h makes blend solution; Wherein organic polymer resin concentration is between 5 ~ 70wt%;
Also can add effumability solvent in above-mentioned solvent, form mixed solvent, the concentration of effumability solvent in mixed solvent is 0 ~ 50wt%;
(2) blend solution prepared by step (1) be poured at the bottom of nonwoven fabric base or be poured directly on glass plate, and scraping the even rete making 20 ~ 100 micron thickness;
(3) under normal pressure, rete prepared by step (2) is placed in immediately the steam atmosphere of non-solvent, temperature controls at 0-100 DEG C, and between control non-solvent concentration is at such a temperature saturated between 10 to 100%, the control time is 0.1 ~ 60 minute;
(4) film prepared by step (3) is placed in deionized water 0.1 ~ 24 hour, is washed away by residual solvent, control temperature is between 0 ~ 100 DEG C.
Described organic solvent is one or two or more kinds in DMSO, DMAC, NMP, DMF; Described effumability non-solvent is one or two or more kinds in methyl alcohol, ethanol, acetone, four lithium furans or n-hexane;
Non-solvent is one or two or more kinds in water, methyl alcohol, ethanol, propyl alcohol or isopropyl alcohol.
Organic polymer resin dissolves in organic solvent by step (1), adds pore creating material, fully stirs 0.5 ~ 24h and make blend solution at temperature is 20 ~ 200 DEG C; Wherein organic polymer resin concentration is between 5 ~ 70wt%; Pore creating material and organic polymer resin mass ratio are 1:(1-10);
Pore creating material is one or more in organic substance PEO, PVP, PVA and inorganic substances silica, titanium oxide, calcium oxide.
When preparing porous septum by controlling the membrance casting conditions such as solvent evaporates time, polymer solution concentration and cosolvent ratio, regulating membrane aperture size, realizing the Selective Separation to different ions, can be used for further in the lithium-sulfur rechargeable battery of different system.
Fig. 1 is the application principle schematic diagram of porous septum in lithium-sulfur rechargeable battery of preparation, can find out, prepared porous septum, by the control to aperture, can intercept both positive and negative polarity polysulfide ion to greatest extent, ensures freely passing through of lithium ion.
Described perforated film can be used in lithium-sulfur rechargeable battery, and described lithium-sulfur rechargeable battery comprises flexible packaging type lithium-sulfur cell and liquid flow pattern lithium-sulfur cell.
Beneficial outcomes of the present invention:
1. the present invention is prepared into porous septum and is applied in lithium-sulfur rechargeable battery, separation between different ions and transmission is realized by controlling pore size, maintain the ion permeable selectivity of film, do not need to introduce any ion-exchange group, the function of amberplex in lithium-sulfur rechargeable battery can be realized.
2. the perforated membrane that prepared by the present invention is different from the perforated membrane carrying out inversion of phases and prepare in non-solvent liquid phase.The present invention carries out inversion of phases in non-solvent gas phase, and inversion of phases process is slow, and pore structure is unique.This structure is conducive to regulating and controlling ion selectivity and the ionic conductance of film, thus obtains high performance lithium-sulfur cell barrier film.
3. such membrane preparation method is simple, and aperture is controlled, and low, the easy realization of cost is produced in enormous quantities.
4. the present invention has widened the kind of lithium-sulfur rechargeable battery membrane material, preparation method and the scope of application.
5. the present invention can realize the controllability to lithium-sulfur rechargeable battery efficiency.
Accompanying drawing explanation
Fig. 1 is the application principle schematic diagram of porous septum in lithium sulphur secondary prepared by humidity induction phase transformation;
Fig. 2 is embodiment 1 (left figure), the sectional view of porous septum prepared by comparative example 1 (right figure);
The film of Fig. 3 prepared by embodiment 1,2 and comparative example 1 is assembled into the charging and discharging curve of lithium sulphur secondary.
Embodiment
The following examples further illustrate of the present invention, instead of limit the scope of the invention.
Embodiment 1
5 grams of polyether sulfones are dissolved in 15gDMAC, add 1g polyethylene glycol and do pore creating material, stir 2 hours, form the polymer solution of homogeneous transparent, with glass bar blade coating on a glass, blade coating thickness is 20 microns.Then glass plate is placed in rapidly 50 DEG C together with resin, humidity is in the air ambient of 80%.After 5 minutes, glass plate is taken out, and immerses perforated membrane washes clean in 5L water.Film surface apertures is about 5nm, and film surface porosity factor is 50%.
Fig. 2 provides the section S EM picture of prepared membrane material, shows the pore structure of rule.Assemble lithium-sulfur cell with the pore separation membrane that has of preparation, commercialization carbon-sulfur compound is positive pole, and metal lithium sheet is negative pole, and the tetraethylene glycol dimethyl ether solution of 1M lithium trifluoromethanesulp,onylimide is electrolyte solution, and film effective area is 1.539cm
-2, discharge-rate is 0.1C.The lithium-sulfur rechargeable battery current efficiency of assembling is 90%, and energy efficiency is 80%.Fig. 3 can find out, initial discharge capacity is at more than 1300mAh/g, and circulate for 100 times rear battery capacity conservation rate >50%.
Comparative example 1
5 grams of polyether sulfones are dissolved in 15gDMAC, add 1g polyethylene glycol and do pore creating material, stir 2 hours, form the polymer solution of homogeneous transparent, with glass bar blade coating on a glass, blade coating thickness is 20 microns.Then glass plate is placed in rapidly the deionized water of 50 DEG C together with resin.After 5 minutes, glass plate is taken out, and immerses perforated membrane washes clean in 5L water.Film surface apertures is about 5nm.Film surface porosity factor is 50%.
Fig. 2 provides the section S EM picture of prepared membrane material, shows the pore structure of rule.Assemble lithium-sulfur cell with the pore separation membrane that has of preparation, commercialization carbon-sulfur compound is positive pole, and metal lithium sheet is negative pole, and the tetraethylene glycol dimethyl ether solution of 1M lithium trifluoromethanesulp,onylimide is electrolyte solution, and film effective area is 1.539cm
-2, discharge-rate is 0.1C.The lithium-sulfur rechargeable battery current efficiency of assembling is 90%, and energy efficiency is 80%.Fig. 3 can find out, initial discharge capacity is only 1100mAh/g, battery capacity conservation rate <50% after 20 circulations.
In fig. 2, can be found out with the SEM picture of comparative example 1 by comparative example 1: although the two resinous principle is identical, its pore structure but differs widely.The film carrying out inversion of phases in water has larger finger-like pore to exist, and then overall aperture is homogeneous to carry out the film of inversion of phases at the air of humidity 100%.This species diversity is that inversion of phases process is closer to thermodynamics stable state because humidity induction inversion of phases is more slow.
Embodiment 2
7.5 grams of polyacrylonitrile are dissolved in 30mlDMSO+10mlTHF, stir 5 hours, form the polymer solution of homogeneous transparent, with glass bar blade coating on a glass, blade coating thickness is 20 microns.Then glass plate is placed in rapidly 50 DEG C together with resin, humidity is in the air of 40%.After 5 minutes, glass plate is taken out, and immerses perforated membrane washes clean in 5L water.
Assemble lithium-sulfur cell with the pore separation membrane that has of preparation, commercialization carbon-sulfur compound is positive pole, and metal lithium sheet is negative pole, and the tetraethylene glycol dimethyl ether solution of 1M lithium trifluoromethanesulp,onylimide is electrolyte solution, and film effective area is 1.539cm
-2, discharge-rate is 0.1C.The lithium-sulfur rechargeable battery current efficiency of assembling is 90%, and energy efficiency is 80%.Fig. 3 can find out, initial discharge capacity is at more than 1400mAh/g, and circulate for 100 times rear battery capacity conservation rate >50%.
Embodiment 3
7.5 grams of PVDF are dissolved in 30mlDMSO+10mlTHF, stir 5 hours, form the polymer solution of homogeneous transparent, with glass bar blade coating on a glass, blade coating thickness is 20 microns.Then glass plate is placed in rapidly 100 DEG C together with resin, humidity is in the air of 40%.After 5 minutes, glass plate is taken out, and immerses perforated membrane washes clean in 5L water.
Assemble lithium-sulfur cell with the pore separation membrane that has of preparation, commercialization carbon-sulfur compound is positive pole, and metal lithium sheet is negative pole, and the tetraethylene glycol dimethyl ether solution of 1M lithium trifluoromethanesulp,onylimide is electrolyte solution, and film effective area is 1.539cm
-2, discharge-rate is 0.1C.The lithium-sulfur rechargeable battery current efficiency of assembling is 85%, and energy efficiency is 85%.Initial discharge capacity is at more than 1300mAh/g, and circulate for 100 times rear battery capacity conservation rate >60%.
Embodiment 4
7.5 grams of polyacrylonitrile are dissolved in 20mlDMACF, stir 5 hours, form the polymer solution of homogeneous transparent, with glass bar blade coating on a glass, blade coating thickness is 20 microns.Then glass plate is placed in rapidly 80 DEG C together with resin, humidity is in the air of 100%.After 5 minutes, glass plate is taken out, and immerses perforated membrane washes clean in 5L water.
Assemble lithium-sulfur cell with the pore separation membrane that has of preparation, commercialization carbon-sulfur compound is positive pole, and metal lithium sheet is negative pole, and the tetraethylene glycol dimethyl ether solution of 1M lithium trifluoromethanesulp,onylimide is electrolyte solution, and film effective area is 1.539cm
-2, discharge-rate is 0.1C.The lithium-sulfur rechargeable battery current efficiency of assembling is 95%, and energy efficiency is 80%.Initial discharge capacity is at more than 1500mAh/g, and circulate for 100 times rear battery capacity conservation rate >70%.
Embodiment 5
5 grams of Polyetherimide, in 30mlNMP, stir 5 hours, form the polymer solution of homogeneous transparent, with glass bar blade coating on a glass, blade coating thickness is 20 microns.Then glass plate is placed in rapidly 80 DEG C together with resin, humidity is in the air of 90%.After 5 minutes, glass plate is taken out, and immerses perforated membrane washes clean in 5L water.
Assemble lithium-sulfur cell with the pore separation membrane that has of preparation, commercialization carbon-sulfur compound is positive pole, and metal lithium sheet is negative pole, and the tetraethylene glycol dimethyl ether solution of 1M lithium trifluoromethanesulp,onylimide is electrolyte solution, and film effective area is 1.539cm
-2, discharge-rate is 0.1C.The lithium-sulfur rechargeable battery current efficiency of assembling is 95%, and energy efficiency is 85%.Initial discharge capacity is at more than 1200mAh/g, and circulate for 100 times rear battery capacity conservation rate >60%.
Claims (6)
1. the application of porous septum in lithium-sulfur rechargeable battery, is characterized in that: described porous septum is raw material by one or two or more kinds in organic polymer resin, is prepared from by gas phase induction phase transformation;
Described organic polymer resin is one or two or more kinds in polysulfones, polyketone, polyimides, polybenzimidazoles, polyphenylene quinoxaline, Kynoar, polyvinyl pyridine, polyacrylonitrile, polypropylene, polyethylene, polybutadiene or cellulose acetate.
2. application according to claim 1, is characterized in that:
Induction gas phase is one or more in steam, alcohol steam, ether, acid, alcohol is one or more in methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, ether is one or both in methyl ether, ether, and acid is one or more in formic acid, acetic acid.
3. application according to claim 1, is characterized in that:
Described porous septum and composite membrane aperture size thereof are 0.05 ~ 10nm, and porosity is 5 ~ 50%, and thickness is 10 ~ 50 μm.
4. the application of porous septum according to claim 1, is characterized in that:
Described porous septum and composite membrane thereof adopt following steps preparation:
(1) organic polymer resin is dissolved in organic solvent, at temperature is 20 ~ 200 DEG C, fully stirs 0.5 ~ 24h makes blend solution; Wherein organic polymer resin concentration is between 5 ~ 70wt%;
Also can add effumability solvent in above-mentioned solvent, form mixed solvent, the concentration of effumability solvent in mixed solvent is 0 ~ 50wt%;
(2) blend solution prepared by step (1) be poured at the bottom of nonwoven fabric base or be poured directly on glass plate, and scraping the even rete making 20 ~ 100 micron thickness;
(3) under normal pressure, rete prepared by step (2) is placed in immediately the steam atmosphere of non-solvent, temperature controls at 0-100 DEG C, and between control non-solvent concentration is at such a temperature saturated between 10 to 100%, the control time is 0.1 ~ 60 minute;
(4) film prepared by step (3) is placed in deionized water 0.1 ~ 24 hour, is washed away by residual solvent, control temperature is between 0 ~ 100 DEG C.
5. the application of porous septum according to claim 4, is characterized in that:
Described organic solvent is one or two or more kinds in DMSO, DMAC, NMP, DMF; Described effumability non-solvent is one or two or more kinds in methyl alcohol, ethanol, acetone, four lithium furans or n-hexane;
Non-solvent is one or two or more kinds in water, methyl alcohol, ethanol, propyl alcohol or isopropyl alcohol.
6. application according to claim 4, is characterized in that: organic polymer resin dissolves in organic solvent by step (1), adds pore creating material, fully stirs 0.5 ~ 24h and make blend solution at temperature is 20 ~ 200 DEG C; Wherein organic polymer resin concentration is between 5 ~ 70wt%; Pore creating material and organic polymer resin mass ratio are 1:(1-10);
Pore creating material is one or more in organic substance PEO, PVP, PVA and inorganic substances silica, titanium oxide, calcium oxide.
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|---|---|---|---|---|
| CN105789521A (en) * | 2016-03-04 | 2016-07-20 | 上海交通大学 | Polybenzimidazole microporous membrane and preparation method and application therefor |
| CN107845761A (en) * | 2016-09-20 | 2018-03-27 | 中国科学院大连化学物理研究所 | A kind of application of polybenzimidazoles porous septum in lithium ion battery |
| CN108134033A (en) * | 2016-12-01 | 2018-06-08 | 中国科学院大连化学物理研究所 | A kind of application of porous septum in lithium-sulfur cell |
| CN109119574A (en) * | 2018-08-15 | 2019-01-01 | 苏州大学 | Porosity lithium ion battery separator and the preparation method and application thereof based on crosslinking with line polymer |
| CN110105604A (en) * | 2019-05-09 | 2019-08-09 | 吉林大学 | A kind of adjustable crystal type poly(aryl ether ketone) perforated membrane in aperture, preparation method and applications |
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| CN111188050A (en) * | 2019-12-31 | 2020-05-22 | 山东东岳未来氢能材料有限公司 | Ultrathin perfluorinated sulfonic acid ion exchange membrane for alkali chloride electrolysis and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105789521A (en) * | 2016-03-04 | 2016-07-20 | 上海交通大学 | Polybenzimidazole microporous membrane and preparation method and application therefor |
| CN107845761A (en) * | 2016-09-20 | 2018-03-27 | 中国科学院大连化学物理研究所 | A kind of application of polybenzimidazoles porous septum in lithium ion battery |
| CN107845761B (en) * | 2016-09-20 | 2020-02-21 | 中国科学院大连化学物理研究所 | Application of polybenzimidazole porous diaphragm in lithium ion battery |
| CN108134033A (en) * | 2016-12-01 | 2018-06-08 | 中国科学院大连化学物理研究所 | A kind of application of porous septum in lithium-sulfur cell |
| CN109119574A (en) * | 2018-08-15 | 2019-01-01 | 苏州大学 | Porosity lithium ion battery separator and the preparation method and application thereof based on crosslinking with line polymer |
| CN109119574B (en) * | 2018-08-15 | 2021-06-18 | 苏州大学 | Porous lithium ion battery diaphragm based on cross-linked and linear polymer and preparation method and application thereof |
| CN110105604A (en) * | 2019-05-09 | 2019-08-09 | 吉林大学 | A kind of adjustable crystal type poly(aryl ether ketone) perforated membrane in aperture, preparation method and applications |
| CN110105604B (en) * | 2019-05-09 | 2022-02-01 | 吉林大学 | Pore size adjustable crystallization type polyaryletherketone porous membrane, preparation method and application thereof |
| CN110923954A (en) * | 2019-12-19 | 2020-03-27 | 广东工业大学 | High-molecular polymer fiber membrane with through hole structure and preparation method and application thereof |
| CN111188050A (en) * | 2019-12-31 | 2020-05-22 | 山东东岳未来氢能材料有限公司 | Ultrathin perfluorinated sulfonic acid ion exchange membrane for alkali chloride electrolysis and preparation method thereof |
| CN111188050B (en) * | 2019-12-31 | 2021-07-09 | 山东东岳高分子材料有限公司 | Ultrathin perfluorinated sulfonic acid ion exchange membrane for alkali chloride electrolysis and preparation method thereof |
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