CN108134033A - A kind of application of porous septum in lithium-sulfur cell - Google Patents
A kind of application of porous septum in lithium-sulfur cell Download PDFInfo
- Publication number
- CN108134033A CN108134033A CN201611088071.7A CN201611088071A CN108134033A CN 108134033 A CN108134033 A CN 108134033A CN 201611088071 A CN201611088071 A CN 201611088071A CN 108134033 A CN108134033 A CN 108134033A
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- Prior art keywords
- porous septum
- lithium
- battery
- heat resistant
- resistant type
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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
-
- 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
-
- 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
-
- 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
-
- 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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- 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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- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a kind of preparation method with good mechanical properties and stability lithium-sulfur cell diaphragm material and its applications in lithium ion battery.It is made using heat resistant type organic polymer resin by raw material, the heat resistant type macromolecule resin includes the one or several kinds in polysulfones, polyether sulfone, polyimides, polyetheramides, polyether-ether-ketone, polytetrafluoroethylene (PTFE), polyacrylonitrile, prepared porous septum is heat-resist, it is preferable with the compatibility of electrolyte, be conducive to the performance of battery performance, while improve the security performance of battery.The present invention also provides a kind of preparation methods of porous septum, using heat resistant type macromolecule as raw material, the pore-forming by the way of inversion of phases pore-forming, so that diaphragm has higher porosity, this procedure is simple simultaneously, and operability is strong, is conducive to further genralrlization application.In addition the porous septum better mechanical property, and hole wall has curvature, can inhibit the generation of cathode lithium piece dendrite, dendrite puncture diaphragm causes battery short circuit during preventing battery use.
Description
Technical field
The present invention relates to a kind of lithium-sulfur cell porous septum, specifically a kind of heat resistant type porous septum and its in lithium sulphur
Application in battery.
Background technology
With the improvement of people's living standards, automobile is as the easily vehicles more and more commonization.It is however, existing
In the main still fossil fuel based on oil of vehicle fuel, increasingly serious problem of environmental pollution can be caused.Electric vehicle
Exploitation be conducive to alleviate problem of environmental pollution, build the living environment of harmonious green.The critical piece of electric vehicle is battery,
Using lithium metal as cathode, sulphur is the lithium-sulfur cell of anode, and since lithium metal has most negative potential, minimum density is best
Electronic conductivity, electrochemistry capacitance reaches 3860mAh/g, and sulphur anode is cheap, environmental-friendly, and battery energy density is high
The features such as (1672mAh/g), is more and more paid attention to.
Although having more than advantage, lithium-sulfur cell also has longer a distance from functionization, in addition to existing in lithium-sulfur cell
Polysulfide " shuttle " effect, as power battery, the security performance of battery is also vital.For polysulfide
" shuttle " effect caused by dissolving migration, people have done many work.As added in additive lithium nitrate in the electrolytic solution
(Electrochimica Acta 70,2012,344-348) makes cathode of lithium surface form protective layer, and then inhibits polysulfide
With reacting for lithium metal, battery performance is improved；Prepare composite polymer gel electrolyte separator (Journal of Power
Sources212,2012,179-185 " shuttle " effect of polysulfide) is also effectively solved.But about raising lithium-sulfur cell
Security performance this respect work carry out it is also fewer, present invention is generally directed to the safety issues of lithium-sulfur cell, provide
A kind of feasible solution.
One of important component of lithium-sulfur cell is diaphragm, and main function is to be physically separated from the positive and negative electrode of battery,
The two poles of the earth is prevented to be in direct contact；Simultaneously channel is provided in the transmission of two interpolars for lithium ion.The performance of diaphragm directly affects the peace of battery
Full property and chemical property, it is to improve one of the important means of battery comprehensive performance to research and develop the diaphragm haveing excellent performance.
The lithium-sulfur cell diaphragm developed and used at present, predominantly polyolefin based materials (polyethylene, polypropylene etc.), it is this kind of
Diaphragm material temperature classification is low (fusing point of PE is 130 DEG C or so, and the fusing point of PP is 160 DEG C or so), and internal temperature of battery is slightly
Height, diaphragm will melt, and short circuit occurs for battery, release amount of heat, and then cause the safety issues such as explosion.
Invention content
Present invention aims at for temperature classification existing for current polyalkene diaphragm it is low the problem of, provide one kind by heat-resisting
Porous septum, preparation method and its application in lithium-sulfur cell prepared by type macromolecule resin.This porous septum tool
There is the features such as good wellability, good mechanical property, high temperature classification, be a kind of diaphragm material of great application prospect.It can effectively carry
The safety issue of high lithium-sulfur cell.
To achieve the above object, the technical solution adopted by the present invention is as follows：
Using heat resistant type macromolecule resin as raw material, porous septum is prepared using phase inversion, and is applied to lithium sulphur electricity
In pond.
Porous septum according to claim 1, it is characterised in that：
The heat resistant type organic polymer resin for being used to prepare porous septum is polysulfones, polyether sulfone, polyimides, polyethers
One kind in amide, polyether-ether-ketone, polytetrafluoroethylene (PTFE), polyacrylonitrile or two kinds or more.
The aperture size of the porous septum isPorosity be 25~85%, thickness for 10~80um it
Between.
Include following preparation process：
(1) organic polymer resin, organic or inorganic solvent are added in, it is sufficiently stirred 8 at a temperature of 0~50 DEG C~it makes for 24 hours
Into macromolecule resin mass concentration in 5~70% uniform casting solutions；
(2) uniform casting solution prepared by step (1) is poured on tablet, striking is into wet film；Then by its mass-impregnation
1~60min in the poor solvent of resin, and impregnate remove residual solvent in deionized water, obtain porous septum；
(3) porous septum prepared by (2) is taken out from deionized water, it is dry.
The solvent is dimethylacetylamide, dimethylformamide, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO), nitric acid, sulphur
It is one or more in acid, methanesulfonic acid.
The poor solvent is methanol, the one or two or more kinds in ethyl alcohol, isopropanol, isobutanol, water.
Beneficial outcomes：
(1) present invention has expanded the type and use scope of lithium-sulfur cell diaphragm.
(2) diaphragm prepared by the present invention has good wetability, mechanical performance and thermal stability, meets power battery pair
In the requirement of diaphragm：Diaphragm generates miniature deformation at 350 DEG C, has good high-temperature stability.
(3) preparation process of the present invention is simple, and operability is strong, is conducive to further genralrlization use.
(4) diaphragm prepared by the present invention is applied in lithium-sulfur cell, improves the safety of battery.
Description of the drawings
Fig. 1 is the porous septum section SEM figures prepared by embodiment 1.
Fig. 2 is the porous septum and charge-discharge performance pair of the comparative example in lithium-sulfur cell under 0.2C prepared by embodiment 1
Than figure.
Specific embodiment
The present invention is further detailed rather than limited the scope of the invention below in conjunction with case study on implementation.
Embodiment 1
(1) polyether-ether-ketone, methanesulfonic acid and sulfuric acid are added in flask, the wherein mass ratio of methanesulfonic acid and sulfuric acid is 10：
20h is sufficiently stirred at a temperature of 1,25 DEG C, uniform casting solution of the polyether-ether-ketone mass concentration 12% is made；
(2) uniform casting solution prepared by step (1) is poured on tablet, striking is into wet film；Then by its mass-impregnation
The 10min in water forms perforated membrane, impregnates remove residual solvent in deionized water, obtain porous septum；
(3) porous septum is taken out from deionized water, it is dry.
It is about 75% by manufactured polyether-ether-ketone porous septum (film thickness 35um) progress porosity test；Contact angle is tested,
As a result it is 30 °.Manufactured film is subjected to heat stability testing, result generates miniature deformation when being 350 DEG C.
It is tested using the porous septum assembling lithium-sulfur cell of preparation.The cathode of lithium-sulfur cell is lithium foil；Anode is using following
It is prepared by method：The Super P carbon of 30wt.%, the elemental sulfur of 60wt.%, the Kynoar of 10wt.% is in N- crassitudes
It is blended, is coated on aluminium foil in ketone, the sulfur content after drying in positive-active layer is 1.0mg/cm2.Electrolyte uses two (trifluoros
Methyl sulphonyl) imine lithium (LiTFSI), solvent is dioxolanes (DOL)/dimethyl ether (DME) (volume ratio 1:1), electrolyte
A concentration of 1mol/L.Said modules are fitted together, and with the layer structure of anode/diaphragm/cathode according to 20uL/cm2
It is sealed after anode area addition electrolyte.It stands 3 hours quality relative to positive active material sulphur and charge and discharge is carried out with 0.2C.
The lithium-sulfur cell specific discharge capacity of assembling is 1128mAh/g, and the specific discharge capacity after continuous charge and discharge 100 recycle still has
596mAh/g。
Comparative example 1
Compared with Example 1, film is changed into Celgard 2325 diaphragms, porosity test is about 40%；Contact angle is tested,
As a result it is 62 °.Manufactured film is subjected to heat stability testing, result has just been melted for 200 DEG C.
The constant assembling lithium-sulfur cell of other conditions carries out electro-chemical test.The lithium-sulfur cell specific discharge capacity of assembling is
1110mAh/g, the specific discharge capacity after continuous charge and discharge 100 recycle still have 556mAh/g.
Compared with 2325 diaphragms of Celgard, polyether-ether-ketone is high for porous septum temperature classification prepared by raw material, porosity
Height, it is more preferable with electrolyte affinity, thus improve the security performance and cycle life of battery.
Embodiment 2
With embodiment 1, organic polymer resin is changed into polysulfones, solvent changes dimethylacetylamide into, and poor solvent is first
Alcohol, other conditions are constant.
Embodiment 3
With embodiment 1, organic polymer resin is changed into polyimides, solvent changes N-Methyl pyrrolidone into, other
Part is constant.
Embodiment 4
With embodiment 1 into, organic polymer resin is changed to the mixture of polyacrylonitrile and polysulfones, solvent changes N- methyl pyrroles into
Pyrrolidone, poor solvent are ethyl alcohol, and other conditions are constant..
Embodiment 5
With embodiment 1 into, organic polymer resin is changed to the mixture of polyether sulfone and polyetheramides, solvent changes dimethyl into
Acetamide, other conditions are constant.
Embodiment 6
With embodiment 1, poor solvent is changed into ethyl alcohol, other conditions are constant.
Claims (5)
1. a kind of application of porous septum in lithium-sulfur cell, porous septum is made of heat resistant type organic polymer resin, described
Heat resistant type macromolecule resin includes：Polysulfones, polyether sulfone, polyimides, polyetheramides, polyether-ether-ketone, polytetrafluoroethylene (PTFE), polypropylene
One kind in nitrile or two kinds or more.
2. application according to claim 1, it is characterised in that：
The aperture size of the porous septum isPorosity is 25-85%, and thickness is between 10-80um.
3. application according to claim 1, which is characterized in that the preparation of the porous septum includes following prepare and walks
Suddenly：
(1) organic polymer resin is added to solvent, is sufficiently stirred 8 at a temperature of 0~50 DEG C~is made macromolecule resin matter for 24 hours
Measure casting solution of the concentration 5~70%；
(2) casting solution prepared by step (1) is poured on tablet, striking is into wet film；Then by its mass-impregnation in resin
1~60min in poor solvent, and impregnate remove residual solvent in deionized water, obtain porous septum；
(3) porous septum prepared by (2) is taken out from deionized water, it is dry.
4. application according to claim 3, it is characterised in that：The solvent for dimethylacetylamide, dimethylformamide,
One or two or more kinds in N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO), nitric acid, sulfuric acid, methanesulfonic acid.
5. application according to claim 3, it is characterised in that：The poor solvent is methanol, ethyl alcohol, isopropanol, isobutyl
One or two or more kinds in alcohol, water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611088071.7A CN108134033A (en) | 2016-12-01 | 2016-12-01 | A kind of application of porous septum in lithium-sulfur cell |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201611088071.7A CN108134033A (en) | 2016-12-01 | 2016-12-01 | A kind of application of porous septum in lithium-sulfur cell |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109244335A (en) * | 2018-10-31 | 2019-01-18 | 贵州梅岭电源有限公司 | A kind of polyimide diaphragm lithium-sulfur cell and preparation method thereof |
| CN110890502A (en) * | 2018-09-07 | 2020-03-17 | 中南大学 | Preparation method of novel composite lithium-sulfur battery diaphragm with POSS grafted carbon nanotubes |
| CN111261913A (en) * | 2018-11-30 | 2020-06-09 | 中国科学院大连化学物理研究所 | Composite membrane for alkaline zinc-based flow battery and preparation and application thereof |
| CN113078342A (en) * | 2020-01-03 | 2021-07-06 | 中国科学院大连化学物理研究所 | Functional composite membrane for alkaline zinc-iron flow battery and preparation method and application thereof |
| WO2023002229A1 (en) * | 2021-07-21 | 2023-01-26 | Некоммерческое Акционерное Общество "Атырауский Университет Имени Х.Досмухамедова" | Polymeric ion-conducting membrane material based on plasticized polysulphone |
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| CN105304847A (en) * | 2014-07-30 | 2016-02-03 | 中国科学院大连化学物理研究所 | Application of heat-resistant porous diaphragm to lithium ion battery |
| CN105322119A (en) * | 2014-07-28 | 2016-02-10 | 中国科学院大连化学物理研究所 | Application of porous diaphragm in lithium sulfur secondary battery |
| CN105633328A (en) * | 2016-01-06 | 2016-06-01 | 河南师范大学 | Polypropylene porous membrane for lithium-ion battery and preparation method of polypropylene porous membrane |
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| CN103682211A (en) * | 2012-09-06 | 2014-03-26 | 中国科学院大连化学物理研究所 | Application of porous diaphragm in flow energy storage battery |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110890502A (en) * | 2018-09-07 | 2020-03-17 | 中南大学 | Preparation method of novel composite lithium-sulfur battery diaphragm with POSS grafted carbon nanotubes |
| CN110890502B (en) * | 2018-09-07 | 2022-11-29 | 中南大学 | Preparation method of POSS (polyhedral oligomeric silsesquioxane) grafted carbon nanotube composite lithium-sulfur battery diaphragm |
| CN109244335A (en) * | 2018-10-31 | 2019-01-18 | 贵州梅岭电源有限公司 | A kind of polyimide diaphragm lithium-sulfur cell and preparation method thereof |
| CN111261913A (en) * | 2018-11-30 | 2020-06-09 | 中国科学院大连化学物理研究所 | Composite membrane for alkaline zinc-based flow battery and preparation and application thereof |
| CN111261913B (en) * | 2018-11-30 | 2021-09-03 | 中国科学院大连化学物理研究所 | Composite membrane for alkaline zinc-based flow battery and preparation and application thereof |
| CN113078342A (en) * | 2020-01-03 | 2021-07-06 | 中国科学院大连化学物理研究所 | Functional composite membrane for alkaline zinc-iron flow battery and preparation method and application thereof |
| WO2023002229A1 (en) * | 2021-07-21 | 2023-01-26 | Некоммерческое Акционерное Общество "Атырауский Университет Имени Х.Досмухамедова" | Polymeric ion-conducting membrane material based on plasticized polysulphone |
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Application publication date: 20180608 |