CN102324481A - Composite diaphragm for lithium ion battery and preparation method thereof - Google Patents
Composite diaphragm for lithium ion battery and preparation method thereof Download PDFInfo
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- CN102324481A CN102324481A CN201110285380A CN201110285380A CN102324481A CN 102324481 A CN102324481 A CN 102324481A CN 201110285380 A CN201110285380 A CN 201110285380A CN 201110285380 A CN201110285380 A CN 201110285380A CN 102324481 A CN102324481 A CN 102324481A
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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 relates to the research field of lithium ion batteries, and discloses a composite diaphragm for lithium ion batteries and a preparation method thereof. Firstly, PVDF-HFP and PDMS are dissolved in a diluent to obtain a mixed system with uniform characters; secondly, a dispersant is added into the mixed system to obtain a dispersion system; finally, the mixture of PVDF-HFP and PDMS is prepared into a film, and the film is extracted by an extractant and is dried to obtain a porous PVDF-HFP and PDMS composite diaphragm. The composite diaphragm prepared by the invention has high a liquid absorption rate, conductivity, and uniform pore distribution. The composite diaphragm has an electrolyte absorptivity of 175-185%, room temperature conductivity of 1.3 mS/cm, and porosity of 60%-75%.
Description
Technical field
The present invention relates to the research field of lithium ion battery, especially relate to the preparation method of a kind of lithium ion battery with the PVDF-HFP/PDMS composite diaphragm.
Background technology
Lithium ion battery has extended cycle life because of its specific energy is high, advantages such as memory-less effect, thereby use very extensively, become the hot research field of secondary power supply.The main effect of lithium ion battery separator is to isolate positive and negative electrode and stop electronics to pass, but the ion in the electrolyte solution is freely passed through between both positive and negative polarity.
Along with present electronic equipment constantly develops to the direction of lighting, the lithium ion battery of its use need have the characteristic of high-energy-density and high power capacity.Be different from first generation lithium ion battery liquid electrolyte commonly used at present, second generation lithium ion battery colloidal polymer electrolyte has the following advantages: high-energy-density, Stability Analysis of Structures, low volatility.Multiple polymers all can be used as the basic framework of polyelectrolyte, comprises according to oxirane (PEO) polyacrylonitrile (PAN), polymethyl methacrylate (PMMA), Kynoar (PVDF) and Kynoar-hexafluoropropylene copolymer (PVDF-HFP) etc.Because the PVDF system material has high-k and stronger electronics stretching functional group! – C – F –), so it is considered to the desirable diaphragm material of high performance lithium ion battery of new generation.But pure PVDF material degree of crystallinity is higher, constraint electrolyte poor stability, so its ionic conductivity is low, has limited its application in the barrier film field.
The PVDF resinoid is because of having bigger dielectric constant (ε=8 ~ 10), and good thermal endurance and mechanical property have preferably become one of desirable matrix of membrane for polymer.But PVDF degree of crystallinity is higher, and can reduce its degree of crystallinity after HFP and the VDF copolymerization, can make dielectric film have excellent mechanical strength like this, can guarantee that again copolymer has the electrolytical ability of good adsorption, and shows excellent chemical property.Therefore, adopt PVDF-HFP to reduce degree of crystallinity to a certain extent, be beneficial to the increase pick up, improve the performance of barrier film.
PDMS is one of rubber membrane material the most commonly used, has the advantage of low surface tension, high-flexibility, low Tg, high temperature resistant, corrosion-resistant, stable height, high-compressibility.With PDMS the PVDF-HFP copolymer is carried out modification, can improve the interface compatibility of PVDF-HFP base electrolyte and metal lithium electrode, the ionic conductivity and the transference number of ions of electrolyte membrance all increase.
Compare with other film-forming method; Phase inversion has following advantage: first; Can just can realize control such as changing diluent kind, polymer molecular weight, polymer initial concentration etc. through regulating simple technological parameter to membrane pore structure and aggregated structure; The second, prepared porous film strength is better, pore-size distribution is narrow; The 3rd, can prepare netted and the good pore structure of connectivity such as ball intergranular pore.Therefore, phase inversion is that preparation is used for the bone porous a kind of Perfected process of lithium ion battery semi liquid state barrier film.
Summary of the invention
The present invention utilizes phase inversion to design and develop to be used for the active porous composite diaphragm of lithium ion battery, and the composite film material of gained will have special activity.
Membrane thicknesses of the present invention is that 15～55 μ m, electrolyte absorptivity are 175～185%, room-temperature conductivity is that 1.3mS/cm, porosity are 60～75%.
The present invention also proposes to have the preparation method of the composite film material of above performance.
May further comprise the steps:
1) mixed diluting: Kynoar-hexafluoropropylene copolymer (PVDF-HFP) and dimethyl silicone polymer (PDMS) are mixed at ambient temperature; And adding diluent; Under 60 ℃ of temperature environment conditions, stirred 6 hours, can obtain the mixed system of proterties homogeneous.
2) system is disperseed: dispersant is added in the said mixed system, stirred at ambient temperature 2 hours, the blend material is further disperseed dilution, can obtain the PVDF-HFP and the PDMS blend of proterties homogeneous.
3) inversion of phases film forming: evenly coat said blend on the glass plate; Said coating thickness is 80～100 μ m; After room temperature leaves standstill 10～15 seconds, after extractant cleaning three times, use extractant submergence glass plate after 48 hours at ambient temperature; Can remove diluent and dispersant, obtain lithium ion battery in 48 hours through 40 ℃ of vacuumizes again and use composite diaphragm.
The present invention utilizes the immersion precipitation phase inversion to design and develop the active porous diaphragm material of the PVDF-HFP/PDMS that is used for lithium ion battery.The PVDF-HFP and the PDMS composite diaphragm of preparation have the characteristics of low-crystallinity, high porosity, high-liquid absorbing rate.This PVDF-HFP and PDMS composite diaphragm are a kind of active membranes with high ionic conductivity and high electrochemical stability, are the first-selected barrier films of good, the safe lithium ion battery of performance.Utilize PDMS to modify the PVDF-HFP polymeric material; The composite diaphragm material of gained will have special activity, and after lithium ion battery was assembled into module, composite diaphragm can be through absorbing the lithium salts liquid electrolyte; Make the electrolyte gelation, thereby improve the combination property of lithium ion battery.Simultaneously, PVDF-HFP and PDMS composite diaphragm have good fail safe, are beneficial to the expanding application of lithium ion battery, promote the continuous lifting development of lithium ion battery industry.In addition, the present invention's safety simple to operate, production cost is lower.
In step 1) according to the invention, the mass ratio that feeds intake of said dimethyl silicone polymer and Kynoar-hexafluoropropylene copolymer is 10～20 ︰ 100.
In said step 1); Said diluent is with repefral (DMP) or N; In the N-dimethylacetylamide (DMAc) at least any one, said diluent consumption is 100%～500% of dimethyl silicone polymer and Kynoar-hexafluoropropylene copolymer gross mass.
In said step 2) in, said dispersant is 1, in 2-propane diols, isopropyl alcohol or the glycerine at least any one, consumption is 10%～15% of dimethyl silicone polymer and Kynoar-hexafluoropropylene copolymer gross mass.
In said step 3), said extractant is that percent by volume is 5%～10% ethanolic solution.
Embodiment
Example 1:
1) 4g Kynoar-hexafluoropropylene copolymer (PVDF-HFP) and 1g dimethyl silicone polymer (PDMS) are mixed at ambient temperature; And adding 10g repefral (DMP) and 10g N; N-dimethylacetylamide (DMAc) diluent; Stirred 6 hours down at 60 ℃, obtain the mixed system of proterties homogeneous.
2) with 0.25g1,2-propane diols and 0.25g glycerine dispersant add in the mixed system, stir at ambient temperature 2 hours, and the blend material is further disperseed dilution, obtain the PVDF-HFP and the PDMS blend of proterties homogeneous.
3) evenly coat the PVDF-HFP/PDMS blend on the glass plate; Coating thickness is 80 μ m; After room temperature leaves standstill 10 seconds; After using 25g10% (percent by volume) ethanolic solution to clean three times respectively, use 75g10% (percent by volume) ethanolic solution submergence glass plate 48 hours at ambient temperature, obtained lithium ion battery in 48 hours with PVDF-HFP and PDMS composite diaphragm through 40 ℃ of vacuumizes again to remove diluent and dispersant.
4) through detecting the characteristic of the composite diaphragm that embodiment 1 processes:
Thickness is 50 μ m.
The electrolyte absorptivity is 180%.
Room-temperature conductivity is 1.3mS/cm.
Porosity is 70%.
Example 2:
1) 4.5gPVDF-HFP and 0.5gPDMS are mixed at ambient temperature, and add the 15gDMAc diluent, stirred 6 hours down, obtain the mixed system of proterties homogeneous at 60 ℃.
2) 0.5g isopropyl alcohol or glycerine dispersant are added in the mixed system, stirred at ambient temperature 2 hours, the blend material is further disperseed dilution, obtain the PVDF-HFP and the PDMS blend of proterties homogeneous.
3) evenly coat PVDF-HFP and PDMS blend on the glass plate; Coating thickness is 100 μ m; After room temperature leaves standstill 15 seconds; After using 35g10% (percent by volume) ethanolic solution to clean three times respectively, use 75g10% (percent by volume) ethanolic solution submergence glass plate 48 hours at ambient temperature, obtained lithium ion battery in 48 hours with PVDF-HFP and PDMS composite diaphragm through 40 ℃ of vacuumizes again to remove diluent and dispersant.
4) through detecting the characteristic of the composite diaphragm that embodiment 2 processes:
Thickness is 45 μ m.
The electrolyte absorptivity is 185%.
Room-temperature conductivity is 1.3mS/cm.
Porosity is 75%.
Claims (6)
1. lithium ion battery is used composite diaphragm, it is characterized in that, said membrane thicknesses is that 15～55 μ m, electrolyte absorptivity are 175～185%, room-temperature conductivity is that 1.3mS/cm, porosity are 60～75%.
2. a lithium ion battery as claimed in claim 1 is characterized in that may further comprise the steps with the preparation method of composite diaphragm:
1) mixed diluting: Kynoar-hexafluoropropylene copolymer and dimethyl silicone polymer are mixed at ambient temperature, and add diluent, under 60 ℃ of temperature environment conditions, stirred 6 hours, obtain mixed system;
2) system is disperseed: dispersant is added in the said mixed system, stirred at ambient temperature 2 hours, obtain blend;
3) inversion of phases film forming: evenly coat said blend on the glass plate; Said coating thickness is 80～100 μ m; After room temperature leaves standstill 10～15 seconds; After extractant cleaning three times, use extractant submergence glass plate after 48 hours at ambient temperature, obtain lithium ion battery in 48 hours through 40 ℃ of vacuumizes again and use composite diaphragm.
3. the preparation method of composite diaphragm according to claim 2 is characterized in that in said step 1), and the mass ratio that feeds intake of said dimethyl silicone polymer and Kynoar-hexafluoropropylene copolymer is 10～20 ︰ 100.
4. the preparation method of composite diaphragm according to claim 2; It is characterized in that in said step 1); Said diluent is with repefral or N; In the N-dimethylacetylamide at least any one, said diluent consumption is 100%～500% of dimethyl silicone polymer and Kynoar-hexafluoropropylene copolymer gross mass.
5. the preparation method of composite diaphragm according to claim 2; It is characterized in that in said step 2) in; Said dispersant is 1; In 2-propane diols, isopropyl alcohol or the glycerine at least any one, consumption is 10%～15% of dimethyl silicone polymer and Kynoar-hexafluoropropylene copolymer gross mass.
6. the preparation method of composite diaphragm according to claim 2 is characterized in that in said step 3), and said extractant is that percent by volume is 5%～10% ethanolic solution.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103094515A (en) * | 2012-12-14 | 2013-05-08 | 深圳中兴创新材料技术有限公司 | Composite membrane and preparation method as well as battery |
| CN105932203A (en) * | 2016-06-15 | 2016-09-07 | 苏州大学 | Porous lithium ion battery separator with interpenetrating polymer network structure, and preparation method and application for porous lithium ion battery separator |
| 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 |
| CN108134034A (en) * | 2017-12-21 | 2018-06-08 | 深圳锂硫科技有限公司 | A kind of method that lithium battery diaphragm is prepared based on mixed solvent multistage Volatilization mechanism |
| CN109285985A (en) * | 2017-07-20 | 2019-01-29 | 天津凯普瑞特新能源科技有限公司 | A kind of PVDP lithium battery diaphragm |
| CN109786821A (en) * | 2018-12-11 | 2019-05-21 | 天津工业大学 | A kind of lithium ion battery electrolyte and preparation method thereof |
| CN109818054A (en) * | 2018-12-11 | 2019-05-28 | 天津工业大学 | A kind of lithium ion battery electrolyte and preparation method thereof having multilevel structure |
| CN113939367A (en) * | 2019-06-14 | 2022-01-14 | 古河机械金属株式会社 | Method for producing inorganic material and apparatus for producing inorganic material |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103094515A (en) * | 2012-12-14 | 2013-05-08 | 深圳中兴创新材料技术有限公司 | Composite membrane and preparation method as well as battery |
| CN103094515B (en) * | 2012-12-14 | 2015-05-27 | 深圳中兴创新材料技术有限公司 | Composite membrane and preparation method as well as battery |
| CN105932203A (en) * | 2016-06-15 | 2016-09-07 | 苏州大学 | Porous lithium ion battery separator with interpenetrating polymer network structure, and preparation method and application for porous lithium ion battery separator |
| CN105932203B (en) * | 2016-06-15 | 2018-09-25 | 苏州大学 | A kind of preparation method of the porosity lithium ion battery separator with inierpeneirating network structure |
| 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 |
| CN109285985A (en) * | 2017-07-20 | 2019-01-29 | 天津凯普瑞特新能源科技有限公司 | A kind of PVDP lithium battery diaphragm |
| CN108134034A (en) * | 2017-12-21 | 2018-06-08 | 深圳锂硫科技有限公司 | A kind of method that lithium battery diaphragm is prepared based on mixed solvent multistage Volatilization mechanism |
| CN109786821A (en) * | 2018-12-11 | 2019-05-21 | 天津工业大学 | A kind of lithium ion battery electrolyte and preparation method thereof |
| CN109818054A (en) * | 2018-12-11 | 2019-05-28 | 天津工业大学 | A kind of lithium ion battery electrolyte and preparation method thereof having multilevel structure |
| CN113939367A (en) * | 2019-06-14 | 2022-01-14 | 古河机械金属株式会社 | Method for producing inorganic material and apparatus for producing inorganic material |
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Application publication date: 20120118 |