CN109216632A - A kind of preparation method of porous polyethylene alcohol battery diaphragm - Google Patents

A kind of preparation method of porous polyethylene alcohol battery diaphragm Download PDF

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Publication number
CN109216632A
CN109216632A CN201811090848.2A CN201811090848A CN109216632A CN 109216632 A CN109216632 A CN 109216632A CN 201811090848 A CN201811090848 A CN 201811090848A CN 109216632 A CN109216632 A CN 109216632A
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polyvinyl alcohol
preparation
film
container
glass plate
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CN109216632B (en
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胡源
王伟
阚永春
宋磊
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University of Science and Technology of China USTC
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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
    • 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
    • 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 & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Cell Separators (AREA)

Abstract

本发明公开了一种多孔聚乙烯醇电池隔膜的制备方法，是利用低温法抑制聚乙烯醇羟基之间氢键作用得到高孔隙率聚乙烯醇隔膜。本发明方法成功解决了聚乙烯醇隔膜在制备过程中由于氢键作用孔径减小或者完全消失的难题，制备得到的高孔隙率聚乙烯醇隔膜具有更大的孔径、更好的电解液相容性。

The invention discloses a preparation method of a porous polyvinyl alcohol battery separator, which is to obtain a high-porosity polyvinyl alcohol separator by suppressing the hydrogen bond between the hydroxyl groups of polyvinyl alcohol by a low temperature method. The method of the invention successfully solves the problem that the pore size of the polyvinyl alcohol separator decreases or disappears completely due to the hydrogen bond effect during the preparation process, and the prepared high-porosity polyvinyl alcohol separator has larger pore size and better electrolyte compatibility. sex.

Description

A kind of preparation method of porous polyethylene alcohol battery diaphragm
Technical field
The present invention relates to a kind of preparation methods of the membrane for polymer of new energy field of batteries, specifically utilize low temperature Method inhibits hydrogen bond action between polyvinyl alcohol hydroxyl to obtain the preparation method of high porosity polyvinyl alcohol membranes.
Background technique
Polyvinyl alcohol can be mass produced, valence as a kind of Biodegradable polymer material by non-petroleum path Lattice are cheap, are provided simultaneously with the characteristics such as oil resistant, solvent resistant and good mechanical performance, have in terms of medicine, food and widely answer With.Due to the ductility and strong mechanical performance of polyvinyl alcohol, it is often used to prepare film class product, is expected in new energy battery It is applied in field: as battery diaphragm.High-performance, environmental protection, low toxicity and safety membrane for polymer be current battery diaphragm neck The research hotspot in domain.
Polyvinyl alcohol battery diaphragm is few what is reported at present.2015, WeiXiao was prepared using non-solvent phase separation method Porous polyethylene alcohol diaphragm is simultaneously applied in lithium battery.However the polyvinyl alcohol membranes electricity that the method for this air drying obtains Solution liquid phase capacitive, aperture are all limited, this is because the hydrogen bond action of the long interchain of polyvinyl alcohol causes.In air drying process In with non-solvent phase ethyl alcohol continuous volatilization, polyvinyl alcohol membranes structure can shrink since hydrogen bond action attracts each other.This Low porosity caused by one phenomenon can make the chemical property of lithium battery decline.Exist currently, how to solve polyvinyl alcohol membranes Report is not yet received in the contraction problem of the aperture as caused by hydrogen bond action in preparation process.Therefore, it explores and simply and effectively inhibits The method of hydrogen bond action in polyvinyl alcohol membranes preparation process is extremely urgent.
Summary of the invention
In order to avoid technical problem present in the above-mentioned prior art, the present invention provides a kind of porous polyethylene alcohol batteries The preparation method of diaphragm, using low temperature process inhibit polyvinyl alcohol hydroxyl between hydrogen bond action obtain high porosity polyvinyl alcohol every Film.
The preparation method of porous polyethylene alcohol battery diaphragm of the present invention, includes the following steps:
Step 1: polyvinylalcohol solids particle and water being added into reactor, is stirred continuously at 80-130 DEG C until poly- second Enol solid particle is completely dissolved, and forms colourless transparent solution, is cooled to room temperature stand-by；
Step 2: poly-vinyl alcohol solution obtained by step 1 being evenly applied on glass plate as coating device, forms one Determine the film of thickness, and it is at the uniform velocity immersed into non-solvent phase liquid, stands 3-24 hours；
Step 3: film being taken out from non-solvent phase liquid and is removed from glass plate, is placed in container and keeps flat It is whole, then in 0 DEG C to -90 DEG C holding 0.2h-6h, finally obtain high porosity polyvinyl alcohol membranes.
In step 1, the alcoholysis degree of the polyvinylalcohol solids particle is 70%-99%.
The mass concentration for the poly-vinyl alcohol solution that step 1 obtains is 1-15wt%.
In step 2, the thickness of film is regulated and controled by coating device, and thickness is 8 μm -500 μm.
In step 2, the non-solvent phase liquid is methanol or ethyl alcohol.
In step 3, film reduces container internal pressure to 0.1Pa- during 0 DEG C to -90 DEG C holding 0.2h-6h 105Pa。
In step 3, film is placed in the temperature in container and is preferably less than -30 DEG C.
Compared with the prior art, the advantages of the present invention are as follows:
1, low temperature process of the present invention prepares high porosity polyvinyl alcohol membranes, at low cost, easily operated, with industrialization can It can property.
2, the method for the present invention successfully solve polyvinyl alcohol membranes during the preparation process due to hydrogen bond action aperture reduce or The problem that person completely disappears.
3, the high porosity polyvinyl alcohol membranes that the method for the present invention is prepared have bigger aperture, better electrolyte Compatibility.
Detailed description of the invention
Fig. 1 is the high porosity polyvinyl alcohol membranes digital photograph of low temperature process preparation in embodiment 1.
Fig. 2 is the polyvinyl alcohol membranes profile scanning electron microscope prepared under the conditions of 25 DEG C and -60 DEG C in embodiment 1.
Contact angle of the Fig. 3 for commercial electrolyte liquid in embodiment 1 on high porosity polyethylene diagrams surface prepared by low temperature process Test.
Specific embodiment
Technical solution of the present invention is described in further detail below in conjunction with attached drawing and specific embodiment.
Embodiment 1:
1, be added in the single-necked flask equipped with magneton 10g polyvinylalcohol solids particle (model: 1799, alcoholysis degree is 99%) with 90g water, the continuous magnetic agitation at 90 DEG C is until polyvinylalcohol solids particle is completely dissolved, and it is poly- to form 10wt% Vinyl alcohol colourless transparent solution is cooled to room temperature stand-by；
2, obtained polyvinyl alcohol water solution is formed into the film of 50 μ m thicks by coating device on glass plate, And at the uniform velocity immerse it in dehydrated alcohol, stand 12 hours；By film from ethyl alcohol take out and removed from glass plate be placed in- In 60 DEG C of container, keep smooth, and reducing internal pressure is that 1Pa keeps 4h, finally obtains high porosity polyvinyl alcohol membranes.
3, comparative test is added herein, is placed under room temperature (25 for removing from glass plate from the film taken out in ethyl alcohol DEG C) volatilization, obtain polyvinyl alcohol film.
Fig. 1 is the high porosity polyvinyl alcohol membranes digital photograph of low temperature process preparation in embodiment 1.It can be seen in figure Out, white, and surfacing is presented in the polyvinyl alcohol membranes of high porosity.
Fig. 2 is the polyvinyl alcohol membranes profile scanning electron microscope prepared under the conditions of 25 DEG C and -60 DEG C in embodiment 1.From As can be seen that the polyvinyl alcohol film section being prepared under room temperature (25 DEG C) is barely perceivable hole in figure, and at -60 DEG C Under on the polyvinyl alcohol film section that is prepared full of hole, hole diameter is about 0.5-1.5 μm.This shows to pass through low temperature Method can capture the long interchain hydrogen bond action of polyvinyl alcohol and obtain high porosity diaphragm, it was demonstrated that the success of experiment.
Contact angle of the Fig. 3 for commercial electrolyte liquid in embodiment 1 on high porosity polyethylene diagrams surface prepared by low temperature process Test.Electrolyte used is general common 1M LiPF6/EC:DMC 1:1v/v.It can be seen from the figure that electrolyte and low temperature Contact angle between the polyvinyl alcohol membranes of method preparation is only 3.0 ° or so, embodies extremely strong compatibility of electrolyte.
Embodiment 2:
1,15g polyvinylalcohol solids particle and 85g water are added in the single-necked flask equipped with magneton, at 110 DEG C constantly Magnetic agitation is completely dissolved up to polyvinylalcohol solids particle, and forms 15wt% polyvinyl alcohol colourless transparent solution, is cooled to Room temperature is stand-by；
2, obtained polyvinyl alcohol water solution is formed into the film of 30 μ m thicks by coating device on glass plate, And at the uniform velocity immerse it in dehydrated alcohol, stand 12 hours；By film from ethyl alcohol take out and removed from glass plate be placed in- In 80 DEG C of container, keep smooth, and reducing internal pressure is that 1Pa keeps 4h, finally obtains high porosity polyvinyl alcohol membranes.
Embodiment 3:
1,5g polyvinylalcohol solids particle and 95g water, the continuous magnetic at 110 DEG C are added in the single-necked flask equipped with magneton Power stirring is completely dissolved up to polyvinylalcohol solids particle, and forms 5wt% polyvinyl alcohol colourless transparent solution, is cooled to room temperature For use；
2, obtained polyvinyl alcohol water solution is formed into the film of 30 μ m thicks by coating device on glass plate, And at the uniform velocity immerse it in anhydrous methanol, stand 6 hours；By film from methanol take out and removed from glass plate be placed in- In 30 DEG C of container, keep smooth, and reducing internal pressure is that 1Pa keeps 6h, finally obtains high porosity polyvinyl alcohol membranes.
Embodiment 4:
1,2g polyvinylalcohol solids particle and 98g water, the continuous magnetic at 100 DEG C are added in the single-necked flask equipped with magneton Power stirring is completely dissolved up to polyvinylalcohol solids particle, and forms 2wt% polyvinyl alcohol colourless transparent solution, is cooled to room temperature For use；
2, obtained polyvinyl alcohol water solution is formed into the film of 200 μ m thicks by coating device on glass plate, And at the uniform velocity immerse it in anhydrous methanol, stand 6 hours；By film from methanol take out and from glass plate removing be placed in 0 DEG C container in, keep it is smooth, and reduce internal pressure be 1Pa keep 12h, finally obtain high porosity polyvinyl alcohol membranes.
Embodiment 5:
1, be added in the single-necked flask equipped with magneton 2g polyvinylalcohol solids particle (model: 1788, alcoholysis degree is 88%) with 98g water, the continuous magnetic agitation at 100 DEG C is until polyvinylalcohol solids particle is completely dissolved, and it is poly- to form 2wt% Vinyl alcohol colourless transparent solution is cooled to room temperature stand-by；
2, obtained polyvinyl alcohol water solution is formed into the film of 400 μ m thicks by coating device on glass plate, And at the uniform velocity immerse it in dehydrated alcohol, stand 12 hours；By film from ethyl alcohol take out and removed from glass plate be placed in- In 50 DEG C of container, keep it is smooth, and reduce internal pressure be 1Pa keep 12h, finally obtain high porosity polyvinyl alcohol every Film.

Claims (8)

1.一种多孔聚乙烯醇电池隔膜的制备方法，其特征在于：利用低温法抑制聚乙烯醇羟基之间氢键作用得到高孔隙率聚乙烯醇隔膜。1. a preparation method of porous polyvinyl alcohol battery separator, is characterized in that: utilize low temperature method to suppress hydrogen bonding between polyvinyl alcohol hydroxyl groups and obtain high porosity polyvinyl alcohol separator. 2.根据权利要求1所述的制备方法，其特征在于包括如下步骤：2. preparation method according to claim 1 is characterized in that comprising the steps: 步骤1：向反应器中加入聚乙烯醇固体颗粒和水，在80-130℃下不断搅拌直至聚乙烯醇固体颗粒完全溶解，并形成无色透明溶液，冷却至室温待用；Step 1: Add polyvinyl alcohol solid particles and water into the reactor, and keep stirring at 80-130 ° C until the polyvinyl alcohol solid particles are completely dissolved, and form a colorless and transparent solution, which is cooled to room temperature for use; 步骤2：通过涂膜装置将步骤1所得聚乙烯醇溶液均匀涂覆于玻璃平板上，形成一定厚度的薄膜，并将其匀速浸入至非溶剂相液体中，静置3-24小时；Step 2: uniformly coat the polyvinyl alcohol solution obtained in step 1 on a glass plate by a film coating device to form a film of a certain thickness, and immerse it into the non-solvent phase liquid at a constant speed, and let it stand for 3-24 hours; 步骤3：将薄膜从非溶剂相液体中取出并从玻璃平板上剥离，置于容器内并保持平整，然后于0℃至-90℃保持0.2h-6h，最终得到高孔隙率聚乙烯醇隔膜。Step 3: The film is taken out from the non-solvent phase liquid and peeled off from the glass plate, placed in a container and kept flat, and then kept at 0°C to -90°C for 0.2h-6h, and finally a high-porosity polyvinyl alcohol membrane is obtained . 3.根据权利要求2所述的制备方法，其特征在于：3. preparation method according to claim 2, is characterized in that: 步骤1中，所述聚乙烯醇固体颗粒的醇解度是70％-99％。In step 1, the alcoholysis degree of the polyvinyl alcohol solid particles is 70%-99%. 4.根据权利要求2所述的制备方法，其特征在于：4. preparation method according to claim 2, is characterized in that: 步骤1获得的聚乙烯醇溶液的质量浓度为1-15wt％。The mass concentration of the polyvinyl alcohol solution obtained in step 1 is 1-15 wt %. 5.根据权利要求2所述的制备方法，其特征在于：5. preparation method according to claim 2, is characterized in that: 步骤2中，薄膜的厚度通过涂膜装置来调控，厚度是8μm-500μm。In step 2, the thickness of the film is regulated by a film coating device, and the thickness is 8 μm-500 μm. 6.根据权利要求2所述的制备方法，其特征在于：6. preparation method according to claim 2, is characterized in that: 步骤2中，所述非溶剂相液体为甲醇或乙醇。In step 2, the non-solvent phase liquid is methanol or ethanol. 7.根据权利要求2所述的制备方法，其特征在于：7. preparation method according to claim 2, is characterized in that: 步骤3中，薄膜于0℃至-90℃保持0.2h-6h的过程中，降低容器内部压强至0.1Pa-105Pa。In step 3, during the process of keeping the film at 0°C to -90°C for 0.2h-6h, the internal pressure of the container is reduced to 0.1Pa-10 5 Pa. 8.根据权利要求2或7所述的制备方法，其特征在于：8. preparation method according to claim 2 or 7 is characterized in that: 步骤3中，薄膜置于容器中的温度为低于-30℃。In step 3, the temperature at which the film is placed in the container is lower than -30°C.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113054321A (en) * 2021-03-17 2021-06-29 西安工程大学 Zinc-air battery diaphragm and preparation process thereof
CN113241501A (en) * 2021-05-10 2021-08-10 中国科学技术大学 Preparation method of flame-retardant and easily-carbonized lithium ion battery diaphragm

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CN105789524A (en) * 2016-04-29 2016-07-20 宁德卓高新材料科技有限公司 Preparation method of polyvinyl alcohol isolating membrane and isolating membrane prepared
CN106953056A (en) * 2015-10-29 2017-07-14 住友化学株式会社 Nonaqueous electrolytic solution secondary battery lamination spacer, nonaqueous electrolytic solution secondary battery part and nonaqueous electrolytic solution secondary battery

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CN106953056A (en) * 2015-10-29 2017-07-14 住友化学株式会社 Nonaqueous electrolytic solution secondary battery lamination spacer, nonaqueous electrolytic solution secondary battery part and nonaqueous electrolytic solution secondary battery
CN105789524A (en) * 2016-04-29 2016-07-20 宁德卓高新材料科技有限公司 Preparation method of polyvinyl alcohol isolating membrane and isolating membrane prepared

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113054321A (en) * 2021-03-17 2021-06-29 西安工程大学 Zinc-air battery diaphragm and preparation process thereof
CN113241501A (en) * 2021-05-10 2021-08-10 中国科学技术大学 Preparation method of flame-retardant and easily-carbonized lithium ion battery diaphragm

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