CN110931686A - Preparation method of polyethylene glycol succinate microsphere emulsion coating type lithium battery diaphragm - Google Patents
Preparation method of polyethylene glycol succinate microsphere emulsion coating type lithium battery diaphragm Download PDFInfo
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- CN110931686A CN110931686A CN201911024718.3A CN201911024718A CN110931686A CN 110931686 A CN110931686 A CN 110931686A CN 201911024718 A CN201911024718 A CN 201911024718A CN 110931686 A CN110931686 A CN 110931686A
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- polyethylene glycol
- glycol succinate
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- microsphere emulsion
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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
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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
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
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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
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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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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Abstract
The invention discloses a preparation method of a polyethylene glycol succinate microsphere emulsion coating type lithium battery diaphragm. After the PBS microsphere emulsion is coated on the surface of the polyolefin microporous diaphragm, the PBS microsphere emulsion forms an organic polymer microsphere layer, when the battery is normally used, pores among the organic polymer microspheres ensure effective transmission of lithium ions, when the internal temperature of the battery rises and reaches the melting temperature of the organic polymer microspheres, the organic polymer microspheres are melted to form a film and block micropores on a polyolefin base film, the transmission of the lithium ions in the battery is cut off, the thermal shutdown of the diaphragm is realized, the further rise of the temperature in the battery is prevented, and the safety of the lithium ion battery is greatly improved.
Description
Technical Field
The invention relates to the field of lithium batteries, in particular to a preparation method of a polyethylene glycol succinate microsphere emulsion coating type lithium battery diaphragm.
Background
Lithium ion batteries have been widely used in various fields including portable electronic products due to their advantages of high energy ratio, long life, no memory effect, etc. The battery separator refers to a thin porous material between the positive electrode and the negative electrode of the battery, and has the functions of preventing physical contact between the positive electrode and the negative electrode, providing ion conduction capability by absorbing electrolyte, and protecting the safety performance of the battery. However, under various complicated application conditions, the lithium ion battery has potential risks of explosion and combustion, and the application of the lithium ion battery in the fields of power batteries and the like is severely restricted.
The unsafe behavior of the lithium ion battery comes from thermal runaway of the lithium ion battery, when the temperature of the battery is increased due to abuse such as short circuit, overcharge and the like, some exothermic side reactions in the battery are initiated successively, and if heat generated by the reactions is not dissipated timely, the temperature of the battery is further increased and the exponential acceleration of the side reactions is caused, so that the battery enters a self-heating thermal runaway state, and the combustion and explosion of the battery are caused.
From an electrochemical point of view, the electrode reactions must involve electron transport and ion transport. If a temperature sensing mechanism is established in the battery, when the temperature of the battery is too high, the mechanism can respond in time and effectively cut off the transmission of electrons or ions, and then the battery reaction can be closed, so that the battery is prevented from being heated greatly and is prevented from entering a self-heating thermal runaway state. Because the electrolyte begins to decompose when the temperature of the battery reaches about 140 ℃, the battery is likely to generate side reaction, and meanwhile, in the manufacturing process of the battery, the drying temperature of the active pole piece of the battery is mostly about 85 ℃, if the temperature of the battery rises to 90-140 ℃, the ion transmission can be cut off, the battery reaction can be closed, thereby avoiding the battery from greatly rising the temperature and preventing the battery from entering a self-heating thermal runaway state. Further, the temperature is preferably 100-. At present, although a widely used polypropylene/polyethylene/polypropylene (PP/PE/PP) three-layer composite diaphragm has a heat sealing function, the difference between the melting point (about 135 ℃) of a PE layer and the melting point (about 165 ℃) of a PP layer, which determine the sealing temperature of the diaphragm, is only about 30 ℃, and after the diaphragm is subjected to heat sealing, the thermal inertia effect easily enables the temperature of a battery to rise to the melting temperature of the PP, so that the diaphragm is melted, and more serious short circuit in the battery is caused.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a polyethylene glycol succinate microsphere emulsion coating type lithium battery diaphragm.
The technical scheme of the invention is as follows:
the preparation method of the polyethylene glycol succinate microsphere emulsion coating type lithium battery diaphragm specifically comprises the following steps:
(1) dissolving the emulsifier and the dispersant by using deionized water under magnetic stirring at 60 ℃ to obtain a water phase; wherein the mass ratio of the emulsifier to the dispersant is 0.1-0.4: 0.1-0.4;
(2) adding 5-20g of polymer polyethylene glycol succinate into a solvent, magnetically stirring and dissolving to obtain an oil phase; the mass ratio of the polymer polyethylene glycol succinate to the emulsifier and the dispersant in the step (1) is 5-20: 0.1-0.4: 0.1-0.4;
(3) slowly dropping the oil phase into the water phase while shearing the water phase at a high speed, and continuously shearing for a plurality of minutes after the dropping is finished;
(4) placing the mixed solution after shearing in a water bath kettle at 60 ℃ for magnetic stirring, and volatilizing the solvent to obtain polyethylene glycol succinate microsphere emulsion;
(5) mixing the obtained polyethylene glycol succinate microsphere emulsion with a wetting agent and a binder to obtain polymer microsphere coating slurry;
(6) and coating the obtained polymer microsphere coating slurry on the surface of the polyolefin microporous diaphragm and drying to obtain the lithium battery diaphragm.
The emulsifier is one or a mixture of sodium dodecyl sulfate, tween-80, triton and sodium dodecyl benzene sulfonate.
The dispersing agent is one or a mixture of fatty alcohol-polyoxyethylene ether, polyvinylpyrrolidone, sodium cellulose sulfate and polyvinyl alcohol.
The solvent in the step (2) is trichloromethane.
The wetting agent in the step (5) is polyether siloxane copolymer or laureth.
The binder in the step (5) is acrylic polymer emulsion.
In the step (1), the content ratio of the emulsifier to the dispersant to the deionized water is 0.1-0.4 g: 0.1-0.4 g: 300 ml.
In the step (2), the content ratio of the polymer polyethylene glycol succinate to the solvent is 5-20 g: 50 ml.
In the step (3), the oil phase is slowly dropped into the water phase while the water phase is sheared at a high speed by a high-speed shearing machine under 6000-10000r/min, and the shearing is continued for 2-4min after the dropping is finished.
In the step (5), the mass ratio of the polyethylene glycol succinate, the wetting agent and the binder in the polyethylene glycol succinate microsphere emulsion is 5-20: 0.05-0.2: 0.5-2.
The invention has the advantages that:
after the PBS microsphere emulsion is coated on the surface of the polyolefin microporous diaphragm, the PBS microsphere emulsion forms an organic polymer microsphere layer, when the battery is normally used, pores among the organic polymer microspheres ensure effective transmission of lithium ions, when the internal temperature of the battery rises and reaches the melting temperature of the organic polymer microspheres, the organic polymer microspheres are melted to form a film and block micropores on a polyolefin base film, the transmission of the lithium ions in the battery is cut off, the thermal shutdown of the diaphragm is realized, the further rise of the temperature in the battery is prevented, and the safety of the lithium ion battery is greatly improved.
Drawings
Fig. 1 is a scanning electron microscope image of a poly (ethylene succinate) microsphere emulsion coating type lithium battery separator prepared in example 1 of the present invention.
FIG. 2 is a comparative graph of air permeability tests of a polyethylene glycol succinate microsphere emulsion coated lithium battery separator prepared in example 1 of the present invention and a base film.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of a polyethylene glycol succinate microsphere emulsion coating type lithium battery diaphragm specifically comprises the following steps:
(1) dissolving 0.1g of Tween-80 and 0.4g of polyvinyl alcohol (PVA) in 300ml of deionized water at 60 ℃ by magnetic stirring to obtain a water phase;
(2) adding 5g of polyethylene glycol succinate (PBS) into 50ml of chloroform, and magnetically stirring for dissolving to obtain an oil phase;
(3) slowly dripping the oil phase into the water phase by a dropper while shearing the water phase at a high speed at 6000r/min by a high-speed shearing machine, and continuously shearing for 2min after dripping is finished;
(4) pouring the mixed solution after shearing into a beaker, placing the beaker in a water bath kettle at 60 ℃ for magnetic stirring, and obtaining PBS microsphere emulsion after the solvent is completely volatilized in an open mouth;
(5) mixing the obtained PBS microsphere emulsion with 0.05g of polyether siloxane copolymer and 0.5g of binder to obtain polymer microsphere coating slurry;
(6) and manually coating the obtained polymer microsphere coating slurry on the surface of the polyolefin microporous diaphragm and drying to obtain the lithium battery diaphragm with the coating thickness of 1 mu m.
The surface of the polyolefin microporous membrane is coated with a layer of thermosensitive microsphere emulsion, so that the battery has a thermal shutdown function, and a scanning electron microscope is shown in figure 1. At the working temperature, pores among the polybutylene succinate microspheres attached to the surface of the diaphragm allow lithium ions to freely pass through; once the temperature of the battery rises to dangerous high temperature due to short circuit, overcharge and the like, the microsphere layer is melted and collapsed, and a compact polymer layer is formed on the surface of the diaphragm, so that the ion transmission between the two electrodes of the electrode is cut off, and the battery reaction is interrupted. Fig. 2 is a comparison graph of the prepared polyethylene glycol succinate microsphere emulsion coating type lithium battery diaphragm and a base film in a ventilation test, and it can be known from the graph that the prepared polyethylene glycol succinate microsphere emulsion coating type lithium battery diaphragm has better ventilation property at different working temperatures.
Example 2
A preparation method of a polyethylene glycol succinate microsphere emulsion coating type lithium battery diaphragm specifically comprises the following steps:
(1) dissolving 0.2g of sodium dodecyl sulfate and 0.4g of fatty alcohol-polyoxyethylene ether by using 300ml of deionized water at 60 ℃ under magnetic stirring to obtain a water phase;
(2) adding 15g of polymer polyethylene glycol succinate (PBS) into 50ml of chloroform, and magnetically stirring for dissolving to obtain an oil phase;
(3) slowly dripping the oil phase into the water phase by a dropper while shearing the water phase at a high speed at 8000r/min by a high-speed shearing machine, and continuously shearing for 2min after dripping is finished;
(4) pouring the mixed solution after shearing into a beaker, placing the beaker in a water bath kettle at 60 ℃ for magnetic stirring, and obtaining PBS microsphere emulsion after the solvent is completely volatilized in an open mouth;
(5) mixing the obtained PBS microsphere emulsion with 0.15g of laureth and 1.5g of binder to obtain polymer microsphere coating slurry;
(6) and manually coating the obtained polymer microsphere coating slurry on the surface of the polyolefin microporous diaphragm and drying to obtain the lithium ion battery diaphragm with the coating thickness of 0.1 mu m.
Example 3
A preparation method of a polyethylene glycol succinate microsphere emulsion coating type lithium battery diaphragm specifically comprises the following steps:
(1) dissolving 0.4g of triton and 0.1g of cellulose sodium sulfate by 300ml of deionized water at 60 ℃ under magnetic stirring to obtain a water phase;
(2) adding 20g of polymer polyethylene glycol succinate (PBS) into 50ml of chloroform, and magnetically stirring for dissolving to obtain an oil phase;
(3) slowly dripping the oil phase into the water phase by a dropper while shearing the water phase at a high speed of 10000r/min by a high-speed shearing machine, and continuously shearing for 2min after dripping is finished;
(4) pouring the mixed solution after shearing into a beaker, placing the beaker in a water bath kettle at 60 ℃ for magnetic stirring, and obtaining PBS microsphere emulsion after the solvent is completely volatilized in an open mouth;
(5) mixing the obtained PBS microsphere emulsion with 0.15g of laureth and 2g of binder to obtain polymer microsphere coating slurry for later use;
(6) and manually coating the obtained polymer microsphere coating slurry on the surface of the polyolefin microporous diaphragm and drying to obtain the lithium ion battery diaphragm with the coating thickness of 2 microns.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. The preparation method of the polyethylene glycol succinate microsphere emulsion coating type lithium battery diaphragm is characterized by comprising the following steps: the method specifically comprises the following steps:
(1) dissolving the emulsifier and the dispersant by using deionized water under magnetic stirring at 60 ℃ to obtain a water phase; wherein the mass ratio of the emulsifier to the dispersant is 0.1-0.4: 0.1-0.4;
(2) adding 5-20g of polymer polyethylene glycol succinate into a solvent, magnetically stirring and dissolving to obtain an oil phase; the mass ratio of the polymer polyethylene glycol succinate to the emulsifier and the dispersant in the step (1) is 5-20: 0.1-0.4: 0.1-0.4;
(3) slowly dropping the oil phase into the water phase while shearing the water phase at a high speed, and continuously shearing for a plurality of minutes after the dropping is finished;
(4) placing the mixed solution after shearing in a water bath kettle at 60 ℃ for magnetic stirring, and volatilizing the solvent to obtain polyethylene glycol succinate microsphere emulsion;
(5) mixing the obtained polyethylene glycol succinate microsphere emulsion with a wetting agent and a binder to obtain polymer microsphere coating slurry;
(6) and coating the obtained polymer microsphere coating slurry on the surface of the polyolefin microporous diaphragm and drying to obtain the lithium battery diaphragm.
2. The method of claim 1, wherein: the emulsifier is one or a mixture of sodium dodecyl sulfate, tween-80, triton and sodium dodecyl benzene sulfonate.
3. The method of claim 1, wherein: the dispersing agent is one or a mixture of fatty alcohol-polyoxyethylene ether, polyvinylpyrrolidone, sodium cellulose sulfate and polyvinyl alcohol.
4. The method of claim 1, wherein: the solvent in the step (2) is trichloromethane.
5. The method of claim 1, wherein: the wetting agent in the step (5) is polyether siloxane copolymer or laureth.
6. The method of claim 1, wherein: the binder in the step (5) is acrylic polymer emulsion.
7. The method of claim 1, wherein: in the step (1), the content ratio of the emulsifier to the dispersant to the deionized water is 0.1-0.4 g: 0.1-0.4 g: 300 ml.
8. The method of claim 1, wherein: in the step (2), the content ratio of the polymer polyethylene glycol succinate to the solvent is 5-20 g: 50 ml.
9. The method of claim 1, wherein: in the step (3), the oil phase is slowly dropped into the water phase while the water phase is sheared at a high speed by a high-speed shearing machine under 6000-10000r/min, and the shearing is continued for 2-4min after the dropping is finished.
10. The method of claim 1, wherein: in the step (5), the mass ratio of the polyethylene glycol succinate, the wetting agent and the binder in the polyethylene glycol succinate microsphere emulsion is 5-20: 0.05-0.2: 0.5-2.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113594634A (en) * | 2021-06-18 | 2021-11-02 | 苏州大学 | High-ionic-conductivity lithium battery diaphragm with self-closing function and preparation method thereof |
| CN114284640A (en) * | 2021-12-24 | 2022-04-05 | 东北师范大学 | Lithium ion battery diaphragm with thermal shutdown function and preparation method thereof |
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| CN101043077A (en) * | 2006-03-24 | 2007-09-26 | 中国科学院大连化学物理研究所 | Application of polyporous material in sodium polysulfide/bromine accumulation energy power cell electric pole |
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| CN106916379A (en) * | 2017-05-03 | 2017-07-04 | 马志明 | A kind of ultracapacitor polypropylene diaphragm |
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2019
- 2019-10-25 CN CN201911024718.3A patent/CN110931686B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| DE10344819A1 (en) * | 2003-09-26 | 2005-04-14 | Sartorius Ag | Adsorption membrane for use e.g. in centrifuge tubes and micro-titration plates, comprises a microporous polymer membrane in which the pores contain porous, hydrocarbon-modified silicon dioxide particles |
| CN101043077A (en) * | 2006-03-24 | 2007-09-26 | 中国科学院大连化学物理研究所 | Application of polyporous material in sodium polysulfide/bromine accumulation energy power cell electric pole |
| US20150072228A1 (en) * | 2013-09-10 | 2015-03-12 | Encell Technology, Inc. | Alkaline battery comprising a gas channeling polymeric separator inlay |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113594634A (en) * | 2021-06-18 | 2021-11-02 | 苏州大学 | High-ionic-conductivity lithium battery diaphragm with self-closing function and preparation method thereof |
| CN114284640A (en) * | 2021-12-24 | 2022-04-05 | 东北师范大学 | Lithium ion battery diaphragm with thermal shutdown function and preparation method thereof |
| CN114284640B (en) * | 2021-12-24 | 2024-05-28 | 东北师范大学 | Lithium ion battery diaphragm with thermal shutdown function and preparation method thereof |
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