CN112490586B - Composite diaphragm with thermal runaway prevention function and lithium ion battery - Google Patents
Composite diaphragm with thermal runaway prevention function and lithium ion battery Download PDFInfo
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- CN112490586B CN112490586B CN202011466745.9A CN202011466745A CN112490586B CN 112490586 B CN112490586 B CN 112490586B CN 202011466745 A CN202011466745 A CN 202011466745A CN 112490586 B CN112490586 B CN 112490586B
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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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 relates to a composite diaphragm and a lithium ion battery with a thermal runaway prevention function. The composite diaphragm can be absorbed in a high-temperature environment and can rapidly generate a polymerization reaction with the electrolyte, so that the electrolyte is consumed before the battery cell is thermally out of control, side reactions are inhibited, and the thermal out of control is blocked.
Description
Technical Field
The invention relates to the field of batteries, in particular to a composite diaphragm with a thermal runaway prevention function and a lithium ion battery.
Background
With the development of new energy, lithium ion batteries are also increasingly applied to daily life of people, especially vehicles such as automobiles. The power battery not only needs to meet the requirements of long endurance, quick charging and the like of the automobile, but also needs to meet high safety. However, in the practical application process of the lithium ion battery, the interior of the battery is easy to generate heat, high temperature is generated, explosion is caused, and potential safety hazards exist. In the process of temperature rise in the battery, the electrolyte can continuously generate side reaction with the positive electrode and the negative electrode, and heat is released, so that the dissolution of the diaphragm and the short circuit between the positive electrode and the negative electrode are caused, the side reaction is intensified, and the heat is released violently until thermal runaway occurs.
At present, people generally improve heat insulation and temperature reduction equipment or electrolyte to play roles in reducing side reactions, accelerating heat diffusion and the like, but the methods have limited effects and higher cost. Therefore, it is of great significance to develop a separator material which can absorb and rapidly generate a polymerization reaction with an electrolyte under a high-temperature environment, so that the electrolyte is consumed before a thermal runaway of a battery cell occurs, and side reactions are inhibited, so that the thermal runaway is blocked.
Disclosure of Invention
In order to solve the above technical problems, an object of the present invention is to provide a composite separator and a lithium ion battery having a function of preventing thermal runaway, in which the composite separator according to the present invention can absorb and rapidly undergo a polymerization reaction with an electrolyte at a high temperature, thereby consuming the electrolyte before thermal runaway occurs in a battery cell, and inhibiting a side reaction to block the thermal runaway.
The invention discloses a composite diaphragm, which comprises a diaphragm substrate and a composite material layer positioned on the surface of the diaphragm substrate, wherein the composite material layer comprises bisphenol A, triphenylphosphine, a binder and a pore-forming agent.
In the invention, triphenylphosphine is used as a catalyst, bisphenol A is used as a reactant with electrolyte, and a pore-forming agent is used for adjusting the porosity of the diaphragm.
Furthermore, the composite material layer comprises, by weight, 5-10 parts of bisphenol A, 0.1-0.5 part of triphenylphosphine, 10-20 parts of a binder and 4-8 parts of a pore-forming agent.
Preferably, the composite material layer comprises 6-9 parts by weight of bisphenol A, 0.2-0.4 part by weight of triphenylphosphine, 14-18 parts by weight of a binder and 5-7 parts by weight of a pore-forming agent.
More preferably, the composite material layer comprises 8 parts by weight of bisphenol A, 0.3 part by weight of triphenylphosphine, 15 parts by weight of binder and 6 parts by weight of pore-forming agent.
Further, the binder is selected from PVDF-HFP (poly (vinylidene fluoride-co-hexafluoropropylene)) or polyacrylate, and other commonly used separator binders.
Further, the pore-forming agent is selected from one or a combination of several of polyvinylpyrrolidone, liCl and polyethylene glycol.
Further, the material of the diaphragm substrate includes polypropylene, polyethylene, and the like.
Further, the thickness of the composite material layer is 4-10 μm.
The composite material layer is arranged on the surface of the diaphragm substrate, and bisphenol A can quickly react with ethylene carbonate serving as a main component in electrolyte to generate a solid polymer under the catalytic action of triphenylphosphine at the temperature of more than 150 ℃, so that the electrolyte is consumed before thermal runaway of a battery cell, side reactions are inhibited, and the thermal runaway is blocked. The reaction principle of bisphenol a with ethylene carbonate is as follows:
further, the preparation method of the composite diaphragm comprises the following steps:
uniformly mixing bisphenol A, triphenylphosphine, a binder and a pore-forming agent in an organic solvent to obtain a mixed solution, then immersing the diaphragm substrate in the mixed solution, and drying to form a composite material layer on the surface of the diaphragm substrate.
Further, the preparation of the mixed solution is carried out at 40 to 60 ℃.
Further, the immersion temperature is room temperature, and the immersion time is 18-48h, preferably 20-40h, and more preferably 24h.
Further, the ratio of the organic solvent to the bisphenol A is 50-100mL:5-10g. Preferably 60 to 80mL:5-10g, more preferably 75mL:5-10g.
Preferably, the organic solvent is acetone.
Further, the preparation method of the composite diaphragm comprises the following steps:
(1) Immersing the diaphragm substrate into absolute ethyl alcohol, and cleaning for 5-20 minutes under the ultrasonic condition;
(2) Dissolving a binder in an organic solvent at 40-60 ℃, then adding bisphenol A, triphenylphosphine and a pore-forming agent, heating and uniformly stirring to obtain a mixed solution, and removing bubbles in the mixed solution;
(3) And (2) soaking the diaphragm matrix in the step (1) in the mixed solution, taking out after soaking for 18-48h at room temperature, washing for 3 times by using deionized water, and drying under a vacuum condition.
Further, in the step (1), the ultrasonic cleaning time is 10 to 15 minutes, more preferably 15 minutes.
Further, in the step (2), the heating temperature is 45 to 55 ℃, more preferably 50 ℃.
The invention adopts the dip-coating method to coat the bisphenol A/triphenylphosphine/binder composite material on the surface of the diaphragm substrate, has simple process operation and is very suitable for large-scale production and application.
The second purpose of the invention is to provide a method for preventing the thermal runaway of a battery cell of a lithium ion battery, wherein the electrolyte of the lithium ion battery comprises ethylene carbonate, and the composite diaphragm is used as a diaphragm.
The third purpose of the invention is to provide a lithium ion battery, which comprises an electrolyte and a diaphragm, wherein the electrolyte comprises ethylene carbonate, and the diaphragm is the composite diaphragm.
By means of the scheme, the invention at least has the following advantages:
the composite material layer is arranged on the surface of the diaphragm substrate in the composite diaphragm, bisphenol A can react with electrolyte under the catalysis of triphenylphosphine to generate hydroxyethylated bisphenol A solid at the temperature of more than 150 ℃, so that the side reaction of the battery cell at high temperature is blocked, the thermal runaway and ignition of the battery cell are prevented, when the coating thickness of the composite material layer reaches 10 mu m, the temperature of the battery cell in a hot box test is kept stable, the highest temperature is only 200 ℃, and the composite diaphragm of the invention basically has no influence on the electrochemical performance of the battery cell.
The preparation method of the composite diaphragm is simple, has low production cost, and is beneficial to large-scale production.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical solutions of the present invention more clearly understood and to implement them in accordance with the contents of the description, the following description is made with reference to the preferred embodiments of the present invention and the accompanying detailed drawings.
Drawings
Fig. 1 is a graph of voltage and temperature over time for a hot box test of composite separator assembled cells of example 3.
Fig. 2 is a graph of voltage and temperature over time for a hot box test of a composite separator assembled cell of comparative example 1.
Fig. 3 is a photo-graph of a composite separator assembled cell of example 3 after a hot box test.
Fig. 4 is a photo-graph of a composite separator assembled cell of comparative example 1 after a hot box test.
Fig. 5 is a graph of cycle stability performance of cells assembled from the composite separator of example 3 and comparative example 1.
Detailed Description
The following examples are given to further illustrate the embodiments of the present invention. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Example 1
In the first step, a polypropylene diaphragm is immersed in absolute ethyl alcohol and cleaned for 15 minutes under ultrasonic conditions. Vacuum drying for later use, and keeping the surface of the diaphragm clean.
And secondly, adding 75mL of acetone and 15g of PVDF-HFP into a spherical flask, heating at 50 ℃ until the PVDF-HFP is completely dissolved, adding bisphenol A (5 g), triphenylphosphine (0.2 g) and polyvinylpyrrolidone (4 g) in sequence, heating and continuously stirring uniformly, and vacuumizing to remove bubbles in the solution. And then, soaking the polypropylene diaphragm obtained in the first step in the solution for 12 hours at room temperature, taking out the polypropylene diaphragm, washing the polypropylene diaphragm with deionized water for 3 times, and drying the polypropylene diaphragm in a vacuum environment at 50 ℃. The coating thickness of the bisphenol A/triphenylphosphine/PVDF-HFP/PP composite material on the surface of the polypropylene diaphragm is 5 mu m.
Example 2
In the first step, a polypropylene diaphragm is immersed in absolute ethyl alcohol and cleaned under ultrasonic conditions for 15 minutes. Vacuum drying for later use, and keeping the surface of the diaphragm clean.
And secondly, adding 75mL of acetone and 15g of PVDF-HFP into a spherical flask, heating at 50 ℃ until the PVDF-HFP is completely dissolved, adding bisphenol A (8 g), triphenylphosphine (0.2 g) and polyvinylpyrrolidone (4 g) in sequence, heating and continuously stirring uniformly, and vacuumizing to remove bubbles in the solution. And then, soaking the polypropylene diaphragm obtained in the first step in the solution for 24 hours at room temperature, taking out the polypropylene diaphragm, washing the polypropylene diaphragm with deionized water for 3 times, and drying the polypropylene diaphragm in a vacuum environment at 50 ℃. The coating thickness of the bisphenol A/triphenylphosphine/PVDF-HFP/PP composite material on the surface of the polypropylene diaphragm is 8 mu m.
Example 3
In the first step, a polypropylene diaphragm is immersed in absolute ethyl alcohol and cleaned under ultrasonic conditions for 15 minutes. Vacuum drying for later use, and keeping the surface of the diaphragm clean.
And secondly, adding 75mL of acetone and 15g of PVDF-HFP into a spherical flask, heating at 50 ℃ until the PVDF-HFP is completely dissolved, adding 10g of bisphenol A, 0.2g of triphenylphosphine and 4g of polyvinylpyrrolidone in sequence, heating and stirring uniformly, and vacuumizing to remove bubbles in the solution. And then, soaking the polypropylene diaphragm obtained in the first step in the solution for 30 hours at room temperature, taking out the polypropylene diaphragm, washing the polypropylene diaphragm with deionized water for 3 times, and drying the polypropylene diaphragm in a vacuum environment at 50 ℃. The coating thickness of the bisphenol A/triphenylphosphine/PVDF-HFP/PP composite material on the surface of the polypropylene diaphragm is 10 mu m.
Comparative example 1
The battery is assembled by adopting a PVDF composite lithium ion battery diaphragm of Shanghai Enjie New Material science and technology Limited, wherein the diaphragm structure is a PVDF layer/a polypropylene layer/a PVDF layer which are sequentially arranged from bottom to top.
The lithium ion batteries were assembled using the separators in the above examples and comparative examples, by the following steps:
1) And (4) preparing an anode. An anode slurry was prepared by adding 96.2wt% of graphite as an anode active material, 1.2wt% of sodium carboxymethyl cellulose (CMC-Na) as a dispersant, 0.8wt% of carbon black as a conductive agent, and 1.8wt% of Styrene Butadiene Rubber (SBR) as a binder to N-methyl-2-pyrrolidone (NMP). The slurry was coated on a 6 μm copper foil to prepare an anode. The anode was then rolled.
2) And (4) preparing a cathode. 97.2wt% of a nickel-cobalt-manganese ternary material as an anode active material, 0.8wt% of a multi-walled carbon nanotube as a conductive agent, 1wt% of carbon black as a conductive agent, and 1wt% of polyvinylidene fluoride (PVDF) as a binder were added to N-methyl-2-pyrrolidone (NMP) to prepare a cathode slurry. The slurry was coated on a 13 μm aluminum foil to prepare a cathode. The cathode was then roll pressed.
3) And (5) preparing the battery. The cathode, the anode and the composite diaphragm prepared in the example and the comparative example are stacked to form a battery core. And then injecting the electrolyte into the battery core to obtain the lithium ion battery. The electrolyte comprises the following components of ethylene carbonate, ethyl methyl carbonate and dimethyl carbonate (the relative mass ratio of ethylene carbonate, ethyl methyl carbonate and dimethyl carbonate is 3.
In order to evaluate the thermal runaway prevention performance of the composite separator at high temperature and the influence of additives in the composite separator on the cycle performance of the lithium ion battery, the following tests were performed on examples and comparative examples:
1. and (3) hot box test: placing 100 percent SOC of the battery core in a hot box at 25 ℃, heating to 60 ℃ at a heating speed of 2 ℃/min, resting for 2h, heating to 130 ℃ at a heating speed of 2 ℃/min, resting for 30min, heating to 200 ℃ at a heating speed of 2 ℃/min, and resting for 60min.
2. And (3) cycle testing: the cells were placed in a 25 ℃ hot box at 1C/1C cycle, a test voltage of 2.8-4.3V,100% DOD cycle.
The test results are shown in table 1 and fig. 1-5. In fig. 1, T1-T6 sequentially represent the temperature at the positive electrode tab of the cell, the temperature near the large surface of the positive electrode cell, the central temperature of the large surface of the cell, the temperature near the large surface of the cell at the negative electrode side, the temperature at the negative electrode tab of the cell, and the central temperature at the side edge of the cell. In FIG. 1, the test curves corresponding to T1-T6 substantially coincide. In fig. 2, T1 to T5 represent the temperature at the positive electrode tab of the cell, the temperature near the large surface of the positive electrode cell, the central temperature of the large surface of the cell, the temperature near the large surface of the negative electrode side cell, and the temperature at the negative electrode tab of the cell in sequence. In FIG. 2, the test curves corresponding to T1-T5 are substantially coincident before 5.7h and slightly different after 5.7 h.
Table 1 performance test results for different batteries
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, it should be noted that, for those skilled in the art, many modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (8)
1. A composite separator for a lithium ion battery, the electrolyte of the lithium ion battery comprising vinyl carbonate, characterized in that: the composite diaphragm comprises a diaphragm substrate and a composite material layer positioned on the surface of the diaphragm substrate, wherein the composite material layer is made of bisphenol A, triphenylphosphine, a binder and a pore-forming agent; the binder is selected from PVDF-HFP or polyacrylate binder, and the pore-forming agent is selected from one or a combination of polyvinylpyrrolidone, liCl and polyethylene glycol.
2. The composite membrane of claim 1, wherein: the composite material layer comprises, by weight, 5-10 parts of bisphenol A, 0.1-0.5 part of triphenylphosphine, 10-20 parts of a binder and 4-8 parts of a pore-forming agent.
3. The composite membrane of claim 1 or 2, wherein: the material of the diaphragm substrate comprises polypropylene or polyethylene.
4. The composite membrane of claim 1 or 2, wherein: the thickness of the composite material layer is 4-10 μm.
5. The composite separator according to claim 1 or 2, characterized in that its preparation method comprises the following steps:
uniformly mixing bisphenol A, triphenylphosphine, a binder and a pore-forming agent in an organic solvent to obtain a mixed solution, immersing the diaphragm substrate in the mixed solution, and drying to form the composite material layer on the surface of the diaphragm substrate.
6. The composite separator according to claim 5, wherein the preparation of the mixed solution is performed at 40-60 ℃.
7. A method for preventing thermal runaway of a battery cell of a lithium ion battery, wherein an electrolyte in the lithium ion battery comprises ethylene carbonate, and the method is characterized in that: use of the composite separator according to claim 1 or 2 as a separator.
8. A lithium ion battery, characterized by: the composite separator comprises an electrolyte and a separator, wherein the electrolyte comprises ethylene carbonate, and the separator is the composite separator in claim 1 or 2.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105140450A (en) * | 2015-09-17 | 2015-12-09 | 中航锂电（洛阳）有限公司 | Lithium ion battery composite separator, preparation method thereof, and lithium ion battery |
| CN105161661A (en) * | 2015-10-14 | 2015-12-16 | 中航锂电（洛阳）有限公司 | Composite diaphragm for lithium ion battery, preparation method of composite diaphragm, and lithium ion battery |
| CN107768589A (en) * | 2016-08-15 | 2018-03-06 | 万向二三股份公司 | A kind of high safety type lithium ion battery with high energy density |
| WO2019221860A1 (en) * | 2018-05-17 | 2019-11-21 | Vissers Battery Corporation | Devices, systems, and methods to mitigate thermal runaway conditions in molten fluid electrode apparatus |
| CN111697187A (en) * | 2020-05-07 | 2020-09-22 | 天津力神电池股份有限公司 | High-safety composite diaphragm and preparation method thereof |
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2020
- 2020-12-14 CN CN202011466745.9A patent/CN112490586B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105140450A (en) * | 2015-09-17 | 2015-12-09 | 中航锂电（洛阳）有限公司 | Lithium ion battery composite separator, preparation method thereof, and lithium ion battery |
| CN105161661A (en) * | 2015-10-14 | 2015-12-16 | 中航锂电（洛阳）有限公司 | Composite diaphragm for lithium ion battery, preparation method of composite diaphragm, and lithium ion battery |
| CN107768589A (en) * | 2016-08-15 | 2018-03-06 | 万向二三股份公司 | A kind of high safety type lithium ion battery with high energy density |
| WO2019221860A1 (en) * | 2018-05-17 | 2019-11-21 | Vissers Battery Corporation | Devices, systems, and methods to mitigate thermal runaway conditions in molten fluid electrode apparatus |
| CN111697187A (en) * | 2020-05-07 | 2020-09-22 | 天津力神电池股份有限公司 | High-safety composite diaphragm and preparation method thereof |
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