CN110690388A - Heat-shrinkage-resistant organic/inorganic composite lithium battery diaphragm and preparation method thereof - Google Patents
Heat-shrinkage-resistant organic/inorganic composite lithium battery diaphragm and preparation method thereof Download PDFInfo
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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
- 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
- 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
- H01M50/431—Inorganic 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
- H01M50/44—Fibrous 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
Abstract
The invention relates to a heat-shrinkage-resistant organic/inorganic composite lithium battery diaphragm and a preparation method thereof, belonging to the field of lithium battery diaphragms. The composite lithium battery diaphragm takes an expanded polytetrafluoroethylene film with a microporous structure as a carrier and polydopamine with extremely strong adhesion as a bonding layer, and nano silicon dioxide ceramic particles are adhered to the whole expanded polytetrafluoroethylene film structure in situ in a self-assembly mode. The thickness of the prepared diaphragm is 10-30 μm, the porosity is 45-65%, and the pore diameter is 0.08-0.70 μm. The expanded polytetrafluoroethylene one-way stretching film with the microporous structure consists of a microstructure with nodes and fibers; the polydopamine bonding layer is formed by oxidative polymerization of dopamine monomers; the nano silicon dioxide has the particle size of 10-50 nm, accounts for 1.5-6.0 wt% of the weight of the composite lithium battery diaphragm, and is prepared by dehydrating and condensing an ethanol solution containing tetraethoxysilane, deionized water and ammonia water. The preparation process is simple and feasible, and the application of the expanded polytetrafluoroethylene film in the field of lithium battery diaphragms is widened.
Description
Technical Field
The invention relates to a heat-shrinkage-resistant organic/inorganic composite lithium battery diaphragm and a preparation method thereof, belonging to the field of lithium battery diaphragms.
Background
In recent years, lithium ion batteries have attracted great attention due to their excellent cycle life, high energy density, environmental friendliness, and the like. As one of the key components of the lithium ion battery, the separator plays an important role in preventing physical contact between the positive and negative electrodes while providing a lithium ion transfer channel. As lithium batteries continue to develop toward high energy density, high safety and long life, and electrode materials continue to be upgraded, separators will face new challenges.
In the past decades, commercial polyolefin separators have dominated the lithium battery separator market due to their good mechanical strength, chemical stability, uniform pore structure and outstanding cost advantages. Inherent defects of polyolefin separators become more pronounced (e.g., low melting point, low electrolyte affinity, etc.) when lithium ion batteries are applied to electric vehicle power supplies. Thermal stability plays an important role in battery safety, and the lower thermal shrinkage temperature of the polyolefin separator can cause a series of safety problems such as thermal runaway of the battery, and the like, which is more serious for a power battery. Coating of ceramic particles on a polyolefin separator is one of effective methods for improving thermal stability, and can maintain the integrity of the separator at a high temperature of 200 ℃. However, the inorganic coating layer will inevitably sacrifice the ion conductivity of the separator due to the increase in the thickness of the separator and the clogging of pores. It is clear that improving the thermal stability of the separator and improving the transport capacity of lithium ions are a pair of contradictory problems in the present state. Therefore, it is a great challenge to obtain a novel separator having excellent thermal stability and lithium ion transport ability.
In recent years, polytetrafluoroethylene materials have attracted much attention due to high temperature resistance, good chemical stability and high mechanical strength, and have been applied to the field of proton exchange membranes to a certain extent. US patent 5547551 uses expanded polytetrafluoroethylene (e-PTFE) with microporous structure as a base membrane supporting layer to fill Nafion ion conductive liquid, and prepares an ultrathin, durable and high-power-density proton exchange membrane. Chinese patent publication No. CN101728549A discloses a preparation method of a high-temperature proton exchange composite membrane, wherein full fluororesin with ion exchange function is filled in a fluorine-containing microporous membrane and covers the surface of the microporous membrane, the thickness of the composite membrane is only 5-15 μm, and the internal resistance of the battery can be greatly reduced when the composite membrane is used for a fuel battery, so that the output power of the battery is improved. However, there have been few reports of the application of polytetrafluoroethylene, particularly expanded polytetrafluoroethylene (e-PTFE), to the field of lithium battery separators. Meanwhile, when polytetrafluoroethylene brings high-temperature resistance and red profit, the problem of electrolyte wettability brought by low surface energy is still a bottleneck for applying polytetrafluoroethylene to a lithium battery system.
Disclosure of Invention
Aiming at the defects of safety performance and battery performance of the conventional lithium battery diaphragm, the invention aims to provide the heat-shrinkage-resistant organic/inorganic composite lithium battery diaphragm and the preparation method thereof.
The technical scheme of the invention is as follows:
an organic/inorganic compound lithium battery diaphragm with heat-resistant shrinkage takes an expanded polytetrafluoroethylene (e-PTFE) film with a microporous structure as a carrier, takes Polydopamine (PDA) with strong adhesion as an adhesive layer, and takes nano silicon dioxide (SiO) in a self-assembly form2) The ceramic particles adhere in situ throughout the e-PTFE structure.
The heat-shrinkage-resistant organic/inorganic composite lithium battery diaphragm is characterized in that an e-PTFE film with a microporous structure is composed of a microstructure with nodes and fibers, the thickness is 10-30 mu m, the porosity is 50-70%, and the pore diameter is 0.1-1 mu m.
The heat-shrinkage-resistant organic/inorganic composite lithium battery diaphragm is characterized in that an e-PTFE film with a microporous structure is a unidirectional stretching film.
The organic/inorganic composite lithium battery diaphragm resisting heat shrinkage is characterized in that nano silicon dioxide formed by self-assembly has the particle size of 10-50 nm and SiO2The weight of (a) is 1.5-6.0 wt.% of the whole separator.
The thickness of the prepared composite lithium battery diaphragm is 10-30 mu m, the porosity is 45-65%, and the pore diameter is 0.08-0.70 mu m.
The preparation method of the organic/inorganic composite lithium battery diaphragm with heat shrinkage resistance comprises the following steps:
(1) the e-PTFE membrane was pre-wetted with ethanol and then dipped into a solution containing dopamine hydrochloride at a concentration of 2g L-1The cosolvent is ethanol and Tris-HCl buffer solution (pH 8.5) in a volume ratio of 1:1 for 5-10 hours to perform self-polymerization reaction of dopamine monomer on the surface of the diaphragm; after the reaction is finished, the prepared diaphragm is washed clean by deionized water and dried in a vacuum oven at the temperature of 40-60 ℃ to constant weight;
(2) immersing the diaphragm prepared in the step (1) into a solution containing 0.25mol L of-1Tetraethoxysilane (TEOS), 7.5mol L-1Deionized water and 0.1mol L-1Carrying out silica sol dehydration condensation reaction in an ethanol solution of ammonia water; fully reacting for 2-10 h at the temperature of 20-50 ℃; and after the reaction is finished, washing the prepared diaphragm by using deionized water, and drying in a vacuum oven at 40-60 ℃ to obtain the prepared diaphragm.
The preparation method of the heat-shrinkage-resistant organic/inorganic composite lithium battery diaphragm comprises the following steps of (1) pre-wetting an e-PTFE film: firstly, immersing an e-PTFE film in a beaker containing ethanol and water in a volume ratio of 1:1, and carrying out ultrasonic treatment for 5-15 min; and then, putting the beaker into a vacuum oven at 15-25 ℃, and standing for 5-15 min in vacuum, thereby ensuring the complete wetting of the diaphragm.
According to the preparation method of the organic/inorganic composite lithium battery diaphragm with heat shrinkage resistance, the heat shrinkage rate of the prepared composite lithium battery diaphragm is less than 5% at 300 ℃.
The design idea of the invention is as follows:
in order to improve the heat-resistant shrinkage performance of the lithium battery diaphragm, the expanded polytetrafluoroethylene film is creatively applied to the lithium battery diaphragm. A layer of polydopamine adhesive layer with extremely strong adhesiveness is modified on the surface of an expanded polytetrafluoroethylene film structure through oxidative self-polymerization of dopamine monomers, and then nano silicon oxide particles prepared by silica sol dehydration condensation are adhered in situ on the basis of not influencing the original pore structure of the diaphragm. The affinity of the electrolyte of the base film is improved by utilizing the affinity of silicon oxide.
The invention has the advantages and beneficial effects that:
1. the invention fully utilizes the high temperature resistance of the polytetrafluoroethylene material and improves the heat shrinkage resistance of the lithium battery diaphragm.
2. According to the invention, by utilizing the excellent adhesion performance of the polydopamine material, nano-scale inorganic particles are adhered in situ on the premise of not influencing the performance of the basal membrane battery, and the electrolyte affinity of the expanded polytetrafluoroethylene-based membrane is improved.
Drawings
FIG. 1 is a scanning electron micrograph and a photomicrograph of an expanded polytetrafluoroethylene film according to the present invention.
Fig. 2 is a scanning electron microscope image and a macro-photograph of the organic/inorganic composite lithium battery separator prepared by the invention.
Fig. 3 is a photograph of a thermal shrinkage resistance test of the organic/inorganic composite lithium battery separator prepared according to the present invention.
Detailed Description
In the specific implementation process, the composite lithium battery diaphragm takes an expanded polytetrafluoroethylene film with a microporous structure as a carrier and polydopamine with strong adhesion as a bonding layer, and nano silicon dioxide ceramic particles are adhered to the whole expanded polytetrafluoroethylene film structure in situ in a self-assembly manner. The thickness of the prepared diaphragm is 10-30 μm, the porosity is 45-65%, and the pore diameter is 0.08-0.70 μm. The expanded polytetrafluoroethylene one-way stretching film with the microporous structure consists of a microstructure with nodes and fibers; the polydopamine bonding layer is formed by oxidative polymerization of dopamine monomers; the nano silicon dioxide has the particle size of 10-50 nm, accounts for 1.5-6.0 wt% of the weight of the composite lithium battery diaphragm, and is prepared by dehydrating and condensing an ethanol solution containing tetraethoxysilane, deionized water and ammonia water.
The present invention is described in detail below with reference to specific examples, which are provided to facilitate understanding of the present invention and are not intended to limit the present invention in any way.
Example 1
In the embodiment, an expanded polytetrafluoroethylene (e-PTFE) unidirectional stretching film with a microporous structure is taken as a carrier,the film consisted of a microstructure of nodes and fibres with a thickness of 30 μm, a porosity of 67% and a pore size of 0.82 μm. Firstly, soaking a diaphragm in a beaker containing ethanol and water in a volume ratio of 1:1, and carrying out ultrasonic treatment for 10 min; and then placing the beaker into a vacuum oven with the temperature of 20 ℃, and standing for 10min in vacuum so as to ensure the complete wetting of the diaphragm. The membrane was then immersed in a solution containing dopamine hydrochloride at a concentration of 2g L-1For self-polymerization of dopamine monomer on the surface of the membrane for 10h in the cosolvent of ethanol and Tris-HCl buffer (pH 8.5) in a volume ratio of 1: 1. After the reaction is finished, the prepared diaphragm is washed clean by deionized water and dried in a vacuum oven at 50 ℃ to constant weight. Finally, the separator was immersed in a solution containing 0.25mol L of-1Tetraethoxysilane (TEOS), 7.5mol L-1Deionized water and 0.1mol L-1And (3) carrying out silica sol dehydration condensation reaction in an ethanol solution of ammonia water. Fully reacting for 5 hours at the temperature of 20 ℃. And after the reaction is finished, washing the prepared diaphragm by using deionized water, and drying in a vacuum oven at 50 ℃ to obtain the prepared diaphragm. The thickness of the prepared composite lithium battery diaphragm is 30 micrometers, the porosity is 56%, and the pore diameter is 0.65 micrometers. Wherein the nano-silica formed by self-assembly had a particle size of 20nm and a weight of 3.3 wt.% of the entire separator.
As shown in fig. 1, the expanded polytetrafluoroethylene-based film has a microporous structure consisting of a microstructure having nodes and fibers.
As shown in figure 2, the prepared diaphragm has uniformly distributed pore channels, and the surface of the prepared diaphragm is covered with SiO2And (3) granules.
As shown in fig. 3, the prepared separator still had a heat shrinkage of less than 5% at 300 ℃.
Example 2
In this example, an expanded polytetrafluoroethylene (e-PTFE) unidirectional stretching film having a microporous structure was used as a support, and the film consisted of a microstructure having nodes and fibers, with a thickness of 25 μm, a porosity of 69%, and a pore diameter of 0.60 μm. Firstly, soaking a diaphragm in a beaker containing ethanol and water in a volume ratio of 1:1, and carrying out ultrasonic treatment for 10 min; and then placing the beaker into a vacuum oven with the temperature of 20 ℃, and standing for 10min in vacuum so as to ensure the complete wetting of the diaphragm. Then, the separator is immersedThe concentration of the dopamine hydrochloride is 2g L-1For self-polymerization of dopamine monomer on the surface of the membrane for 8h in the cosolvent of (1: 1) ethanol and Tris-HCl buffer (pH 8.5) by volume. After the reaction is finished, the prepared diaphragm is washed clean by deionized water and dried in a vacuum oven at 50 ℃ to constant weight. Finally, the separator was immersed in a solution containing 0.25mol L of-1Tetraethoxysilane (TEOS), 7.5mol L-1Deionized water and 0.1mol L-1And (3) carrying out silica sol dehydration condensation reaction in an ethanol solution of ammonia water. Fully reacting for 8 hours at the temperature of 20 ℃. And after the reaction is finished, washing the prepared diaphragm by using deionized water, and drying in a vacuum oven at 50 ℃ to obtain the prepared diaphragm. The thickness of the prepared composite lithium battery diaphragm is 27 micrometers, the porosity is 50%, and the pore diameter is 0.45 micrometers. Wherein the nano-silica formed by self-assembly has a particle size of 40nm and a weight of 5.8 wt.% of the entire separator.
Example 3
In this example, an expanded polytetrafluoroethylene (e-PTFE) unidirectional stretching film having a microporous structure was used as a support, and the film consisted of a microstructure having nodes and fibers, and had a thickness of 15 μm, a porosity of 69%, and a pore diameter of 0.40 μm. Firstly, soaking a diaphragm in a beaker containing ethanol and water in a volume ratio of 1:1, and carrying out ultrasonic treatment for 10 min; and then placing the beaker into a vacuum oven with the temperature of 20 ℃, and standing for 10min in vacuum so as to ensure the complete wetting of the diaphragm. The membrane was then immersed in a solution containing dopamine hydrochloride at a concentration of 2g L-1For self-polymerization of dopamine monomer on the surface of the membrane for 6h in the cosolvent of ethanol and Tris-HCl buffer (pH 8.5) in a volume ratio of 1: 1. After the reaction is finished, the prepared diaphragm is washed clean by deionized water and dried in a vacuum oven at 50 ℃ to constant weight. Finally, the separator was immersed in a solution containing 0.25mol L of-1Tetraethoxysilane (TEOS), 7.5mol L-1Deionized water and 0.1mol L-1And (3) carrying out silica sol dehydration condensation reaction in an ethanol solution of ammonia water. Fully reacting for 6 hours at the temperature of 20 ℃. And after the reaction is finished, washing the prepared diaphragm by using deionized water, and drying in a vacuum oven at 50 ℃ to obtain the prepared diaphragm. The thickness of the prepared composite lithium battery diaphragm is 16 mu m,the porosity was 60% and the pore diameter was 0.32. mu.m. Wherein the nano-silica formed by self-assembly had a particle size of 35nm and a weight of 6.0 wt.% of the entire separator.
The results of the examples show that the thermal shrinkage of the separator made according to the present invention is less than 5% at 300 ℃. The preparation process is simple and feasible, and the application of the expanded polytetrafluoroethylene film in the field of lithium battery diaphragms is widened.
The above embodiments are intended to illustrate the features of the present invention, but the present invention is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art, and the scope of the present invention should be construed.
Claims (8)
1. The organic/inorganic compound lithium battery diaphragm with heat shrinkage resistance is characterized in that an expanded polytetrafluoroethylene (e-PTFE) film with a microporous structure is used as a carrier, Polydopamine (PDA) with strong adhesion is used as a bonding layer, and nano silicon dioxide (SiO) is self-assembled2) The ceramic particles adhere in situ throughout the e-PTFE structure.
2. The organic/inorganic composite lithium battery separator resistant to thermal shrinkage according to claim 1, wherein the e-PTFE film having a microporous structure is composed of a microstructure having nodes and fibers, and has a thickness of 10 to 30 μm, a porosity of 50 to 70%, and a pore diameter of 0.1 to 1 μm.
3. The organic/inorganic composite lithium battery separator resistant to thermal shrinkage according to claim 1, wherein the e-PTFE film having a microporous structure is a uniaxially stretched film.
4. The organic/inorganic composite lithium battery separator resistant to thermal shrinkage according to claim 1, wherein the nano-silica formed by self-assembly has a particle size of 10 to 50nm and SiO2The weight of (a) is 1.5-6.0 wt.% of the whole separator.
5. The organic/inorganic composite lithium battery separator resistant to thermal shrinkage according to claim 1, wherein the prepared composite lithium battery separator has a thickness of 10 to 30 μm, a porosity of 45 to 65%, and a pore diameter of 0.08 to 0.70 μm.
6. A method for preparing the organic/inorganic composite lithium battery separator resistant to thermal shrinkage according to any one of claims 1 to 5, comprising the steps of:
(1) the e-PTFE membrane was pre-wetted with ethanol and then dipped into a solution containing dopamine hydrochloride at a concentration of 2g L-1The cosolvent is ethanol and Tris-HCl buffer solution (pH 8.5) in a volume ratio of 1:1 for 5-10 hours to perform self-polymerization reaction of dopamine monomer on the surface of the diaphragm; after the reaction is finished, the prepared diaphragm is washed clean by deionized water and dried in a vacuum oven at the temperature of 40-60 ℃ to constant weight;
(2) immersing the diaphragm prepared in the step (1) into a solution containing 0.25mol L of-1Tetraethoxysilane (TEOS), 7.5mol L-1Deionized water and 0.1mol L-1Carrying out silica sol dehydration condensation reaction in an ethanol solution of ammonia water; fully reacting for 2-10 h at the temperature of 20-50 ℃; and after the reaction is finished, washing the prepared diaphragm by using deionized water, and drying in a vacuum oven at 40-60 ℃ to obtain the prepared diaphragm.
7. The preparation method of the organic/inorganic composite lithium battery separator resistant to thermal shrinkage according to claim 6, wherein the pre-wetting method of the e-PTFE film involved in the step (1) comprises the following steps: firstly, immersing an e-PTFE film in a beaker containing ethanol and water in a volume ratio of 1:1, and carrying out ultrasonic treatment for 5-15 min; and then, putting the beaker into a vacuum oven at 15-25 ℃, and standing for 5-15 min in vacuum, thereby ensuring the complete wetting of the diaphragm.
8. The method for preparing the organic/inorganic composite lithium battery separator resistant to thermal shrinkage according to claim 6, wherein the thermal shrinkage of the prepared composite lithium battery separator is less than 5% at 300 ℃.
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