CN113131087B - Bio-based lithium battery diaphragm and preparation method thereof - Google Patents

Bio-based lithium battery diaphragm and preparation method thereof Download PDF

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CN113131087B
CN113131087B CN202110392063.6A CN202110392063A CN113131087B CN 113131087 B CN113131087 B CN 113131087B CN 202110392063 A CN202110392063 A CN 202110392063A CN 113131087 B CN113131087 B CN 113131087B
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furan
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lithium battery
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CN113131087A (en
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傅尧
李锋
柯卓
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University of Science and Technology of China USTC
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/40Polyamides containing oxygen in the form of ether groups
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/42Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/10Energy storage using batteries

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Abstract

A furan-based polymer coating liquid, a bio-based lithium battery diaphragm and a preparation method thereof are provided, the preparation method of the furan-based polymer coating liquid comprises the steps of adding 2, 5-furandicarboxylic acid dichloride into an organic solvent containing p-phenylenediamine in an inert atmosphere, heating to 35-45 ℃, adjusting the pH value, and forming a first solution after a polymerization reaction; adding ceramic particles into the first solution, mixing and stirring to form a second solution; and mixing the second solution with a viscosity regulator to obtain the furan-based polymer coating liquid. The lithium battery diaphragm prepared by the invention has the advantages that the needling strength reaches 8.5N, and the longitudinal tensile strength reaches 1995Kgf/cm 2 Transverse tensile Strength 1987Kgf/cm 2 The diaphragm has strong puncture resistance, can effectively avoid short circuit and improve safety.

Description

Bio-based lithium battery diaphragm and preparation method thereof
Technical Field
The invention belongs to the technical field of battery diaphragms, and particularly relates to a bio-based lithium battery diaphragm and a preparation method thereof.
Background
The lithium ion battery has the advantages of high energy density, long cycle life, no memory effect and the like, and becomes an important component in the development of new energy industry at present. The lithium ion battery is applied to a plurality of fields such as power batteries, energy storage power stations and the like, the social development is greatly promoted, and as a key material influencing the performance of the lithium ion battery, the lithium battery diaphragm has great commercial value, and the performance and the cost of the lithium battery diaphragm have very important influence on the lithium ion battery.
The traditional lithium battery diaphragm coating material mainly comprises aramid fiber and ceramic. However, aramid has poor solubility, strict requirements on the molecular weight of aramid in the processing process, difficult coating due to overlarge molecular weight, too small molecular weight, poor heat resistance and low strength. And the aramid fiber dissolving process is time-consuming and power-consuming, which results in high coating process cost. The ceramic diaphragm is used for a long time, and the coating is easy to fall off. The traditional aramid fiber is not degradable and causes environmental pollution.
The furan group high molecular compound has oxygen atoms in the furan ring, so that the intramolecular hydrogen bond acting force is reduced; meanwhile, oxygen atoms are introduced to easily form intermolecular hydrogen bonds, intermolecular van der waals force is enhanced, polymer solubility and processability are obviously enhanced, and the rigid furan ring endows the material with higher strength and better heat resistance and has the advantage of degradability.
Therefore, the development of the environment-friendly biomass furan-based polymer coating lithium battery diaphragm which has high strength and is easy to process has great significance.
Disclosure of Invention
In view of the above, one of the main objectives of the present invention is to provide a bio-based lithium battery separator and a method for preparing the same, which are intended to at least partially solve at least one of the above technical problems.
In order to achieve the above object, as one aspect of the present invention, there is provided a method for preparing a furan-based polymer coating liquid, comprising:
adding 2, 5-furandicarboxylic acid dichloride into an organic solvent containing p-phenylenediamine in an inert atmosphere, heating to 35-45 ℃, adjusting the pH value, and performing a polymerization reaction to form a first solution; adding ceramic particles into the first solution, mixing and stirring to form a second solution;
and mixing the second solution with a viscosity regulator to obtain the furan-based polymer coating liquid.
As another aspect of the invention, the invention also provides a furan-based polymer coating liquid obtained by the preparation method.
As still another aspect of the present invention, there is also provided a method of preparing a lithium battery separator, including:
coating the furan-based polymer coating solution on one side of a base film to form an oily coating;
extracting the oily coating by using an extracting agent;
and drying the oily coating extracted by the extractant to obtain the lithium battery diaphragm.
As a further aspect of the present invention, there is also provided a lithium battery separator obtained by the above-described preparation method.
Based on the technical scheme, compared with the prior art, the bio-based lithium battery diaphragm and the preparation method thereof have at least one or part of the following advantages:
1. the lithium battery diaphragm prepared by the method has the needling strength of 8.5N, can resist piercing, avoid short circuit and improve safety;
2. the lithium battery diaphragm prepared by the invention has the longitudinal tensile strength of 1995Kgf/cm 2 Transverse tensile Strength 1987Kgf/cm 2 When the temperature of the thermal shrinkage rate is 2.3 percent (120 ℃, 1h), no obvious shrinkage or wrinkling phenomenon occurs, and the insulation effect of the positive and negative electrodes is continuously achieved, so that the short circuit caused by the contact of the two electrodes is prevented.
Drawings
FIG. 1 is a diagram of a furan-based lithium battery separator sample in an example of the present invention;
FIG. 2 is an SEM image of a furan-based lithium battery separator in an example of the invention.
Detailed Description
In order that the objects, technical solutions and advantages of the present invention will become more apparent, the present invention will be further described in detail with reference to the accompanying drawings in conjunction with the following specific embodiments.
Based on the technical problems in the background art, the invention provides the environment-friendly and easily-processed bio-based polymer coating liquid, the lithium battery diaphragm and the preparation method thereof, and the diaphragm has higher needling strength and tensile strength. According to the method, 2, 5-furan diformyl chloride from biomass is used as a raw material, ceramic particles are added in the synthesis process of a polymerization solution, and after the synthesis is finished, organic matters are added to adjust the viscosity, so that a coating solution is obtained.
The invention discloses a preparation method of a furan-based polymer coating liquid, which comprises the following steps:
adding 2, 5-furandicarboxylic acid dichloride into an organic solvent containing p-phenylenediamine in an inert atmosphere, heating to 35-45 ℃, adjusting the pH value, and performing polymerization reaction to form a first solution; adding ceramic particles into the first solution, mixing and stirring to form a second solution;
and mixing the second solution with a viscosity regulator to obtain the furan-based polymer coating liquid.
In some embodiments of the present invention, the temperature of the addition of 2, 5-furandicarboxylic acid dichloride to the organic solvent containing p-phenylenediamine is raised to 35 to 45 ℃, for example, 35 ℃, 36 ℃, 37 ℃, 38 ℃, 39 ℃, 40 ℃, 41 ℃, 42 ℃, 43 ℃, 44 ℃ and 45 ℃.
In some embodiments of the present invention, the mass ratio of the organic solvent to the p-phenylenediamine in the organic solvent containing p-phenylenediamine is 1: (5 to 10), for example 1: 5, 1: 6, 1: 7, 1: 8, 1: 9, 1: 10;
in some embodiments of the invention, the molar ratio of p-phenylenediamine to 2, 5-furandicarboxylic acid dichloride is 1: 1 (1 to 1.3), for example, 1: 1, 1: 1.1, 1: 1.2, 1: 1.3;
in some embodiments of the invention, the mass ratio of the ceramic particles to the organic solvent is (5 to 10) to 100, for example, 5: 100, 6: 100, 7: 100, 8: 100, 9: 100, 10: 100.
In some embodiments of the invention, the reaction time of the polymerization reaction is 0.5 to 3 hours, e.g., 0 hour, 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours;
in some embodiments of the invention, the source of 2, 5-furandicarboxylic acid dichloride comprises biomass.
In some embodiments of the invention, in the adjusting pH step, the pH is adjusted to (7 to 8), for example 7, 7.5, 8;
in some embodiments of the invention, the pH adjusting agent comprises any one of lithium hydroxide, potassium hydroxide, and sodium hydroxide.
In some embodiments of the invention, the viscosity adjusting step adjusts the viscosity to 200 to 500mpa.s, and adjusts the viscosity to 200 to 500mpa.s, such as 200mpa.s, 300mpa.s, 400mpa.s, 500 mpa.s.
In some embodiments of the invention, the viscosity modifier comprises at least one of dimethyl carbonate, N-methyl pyrrolidone, diphenyl carbonate.
In some embodiments of the invention, the ceramic particles comprise at least one of alumina, silica, magnesium hydroxide, barium titanate, or barium sulfate;
in some embodiments of the invention, the ceramic particles have a particle size of 0.2 to 0.9 μm, such as 0.2 μm, 0.3 μm, 0.4 μm, 0.5 μm, 0.6 μm, 0.7 μm, 0.8 μm, 0.9 μm;
in some embodiments of the invention, the organic solvent comprises at least one of dimethylacetamide, N-dimethylacetamide, N-methylpyrrolidone, acetone.
The invention also discloses a furan-based polymer coating solution which is obtained by adopting the preparation method.
The invention also discloses a preparation method of the lithium battery diaphragm, which comprises the following steps:
coating the furan-based polymer coating solution on one side of a base film to form an oily coating;
extracting the oily coating by using an extracting agent;
and drying the oily coating extracted by the extractant to obtain the lithium battery diaphragm.
In some embodiments of the present invention, the thickness of the coating liquid of the furan-based polymeric compound in the oily coating layer is formed to be 4 μm to 5 μm, for example, 4 μm, 4.5 μm, 5 μm;
in some embodiments of the invention, the extractant comprises at least one of water, methanol, tetrahydrofuran;
in some embodiments of the invention, the drying temperature is 50-160 ℃, such as 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃;
in some embodiments of the present invention, the base film comprises a polyethylene base film or a polypropylene base film.
The invention also discloses a bio-based lithium battery diaphragm obtained by adopting the preparation method.
The technical solution of the present invention is further illustrated by the following specific embodiments in conjunction with the accompanying drawings. It should be noted that the following specific examples are given by way of illustration only and the scope of the present invention is not limited thereto.
The chemicals and raw materials used in the following examples were either commercially available or self-prepared by a known preparation method.
Example 1
The preparation method of the furan-based polymer coating liquid of the embodiment comprises the following steps:
under the protection of inert gas, sequentially adding 500g of dimethylacetamide and 54g of p-phenylenediamine, cooling to 0-10 ℃ after stirring, adding 96g of 2, 5-furandicarboxylic acid dichloride, stirring for 1 hour, heating to 40-45 ℃ after stirring, adding 24g of lithium hydroxide, stirring, adding 25g of aluminum oxide, and stirring to obtain a first mixed solution. Adding N, N-dimethylacetamide and the first mixed solution, mixing and stirring to obtain the furan-based high molecular compound coating solution.
Example 2
The preparation method of the furan-based polymer coating liquid of the embodiment comprises the following steps:
under the protection of inert gas, sequentially adding 500g of dimethylacetamide and 54g of p-phenylenediamine, cooling to 0-10 ℃ after stirring, adding 116g of 2, 5-furandicarboxylic acid dichloride, stirring for 1 hour, heating to 40-45 ℃ after stirring, adding 24g of lithium hydroxide, stirring, adding 25g of aluminum oxide, and stirring to obtain a first mixed solution. Adding N, N-dimethylacetamide and the first mixed solution, mixing and stirring to obtain the furan-based high molecular compound coating solution.
Example 3
The preparation method of the furan-based polymer coating liquid of the embodiment comprises the following steps:
under the protection of inert gas, sequentially adding 500g of dimethylacetamide and 54g of p-phenylenediamine, cooling to 0-10 ℃ after stirring, adding 96g of 2, 5-furandicarboxylic acid dichloride, stirring for 1.5 hours, heating to 40-45 ℃ after stirring, adding 24g of lithium hydroxide, stirring, adding 25g of aluminum oxide, and stirring to obtain a first mixed solution. Adding N, N-dimethylacetamide and the first mixed solution, mixing and stirring to obtain the furan-based high molecular compound coating solution.
Example 4
The preparation method of the furan-based polymer coating liquid of the embodiment comprises the following steps: under the protection of inert gas, sequentially adding 500g N-methyl pyrrolidone and 54g of p-phenylenediamine, cooling to 0-10 ℃ after stirring, adding 96g of 2, 5-furandicarboxylic acid dichloride, stirring for 1.5 hours, heating to 40-45 ℃ after stirring, adding 24g of lithium hydroxide, stirring, adding 25g of aluminum oxide, and stirring to obtain a first mixed solution. Adding N-methyl pyrrolidone into the first mixed solution, mixing and stirring to obtain the furan-based high molecular compound coating solution.
Example 5
The preparation method of the furan-based polymer coating liquid of the embodiment comprises the following steps:
under the protection of inert gas, sequentially adding 500g of dimethylacetamide and 54g of p-phenylenediamine, cooling to 0-10 ℃ after stirring, adding 96g of 2, 5-furandicarboxylic acid dichloride, stirring for 1 hour, heating to 40-45 ℃ after stirring, adding 48g of lithium hydroxide, stirring, adding 25g of silicon dioxide, and stirring to obtain a first mixed solution. Adding N, N-dimethylacetamide and the first mixed solution, mixing and stirring to obtain the furan-based high molecular compound coating solution.
Example 6
The preparation method of the furan-based polymer coating liquid of the embodiment comprises the following steps:
under the protection of inert gas, sequentially adding 500g of dimethylacetamide and 54g of p-phenylenediamine, cooling to 0-10 ℃ after stirring, adding 96g of 2, 5-furandicarboxylic acid dichloride, stirring for 1 hour, heating to 40-45 ℃ after stirring, adding 48g of lithium hydroxide, stirring, adding 25g of silicon dioxide, and stirring to obtain a first mixed solution. And adding pyrrolidone into the mixture, mixing and stirring the mixture and the first mixed solution to obtain the furan-based high molecular compound coating solution.
Example 7
The preparation method of the furan-based polymer coating liquid of the embodiment comprises the following steps:
under the protection of inert gas, sequentially adding 500g N-methyl pyrrolidone and 54g of p-phenylenediamine, cooling to 0-10 ℃ after stirring, then adding 96g of 2, 5-furandicarboxylic acid dichloride, stirring for 1 hour, heating to 40-45 ℃ after stirring, adding 24g of lithium hydroxide, stirring, adding 37.5g of aluminum oxide, and stirring to obtain a first mixed solution. Adding dimethyl carbonate and the first mixed solution, mixing and stirring to obtain the furan-based high molecular compound coating solution.
Example 8
The preparation method of the furan-based polymer compound coating liquid coating membrane comprises the following steps:
the coating solution of the furan-based polymer compound prepared in example 1 was coated on a polyethylene-based film or a polypropylene film having a thickness of 12 μm, extracted with water to obtain a separator, and dried at 100 deg.c to prepare a separator sample as shown in fig. 1.
An electron micrograph of a membrane coated with the coating liquid of the furan-based polymer compound obtained in example 8 is shown in fig. 2, pore-forming is uniform, and the coverage rate of the furan-based polymer compound is high.
Comparative example 1
The furan-based polymer coated membrane prepared in example 8 was tested with a commercially available aramid membrane, and the results are shown in table 1:
TABLE 1 Furanyl lithium battery separator Performance
Figure BDA0003015423000000071
As can be seen from the data in Table 1, the needling strength and the tensile strength of the bio-based polymer coating diaphragm provided by the invention are higher than those of an aramid diaphragm, so that the safety of a lithium battery is improved, and the service life of the lithium battery is prolonged.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (8)

1. A preparation method of a bio-based lithium battery diaphragm comprises the following steps:
preparing a furan-based polymer coating solution;
coating the furan-based polymer coating liquid on one side of a base film to form an oily coating;
extracting the oily coating by using an extracting agent;
drying the oily coating extracted by the extractant to obtain the lithium battery diaphragm;
wherein the preparation method of the furan-based polymer coating liquid comprises the following steps:
adding 2, 5-furandicarboxylic acid dichloride into an organic solvent containing p-phenylenediamine in an inert atmosphere, heating to 35-45 ℃, adjusting the pH value, and performing a polymerization reaction to form a first solution; adding ceramic particles into the first solution, mixing and stirring to form a second solution;
mixing the second solution with a viscosity regulator to obtain the furan-based polymer coating solution;
wherein the molar ratio of the p-phenylenediamine to the 2, 5-furandicarboxylic acid dichloride is 1: (1 to 1.3), the source of 2, 5-furandicarboxylic acid dichloride comprises biomass.
2. The method according to claim 1,
the mass ratio of the organic solvent to the p-phenylenediamine in the organic solvent containing the p-phenylenediamine is 1: (5 to 10);
the mass ratio of the ceramic particles to the organic solvent is (5 to 10): 100.
3. the production method according to claim 1,
the reaction time of the polymerization reaction is 0.5 to 3 hours.
4. The production method according to claim 1,
in the step of adjusting the pH, the pH is adjusted to be (7 to 8);
the regulator used for adjusting the pH comprises any one of lithium hydroxide, potassium hydroxide and sodium hydroxide.
5. The production method according to claim 1,
in the step of adjusting the viscosity, the viscosity is adjusted to be 200 to 500 mpa.s;
the viscosity regulator comprises at least one of dimethyl carbonate, N-methyl pyrrolidone and diphenyl carbonate.
6. The production method according to claim 1,
the ceramic particles comprise at least one of alumina, silica, magnesium hydroxide, barium titanate or barium sulfate;
the ceramic particles have a particle size of 0.2 to 0.9 μm;
the organic solvent comprises at least one of dimethylacetamide, N-dimethylacetamide, N-methylpyrrolidone and acetone.
7. The production method according to claim 1,
the thickness of the furan-based polymer coating liquid in the oily coating layer is formed to be 4 to 5 μm;
the extractant comprises at least one of water, methanol and tetrahydrofuran;
the drying temperature is 50-160 ℃;
the base film comprises a polyethylene base film or a polypropylene base film.
8. A bio-based lithium battery separator obtained by the production method as recited in any one of claims 1 to 7.
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CN115332722A (en) * 2022-08-16 2022-11-11 合肥国轩高科动力能源有限公司 Modified high-heat-resistance polyamide coating diaphragm and preparation method and application thereof

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