CN108807799B - Expanded dickite modified lithium ion battery diaphragm and preparation method thereof - Google Patents
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- 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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- 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
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- 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
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- 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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- 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
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Abstract
The invention relates to a lithium ion battery diaphragm modified by expanded dickite and a preparation method thereof. According to the method, dimethyl sulfoxide, hydrazine hydrate and urea are used for sequentially intercalating the dickite, urea molecules enter the interlayer of the dickite, and the characteristic that the urea outside the layer can perform explosive reaction with potassium chlorate is utilized to swell the lamellar structure of the dickite, so that the swelled dickite powder with a through mesh structure is obtained. Mixing the expanded dickite with basalt fiber, a modifier, vinylidene fluoride and N-N dimethylformamide for pulping, and preparing the diaphragm material for the lithium ion battery by using a phase transfer method. The expanded dickite can obviously improve the heat resistance of the diaphragm, and the aperture size, porosity and liquid absorption rate of the diaphragm, thereby being beneficial to the transmission of lithium ions in the diaphragm and improving the rate capability of the battery. In addition, the use of the basalt fibers can effectively improve the mechanical strength of the diaphragm and improve the usability and safety of the diaphragm.
Description
The technical field is as follows:
the invention belongs to the technical field of lithium ion battery diaphragms, and relates to a high-temperature-resistant power type lithium ion battery diaphragm suitable for large-current charging and discharging and a preparation method thereof.
Background art:
the battery diaphragm is a layer of diaphragm material between the positive electrode and the negative electrode of the battery, and has the main functions of isolating the positive electrode and the negative electrode and insulating electrons, but ions in the electrolyte can be freely transmitted between the positive electrode and the negative electrode, so that the battery reaction is completed. At present, commercial lithium ion battery separator materials are mainly porous polyolefin such as Polyethylene (PE) or polypropylene (PP), and although polyolefin separators have many advantages when used in lithium ion batteries, the melting points of polyolefin separators are low, and the melting points of polyethylene and polypropylene are 130 ℃ and 150 ℃, respectively, and the separators melt to cause short circuits of batteries when exceeding the temperature. In practical application, the battery can be heated up to 200 ℃ rapidly, particularly the power lithium ion battery used by electric automobiles, and the fire-starting combustion event of some electric automobiles is caused by the high-temperature failure of the polyolefin diaphragm. Therefore, it is urgent to develop a novel high heat-resistant separator product suitable for a power lithium ion battery.
Polyvinylidene fluoride (PVDF), the second largest fluorine material to polytetrafluoroethylene, has excellent film-forming properties, high thermal and chemical stability, and thus is one of the most advantageous polymers for preparing lithium ion battery separators. But because PVDF has a strong crystallization tendency and is easy to form a microporous structure containing spherulites, and larger cavities are formed among the spherulites, the control of the microporous structure of the PVDF diaphragm is limited. The inorganic additive is added in the PVDF film forming process, so that the crystallinity of the PVDF can be effectively reduced, and an asymmetric or anisotropic microporous structure can be obtained. For example, Chinese patent CN106784534A discloses a preparation method of PVDF and copolymer ceramic coating diaphragm thereof. The use of the ceramic filler reduces the crystallinity of PVDF and improves the liquid absorption rate of the diaphragm. For another example, chinese patent CN106684296A discloses a PVDF mixed coating membrane with good safety and a preparation method thereof. The invention is prepared by mixing PVDF and Mg (OH)2Direct mixing of the particles, Mg (OH)2The crystallinity of PVDF is reduced, the amorphous area of lithium ion conduction is improved, and the rate discharge and cycle performance of the lithium battery are improved. In order to further improve the porosity, liquid absorption, electrolyte wettability and mechanical properties of the separator, the research on novel inorganic fillers is still a hot problem at present.
The dickite is a common industrial raw material, has a 1:1 type layer structure, has relatively weak acting force between unit layers of a structural unit layer, and can realize the expansion of a dickite layer after organic small molecule intercalation-desorption treatment, thereby obtaining the expanded dickite powder with a through mesh structure. The powder is filled in a PVDF matrix, so that PVDF crystallization can be effectively inhibited, and diaphragm pore-forming is promoted. Meanwhile, the through meshes of the expanded dickite can form a porous structure with developed pore passages and high porosity in the PVDF matrix, so that the transmission of lithium ions in the PVDF matrix is promoted. In addition, the dickite unit layer surface contains abundant functional groups, has good adaptability to aqueous electrolyte and organic electrolyte, and can improve the wettability of the diaphragm to different electrolytes, thereby reducing the impedance of the battery and improving the rate capability and cycle performance of the battery. In addition, in order to improve the mechanical property of the diaphragm, in the preparation process of the diaphragm, basalt chopped fiber is used as a reinforcing fiber to improve the mechanical strength and flexibility of the composite diaphragm.
The unique structural characteristics of the matrix expanded dickite and the application prospect in the field of lithium ion battery separators. The invention provides a method for preparing a novel lithium ion battery diaphragm by using expanded dickite as a filler, basalt fiber as a reinforcing agent and PVDF as a substrate.
The invention content is as follows:
the preparation method comprises the steps of firstly preparing expanded dickite powder with a through mesh structure, and filling the powder into a PVDF substrate to form a diaphragm material with developed pore channels and high porosity. Meanwhile, basalt chopped fiber is added into the PVDF matrix to serve as reinforcing fiber, so that the mechanical strength and flexibility of the composite diaphragm are improved.
The invention is realized by the following technical scheme:
a lithium ion battery diaphragm modified by expanded dickite and reinforced by basalt fiber and a preparation method thereof comprise the following steps:
a. preparation of expanded dickite
Dickite and dimethyl sulfoxide were mixed according to a ratio of 1: mixing at a mass ratio of 20, heating and stirring at 40-80 ℃ for 24-48 hours, centrifuging to remove the upper liquid, adding a hydrazine hydrate aqueous solution with a certain volume of 80%, heating and stirring at 30-40 ℃ for 12-24 hours, centrifuging to remove the upper liquid, adding a urea solution with a certain volume of 10mol/L, heating and stirring at 60-90 ℃ for 4-8 hours, centrifuging again, and drying the lower solid at 80 ℃ to obtain a sample A; mixing and grinding the sample A, urea and potassium chlorate with certain mass for 2 hours to obtain a sample B, and calcining the sample B in an electric furnace at 450 ℃ for 30 seconds to obtain expanded dickite powder;
b. preparation of separator Material
Dispersing expanded dickite, basalt chopped fiber and a modifier in N-N dimethylformamide to obtain a suspension C, dissolving vinylidene fluoride in N-N dimethylformamide to obtain a solution D, mixing the suspension C and the solution D, stirring for 2 hours to form a mixed slurry, and then coating the slurry on a glass plate in a blade mode; and finally, slowly immersing the glass plate in distilled water containing ethanol and n-butanol, keeping for 30 seconds, taking out, and drying in vacuum at 40 ℃ to obtain the lithium ion battery diaphragm material.
The content of other siliceous heterogeneous phases in the dickite is less than 5 percent; the usage amount of 80% hydrazine hydrate aqueous solution is 1.2 times of the volume of dimethyl sulfoxide; the usage amount of the 10mol/L urea solution is 0.75 time of the volume of the dimethyl sulfoxide; the mass ratio of the sample A to the urea to the potassium chlorate is 1: 0.2-1: 0.1 to 0.5; in the process of preparing the membrane material, the mass ratio of the expanded dickite to the basalt chopped fibers to the modifier to the polyvinylidene fluoride is 30-60: 1-5: 0.5-2: 40-70; the modifier is any one of aluminate coupling agents DL-411, DL-411AF and DL-411D; when preparing the suspension C, the using amount of N-N dimethylformamide is three times of the mass of the expanded dickite; when the solution D is prepared, the using amount of the N-N dimethylformamide is four times of the mass of the vinylidene fluoride; the concentrations of ethanol and n-butanol in distilled water were 5 wt% and 2 wt%, respectively; the thickness of the slurry was controlled to 40 microns.
Drawings
FIG. 1 shows rate capability of lithium iron phosphate/lithium battery using the composite diaphragm
The specific implementation mode is as follows:
the present invention will be described in further detail with reference to examples:
a. dickite and dimethyl sulfoxide were mixed according to a ratio of 1: mixing at a mass ratio of 20, heating and stirring at 40-80 ℃ for 24-48 hours, centrifuging to remove the upper liquid, adding 80% hydrazine hydrate aqueous solution with the volume 1.2 times that of dimethyl sulfoxide, heating and stirring at 30-40 ℃ for 12-24 hours, centrifuging to remove the upper liquid, adding 10mol/L urea solution with the volume 0.75 time that of dimethyl sulfoxide, heating and stirring at 60-90 ℃ for 4-8 hours, centrifuging again, and drying the lower solid at 80 ℃ to obtain a sample A;
b. mixing the sample A with urea and potassium chlorate according to the mass ratio of 1: 0.2-1: 0.1-0.5, mixing and grinding for 2 hours to obtain a sample B, and calcining the sample B in an electric furnace at 450 ℃ for 30 seconds to obtain expanded dickite powder;
c. dispersing expanded dickite, basalt chopped fiber and a modifier in N-N dimethylformamide to obtain a suspension C, dissolving vinylidene fluoride in N-N dimethylformamide to obtain a solution D, wherein the mass ratio of the expanded dickite to the basalt chopped fiber to the modifier to the vinylidene fluoride is 30-60: 1-5: 0.5-2: 40-70;
d. mixing and stirring the suspension C and the solution D for 2 hours to form mixed slurry, and then coating the slurry on a glass plate in a scraping mode, wherein the scraping thickness of the slurry is controlled to be 40 micrometers;
e. slowly immersing the glass plate in distilled water containing ethanol and n-butanol, keeping for 30 seconds, taking out, and drying in vacuum at 40 ℃ to obtain the lithium ion battery diaphragm material.
Example 1
a. Dickite and dimethyl sulfoxide were mixed according to a ratio of 1: mixing at a mass ratio of 20, heating and stirring at 40 ℃ for 24-48 hours, centrifugally separating to remove upper-layer liquid, adding 80% hydrazine hydrate aqueous solution with the volume 1.2 times that of dimethyl sulfoxide, heating and stirring at 30 ℃ for 24 hours, centrifugally separating to remove upper-layer liquid, adding 10mol/L urea solution with the volume 0.75 time that of dimethyl sulfoxide, heating and stirring at 70 ℃ for 4 hours, centrifugally separating again, and drying lower-layer solid at 80 ℃ to obtain a sample A;
b. mixing the sample A with urea and potassium chlorate according to the mass ratio of 1: 0.2: 0.5, mixing and grinding for 2 hours to obtain a sample B, and then putting the sample B into an electric furnace at 450 ℃ to calcine for 30 seconds to obtain expanded dickite powder;
c. dispersing expanded dickite, basalt chopped fiber and a modifier in N-N dimethylformamide to obtain a suspension C, dissolving vinylidene fluoride in N-N dimethylformamide to obtain a solution D, wherein the mass ratio of the expanded dickite to the basalt chopped fiber to the modifier to the vinylidene fluoride is 30: 1: 2: 70;
d. mixing and stirring the suspension C and the solution D for 2 hours to form mixed slurry, and then coating the slurry on a glass plate in a scraping mode, wherein the scraping thickness of the slurry is controlled to be 40 micrometers;
e. slowly immersing the glass plate in distilled water containing ethanol and n-butanol, keeping for 30 seconds, taking out, and drying in vacuum at 40 ℃ to obtain the lithium ion battery diaphragm material.
When the diaphragm is used in a lithium iron phosphate/lithium battery system, the porosity reaches 65%. The 4C cell discharge capacity reached 110Amh/g higher than the cell using a pure PVDF separator (102 Amh/g). The tensile strength of the basalt chopped fiber diaphragm is 3.4MPa higher than that of a pure PVDF diaphragm (2.1 MPa).
Example 2
a. Dickite and dimethyl sulfoxide were mixed according to a ratio of 1: mixing at a mass ratio of 20, heating and stirring at 70 ℃ for 24 hours, centrifugally separating to remove upper-layer liquid, adding 80% hydrazine hydrate aqueous solution with the volume 1.2 times that of dimethyl sulfoxide, heating and stirring at 30 ℃ for 20 hours, centrifugally separating to remove upper-layer liquid, adding 10mol/L urea solution with the volume 0.75 time that of dimethyl sulfoxide, heating and stirring at 60 ℃ for 8 hours, centrifugally separating again, and drying lower-layer solid at 80 ℃ to obtain a sample A;
b. mixing the sample A with urea and potassium chlorate according to the mass ratio of 1: 0.4: 0.1, mixing and grinding for 2 hours to obtain a sample B, and then putting the sample B into an electric furnace at 450 ℃ to calcine for 30 seconds to obtain expanded dickite powder;
c. dispersing expanded dickite, basalt chopped fiber and a modifier in N-N dimethylformamide to obtain a suspension C, dissolving vinylidene fluoride in N-N dimethylformamide to obtain a solution D, wherein the mass ratio of the expanded dickite to the basalt chopped fiber to the modifier to the vinylidene fluoride is 40: 3: 1.5: 60, adding a solvent to the mixture;
d. mixing and stirring the suspension C and the solution D for 2 hours to form mixed slurry, and then coating the slurry on a glass plate in a scraping mode, wherein the scraping thickness of the slurry is controlled to be 40 micrometers;
e. slowly immersing the glass plate in distilled water containing ethanol and n-butanol, keeping for 30 seconds, taking out, and drying in vacuum at 40 ℃ to obtain the lithium ion battery diaphragm material.
When the diaphragm is used in a lithium iron phosphate/lithium battery system, the porosity reaches 68 percent. The 4C cell discharge capacity reached 115Amh/g higher than the cell using a pure PVDF separator (102 Amh/g). The tensile strength of the basalt chopped fiber diaphragm is 3.0MPa higher than that of a pure PVDF diaphragm (2.1 MPa).
Example 3
a. Dickite and dimethyl sulfoxide were mixed according to a ratio of 1: mixing at a mass ratio of 20, heating and stirring at 80 ℃ for 36 hours, centrifugally separating to remove upper-layer liquid, adding 80% hydrazine hydrate aqueous solution with the volume 1.2 times that of dimethyl sulfoxide, heating and stirring at 40 ℃ for 12 hours, centrifugally separating to remove upper-layer liquid, adding 10mol/L urea solution with the volume 0.75 time that of dimethyl sulfoxide, heating and stirring at 90 ℃ for 5 hours, centrifugally separating again, and drying lower-layer solid at 80 ℃ to obtain a sample A;
b. mixing the sample A with urea and potassium chlorate according to the mass ratio of 1: 0.6: 0.2, mixing and grinding for 2 hours to obtain a sample B, and then putting the sample B into an electric furnace at 450 ℃ to calcine for 30 seconds to obtain expanded dickite powder;
c. dispersing expanded dickite, basalt chopped fiber and a modifier in N-N dimethylformamide to obtain a suspension C, dissolving vinylidene fluoride in N-N dimethylformamide to obtain a solution D, wherein the mass ratio of the expanded dickite to the basalt chopped fiber to the modifier to the vinylidene fluoride is 50: 4: 1: 50;
d. mixing and stirring the suspension C and the solution D for 2 hours to form mixed slurry, and then coating the slurry on a glass plate in a scraping mode, wherein the scraping thickness of the slurry is controlled to be 40 micrometers;
e. slowly immersing the glass plate in distilled water containing ethanol and n-butanol, keeping for 30 seconds, taking out, and drying in vacuum at 40 ℃ to obtain the lithium ion battery diaphragm material.
When the diaphragm is used in a lithium iron phosphate/lithium battery system, the porosity reaches 72 percent. The 4C cell discharge capacity reached 117Amh/g higher than the cell using a pure PVDF separator (102 Amh/g). The tensile strength of the basalt chopped fiber diaphragm is 3.1MPa higher than that of a pure PVDF diaphragm (2.1 MPa).
Example 4
a. Dickite and dimethyl sulfoxide were mixed according to a ratio of 1: mixing at a mass ratio of 20, heating and stirring at 50 ℃ for 48 hours, centrifugally separating to remove upper-layer liquid, adding 80% hydrazine hydrate aqueous solution with the volume 1.2 times that of dimethyl sulfoxide, heating and stirring at 40 ℃ for 16 hours, centrifugally separating to remove upper-layer liquid, adding 10mol/L urea solution with the volume 0.75 time that of dimethyl sulfoxide, heating and stirring at 80 ℃ for 7 hours, centrifugally separating again, and drying lower-layer solid at 80 ℃ to obtain a sample A;
b. mixing the sample A with urea and potassium chlorate according to the mass ratio of 1: 1: 0.4, mixing and grinding for 2 hours to obtain a sample B, and then putting the sample B into an electric furnace at 450 ℃ to calcine for 30 seconds to obtain expanded dickite powder;
c. dispersing expanded dickite, basalt chopped fiber and a modifier in N-N dimethylformamide to obtain a suspension C, dissolving vinylidene fluoride in N-N dimethylformamide to obtain a solution D, wherein the mass ratio of the expanded dickite to the basalt chopped fiber to the modifier to the vinylidene fluoride is 60: 5: 0.5: 40;
d. mixing and stirring the suspension C and the solution D for 2 hours to form mixed slurry, and then coating the slurry on a glass plate in a scraping mode, wherein the scraping thickness of the slurry is controlled to be 40 micrometers;
e. slowly immersing the glass plate in distilled water containing ethanol and n-butanol, keeping for 30 seconds, taking out, and drying in vacuum at 40 ℃ to obtain the lithium ion battery diaphragm material.
When the diaphragm is used in a lithium iron phosphate/lithium battery system, the porosity reaches 75 percent. The 4C cell discharge capacity reached 116Amh/g higher than the cell using a pure PVDF separator (102 Amh/g). The tensile strength of the basalt chopped fiber diaphragm is 3.8MPa higher than that of a pure PVDF diaphragm (2.1 MPa).
Claims (3)
1. A preparation method of a lithium ion battery diaphragm modified by expanded dickite is characterized by comprising the following steps:
a. preparation of expanded dickite
Dickite and dimethyl sulfoxide were mixed according to a ratio of 1: mixing at a mass ratio of 20, heating and stirring at 40-80 ℃ for 24-48 hours, centrifuging to remove the upper liquid, adding a hydrazine hydrate aqueous solution with a certain volume of 80%, heating and stirring at 30-40 ℃ for 12-24 hours, centrifuging to remove the upper liquid, adding a urea solution with a certain volume of 10mol/L, heating and stirring at 60-90 ℃ for 4-8 hours, centrifuging again, and drying the lower solid at 80 ℃ to obtain a sample A; mixing and grinding the sample A, urea and potassium chlorate with certain mass for 2 hours to obtain a sample B, and calcining the sample B in an electric furnace at 450 ℃ for 30 seconds to obtain expanded dickite powder;
b. preparation of separator Material
Dispersing expanded dickite, basalt chopped fiber and a modifier in N-N dimethylformamide to obtain a suspension C, dissolving vinylidene fluoride in N-N dimethylformamide to obtain a solution D, mixing the suspension C and the solution D, stirring for 2 hours to form a mixed slurry, and then coating the slurry on a glass plate in a blade mode; and finally, slowly immersing the glass plate in distilled water containing ethanol and n-butanol, keeping for 30 seconds, taking out, and drying in vacuum at 40 ℃ to obtain the lithium ion battery diaphragm material.
2. The method for preparing the expanded dickite-modified lithium ion battery separator according to claim 1, wherein the content of other siliceous heterogeneous phases in the dickite is less than 5%; the usage amount of 80% hydrazine hydrate aqueous solution is 1.2 times of the volume of dimethyl sulfoxide; the usage amount of the 10mol/L urea solution is 0.75 time of the volume of the dimethyl sulfoxide; the mass ratio of the sample A to the urea to the potassium chlorate is 1: 0.2-1: 0.1 to 0.5; in the process of preparing the membrane material, the mass ratio of the expanded dickite to the basalt chopped fibers to the modifier to the polyvinylidene fluoride is 30-60: 1-5: 0.5-2: 40-70; the modifier is any one of aluminate coupling agents DL-411, DL-411AF and DL-411D; when preparing the suspension C, the using amount of N-N dimethylformamide is three times of the mass of the expanded dickite; when the solution D is prepared, the using amount of the N-N dimethylformamide is four times of the mass of the vinylidene fluoride; the concentrations of ethanol and n-butanol in distilled water were 5 wt% and 2 wt%, respectively; the thickness of the slurry was controlled to 40 microns.
3. The utility model provides a lithium ion battery diaphragm of popped dickite modification which characterized in that: obtainable by the process according to any one of claims 1-2.
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| CN116083955B (en) * | 2023-04-11 | 2023-06-30 | 四川亚联氢能科技股份有限公司 | High-temperature-resistant basalt modified diaphragm and preparation process thereof |
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