CN109509860B - Preparation method of polyvinylidene fluoride/glass fiber/silicon dioxide porous battery diaphragm - Google Patents
Preparation method of polyvinylidene fluoride/glass fiber/silicon dioxide porous battery diaphragm Download PDFInfo
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- CN109509860B CN109509860B CN201811424438.7A CN201811424438A CN109509860B CN 109509860 B CN109509860 B CN 109509860B CN 201811424438 A CN201811424438 A CN 201811424438A CN 109509860 B CN109509860 B CN 109509860B
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- glass fiber
- polyvinylidene fluoride
- diaphragm
- silicon dioxide
- casting solution
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
-
- 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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- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Cell Separators (AREA)
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Abstract
The invention discloses a preparation method of a polyvinylidene fluoride/glass fiber/silicon dioxide porous battery diaphragm, which is characterized in that a porous battery diaphragm with a sandwich structure is prepared by taking a glass fiber woven fabric as an intermediate layer and a polyvinylidene fluoride film as an upper layer and a lower layer, and silicon dioxide particles are added into the intermediate layer in the process to prepare the battery diaphragm with extremely high dimensional stability, thermal stability, electrolyte affinity and mechanical strength.
Description
Technical Field
The invention relates to a preparation method of a battery diaphragm, in particular to a preparation method of a polyvinylidene fluoride/glass fiber/silicon dioxide porous battery diaphragm.
Background
The lithium ion battery is taken as the most popular energy storage system at present and consists of a positive electrode material, a negative electrode material, a diaphragm, electrolyte and a packaging material, wherein the main functions of the diaphragm are two, namely, the positive electrode material and the negative electrode material are separated to prevent the occurrence of internal short circuit, and a channel is provided for the high-speed transmission of lithium ions.
Polyolefin microporous membranes have suitable chemical stability, thickness, pore size and the like, and are widely applied to lithium ion battery separators. However, polyolefin microporous membranes have poor heat resistance, cannot operate at high temperatures for a long time, and are prone to cause safety accidents at high temperatures. The wettability of the common electrolyte on a polyolefin microporous membrane is extremely poor, and the internal resistance of the diaphragm and the transmission speed of lithium ions are influenced. The diaphragm is inevitably subjected to external force in the using process, the polyolefin diaphragm is extremely easy to be damaged, cracks are generated on the diaphragm, and the overall performance of the battery is influenced.
At present, coating inorganic particles on the surface of polyolefin microporous membrane is a general solution to solve the above problems. However, particles soaked in the electrolyte for a long period of time, particularly particles on the surface of the separator, are easily detached from the polyolefin body, resulting in a limitation in the service life of the battery.
Disclosure of Invention
The invention aims to solve the problem that the battery diaphragm prepared by the prior art cannot realize the application of a lithium battery at high temperature.
The technical scheme adopted by the invention for solving the problems is as follows:
a preparation method of a polyvinylidene fluoride/Glass fiber/silicon dioxide porous battery diaphragm is characterized in that a porous battery diaphragm with a sandwich structure is prepared by taking Glass Fiber (GF) woven fabric as an intermediate layer and polyvinylidene fluoride (PVDF) film as an upper layer and a lower layer, and silicon dioxide (SiO) is added into the intermediate layer in the process2) The particle comprises the following specific process steps:
the first step is as follows: dissolving PVDF-HFP powder in 1-methyl-2-pyrrolidone (NMP) solution to obtain transparent solution, adding ammonia water into the transparent solution, and stirring uniformly to obtain membrane casting solution;
the second step is that: uniformly coating the casting solution obtained in the first step on one surface of a glass fiber fabric;
the third step: reacting the glass fiber woven fabric coated with the membrane casting solution in the second step with deionized water to perform a phase conversion process, and exchanging water with NMP to form a wet film;
the fourth step: drying the film obtained in the third step in a wet state to obtain a dry semi-formed diaphragm;
the fifth step: spraying silicon dioxide particles on the surface, which is not coated with the membrane casting solution, of the semi-formed membrane obtained in the fourth step;
and a sixth step: uniformly coating the casting solution obtained in the first step on one surface, which is sprayed with silicon dioxide particles, of the semi-formed diaphragm obtained in the fifth step, and wrapping the silicon dioxide particles in the semi-formed diaphragm;
the seventh step: reacting the diaphragm coated with the casting solution in the sixth step with deionized water to perform a phase conversion process, and exchanging water with NMP to form a wet film;
eighth step: and drying the diaphragm obtained in the seventh step in the wet state to obtain a dry-state formed diaphragm.
Preferably, the mass concentration of the transparent solution in the first step is 6%, and 2.5% by volume of ammonia water is added to the transparent solution.
Preferably, the coating amount of the casting solution in the second step is 0.1mL/cm2。
Preferably, the drying temperature in the fourth step is 70 ℃.
Preferably, the diameter of the silica particles in the fifth step is 1-3 μm, and the weight ratio of the silica to the polyvinylidene fluoride film is 1: 10.
preferably, the formed diaphragm prepared in the eighth step is in a porous form, the average pore diameter is 300nm, and the pore diameter is distributed between 100 nm and 450 nm.
The invention uses glass fiber woven fabric as an intermediate layer, uses a polyvinylidene fluoride film as an upper layer and a lower layer, and then adds silicon dioxide particles into the intermediate layer to prepare the battery diaphragm with extremely high dimensional stability, thermal stability, electrolyte affinity and mechanical strength. Compared with the prior art, the invention has the following advantages:
(1) the PVDF film is used as the upper layer and the lower layer, so that the PVDF film has extremely high porosity and electrolyte affinity, provides good liquid absorption rate for the whole diaphragm, and accelerates the transmission speed of lithium ions between the anode material and the cathode material.
(2) The glass fiber woven fabric is used as the middle layer, so that the mechanical strength of the diaphragm can be effectively improved, and the diaphragm is prevented from being broken in the using process.
(3) Wrapping the SiO2 particles in the middle can effectively prevent the particles from escaping into the electrolyte.
(4) The SiO2 particles can react with lithium dendrites, the growth speed of the lithium dendrites is slowed down, and the service life of the battery is prolonged.
(5) The glass fiber and the silica particle are excellent in heat resistance, providing the separator with excellent thermal stability and dimensional stability.
Detailed Description
In order to make the invention more comprehensible, preferred embodiments are described in detail below.
Examples
A preparation method of a polyvinylidene fluoride/glass fiber/silicon dioxide porous battery diaphragm comprises the following steps:
dissolving PVDF powder in an NMP solution to obtain a transparent solution with the mass concentration of 6%, adding ammonia water with the volume ratio of 2.5% into the transparent solution, and uniformly stirring to obtain a membrane casting solution;
the glass fiber woven fabric was laid flat on a glass plate, previously moved at a speed of 20mm/s, and applied at 0.1mL/cm with a doctor blade2Uniformly coating the casting solution on the glass fiber woven fabric;
conveying the glass fiber woven fabric coated with the casting solution to a water tank filled with deionized water, carrying out a phase inversion process, and exchanging water and NMP to form a wet semi-formed diaphragm;
the semi-formed diaphragm was conveyed below an infrared heater and dried at a temperature of 70 ℃. Turning over the dried semi-formed diaphragm, wherein the surface coated with the casting solution is downward, and the surface not coated with the casting solution is upward;
randomly spreading 10% (SiO) on the overturned semi-formed diaphragm2Weight: PVDF weight) SiO with a diameter of 1 to 3 μm2Particles;
and coating the casting solution on a semi-formed diaphragm scattered with SiO2 particles, performing phase inversion in a deionized water tank, and drying under an infrared heater to obtain the formed diaphragm.
The porosity of the battery separator was found to be 74.35%, the stress in the dry state was found to be 27.2MPa, and the stress in the wet state was found to be 22.4 MPa. The diaphragm is placed under high temperature condition, when the temperature reaches 500 ℃, the weight of the diaphragm becomes 70% of the initial weight, and after 120s of continuous combustion, the structure of the diaphragm is not damaged. The ionic conductivity of the diaphragm is 0.4624mS/cm, the voltage is reduced from 4.7V to 2.5V when the battery is charged and discharged under constant current, the discharge capacity of the battery is 162.4mAh/g, and the discharge capacity of the battery is 151.7mAh/g after 100 charge and discharge cycles.
Claims (6)
1. A preparation method of a polyvinylidene fluoride/glass fiber/silicon dioxide porous battery diaphragm is characterized in that a porous battery diaphragm with a sandwich structure is prepared by taking a glass fiber woven fabric as an intermediate layer and taking a polyvinylidene fluoride film as an upper layer and a lower layer, and silicon dioxide particles are added into the intermediate layer in the process, and the specific process steps are as follows:
the first step is as follows: dissolving PVDF-HFP powder in a 1-methyl-2-pyrrolidone solution to obtain a transparent solution, adding ammonia water into the transparent solution, and uniformly stirring to obtain a membrane casting solution;
the second step is that: uniformly coating the casting solution obtained in the first step on one side of the glass fiber woven fabric;
the third step: reacting the glass fiber woven fabric coated with the membrane casting solution in the second step with deionized water to perform a phase conversion process, and exchanging water with NMP to form a wet film;
the fourth step: drying the film obtained in the third step in a wet state to obtain a dry semi-formed diaphragm;
the fifth step: spraying silicon dioxide particles on the surface, which is not coated with the membrane casting solution, of the semi-formed membrane obtained in the fourth step;
and a sixth step: uniformly coating the casting solution obtained in the first step on one surface, which is sprayed with silicon dioxide particles, of the semi-formed diaphragm obtained in the fifth step, and wrapping the silicon dioxide particles in the semi-formed diaphragm;
the seventh step: reacting the diaphragm coated with the casting solution in the sixth step with deionized water to perform a phase conversion process, and exchanging water with NMP to form a wet film;
eighth step: and drying the diaphragm obtained in the seventh step in the wet state to obtain a dry-state formed diaphragm.
2. The method for preparing a polyvinylidene fluoride/glass fiber/silica porous battery separator according to claim 1, wherein the transparent solution in the first step has a mass concentration of 6% and aqueous ammonia of 2.5% by volume is added to the transparent solution.
3. The method for preparing a polyvinylidene fluoride/glass fiber/silica porous battery separator according to claim 1, wherein the coating amount of the casting solution in the second step is 0.1mL/cm2。
4. The method for preparing a polyvinylidene fluoride/glass fiber/silica porous battery separator according to claim 1, wherein the drying temperature in the fourth step is 70 ℃.
5. The method for preparing a polyvinylidene fluoride/glass fiber/silica porous battery separator according to claim 1, wherein the diameter of the silica particles in the fifth step is 1 to 3 μm, and the weight ratio of silica to polyvinylidene fluoride film is 1: 10.
6. the method for preparing a polyvinylidene fluoride/glass fiber/silica porous battery separator according to claim 1, wherein the formed separator prepared in the eighth step is porous, has an average pore size of 300nm, and has a pore size distribution of 100 to 450 nm.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811424438.7A CN109509860B (en) | 2018-11-27 | 2018-11-27 | Preparation method of polyvinylidene fluoride/glass fiber/silicon dioxide porous battery diaphragm |
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| CN201811424438.7A CN109509860B (en) | 2018-11-27 | 2018-11-27 | Preparation method of polyvinylidene fluoride/glass fiber/silicon dioxide porous battery diaphragm |
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| CN109509860B true CN109509860B (en) | 2020-08-11 |
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| WO2019195605A1 (en) * | 2018-04-04 | 2019-10-10 | Ab Systems, Inc. (Us) | Glass fiber composite separator |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105619991A (en) * | 2016-03-16 | 2016-06-01 | 东华大学 | Composite lithium-ion battery separator material and preparation method thereof |
| CN106159173A (en) * | 2015-04-14 | 2016-11-23 | 比亚迪股份有限公司 | Composite membrane of polymer prepared by a kind of composite membrane of polymer and preparation method thereof, the method, gel electrolyte, lithium ion battery |
| CN106654119A (en) * | 2016-11-14 | 2017-05-10 | 宁波中车新能源科技有限公司 | Mixed coating diaphragm and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US9231239B2 (en) * | 2007-05-30 | 2016-01-05 | Prologium Holding Inc. | Electricity supply element and ceramic separator thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106159173A (en) * | 2015-04-14 | 2016-11-23 | 比亚迪股份有限公司 | Composite membrane of polymer prepared by a kind of composite membrane of polymer and preparation method thereof, the method, gel electrolyte, lithium ion battery |
| CN105619991A (en) * | 2016-03-16 | 2016-06-01 | 东华大学 | Composite lithium-ion battery separator material and preparation method thereof |
| CN106654119A (en) * | 2016-11-14 | 2017-05-10 | 宁波中车新能源科技有限公司 | Mixed coating diaphragm and preparation method and application thereof |
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