CN115275504A - Aramid fiber diaphragm and preparation method and application thereof - Google Patents
Aramid fiber diaphragm and preparation method and application thereof Download PDFInfo
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- CN115275504A CN115275504A CN202210740222.1A CN202210740222A CN115275504A CN 115275504 A CN115275504 A CN 115275504A CN 202210740222 A CN202210740222 A CN 202210740222A CN 115275504 A CN115275504 A CN 115275504A
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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Images
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
- H01M50/406—Moulding; Embossing; Cutting
-
- 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
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
-
- 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 & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Cell Separators (AREA)
Abstract
The invention relates to the technical field of aramid fiber membranes, and discloses an aramid fiber membrane and a preparation method and application thereof. The preparation method of the aramid fiber membrane comprises the following steps: (1) preparation of aramid polymer dispersion: mixing an aramid polymer with a dispersion solvent, and stirring to obtain an aramid polymer dispersion liquid; (2) preparing an aramid fiber membrane precursor: after gas-jet atomization treatment, directly spraying the aramid polymer dispersion liquid on a collecting roller, and obtaining an aramid diaphragm precursor after pre-coagulation bath; (3) preparing an aramid fiber membrane: and (3) carrying out bidirectional stretching on the aramid fiber membrane precursor, and finally curing and drying to obtain the aramid fiber membrane. The method has the advantages of simple operation, convenience and easiness, universality in process, high production efficiency, good quality and suitability for industrial continuous production, the prepared diaphragm has a unique net-shaped structure, the specific surface area is larger, the porosity and the ion penetration rate are high, the electrochemical performance and the use safety performance of the aramid fiber diaphragm are improved, and the method can be applied to the field of lithium ion batteries.
Description
Technical Field
The invention relates to the technical field of aramid fiber membranes, and particularly relates to an aramid fiber membrane and a preparation method and application thereof.
Background
The diaphragm is an important component of the lithium ion battery, the main function of the diaphragm is to avoid short circuit caused by direct contact of the anode and the cathode, and the diaphragm with excellent performance has an important function of improving the comprehensive performance of the lithium battery. At present, commercial lithium ion battery separators are mainly polyolefin microporous membranes, including polyethylene, polypropylene, and multi-layer membranes made of multiple materials. The polyolefin diaphragm is low in price, has excellent mechanical property and insulating property, but has the obvious defects of obvious shrinkage at high temperature, poor electrolyte wettability, low porosity and the like, and can affect the safety performance and the electrochemical performance of the battery. In order to compensate for the deficiencies of polyolefin separators, different types of composite separators have been developed.
At present, most of the production of the diaphragm is dry method, wet method, electrostatic spinning and the like. The dry process, i.e. melt extrusion stretching process, is a process for preparing microporous membrane from polymer through melt extrusion casting, spherulite culture, stretching to form hollow and heat setting. The wet method, i.e. thermal phase separation or non-solvent phase separation, is characterized by that the condition is changed to reduce the dissolving capacity of polymer and induce the crystallization of polymer to produce liquid-liquid or solid-liquid phase separation, the polymer phase and diluent phase can be formed into interphase structure, then the diluent is removed by using extracting agent, the space occupied by original diluent in the mixture is changed into pores, and finally a coherent microporous structure is formed. The wet method has its own advantages over the dry method, but has the obvious disadvantages that the pore size is difficult to control, and a dense skin layer and closed pores are easy to generate. The electrostatic spinning method has low efficiency, is not suitable for industrial production, has low strength of the prepared diaphragm, is influenced by various factors, and is difficult to control.
The aromatic polyamide (aramid) material is widely applied in the field of high-performance fibers, and a large number of benzene rings and amide bonds in the molecular structure endow the aromatic polyamide material with excellent heat resistance and mechanical properties. The aramid fiber-based battery diaphragm has the advantages of being capable of keeping dimensional stability at high temperature, strong in external force puncture resistance and the like, and becomes a hotspot of novel power technology research in recent years. The existing method for preparing the diaphragm by using the aramid fiber material is generally an electrostatic spinning method, a suction filtration method, a coating method, an extrusion method and the like, for example, chinese patent 201810385938.8 discloses a method for successfully preparing the lithium ion diaphragm by using an electrostatic spinning method and using inorganic nano ceramic particle blending modified para-aramid fiber polymer as a raw material; chinese patents 202010069898.3, 202110780179.7 and 202110780799.0 adopt a strategy of 'from bottom to top' to firstly carry out a series of chemical treatments on aramid fibers to obtain micro-nano level aramid fibers, and then the aramid fibers are subjected to suction filtration to prepare an aramid film material; as another example, chinese patents 201911039748.1 and 202210174186.7 disclose that a coating of an aramid polymer or a mixed inorganic-organic polymer is coated on the surface of a base film to obtain an aramid separator; chinese patent 202010339804.X discloses that a meta-aramid pulp is subjected to extrusion, transverse stretching, vertical stretching, extraction and solidification to obtain a meta-aramid diaphragm.
In summary, the currently reported methods for preparing the aramid fiber diaphragm include an electrostatic spinning method, a suction filtration method, a coating method, an extrusion method, and the like. Although the aramid fiber membrane material can be obtained by the disclosed technology, the aramid fiber membrane material has obvious disadvantages: the electrostatic spinning method has low yield and large difficulty in industrial production; although the strength of the membrane prepared by the aramid micro-nanofiber suction filtration method is high, a compact structure is easy to form, and the obtained membrane is essentially a nanofiltration membrane, and if high porosity is to be realized, the technical difficulty is high; the coating method coats the treated aramid polymer on the surface of the existing membrane material, and because of the unique chemical composition of the aramid material, the development and application of the coating membrane are seriously influenced by the combination property of the aramid coating and the base membrane; and the conventional extrusion stretching film is easy to break in the process and uneven in structure, and the finally manufactured diaphragm is brittle and has low strength, so that the safety performance of the lithium battery is not improved when the diaphragm is applied to the diaphragm. The technical defects limit the industrialization process and the application range of the aramid fiber diaphragm.
Therefore, the fast and effective preparation technology of the high-performance aramid fiber membrane is of great significance for realizing functionalization and high performance of the aramid fiber membrane and cross diversified application of the aramid fiber membrane in various fields such as reinforced materials, battery membranes, electric insulation nano paper, flexible electronic devices, adsorption filter media and the like.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention mainly aims to provide the aramid fiber membrane.
The invention also aims to provide an efficient preparation method of the aramid fiber membrane.
The invention also aims to provide application of the aramid fiber membrane.
The purpose of the invention is realized by the following technical scheme:
a preparation method of an aramid fiber membrane comprises the following steps:
(1) Preparing an aramid polymer dispersion liquid: mixing an aramid polymer with a dispersing solvent, and stirring to obtain an aramid polymer dispersion liquid with the mass fraction of 0.1-20%;
(2) Preparing an aramid fiber membrane precursor: after gas-jet atomization treatment, directly spraying the aramid polymer dispersion liquid on a collecting roller, and obtaining an aramid diaphragm precursor after pre-coagulation bath;
(3) Preparing an aramid fiber membrane: and (3) performing bidirectional stretching on the aramid fiber membrane precursor, and finally curing and drying to obtain the aramid fiber membrane.
Preferably, the concentration of the aramid polymer dispersion liquid in the step (1) is 10-16%, and the dispersion solvent is one or more of dimethylacetamide, dimethylformamide, dimethyl sulfoxide and acetone.
Preferably, the aramid polymer in step (1) may be one or more of poly (m-phenylene isophthalamide), poly (p-phenylene terephthalamide), and polyamide polymer containing heterocyclic ring mechanism.
Preferably, the gas spray atomization treatment conditions in the step (2) are as follows: the spinneret orifices are inner air inlet holes and outer liquid inlet holes, the aperture range of the pneumatic atomizer is 0.1-8.0 mm, and the pressure range of the air compressor is 0.1-1.2 MPa; the gas source can be single gas or mixed gas such as air, nitrogen, argon and the like.
Preferably, the collecting roller in the step (2) is a rotating roller wrapped by an endless mesh cloth, and the linear distance between the nozzle and the collecting roller is 20-35cm; the roller can be made of nylon, stainless steel, ceramic or other suitable materials; the endless mesh fabric may be made of teflon, nylon or other suitable materials.
Preferably, the pre-setting condition of step (2): the pre-coagulation bath is a mixed solution of dimethylacetamide and a curing agent, the curing agent is one or more of reagents with curing effects such as glycerol, ethanol and water, and the mass ratio of dimethylacetamide to the curing agent is (5-9): (1-5) and the temperature is 0-50 ℃.
Preferably, the curing conditions in step (3) are as follows: the coagulating bath is a dimethyl acetamide water solution with the mass fraction of 10-90%, and the temperature is 0-50 ℃.
Preferably, the biaxial stretching in the step (3) is specifically stretching 1.5 to 5.0 times in the transverse direction and stretching 1.3 to 4.0 times in the longitudinal direction, more preferably stretching 1.8 to 3.5 times in the transverse direction and stretching 2.0 to 3.8 times in the longitudinal direction; the drying condition is that the temperature is 80-300 ℃ and the time is 0.1-60 min.
Preferably, the stirring condition in the step (1) is magnetic rotor stirring or mechanical paddle type stirring dispersion, the rotating speed is 50-1000 rpm, and the stirring time is 1-60 min.
Preferably, the thickness is 10 to 21 μm, the porosity is 80 to 95%, the liquid absorption rate is 200 to 450%, the longitudinal tensile strength is 130 to 550MPa, the transverse tensile strength is 120 to 350MPa, and the puncture strength is 200 to 550g/mil.
Preferably, the thickness is 12 to 18 μm, the porosity is 82 to 92%, the liquid absorption rate is 240 to 400%, the longitudinal tensile strength is 200 to 500MPa, the transverse tensile strength is 200 to 320MPa, and the puncture strength is 300 to 500g/mil.
The aramid fiber diaphragm and the preparation method and application thereof have the advantages of simple operation, convenience and easiness in implementation, universality in process, higher production efficiency and good quality compared with the conventional preparation method at present, are suitable for industrial continuous production, have a unique net-shaped structure, are larger in specific surface area and high in porosity and ion penetration rate, improve the electrochemical performance and the use safety performance of the aramid fiber diaphragm, and can be applied to the field of lithium ion batteries.
Compared with the prior art, the invention has the following advantages and effects:
(1) The invention adopts the injection technology of inner air inlet flow and outer liquid inlet flow to prepare the size-controllable and adjustable high-performance aramid fiber diaphragm with the average aperture smaller than 1 mu m. The liquid material is scattered and dispersed by the incoming high-speed flowing compressed gas, the aramid fiber diaphragm precursor is collected by a collecting roller, and the aramid fiber diaphragm precursor is subjected to double diffusion in a pre-coagulation bath to be initially solidified so as to meet the strength requirement of a subsequent stretching operation. After the aramid fiber membrane is stretched longitudinally and transversely, the pore structure of the aramid fiber membrane is further improved, the porosity and the mechanical property are obviously improved, and finally, the high-performance aramid fiber membrane material is obtained through curing and drying. The prepared aramid fiber membrane has a unique net-shaped structure and larger specific surface area, can obviously improve the bonding strength of the fiber interface in the aramid fiber membrane, effectively improves the mechanical strength and the electrochemical performance of the aramid fiber membrane, and can be widely applied to the field of new membrane materials. The ideal mechanical strength and piercing strength can avoid short circuit caused by piercing of the diaphragm due to some burrs or lithium dendrites, and improve the safety performance of the lithium battery. In addition, the lithium battery diaphragm has excellent electrolyte adsorption capacity and electrolyte retention capacity, can effectively reduce the interface resistance of the lithium battery, optimize the electrical property of the lithium battery, prolong the service life of the lithium battery and the like.
(2) Compared with the existing reported preparation methods of aramid fiber membranes, such as an electrostatic spinning method, a suction filtration method, a coating method, an extrusion method and the like, the technical scheme of the invention is simple and convenient to operate and easy to realize industrial production; the pore structure of the diaphragm is adjustable and controllable, and the electrochemical performance requirement of use is met; the diaphragm is prepared by one-step forming, the inside of the diaphragm is composed of micro-nano aramid fibers, compared with conventional aramid chopped fibers and other raw materials, the micro-nano aramid fibers have the advantages of smaller diameter, higher specific surface area and chemical activity, after the diaphragm is stretched longitudinally and transversely, residual stress is eliminated, molecular chains or crystals of the micro-nano aramid fibers are orderly arranged along the plane direction, macromolecular oriented structures are fixed in a tightened or loosened state, fiber interfaces are also tightly combined under the action of tension, the technical problems that a conventional method for manufacturing the diaphragm is fragile and easy to break are solved, and the mechanical strength and the pore structure are further improved. The technical scheme further expands the industrialization process and the application range of the aramid fiber diaphragm.
(3) The efficient preparation technology of the aramid fiber membrane can also increase the functional and high-performance application of the aramid fiber membrane by adding functional elements into the aramid fiber polymer. Has important significance for the crossed and diversified application of aramid fiber materials in various fields such as battery diaphragms, electric insulation nano-paper, flexible electronic devices, adsorption filter media and the like.
Drawings
Fig. 1 is a schematic process diagram of an efficient preparation method of a high-performance aramid fiber membrane.
Fig. 2 is an SEM image of the surface of the prepared high-performance aramid membrane.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
The starting materials for the preparation process of the present invention are commercially available or may be prepared according to prior art methods. The aramid fiber used in the embodiment of the invention is meta-aramid fiber, but is not limited in this way. In this example, the aramid polymer was supplied by Ganzhou Longbang materials technology Inc. and the atomizer was self-made by the laboratory, but the raw materials and equipment required were not limited to the above. The stretching direction is defined as follows: the stretching direction is parallel to the moving direction of the film and is longitudinal stretching, and the stretching direction is vertical to the moving direction of the film and is transverse stretching.
The detection method comprises the following steps: thickness (GB/T20628.2-2006); the tensile strength and the elongation at break are tested by adopting a strip-shaped sample method according to the regulations in GB/T29627.2-2013; the water content is measured according to GB/T29627.2-2013; the electrical strength is measured according to GB/T29627.2-2013; the dielectric loss factor is measured according to GB/T29627.2-2013; the liquid absorption rate measuring method comprises the following steps: and (3) putting the circular diaphragm with the diameter of 18mm into the lithium hexafluorophosphate electrolyte for soaking for 4h, and weighing the soaked mass. Liquid absorption rate = [ (M)1-M0)/M0]X 100; in the formula, M0And M1The mass of the diaphragm before and after soaking in the electrolyte is unit g; puncture resistance is measured with reference to ASTM F1306-90; the puncture strength is determined by reference to GB/T21302-2007; the porosity was tested by n-butanol imbibition: soaking a circular diaphragm with the diameter of 18mm in n-butyl alcohol solution for 4h, weighing the mass after soaking, and calculating the porosity = [ (M) by adopting a formula1-M0)/ρV]×100，M0And M1The mass of the membrane before and after soaking in n-butanol,the unit g; rho is the density of n-butanol and is 0.81g/cm3(ii) a V is the volume of the diaphragm in cm3(ii) a The ionic conductivity was calculated by measuring the bulk impedance of the simulated cell, the ionic conductivity = L/(R × a) where: l is the thickness of the diaphragm; a is the effective contact area of the diaphragm, and R is the bulk resistance (omega) of the diaphragm; the battery has the cycle performance that a diaphragm soaked with electrolyte, a positive electrode and a negative electrode are assembled into a CR2025 type button battery in a glove box, the battery is charged and discharged for 100 times at a constant current of 0.5C, and the voltage ranges are as follows: 2.75V-4.2V, and the capacity after 100 times of test cycle is divided by the capacity of the first test to calculate the capacity retention rate (%).
Example 1
An aramid fiber diaphragm and a preparation method and application thereof are disclosed, wherein the preparation method comprises the following steps:
(1) Preparing an aramid polymer dispersion liquid: dispersing polyisophthaloyl metaphenylene diamine in a dimethylacetamide solution at room temperature according to the mass percent, and continuously stirring, dispersing and filtering to obtain an aramid polymer dispersion liquid with the mass fraction of 0.1%;
(2) Preparing an aramid fiber membrane precursor: carrying out air-jet atomization treatment on the aramid polymer dispersion liquid in a mode of internal gas flow and external liquid flow, wherein the size of an atomization hole is 1.0mm, air is used as a gas source, and the gas pressure range is 0.3MPa; directly spraying the mixture on a collecting roller, wherein the linear distance between a nozzle and a receiving roller is 30cm; obtaining an aramid fiber membrane precursor after a pre-coagulation bath, wherein the mass ratio of the pre-coagulation bath is dimethylacetamide: glycerol =5: and 5, the temperature of the coagulation bath is room temperature.
(3) Preparing an aramid fiber membrane: and (3) performing bidirectional stretching on the aramid fiber membrane precursor, and finally curing and drying to obtain the high-performance aramid fiber membrane. The longitudinal stretching multiple is 1.2 times, and the transverse stretching multiple is 1.1 times; the solidification condition is a coagulating bath with the mass proportion of the dimethylacetamide aqueous solution being 10 percent, and the temperature is room temperature; washing with water, and drying at 80 deg.C for 20min.
Various tests were performed on the prepared aramid membranes, and other test results are shown in table 1.
Example 2
An aramid fiber diaphragm and a preparation method and application thereof are disclosed, wherein the preparation method comprises the following steps:
(1) Preparing an aramid polymer dispersion liquid: according to the mass percentage, poly (m-phenylene isophthalamide) is dispersed in a dimethylacetamide solution at room temperature, and is continuously stirred, dispersed and filtered to obtain an aramid polymer dispersion liquid with the mass fraction of 20%;
(2) Preparing an aramid fiber membrane precursor: carrying out air-jet atomization treatment on the aramid polymer dispersion liquid in a mode of internal gas flow and external liquid flow, wherein the size of an atomization hole is 8.0mm, air is used as a gas source, and the gas pressure range is 1.2MPa; directly spraying the mixture on a collecting roller, wherein the linear distance between a nozzle and a receiving roller is 20cm; obtaining an aramid fiber membrane precursor after a pre-coagulation bath, wherein the mass ratio of the pre-coagulation bath is dimethylacetamide: glycerol =6: and 4, the temperature of the coagulation bath is room temperature.
(3) Preparing an aramid fiber membrane: and (3) performing bidirectional stretching on the aramid fiber membrane precursor, and finally curing and drying to obtain the high-performance aramid fiber membrane. The longitudinal stretching multiple is 1.5 times, and the transverse stretching multiple is 1.3 times; the solidification condition is a coagulating bath with the mass proportion of the dimethylacetamide aqueous solution being 20 percent, and the temperature is room temperature; washing with water, and drying at 150 deg.C for 10min.
Various tests were performed on the prepared aramid membranes, and other test results are shown in table 1.
Example 3
An aramid fiber diaphragm and a preparation method and application thereof, wherein the preparation method comprises the following steps:
(1) Preparing an aramid polymer dispersion liquid: dispersing poly (m-phenylene isophthalamide) in a dimethylacetamide solution at room temperature according to the mass percentage, and continuously stirring, dispersing and filtering to obtain an aramid polymer dispersion liquid with the mass fraction of 15.6%;
(2) Preparing an aramid fiber membrane precursor: carrying out air-jet atomization treatment on the aramid polymer dispersion liquid in a mode of internal gas flow and external liquid flow, wherein the size of an atomization hole is 4mm, air is used as a gas source, and the gas pressure range is 0.8MPa; directly spraying the mixture on a collecting roller, wherein the linear distance between a nozzle and a receiving roller is 35cm; obtaining an aramid fiber membrane precursor after a pre-coagulation bath, wherein the mass ratio of the pre-coagulation bath is dimethylacetamide: glycerol =7: and 3, setting the temperature of the coagulation bath to be room temperature.
(3) Preparing an aramid fiber membrane: and (3) performing bidirectional stretching on the aramid fiber membrane precursor, and finally curing and drying to obtain the high-performance aramid fiber membrane. The longitudinal stretching multiple is 2.2 times, and the transverse stretching multiple is 1.8 times; the solidification condition is a coagulating bath with the mass percentage of the dimethylacetamide aqueous solution being 15%, and the temperature is room temperature; washing with water, and drying at 200 deg.C for 5min.
Various tests were performed on the prepared aramid membranes, and other test results are shown in table 1.
Example 4
An aramid fiber diaphragm and a preparation method and application thereof are disclosed, wherein the preparation method comprises the following steps:
(1) Preparing an aramid polymer dispersion liquid: dispersing poly (m-phenylene isophthalamide) in a dimethylacetamide solution at room temperature according to the mass percentage, and continuously stirring, dispersing and filtering to obtain an aramid polymer dispersion liquid with the mass fraction of 12.1%;
(2) Preparing an aramid fiber membrane precursor: carrying out air-jet atomization treatment on the aramid polymer dispersion liquid in a mode of internal gas flow and external liquid flow, wherein the size of an atomization hole is 3.0mm, air is used as a gas source, and the gas pressure range is 0.9MPa; directly spraying the mixture on a collecting roller, wherein the linear distance between a nozzle and a receiving roller is 30cm; obtaining an aramid fiber membrane precursor after a pre-coagulation bath, wherein the mass ratio of the pre-coagulation bath is dimethylacetamide: glycerol =7.5:2.5, the temperature of the coagulation bath is room temperature.
(3) Preparing an aramid fiber membrane: and (3) performing bidirectional stretching on the aramid fiber membrane precursor, and finally curing and drying to obtain the high-performance aramid fiber membrane. The longitudinal stretching multiple is 3.5 times, and the transverse stretching multiple is 3.3 times; the solidification condition is that the mass percentage of the dimethylacetamide aqueous solution is 25 percent of the coagulating bath, and the temperature is room temperature; washing with water, and drying at 260 deg.C for 1min.
Various tests were performed on the prepared aramid membranes, and other test results are shown in table 1.
Example 5
The present embodiment is different from embodiment 3 in that: the concentration of the aramid polymer dispersion liquid in the step (1) is 10.3.
Example 6
The present embodiment is different from embodiment 3 in that: in the step (2), the longitudinal stretching multiple is 3.0 times, and the transverse stretching multiple is 2.5 times.
Comparative example 1
An aramid fiber diaphragm and a preparation method and application thereof, wherein the preparation method comprises the following steps:
(1) Preparing an aramid polymer dispersion liquid: dispersing polyisophthaloyl metaphenylene diamine in a dimethylacetamide solution at room temperature according to the mass percent, and continuously stirring, dispersing and filtering to obtain an aramid polymer dispersion liquid with the mass fraction of 12.1%;
(2) Preparing an aramid fiber membrane precursor: carrying out air-jet atomization treatment on the aramid polymer dispersion liquid in a mode of internal gas flow and external liquid flow, wherein the size of an atomization hole is 3.0mm, air is used as a gas source, and the gas pressure range is 0.9MPa; directly spraying the powder into a coagulating bath, wherein the straight line distance between a nozzle and the surface of the coagulating bath is 30cm, and the mass ratio of the coagulating bath is that dimethyl acetamide: glycerol =7.5: and 2.5, fully washing the aramid micro-nanofibers after high-speed shearing at 2000r at the solidification bath temperature of room temperature to prepare the aramid micro-nanofibers.
(3) Preparing an aramid fiber membrane: and (3) forming the aramid fiber micro-nano fiber into a film by adopting a suction filtration method, wherein the drying condition is 260 ℃ for 1min.
Various tests were performed on the prepared aramid membranes, and other test results are shown in table 1. The comparison shows that the aramid micro-nanofibers directly obtained by the jet method can also be used for preparing aramid films, but the aramid micro-nanofibers are small in size and large in specific surface area, and a large amount of integrated films are formed after suction filtration, lamination and assembly, but aramid polymer molecular chains in the aramid micro-nanofibers prepared by the method are not fully stretched and oriented, so that the strength of the obtained aramid films is lower than that of the aramid films prepared by the method.
Comparative example 2
An aramid fiber diaphragm and a preparation method and application thereof, wherein the preparation method comprises the following steps:
(1) Preparing an aramid polymer dispersion liquid: dispersing polyisophthaloyl metaphenylene diamine in a dimethylacetamide solution at room temperature according to the mass percent, and continuously stirring, dispersing and filtering to obtain an aramid polymer dispersion liquid with the mass fraction of 12.1%;
(2) Preparing an aramid fiber membrane precursor: carrying out air-jet atomization treatment on the aramid polymer dispersion liquid in a mode of internal gas flow and external liquid flow, wherein the size of an atomization hole is 3.0mm, air is used as a gas source, and the gas pressure range is 0.9MPa; directly spraying the powder into a coagulating bath, wherein the straight line distance between a nozzle and the surface of the coagulating bath is 30cm, and the mass ratio of the coagulating bath is that dimethyl acetamide: glycerol =7.5: and 2.5, fully washing the aramid micro-nanofibers after high-speed shearing at 2000r at the coagulation bath temperature of room temperature to prepare the aramid micro-nanofibers.
(3) Preparing an aramid fiber membrane: forming a film on the aramid micro-nano fiber by adopting a suction filtration method, wherein the longitudinal stretching multiple is 1.3 times, and the transverse stretching multiple is 1.3 times; the drying condition was 260 ℃ for 1min.
Various tests were performed on the prepared aramid membranes, and other test results are shown in table 1. In the comparative example 2, the aramid micro-nanofibers are prepared by curing at first, the chemical inertness of the fiber surface is realized, and the aramid micro-nanofibers are simply arranged in a staggered manner in the suction filtration process, so that the stretching rate of the aramid film is limited, and the high-rate stretching is difficult to perform, and therefore, the bidirectional 1.3-time stretching is selected for the comparative example.
TABLE 1 summary of test results for high performance aramid fiber membranes
As can be seen from table 1, the aramid fiber membrane prepared by the invention has significantly improved mechanical properties such as tensile strength and piercing strength, can effectively avoid safety accidents such as short circuit, combustion and even explosion caused by fracture of the membrane when the membrane is impacted by heavy objects and extruded, and improves the safety of the membrane. The high-performance aramid fiber membrane has obvious application effect and wide application prospect in the field of high-performance aramid fiber paper.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. The preparation method of the aramid fiber membrane is characterized by comprising the following steps of:
(1) Preparing an aramid polymer dispersion liquid: mixing an aramid polymer with a dispersion solvent, and stirring to obtain an aramid polymer dispersion liquid with the mass fraction of 0.1-20%;
(2) Preparing an aramid fiber membrane precursor: after gas-jet atomization treatment, directly spraying the aramid polymer dispersion liquid on a collecting roller, and obtaining an aramid diaphragm precursor after pre-coagulation bath;
(3) Preparing an aramid fiber membrane: and (3) performing bidirectional stretching on the aramid fiber membrane precursor, and finally curing and drying to obtain the aramid fiber membrane.
2. The method of claim 1, wherein: in the step (1), the concentration of the aramid polymer dispersion liquid is 10-16%, and the dispersion solvent is one or more of dimethylacetamide, dimethylformamide, dimethyl sulfoxide and acetone.
3. The production method according to claim 1, characterized in that: the aramid polymer in the step (1) can be one or more of poly (m-phenylene isophthalamide), poly (p-phenylene terephthalamide) and polyamide polymer containing a heterocyclic ring mechanism.
4. The method of claim 1, wherein: the gas-jet atomization treatment conditions in the step (2) are as follows: the aperture range of the atomization hole is 0.1-8.0 mm, and the pressure range of the air compressor is 0.1-1.2 MPa; the collecting roller is a rotating roller wrapped by an endless mesh cloth, and the linear distance between the nozzle and the collecting roller is 20-35cm.
5. The production method according to any one of claims 1 to 4, characterized in that: the pre-solidification condition in the step (2): the pre-coagulation bath is a mixed solution of dimethylacetamide and a curing agent, the curing agent is one or more of glycerol, ethanol and water, and the mass ratio of dimethylacetamide to the curing agent is (5-9): (1-5) and the temperature is 0-50 ℃.
6. The method of claim 5, wherein: the curing conditions in the step (3) are as follows: the coagulating bath is a dimethyl acetamide water solution with the mass fraction of 10-90%, and the temperature is 0-50 ℃.
7. The method of manufacturing according to claim 6, characterized in that: the bidirectional stretching in the step (3) is transverse stretching by 1.5-5.0 times and longitudinal stretching by 1.3-4.0 times; the drying condition is that the temperature is 80-300 ℃ and the time is 0.1-60 min; the stirring condition in the step (1) is magnetic rotor stirring or mechanical blade type stirring dispersion, the rotating speed is 50-1000 rpm, and the stirring time is 1-60 min.
8. The aramid membrane prepared by the method of any one of claims 1 to 7, characterized in that: the thickness is 10-21 μm, the porosity is 80-95%, the liquid absorption rate is 200-450%, the longitudinal tensile strength is 130-550MPa, the transverse tensile strength is 120-350MPa, and the puncture strength is 200-550g/mil.
9. The aramid membrane of claim 8, characterized in that: the thickness is 12-18 μm, the porosity is 82-92%, the liquid absorption rate is 240-400%, the longitudinal tensile strength is 200-500MPa, the transverse tensile strength is 200-320MPa, and the puncture strength is 300-500g/mil.
10. The aramid separator of claim 9 is used in a lithium ion battery.
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