CN115275504B - 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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- CN115275504B CN115275504B CN202210740222.1A CN202210740222A CN115275504B CN 115275504 B CN115275504 B CN 115275504B CN 202210740222 A CN202210740222 A CN 202210740222A CN 115275504 B CN115275504 B CN 115275504B
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- 229920006231 aramid fiber Polymers 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title claims abstract description 57
- 239000004760 aramid Substances 0.000 claims abstract description 83
- 229920003235 aromatic polyamide Polymers 0.000 claims abstract description 82
- 238000000034 method Methods 0.000 claims abstract description 35
- 239000007788 liquid Substances 0.000 claims abstract description 34
- 239000004815 dispersion polymer Substances 0.000 claims abstract description 29
- 239000002243 precursor Substances 0.000 claims abstract description 24
- 230000001112 coagulating effect Effects 0.000 claims abstract description 19
- 238000000889 atomisation Methods 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 16
- 229920000642 polymer Polymers 0.000 claims abstract description 16
- 238000011282 treatment Methods 0.000 claims abstract description 14
- 238000005507 spraying Methods 0.000 claims abstract description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 24
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 24
- 239000006185 dispersion Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- YCGKJPVUGMBDDS-UHFFFAOYSA-N 3-(6-azabicyclo[3.1.1]hepta-1(7),2,4-triene-6-carbonyl)benzamide Chemical compound NC(=O)C1=CC=CC(C(=O)N2C=3C=C2C=CC=3)=C1 YCGKJPVUGMBDDS-UHFFFAOYSA-N 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 238000010521 absorption reaction Methods 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- -1 poly p-phenylene terephthalamide Polymers 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000007711 solidification Methods 0.000 claims description 4
- 230000008023 solidification Effects 0.000 claims description 4
- 239000004952 Polyamide Substances 0.000 claims description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N dimethylacetone Natural products CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 claims description 2
- 239000004744 fabric Substances 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- 230000007246 mechanism Effects 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 7
- 150000002500 ions Chemical class 0.000 abstract description 4
- 238000010924 continuous production Methods 0.000 abstract description 2
- 230000035515 penetration Effects 0.000 abstract description 2
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- 238000012360 testing method Methods 0.000 description 15
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- 238000005345 coagulation Methods 0.000 description 12
- 230000015271 coagulation Effects 0.000 description 12
- 239000002121 nanofiber Substances 0.000 description 9
- 238000000967 suction filtration Methods 0.000 description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 229910052744 lithium Inorganic materials 0.000 description 8
- 238000010041 electrostatic spinning Methods 0.000 description 7
- 238000001125 extrusion Methods 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
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- 239000011248 coating agent Substances 0.000 description 4
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- 230000000694 effects Effects 0.000 description 4
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- 239000003085 diluting agent Substances 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000002657 fibrous material Substances 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000001728 nano-filtration Methods 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 238000004880 explosion Methods 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- 229920006253 high performance fiber Polymers 0.000 description 1
- 238000005213 imbibition Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
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- 239000007791 liquid phase Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000889 poly(m-phenylene isophthalamide) Polymers 0.000 description 1
- 229920003366 poly(p-phenylene terephthalamide) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000002145 thermally induced phase separation Methods 0.000 description 1
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
Landscapes
- 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 diaphragms, and discloses an aramid fiber diaphragm, a preparation method and application thereof. The preparation method of the aramid fiber diaphragm comprises the following steps: (1) preparation of an aramid polymer dispersion: mixing an aramid polymer with a dispersing solvent, and stirring to obtain an aramid polymer dispersion; (2) preparation of aramid separator precursor: the aramid fiber polymer dispersion liquid is directly sprayed on a collecting roller after being subjected to gas spraying atomization treatment, and an aramid fiber diaphragm precursor is obtained after a pre-coagulating bath; (3) preparation of an aramid fiber diaphragm: and (3) biaxially stretching the aramid fiber diaphragm precursor, and finally curing and drying to obtain the aramid fiber diaphragm. The preparation method is simple in operation, convenient and easy to implement, has universality in process, high production efficiency and good quality, is suitable for industrial continuous production, and the prepared diaphragm has a unique net structure, is larger in specific surface area and high in porosity and ion penetration rate, improves the electrochemical performance and the use safety performance of the aramid diaphragm, and can be applied to the field of lithium ion batteries.
Description
Technical Field
The invention relates to the technical field of aramid fiber diaphragms, in particular to an aramid fiber diaphragm and a preparation method and application thereof.
Background
The diaphragm is an important component of the lithium ion battery, and has the main function of avoiding short circuit caused by direct contact of the anode and the cathode, and has an important function of improving the comprehensive performance of the lithium ion battery. Currently, commercial lithium ion battery separators are mainly polyolefin microporous films, including polyethylene, polypropylene, and multi-layer films compounded by various materials. The polyolefin diaphragm has low price, excellent mechanical property and insulating property, but has obvious defects of obvious shrinkage at high temperature, poor electrolyte wettability, low porosity and the like, and can influence the safety performance and electrochemical performance of the battery. In order to make up for the deficiencies of polyolefin separators, different types of composite separators have been developed.
At present, the production of the diaphragm is mostly dry method, wet method, electrostatic spinning and the like. The dry method, that is, the melt extrusion stretching method, is a process method for preparing microporous membrane by the processes of melt extrusion casting, spherulitic culture, stretching into blank, heat setting and the like. Wet process, i.e. thermally induced phase separation or non-solvent induced phase separation, is caused by the decrease of polymer dissolution capacity and the induced liquid-liquid or solid-liquid phase separation of polymer crystallization factor, the polymer phase and the diluent phase form an interphase structure, and then the diluent is removed by the extractant, the space occupied by the original diluent in the mixture becomes pores, and finally a coherent microporous structure is formed. The wet method has its own advantages over the dry method, but the disadvantages are also obvious, the pore diameter is difficult to control, and a dense cortex and a closed pore are easy to generate. The electrostatic spinning method has low efficiency, is not suitable for industrial production, has lower strength of the prepared membrane and is influenced by various factors, and the membrane is difficult to control.
Aromatic polyamide (aramid) materials are widely applied in the field of high-performance fibers, and a large number of benzene rings and amide bonds in the molecular structure of the aromatic polyamide materials endow the aromatic polyamide materials with excellent heat resistance and mechanical properties. The aramid fiber-based battery diaphragm has the advantages of being capable of maintaining dimensional stability at high temperature, strong in external force puncture resistance and the like, and becomes a hot spot for novel power supply technology research in recent years. The existing method for preparing the diaphragm by using the aramid fiber material is usually an electrostatic spinning method, a suction filtration method, a coating method, an extrusion method and the like, and as disclosed in Chinese patent 201810385938.8, the lithium electronic diaphragm is successfully prepared by using an electrostatic spinning method by taking inorganic nano ceramic particle blending modified para-aramid fiber polymer as a raw material; the Chinese patent 202010069898.3, 202110780179.7 and 202110780799.0 adopt a strategy of 'from bottom to top', firstly, carrying out a series of chemical treatments on the aramid fiber to obtain micro-nano grade aramid fiber, and then carrying out suction filtration to prepare an aramid film material; for another example, chinese patent nos. 201911039748.1 and 202210174186.7 disclose that an aramid separator is obtained by coating a coating of an aramid polymer or a mixed inorganic-organic polymer on the surface of a base film; chinese patent 202010339804.X discloses that meta-aramid fiber membrane is obtained by extruding, transversely stretching, vertically stretching, extracting and solidifying meta-aramid fiber slurry.
In summary, the preparation methods of the aramid fiber diaphragm reported in the prior art include an electrostatic spinning method, a suction filtration method, a coating method, an extrusion method and the like. Although the aramid fiber diaphragm material can be obtained by the above disclosed technology, the obvious disadvantages exist: the electrostatic spinning method has low yield and large industrial production difficulty; the aramid micro-nanofiber membrane is prepared by a suction filtration method, although the strength is high, a compact structure is easy to form, and the obtained nano-filtration membrane is basically a nano-filtration membrane, if high porosity is to be realized, the technical difficulty is high; the coating method is to coat the treated aramid polymer on the surface of the existing film material, and due to the unique chemical composition of the aramid material, the combination property of the aramid coating and the base film is determined to seriously influence the development and application of the coating film; the conventional extrusion stretching film is easy to break in the process, the structure is uneven, and the finally manufactured diaphragm has smaller brittleness and strength, and is not beneficial to improving the safety performance of the lithium battery when being applied to the diaphragm. The technical defects limit the industrialization progress and the application range of the aramid fiber diaphragm.
Therefore, the quick and effective preparation technology of the high-performance aramid fiber diaphragm is found to have important significance for realizing functionalization and high-performance of the aramid fiber diaphragm and diversified application of the aramid fiber diaphragm in various fields of reinforcing materials, battery diaphragms, electric insulation nanometer paper, flexible electronic devices, adsorption filter media and the like.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the primary purpose of the invention is to provide an aramid fiber diaphragm.
The invention also aims to provide a high-efficiency preparation method of the aramid fiber diaphragm.
Another object of the present invention is to provide an application of the above-mentioned aramid separator.
The aim of the invention is achieved by the following technical scheme:
the preparation method of the aramid fiber diaphragm comprises the following steps:
(1) Preparation of an aramid polymer dispersion: 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) Preparation of an aramid separator precursor: the aramid fiber polymer dispersion liquid is directly sprayed on a collecting roller after being subjected to gas spraying atomization treatment, and an aramid fiber diaphragm precursor is obtained after a pre-coagulating bath;
(3) Preparation of an aramid fiber diaphragm: and (3) biaxially stretching the aramid fiber diaphragm precursor, and finally curing and drying to obtain the aramid fiber diaphragm.
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 the step (1) may be one or more of poly (m-phenylene isophthalamide), poly (p-phenylene terephthalamide), and polyamide polymer containing a heterocyclic mechanism.
Preferably, the air-spraying atomization treatment condition in the step (2) is as follows: the spinneret orifice is an inner air inlet hole and an outer liquid inlet hole, 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 air, nitrogen, argon and other single gas or mixed gas.
Preferably, the collecting roller in the step (2) is a rotating roller wrapped by endless mesh cloth, and the linear distance between the nozzle and the collecting roller is 20-35cm; the roller material can be nylon, stainless steel, ceramic or other applicable materials; the endless mesh material can be polytetrafluoroethylene, nylon or other suitable materials.
Preferably, the pre-solidification conditions of step (2): the pre-coagulating 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 described in step (3) are: the coagulating bath is a dimethylacetamide aqueous solution with the mass fraction of 10-90% and the temperature of 0-50 ℃.
Preferably, the biaxial stretching in the step (3) is specifically 1.5-5.0 times of transverse stretching and 1.3-4.0 times of longitudinal stretching, more preferably 1.8-3.5 times of transverse stretching and 2.0-3.8 times of longitudinal stretching; 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 blade stirring and dispersing, the rotating speed is 50-1000 rpm, and the stirring time is 1-60 min.
Preferably, 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.
Preferably, 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.
The aramid fiber diaphragm and the preparation method and application thereof have the advantages of simple operation, convenience and practicability, universality, high production efficiency and good quality compared with the conventional preparation method at present, suitability for industrial continuous production, unique net-shaped structure of the prepared diaphragm, larger specific surface area, high porosity and ion penetration rate, and capability of improving 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 air inlet flow to prepare the size-controllable and adjustable high-performance aramid fiber diaphragm with the average pore diameter smaller than 1 mu m. The liquid material is dispersed and dispersed by the compressed gas flowing at high speed, the aramid diaphragm precursor is collected by a collecting roller, and is initially solidified by double diffusion in a pre-solidification bath so as to meet the strength requirement of the subsequent stretching operation. After longitudinal and transverse biaxial stretching, the pore structure of the aramid fiber diaphragm is further improved, the porosity and the mechanical property are obviously improved, and finally the high-performance aramid fiber diaphragm material is obtained through solidification and drying. The prepared aramid fiber diaphragm has a unique net structure, has larger specific surface area, can obviously improve the bonding strength of the fiber interface in the aramid fiber diaphragm, effectively improves the mechanical strength and the electrochemical performance of the aramid fiber diaphragm, and can be widely applied to the field of novel diaphragm materials. The ideal mechanical strength and the piercing strength can avoid the membrane from being pierced and short-circuited 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 holding capacity, can effectively reduce the interface resistance of the lithium battery, optimize the electrical performance of the lithium battery, prolong the service life of the lithium battery and the like.
(2) Compared with the prior reported preparation methods of the aramid fiber diaphragm, 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 is easy to realize industrial production; the pore structure of the diaphragm is adjustable and controllable, and the electrochemical performance requirement of the diaphragm is met; the membrane is prepared by one-step molding, the interior of the membrane is composed of micro-nano-scale aramid fibers, the micro-nano-scale aramid fibers have finer diameter, higher specific surface area and chemical activity than the conventional aramid chopped fibers and other raw materials, after the membrane is stretched vertically and horizontally, residual stress is eliminated, molecular chains or crystals of the membrane are orderly arranged along the plane direction, the orientation structure of macromolecules is fixed in a tightening or loosening state, fiber interfaces are tightly combined under the action of tension, the technical problems that the membrane is brittle and easy to break in the conventional method are overcome, and the mechanical strength and the pore structure are further improved. The technical scheme further expands the industrialization progress and application range of the aramid fiber diaphragm.
(3) The efficient preparation technology of the aramid fiber diaphragm can also increase the application of functionalization and high performance by adding functional elements into the aramid fiber polymer. Has important significance for the cross diversified application of the aramid fiber material in various fields such as battery diaphragms, electric insulation nanometer paper, flexible electronic devices, adsorption filter media and the like.
Drawings
FIG. 1 is a schematic process diagram of a high-performance aramid separator.
Fig. 2 is an SEM image of the surface of the prepared high-performance aramid separator.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but embodiments of the present invention are not limited thereto.
The starting materials in the preparation process according to the invention are commercially available or can 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 to this mode. In this example, aramid polymer was supplied by the materials technology limited of the state Long Bang, and atomizer was made by laboratory, but the required raw materials and equipment acquisition was not limited to the above. The stretching direction defines: the stretching direction is parallel to the film moving direction and is longitudinal stretching, and the stretching direction is perpendicular to the film moving direction 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 specification in GB/T29627.2-2013; moisture was 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 a circular diaphragm with the diameter of 18mm into lithium hexafluorophosphate electrolyte for soaking for 4 hours, and weighing the soaked mass. Liquid absorption = [ (M) 1 -M 0 )/M 0 ]X 100; wherein M is 0 And M 1 The mass of the diaphragm before and after the diaphragm is soaked in electrolyte is g; puncture resistance is measured with reference to ASTM F1306-90; puncture strength was determined with reference to GB/T21302-2007; porosity was measured using n-butanol imbibition: soaking a circular diaphragm with the diameter of 18mm in n-butanol solution for 4 hours, weighing the soaked mass, and calculating the porosity = [ (M) by adopting a formula 1 -M 0 )/ρV]×100，M 0 And M 1 The mass of the membrane before and after soaking n-butanol is g; ρ is the density of n-butanol, 0.81g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the V is the volume of the diaphragm, in cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The ion conductivity is calculated by measuring the bulk impedance of the analog cell, where the ion conductivity=l/(r×a) formula: l is the thickness of the separator; a is the effective contact area of the diaphragm, R is the body resistance (omega) of the diaphragm; the diaphragm soaked with electrolyte and the anode and the cathode are assembled into a CR2025 button battery in a glove box according to the cycle performance of the battery, and the battery is charged and discharged for 100 times at a constant current density of 0.5 ℃, and the voltage ranges are as follows: the capacity retention (%) was calculated by dividing the capacity after 100 test cycles by the capacity of the first test, from 2.75V to 4.2V.
Example 1
An aramid fiber diaphragm and a preparation method and application thereof, wherein the preparation method is as follows:
(1) Preparation of an aramid polymer dispersion: according to the mass percentage, the poly-m-phenylene isophthalamide is dispersed in a dimethylacetamide solution at room temperature, and after continuous stirring, dispersion and filtration, the aramid polymer dispersion liquid with the mass percentage of 0.1 percent is obtained;
(2) Preparation of an aramid separator precursor: carrying out air-jet atomization treatment on the aramid polymer dispersion liquid in an inner air flow and outer liquid inlet flow mode, wherein the size of an atomization hole is 1.0mm, air is used as an air source, and the air pressure range is 0.3MPa; directly spraying on the collecting roller, wherein the linear distance between the nozzle and the receiving roller is 30cm; obtaining an aramid fiber diaphragm precursor after a pre-coagulation bath, wherein the mass ratio of the pre-coagulation bath is dimethylacetamide: glycerol = 5:5, the coagulation bath temperature is room temperature.
(3) Preparation of an aramid fiber diaphragm: and (3) biaxially stretching the aramid fiber diaphragm precursor, and finally curing and drying to obtain the high-performance aramid fiber diaphragm. The longitudinal stretching multiple is 1.2 times, and the transverse stretching multiple is 1.1 times; the curing condition is a coagulating bath with the mass fraction of dimethylacetamide aqueous solution of 10 percent and the temperature is room temperature; washing with water, and drying at 80deg.C for 20min.
Each test was performed on the prepared aramid separator, and other test results are shown in table 1.
Example 2
An aramid fiber diaphragm and a preparation method and application thereof, wherein the preparation method is as follows:
(1) Preparation of an aramid polymer dispersion: according to the mass percentage, the poly-m-phenylene isophthalamide is dispersed in a dimethylacetamide solution at room temperature, and after continuous stirring, dispersion and filtration, an aramid polymer dispersion liquid with the mass percentage of 20% is obtained;
(2) Preparation of an aramid separator precursor: carrying out air-jet atomization treatment on the aramid polymer dispersion liquid in an inner air flow and outer liquid inlet flow mode, wherein the size of an atomization hole is 8.0mm, air is used as an air source, and the air pressure range is 1.2MPa; directly spraying on the collecting roller, wherein the linear distance between the nozzle and the receiving roller is 20cm; obtaining an aramid fiber diaphragm precursor after a pre-coagulation bath, wherein the mass ratio of the pre-coagulation bath is dimethylacetamide: glycerol = 6:4, the coagulation bath temperature is room temperature.
(3) Preparation of an aramid fiber diaphragm: and (3) biaxially stretching the aramid fiber diaphragm precursor, and finally curing and drying to obtain the high-performance aramid fiber diaphragm. The longitudinal stretching multiple is 1.5 times, and the transverse stretching multiple is 1.3 times; the curing condition is a coagulating bath with the mass fraction of the dimethylacetamide aqueous solution of 20 percent and the temperature is room temperature; washing with water, and drying at 150deg.C for 10min.
Each test was performed on the prepared aramid separator, 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 is as follows:
(1) Preparation of an aramid polymer dispersion: according to the mass percentage, the poly-m-phenylene isophthalamide is dispersed in a dimethylacetamide solution at room temperature, and after continuous stirring, dispersion and filtration, an aramid polymer dispersion liquid with the mass percentage of 15.6% is obtained;
(2) Preparation of an aramid separator precursor: carrying out air-jet atomization treatment on the aramid polymer dispersion liquid in an inner air flow and outer liquid inlet flow mode, wherein the size of an atomization hole is 4mm, air is an air source, and the air pressure range is 0.8MPa; directly spraying on the collecting roller, wherein the linear distance between the nozzle and the receiving roller is 35cm; obtaining an aramid fiber diaphragm precursor after a pre-coagulation bath, wherein the mass ratio of the pre-coagulation bath is dimethylacetamide: glycerol = 7:3, the coagulation bath temperature is room temperature.
(3) Preparation of an aramid fiber diaphragm: and (3) biaxially stretching the aramid fiber diaphragm precursor, and finally curing and drying to obtain the high-performance aramid fiber diaphragm. The longitudinal stretching multiple is 2.2 times and the transverse stretching multiple is 1.8 times; the curing condition is a coagulating bath with the mass fraction of dimethylacetamide aqueous solution of 15%, and the temperature is room temperature; washing with water, and drying at 200deg.C for 5min.
Each test was performed on the prepared aramid separator, and other test results are shown in table 1.
Example 4
An aramid fiber diaphragm and a preparation method and application thereof, wherein the preparation method is as follows:
(1) Preparation of an aramid polymer dispersion: according to the mass percentage, the poly-m-phenylene isophthalamide is dispersed in a dimethylacetamide solution at room temperature, and after continuous stirring, dispersion and filtration, an aramid polymer dispersion liquid with the mass percentage of 12.1% is obtained;
(2) Preparation of an aramid separator precursor: carrying out air-jet atomization treatment on the aramid polymer dispersion liquid in an inner air flow and outer liquid inlet flow mode, wherein the size of an atomization hole is 3.0mm, air is used as an air source, and the air pressure range is 0.9MPa; directly spraying on the collecting roller, wherein the linear distance between the nozzle and the receiving roller is 30cm; obtaining an aramid fiber diaphragm precursor after a pre-coagulation bath, wherein the mass ratio of the pre-coagulation bath is dimethylacetamide: glycerol = 7.5:2.5, the coagulation bath temperature is room temperature.
(3) Preparation of an aramid fiber diaphragm: and (3) biaxially stretching the aramid fiber diaphragm precursor, and finally curing and drying to obtain the high-performance aramid fiber diaphragm. The longitudinal stretching multiple is 3.5 times, and the transverse stretching multiple is 3.3 times; the curing condition is a coagulating bath with the mass fraction of dimethylacetamide aqueous solution of 25%, and the temperature is room temperature; washing with water, and drying at 260 deg.C for 1min.
Each test was performed on the prepared aramid separator, and other test results are shown in table 1.
Example 5
This embodiment differs from embodiment 3 in that: the concentration of the aramid polymer dispersion in the step (1) was 10.3.
Example 6
This embodiment differs from embodiment 3 in that: the longitudinal stretching multiple in the step (2) 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 is as follows:
(1) Preparation of an aramid polymer dispersion: according to the mass percentage, the poly-m-phenylene isophthalamide is dispersed in a dimethylacetamide solution at room temperature, and after continuous stirring, dispersion and filtration, an aramid polymer dispersion liquid with the mass percentage of 12.1% is obtained;
(2) Preparation of an aramid separator precursor: carrying out air-jet atomization treatment on the aramid polymer dispersion liquid in an inner air flow and outer liquid inlet flow mode, wherein the size of an atomization hole is 3.0mm, air is used as an air source, and the air pressure range is 0.9MPa; directly spraying the water into the coagulating bath, wherein the linear distance between the nozzle and the liquid level of the coagulating bath is 30cm, and the mass ratio of the coagulating bath is dimethylacetamide: glycerol = 7.5:2.5, the coagulating bath temperature is room temperature, and the aramid micro-nano fiber is prepared by fully washing after 2000r high-speed shearing.
(3) Preparation of an aramid fiber diaphragm: and (3) forming a film on the aramid micro-nano fiber by adopting a suction filtration method, wherein the drying condition is 260 ℃ for 1min.
Each test was performed on the prepared aramid separator, and other test results are shown in table 1. Compared with the prior art, the aramid micro-nano fiber directly obtained by adopting the spraying method can be used for preparing the aramid film, but because the aramid micro-nano fiber has small size and large specific surface area, and is gathered into a large amount of film after being assembled by suction filtration layers, the molecular chains of the aramid polymer in the aramid micro-nano fiber prepared by the method are not sufficiently stretched and oriented, so that the strength of the obtained aramid film is lower than that of the aramid film prepared by the method.
Comparative example 2
An aramid fiber diaphragm and a preparation method and application thereof, wherein the preparation method is as follows:
(1) Preparation of an aramid polymer dispersion: according to the mass percentage, the poly-m-phenylene isophthalamide is dispersed in a dimethylacetamide solution at room temperature, and after continuous stirring, dispersion and filtration, an aramid polymer dispersion liquid with the mass percentage of 12.1% is obtained;
(2) Preparation of an aramid separator precursor: carrying out air-jet atomization treatment on the aramid polymer dispersion liquid in an inner air flow and outer liquid inlet flow mode, wherein the size of an atomization hole is 3.0mm, air is used as an air source, and the air pressure range is 0.9MPa; directly spraying the water into the coagulating bath, wherein the linear distance between the nozzle and the liquid level of the coagulating bath is 30cm, and the mass ratio of the coagulating bath is dimethylacetamide: glycerol = 7.5:2.5, the coagulating bath temperature is room temperature, and the aramid micro-nano fiber is prepared by fully washing after 2000r high-speed shearing.
(3) Preparation of an aramid fiber diaphragm: 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 is 260 ℃ for 1min.
Each test was performed on the prepared aramid separator, and other test results are shown in table 1. In comparative example 2, the aramid micro-nano fibers are prepared by curing, the surfaces of the fibers are chemically inert, and the fibers are simply staggered in the suction filtration process, so that the stretching multiplying power of the aramid film is limited, and high-multiplying-power stretching is difficult to carry out, and the comparative example adopts bidirectional stretching of 1.3 times.
TABLE 1 high Performance aramid diaphragm test results summary table
As can be seen from Table 1, the mechanical properties such as tensile strength and puncture strength of the aramid fiber diaphragm prepared by the invention are obviously improved, and the safety accidents such as short circuit, combustion, even explosion and the like caused by rupture of the diaphragm when the diaphragm is subjected to the safety problems such as heavy impact and extrusion can be effectively avoided, so that the safety of the diaphragm is improved. The high-performance aramid fiber diaphragm has remarkable application effect and wide application prospect in the field of high-performance aramid fiber paper.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (9)
1. The preparation method of the aramid fiber diaphragm is characterized by comprising the following steps of:
(1) Preparation of an aramid polymer dispersion: mixing an aramid polymer with a dispersing solvent, and stirring to obtain an aramid polymer dispersion liquid with the mass fraction of 10-16%;
(2) Preparation of an aramid separator precursor: the aramid fiber polymer dispersion liquid is directly sprayed on a collecting roller after being subjected to gas spraying atomization treatment, and an aramid fiber diaphragm precursor is obtained after a pre-coagulating bath;
(3) Preparation of an aramid fiber diaphragm: biaxially stretching the aramid fiber diaphragm precursor, and finally curing and drying to obtain an aramid fiber diaphragm;
the conditions of the air spraying atomization treatment 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 straight line distance between the nozzle and the collecting roller is 20-35cm;
the pre-solidification conditions of step (2): the pre-coagulating bath is a mixed solution of dimethylacetamide and a curing agent, the curing agent is one or more of glycerol, ethanol and water, wherein the mass ratio of the dimethylacetamide to the curing agent is (5-9): (1-5), the temperature is 0-50 ℃;
the biaxial stretching in the step (3) is specifically 1.5-5.0 times of transverse stretching and 1.3-4.0 times of longitudinal stretching.
2. The method of manufacturing according to claim 1, characterized in that: the dispersion solvent in the step (1) is one or more of dimethylacetamide, dimethylformamide, dimethyl sulfoxide and acetone.
3. The method of manufacturing according to claim 1, characterized in that: the aramid polymer in the step (1) is one or more of poly m-phenylene isophthalamide, poly p-phenylene terephthalamide and polyamide polymer containing heterocyclic mechanism.
4. The method of manufacturing according to claim 1, characterized in that: the collecting roller in the step (2) is a rotating roller wrapped by endless mesh cloth.
5. The preparation method according to any one of claims 1 to 4, characterized in that: the curing conditions of step (3) are: the coagulating bath is a dimethylacetamide aqueous solution with the mass fraction of 10-90% and the temperature of 0-50 ℃.
6. The preparation method according to any one of claims 1 to 4, characterized in that: the drying condition in the step (3) 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 stirring and dispersing, the rotating speed is 50-1000 rpm, and the stirring time is 1-60 min.
7. The aramid separator prepared by the method of any one of claims 1 to 6, characterized in that: the thickness is 10-21 mu m, 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.
8. The aramid separator as claimed in claim 7, wherein: the thickness is 12-18 mu m, 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.
9. Use of the aramid separator of claim 7 or 8 in a lithium ion battery.
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