CN116315456B - Five-layer co-extrusion lithium battery microporous diaphragm and preparation method thereof - Google Patents
Five-layer co-extrusion lithium battery microporous diaphragm and preparation method thereof Download PDFInfo
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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
- H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- 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
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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
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
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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
- H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
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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
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
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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
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/491—Porosity
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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
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/494—Tensile strength
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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
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/497—Ionic conductivity
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- 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
Abstract
The invention relates to the field of lithium battery diaphragms, and discloses a five-layer co-extrusion lithium battery microporous diaphragm and a preparation method thereof, wherein the structure of the five-layer co-extrusion lithium battery microporous diaphragm is a symmetrical structure of A/B/C/B/A; the layer A raw material comprises hydroxyethyl methacrylate grafted polypropylene; the B layer of raw materials comprise homopolypropylene and modified polyether-ether-ketone micropowder; the C layer raw material comprises isotactic polybutene-1 and propylene butene copolymer; the preparation method of the modified polyether-ether-ketone micropowder comprises the following steps: sulfonation modification is carried out on polyether-ether-ketone micro powder by concentrated sulfuric acid, and then NH is carried out in a volume ratio of 1-2:1 3 And (3) carrying out low-temperature plasma treatment on the sulfonated modified micro powder in Ar atmosphere. The microporous membrane provided by the invention has the advantages that through the cooperation of the five layers of structures, the capacity of the membrane for closed pore self-closing and high temperature resistance at a lower temperature are improved, and the mechanical property of the membrane is improved; and the liquid absorption and retention performance of the diaphragm and the adhesion between the diaphragm and the anode are greatly improved.
Description
Technical Field
The invention relates to the technical field of lithium battery diaphragms, in particular to a five-layer co-extrusion lithium battery microporous diaphragm and a preparation method thereof.
Background
The battery separator is used as a main component of a liquid lithium ion battery and plays a vital role in the battery. The diaphragm material is a polymer material with insulating property, and the main body of the diaphragm material is an insulating film with a large number of micropore structures between the anode and the cathode of the lithium battery. The diaphragm has two main functions: firstly, isolating the positive electrode and the negative electrode in the battery, preventing the two electrodes from being in direct contact and short circuit, and simultaneously needing to be thin to the greatest extent on the premise of ensuring safety so as to reduce the distance between the two electrodes and reduce the internal resistance of the battery; secondly, the electrolyte can be stored and kept enough, and the micropore structure allows Li in the electrolyte to be stored and kept + Freely pass through, realize Li + And rapidly transmitting between the anode and the cathode. Therefore, the performance of the battery separator can directly influence the capacity, the cycle performance, the charge-discharge current density and other key performances of the lithium battery.
Therefore, in order to realize the barrier capability of the separator, the separator is required to have high temperature resistance, and the separator is not fused to cause direct contact between the positive electrode and the negative electrode when the battery reaction is out of control. Meanwhile, in the initial stage of the out-of-control reaction of the battery, if the diaphragm can realize closed-pore self-closing, the further occurrence of charge and discharge reaction can be timely prevented. In addition, the liquid absorption and retention capacity of the diaphragm plays a very critical role in electrochemical performances such as internal resistance, circularity and the like of the battery.
Currently, the mainstream preparation methods of battery separators are divided into dry-process unidirectional stretching separators and wet-process bidirectional stretching separators. The dry-method unidirectional stretching diaphragm adopts polypropylene as a raw material and has relatively high temperature resistance, and the wet-method bidirectional stretching diaphragm adopts polyethylene as a raw material and can realize closed pores at a lower temperature. However, with the increase of the energy density and the power of the battery cell, the performance of the conventional diaphragm in the aspects of temperature resistance, closed pore temperature and the like is difficult to meet the performance requirements of high-power charge and discharge. In addition, the surface energy of the dry-method and wet-method diaphragms is low, the wettability to electrolyte is poor, the adhesion between the dry-method and the wet-method diaphragms and the anode is poor, and the electrochemical performance of the battery is also affected.
In the prior art, the conventional method is to increase the adhesion between the separator and the positive and negative electrodes by coating PVDF or PMMA on the surface of the separator. For example, in the publication of "a PVDF-coated lithium ion battery separator and a method for preparing the same" disclosed in chinese patent document, the publication No. CN105552277a, the PVDF-coated lithium ion battery separator is composed of a base film and a coating layer coated on one side or both sides of the base film, the coating layer is obtained by coating and drying a slurry, the thickness of the coating layer is 0.1-0.5 μm, and the coating layer contains uniformly arranged PVDF spherical particles. However, this method can increase the overall thickness of the separator, reduce the overall energy density of the battery, and the coating can also cause the pores on the surface of the separator to be blocked, thereby affecting the air permeability of the separator.
Disclosure of Invention
The invention provides a five-layer co-extrusion lithium battery microporous membrane and a preparation method thereof, and aims to solve the problems that a lithium battery membrane in the prior art cannot have high heat resistance and low-temperature closed pore performance at the same time, electrolyte infiltration is affected by lower surface energy of the membrane, and adhesive force between the membrane and positive and negative electrodes is poor; compared with the traditional diaphragm, the liquid absorption and retention performance and the adhesion between the microporous diaphragm and the anode are greatly improved, and the electrochemical performance of the battery is improved.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a five-layer co-extrusion lithium battery microporous diaphragm has a symmetrical structure of A/B/C/B/A;
a is an outer lyophile layer, and the raw materials comprise hydroxyethyl methacrylate grafted polypropylene;
b is an intermediate temperature resistant layer, and the raw materials comprise homopolymerized polypropylene and modified polyether-ether-ketone micropowder;
c is an internal shut-off layer, and the raw materials comprise isotactic polybutene-1 and propylene butene copolymer;
the preparation method of the modified polyether-ether-ketone micropowder comprises the following steps: placing polyether-ether-ketone micropowder into concentrated sulfuric acid, stirring for reaction, and then cleaning and drying to obtain sulfonated modified micropowder; carrying out low-temperature plasma treatment on the sulfonated modified micro powder to obtain the modified polyether-ether-ketone micro powder; the atmosphere of the low-temperature plasma treatment is NH with the volume ratio of 1-2:1 3 And Ar.
The membrane adopts a symmetrical structure of A/B/C/B/A, and the polypropylene grafted by the hydroxyethyl methacrylate is used as a raw material in an outer parent liquid layer, compared with the polypropylene, the molecular structure of the hydroxyethyl methacrylate contains a large number of polar groups such as ester groups, hydroxyl groups and the like, and a strong-polarity side group is introduced into a nonpolar polypropylene main chain, so that the adhesive force of the polypropylene and a polar material can be greatly improved. Therefore, the grafted polypropylene is used as the surface layer of the five-layer co-extrusion microporous membrane, so that the adhesiveness of the membrane to the anode and the cathode and the wettability of the membrane to electrolyte can be greatly improved, on one hand, the separation of the membrane and the pole piece after hot pressing in the process of assembling the battery cell is avoided, and meanwhile, the electrochemical performance of the battery cell is also improved. Compared with the traditional mode of coating on the surface of the diaphragm, the hydroxyethyl methacrylate grafted polypropylene is adopted, so that the loss of air permeability caused by coating is avoided, the thickness of the diaphragm is not increased, and the additional cost of diaphragm coating is reduced.
The invention uses homopolymerized polypropylene as raw material in the middle temperature-resistant layer, and modified polyether-ether-ketone micropowder is added. The homo-polypropylene has very high regularity, so that the homo-polypropylene has high strength after film formation; the polyether-ether-ketone micropowder has the characteristics of high strength and high temperature resistance, and is added into the middle layer to play a role in enhancing on one hand, so that the mechanical property of the middle layer is improved; meanwhile, the high melting point of the polyether-ether-ketone micro powder further improves the temperature resistance of the diaphragm; in addition, the polyether-ether-ketone also has a large number of polar groups such as ether bonds, ketone bonds and the like, and has better wettability with electrolyte. In addition, the invention further carries out sulfonation and NH on the polyether-ether-ketone micropowder 3 And low-temperature plasma modification under Ar atmosphere, the modification method can improve the surface roughness of the polyether-ether-ketone micro powder and introduce the polyether-ether-ketone micro powder on the surface of the polyether-ether-ketone micro powderThe surface performance of the lithium ion battery is further improved by adding the modified polyether-ether-ketone micropowder into the intermediate layer, so that the liquid absorption capacity of the diaphragm can be further improved, and the lithium ion transmission capacity of the lithium ion battery is further improved.
In the invention, the isotactic polybutene-1 is used as a raw material in the internal closing layer, and compared with polypropylene in the surface layer and the middle layer, the isotactic polybutene-1 has a lower melting point (120 ℃), can realize self-closing at the initial closing hole of uncontrollable reaction of the battery core, further blocks the reaction of the battery, and improves the safety of the battery at high temperature. The isotactic polybutene-1 has lower melting point than the polyethylene used in traditional diaphragm, so that it can be used as inner layer to make the diaphragm close cell fast and self-closing at lower temperature. Meanwhile, the propylene-butene copolymer is also added into the inner layer; the addition of the propylene-butene copolymer can regulate the difference of the polypropylene in the inner layer polybutene and the middle layer in processing performance, ensure that the five-layer co-extrusion microporous diaphragm can not be layered during extrusion, and improve the integrity of the diaphragm.
The invention adopts a five-layer co-extrusion structure, different materials are respectively used in five layers, and the apertures with different sizes and distribution can appear after the stretching, so that the five-layer structure formed has a staggered pore canal structure, the mechanical properties such as the whole puncture strength of the diaphragm can be further improved, and the safety of the battery is improved. Therefore, the microporous membrane provided by the invention further strengthens the capability of the membrane for closed-pore self-closing and high temperature resistance at a lower temperature through the coordination of five layers of structures, improves the mechanical properties of the membrane, and can simultaneously meet the requirements of various fields such as power batteries, energy storage batteries and the like on the safety of the membrane; compared with the traditional diaphragm, the liquid absorption and retention performance and the adhesion between the microporous diaphragm and the anode are greatly improved, and the electrochemical performance of the battery is improved. The membrane has the air permeability value less than or equal to 350s/100mL, the closed pore temperature less than or equal to 120 ℃, the membrane breaking temperature more than or equal to 170 ℃, and the longitudinal tensile strength more than or equal to 1800kgf/cm 2 The transverse tensile strength is more than or equal to 170kgf/cm 2 Puncture strength is more than or equal to 550kgf/cm 2 。
Preferably, the preparation method of the hydroxyethyl methacrylate grafted polypropylene comprises the following steps: dissolving polypropylene in an organic solvent, adding a hydroxyethyl methacrylate monomer and a benzoyl peroxide initiator, reacting for 1-3 hours at 100-120 ℃, and drying the product to obtain the hydroxyethyl methacrylate grafted polypropylene.
Preferably, the weight average molecular weight of the polypropylene is 40-50 ten thousand, and the mass ratio of the polypropylene to the hydroxyethyl methacrylate monomer is 90:10-95:5.
Preferably, in the middle temperature-resistant layer, the mass ratio of the homopolymerized polypropylene to the modified polyether-ether-ketone micropowder is 90:10-99:1; the isotacticity of the homo-polypropylene is more than or equal to 98 percent, and the melt index at 230 ℃ is 1-5 g/10min.
Preferably, in the preparation process of the modified polyether-ether-ketone micropowder,
the particle size of the polyether-ether-ketone micropowder in the step A) is 10-50 nm, and the stirring reaction time is 5-10 min;
the discharge power in the low-temperature plasma treatment in the step B) is 500-800W, and the treatment time is 10-15 min.
Preferably, in the internal shutoff layer, the mass ratio of the isotactic polybutene-1 to the propylene butene copolymer is 80:20-90:10; the weight average molecular weight of the isotactic polybutene-1 is 30-50 ten thousand, the melt index at 190 ℃ is 0.5-2 g/10min, and the melting point is less than or equal to 120 ℃; in the propylene-butene copolymer, the mass content of propylene units is 60-80%, and the mass content of butene units is 20-40%.
Preferably, the microporous membrane has a total thickness of 12-20 μm, the inner shutdown layer has a thickness of 20-30% of the total thickness, and the intermediate heat-resistant layer has a thickness of 40-50% of the total thickness.
The invention also provides a preparation method of the five-layer co-extrusion lithium battery microporous membrane, which comprises the following steps:
(1) Casting sheet: respectively mixing the raw materials in the outer hydrophilic layer, the middle temperature-resistant layer and the inner closing layer in proportion, and performing five-layer coextrusion, traction and cooling to obtain a cast sheet;
(2) Stretching and film forming: and sequentially carrying out heat treatment, longitudinal cold stretching, longitudinal hot stretching and heat setting on the obtained cast sheet to obtain the five-layer co-extruded lithium battery microporous membrane.
Preferably, the extrusion temperature in the five-layer coextrusion in the step (1) is 250-270 ℃; the cooling temperature is 80-100 ℃, and the traction speed is 20-50 m/min.
Preferably, the heat treatment temperature in the step (2) is 120-145 ℃ and the heat treatment time is 4-12 h; the longitudinal cold stretching temperature is 40-70 ℃ and the stretching ratio is 1.2-1.5; the longitudinal hot stretching temperature is 130-150 ℃ and the stretching ratio is 1.5-3.0; the heat setting temperature is 130-145 ℃ and the heat setting time is 1-5 min.
Therefore, the invention has the following beneficial effects:
(1) The polypropylene grafted by the hydroxyethyl methacrylate is used as a raw material in the outer lyophile layer, a small amount of hydroxyethyl methacrylate is grafted on a polypropylene main chain, a strong polar group is introduced, the polarity of the polypropylene is improved, the better cohesiveness of a diaphragm and a pole piece and the liquid absorbing and retaining capacity are endowed, and the safety and the electrochemical performance of the battery are improved;
(2) The middle temperature resistant layer is prepared from the homopolymerized polypropylene which has higher isotacticity and meets the requirements of the diaphragm on strength and temperature resistance, and the modified polyether-ether-ketone micropowder is added; the polyether-ether-ketone micropowder has the characteristics of high melting point and high strength, and can effectively improve the temperature resistance and strength of the diaphragm; the surface modification is carried out on the polyether-ether-ketone micropowder, so that the liquid absorption capacity of the diaphragm can be improved, and the lithium ion transmission capacity in the lithium battery is further improved;
(3) The isotactic polybutene-1 is used as a raw material in an internal closing layer, so that the self-closing can be realized at the initial closing hole of the uncontrollable reaction of the battery core, the reaction of the battery is blocked, and the safety of the battery at high temperature is improved;
(4) The propylene-butene copolymer is added into the inner shut-off layer, so that the difference of the processability between the inner shut-off layer and the middle temperature-resistant layer is regulated, the situation that the five-layer co-extrusion microporous diaphragm cannot be layered during extrusion is ensured, and the integrity of the diaphragm is improved;
(5) The five-layer co-extrusion structure is adopted, different materials are respectively used in five layers, the pore diameters with different sizes and distribution can appear after the stretching, the five-layer structure formed has a staggered pore canal structure, the overall puncture strength and other mechanical properties of the diaphragm can be further improved, and the safety of the battery is improved.
Detailed Description
The invention is further described below in connection with the following detailed description.
General examples
The five-layer co-extrusion lithium battery microporous diaphragm has a symmetrical structure of A/B/C/B/A and a thickness of 12-20 mu m; a is an outer lyophile layer, and the raw materials comprise hydroxyethyl methacrylate grafted polypropylene; the preparation method of the hydroxyethyl methacrylate grafted polypropylene comprises the following steps: dissolving polypropylene in an organic solvent, adding a hydroxyethyl methacrylate monomer and a benzoyl peroxide initiator, reacting for 1-3 hours at 100-120 ℃, and drying the product to obtain the hydroxyethyl methacrylate grafted polypropylene; the weight average molecular weight of the polypropylene is 40-50 ten thousand, and the mass ratio of the polypropylene to the hydroxyethyl methacrylate monomer is 90:10-95:5; b is an intermediate temperature-resistant layer, and the total thickness of the two layers B is 40-50% of the total thickness of the diaphragm; the raw materials comprise homo-polypropylene and modified polyether-ether-ketone micropowder with the mass ratio of 90:10-99:1; the isotacticity of the homo-polypropylene is more than or equal to 98 percent, and the melt index at 230 ℃ is 1-5 g/10min; the preparation method of the modified polyether-ether-ketone micropowder comprises the following steps: placing polyether-ether-ketone micropowder with the particle size of 10-50 nm into concentrated sulfuric acid, stirring and reacting for 5-10 min, and then cleaning and drying to obtain sulfonated modified micropowder; carrying out low-temperature plasma treatment on the sulfonated modified micro powder to obtain the modified polyether-ether-ketone micro powder; the atmosphere of the low-temperature plasma treatment is NH with the volume ratio of 1-2:1 3 And Ar; the discharge power is 500-800W, and the treatment time is 10-15 min;
c is an internal closing layer, and the thickness is 20-30% of the total thickness of the diaphragm; the raw materials comprise isotactic polybutene-1 and propylene butene copolymer with the mass ratio of 80:20-90:10; the weight average molecular weight of the isotactic polybutene-1 is 30-50 ten thousand, the melt index at 190 ℃ is 0.5-2 g/10min, and the melting point is less than or equal to 120 ℃; in the propylene-butene copolymer, the mass content of propylene units is 60-80%, and the mass content of butene units is 20-40%.
The preparation method of the five-layer co-extrusion lithium battery microporous membrane comprises the following steps:
(1) Casting sheet: respectively mixing the raw materials in the outer hydrophilic layer, the middle temperature-resistant layer and the inner closing layer in proportion, and performing five-layer coextrusion, traction and cooling to obtain a cast sheet; the extrusion temperature of the five-layer coextrusion is 250-270 ℃; the cooling temperature is 80-100 ℃, and the traction speed is 20-50 m/min;
(2) Stretching and film forming: sequentially carrying out heat treatment, longitudinal cold stretching, longitudinal hot stretching and heat setting on the obtained cast sheet to obtain the five-layer co-extrusion microporous membrane; the heat treatment temperature is 120-145 ℃ and the heat treatment time is 4-12 h; the longitudinal cold stretching temperature is 40-70 ℃ and the stretching ratio is 1.2-1.5; the longitudinal hot stretching temperature is 130-150 ℃ and the stretching ratio is 1.5-3.0; the heat setting temperature is 130-145 ℃ and the heat setting time is 1-5 min.
Example 1:
a five-layer co-extrusion lithium battery microporous diaphragm has a symmetrical structure of A/B/C/B/A and a total thickness of 20 mu m;
a is an outer lyophile layer, and the thickness of each layer A is 3 mu m; the raw material is hydroxyethyl methacrylate grafted polypropylene; the preparation method of the hydroxyethyl methacrylate grafted polypropylene comprises the following steps: polypropylene (commercially available, 35 ten thousand weight average molecular weight, melt index at 230 ℃ is 2.0g/10 min) is dissolved in toluene, hydroxyethyl methacrylate monomer and benzoyl peroxide initiator are added, the mass ratio of polypropylene to hydroxyethyl methacrylate monomer is 95:5, and the addition amount of benzoyl peroxide is 3%; reacting for 2 hours at 110 ℃, and drying the product to obtain hydroxyethyl methacrylate grafted polypropylene;
b is an intermediate temperature resistant layer, and the thickness of each layer B is 4 mu m; the raw materials comprise homopolypropylene (commercial with isotacticity of 98 percent and melt index of 1.0g/10min at 230 ℃) and modified polyether-ether-ketone micropowder with the mass ratio of 99:1; the preparation method of the modified polyether-ether-ketone micropowder comprises the following steps: a) Placing commercial polyether-ether-ketone micropowder with the particle size of 30nm into 98wt% concentrated sulfuric acid, stirring and reacting for 8min, and then washing with deionized water and drying to obtain sulfonated modified micropowder; b) For sulfonationCarrying out low-temperature plasma treatment on the modified micro powder to obtain the modified polyether-ether-ketone micro powder; the atmosphere of the low-temperature plasma treatment is NH with the volume ratio of 1:1 3 Ar, the discharge power is 700W, and the treatment time is 12min;
c is an internal closing layer with the thickness of 6 mu m; the raw materials comprise isotactic polybutene-1 (commercially available with a weight average molecular weight of 30 ten thousand, a melt index at 190 ℃ C. Of 2.0g/10min, a melting point of 115 ℃ C.) and a propylene butene copolymer (commercially available with a weight average molecular weight of 30 ten thousand, a mass content of propylene units of 60% and a mass content of butene units of 40%).
The preparation method of the five-layer co-extrusion lithium battery microporous membrane comprises the following steps:
(1) Casting sheet: the hydroxyethyl methacrylate grafted polypropylene is subjected to electronic scale metering and is put into a first double-screw extruder; metering the homo-polypropylene and modified polyether-ether-ketone micropowder by an electronic scale, mixing in a mixing bin, and then putting into a second double-screw extruder; metering isotactic polybutene-1 and propylene butene copolymer through an electronic scale, mixing in a mixing bin, and feeding into a third double-screw extruder; the temperature of the extruder is regulated to 260 ℃, after melting, filtering is carried out, the material extruded by the first double-screw extruder is used as an outer hydrophilic layer (A), the material extruded by the second double-screw extruder is used as an intermediate temperature-resistant layer (B), and the material extruded by the third double-screw extruder is used as an inner closing layer (C) to be subjected to multi-layer co-extrusion and five-layer die head in-die composite extrusion. The melt extruded by the die head is cooled at the temperature of 90 ℃ and five-layer composite cast sheet is obtained at the traction speed of 40 m/min;
(2) Stretching and film forming: carrying out heat treatment on the obtained cast sheet at the temperature of 135 ℃ for 6 hours; then the heat-treated cast sheet is firstly subjected to longitudinal cold stretching at the temperature of 65 ℃ with the stretching multiplying power of 1.2, then is subjected to longitudinal hot stretching at the temperature of 140 ℃ with the stretching multiplying power of 2.0, and is subjected to heat setting at the temperature of 140 ℃ for 2min; and finally, after traction and thickness measurement, rolling to obtain the five-layer co-extrusion lithium battery microporous diaphragm.
Example 2:
example 2 differs from example 1 in that when the hydroxyethyl methacrylate grafted polypropylene in the outer lyophile layer was prepared, the mass ratio of polypropylene to hydroxyethyl methacrylate was 90:10, the remainder being the same as in example 1.
Example 3:
example 3 differs from example 1 in that the mass ratio of the homo-polypropylene to the modified polyether-ether-ketone micropowder in the intermediate heat-resistant layer is 90:10, and the rest is the same as in example 1.
Example 4:
example 4 differs from example 1 in that the mass ratio of isotactic polybutene-1 to propylene butene copolymer in the internal shut-off layer is 80:20, the remainder being the same as in example 1.
Comparative example 1:
comparative example 1 was different from example 1 in that the raw material of the outer lyophile layer was polypropylene not grafted with hydroxyethyl methacrylate, and the rest was the same as in example 1.
Comparative example 2:
comparative example 2 was different from example 1 in that no modified polyether ether ketone micropowder was added to the intermediate heat-resistant layer, and the rest was the same as in example 1.
Comparative example 3:
comparative example 3 is different from example 1 in that the sulfonation modification in step a) was not performed in the preparation of the modified polyetheretherketone micropowder in the intermediate heat-resistant layer, and only the modification by low-temperature plasma treatment was performed, and the rest was the same as in example 1.
Comparative example 4:
comparative example 4 differs from example 1 in that only the sulfonation modification of step a) was performed during the preparation of the modified polyetheretherketone micropowder in the intermediate heat-resistant layer, and no low-temperature plasma treatment was performed, and the rest was the same as in example 1.
Comparative example 5:
comparative example 5 differs from example 1 in that in the preparation of the modified polyetheretherketone micropowder in the intermediate temperature-resistant layer, the low-temperature plasma treatment atmosphere of step B) was pure Ar, and the rest was the same as in example 1.
Comparative example 6:
comparative example 6 was different from example 1 in that propylene butene copolymer was not added to the inner shutoff layer, and the rest was the same as in example 1.
Comparative example 7:
comparative example 7 was different from example 1 in that no layer C was provided in the microporous separator membrane, and the rest was the same as in example 1.
The microporous separator membranes prepared in the above examples and comparative examples were cut to A4 size, and various mechanical properties and thermal properties were tested, and the results are shown in table 1.
The test items and methods are as follows:
(1) Average thickness of
Measuring the thickness of the five-layer co-extrusion microporous membrane at different positions by using a spiral micrometer, and calculating the average value;
(2) Tensile Strength
Testing the longitudinal and transverse tensile strength of the five-layer co-extrusion microporous membrane by adopting a co-strength CTM universal tester, testing 5 sample bars in each direction, and calculating the average value;
(3) Puncture strength
Testing the puncture strength of the five-layer co-extrusion microporous membrane by adopting a synergistic CTM universal tester, testing 5 sample bars, and calculating the average value;
(4) Closed cell temperature
Testing the closed pore temperature of the five-layer co-extrusion microporous membrane by adopting a hot stage microscope, recording the temperature of the membrane when the membrane starts to melt, testing 5 samples, and calculating the average value of the 5 samples;
(5) Rupture of membranes temperature
Testing the rupture temperature of the five-layer co-extrusion microporous membrane by adopting a hot stage microscope, recording the temperature of the membrane when the membrane starts to melt, testing 5 samples, and calculating the average value of the 5 samples;
(6) Air permeability
Adopting an air permeability tester to test the air permeability of the five-layer co-extrusion microporous membrane, testing 5 samples, and calculating the average value;
(7) Liquid absorption rate
The liquid absorption rate of the coated diaphragm is tested by adopting a weighing method, firstly, the diaphragm is completely dried, then the quality is recorded, then the completely dried diaphragm is soaked in electrolyte for 24 hours, the weight of the diaphragm is recorded again after the surface electrolyte is wiped, and the liquid absorption rate of the diaphragm is obtained by the difference value recorded in the two times. Testing 5 samples, and calculating the average value of the 5 samples;
(8) Adhesion to positive electrode sheet
And testing the bonding strength of the coated diaphragm and the positive plate after hot pressing by adopting a synergistic CTM universal tester, testing 5 sample strips, and calculating the average value of the sample strips.
Table 1: microporous separator performance test results.
As can be seen from the test results in Table 1, the five-layer co-extrusion microporous membrane adopting the structure in examples 1-4 can effectively improve the liquid absorption and retention capacity and the adhesive force with the anode and the cathode of the membrane, has high membrane breaking temperature, low closed pore temperature and high stretching and puncture performance, and does not influence the air permeability of the membrane.
In comparative example 1, polypropylene not grafted with hydroxyethyl methacrylate was used as a raw material for the outer hydrophilic layer, and the liquid absorption and retention ability of the separator and the adhesion to the positive and negative electrodes were significantly reduced as compared with example 1.
The middle temperature-resistant layer in comparative example 2 is not added with modified polyether-ether-ketone micropowder, and the temperature resistance, liquid absorption and retention capacity and mechanical properties of the diaphragm are reduced compared with those of example 1, which shows that the added modified polyether-ether-ketone micropowder can improve the strength and temperature resistance of polypropylene and the wettability of electrolyte.
In comparative examples 3 and 4, the polyether-ether-ketone micropowder is not subjected to sulfonation modification or low-temperature plasma treatment, and the liquid absorption and retention capacity and the tensile strength of the diaphragm are reduced compared with those in example 1, so that the combination of sulfonation and low-temperature plasma treatment can effectively improve the surface properties of the polyether-ether-ketone micropowder and is beneficial to improving the liquid absorption and retention capacity and the mechanical properties of the diaphragm.
In comparative example 5, the polyether-ether-ketone micropowder is subjected to low-temperature plasma treatment only in a single atmosphere, and the liquid absorption and retention capacity and mechanical properties of the diaphragm are reduced as compared with those of example 1, which shows that the atmosphere condition during the low-temperature plasma treatment has a significant influence on the surface properties of the polyether-ether-ketone micropowder, thereby influencing the liquid absorption and retention capacity and mechanical properties of the diaphragm.
The inner shutdown layer of comparative example 6 was not added with propylene butene copolymer, and delamination of the inner shutdown layer and the intermediate temperature resistant layer occurred upon extrusion, resulting in a significant decrease in mechanical properties of the separator compared to example 1.
The separator of comparative example 7 was not provided with a C layer (inner shutdown layer), and the closed cell temperature of the separator was significantly higher than that of example 1, and self shutdown could not be achieved at the initial closed cell where the uncontrolled reaction of the battery cell occurred, and thus the reaction of the battery was blocked, and the safety of the battery at high temperature was lowered.
The foregoing description is only of the preferred embodiments of the present invention, and is not intended to limit the scope of the present invention. All equivalent changes and modifications made in accordance with the present invention are intended to be covered by the scope of the appended claims.
Claims (10)
1. A five-layer co-extrusion lithium battery microporous diaphragm is characterized in that the structure is a symmetrical structure of A/B/C/B/A;
a is an outer lyophile layer, and the raw materials comprise hydroxyethyl methacrylate grafted polypropylene;
b is an intermediate temperature resistant layer, and the raw materials comprise homopolymerized polypropylene and modified polyether-ether-ketone micropowder;
c is an internal shut-off layer, and the raw materials comprise isotactic polybutene-1 and propylene butene copolymer;
the preparation method of the modified polyether-ether-ketone micropowder comprises the following steps: placing polyether-ether-ketone micropowder into concentrated sulfuric acid, stirring for reaction, and then cleaning and drying to obtain sulfonated modified micropowder; carrying out low-temperature plasma treatment on the sulfonated modified micro powder to obtain the modified polyether-ether-ketone micro powder; the atmosphere of the low-temperature plasma treatment is NH with the volume ratio of 1-2:1 3 And Ar.
2. The five-layer co-extruded lithium battery microporous membrane according to claim 1, wherein the preparation method of the hydroxyethyl methacrylate grafted polypropylene is as follows: and dissolving polypropylene in an organic solvent, adding a hydroxyethyl methacrylate monomer and a benzoyl peroxide initiator, reacting for 1-3 hours at 100-120 ℃, and drying the product to obtain the hydroxyethyl methacrylate grafted polypropylene.
3. The five-layer co-extruded lithium battery microporous membrane according to claim 2, wherein the weight average molecular weight of the polypropylene is 40-50 ten thousand, and the mass ratio of the polypropylene to the hydroxyethyl methacrylate monomer is 90:10-95:5.
4. The five-layer co-extruded lithium battery microporous membrane according to claim 1, wherein the mass ratio of the homo-polypropylene to the modified polyether-ether-ketone micro powder in the middle temperature-resistant layer is 90:10-99:1; the isotacticity of the homo-polypropylene is more than or equal to 98 percent, and the melt index at 230 ℃ is 1-5 g/10min.
5. The five-layer co-extruded lithium battery microporous membrane according to claim 1 or 4, wherein in the preparation process of the modified polyether-ether-ketone micropowder, the particle size of the used polyether-ether-ketone micropowder is 10-50 nm, and the stirring reaction time is 5-10 min; the discharge power during low-temperature plasma treatment is 500-800W, and the treatment time is 10-15 min.
6. The five-layer co-extruded lithium battery microporous separator according to claim 1, wherein in the internal shut-off layer, the mass ratio of isotactic polybutene-1 to propylene butene copolymer is 80:20-90:10;
the weight average molecular weight of the isotactic polybutene-1 is 30-50 ten thousand, the melt index at 190 ℃ is 0.5-2 g/10min, and the melting point is less than or equal to 120 ℃;
in the propylene-butene copolymer, the mass content of propylene units is 60-80%, and the mass content of butene units is 20-40%.
7. The five-layer co-extruded lithium battery microporous membrane according to claim 1, wherein the total thickness of the microporous membrane is 12-20 μm, the thickness of the internal shut-off layer is 20-30% of the total thickness, and the thickness of the intermediate heat-resistant layer is 40-50% of the total thickness.
8. A method for preparing the five-layer co-extrusion lithium battery microporous membrane according to any one of claims 1 to 7, which is characterized by comprising the following steps:
(1) Casting sheet: respectively mixing the raw materials in the outer hydrophilic layer, the middle temperature-resistant layer and the inner closing layer in proportion, and performing five-layer coextrusion, traction and cooling to obtain a cast sheet;
(2) Stretching and film forming: and sequentially carrying out heat treatment, longitudinal cold stretching, longitudinal hot stretching and heat setting on the obtained cast sheet to obtain the five-layer co-extruded lithium battery microporous membrane.
9. The preparation method of claim 8, wherein the extrusion temperature in the five-layer coextrusion in the step (1) is 250-270 ℃; the cooling temperature is 80-100 ℃, and the traction speed is 20-50 m/min.
10. The preparation method according to claim 8, wherein the heat treatment temperature in the step (2) is 120-145 ℃ and the heat treatment time is 4-12 hours; the longitudinal cold stretching temperature is 40-70 ℃, and the stretching ratio is 1.2-1.5; the longitudinal hot stretching temperature is 130-150 ℃, and the stretching ratio is 1.5-3.0; the heat setting temperature is 130-145 ℃, and the heat setting time is 1-5 min.
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