CN112397849B - High-temperature-resistant flame-retardant battery diaphragm and preparation method and application thereof - Google Patents
High-temperature-resistant flame-retardant battery diaphragm and preparation method and application thereof Download PDFInfo
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
- D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0092—Electro-spinning characterised by the electro-spinning apparatus characterised by the electrical field, e.g. combined with a magnetic fields, using biased or alternating fields
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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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 provides a high-temperature-resistant flame-retardant battery diaphragm and a preparation method and application thereof. The high-temperature-resistant flame-retardant battery diaphragm comprises nano cellulose fibers and basalt fibers; the mass fraction of the nano cellulose fiber is 99-60%, and the mass fraction of the basalt fiber is 1-40%. The diaphragm prepared by optimally combining the nano-cellulose fiber and the basalt fiber exerts the advantages of the nano-cellulose and the basalt fiber, has high porosity, good electrolyte wettability, excellent heat resistance and mechanical properties, and can improve the rate capability, service life and safety of the battery.
Description
Technical Field
The invention relates to the technical field of battery diaphragm materials, in particular to a high-temperature-resistant flame-retardant battery diaphragm and a preparation method and application thereof.
Background
The battery diaphragm is a layer of diaphragm material between the positive electrode and the negative electrode of the battery and is used as a key material of the lithium battery, the diaphragm plays a role in isolating electrons in the battery diaphragm, prevents the positive electrode and the negative electrode from being in direct contact, allows lithium ions in electrolyte to freely pass through, and plays a vital role in ensuring the safe operation of the battery. Currently, commercially available lithium battery separators in the market are mainly microporous polyolefin separators mainly made of Polyethylene (PE) and polypropylene (PP), and such separators are widely used in lithium battery separators due to their advantages of low cost, good mechanical properties, excellent chemical stability and electrochemical stability. But the porous polyolefin diaphragm has larger thermal expansion coefficient and lower melting point, and the melting points of the polyethylene and the polypropylene are 130 ℃ and 150 ℃ respectively. The separator structure is damaged at a temperature exceeding 160 c to cause short-circuiting of the battery. In practical application, the temperature of the battery can reach more than 200 ℃ in a short time, which is far higher than the melting point of the polyethylene and polypropylene diaphragm, so that the diaphragm fails, and the occurrence of electric automobile ignition and combustion events is easily caused.
The traditional ceramic lithium battery diaphragm is characterized in that one side or two sides of a diaphragm substrate are coated with a layer of coating containing ceramic particles, so that the use safety of the diaphragm is improved, but the coating process is complex, the controllability is poor, the ceramic particle coating is easy to cause uneven coating or unevenness, and the stability of the lithium battery diaphragm at high temperature is reduced. Because the lithium cell is widely used in fields such as cell-phone, computer, electric automobile, the voltage and the capacity that the lithium cell bore are constantly increased, have had higher requirement to lithium battery diaphragm's high temperature stability, and traditional pottery lithium battery diaphragm is when high temperature work, and coated ceramic particle very easily drops, leads to the positive negative pole of lithium cell to take place the short circuit to produce serious incident. Therefore, the development of a new high-temperature-resistant flame-retardant lithium battery diaphragm material is urgently needed.
Disclosure of Invention
The invention aims to provide a novel high-temperature-resistant flame-retardant battery diaphragm material, which has the advantages of good flame-retardant and heat-resistant performances, good mechanical properties, corrosion resistance and higher ionic conductivity, and is a green environment-friendly material.
The high-temperature-resistant flame-retardant battery diaphragm comprises nano cellulose fibers and basalt fibers; the mass fraction of the nano cellulose fiber is 99-60%, and the mass fraction of the basalt fiber is 1-40%.
The cellulose is a renewable resource with abundant reserves in nature, and the material produced by taking the cellulose as a raw material has many excellent characteristics, such as high dielectric constant, strong puncture resistance, good chemical stability, good thermal stability, degradability and the like, and is widely applied to the fields of papermaking, electronic products, industrial processing, medicine and the like. In recent years, many researchers have been dedicated to research and develop a low-cost and renewable cellulose raw material to prepare a high-performance separator, especially a lithium ion battery separator using cellulose and modified and reinforced cellulose as main raw materials, and compared with a polyolefin separator in the aspects of heat resistance, puncture resistance, strength, resistance, high voltage resistance and the like. Under the action of hydrogen bonds in cellulose molecules and among molecules and van der waals force, cellulose macromolecular chains are aggregated together to form cellulose element fibrils with a cellulose crystal structure. However, cellulose aggregates are not a perfect crystalline structure in nature, and a large number of amorphous regions are present. The cellulose element fibrils can be effectively and completely stripped from the natural cellulose aggregation state through physical and chemical means. Meanwhile, the basalt fiber is a fiber material with excellent comprehensive performance and high cost performance, and has good corrosion resistance, chemical stability, environmental protection performance and composite compatibility with other materials. The basalt fiber used as the lithium battery diaphragm material is expected to remarkably improve the heat resistance stability of the diaphragm material and the use safety of a lithium battery.
The high temperature resistant flame retardant battery separator of the present invention can be prepared using nanocellulose fibers and basalt fibers in a specific ratio using methods conventional in the art. The high temperature resistant flame retardant battery separator may be preferably prepared by using nanocellulose fibers and basalt fibers through an electrospinning technique. The high-temperature-resistant flame-retardant battery diaphragm provided by the invention needs to ensure that the nano cellulose fiber and the basalt fiber are contained at the ratio, and other materials can be added into the high-temperature-resistant flame-retardant battery diaphragm to enhance other performances of the diaphragm. In a preferred embodiment of the present invention, the high temperature resistant flame retardant battery separator is made of nanocellulose fibers and basalt fibers by electrospinning. Namely, the high-temperature-resistant flame-retardant battery separator is composed of nanocellulose fibers and basalt fibers.
The electrospinning method is a spinning method in which a polymer mixed solution or melt is subjected to jet drawing under the action of static electricity to obtain ultrafine fibers. The diameter of the fiber prepared by adopting the electrostatic spinning technology can reach the nanometer level, can be adjusted from the nanometer level to the micrometer level, can meet the spinning requirements of cellulose and basalt fiber, and is incomparable with the traditional method. The electrostatic spinning preparation device has the advantages of simplicity, low spinning cost, wide raw material source, strong process controllability and the like, thereby being widely applied to the preparation of various polymer nano fibers and nano fiber membranes. The prepared nano-fiber membrane material generally has the outstanding advantages of high porosity, large specific surface area, high fiber fineness and uniformity, large length-diameter ratio and the like, so the method is preferably used for preparing the high-performance battery diaphragm material.
In a preferred embodiment of the present invention, the cellulose in the nanocellulose fiber is natural cellulose or a cellulose derivative; the natural cellulose is one or more of cotton, wood pulp, bamboo pulp, flax and straw, and is preferably cotton; the cellulose derivative is one or more of cellulose nitrate, cellulose acetate, methyl cellulose, ethyl cellulose, cellulose acetate butyrate, hydroxypropyl cellulose and carboxymethyl cellulose; preferably carboxymethyl cellulose or cellulose nitrate, more preferably cellulose nitrate.
In a preferred embodiment of the present invention, the diameter of the nanocellulose fiber is 2 to 500nm, and the aspect ratio is 15 to 100. More preferably, the diameter of the nanocellulose fiber is 10 to 100nm, and the aspect ratio is 20 to 70. More preferably, the diameter of the nanocellulose fiber is 50 to 60nm, and the aspect ratio is 50 to 60.
In a preferred embodiment of the present invention, the basalt fiber has a diameter of 3 to 25 μm and a length of 20 to 100 μm. More preferably, the basalt fiber has a diameter of 5 to 15 μm and a length of 30 to 80 μm.
In the invention, the battery diaphragm material with the required performance can be obtained when the mass fraction of the nano cellulose fiber is 99-60% and the mass fraction of the basalt fiber is 1-40%, and a large number of experiments prove that in the invention, when the content of the basalt fiber is too high, the film forming effect of the diaphragm is poor, and the requirements of the invention on the performance of the diaphragm material are not met. In a preferred embodiment of the invention, the mass fraction of the nano cellulose fiber in the high-temperature resistant and flame-retardant battery separator is 90-70%, and the mass fraction of the basalt fiber is 10-30%.
In a preferred embodiment of the present invention, the high temperature resistant and flame retardant lithium battery separator has a thickness of 5 to 50 μm, a porosity of 30 to 60%, and a pore size distribution of 0.01 to 0.3 μm. More preferably, the thickness is 15 to 35 μm, the porosity is 50 to 60%, and the pore size distribution is 0.1 to 0.2 μm.
In a preferred embodiment of the present invention, the preparation method of the high temperature resistant flame retardant battery separator comprises the following steps: and uniformly mixing the nano cellulose fiber and the basalt fiber, and forming a film through electrostatic spinning. In general, a dispersion is carried out using good solvents for each of nanocellulose fibers and basalt fibers, and the dispersion is mixed uniformly to form a film by electrospinning. Among them, the good solvent of the nanocellulose fiber is preferably an ionic liquid, and the good solvent of the basalt fiber is preferably N-methylpyrrolidone.
The invention also aims to provide a preparation method of the high-temperature-resistant flame-retardant battery diaphragm, which comprises the following steps:
(1) Dissolving the nano cellulose fiber in ionic liquid, and hydrolyzing at 80-160 ℃ to obtain nano cellulose fiber suspension;
(2) Dissolving the basalt fiber in an organic solvent, adding a silane coupling agent, and uniformly stirring to obtain basalt fiber slurry;
(3) And mixing the nano cellulose fiber suspension and the basalt fiber slurry according to a proportion to obtain a mixed solution, defoaming, performing electrostatic spinning to form a film, and drying to obtain the nano cellulose fiber composite material.
Wherein, in the step (1), the ionic liquid is preferably 1-ethyl-3-methylimidazolium acetate.
In the step (2), the silane coupling agent is preferably KH550 and/or KH560, and the organic solvent is preferably N-methylpyrrolidone.
In the step (3), the specific process of electrostatic spinning is preferably as follows: the voltage is 10-40kV, the receiving distance is 8-25cm, the flow is 0.1-15ml/h, the spinning temperature is 50-70 ℃, and the rotating speed of the receiving roller is 5-30m/h. More preferably, the specific process of electrostatic spinning is as follows: the voltage is 30-35kV, the receiving distance is 18-20cm, the flow is 10-12ml/h, the spinning temperature is 60-65 ℃, and the rotating speed of the receiving roller is 20-25m/h.
The specific steps of drying are preferably: and (3) putting the diaphragm formed by electrostatic spinning into a vacuum oven, and drying at the temperature of 60-120 ℃ for 10-15h to obtain the composite material.
The invention also aims to provide the application of the high-temperature-resistant flame-retardant battery separator or the preparation method in the preparation of lithium ion batteries, sodium ion batteries or potassium ion batteries. The high-temperature-resistant flame-retardant battery diaphragm provided by the invention is more suitable for lithium ion batteries.
The diaphragm prepared by the invention has the following heat resistance: the closed pore temperature is 165-185 ℃, the film breaking temperature is above 260 ℃, and the battery diaphragm does not shrink obviously after 0.5h treatment at 220 ℃. The battery performance is as follows: the capacity retention rate of the battery is at least 98% after 100 complete charge-discharge cycles under the current of 1C. The high-temperature-resistant flame-retardant battery diaphragm new material prepared by the invention is used for lithium batteries, sodium batteries and potassium batteries.
Compared with the prior art, the invention has the advantages that:
(1) The diaphragm prepared by optimally combining the nano-cellulose fiber and the basalt fiber plays the advantages of the nano-cellulose and the basalt fiber, has high porosity, good electrolyte wettability, excellent heat resistance and mechanical properties, and can improve the rate capability, service life and safety of the battery. According to the invention, the battery diaphragm is prepared by compounding the nano cellulose fiber and the basalt fiber, and the two fibers are spatially interwoven, so that the temperature resistance, the cycle stability and the battery capacity retention rate of the diaphragm are further increased.
(2) The basalt fiber used in the preparation process of the invention enables the lithium ion battery diaphragm to have excellent heat insulation and flame retardant properties, mechanical properties and corrosion resistance, and the basalt fiber belongs to green and environment-friendly materials and has little influence on the ecological environment, and in addition, the basalt fiber has wide distribution, high content and low production cost. The cellulose fiber used in the preparation process of the invention enables the lithium ion battery diaphragm to have better porosity, specific surface area and lithium ion conductivity. The natural cellulose fiber is pure natural and harmless, has wide distribution, high content and lower production cost.
(3) The invention preferably adopts an electrostatic spinning method to prepare the lithium ion battery diaphragm, and has the advantages of simple operation, short flow and high safety.
(4) The invention is obtained by mixing the nanofiber suspension and the basalt fiber slurry and then spinning preferably, and has the advantages of high heat insulation and flame retardant performance, good porosity, mechanical property, corrosion resistance and lithium ion conductivity.
Drawings
FIG. 1 is a graph showing the variation of the number of charge-discharge cycles and the capacity retention rate of the button lithium battery obtained in example 2.
Detailed Description
The following examples are given to further illustrate embodiments of the present invention. The following examples are provided to illustrate the present invention, but are not intended to limit the scope of the present invention.
Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art, and the raw materials used are commercially available. In the present invention, unless otherwise specified, all the percentages referred to are mass percentages.
Example 1
The embodiment provides a high-temperature-resistant flame-retardant battery diaphragm, and the preparation method comprises the following steps:
(1) Preparation of nanocellulose suspension: adding carboxymethyl cellulose into ionic liquid (1 ethyl-3-methylimidazole acetate) for dissolving, and hydrolyzing at 160 ℃ for 12h to obtain a nanocellulose fiber suspension, wherein the diameter of the nanocellulose fiber is 2nm, and the length-diameter ratio is 100.
(2) Preparing basalt fiber slurry: adding basalt fiber with the diameter of 3 mu m and the length of 20 mu m into a solvent (N-methyl pyrrolidone), adding a silane coupling agent KH550, wherein the dosage of the silane coupling agent is 0.5wt% of the basalt fiber, and stirring for 2 hours to form slurry.
(3) Spinning: and (3) mixing the nano cellulose fiber suspension in the step (1) with the basalt slurry in the step (2) to obtain a mixed solution, wherein the volume fractions of the nano cellulose fiber suspension and the basalt slurry are respectively 98% and 2%. The mass fractions of the nanocellulose fiber and the basalt fiber are respectively 99% and 1%. And then the mixed solution is defoamed in vacuum to obtain spinning solution after defoaming, the spinning solution is added into an injector to form a diaphragm, and electrostatic spinning is carried out under the conditions that the voltage is 10kV, the receiving distance is 8cm, the flow is 0.1ml/h, the spinning temperature is 50 ℃, and the rotating speed of a receiving roller is 5m/h to form the diaphragm. And (3) putting the diaphragm formed by electrostatic spinning into a vacuum oven, and drying for 15h at the temperature of 60 ℃.
The thickness of the prepared diaphragm is 5 mu m, the porosity is 30%, the aperture is 0.01 mu m, the obturator temperature of the diaphragm is 165 ℃, and the diaphragm breaking temperature is 265 ℃. After the separator is subjected to heat treatment at 220 ℃ for 0.5h, the battery separator does not shrink obviously.
The lithium battery diaphragm is assembled into a button type lithium ion battery according to the prior art to be tested, and the battery performance test result is as follows: under the current of 1C, the capacity retention rate of the battery after 100 complete charge-discharge cycles is 98%.
Example 2
The embodiment provides a high-temperature-resistant flame-retardant battery diaphragm, and a preparation method of the battery diaphragm comprises the following steps:
(1) Preparation of nanocellulose suspension: adding cellulose nitrate into ionic liquid (1 ethyl-3-methylimidazole acetate) for dissolving, and hydrolyzing at 120 ℃ for 12h to obtain a nanocellulose fiber suspension, wherein the diameter of the nanocellulose fiber is 50nm, and the length-diameter ratio is 60.
(2) Preparing basalt fiber slurry: adding basalt fibers with the diameter of 15 mu m and the length of 70 mu m into a solvent (N-methyl pyrrolidone), adding a silane coupling agent KH560, wherein the dosage of the silane coupling agent is 0.5wt% of the basalt fibers, and stirring for 4 hours to form slurry.
(3) Spinning: and (3) mixing the nano cellulose fiber suspension in the step (1) with the basalt slurry in the step (2) to obtain a mixed solution, wherein the volume fractions of the nano cellulose fiber suspension and the basalt slurry are 55% and 45% respectively. The mass fractions of the nanocellulose fibers and the basalt fibers are 70% and 30%, respectively. And then the mixed solution is subjected to vacuum defoaming to obtain a spinning solution after the defoaming, the spinning solution is added into an injector to form a diaphragm, and electrostatic spinning is carried out under the conditions that the voltage is 30kV, the receiving distance is 20cm, the flow is 10ml/h, the spinning temperature is 60 ℃, and the receiving roller rotating speed is 20m/h to form the diaphragm. And (3) putting the diaphragm formed by electrostatic spinning into a vacuum oven, and drying for 10 hours at the temperature of 100 ℃.
The thickness of the prepared diaphragm is 25 mu m, the porosity is 60%, the pore diameter is 0.15 mu m, the closed pore temperature of the diaphragm is 185 ℃, and the diaphragm breaking temperature is 280 ℃. After the separator is subjected to heat treatment at 220 ℃ for 0.5h, the battery separator does not shrink obviously.
The lithium battery diaphragm is assembled into a button type lithium ion battery according to the prior art for testing, and the battery performance test result is as follows: under the current of 1C, the capacity retention rate of the battery after 100 complete charge-discharge cycles is 99%. The capacity retention rate is shown in FIG. 1.
Example 3
The embodiment provides a high-temperature-resistant flame-retardant battery diaphragm, and the preparation method comprises the following steps:
(1) Preparation of nanocellulose suspension: adding natural fibers extracted from cotton into ionic liquid (1 ethyl-3-methylimidazolium acetate) for dissolving, and hydrolyzing at 80 ℃ for 12h to obtain a nanocellulose fiber suspension, wherein the diameter of the nanocellulose fiber suspension is 500nm, and the length-diameter ratio of the nanocellulose fiber suspension is 15.
(2) Preparing basalt fiber slurry: adding basalt fibers with the diameter of 25 mu m and the length of 100 mu m into a solvent (N-methyl pyrrolidone), adding a silane coupling agent KH560, wherein the dosage of the silane coupling agent is 0.5wt% of the basalt fibers, and stirring for 4 hours to form slurry.
(3) Spinning: and (3) mixing the nano cellulose fiber suspension in the step (1) with the basalt slurry in the step (2) to obtain a mixed solution, wherein the volume fractions of the nano cellulose fiber suspension and the basalt slurry are 50% and 50% respectively. The mass fractions of the nanocellulose fiber and the basalt fiber are 60% and 40%, respectively. And then carrying out vacuum defoaming on the mixed solution to obtain a spinning solution after defoaming, adding the spinning solution into a syringe to form a diaphragm, and carrying out electrostatic spinning under the conditions that the voltage is 40kV, the receiving distance is 25cm, the flow is 15ml/h, the spinning temperature is 70 ℃, and the receiving roller rotating speed is 30m/h to form the diaphragm. And (3) putting the diaphragm formed by electrostatic spinning into a vacuum oven, and drying for 10 hours at the temperature of 120 ℃.
The prepared diaphragm has the thickness of 50 mu m, the porosity of 40 percent and the aperture of 0.3 mu m, the closed pore temperature of the diaphragm is 178 ℃, and the diaphragm breaking temperature is 270 ℃. After the separator is subjected to heat treatment at 220 ℃ for 0.5h, the battery separator does not shrink obviously.
The lithium battery diaphragm is assembled into a button type lithium ion battery according to the prior art for testing, and the battery performance test result is as follows: under the current of 1C, the capacity retention rate of the battery after 100 complete charge-discharge cycles is 98%.
Example 4
The embodiment provides a high-temperature-resistant flame-retardant battery diaphragm, and the preparation method is the same as the steps in the embodiment 2, and the difference is that: the diameter of the nano cellulose fiber is 60nm, and the length-diameter ratio is 50; the diameter of the basalt fiber is 5 μm, and the length is 30 μm; the mass fractions of the nanocellulose fiber and the basalt fiber are respectively 90% and 10%.
The thickness of the prepared diaphragm is 20 micrometers, the porosity is 45%, the pore diameter is 0.16 micrometers, the obturator temperature of the prepared diaphragm is 183 ℃, and the diaphragm breaking temperature is 276 ℃. After the separator is subjected to heat treatment at 220 ℃ for 0.5h, the battery separator does not shrink obviously.
Example 5
The embodiment provides a high-temperature-resistant flame-retardant battery diaphragm, and the preparation method is the same as the steps in the embodiment 2, and the difference is that: the diameter of the nano cellulose fiber is 10nm, and the length-diameter ratio is 70; the diameter of the basalt fiber is 3 μm, and the length is 20 μm; the mass fractions of the nanocellulose fiber and the basalt fiber are respectively 90% and 10%.
The thickness of the prepared diaphragm is 22 mu m, the porosity is 43 percent, the pore diameter is 0.12 mu m, the obturator temperature of the prepared diaphragm is 181 ℃, and the diaphragm breaking temperature is 274 ℃. The separator did not shrink significantly after heat treatment at 220 ℃ for 0.5 h.
Example 6
The embodiment provides a high-temperature-resistant flame-retardant battery diaphragm, and the preparation method is the same as the steps in the embodiment 1, except that: the cellulose derivative is methylcellulose.
The thickness of the prepared diaphragm is 10 mu m, the porosity is 28%, the pore diameter is 0.03 mu m, the closed pore temperature of the prepared diaphragm is 163 ℃, and the diaphragm breaking temperature is 262 ℃. The separator did not shrink significantly after heat treatment at 220 ℃ for 0.5 h.
Example 7
The embodiment provides a high-temperature-resistant flame-retardant battery diaphragm, and the preparation method is the same as the steps in the embodiment 3, except that: the cotton is replaced by flax.
The thickness of the prepared diaphragm is 48 mu m, the porosity is 35%, the pore diameter is 0.28 mu m, the closed pore temperature of the prepared diaphragm is 173 ℃, and the diaphragm breaking temperature is 264 ℃. The separator did not shrink significantly after heat treatment at 220 ℃ for 0.5 h.
Comparative example 1
This comparative example provides a battery separator prepared according to the same procedure as in example 2, except that: the basalt fiber is replaced by diatomite.
The closed pore temperature of the prepared diaphragm is 145 ℃, and the diaphragm breaking temperature is 250 ℃. After the diaphragm is subjected to heat treatment for 0.5h at 220 ℃, the battery diaphragm has obvious shrinkage.
The lithium battery diaphragm is assembled into a button type lithium ion battery according to the prior art for testing, and the battery performance test result is as follows: at a current of 1C, the capacity retention rate of the battery after 100 complete charge-discharge cycles is 87%.
Comparative example 2
This comparative example provides a battery separator prepared according to the same procedure as in example 2, except that: the basalt fiber is replaced by a silicon dioxide fiber.
The prepared diaphragm has the obturator temperature of 160 ℃ and the diaphragm breaking temperature of 260 ℃. After the separator is subjected to heat treatment at 220 ℃ for 0.5h, the battery separator does not shrink obviously.
Comparative example 3
This comparative example provides a battery separator prepared according to the same procedure as in example 2, except that: the mass fractions of the nanocellulose fiber and the basalt fiber are 50% and 50%, respectively. Because the content of basalt is too high, the membrane forming effect of the membrane is poor, the porosity is 65%, the pore diameter is 0.52 mu m, the bending degree is small, and the membrane is not suitable to be used as a lithium battery membrane material from the aspects of lithium battery preparation process and safety.
Finally, the method of the present invention is only a preferred embodiment and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A high-temperature resistant flame-retardant battery diaphragm is characterized by consisting of nano cellulose fibers and basalt fibers; the mass fraction of the nano cellulose fiber is 99-60%, and the mass fraction of the basalt fiber is 1-40%;
the high-temperature-resistant flame-retardant lithium battery diaphragm is prepared from nano cellulose fibers and basalt fibers through electrostatic spinning;
the thickness of the high-temperature resistant flame-retardant lithium battery diaphragm is 5-50 mu m, the porosity is 30-60%, and the pore size distribution is 0.01-0.3 mu m;
the battery performance of the high-temperature-resistant flame-retardant lithium battery diaphragm is as follows: under the current of 1C, the capacity retention rate of the battery is at least 98% after 100 complete charge-discharge cycles;
the diameter of the nano cellulose fiber is 2-500 nm, and the length-diameter ratio is 15-100;
the diameter of the basalt fiber is 3-25 μm, and the length is 20-100 μm.
2. The high temperature resistant flame retardant battery separator according to claim 1, wherein the cellulose in the nanocellulose fibers is natural cellulose or a cellulose derivative.
3. The high temperature resistant flame retardant battery separator according to claim 2, wherein the natural cellulose is one or more of cotton, wood pulp, bamboo pulp, flax, straw;
the cellulose derivative is one or more of cellulose nitrate, cellulose acetate, methyl cellulose, ethyl cellulose, cellulose acetate butyrate, hydroxypropyl cellulose and carboxymethyl cellulose.
4. The method for preparing the high-temperature-resistant flame-retardant battery separator as claimed in any one of claims 1 to 3, characterized by comprising the steps of:
(1) Dissolving the nano cellulose fiber in ionic liquid, and hydrolyzing at 80-160 ℃ to obtain a nano cellulose fiber suspension;
(2) Dissolving the basalt fiber in an organic solvent, adding a silane coupling agent, and uniformly stirring to obtain basalt fiber slurry;
(3) And mixing the nano cellulose fiber suspension and the basalt fiber slurry according to a proportion to obtain a mixed solution, defoaming, performing electrostatic spinning to form a film, and drying to obtain the nano cellulose fiber composite material.
5. The method according to claim 4, wherein in the step (1), the ionic liquid is 1-ethyl-3-methylimidazolium acetate.
6. The process according to claim 4, wherein in the step (2), the silane coupling agent is KH550 and/or KH560, and the organic solvent is N-methylpyrrolidone.
7. The preparation method according to claim 4, wherein in the step (3), the specific process of electrostatic spinning is as follows: the voltage is 10-40kV, the receiving distance is 8-25cm, the flow is 0.1-15ml/h, the spinning temperature is 50-70 ℃, and the rotating speed of the receiving roller is 5-30m/h.
8. Use of the high temperature resistant flame retardant battery separator of any of claims 1 to 3 or the method of manufacture of any of claims 4 to 7 in the manufacture of lithium ion batteries, sodium ion batteries and potassium ion batteries.
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| CN116083955B (en) * | 2023-04-11 | 2023-06-30 | 四川亚联氢能科技股份有限公司 | High-temperature-resistant basalt modified diaphragm and preparation process thereof |
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