CN113285174B - Sea-island polyphenylene sulfide composite battery diaphragm and preparation method thereof - Google Patents
Sea-island polyphenylene sulfide composite battery diaphragm and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of battery diaphragm manufacturing, and discloses a sea-island polyphenylene sulfide composite battery diaphragm and a preparation method thereof. The preparation process is simple and convenient, an organic solvent is not required, the preparation method is suitable for large-scale production, the electrolyte absorbency of the battery diaphragm is improved, and the prepared sea-island type polyphenylene sulfide composite battery diaphragm has good thermal stability, chemical stability, mechanical property, flame retardance and the like. The preparation method is suitable for preparing the sea-island polyphenylene sulfide composite battery diaphragm, and the prepared sea-island polyphenylene sulfide composite battery diaphragm is suitable for a lithium battery.
Description
Technical Field
The invention belongs to the technical field of battery diaphragm manufacturing, and relates to polyphenylene sulfide composite fibers, in particular to a sea-island polyphenylene sulfide composite battery diaphragm and a preparation method thereof.
Background
Lithium ion batteries are representative of high-performance batteries because of a series of advantages such as high energy density, small self-discharge, long cycle life, no memory effect, small environmental pollution and the like, and are widely applied to the fields of small household appliances such as smart phones, notebook computers, digital cameras, MP3 and the like. In the composition of the lithium ion battery, the diaphragm occupies a very important position, and the service performance and the safety of the lithium ion battery are directly influenced. At present, the polyolefin diaphragm occupies a leading position in the diaphragm market due to the advantages of stable chemical property, low cost, uniform pore size distribution and the like. However, polyolefin separators also have disadvantages such as poor wettability of the electrolyte and poor thermal stability. In order to meet the requirements of high-power lithium ion batteries on the high-temperature dimensional stability and the electrolyte absorption performance of the diaphragm, the development of high-performance diaphragms becomes the focus of attention of researchers.
Polyphenylene Sulfide (PPS) is a polymer containing a p-phenylene sulfide repeating structural unit in a molecule, is a novel functional engineering plastic, has good heat resistance, excellent chemical corrosion resistance and flame retardance, and can be used as a promising substitute of a lithium ion battery diaphragm.
The invention patent of Chinese patent No. CN104795525A discloses a melt-blown polyphenylene sulfide non-woven fabric lithium battery diaphragm and a preparation method thereof, wherein the preparation method comprises the steps of preparing polyphenylene sulfide superfine fibers by a melt-blowing method, and then carrying out hot rolling and heat setting treatment on the superfine fiber net to obtain the melt-blown polyphenylene sulfide non-woven fabric lithium battery diaphragm. The PPS non-woven fabric base material prepared by the melt-blowing method forms a three-dimensional fiber network structure through fibers intertwined together, the structure provides high porosity for the lithium ion battery diaphragm, but the fibers prepared by the melt-blowing method are low in strength, large in diaphragm pore size and uneven in distribution. The invention patent of Chinese patent No. CN112054146A discloses a method for producing battery diaphragm by PPS material and a prepared film, the preparation method in the patent is that the PPS material is added into PP and PE according to the weight ratio of 1-70%, and then the film filled with PPS material and having abundant nanometer micropores is produced by the steps of extrusion, stretching, extension and the like according to the PE film forming process, but the method has complex process and great technical difficulty and is not suitable for large-scale production.
Disclosure of Invention
The invention aims to provide a sea-island polyphenylene sulfide composite battery diaphragm and a preparation method thereof, which overcome the defects in the prior art.
In order to achieve the purpose, the technical method comprises the following steps:
a preparation method of a sea-island polyphenylene sulfide composite battery diaphragm comprises the following steps:
s1, preparing sea-island polyphenylene sulfide composite fibers: mixing polyphenylene sulfide and alkali soluble polyester, and performing melt spinning to obtain sea-island polyphenylene sulfide composite fiber;
s2, preparing the sea-island type polyphenylene sulfide composite battery diaphragm: the sea-island polyphenylene sulfide composite battery diaphragm is obtained by heat treatment, cutting, mixing with the nanofiber, dispersing and pulping, defibering, papermaking and hot pressing.
As a limitation: in the step S1, the melt index of the polyphenylene sulfide is 50-500g/10min, the melt index of the alkali-soluble polyester is 10-50g/10min, the polyphenylene sulfide and the alkali-soluble polyester are dried before being mixed, the drying temperature is 80-160 ℃, and the drying time is 12-24h.
As a further limitation: the mass ratio of the polyphenylene sulfide to the alkali-soluble polyester is 3.
As a further limitation: the fineness of the sea-island polyphenylene sulfide composite fiber prepared in the step S1 is 0.9-5 mu m, and the fiber is round; in the sea-island polyphenylene sulfide composite fiber cut in the step S2, the mass fraction of the sea-island polyphenylene sulfide composite fiber with the length of 5-8mm is 0-25%, the mass fraction of the sea-island polyphenylene sulfide composite fiber with the length of 1-2mm is 0-25%, and the mass fraction of the sea-island polyphenylene sulfide composite fiber with the length of 2-5mm is 50-100%.
As another limitation: the temperature of the heat treatment in the step S2 is 80-150 ℃, and the heat treatment time is 10-60min.
As a limitation: the nano-fiber in the step S2 is aromatic nano-fiber which is cut by an electrostatic spinning and high-speed carding machine, the fiber is round, the diameter is 100-1000nm, the fiber length is 1-3mm, the mass fraction of the polyphenylene sulfide composite fiber cut short in the mixture of the aromatic nano-fiber and the polyphenylene sulfide composite fiber cut short is 80-95%, the rest is the aromatic nano-fiber, the dispersion medium is water, the beating concentration is 3-5 wt%, the rotating speed of a stirring impeller in the defibering process is 3000-3500rad/min, the defibering time is 10-15min, the online concentration in the paper making process is 0.03-0.8%, the hot pressing pressure in the hot pressing process is 10-20MPa, and the hot pressing temperature is 150-230 ℃.
As another limitation: the nano-fiber in the step S2 is natural nano-fiber which is cut by a dissolution method and a high-speed carding machine, the fiber is round, the diameter is 100-1000nm, the fiber length is 1-3mm, the mass fraction of the polyphenylene sulfide composite fiber after being cut in the mixture of the natural nano-fiber and the polyphenylene sulfide composite fiber after being cut is 80-95%, the rest is the natural nano-fiber, the dispersion medium is water, the beating concentration is 3-5 wt%, the rotating speed of a stirring impeller in the defibering process is 3000-3500rad/min, the defibering time is 10-15min, the net surfing concentration in the paper making process is 0.03-0.8%, the hot pressing pressure in the hot pressing process is 10-20MPa, and the hot pressing temperature is 150-230 ℃.
As a further limitation: the nano-fiber in the step S2 is inorganic nano-fiber which is cut by a flame method and a high-speed carding machine, the fiber is round, the diameter is 100-1000nm, the fiber length is 1-3mm, the mass fraction of the polyphenylene sulfide composite fiber after being cut short in the mixture of the inorganic nano-fiber and the polyphenylene sulfide composite fiber after being cut short is 80-95%, the rest is the inorganic nano-fiber, the dispersion medium is water, the beating concentration is 3-5 wt%, the rotating speed of a stirring impeller in the defibering process is 3000-3500rad/min, the defibering time is 10-15min, the net surfing concentration in the paper making process is 0.03-0.8%, the hot pressing pressure in the hot pressing process is 10-20MPa, and the hot pressing temperature is 150-230 ℃.
The invention also provides the sea-island polyphenylene sulfide composite battery diaphragm prepared by the preparation method of the sea-island polyphenylene sulfide composite battery diaphragm, wherein the prepared sea-island polyphenylene sulfide composite battery diaphragm has the porosity of 40-70%, the pore diameter of 0.1-1 mu m, the thickness of 10-30 mu m, the liquid absorption rate of electrolyte of 250-350%, the tensile strength of 15-50MPa and the limiting oxygen index of 38-40.
Due to the adoption of the scheme, compared with the prior art, the invention has the beneficial effects that:
(1) According to the preparation method of the island-type polyphenylene sulfide composite battery diaphragm, polyphenylene sulfide (PPS) has good heat resistance, excellent chemical corrosion resistance and flame retardance, aromatic nanofibers have excellent thermal stability, mechanical property, chemical stability, corrosion resistance and other properties, natural nanofibers have excellent mechanical property, excellent biodegradability and other properties, inorganic nanofibers have excellent thermal stability, flame retardance and other properties, and the island-type polyphenylene sulfide composite battery diaphragm prepared by mixing, dispersing and pulping, defibering, papermaking and hot pressing the island-type polyphenylene sulfide composite fibers and the nanofibers has excellent mechanical strength, uniformity, flame retardance, puncture resistance, thermal stability, chemical stability and other properties, is simple and convenient in preparation process, does not need to use an organic solvent, and is suitable for large-scale production;
(2) According to the sea-island polyphenylene sulfide composite battery diaphragm and the preparation method thereof, the sea-island polyphenylene sulfide composite fibers with different lengths and different titer preliminarily regulate and control the porosity, the aperture and the diaphragm thickness of the battery diaphragm, and a small amount of nano fibers are mixed, so that the uniformity and the micronization of the aperture of the battery diaphragm are further realized, and meanwhile, the electrolyte absorption of the battery diaphragm is improved;
(3) The sea-island polyphenylene sulfide composite battery diaphragm prepared by the preparation method provided by the invention has higher electrolyte absorbency, and has good thermal stability, chemical stability, mechanical properties, flame retardance and the like, so that the requirements of the lithium ion battery diaphragm are met, the safety of the lithium ion battery is improved, and the service life of the lithium ion battery is prolonged.
In conclusion, the preparation method of the sea-island polyphenylene sulfide composite battery diaphragm provided by the invention is simple and convenient in preparation process, does not need to use an organic solvent, is suitable for large-scale production, regulates and controls the battery diaphragm, improves the electrolyte absorbency of the battery diaphragm, has good thermal stability, chemical stability, mechanical properties, flame retardance and the like, improves the safety of a lithium ion battery, and prolongs the service life of the lithium ion battery.
The preparation method is suitable for preparing the sea-island polyphenylene sulfide composite battery diaphragm, and the prepared sea-island polyphenylene sulfide composite battery diaphragm is suitable for lithium batteries.
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The invention is described in further detail below with reference to the following figures and specific examples.
FIGS. 1a and 1b are SEM images of polyphenylene sulfide ultrafine fibers, FIGS. 1c and 1d are SEM images of polyimide nanofibers, and FIGS. 1e and 1f are SEM images of sea-island type polyphenylene sulfide composite battery separators prepared in example 1 of the present invention;
FIG. 2 is a mapping chart of a sea-island type polyphenylene sulfide composite battery separator prepared in example 1 of the present invention;
FIGS. 3a-e are graphs comparing thermal stability of sea-island type polyphenylene sulfide composite battery separator prepared in example 1 according to the present invention with Celgard commercial membrane;
FIGS. 4a and 4b are flame retardant performance test charts for Celgard commercial membranes; FIGS. 4c and 4d are graphs for testing flame retardant properties of the sea-island type polyphenylene sulfide composite battery separator prepared in example 1 according to the present invention;
FIGS. 5a and 5b are SEM images of polyphenylene sulfide ultrafine fibers, FIGS. 5c and 5d are SEM images of cellulose nanofibers, and FIGS. 5e and 5f are SEM images of sea-island type polyphenylene sulfide composite battery separators prepared in example 7 of the present invention;
FIG. 6 is a mapping chart of sea-island type polyphenylene sulfide composite battery separator prepared in example 7 of the present invention;
FIGS. 7a-e are graphs comparing the thermal stability of sea-island polyphenylene sulfide composite battery separator prepared in example 7 of the present invention with that of Celgard commercial membrane;
FIGS. 8a and 8b are flame retardant performance test charts for Celgard commercial membranes; FIGS. 8c and 8d are graphs for testing flame retardant properties of sea-island type polyphenylene sulfide composite battery separators prepared in example 7 according to the present invention;
FIGS. 9a and 9b are SEM images of polyphenylene sulfide ultrafine fibers, FIGS. 9c and 9d are SEM images of glass nanofibers, and FIGS. 9e and 9f are SEM images of sea-island type polyphenylene sulfide composite battery separators prepared in example 13 according to the present invention;
FIG. 10 is a mapping chart of a sea-island type polyphenylene sulfide composite battery separator prepared in example 13 of the present invention;
FIGS. 11a-e are graphs comparing thermal stability of sea-island polyphenylene sulfide composite battery separator membrane prepared in example 13 of the present invention with Celgard commercial membrane;
FIGS. 12a and 12b are flame retardant performance test charts for Celgard commercial membranes; fig. 12c and 12d are flame retardant property test charts of the sea-island type polyphenylene sulfide composite battery separator prepared in example 13 of the present invention.
Detailed Description
The present invention is further described with reference to the following examples, but it should be understood by those skilled in the art that the present invention is not limited to the following examples, and any modifications and equivalent changes based on the specific examples of the present invention are within the scope of the claims of the present invention.
EXAMPLES 1-6 preparation of sea-island type polyphenylene sulfide composite Battery separator
Examples 1 to 6 are respectively a method for preparing a sea-island type polyphenylene sulfide composite battery separator, the process parameters in the preparation process are shown in table 1, and the specific preparation process comprises the following steps:
s1, preparing sea-island polyphenylene sulfide composite fibers: the sea-island polyphenylene sulfide (PPS) with the melt index of 50-500g/10min and the alkali-soluble Polyester (PET) with the melt index of 10-50g/10min are dried at the drying temperature of 80-160 ℃ for 12-24h, then are mixed according to the mass ratio of 3Composite fibers; the screw extrusion temperature is 315-325 ℃, the screw melt pressure is 60-120bar, the spinning box temperature is 315-325 ℃, and the spinning component pressure is less than 60kgf/cm in the melt spinning process 2 The spinning speed is 600-1000m/min, and the drafting multiple is 3.6-4.3 times.
S2, preparing the sea-island polyphenylene sulfide composite battery diaphragm: cutting the sea-island polyphenylene sulfide composite fiber after heat treatment, wherein the heat treatment temperature is 80-150 ℃, the heat treatment time is 10-60min, weighing the relevant data in table 1, the mass fraction of the sea-island polyphenylene sulfide composite fiber with the length of 5-8mm in the cut sea-island polyphenylene sulfide composite fiber is 0-25%, the mass fraction of the sea-island polyphenylene sulfide composite fiber with the length of 1-2mm is 0-25%, the mass fraction of the sea-island polyphenylene sulfide composite fiber with the length of 2-5mm is 50-100%, the cut sea-island polyphenylene sulfide composite fiber is formed by cutting through an electrostatic spinning and a high-speed carding machine, the fiber is circular, the diameter is 100-1000nm, the aromatic nano fiber with the fiber length of 1-3mm is mixed, wherein the mass fraction of the cut sea-island polyphenylene sulfide composite fiber is 80-95%, the rest is the aromatic nano fiber, dispersing beating is carried out by using a water level dispersion medium, the beating concentration is 3-5 wt, then carrying out heat pressing on the sea-island polyphenylene sulfide composite paper with the rotating speed of stirring 3000-3500rad/min, the defibering time is 10-15min, the net beating pressure is 0.03-15 min, and the final hot pressing temperature is 20-230 ℃ and the hot pressing temperature is 10-20 MPa.
The aromatic nanofibers in examples 1-6 are one of polyimide nanofibers, polysulfonamide nanofibers, aramid nanofibers, and polyetheretherketone nanofibers.
Table 1 examples 1-6 process parameters in preparation of sea-island type polyphenylene sulfide composite battery separator
The specific performance indexes of the sea-island polyphenylene sulfide composite battery diaphragm prepared by the preparation method are shown in table 2.
TABLE 2 Performance indices of sea-island type polyphenylene sulfide composite battery separators prepared in examples 1 to 6
As is clear from Table 2, the sea-island polyphenylene sulfide composite battery separators obtained in examples 1 to 6 had a porosity of 40 to 70%, a pore diameter of 0.1 to 1 μm, a thickness of 10 to 30 μm, a uniform and fine pore diameter, an electrolyte absorption rate of 250 to 350%, a high electrolyte absorption capacity, a tensile strength of 15 to 50MPa, and good mechanical properties. In addition, the limited oxygen index of the sea-island polyphenylene sulfide composite battery diaphragm prepared in the examples 1-6 is 38-40, and the limited oxygen index of the existing Celgard commercial membrane is 18, so that the sea-island polyphenylene sulfide composite battery diaphragm prepared in the examples 1-6 of the invention has good flame retardant property.
FIGS. 1a and 1b are SEM images of polyphenylene sulfide (PPS) microfibers, FIGS. 1c and 1d are SEM images of polyimide nanofibers, and FIGS. 1e and 1f are SEM images of sea-island PPS composite battery separators prepared in example 1. As is clear from FIG. 1, the pore diameter of the sea-island PPS composite battery separator after polyimide nanofibers are added is reduced. The mapping graph of the sea-island polyphenylene sulfide composite battery diaphragm prepared in example 1 is shown in fig. 2, the comparison graph of the thermal stability performance of the sea-island polyphenylene sulfide composite battery diaphragm and the Celgard commercial membrane is shown in fig. 3, the a-e in fig. 3 sequentially show the dimensional changes of the sea-island polyphenylene sulfide composite battery diaphragm and the Celgard commercial membrane at 25 ℃, 150 ℃, 175 ℃, 200 ℃ and 230 ℃, celgard represents the Celgard commercial membrane, and PSS/PI represents the sea-island polyphenylene sulfide composite battery diaphragm of example 1, wherein PSS is polyphenylene sulfide and PI is polyimide, and as can be seen from fig. 3, the dimensions of the sea-island polyphenylene sulfide composite battery diaphragm at 25 ℃, 150 ℃, 175 ℃, 200 ℃ and 230 ℃ are almost unchanged, while the dimensional changes of the Celgard commercial membrane at 5 ℃, 150 ℃, 175 ℃, 200 ℃ and 230 ℃ are obvious, so the thermal stability performance of the sea-island polyphenylene sulfide composite battery diaphragm is superior to the Celgard commercial membrane; the figure for comparing the flame retardant performance of the sea-island polyphenylene sulfide composite battery diaphragm with the Celgard commercial membrane is shown in FIG. 4, wherein FIG. 4a is the Celgard commercial membrane before combustion, FIG. 4b is the Celgard commercial membrane after combustion, FIG. 4c is the sea-island polyphenylene sulfide composite battery diaphragm before combustion, and FIG. 4d is the sea-island polyphenylene sulfide composite battery diaphragm after combustion, and it can be seen from FIG. 4 that the flame retardant performance of the sea-island polyphenylene sulfide composite battery diaphragm is better than that of the Celgard commercial membrane, and the sea-island polyphenylene sulfide composite battery diaphragms prepared in examples 2-6 have similar performance to that of the sea-island polyphenylene sulfide composite battery diaphragm prepared in example 1.
Examples 7-12 sea-island type polyphenylene sulfide composite Battery separator preparation method
Examples 7 to 12 are respectively a method for preparing a sea-island type polyphenylene sulfide composite battery separator, the process parameters in the preparation process are shown in table 3, and the specific preparation process comprises the following steps:
s1, preparing sea-island polyphenylene sulfide composite fibers: the sea-island polyphenylene sulfide composite fiber with the titer of 0.9-5 mu m and the round fiber is obtained by drying polyphenylene sulfide (PPS) with the melt index of 50-500g/10min and alkali-soluble Polyester (PET) with the melt index of 10-50g/10min at the drying temperature of 80-160 ℃ for 12-24h, mixing the materials in a mass ratio of 3; the extrusion temperature of the screw is 315-325 ℃, the melt pressure of the screw is 60-120bar, the temperature of the spinning manifold is 315-325 ℃, and the pressure of the spinning component is less than 60kgf/cm in the melt spinning process 2 The spinning speed is 600-1000m/min, and the drafting multiple is 3.6-4.3 times.
S2, preparing the sea-island polyphenylene sulfide composite battery diaphragm: cutting the sea-island polyphenylene sulfide composite fiber after heat treatment, wherein the heat treatment temperature is 80-150 ℃, the heat treatment time is 10-60min, weighing the relevant data in table 3, the mass fraction of the sea-island polyphenylene sulfide composite fiber with the length of 5-8mm in the cut sea-island polyphenylene sulfide composite fiber is 0-25%, the mass fraction of the sea-island polyphenylene sulfide composite fiber with the length of 1-2mm is 0-25%, the mass fraction of the sea-island polyphenylene sulfide composite fiber with the length of 2-5mm is 50-100%, the cut sea-island polyphenylene sulfide composite fiber is formed by cutting the sea-island polyphenylene sulfide composite fiber with the length of 1-3mm by a dissolution method and a high-speed carding machine, the fiber is circular, the diameter is 100-1000nm, the natural nano fiber with the fiber length of 1-3mm is mixed, wherein the mass fraction of the cut-island polyphenylene sulfide composite fiber is 80-95%, the rest is the natural nano fiber, dispersing and pulping is carried out pulping by a water level dispersion medium, the pulping concentration is 3-5 wt, then carrying out pyrolysis by stirring at the rotating speed of 3000-3500rad/min, the final hot-pressing of the polyphenylene sulfide battery with the concentration of 0.03-230-20 ℃, and finally carrying out hot pressing, and obtaining the hot-pressing.
The natural nanofibers of examples 7-12 are one of cellulose nanofibers, chitin nanofibers, and lignin nanofibers.
Table 3 examples 7-12 process parameters and performance indexes in preparation of sea-island type polyphenylene sulfide composite battery separator
The specific performance indexes of the sea-island polyphenylene sulfide composite battery diaphragm prepared by the preparation method are shown in table 4.
TABLE 4 Performance indices of sea-island type polyphenylene sulfide composite battery separators obtained in examples 7 to 12
As is clear from Table 4, the sea-island polyphenylene sulfide composite battery separators obtained in examples 7 to 12 had a porosity of 40 to 70%, a pore diameter of 0.1 to 1 μm, a thickness of 10 to 30 μm, a uniform and fine pore diameter, an electrolyte absorption rate of 250 to 350%, a high electrolyte absorption performance, a tensile strength of 15 to 50MPa, and good mechanical properties. In addition, the limited oxygen index of the sea-island polyphenylene sulfide composite battery diaphragm prepared in the example 7-12 is 38-40, and the limited oxygen index of the existing Celgard commercial membrane is 18, so that the sea-island polyphenylene sulfide composite battery diaphragm prepared in the example 7-12 has good flame retardant property.
FIGS. 5a and 5b are SEM images of polyphenylene sulfide superfine fibers, FIGS. 5c and 5d are SEM images of cellulose nanofibers, and FIGS. 5e and 5f are SEM images of sea-island polyphenylene sulfide composite battery separators prepared in example 7. As is clear from FIG. 5, the pore diameter of the sea-island polyphenylene sulfide composite battery separator after the addition of the cellulose nanofibers is reduced. A mapping graph of the sea-island polyphenylene sulfide composite battery diaphragm prepared in example 7 is shown in fig. 6, a comparison graph of the thermal stability of the sea-island polyphenylene sulfide composite battery diaphragm and the Celgard commercial membrane is shown in fig. 7, and a-e in the sequence of the sea-island polyphenylene sulfide composite battery diaphragm and the Celgard commercial membrane in fig. 7 are shown, wherein Celgard represents the Celgard commercial membrane, and PSS/CNF represents the sea-island polyphenylene sulfide composite battery diaphragm of example 7, wherein PSS is polyphenylene sulfide, CNF is cellulose nanofiber, as can be seen from fig. 7, the dimensions of the sea-island polyphenylene sulfide composite battery diaphragm at 25 ℃, 150 ℃, 175 ℃, 200 ℃ and 230 ℃ are hardly changed, while the dimensional changes of the Celgard commercial membrane at 5 ℃, 150 ℃, 175 ℃, 200 ℃ and 230 ℃ are obvious, so that the thermal stability of the sea-island polyphenylene sulfide composite battery diaphragm is superior to that of the Celgard commercial membrane; the figure of the comparison of the flame retardant performance of the sea-island polyphenylene sulfide composite battery diaphragm and the Celgard commercial membrane is shown in FIG. 8, wherein FIG. 8a is the Celgard commercial membrane before combustion, FIG. 8b is the Celgard commercial membrane after combustion, FIG. 8c is the sea-island polyphenylene sulfide composite battery diaphragm before combustion, and FIG. 8d is the sea-island polyphenylene sulfide composite battery diaphragm after combustion, it can be seen from FIG. 8 that the flame retardant performance of the sea-island polyphenylene sulfide composite battery diaphragm is better than that of the Celgard commercial membrane, and the sea-island polyphenylene sulfide composite battery diaphragms prepared in examples 8-12 have similar performance to that of the sea-island polyphenylene sulfide composite battery diaphragm prepared in example 7.
Examples 13-18 preparation of sea-island type polyphenylene sulfide composite Battery separator
Examples 13 to 18 are methods for preparing sea-island type polyphenylene sulfide composite battery separators, respectively, the process parameters in the preparation process are shown in table 5, and the specific preparation process comprises the following steps:
s1, preparing sea-island polyphenylene sulfide composite fibers: the sea-island polyphenylene sulfide composite fiber with the titer of 0.9-5 mu m and the round fiber is obtained by drying polyphenylene sulfide (PPS) with the melt index of 50-500g/10min and alkali-soluble Polyester (PET) with the melt index of 10-50g/10min at the drying temperature of 80-160 ℃ for 12-24h, mixing the materials in a mass ratio of 3; the extrusion temperature of the screw is 315-325 ℃, the melt pressure of the screw is 60-120bar, the temperature of the spinning manifold is 315-325 ℃, and the pressure of the spinning component is less than 60kgf/cm in the melt spinning process 2 The spinning speed is 600-1000m/min, and the drafting multiple is 3.6-4.3 times.
S2, preparing the sea-island type polyphenylene sulfide composite battery diaphragm: cutting the sea-island polyphenylene sulfide composite fiber after heat treatment, wherein the heat treatment temperature is 80-150 ℃, the heat treatment time is 10-60min, weighing the relevant data in table 5, the mass fraction of the sea-island polyphenylene sulfide composite fiber with the length of 5-8mm in the cut sea-island polyphenylene sulfide composite fiber is 0-25%, the mass fraction of the sea-island polyphenylene sulfide composite fiber with the length of 1-2mm is 0-25%, the mass fraction of the sea-island polyphenylene sulfide composite fiber with the length of 2-5mm is 50-100%, the cut sea-island polyphenylene sulfide composite fiber is formed by cutting the sea-island polyphenylene sulfide composite fiber with the length of 1-3mm by a flame method and a high-speed carding machine, the fiber is circular, the diameter is 100-1000nm, the inorganic nano fiber with the fiber length of 1-3mm is mixed, wherein the mass fraction of the cut-island polyphenylene sulfide composite fiber is 80-95%, the rest is the inorganic nano fiber, dispersing and pulping is carried out beating by a water level dispersion medium, the beating concentration is 3-5 wt, then carrying out hot pressing on the sea-island polyphenylene sulfide composite paper with the rotating speed of stirring 3000-3500rad/min, the defibering time is 10-15min, the final hot pressing temperature is 0.03-20 MPa, and the final hot pressing temperature is 10-20 MPa.
The inorganic nanofibers of examples 7-12 are one of glass nanofibers, ceramic nanofibers, quartz nanofibers, and silicon boron nitrogen nanofibers.
TABLE 5 Process parameters and Performance indices for sea-island polyphenylene sulfide composite Battery separator preparation of examples 13-18
The specific performance indexes of the sea-island polyphenylene sulfide composite battery diaphragm prepared by the preparation method are shown in table 6.
TABLE 6 Performance indexes of sea-island type polyphenylene sulfide composite battery separators prepared in examples 13 to 18
As is clear from Table 6, the sea-island type polyphenylene sulfide composite battery separators obtained in examples 13 to 18 had a porosity of 40 to 70%, a pore diameter of 0.1 to 1 μm, a thickness of 10 to 30 μm, a uniform and fine pore diameter of the battery separator, an electrolyte absorption rate of 250 to 350%, a high electrolyte absorption performance, a tensile strength of 15 to 50MPa, and good mechanical properties. In addition, the limit oxygen index of the sea-island polyphenylene sulfide composite battery diaphragm prepared in the example 13-18 is 38-40, and the limit oxygen index of the existing Celgard commercial membrane is 18, so that the sea-island polyphenylene sulfide composite battery diaphragm prepared in the example 13-18 of the invention has good flame retardant property.
FIGS. 9a and 9b are SEM images of polyphenylene sulfide ultrafine fibers, FIGS. 9c and 9d are SEM images of glass nanofibers, and FIGS. 9e and 9f are SEM images of sea-island polyphenylene sulfide composite battery separators obtained in example 13, and it is clear from FIG. 9 that the pore diameter of the sea-island polyphenylene sulfide composite battery separator after the addition of polyimide nanofibers is decreased. The mapping chart of the sea-island polyphenylene sulfide composite battery diaphragm prepared in example 13 is shown in fig. 10, the comparison chart of the thermal stability performance of the sea-island polyphenylene sulfide composite battery diaphragm and the Celgard commercial membrane is shown in fig. 11, the dimensional changes of the sea-island polyphenylene sulfide composite battery diaphragm and the Celgard commercial membrane with the sequence of a-e of 25 ℃, 150 ℃, 175 ℃, 200 ℃ and 230 ℃ in fig. 11, celgard represents the Celgard commercial membrane, and PSS/GNF represents the sea-island polyphenylene sulfide composite battery diaphragm of example 13, wherein PSS is polyphenylene sulfide, GNF is glass nanofiber, as can be seen in fig. 11, the dimensions of the sea-island polyphenylene sulfide composite battery diaphragm at 25 ℃, 150 ℃, 175 ℃, 200 ℃ and 230 ℃ are almost unchanged, while the dimensional changes of the Celgard commercial membrane at 5 ℃, 150 ℃, 175 ℃, 200 ℃ and 230 ℃ are obvious, so the thermal stability performance of the sea-island polyphenylene sulfide composite battery diaphragm is better than the Celgard commercial membrane; fig. 12 shows a graph of comparing flame retardant properties of a sea-island type polyphenylene sulfide composite battery diaphragm with a Celgard commercial membrane, fig. 12a shows the Celgard commercial membrane before combustion, fig. 12b shows the Celgard commercial membrane after combustion, fig. 12c shows the sea-island type polyphenylene sulfide composite battery diaphragm before combustion, and fig. 12d shows the sea-island type polyphenylene sulfide composite battery diaphragm after combustion, and as can be seen from fig. 12, the flame retardant properties of the sea-island type polyphenylene sulfide composite battery diaphragm are superior to those of the Celgard commercial membrane, and the sea-island type polyphenylene sulfide composite battery diaphragms prepared in examples 14 to 18 are similar to those of the sea-island type polyphenylene sulfide composite battery diaphragm prepared in example 13.
Claims (5)
1. A preparation method of a sea-island polyphenylene sulfide composite battery diaphragm is characterized by comprising the following steps:
s1, preparing sea-island polyphenylene sulfide composite fibers: the preparation method comprises the following steps of drying and mixing polyphenylene sulfide and alkali-soluble polyester, and carrying out melt spinning after mixing to obtain the sea-island type polyphenylene sulfide composite fiber; the prepared sea-island polyphenylene sulfide composite fiber is circular; the melt index of the polyphenylene sulfide is 50-500g/10min, the melt index of the alkali-soluble polyester is 10-50g/10min, the drying temperature of the polyphenylene sulfide and the alkali-soluble polyester is 80-160 ℃, and the drying time is 12-24h; the mass ratio of the polyphenylene sulfide to the alkali-soluble polyester is 3;
s2, preparing the sea-island type polyphenylene sulfide composite battery diaphragm: cutting the sea-island polyphenylene sulfide composite fiber after heat treatment, mixing with the nanofiber, and obtaining the sea-island polyphenylene sulfide composite battery diaphragm through dispersion pulping, defibering, papermaking and hot pressing; wherein the mass fraction of the chopped polyphenylene sulfide composite fiber in the mixture of the nano fiber and the chopped polyphenylene sulfide composite fiber is 80-95%; the mass fraction of the sea-island polyphenylene sulfide composite fiber with the length of 5-8mm in the cut sea-island polyphenylene sulfide composite fiber is 0-25%, the mass fraction of the sea-island polyphenylene sulfide composite fiber with the length of 1-2mm is 0-25%, and the mass fraction of the sea-island polyphenylene sulfide composite fiber with the length of 2-5mm is 50-100%; the heat treatment temperature is 80-150 deg.C, and the heat treatment time is 10-60min.
2. The method for preparing a sea-island type polyphenylene sulfide composite battery separator according to claim 1, wherein the nanofibers in step S2 are aromatic nanofibers, the aromatic nanofibers are one of polyimide nanofibers, polysulfonamide nanofibers, aramid nanofibers, and polyetheretherketone nanofibers, the aromatic nanofibers are cut by electrospinning and a high-speed carding machine, the fibers are round, the diameter is 100 to 1000nm, the fiber length is 1 to 3mm, the mass fraction of the polyphenylene sulfide composite fibers cut from a mixture of the aromatic nanofibers and the cut polyphenylene sulfide composite fibers is 80 to 95%, the rest is the aromatic nanofibers, the dispersion medium is water, the beating concentration is 3 to 5 wt, the rotation speed of a stirring impeller in the beating process is 3000 to 3500rad/min, the defibering time is 10 to 15min, the web concentration in the paper making process is 0.03 to 0.8%, the hot-pressing pressure in the hot-pressing process is 10 to 20MPa, and the hot-pressing temperature is 150 to 230 ℃.
3. The method of claim 1, wherein the nanofibers are formed by cutting the nanofibers into a circular shape having a diameter of 100-1000nm and a length of 1-3mm by a dissolution method and a high speed carding machine, the diameter of the fibers is 100-1000nm, the mass fraction of the chopped polyphenylene sulfide composite fibers in the mixture of the natural nanofibers and the chopped polyphenylene sulfide composite fibers is 80-95%, the remainder is the natural nanofibers, the dispersion medium is water, the beating concentration is 3-5 wt, the rotation speed of the impeller is 3000-3500rad/min during the beating, the beating time is 10-15min, the web concentration is 0.03-0.8% during the paper making, the hot pressing pressure is 10-20MPa during the hot pressing, and the hot pressing temperature is 150-230 ℃.
4. The method of claim 1, wherein the nanofibers in step S2 are made of inorganic nanofibers selected from the group consisting of glass nanofibers, ceramic nanofibers, quartz nanofibers, and silicon boron nitrogen nanofibers, the inorganic nanofibers are cut by a flame method and a high speed carding machine, the fibers are round, the diameter is 100 to 1000nm, the fiber length is 1 to 3mm, the mass fraction of the polyphenylene sulfide composite fibers cut from a mixture of the inorganic nanofibers and the cut polyphenylene sulfide composite fibers is 80 to 95%, the balance is the inorganic nanofibers, the dispersion medium is water, the beating concentration is 3 to 5 wt%, the rotational speed of the impeller during the beating process is 3000 to 3500rad/min, the beating time is 10 to 15min, the web concentration during the paper making process is 0.03 to 0.8%, the hot pressing pressure during the hot pressing process is 10 to 20MPa, and the hot pressing temperature is 150 to 230 ℃.
5. The sea-island type polyphenylene sulfide composite battery separator prepared by the method for preparing a sea-island type polyphenylene sulfide composite battery separator according to any one of claims 1 to 4, wherein the sea-island type polyphenylene sulfide composite battery separator is prepared with a porosity of 40 to 70%, a pore diameter of 0.1 to 1 μm, a thickness of 10 to 30 μm, an electrolyte imbibition rate of 250 to 350%, a tensile strength of 15 to 50MPa, and a limiting oxygen index of 38 to 40.
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