CN111933881B - Microporous polymer membrane - Google Patents
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- CN111933881B CN111933881B CN202011103458.1A CN202011103458A CN111933881B CN 111933881 B CN111933881 B CN 111933881B CN 202011103458 A CN202011103458 A CN 202011103458A CN 111933881 B CN111933881 B CN 111933881B
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Abstract
The invention discloses a microporous polymer membrane which comprises the following raw materials in parts by mass: 50-68 parts of polypropylene, 0.8-1.2 parts of nucleating agent, 0.4-0.9 part of thickening agent, 3-5 parts of binder, 0.2-0.5 part of wetting agent, 3-6 parts of triethylene glycol dimethacrylate, 0.3-0.7 part of sodium hexadecylbenzene sulfonate, 2-5 parts of sodium trimethylsilanolate and 1-2 parts of pentaerythritol zinc. The microporous polymer membrane of the invention has the advantages of continuous production, simple process flow operation, low energy consumption and the like; in addition, the microporous polymer membrane has high longitudinal tensile strength and long service life, and can meet the requirements of popularization and application.
Description
Technical Field
The invention belongs to the technical field of diaphragm preparation, and particularly relates to a microporous polymer membrane.
Background
Lithium ion batteries operate primarily by movement of lithium ions between a positive electrode and a negative electrode. Between the positive and negative electrodes of a lithium ion battery is a layer of film material, commonly referred to as a separator, which is an important component of the lithium ion battery. The separator has two basic functions: isolating the positive and negative electrodes to prevent short circuit in the battery; can be wetted by the electrolyte to form a channel for ion migration. The following characteristics should be provided in practical application: (1) the insulation of electrons; (2) high electrical conductivity; (3) good mechanical property, can be used for mechanical manufacturing treatment; (4) the thickness is uniform; (5) the amount of dimensionally stable deformation is small when heated.
The performance of the membrane is related to porosity, pore size and distribution, air permeability, thermal properties, mechanical properties, and the like. The microporous film of Polyethylene (PE) and polypropylene (PP) has higher porosity, lower resistance, higher tear strength, better acid and alkali resistance, good elasticity and retention performance to aprotic solvents, so that the microporous film is used as a diaphragm material in the initial research and development stage of lithium ion batteries. With the continuous expansion of the application range of lithium batteries, the application range of lithium batteries is from digital to electric automobiles, electric tools and the like. The requirements for lithium battery separators are continuously improved, and the traditional polyolefin porous membrane cannot meet the requirements of electrical property and safety at the same time.
Chinese patent application document "a polypropylene microporous membrane and a preparation method thereof and a lithium battery diaphragm (application publication No. CN 110277527A)" discloses a preparation method of a polypropylene microporous membrane, which comprises the following steps: mixing polypropylene and a nucleating agent, and then sequentially performing extrusion and tape casting to obtain a tape casting sheet; performing bidirectional synchronous stretching on the casting sheet to obtain a polypropylene microporous membrane; the bidirectional synchronous stretching is to simultaneously perform longitudinal stretching and transverse stretching. The method provided by the invention has the advantages of continuous production, simple process flow operation, low energy consumption, no environmental pollution and the like; meanwhile, the polypropylene microporous membrane prepared by the method provided by the invention has good mechanical properties, especially higher puncture strength, but has the problems of poor tensile strength and incapability of meeting application requirements.
Disclosure of Invention
The invention provides a microporous polymer membrane, which aims to solve the problem of poor tensile strength of the existing membrane.
In order to solve the technical problems, the invention adopts the following technical scheme:
a microporous polymer membrane comprises the following raw materials in parts by mass: 50-68 parts of polypropylene, 0.8-1.2 parts of nucleating agent, 0.4-0.9 part of thickening agent, 3-5 parts of binder, 0.2-0.5 part of wetting agent, 3-6 parts of triethylene glycol dimethacrylate, 0.3-0.7 part of sodium hexadecylbenzene sulfonate, 2-5 parts of sodium trimethylsilanolate and 1-2 parts of pentaerythritol zinc;
the preparation method of the microporous polymer membrane comprises the following steps:
(1) mixing the raw materials in parts by mass, and stirring for 16-23min at the microwave power of 120-250W, the temperature of 48-55 ℃ and the rotating speed of 200-300r/min to obtain a mixture;
(2) extruding and casting the mixture prepared in the step (1) by using an extruder to obtain a casting sheet, wherein the temperature of a first zone of the extruder is 165-173 ℃, the temperature of a second zone of the extruder is 191-197 ℃, the temperature of a third zone of the extruder is 210-218 ℃, the temperature of a fourth zone of the extruder is 232-239 ℃, and the temperature of a neck mold is 232-240 ℃ in the extrusion process; in the casting process, the rotating speed of a screw is 47-52r/min, and the rotating speed of a metering pump is 15-20 r/min;
(3) carrying out bidirectional synchronous stretching on the casting sheet prepared in the step (2), namely simultaneously carrying out transverse stretching and longitudinal stretching to prepare a microporous polymer membrane; the temperature of the transverse stretching and the longitudinal stretching is 123-138 ℃, the magnification of the longitudinal stretching is 1.5-2.2 times, and the magnification of the transverse stretching is 3.1-3.8 times.
Preferably, the microporous polymer membrane comprises the following raw materials in parts by mass: 60 parts of polypropylene, 1 part of nucleating agent, 0.7 part of thickening agent, 4 parts of binder, 0.3 part of wetting agent, 5 parts of triethylene glycol dimethacrylate, 0.6 part of sodium hexadecylbenzene sulfonate, 3 parts of sodium trimethylsilanolate and 1.6 parts of pentaerythritol zinc.
Preferably, the isotacticity of the polypropylene is more than or equal to 98 percent.
Preferably, the nucleating agent comprises one or more of a complex of a metal salt and a dicarboxylic acid, a fused ring compound, an aromatic amine compound and a rare earth compound.
Preferably, the thickener is carboxymethyl ethyl ether cellulose.
Preferably, the binder is methyl 3-methoxyacrylate
Preferably, the wetting agent is polyoxyethylene lauryl ether.
Preferably, in the step (1), the raw materials are mixed according to the parts by mass, and then stirred for 20min under the conditions that the microwave power is 200W, the temperature is 52 ℃ and the rotating speed is 250r/min, so as to obtain the mixture.
Preferably, the thickness of said casting sheet in the step (2) is 74 to 115 μm.
The invention has the following beneficial effects:
(1) the longitudinal tensile strength of the microporous polymer membrane prepared by the invention is obviously superior to that of the microporous polymer membrane prepared by the prior art, the strength is higher than 61.97%, and the technical problem that the microporous polymer membrane prepared by the prior art is poor in longitudinal tensile strength is solved.
(2) The triethylene glycol dimethacrylate, the sodium hexadecylbenzene sulfonate, the sodium trimethylsilanolate and the pentaerythritol zinc are simultaneously added to play a synergistic role in preparing the microporous polymer membrane, and the longitudinal tensile strength is synergistically improved because: the sodium hexadecylbenzene sulfonate has good dispersing and activating effects, can increase pores on the surface of a polypropylene material, and can enable sodium trimethylsilanolate to permeate into the polypropylene material to form a stable connecting structure, so that the sodium hexadecylbenzene sulfonate can promote the effects of triethylene glycol dimethacrylate, pentaerythritol zinc and polypropylene, and the triethylene glycol dimethacrylate can improve the toughness of a polypropylene bonding layer, therefore, the sodium hexadecylbenzene sulfonate can promote the improvement of the structural toughness of the polypropylene and the longitudinal tensile strength of a microporous polymer film; the sodium trimethylsilanolate has strong permeability, can improve the adhesive force among polypropylene, triethylene glycol dimethacrylate and pentaerythritol zinc, enables the polypropylene, the triethylene glycol dimethacrylate and the pentaerythritol zinc to be uniformly dispersed in a polypropylene material, provides an acting point for surface modification of the polypropylene material, and is beneficial to improving the longitudinal tensile strength of a microporous polymer membrane.
(3) The microporous polymer membrane of the invention has the advantages of continuous production, simple process flow operation, low energy consumption and the like; in addition, the microporous polymer membrane has high longitudinal tensile strength and long service life, and can meet the requirements of popularization and application.
Detailed Description
In order to facilitate a better understanding of the invention, the following examples are given to illustrate, but not to limit the scope of the invention.
In the embodiment, the microporous polymer membrane comprises the following raw materials in parts by mass: 50-68 parts of polypropylene, 0.8-1.2 parts of nucleating agent, 0.4-0.9 part of thickening agent, 3-5 parts of binder, 0.2-0.5 part of wetting agent, 3-6 parts of triethylene glycol dimethacrylate, 0.3-0.7 part of sodium hexadecylbenzene sulfonate, 2-5 parts of sodium trimethylsilanolate and 1-2 parts of pentaerythritol zinc, wherein the nucleating agent comprises one or more of a compound of metal salt and dicarboxylic acid, a fused ring compound, an aromatic amine compound and a rare earth compound; the thickening agent is carboxymethyl ethyl ether cellulose; the binder is 3-methoxy methyl acrylate; the wetting agent is polyoxyethylene lauryl ether; the preparation method comprises the following steps:
(1) mixing the raw materials in parts by mass, and stirring for 16-23min at the microwave power of 120-250W, the temperature of 48-55 ℃ and the rotating speed of 200-300r/min to obtain a mixture;
(2) extruding and casting the mixture prepared in the step (1) by using an extruder to obtain a casting sheet, wherein the temperature of a first zone of the extruder is 165-173 ℃, the temperature of a second zone of the extruder is 191-197 ℃, the temperature of a third zone of the extruder is 210-218 ℃, the temperature of a fourth zone of the extruder is 232-239 ℃, and the temperature of a neck mold is 232-240 ℃ in the extrusion process; in the casting process, the rotating speed of a screw is 47-52r/min, and the rotating speed of a metering pump is 15-20 r/min; the thickness of the obtained casting sheet is 74 to 115 μm;
(3) carrying out bidirectional synchronous stretching on the casting sheet prepared in the step (2), namely simultaneously carrying out transverse stretching and longitudinal stretching to prepare a microporous polymer membrane; the temperature of the transverse stretching and the longitudinal stretching is 123-138 ℃, the magnification of the longitudinal stretching is 1.5-2.2 times, and the magnification of the transverse stretching is 3.1-3.8 times.
The following is a more specific example.
Example 1
A microporous polymer membrane comprises the following raw materials in parts by mass: 60 parts of polypropylene (a product of F401 type provided by China petrochemical Yangzi petrochemical company, the isotacticity of which is 98%), 1 part of nucleating agent (a product of DX-Z3C type provided by Dingxin Plastic materials Co., Ltd., Dongguan), 0.7 part of thickening agent, 4 parts of binder, 0.3 part of wetting agent, 5 parts of triethylene glycol dimethacrylate, 0.6 part of sodium hexadecylbenzene sulfonate, 3 parts of sodium trimethylsilanolate and 1.6 parts of pentaerythritol zinc; the thickening agent is carboxymethyl ethyl ether cellulose; the binder is 3-methoxy methyl acrylate; the wetting agent is polyoxyethylene lauryl ether; the preparation method comprises the following steps:
(1) mixing the raw materials in parts by mass, and stirring for 20min at the microwave power of 200W, the temperature of 52 ℃ and the rotating speed of 250r/min to prepare a mixture;
(2) extruding and casting the mixture prepared in the step (1) by using an extruder to obtain a casting sheet, wherein the temperature of a first zone of the extruder is 170 ℃, the temperature of a second zone of the extruder is 195 ℃, the temperature of a third zone of the extruder is 216 ℃, the temperature of a fourth zone of the extruder is 235 ℃ and the temperature of a neck mold is 237 ℃; in the casting process, the rotating speed of a screw is 50r/min, and the rotating speed of a metering pump is 18 r/min; the thickness of the obtained casting sheet was 104 μm;
(3) carrying out bidirectional synchronous stretching on the casting sheet prepared in the step (2), namely simultaneously carrying out transverse stretching and longitudinal stretching to prepare a microporous polymer membrane; the temperature of the transverse stretching and the longitudinal stretching are both 132 ℃, the magnification of the longitudinal stretching is 2 times, and the magnification of the transverse stretching is 3.5 times.
Example 2
A microporous polymer membrane comprises the following raw materials in parts by mass: 52 parts of polypropylene (a product of F401 type provided by China petrochemical Yangzi petrochemical company, the isotacticity of which is 98%), 0.8 part of nucleating agent (a product of DX-Z3C type provided by ancient cooking plastics materials Co., Ltd., Dongguan), 0.5 part of thickening agent, 3 parts of binder, 0.2 part of wetting agent, 3 parts of triethylene glycol dimethacrylate, 0.3 part of sodium hexadecylbenzene sulfonate, 2.3 parts of sodium trimethylsilanolate and 1 part of pentaerythritol zinc; the thickening agent is carboxymethyl ethyl ether cellulose; the binder is 3-methoxy methyl acrylate; the wetting agent is polyoxyethylene lauryl ether; the preparation method comprises the following steps:
(1) mixing the raw materials in parts by mass, and stirring for 22min at the microwave power of 150W, the temperature of 48 ℃ and the rotating speed of 200r/min to prepare a mixture;
(2) extruding and casting the mixture prepared in the step (1) by using an extruder to obtain a casting sheet, wherein the temperature of a first zone of the extruder is 167 ℃, the temperature of a second zone of the extruder is 192 ℃, the temperature of a third zone of the extruder is 212 ℃, the temperature of a fourth zone of the extruder is 232 ℃ and the temperature of a neck mold is 232 ℃ in the extrusion process; in the casting process, the rotating speed of a screw is 48r/min, and the rotating speed of a metering pump is 15 r/min; the thickness of the obtained cast sheet was 80 μm;
(3) carrying out bidirectional synchronous stretching on the casting sheet prepared in the step (2), namely simultaneously carrying out transverse stretching and longitudinal stretching to prepare a microporous polymer membrane; the temperature of the transverse stretching and the longitudinal stretching are both 125 ℃, the magnification of the longitudinal stretching is 1.6 times, and the magnification of the transverse stretching is 3.2 times.
Example 3
A microporous polymer membrane comprises the following raw materials in parts by mass: 66 parts of polypropylene (a product of F401 type provided by China petrochemical Yangzi petrochemical company, the isotacticity of which is 98%), 1.2 parts of nucleating agent (a product of DX-Z3C type provided by ancient cooking plastics materials Co., Ltd., Dongguan), 0.8 part of thickening agent, 5 parts of binder, 0.4 part of wetting agent, 6 parts of triethylene glycol dimethacrylate, 0.7 part of sodium hexadecylbenzene sulfonate, 4.5 parts of sodium trimethylsilanolate and 2 parts of pentaerythritol zinc; the thickening agent is carboxymethyl ethyl ether cellulose; the binder is 3-methoxy methyl acrylate; the wetting agent is polyoxyethylene lauryl ether; the preparation method comprises the following steps:
(1) mixing the raw materials in parts by mass, and stirring for 17min at the microwave power of 230W, the temperature of 53 ℃ and the rotating speed of 300r/min to prepare a mixture;
(2) extruding and casting the mixture prepared in the step (1) by using an extruder to obtain a casting sheet, wherein the first zone temperature of the extruder is 172 ℃, the second zone temperature is 196 ℃, the third zone temperature is 218 ℃, the fourth zone temperature is 238 ℃ and the neck mold temperature is 238 ℃ in the extrusion process; in the casting process, the rotating speed of a screw is 51r/min, and the rotating speed of a metering pump is 16 r/min; the thickness of the obtained cast sheet was 112 μm;
(3) carrying out bidirectional synchronous stretching on the casting sheet prepared in the step (2), namely simultaneously carrying out transverse stretching and longitudinal stretching to prepare a microporous polymer membrane; the temperature of the transverse stretching and the longitudinal stretching is 136 ℃, the magnification of the longitudinal stretching is 2 times, and the magnification of the transverse stretching is 3.8 times.
Comparative example 1
The process for preparing a microporous polymer membrane was substantially the same as that of example 1 except that the raw materials lacked triethylene glycol dimethacrylate, sodium hexadecylbenzene sulfonate, sodium trimethylsilanolate, and zinc pentaerythritol.
Comparative example 2
Essentially the same procedure as in example 1 was used to prepare a microporous polymeric membrane, except that the starting material lacked triethylene glycol dimethacrylate.
Comparative example 3
Essentially the same procedure as in example 1 was used to prepare a microporous polymeric membrane, except that the starting material was devoid of sodium hexadecylbenzene sulfonate.
Comparative example 4
Essentially the same procedure as in example 1 for preparing a microporous polymeric membrane, except that the starting material lacks sodium trimethylsilanolate.
Comparative example 5
Essentially the same procedure as in example 1 was used to prepare a microporous polymeric membrane, except that the starting material lacked zinc pentaerythritol.
Comparative example 6
The microporous polymer membrane was prepared by the methods of examples 1 to 10 of "a polypropylene microporous membrane and a method for preparing the same and a lithium battery separator (application publication No. CN 110277527A)" in chinese patent application.
The microporous polymer membranes of examples 1 to 3 and comparative examples 1 to 6 were tested for machine direction tensile strength with reference to the standard GB/T1040.3-2006 test for tensile Properties of plastics, the results of which are shown in the following Table:
| experimental project | Longitudinal tensile Strength (MPa) |
| Example 1 | 224.3 |
| Example 2 | 211.7 |
| Example 3 | 215.2 |
| Comparative example 1 | 134.3 |
| Comparative example 2 | 206.2 |
| Comparative example 3 | 209.6 |
| Comparative example 4 | 203.4 |
| Comparative example 5 | 199.8 |
| Comparative example 6 | 76.3-130.7 |
As can be seen from the above table, (1) the longitudinal tensile strength of the microporous polymer membrane of the present invention reached 211.7MPa or more, and from the comparison of the longitudinal tensile strength data of examples 1 to 3, it can be seen that example 1 is the most preferable example and the longitudinal tensile strength of the microporous polymer membrane reached 224.3 MPa.
(2) As can be seen from the data of example 1 and comparative examples 1 to 5, the simultaneous addition of triethylene glycol dimethacrylate, sodium hexadecylbenzene sulfonate, sodium trimethylsilanolate, and zinc pentaerythritol provided a synergistic effect in the preparation of the microporous polymer membrane, which synergistically increased the longitudinal tensile strength because: the sodium hexadecylbenzene sulfonate has good dispersing and activating effects, can increase pores on the surface of a polypropylene material, and can enable sodium trimethylsilanolate to permeate into the polypropylene material to form a stable connecting structure, so that the sodium hexadecylbenzene sulfonate can promote the effects of triethylene glycol dimethacrylate, pentaerythritol zinc and polypropylene, and the triethylene glycol dimethacrylate can improve the toughness of a polypropylene bonding layer, therefore, the sodium hexadecylbenzene sulfonate can promote the improvement of the structural toughness of the polypropylene and the longitudinal tensile strength of a microporous polymer film; the sodium trimethylsilanolate has strong permeability, can improve the adhesive force among polypropylene, triethylene glycol dimethacrylate and pentaerythritol zinc, enables the polypropylene, the triethylene glycol dimethacrylate and the pentaerythritol zinc to be uniformly dispersed in a polypropylene material, provides an acting point for surface modification of the polypropylene material, and is beneficial to improving the longitudinal tensile strength of a microporous polymer membrane.
(3) As can be seen from the data of examples 1-3 and comparative example 6, the longitudinal tensile strength of the microporous polymer membrane prepared by the invention is obviously superior to that of the microporous polymer membrane prepared by the prior art, and the strength is 61.97% higher, thereby solving the technical problem that the microporous polymer membrane prepared by the prior art has poor longitudinal tensile strength.
The above description should not be taken as limiting the invention to the embodiments, but rather, as will be apparent to those skilled in the art to which the invention pertains, numerous simplifications or substitutions may be made without departing from the spirit of the invention, which shall be deemed to fall within the scope of the invention as defined by the claims appended hereto.
Claims (9)
1. A microporous polymer membrane is characterized by comprising the following raw materials in parts by mass: 50-68 parts of polypropylene, 0.8-1.2 parts of nucleating agent, 0.4-0.9 part of thickening agent, 3-5 parts of binder, 0.2-0.5 part of wetting agent, 3-6 parts of triethylene glycol dimethacrylate, 0.3-0.7 part of sodium hexadecylbenzene sulfonate, 2-5 parts of sodium trimethylsilanolate and 1-2 parts of pentaerythritol zinc;
the preparation method of the microporous polymer membrane comprises the following steps:
(1) mixing the raw materials in parts by mass, and stirring for 16-23min at the microwave power of 120-250W, the temperature of 48-55 ℃ and the rotating speed of 200-300r/min to obtain a mixture;
(2) extruding and casting the mixture prepared in the step (1) by using an extruder to obtain a casting sheet, wherein the temperature of a first zone of the extruder is 165-173 ℃, the temperature of a second zone of the extruder is 191-197 ℃, the temperature of a third zone of the extruder is 210-218 ℃, the temperature of a fourth zone of the extruder is 232-239 ℃, and the temperature of a neck mold is 232-240 ℃ in the extrusion process; in the casting process, the rotating speed of a screw is 47-52r/min, and the rotating speed of a metering pump is 15-20 r/min;
(3) carrying out bidirectional synchronous stretching on the casting sheet prepared in the step (2), namely simultaneously carrying out transverse stretching and longitudinal stretching to prepare a microporous polymer membrane; the temperature of the transverse stretching and the longitudinal stretching is 123-138 ℃, the magnification of the longitudinal stretching is 1.5-2.2 times, and the magnification of the transverse stretching is 3.1-3.8 times.
2. The microporous polymer membrane of claim 1, comprising the following raw materials in parts by mass: 60 parts of polypropylene, 1 part of nucleating agent, 0.7 part of thickening agent, 4 parts of binder, 0.3 part of wetting agent, 5 parts of triethylene glycol dimethacrylate, 0.6 part of sodium hexadecylbenzene sulfonate, 3 parts of sodium trimethylsilanolate and 1.6 parts of pentaerythritol zinc.
3. The microporous polymeric membrane of claim 1 or 2, wherein the polypropylene has an isotacticity of 98% or more.
4. The microporous polymer membrane of claim 1 or 2, wherein the nucleating agent comprises one or more of a complex of a metal salt and a dicarboxylic acid, a fused ring compound, an aromatic amine compound, and a rare earth compound.
5. The microporous polymer membrane of claim 1 or 2, wherein the thickener is carboxymethylethylether cellulose.
6. The microporous polymeric membrane of claim 1 or 2, wherein the binder is methyl 3-methoxyacrylate.
7. The microporous polymeric membrane of claim 1 or 2, wherein the wetting agent is laureth.
8. The microporous polymer membrane of claim 1, wherein the raw materials are mixed in step (1) and stirred at a microwave power of 200W, a temperature of 52 ℃ and a rotation speed of 250r/min for 20min to obtain a mixture.
9. The microporous polymer membrane of claim 1, wherein the thickness of the cast sheet in step (2) is 74 to 115 μm.
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