CN113285173A - Flame-retardant glass nanofiber composite battery diaphragm and preparation method thereof - Google Patents
Flame-retardant glass nanofiber composite battery diaphragm and preparation method thereof Download PDFInfo
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- CN113285173A CN113285173A CN202110549017.2A CN202110549017A CN113285173A CN 113285173 A CN113285173 A CN 113285173A CN 202110549017 A CN202110549017 A CN 202110549017A CN 113285173 A CN113285173 A CN 113285173A
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 239000003063 flame retardant Substances 0.000 title claims abstract description 87
- 239000011521 glass Substances 0.000 title claims abstract description 80
- 239000002121 nanofiber Substances 0.000 title claims abstract description 80
- 239000002131 composite material Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000003792 electrolyte Substances 0.000 claims abstract description 12
- 229920006253 high performance fiber Polymers 0.000 claims description 19
- 229920001169 thermoplastic Polymers 0.000 claims description 19
- 239000004416 thermosoftening plastic Substances 0.000 claims description 19
- 239000012528 membrane Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 239000000835 fiber Substances 0.000 claims description 9
- 239000003365 glass fiber Substances 0.000 claims description 9
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 7
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 6
- 238000010521 absorption reaction Methods 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 238000007731 hot pressing Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229920000106 Liquid crystal polymer Polymers 0.000 claims description 3
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 3
- 238000009960 carding Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229920002530 polyetherether ketone Polymers 0.000 claims description 3
- 238000004537 pulping Methods 0.000 claims description 3
- 239000004974 Thermotropic liquid crystal Substances 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 12
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 12
- 239000000126 substance Substances 0.000 abstract description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 229910052744 lithium Inorganic materials 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000001000 micrograph Methods 0.000 description 7
- 238000002485 combustion reaction Methods 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62C—FIRE-FIGHTING
- A62C3/00—Fire prevention, containment or extinguishing specially adapted for particular objects or places
- A62C3/16—Fire prevention, containment or extinguishing specially adapted for particular objects or places in electrical installations, e.g. cableways
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Public Health (AREA)
- Business, Economics & Management (AREA)
- Emergency Management (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Cell Separators (AREA)
Abstract
The invention belongs to the technical field of battery diaphragm manufacturing, and discloses a flame-retardant glass nanofiber composite battery diaphragm and a preparation method thereof. The preparation process is simple and convenient, is suitable for large-scale production, improves the mechanical property of the battery diaphragm, realizes uniform regulation and control of the aperture of the battery diaphragm, improves the electrolyte absorbency of the battery diaphragm, and the prepared flame-retardant glass nanofiber composite battery diaphragm has good electrolyte wettability, thermal stability, chemical stability, mechanical property and flame-retardant property, 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 flame-retardant glass nanofiber composite battery diaphragm, and the prepared flame-retardant glass nanofiber 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 flame-retardant glass nanofiber, in particular to a flame-retardant glass nanofiber composite battery diaphragm and a preparation method thereof.
Background
Lithium Ion Batteries (LIBs) have high energy density and long cycle life and are the most important and reliable energy storage devices generally accepted in portable electronic products and electronic automobiles. 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. Up to now, microporous polyolefin (polyethylene, polypropylene or composites thereof) membranes dominate the commercial LIBs separator market by virtue of their uniform pore size, strong mechanical strength and excellent electrochemical stability. However, polyolefin separators widely used in the market have the disadvantages of poor thermal stability, poor electrolyte wettability and the like, and in order to meet the requirements of high-temperature dimensional stability and electrolyte absorption performance of separators of high-power lithium ion batteries, development of high-performance separators has become a focus of attention of researchers.
The glass fiber is an inorganic material, can be used as a diaphragm of a lead-acid storage battery, a primary lithium battery and the like, isolates the positive electrode and the negative electrode of the battery to prevent short circuit, absorbs enough electrolyte to supply chemical reaction for the charging and discharging of the battery, most of the existing glass fiber diaphragms are formed by glue dipping or spraying, are not suitable for being used at high temperature, have low strength and seriously limit the development of the diaphragm.
The invention patent of Chinese patent No. CN102522513A discloses a glass fiber battery diaphragm and a preparation method thereof, wherein the glass fiber battery diaphragm is obtained by forming wet paper sheets by glass fibers and organic fibers such as polyester and polyamide chopped fibers, and then carrying out gum dipping or gum spraying treatment and drying. The method is simple and feasible, and has excellent thermal stability and chemical stability, but the prepared diaphragm is too thick (160-180 um) and has poor strength, so that the method is not suitable for being applied to battery diaphragms. Therefore, it is of great significance to develop a high-strength, thin glass fiber separator.
Disclosure of Invention
The invention aims to provide a flame-retardant glass nanofiber composite battery diaphragm and a preparation method thereof, so as to 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 flame-retardant glass nanofiber composite battery diaphragm comprises the following steps: and mixing the flame-retardant glass nano-fiber and the thermoplastic high-performance fiber, and dispersing, pulping, papermaking and hot-pressing to obtain the flame-retardant glass fiber composite battery diaphragm.
As a limitation: in the mixture of the flame-retardant glass nano-fiber and the thermoplastic high-performance fiber, the mass fraction of the flame-retardant glass nano-fiber is 70-95%, and the balance is the thermoplastic high-performance fiber.
As a further limitation: the thermoplastic high-performance fiber is one of polyether-ether-ketone, polyphenylene sulfide and thermotropic liquid crystal polymer, the mass fraction of the part serving as the high-temperature binder in the thermoplastic high-performance fiber is 30-70%, and the rest is used as a support structure.
As another limitation: the flame-retardant glass nano-fiber is cut by a flame method and a high-speed carding machine, the fiber is circular, the diameter is 100-1000nm, and the fiber length is 0-5 mm.
As a further limitation: the flame-retardant glass nanofiber comprises 0-25% of flame-retardant glass nanofiber with the length of 0-2mm by mass, 50-100% of flame-retardant glass nanofiber with the length of 2-4mm by mass and 0-25% of flame-retardant glass nanofiber with the length of 4-5mm by mass.
The invention also provides the flame-retardant glass nanofiber composite battery diaphragm prepared by the preparation method of the flame-retardant glass nanofiber composite battery diaphragm, the porosity of the prepared sea flame-retardant glass nanofiber composite battery diaphragm is 40-70%, the pore diameter is 0.1-0.6 mu m, the thickness is 15-25 mu m, the liquid absorption rate of the electrolyte is 250-350%, the tensile strength is 20-40MPa, and the limiting oxygen index is 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 flame-retardant glass nanofiber composite battery diaphragm, the flame-retardant glass nanofiber is mixed with a small amount of thermoplastic high-performance fiber, and the thermoplastic high-performance fiber is used as a high-temperature fibrous binder and a supporting structure, so that the mechanical property of the battery diaphragm is improved; in addition, the preparation method has simple preparation process and is suitable for large-scale production;
(2) according to the preparation method of the flame-retardant glass nanofiber composite battery diaphragm, the flame-retardant glass nanofibers with different lengths and different titer are stacked and arranged, so that the porosity, the aperture and the thickness of the battery diaphragm are regulated, and the aperture of the battery diaphragm is homogenized;
(3) the flame-retardant glass nanofiber composite battery diaphragm prepared by the preparation method provided by the invention is prepared by mixing the flame-retardant glass nanofibers with a small amount of thermoplastic high-performance fibers, dispersing, pulping, papermaking and hot pressing, and based on the excellent thermal stability and flame retardance of the flame-retardant glass nanofibers, the prepared battery diaphragm has good electrolyte wettability, thermal stability, chemical stability, mechanical property and flame retardance, the requirements of a 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 flame-retardant glass nanofiber composite battery diaphragm provided by the invention is simple and convenient in preparation process, is suitable for large-scale production, improves the mechanical property of the battery diaphragm, realizes uniform regulation and control of the aperture of the battery diaphragm, improves the electrolyte absorbency of the battery diaphragm, has good electrolyte wettability, thermal stability, chemical stability, mechanical property and flame retardant property, 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 flame-retardant glass nanofiber composite battery diaphragm, and the prepared flame-retardant glass nanofiber composite battery diaphragm is suitable for a lithium battery.
Drawings
The invention is described in further detail below with reference to the figures and the embodiments.
FIG. 1 is a scanning electron microscope image of a flame-retardant glass nanofiber composite battery separator prepared in example 1 of the present invention;
FIG. 2 is a scanning electron microscope image of a flame-retardant glass nanofiber composite battery separator prepared in example 2 of the present invention;
FIG. 3 is a scanning electron microscope image of a flame-retardant glass nanofiber composite battery separator prepared in example 3 of the present invention;
FIG. 4 is a scanning electron microscope image of a flame-retardant glass nanofiber composite battery separator prepared in example 4 of the present invention;
FIG. 5 is a scanning electron microscope image of a flame-retardant glass nanofiber composite battery separator prepared in example 5 of the present invention;
FIG. 6 is a scanning electron microscope image of a flame-retardant glass nanofiber composite battery separator prepared in example 6 of the present invention;
FIGS. 7a-e are graphs comparing the thermal stability of the flame retardant glass nanofiber composite battery separator made in example 1 of the present invention with a commercial Celgard membrane;
fig. 8a and 8b are test charts of flame retardancy of Celgard commercial membrane, and fig. 8c and 8d are test charts of flame retardancy of the flame retardant glass nanofiber composite battery separator prepared in example 1 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 flame retardant glass nanofiber composite battery separator
Examples 1 to 6 are respectively a method for preparing a flame-retardant glass nanofiber composite battery separator, wherein the process parameters in the preparation process are shown in table 1, and the specific preparation process comprises the following steps:
a preparation method of a flame-retardant glass nanofiber composite battery diaphragm comprises the following steps: the flame-retardant glass nanofiber is cut by a flame method and a high-speed carding machine, the fiber is circular, the diameter is 100-1000nm, the flame-retardant glass nanofiber with the fiber length of 0-5mm is mixed with the thermoplastic high-performance fiber, the mass fraction of 0-2mm in length in the flame-retardant glass nanofiber is 0-25%, the mass fraction of 2-4mm in length is 50-100%, and the mass fraction of 4-5mm in length is 0-25%; the mass fraction of the part of the thermoplastic high-performance fiber used as the high-temperature binder is 30-70%, the rest is used as a support structure, the mass fraction of the flame-retardant glass nano-fiber in the mixture of the flame-retardant glass nano-fiber and the thermoplastic high-performance fiber is 70-95%, the rest is the thermoplastic high-performance fiber, the mixture of the glass nano-fiber and the thermoplastic high-performance fiber is dispersed, pulped at the concentration of 0.3-5%, and then subjected to papermaking and hot pressing at the temperature of 260-320 ℃ and under the pressure of 10-40 MPa, so as to obtain the flame-retardant glass fiber composite battery diaphragm.
The thermoplastic high performance fibers of examples 1-6 were one of polyphenylene sulfide, polyetheretherketone, and thermotropic liquid crystalline polymers.
Table 1 examples 1-6 process parameters in the preparation of flame retardant glass nanofiber composite battery separators
The specific performance indexes of the flame-retardant glass nanofiber composite battery diaphragm prepared by the preparation method are shown in table 2.
TABLE 2 Performance indices of the flame retardant glass nanofiber composite battery separators prepared in examples 1-6
As shown in Table 2, the porosity of the flame-retardant glass nanofiber composite battery separator prepared in examples 1-6 is 40-70%, the pore diameter is 0.1-0.6 μm, the thickness is 15-25 μm, the pore diameter of the battery separator is uniform and fine, the liquid absorption rate of the electrolyte is 250-350%, the liquid absorption performance of the electrolyte is high, the tensile strength is 20-40MPa, and the mechanical performance is good. In addition, the limit oxygen index of the sea-island polyphenylene sulfide composite battery diaphragm prepared in the examples 1-6 is 38-40, and the limit oxygen index of the existing Celgard commercial film is 18, so that the flame retardant glass nanofiber composite battery diaphragm prepared in the examples 1-6 of the invention has good flame retardant property.
FIGS. 1 to 6 are scanning electron microscope images of the flame-retardant glass nanofiber composite battery separator prepared in examples 1 to 6 in sequence, and as can be seen from FIGS. 1 to 6, polyphenylene sulfide fibers are used as a binder and a support structure to wrap the flame-retardant glass nanofibers, the pore diameter of the whole separator is controlled within 1 μm, the porosity is high, and the separator is suitable for a lithium ion battery separator; fig. 7 shows a comparison graph of thermal stability of the flame-retardant glass nanofiber composite battery separator and the Celgard commercial membrane, wherein a-e in the graph 7 sequentially show dimensional changes of the flame-retardant glass nanofiber composite battery separator and the Celgard commercial membrane at 25 ℃, 150 ℃, 175 ℃, 200 ℃ and 230 ℃, Celgard represents the Celgard commercial membrane, GNF/PPS represents the flame-retardant glass nanofiber composite battery separator of example 1, wherein PSS is polyphenylene sulfide, and GNF is the flame-retardant glass nanofiber, as can be seen from fig. 7, the size of the flame-retardant glass nanofiber composite battery separator at 25 ℃, 150 ℃, 175 ℃, 200 ℃ and 230 ℃ is almost unchanged, while the dimensional changes of the Celgard commercial membrane at 5 ℃, 150 ℃, 175 ℃, 200 ℃ and 230 ℃ are obvious, so the thermal stability of the flame-retardant glass nanofiber composite battery separator is better than that of the Celgard commercial membrane; the figure for comparing the flame retardant performance of the flame retardant glass nanofiber composite battery diaphragm with the Celgard commercial membrane is shown in fig. 8, fig. 8a is the Celgard commercial membrane before combustion, fig. 8b is the Celgard commercial membrane after combustion, fig. 8c is the flame retardant glass nanofiber composite battery diaphragm before combustion, and fig. 8d is the flame retardant glass nanofiber composite battery diaphragm after combustion, and it can be seen from fig. 8 that the flame retardant performance of the flame retardant glass nanofiber composite battery diaphragm is superior to that of the Celgard commercial membrane, and the flame retardant glass nanofiber composite battery diaphragms prepared in examples 2-6 have similar performance to that of the flame retardant glass nanofiber composite battery diaphragm prepared in example 1.
Claims (6)
1. A preparation method of a flame-retardant glass nanofiber composite battery diaphragm is characterized by comprising the following steps: and mixing the flame-retardant glass nano-fiber and the thermoplastic high-performance fiber, and dispersing, pulping, papermaking and hot-pressing to obtain the flame-retardant glass fiber composite battery diaphragm.
2. The method for preparing the flame-retardant glass nanofiber composite battery separator as claimed in claim 1, wherein in the mixture of the flame-retardant glass nanofibers and the thermoplastic high-performance fibers, the mass fraction of the flame-retardant glass nanofibers is 70-95%, and the balance is the thermoplastic high-performance fibers.
3. The method for preparing the flame-retardant glass nanofiber composite battery separator as claimed in claim 2, wherein the thermoplastic high-performance fiber is one of polyetheretherketone, polyphenylene sulfide and thermotropic liquid crystal polymer, the mass fraction of the thermoplastic high-performance fiber as a high-temperature binder part is 30-70%, and the rest is used as a support structure.
4. The method for preparing the flame-retardant glass nanofiber composite battery separator as claimed in any one of claims 1-3, wherein the flame-retardant glass nanofiber is cut by a flame method and a high-speed carding machine, the fiber is circular, the diameter is 100-1000nm, and the fiber length is 0-5 mm.
5. The method for preparing the flame-retardant glass nanofiber composite battery separator as claimed in claim 4, wherein the flame-retardant glass nanofiber has a mass fraction of 0-25% for a length of 0-2mm, a mass fraction of 50-100% for a length of 2-4mm, and a mass fraction of 0-25% for a length of 4-5 mm.
6. The membrane of the flame-retardant glass nano-fiber composite battery prepared by the method for preparing the membrane of the flame-retardant glass nano-fiber composite battery as claimed in any one of claims 1 to 5, which is characterized in that the prepared membrane of the flame-retardant glass nano-fiber composite battery has the porosity of 40-70%, the pore diameter of 0.1-0.6 μm, the thickness of 15-25 μm, the liquid absorption rate of electrolyte of 250-350%, the tensile strength of 20-40MPa and the limiting oxygen index of 38-40.
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| CN202110549017.2A CN113285173A (en) | 2021-05-20 | 2021-05-20 | Flame-retardant glass nanofiber composite battery diaphragm and preparation method thereof |
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| CN202110549017.2A CN113285173A (en) | 2021-05-20 | 2021-05-20 | Flame-retardant glass nanofiber composite battery diaphragm and preparation method thereof |
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|---|---|---|---|---|
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| CN101728504A (en) * | 2009-12-04 | 2010-06-09 | 中国海诚工程科技股份有限公司 | Lithium ion battery diaphragm flexible substrate by wet papermaking and manufacturing method thereof |
| CN102522513A (en) * | 2011-12-19 | 2012-06-27 | 中材科技股份有限公司 | Glass fiber battery membrane and preparation method thereof |
| WO2016158654A1 (en) * | 2015-03-30 | 2016-10-06 | 日本板硝子株式会社 | Separator for nonaqueous electrolyte secondary batteries, and nonaqueous electrolyte secondary battery |
| CN108682774A (en) * | 2018-06-12 | 2018-10-19 | 桑德集团有限公司 | Diaphragm and preparation method thereof, lithium battery |
| CN109428035A (en) * | 2017-08-31 | 2019-03-05 | 比亚迪股份有限公司 | Battery diaphragm and preparation method thereof and lithium ion battery |
| CN109585751A (en) * | 2018-10-30 | 2019-04-05 | 东莞理工学院 | A kind of high strength fibre structure lithium electric separator and its preparation method and application |
| CN110528314A (en) * | 2019-06-19 | 2019-12-03 | 武汉纺织大学 | A kind of composite sheet and its preparation method and application of the polyphenylene sulfide superfine fiber containing melt-blown |
-
2021
- 2021-05-20 CN CN202110549017.2A patent/CN113285173A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85108034A (en) * | 1985-11-04 | 1987-07-22 | 国家建筑材料工业局南京玻璃纤维研究设计院 | Fibreglass diaphragm for lithium cell |
| CN101728504A (en) * | 2009-12-04 | 2010-06-09 | 中国海诚工程科技股份有限公司 | Lithium ion battery diaphragm flexible substrate by wet papermaking and manufacturing method thereof |
| CN102522513A (en) * | 2011-12-19 | 2012-06-27 | 中材科技股份有限公司 | Glass fiber battery membrane and preparation method thereof |
| WO2016158654A1 (en) * | 2015-03-30 | 2016-10-06 | 日本板硝子株式会社 | Separator for nonaqueous electrolyte secondary batteries, and nonaqueous electrolyte secondary battery |
| CN109428035A (en) * | 2017-08-31 | 2019-03-05 | 比亚迪股份有限公司 | Battery diaphragm and preparation method thereof and lithium ion battery |
| CN108682774A (en) * | 2018-06-12 | 2018-10-19 | 桑德集团有限公司 | Diaphragm and preparation method thereof, lithium battery |
| CN109585751A (en) * | 2018-10-30 | 2019-04-05 | 东莞理工学院 | A kind of high strength fibre structure lithium electric separator and its preparation method and application |
| CN110528314A (en) * | 2019-06-19 | 2019-12-03 | 武汉纺织大学 | A kind of composite sheet and its preparation method and application of the polyphenylene sulfide superfine fiber containing melt-blown |
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Application publication date: 20210820 |