CN1632968A - Polymer membrane for polymer lithium ion battery and method for making same - Google Patents
Polymer membrane for polymer lithium ion battery and method for making same Download PDFInfo
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Abstract
This invention provides a polymer lithium ion battery diaphragm and its process method, which comprises the following steps: to solve the polymer single material into the single solvable agent; then to join abio-powder and with even shaking to join the non-solvable agent of the single material; to automatically coat the above liquid on the base band; to make the coating thickness as needed through coating machine control; to vaporize the agent under normal temperature or heating conditions to form polymer diaphragm.
Description
Technical field
The present invention relates to membrane for polymer of a kind of lithium ion battery and preparation method thereof, relate in particular to membrane for polymer of a kind of polymer Li-ion battery and preparation method thereof.
Background technology
Lithium ion battery is divided into liquid electrolyte lithium ion battery and polymer Li-ion battery usually.Polymer Li-ion battery adopts membrane for polymer, and its major advantage is to have high-energy-density and long circulation life; Have high reliability and suitable processability; Self-discharge of battery is low; Can make all-plastic structure, be easier to assembling; Do not have free electrolyte, the phenomenon of leakage can not take place; Can adopt light plastics package and unlike traditional lithium ion battery, need use metal shell; Safe in utilization.In addition, membrane for polymer and plastic electrode closely superimposed makes polymer battery can shape flexible, even can make the slimline battery less than 0.6mm, and from application point, outlet is broad more.Battery can be deacclimatized the dimensional requirement of power consumption equipment on one's own initiative, rather than has only standardized specification selective; Therefore, battery research and production unit have been attracted since autohemagglutination compound lithium ion battery comes out strongly.Its technology, technology are just in fast degree development and maturation.
The manufacture method that U.S. BELL Communication Studies institute announced a kind of polymer Li-ion battery in 1994, wherein announced the manufacture method of membrane for polymer, P (VDF-HFP) copolymer is dissolved in acetone or N-methyl pyrrolidone or their mixed liquor, add the plasticizer of ormal weight, also can add gas phase SiO again
2Or Al
2O
3Deng, the furnishing pasty state is made certain thickness sheet film with coating machine, and solvent evaporation is got wet film, becomes dry film after with extractant plasticizer being extracted drying.The disadvantage of this method maximum is that technology is too complicated, and cost is higher.
Summary of the invention
The invention provides membrane for polymer of a kind of polymer Li-ion battery and preparation method thereof.Membrane for polymer function admirable of the present invention, and manufacture method work simplification, thus overcome the high problem of complex process, cost that present production membrane for polymer exists.
The component and the percentage by weight of the membrane for polymer of polymer Li-ion battery of the present invention consist of:
Solid material 2-50%,
Solvent 50-98%,
The component and the percentage by weight of described solid material consist of:
Polymer monomer material 75-100%,
Inorganic powder 0-25%,
Wherein the component of polymer monomer material and percentage by weight consist of:
Dissolve in monomer material 0-99% that electrolyte becomes gel,
The monomer material 1-100% of stable existence in electrolyte,
The component and the percentage by weight of described solvent consist of:
Polymer monomer material suitable solvents 10-95%,
Polymer monomer material non-solubility solvent 5-90%,
Dissolving in electrolyte in the polymer monomer material becomes the monomer material of gel to be: polymethyl methacrylate, polyethyl methacrylate, polypropylmethacryla,es, polybutyl methacrylate, polyisobutyl methacrylate, polyallylmethacrylate, polymethyl acrylate, polyethyleneglycol diacrylate, polyacrylonitrile, acrylonitrile butadiene rubber, the acrylonitrile vinyl chloride resin, the acrylonitrile methacrylic resin, one of acrylonitrile acrylic resin or combination in any, in the polymer monomer material in electrolyte the monomer material of stable existence be: Kynoar, polytetrafluoroethylene, one of Kynoar-be total to-hexafluoropropylene or combination in any;
Inorganic powder is: SiO
2, Al
2O
3, Fe
2O
3, TiO
2, ZrO
2, TiB
2, PbTiO
3, CaSiO
3One of or combination in any.
Polymer monomer material suitable solvents is in the solvent: one of acetone, butanone, oxolane, dimethyl formamide, N-methyl pyrrolidone or combination in any, and polymer monomer material non-solubility solvent is in the solvent: one of deionized water, methyl alcohol, ethanol, glycerol, butanols or combination in any;
The preparation preparation process is as follows:
(1) with in the required polymer monomer material in electrolyte the monomer material of stable existence put into glass or stainless steel ware, add required monomer material suitable solvents, be stirred to abundant dissolving; Add required inorganic powder again, stir; Add again and dissolve in the monomer material that electrolyte becomes gel in the required monomer material, fully dissolve and mix; Slowly add required monomer material non-solubility solvent while stirring again, mix, make the mobile liquid that has of certain viscosity;
(2) aforesaid liquid is coated on the base band with automatic coating machine, making coating thickness by the scraper gap of controlling coating machine is desired thickness;
(3) under normal temperature or heating condition, make solvent evaporates, form membrane for polymer.
In the above-mentioned preparation process (3), as take to make solvent evaporates under the heating condition, heating and temperature control is at 35 ± 5 ℃-120 ± 5 ℃, 50 ± 5 ℃-85 ± 5 ℃ of optimum ranges, and humidity is controlled at 40-60%RH.In the above-mentioned preparation process (2), coated thickness is 15 ± 2 μ m-150 ± 2 μ m.
The component and the preferred weight percent of the membrane for polymer of polymer Li-ion battery of the present invention consist of:
Solid material 5-25%,
Solvent 75-95%,
The component and the preferred weight percent of described solid material consist of:
Polymer monomer material 85-99%,
Inorganic powder 1-15%,
Wherein the component of polymer monomer material and preferred percent consist of:
Dissolve in monomer material 10-90% that electrolyte becomes gel,
The monomer material 10-90% of stable existence in electrolyte,
The component and the preferred weight percent of described solvent consist of:
Polymer monomer material suitable solvents 40-90%,
Polymer monomer material non-solubility solvent 10-60%.
The present invention adopts the solvent pairs phase separation method.The solvent pairs phase separation method is meant and adopts and soluble solvent of polymer monomer material and non-solubility solvent, suitable solvents can make polymer monomer material and powder well be uniformly dispersed in manufacturing process, and at first volatilization after being coated on the base band, polymer monomer material and non-solubility solvent are separated afterwards, after the non-solubility solvent evaporates, poly-and thing unit materials forms loose structure, thereby has avoided complicated technology such as plasticizer extracting.This loose structure has not only improved electrolyte suction amount but also provide passage for ion moves.Contain in the polymer monomer material in the time of the monomer material of good intermiscibility being arranged with electrolyte, made film can form the gel state amorphous phase with electrolyte after sucking electrolyte, thereby improves the liquid absorption of battery.When containing the monomer material of stable existence in the electrolyte in the polymer monomer material, it can provide stable skeleton supporting role to membrane for polymer, and the mechanical strength of membrane for polymer is improved greatly, is suitable for producing.Therefore when the polymer monomer material adopts above-mentioned two class monomer materials simultaneously membrane for polymer not only pick up height, porosity height, conductivity big, have good cycle performance, and mechanical strength is bigger, is suitable for producing.
Embodiment
The polymer Li-ion battery that the membrane for polymer that adopts the present invention to prepare is made is 220% of a general battery pick up, and porosity reaches 75%, and ionic conductivity is 2.1 * 10
-3S/cm.By test shows, the polymer Li-ion battery that adopts membrane for polymer of the present invention to make has the excellent cycle performance.Comprehensively above-mentioned, the polymer Li-ion battery that adopts membrane for polymer of the present invention to make has high power capacity, good cycle life and the advantage that capacity guarantees, fail safe is good, and owing to production process simply has the low advantage of production cost.
Raw material required for the present invention all can be bought in market.
Embodiment 1
1.6kg Kynoar-common-hexafluoropropylene is dissolved in glassware in the 15.8kg acetone, is stirred to abundant dissolving; Again with the SiO of 0.2kg
2Add in the above-mentioned solution, stir, again the 0.2kg polymethyl methacrylate is put into aforesaid liquid, fully dissolve and mix; While stirring the ethanol that slowly adds 3.95kg, mix again, make the mobile liquid that has with certain viscosity; Then aforesaid liquid is coated on the base band with automatic coating machine, making coating thickness by the gap of controlling scraper is 0.55mm, and the membrane thicknesses that obtains is 40 ± 2 μ m; Temperature is controlled at 60 ± 5 ℃, and humidity is controlled under 40～60%RH situation, makes solvent evaporates, can obtain membrane for polymer.
Embodiment 2
Kynoar-common-hexafluoropropylene of 3.0kg is dissolved in stainless steel ware in the 3.0kg acetone, is stirred to abundant dissolving; Again with the SiO of 0.09kg
2Add in the above-mentioned solution, stir, again 0.02kg polymethylacrylic acid alkene butyl ester is put into aforesaid liquid, fully dissolve and mix; While stirring the deionized water that slowly adds 0.16kg, mix again, make the mobile liquid that has with certain viscosity; Then aforesaid liquid is coated on the base band with automatic coating machine, making coating thickness by the gap of controlling scraper is 1.56mm, and the membrane thicknesses that obtains is 145 ± 2 μ m; Temperature is controlled at 40 ± 5 ℃, and humidity is controlled under 40～60%RH situation, makes solvent evaporates, can obtain membrane for polymer.
Embodiment 3
Kynoar-common-hexafluoropropylene of 0.01kg is dissolved in glassware in the 19.8kg acetone, is stirred to abundant dissolving; Again with the SiO of 0.01kg
2Add in the above-mentioned solution, stir, again the 0.99kg polymethyl methacrylate is put into aforesaid liquid, fully dissolve and mix; While stirring the ethanol that slowly adds 29.6kg, mix again, make the mobile liquid that has with certain viscosity; Then aforesaid liquid is coated on the base band with automatic coating machine, making coating thickness by the gap of controlling scraper is 0.40mm, and the membrane thicknesses that obtains is 22 ± 2 μ m; Temperature is controlled at 115 ± 5 ℃, and humidity is controlled under 40～60%RH situation, makes solvent evaporates, can obtain membrane for polymer.
Embodiment 4
Kynoar-common-hexafluoropropylene of 1.3kg is dissolved in glassware in the 3.5kg acetone, is stirred to abundant dissolving,, mix, make the mobile liquid that has with certain viscosity while stir the glycerol that slowly adds 0.4kg again; Then aforesaid liquid is coated on the base band with automatic coating machine, making coating thickness by the gap of controlling scraper is 0.70mm, and the membrane thicknesses that obtains is 60 ± 2 μ m; Temperature is controlled at 40 ± 5 ℃, and humidity is controlled under 40～60%RH situation, makes solvent evaporates, can obtain membrane for polymer.
Embodiment 5
The Kynoar of 6.0kg is dissolved in glassware in the 15.8kg butanone, is stirred to abundant dissolving,, mix, make the mobile liquid that has with certain viscosity while stir the butanols that slowly adds 4.0kg again; Then aforesaid liquid is coated on the base band with automatic coating machine, making coating thickness by the gap of controlling scraper is 0.66mm, and the membrane thicknesses that obtains is 50 ± 2 μ m; Temperature is controlled at 50 ± 5 ℃, and humidity is controlled under 40～60%RH situation, makes solvent evaporates, can obtain membrane for polymer.
Embodiment 6
The Kynoar of 0.2kg is dissolved in stainless steel ware in the 20.0kg acetone, is stirred to abundant dissolving; Again with the Al of 0.15kg
2O
3Add in the above-mentioned solution, stir, again the 0.16kg polyethyl methacrylate is put into aforesaid liquid, fully dissolve and mix; While stirring the methyl alcohol that slowly adds 2.3kg, mix again, make the mobile liquid that has with certain viscosity; Then aforesaid liquid is coated on the base band with automatic coating machine, making coating thickness by the gap of controlling scraper is 0.53mm, and the membrane thicknesses that obtains is 40 ± 2 μ m; Temperature is controlled at 80 ± 5 ℃, and humidity is controlled under 40～60%RH situation, makes solvent evaporates, can obtain membrane for polymer.
Embodiment 7
The polytetrafluoroethylene of 0.8kg is dissolved in stainless steel ware in the oxolane mixed liquor of the butanone of 8.0kg acetone, 1.0kg and 1.0kg, is stirred to abundant dissolving, again with the SiO of 0.1kg
2Al with 0.1kg
2O
3Add in the aforesaid liquid, stir; Again the polypropylmethacryla,es of 1.2kg is put into aforesaid liquid, fully dissolve and mix; While stirring the ethanol that slowly adds 3.0kg, mix again, make the mobile liquid that has with certain viscosity; Then aforesaid liquid is coated on the base band with automatic coating machine, making coating thickness by the gap of controlling scraper is 0.57mm, and the membrane thicknesses that obtains is 48 ± 2 μ m; Temperature is controlled at 55 ± 5 ℃, and humidity is controlled under 40～60%RH situation, makes solvent evaporates, can obtain membrane for polymer.
Embodiment 8
With the Kynoar-common-hexafluoropropylene of 1.0kg and the Kynoar of 0.2kg, in stainless steel ware, be dissolved in the 1.2kg dimethylformamide, be stirred to abundant dissolving; Again with the TiO of 0.2kg
2And 0.15kgFe
2O
3Add in the above-mentioned solution, stir, the polyacrylonitrile with the polymethyl methacrylate of 0.5kg, 0.3kg adds in the aforesaid liquid again, fully dissolves and mixes; While ethanol that stirs slowly adding 5.0 and the methyl alcohol of 5.0kg, mix again, make the mobile solution that has with certain viscosity; Then aforesaid liquid is coated on the base band with automatic coating machine, making coating thickness by the gap of controlling scraper is 1.23mm, and the membrane thicknesses that obtains is 72 ± 2 μ m; Temperature is controlled at 60 ± 5 ℃, and humidity is controlled under 40～60%RH situation, makes solvent evaporates, can obtain membrane for polymer.
Embodiment 9
The polytetrafluoroethylene of the Kynoar of 1.8kg-altogether-hexafluoropropylene, 0.1kg Kynoar and 0.1kg is dissolved in stainless steel ware in the 13.0kg N-methyl pyrrolidone, is stirred to abundant dissolving; Again with the SiO of 0.4kg
2, 0.2kg ZrO
2And the TiB of 0.05kg
2Add in the above-mentioned solution, stir,, mix, make the mobile liquid that has with certain viscosity while stir the butanols that slowly adds 1.0kg again; Then aforesaid liquid is coated on the base band with automatic coating machine, making coating thickness by the gap of controlling scraper is 1.08mm, and the membrane thicknesses that obtains is 80 ± 2 μ m; Temperature is controlled at 50 ± 5 ℃, and humidity is controlled under 40～60%RH situation, makes solvent evaporates, can obtain membrane for polymer.
Embodiment 10
Kynoar-common-hexafluoropropylene of 0.02kg is dissolved in stainless steel ware in the acetone mixed liquor of 1.1kg N-methyl pyrrolidone and 1.0kg, is stirred to abundant dissolving; Again with the Al of 0.05kg
2O
3And the PbTiO of 0.05kg
3Add in the above-mentioned solution, stir, again the polyethyl methacrylate of 0.9kg, 0.5kg polyisobutyl methacrylate and 0.48kg polymethyl acrylate are added in the aforesaid liquid, fully dissolve and mix; While stirring the butanols that slowly adds 2.0kg, mix again, make the mobile solution that has with certain viscosity; Then aforesaid liquid is coated on the base band with automatic coating machine, making coating thickness by the gap of controlling scraper is 1.32mm, and the membrane thicknesses that obtains is 120 ± 2 μ m; Temperature is controlled at 90 ± 5 ℃, and humidity is controlled under 40～60%RH situation, makes solvent evaporates, can obtain membrane for polymer.
Embodiment 11
Kynoar-common-hexafluoropropylene of 1.6kg is dissolved in stainless steel ware in the 35kg acetone, is stirred to abundant dissolving; Again with the PbTiO of 0.01kg
3And 0.01kgCaSiO
3Add in the above-mentioned solution, stir, again the acrylonitrile butadiene rubber of the glycol diacrylate of 0.2kg, 0.1kg and the acrylonitrile vinyl chloride resin of 0.1kg are added in the aforesaid liquid, fully dissolve and mix; While stirring the ethanol that slowly adds 3.5kg, mix again, make the mobile liquid that has with certain viscosity; Then aforesaid liquid is coated on the base band with automatic coating machine, making coating thickness by the gap of controlling scraper is 0.39mm, and the membrane thicknesses that obtains is 25 ± 2 μ m; Temperature is controlled at 60 ± 5 ℃, and humidity is controlled under 40～60%RH situation, makes solvent evaporates, can obtain membrane for polymer.
Embodiment 12
Kynoar-common-hexafluoropropylene of 0.4kg is dissolved in stainless steel ware in the 15kg acetone, is stirred to abundant dissolving; Again with the Fe of 0.05kg
2O
3Add in the above-mentioned solution, stir, again with the acrylonitrile methacrylic resin of 0.4kg acrylonitrile acrylic resin, 0.2kg and 1.0kg polymethyl acrylate put into aforesaid liquid, fully dissolve and mix; While stirring the butanols that slowly adds 3kg, mix again, make the mobile liquid that has with certain viscosity; Then aforesaid liquid is coated on the base band with automatic coating machine, making coating thickness by the gap of controlling scraper is 0.64mm, and the membrane thicknesses that obtains is 45 ± 2 μ m; Temperature is controlled at 40 ± 5 ℃, and humidity is controlled under 40～60%RH situation, makes solvent evaporates, can obtain membrane for polymer.
Claims (8)
1. the membrane for polymer of a polymer Li-ion battery is characterized in that, its component and percentage by weight consist of:
Solid material 2-50%,
Solvent 50-98%,
The component and the percentage by weight of described solid material consist of:
Polymer monomer material 75-100%,
Inorganic powder 0-25%,
Wherein the component of polymer monomer material and percentage by weight consist of:
Dissolve in monomer material 0-99% that electrolyte becomes gel,
The monomer material 1-100% of stable existence in electrolyte,
The component and the percentage by weight of described solvent consist of:
Polymer monomer material suitable solvents 10-95%,
Polymer monomer material non-solubility solvent 5-90%;
Dissolving in electrolyte in the polymer monomer material becomes the monomer material of gel to be: polymethyl methacrylate, polyethyl methacrylate, polypropylmethacryla,es, polybutyl methacrylate, polyisobutyl methacrylate, polyallylmethacrylate, polymethyl acrylate, polyethyleneglycol diacrylate, polyacrylonitrile, acrylonitrile butadiene rubber, the acrylonitrile vinyl chloride resin, the acrylonitrile methacrylic resin, one of acrylonitrile acrylic resin or combination in any, in the polymer monomer material in electrolyte the monomer material of stable existence be: Kynoar, polytetrafluoroethylene, one of Kynoar-be total to-hexafluoropropylene or combination in any;
Inorganic powder is: SiO
2, Al
2O
3, Fe
2O
3, TiO
2, ZrO
2, TiB
2, PbTiO
3, CaSiO
3One of or combination in any.
Polymer monomer material suitable solvents is in the solvent: one of acetone, butanone, oxolane, dimethyl formamide, N-methyl pyrrolidone or combination in any, and polymer monomer material non-solubility solvent is in the solvent: one of deionized water, methyl alcohol, ethanol, glycerol, butanols or combination in any;
2. the membrane for polymer of polymer Li-ion battery as claimed in claim 1 is characterized in that, its component and percentage by weight consist of:
Solid material 5-25%,
Solvent 75-95%,
The component and the percentage by weight of described solid material consist of:
Polymer monomer material 85-99%,
Inorganic powder 1-15%.
3. the membrane for polymer of polymer Li-ion battery as claimed in claim 2 is characterized in that, wherein the component of polymer monomer material and percentage by weight consist of:
Dissolve in monomer material 10-90% that electrolyte becomes gel,
The monomer material 10-90% of stable existence in electrolyte,
4. the membrane for polymer of polymer Li-ion battery as claimed in claim 3 is characterized in that, the component and the percentage by weight of described solvent consist of:
Polymer monomer material suitable solvents 40-90%,
Polymer monomer material non-solubility solvent 10-60%.
5. the preparation method of the membrane for polymer of polymer Li-ion battery as claimed in claim 1 is characterized in that, preparation process is as follows:
(1) with in the required polymer monomer material in electrolyte the monomer material of stable existence put into glass or stainless steel ware, add required monomer material suitable solvents, be stirred to abundant dissolving; Add required inorganic powder again, stir; Add again and dissolve in the monomer material that electrolyte becomes gel in the required monomer material, fully dissolve and mix; Slowly add required monomer material non-solubility solvent while stirring again, mix, make the mobile liquid that has of certain viscosity;
(2) aforesaid liquid is coated on the base band with automatic coating machine, making coating thickness by the scraper gap of controlling coating machine is desired thickness;
(3) under normal temperature or heating condition, make solvent evaporates, form membrane for polymer.
6. the preparation method of the membrane for polymer of polymer Li-ion battery as claimed in claim 5, it is characterized in that, in the described preparation process (3), as take to make solvent evaporates under the heating condition, heating and temperature control is at 35 ± 5 ℃-120 ± 5 ℃, and humidity is controlled at 40-60%RH.
7. the preparation method of the membrane for polymer of polymer Li-ion battery as claimed in claim 6 is characterized in that, heating and temperature control is at 50 ± 5 ℃-85 ± 5 ℃.
8. the preparation method of the membrane for polymer of polymer Li-ion battery as claimed in claim 7 is characterized in that, in the described preparation process (2), coated thickness is 15 ± 2 μ m-150 ± 2 μ m.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100029636A CN100341168C (en) | 2005-01-27 | 2005-01-27 | Polymer membrane for polymer lithium ion battery and method for making same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100029636A CN100341168C (en) | 2005-01-27 | 2005-01-27 | Polymer membrane for polymer lithium ion battery and method for making same |
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| Publication Number | Publication Date |
|---|---|
| CN1632968A true CN1632968A (en) | 2005-06-29 |
| CN100341168C CN100341168C (en) | 2007-10-03 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101271965B (en) * | 2008-04-30 | 2010-06-09 | 中南大学 | Lithium ion battery septum and method for producing the same |
| CN101872853A (en) * | 2010-04-21 | 2010-10-27 | 东莞新能源电子科技有限公司 | Polymer lithium ion secondary battery and isolating membrane thereof |
| WO2012119361A1 (en) * | 2011-03-09 | 2012-09-13 | 天津东皋膜技术有限公司 | Co-extruded composite membrane comprising nano-sized pre-crosslinked rubber micropowder and lithium-ion battery using same |
| CN105514321A (en) * | 2015-12-14 | 2016-04-20 | 苏州锂盾储能材料技术有限公司 | High efficiency diaphragm material of lithium ion battery and preparation method of diaphragm material |
| US10141558B2 (en) | 2013-08-28 | 2018-11-27 | Byd Company Limited | Separator for lithium-ion battery and method for preparing the same |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1096591A1 (en) * | 1999-10-26 | 2001-05-02 | MERCK PATENT GmbH | Polymer electrolyte membrane for use in lithium batteries |
| CN1399594A (en) * | 1999-10-29 | 2003-02-26 | 霍林斯沃思及沃斯公司 | Graft polymerization, separators, and batteries including the separators |
| CN1479399A (en) * | 2002-08-29 | 2004-03-03 | 南通硬派电池有限公司 | Manufacturing process electrolyte membrane special for solid lithium ion battery |
-
2005
- 2005-01-27 CN CNB2005100029636A patent/CN100341168C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101271965B (en) * | 2008-04-30 | 2010-06-09 | 中南大学 | Lithium ion battery septum and method for producing the same |
| CN101872853A (en) * | 2010-04-21 | 2010-10-27 | 东莞新能源电子科技有限公司 | Polymer lithium ion secondary battery and isolating membrane thereof |
| CN101872853B (en) * | 2010-04-21 | 2013-03-20 | 东莞新能源电子科技有限公司 | Polymer lithium ion secondary battery and isolating membrane thereof |
| WO2012119361A1 (en) * | 2011-03-09 | 2012-09-13 | 天津东皋膜技术有限公司 | Co-extruded composite membrane comprising nano-sized pre-crosslinked rubber micropowder and lithium-ion battery using same |
| CN102683628A (en) * | 2011-03-09 | 2012-09-19 | 天津东皋膜技术有限公司 | Co-extruded composite diaphragm containing nano pre-crosslinked rubber micropowder and lithium ion battery using co-extruded composite diaphragm |
| CN102683628B (en) * | 2011-03-09 | 2016-02-03 | 天津东皋膜技术有限公司 | Coextru-lamination barrier film containing nanometer precrosslinked rubber micro mist and use its lithium ion battery |
| US10141558B2 (en) | 2013-08-28 | 2018-11-27 | Byd Company Limited | Separator for lithium-ion battery and method for preparing the same |
| CN105514321A (en) * | 2015-12-14 | 2016-04-20 | 苏州锂盾储能材料技术有限公司 | High efficiency diaphragm material of lithium ion battery and preparation method of diaphragm material |
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| Publication number | Publication date |
|---|---|
| CN100341168C (en) | 2007-10-03 |
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