CN103219483B - Composite lithium battery diaphragm and preparation method thereof - Google Patents
Composite lithium battery diaphragm and preparation method thereof Download PDFInfo
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- CN103219483B CN103219483B CN201310154350.9A CN201310154350A CN103219483B CN 103219483 B CN103219483 B CN 103219483B CN 201310154350 A CN201310154350 A CN 201310154350A CN 103219483 B CN103219483 B CN 103219483B
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Abstract
The invention relates to a composite lithium battery diaphragm which is formed by compounding an upper nanometer fiber membrane, a middle micrometer fiber membrane and a lower nanometer fiber membrane, wherein the fiber diameters of the upper nanometer fiber membrane and the lower nanometer fiber membrane are 1-200 nanometers, and the fiber diameter of the middle micrometer fiber membrane is 1-10 micrometers. The preparation method comprises the steps of respectively preparing the upper nanometer fiber membrane, the middle micrometer fiber membrane and the lower nanometer fiber membrane through a solution electrostatic spinning method by using the polymeric materials of the upper nanometer fiber membrane, the middle micrometer fiber membrane and the lower nanometer fiber membrane; then sequentially releasing and winding laminated layers; then placing into a curing furnace, and heating to remove a solvent; and finally carrying out roll forming on a press roll by controlling temperature. The composite lithium battery diaphragm disclosed by the invention has the advantages of high poriness, good safety, good high-temperature resistance, good mechanical strength and fast charge-discharge and can be used for automobile power lithium batteries.
Description
Technical field
The present invention relates to a kind of lithium ion battery separator and preparation method thereof, especially the manufacturing technology of composite lithium battery membrane and product.
Background technology
Lithium ion battery separator point mainly contains simple tension technique and stretch processes at present from manufacturing technology, also have wet method synchro-draw and dry method tension, no matter adopt any production technology, mostly lithium battery diaphragm raw material used are polyethylene, polypropylene, recently the report of PVDF lithium battery diaphragm manufacturing technology is also had, what adopt is the tape casting or knife coating procedure, without stretching film forming.For monofilm PE, PP, their heat resistance is bad, and porosity is lower (30 ~ 40%) also, poor stability; And sandwich diaphragm PP/PE/PP has good fail safe (intermediate layer PE melts when temperature is higher, closes ion channel, plays the effect of protection cell safety), but temperature tolerance is bad, and porosity is low; In order to improve the temperature tolerance of barrier film, also have people at membrane surface blade coating (spraying, dipping, the deposition) PVDF of PP, PE, PP, PP/PE/PP or pottery, although the temperature tolerance of such barrier film improves, porosity but reduces relatively.Therefore these barrier films can only do consumer lithium battery diaphragm, can not high-power fast charging and discharging.
Wet method bi-directional synchronization drawing process (simple tension and longitudinal stretching synchro-draw machine once complete), be only applicable to PE raw material, it comes from Japan, and the pass of barrier film is that the distribution in circular, aperture and hole is relatively more even, employing be Thermal inactive principle pore-forming; Dry method simple tension technique (only stretch in machine direction and extrude slab film forming), be suitable for PP and PE two kinds of raw materials, PP/PE/PP composite diaphragm can also be produced simultaneously, also have and adopt this technique to manufacture the research report of barrier film with PMP, POM material, but do not form market products, it comes from the U.S., barrier film pass is rectangle, than wet method barrier film heatproof, what it adopted is that crystalline phase is separated pore-forming principle; The two-way asynchronous drawing process of dry method (first to slab longitudinal stretching and then cross directional stretch), be suitable only for PP raw material, pass is indefinite, the skewness in aperture and hole, and porosity is very low, and it comes from China, employing be crystal formation conversion pore-forming principle.
Summary of the invention
The object of the invention is the problem that temperature tolerance is bad, porosity is low solving lithium battery diaphragm in prior art, a kind of composite lithium battery membrane is provided, make that its porosity is high, fail safe good, high temperature resistant good, mechanical strength is good, and can fast charging and discharging, can be used in lithium battery for automobile power.
Principle of the present invention: raw material that select heatproof, that be suitable as lithium battery diaphragm, adopt electrostatic spinning technique, raw material is made the compound nonwoven cloth of nm/ μm/nm distribution of fiber diameters, the one composite fiber web of sandwich formats is formed, as power lithium battery diaphragm through solvent evaporates and (or) temperature, Stress control.Wherein intermediate layer fiber more slightly plays a part supporting layer, simultaneously because its melt temperature is a little less than epidermal area, can melt closedown ion channel when temperature is too high in battery, plays the effect of protection cell safety.Epidermal area fibre diameter is thin, fiber aperture is little, belong to nanoscale aperture, porosity is higher, a large amount of lithium ion is allowed to pass through barrier film in a short period of time, realize fast charging and discharging, and choosing of diaphragm material can bear the heat that in the short time, discharge and recharge produces, use so be applicable to automobile dynamic lithium battery.
Technical scheme
A kind of composite lithium battery membrane, be composited by upper strata nano fibrous membrane, intermediate layer micrometer fibers film and lower floor's nano fibrous membrane, the fibre diameter of upper strata nano fibrous membrane and lower floor's nano fibrous membrane is 1 ~ 200nm, and the fibre diameter of intermediate layer micrometer fibers film is 1 ~ 10 μm.The aperture of upper strata nano fibrous membrane and lower floor's nano fibrous membrane is little, porosity is high, can by electrolyte complete wetting, allow a large amount of lithium ion to pass through, thus reach the object of fast charging and discharging.The function of intermediate layer micrometer fibers film is play mechanical support effect when ensureing that porosity is not less than levels primarily of two kinds: one; meet the requirement that lithium battery manufactures; two is be fused into liquid when battery temperature reaches this one polymer fusing point to block bilevel hole; block ion channel, play the effect of safeguard protection.
The gross thickness of described composite lithium battery membrane is 6 ~ 40 μm.
The preparation method of composite lithium battery membrane: by the polymeric material of upper strata nano fibrous membrane, intermediate layer micrometer fibers film and lower floor's nano fibrous membrane, by the method for solution electrostatic spinning, prepare upper strata nano fibrous membrane, intermediate layer micrometer fibers film and lower floor's nano fibrous membrane respectively, then lamination is unreeled in order, be placed in heating in curing oven again and remove desolventizing, finally by temperature control to pressure roller roll-forming, to obtain final product.
The polymeric material of described upper strata nano fibrous membrane and lower floor's nano fibrous membrane is any one in the high-melting-point polymers such as polyimides (PI), polyether-ether-ketone (PEEK), polyphenylene sulfide (PPS), Kynoar (PVDF), polytetrafluoroethylene (PTFE), aramid fiber (Kevlar), polyaryl thioether sulfone (PASS), ketone acid anhydride type polyamic acid (PAA).
The polymeric material of described intermediate layer micrometer fibers film is any one in the low melting point polymers such as polypropylene (PP), polyethylene (PE), polyurethane (PU), polyvinyl alcohol (PVA), polysulfones (PSU).
The weight ratio of described upper strata nano fibrous membrane, intermediate layer micrometer fibers film and lower floor's nano fibrous membrane is (5 ~ 15): (70 ~ 90): (5 ~ 15), the object controlling this weight ratio has two: one to be control aperture size, and two is meet necessary mechanical strength.When mechanical strength and aperture size meet, Bao Yuehao is got in the upper and lower, the tortuosity that minimizing ion passes through and resistance.
In described curing oven, heating removes the temperature of desolventizing is 100 ~ 260 DEG C.
Described temperature control is 50 ~ 230 DEG C to roller temperature.
Described solution electrostatic spinning, specifically comprises the steps:
(1) solution preparation: by the polymeric material of upper strata nano fibrous membrane, intermediate layer micrometer fibers film and lower floor's nano fibrous membrane, be dissolved in respective solvent respectively, preparation quality concentration is the polymer solution of 5-40%;
(2) electrode system: adopt needle-less electrode system, it is made up of high voltage source, electrode, control system three part, the positive pole receiving electrode of high voltage source, negative pole connects collection silk device, forms electric field between electrode and collection silk device;
(3) preparation of tunica fibrosa: the polymer solution that step (1) prepares is transported in reservoir, the electrode contact of the polymer solution in reservoir and needle-less electrode system, polymer solution under the effect of electric field force in reservoir formed taylor cone before this on electrode, then become jet directive collection silk device, form tunica fibrosa.
In step (1), the solvent of the polymeric material of described upper strata nano fibrous membrane and lower floor's nano fibrous membrane has: dimethylacetylamide (DMAc), Hexafluoro acetone (HFAH), dimethylformamide (DMF), oxolane (THF), hexamethyl-phosphoramide (HMPA), 1-METHYLPYRROLIDONE (NMP) etc., can be used alone, also can several solvent use in proportion, this depends on the kind of polymer.
In step (1), the solvent of the polymeric material of described intermediate layer micrometer fibers film has: hexafluoroisopropanol (HFIP), trifluoroacetic acid (TFA), dimethylformamide (DMF), carbon disulfide (CS2), oxolane (THF) etc., can be used alone, also can be two or more used in combination in any proportion.
In step (2), electrode is 8 ~ 600mm with the distance of collection silk device, and the kind etc. of the distance of the size of the diameter of fiber and the concentration of polymer solution, electric field force, collection silk device and electrode, ambient temperature and humidity, selected solvent has direct relation.
In step (3), solution is transported to conveying capacity in reservoir and electrode fluid volume keeps balance, thus can guarantee that the fibre diameter that spins out and form stable are in available scope.
The invention is not restricted to solution electrospinning process, can also be melt extrusion electrostatic spinning, and when adopting melt extrusion electrostatic spinning, spinning temperature 130 ~ 370 DEG C, electrode voltage is 8 ~ 500kv, electrode and the distance 100 ~ 700mm collecting silk device.
Accompanying drawing explanation
Fig. 1 is the structural representation of the embodiment of the present invention 1 composite lithium battery membrane.
Embodiment
Below in conjunction with drawings and Examples, the invention will be further described.
Embodiment 1
As shown in Figure 1, the composite lithium battery membrane of the present embodiment, is composited by upper strata nano fibrous membrane 1, intermediate layer micrometer fibers film 2 and lower floor's nano fibrous membrane 3.The fibre diameter of upper strata nano fibrous membrane 1 and lower floor's nano fibrous membrane 3 is 100nm, and the fibre diameter of intermediate layer micrometer fibers film is 2.5 μm, and the gross thickness of described composite lithium battery membrane is 15 μm.
Preparation method:
Polyimides is used as the polymeric material of upper strata nano fibrous membrane and lower floor's nano fibrous membrane, styrene-maleic anhydride copolymer is used as the polymeric material of intermediate layer micrometer fibers film, by the method for solution electrostatic spinning, prepare upper strata nano fibrous membrane, intermediate layer micrometer fibers film and lower floor's nano fibrous membrane respectively, then lamination is unreeled in order, be placed in again in curing oven and remove desolventizing in 150 DEG C of heating, finally by temperature control to pressure roller roll-forming at 160 DEG C, to obtain final product.Wherein, the weight ratio of upper strata nano fibrous membrane, intermediate layer micrometer fibers film and lower floor's nano fibrous membrane is 10:80:10.
Solution electrostatic spinning process parameter:
Upper strata nano fibrous membrane and lower floor's nano fibrous membrane: select polyimides as polymeric material, DMF is as solvent, preparation quality concentration is the polymer material solution of 23.5%, the distance 180mm of electrode pair collection silk device, voltage 23kv, obtained nano fibrous membrane fibre diameter 100nm, fleece porosity 95%.
Intermediate layer micrometer fibers film: select styrene-maleic anhydride copolymer as polymeric material, acetone/DMF ratio: 2:1 is as solvent, preparation quality concentration is the polymer material solution of 40%, electrode spacing collection silk device distance 220mm, voltage 15kv, obtained tunica fibrosa fibre diameter 2.5 μm, fleece porosity 83%.
The intermediate layer micrometer fibers film of the present embodiment melts 160 DEG C time, can close the duct of composite diaphragm when temperature is too high in battery, thus cuts off electric current, serves safety effect.
After the composite lithium battery membrane that the present embodiment is obtained is used for lithium battery, the battery made can charge 95% in 11 minutes.
Embodiment 2
The composite lithium battery membrane of the present embodiment, is composited by upper strata nano fibrous membrane, intermediate layer micrometer fibers film and lower floor's nano fibrous membrane.The fibre diameter of upper strata nano fibrous membrane and lower floor's nano fibrous membrane is 120nm, and the fibre diameter of intermediate layer micrometer fibers film is 2.9 μm, and the gross thickness of described composite lithium battery membrane is 25 μm.
Preparation method:
Kynoar is used as the polymeric material of upper strata nano fibrous membrane and lower floor's nano fibrous membrane, polyvinyl alcohol is used as the polymeric material of intermediate layer micrometer fibers film, by the method for solution electrostatic spinning, prepare upper strata nano fibrous membrane, intermediate layer micrometer fibers film and lower floor's nano fibrous membrane respectively, then lamination is unreeled in order, be placed in again in curing oven and remove desolventizing in 240 DEG C of heating, finally by temperature control to pressure roller roll-forming at 210 DEG C, to obtain final product.Wherein, the weight ratio of upper strata nano fibrous membrane, intermediate layer micrometer fibers film and lower floor's nano fibrous membrane is 15:70:15.
Solution electrostatic spinning process parameter:
Upper strata nano fibrous membrane and lower floor's nano fibrous membrane: select Kynoar (PVDF) as polymeric material, acetone/DMAC ratio: 3:1 is as solvent, and preparation quality concentration is the polymer material solution of 10%; Spinning voltage 50kv, electrode is to the distance 210mm of collection silk device, and obtained nano fibrous membrane fibre diameter is 120nm, fleece porosity 92%.
Intermediate layer nanofiber nethike embrane: select polyvinyl alcohol (PVA) to be polymeric material, DMAC is solvent, and preparation quality concentration is the polymer material solution of 12%, voltage 40kv, electrode to the distance 200mm of collection silk device, obtained tunica fibrosa fibre diameter 2.9 μm, fleece porosity 86%.
The intermediate layer PVA micrometer fibers nethike embrane of the present embodiment melts 200 DEG C time, and when in battery, temperature is too high, PVA melt closes the duct of barrier film, thus cuts off electric current, plays safeguard protection effect.
After the composite lithium battery membrane that the present embodiment is obtained is used for lithium battery, the battery made can charge 89% in 15 minutes.
Embodiment 3
The composite lithium battery membrane of the present embodiment, is composited by upper strata nano fibrous membrane, intermediate layer micrometer fibers film and lower floor's nano fibrous membrane.The fibre diameter of upper strata nano fibrous membrane and lower floor's nano fibrous membrane is 138nm, and the fibre diameter of intermediate layer micrometer fibers film is 3.4 μm, and the gross thickness of described composite lithium battery membrane is 40 μm.
Preparation method:
Polyaryl thioether sulfone is used as the polymeric material of upper strata nano fibrous membrane and lower floor's nano fibrous membrane, polyurethane is used as the polymeric material of intermediate layer micrometer fibers film, by the method for solution electrostatic spinning, prepare upper strata nano fibrous membrane, intermediate layer micrometer fibers film and lower floor's nano fibrous membrane respectively, then lamination is unreeled in order, be placed in again in curing oven and remove desolventizing in 200 DEG C of heating, finally by temperature control to pressure roller roll-forming at 180 DEG C, to obtain final product.Wherein, the weight ratio of upper strata nano fibrous membrane, intermediate layer micrometer fibers film and lower floor's nano fibrous membrane is 12:76:12.
Solution electrostatic spinning process parameter:
Upper strata nano fibrous membrane and lower floor's nano fibrous membrane: select polyaryl thioether sulfone (PASS) as polymeric material, 1-METHYLPYRROLIDONE (NMP) is solvent.Preparation quality concentration is the polymer material solution of 20%, in the insulation of electrostatic spinning process need, avoids solution to become colloid, voltage 15kv, the distance 190mm of electrode spacing collection silk device, obtained nano fibrous membrane fibre diameter 138nm, porosity 90%.
Intermediate layer micrometer fibers film: select polyurethane (PU) as polymeric material, select dimethylformamide (DMF) and oxolane (THF) as solvent, the mixing ratio of DMF and THF is 2:1, preparation quality concentration is the polymer material solution of 21%, voltage 22KV, electrode spacing collection silk device distance 260mm, obtained tunica fibrosa fibre diameter 3.4 μm, porosity 89%.
The intermediate layer micrometer fibers nethike embrane of the present embodiment is fine to be melted 170 DEG C time, and when in battery, temperature is too high, the duct in fiber nethike embrane is closed by melt, thus cuts off electric current, plays a part safeguard protection.
After the composite lithium battery membrane that the present embodiment is obtained is used for lithium battery, the battery made can charge 91% in 10 minutes.
Embodiment 4
The composite lithium battery membrane of the present embodiment, is composited by upper strata nano fibrous membrane, intermediate layer micrometer fibers film and lower floor's nano fibrous membrane.The fibre diameter of upper strata nano fibrous membrane and lower floor's nano fibrous membrane is 140nm, and the fibre diameter of intermediate layer micrometer fibers film is 6 μm, and the gross thickness of described composite lithium battery membrane is 30 μm.
Preparation method:
Ketone acid anhydride type polyamic acid is used as the polymeric material of upper strata nano fibrous membrane and lower floor's nano fibrous membrane, polypropylene is used as the polymeric material of intermediate layer micrometer fibers film, by the method for solution electrostatic spinning, prepare upper strata nano fibrous membrane and lower floor's nano fibrous membrane respectively, intermediate layer micrometer fibers film is prepared by melt extrusion electrospinning process, then lamination is unreeled in order, be placed in again in curing oven and remove desolventizing in 200 DEG C of heating, finally by temperature control to pressure roller roll-forming at 190 DEG C, to obtain final product.Wherein, the weight ratio of upper strata nano fibrous membrane, intermediate layer micrometer fibers film and lower floor's nano fibrous membrane is 13:74:13.
Electrostatic spinning process parameter:
Upper strata nano fibrous membrane and lower floor's nano fibrous membrane: select ketone acid anhydride type polyamic acid (PAA) as polymeric material, dimethylformamide (DMF) is solvent, at temperature 25 DEG C, preparation quality concentration is the polymer material solution of 23%, voltage 17kv, the distance 200mm of electrode spacing collection silk device, obtained nano fibrous membrane fibre diameter 140nm, fleece porosity 90%.
Intermediate layer micrometer fibers nethike embrane: adopt melt extrusion method of electrostatic spinning to prepare polypropylene (PP) micrometer fibers nethike embrane,
The polypropylene melt flow rate selected is: 1160g/10min(240 DEG C, 2.16g), spinning voltage 27kv, spinning temperature 215 DEG C, electrode and collection silk device distance 100mm, obtained tunica fibrosa fibre diameter is 6 μm, porosity 84%.
The intermediate layer fleece membrane fiber of the present embodiment 165 DEG C of fusings, shutoff fleece duct, thus when internal temperature of battery is too high cut off electric current, play a part safeguard protection.
After the composite lithium battery membrane that this example is obtained is used for lithium battery lithium battery, the lithium battery of manufacture can charge 93% at 13 minutes.
Performance test:
The composite lithium battery membrane that embodiment is obtained carries out performance test, the results are shown in following table:
| Porosity/% | Thickness/μm | High temperature integrity/DEG C | Tensile strength/psi | |
| Embodiment 1 | 82 | 15 | ＞230 | 1100 |
| Embodiment 2 | 86 | 25 | ＞210 | 1300 |
| Embodiment 3 | 84 | 40 | ＞225 | 1700 |
| Embodiment 4 | 80 | 30 | ＞230 | 1260 |
Note: high temperature integrity test is placed in stove by composite lithium battery membrane to heat, and observes temperature during diaphragm deflection.
As can be seen from test result, the composite lithium battery membrane porosity adopting the present embodiment method obtained high, high temperature resistant good, mechanical strength is good, fail safe is good, and can fast charging and discharging, can be used in lithium battery for automobile power.
Claims (7)
1. a composite lithium battery membrane, it is characterized in that, be composited by upper strata nano fibrous membrane, intermediate layer micrometer fibers film and lower floor's nano fibrous membrane, the fibre diameter of upper strata nano fibrous membrane and lower floor's nano fibrous membrane is 1 ~ 200nm, the fibre diameter of intermediate layer micrometer fibers film is 1 ~ 10 μm, and the gross thickness of described composite lithium battery membrane is 6 ~ 40 μm;
The preparation method of described composite lithium battery membrane: by the polymeric material of upper strata nano fibrous membrane, intermediate layer micrometer fibers film and lower floor's nano fibrous membrane, by the method for solution electrostatic spinning, prepare upper strata nano fibrous membrane, intermediate layer micrometer fibers film and lower floor's nano fibrous membrane respectively, then lamination is unreeled in order, be placed in heating in curing oven again and remove desolventizing, finally by temperature control to pressure roller roll-forming, to obtain final product;
The polymeric material of described upper strata nano fibrous membrane and lower floor's nano fibrous membrane is selected from the one in polyimides, polyether-ether-ketone, polyphenylene sulfide, Kynoar, polytetrafluoroethylene, aramid fiber, polyaryl thioether sulfone or ketone acid anhydride type polyamic acid; The polymeric material of described intermediate layer micrometer fibers film is selected from the one in polypropylene, polyethylene, polyurethane, polyvinyl alcohol or polysulfones;
The weight ratio of described upper strata nano fibrous membrane, intermediate layer micrometer fibers film and lower floor's nano fibrous membrane is (5 ~ 15): (70 ~ 90): (5 ~ 15).
2. composite lithium battery membrane as claimed in claim 1, is characterized in that, in described curing oven, heating removes the temperature of desolventizing is 100 ~ 260 DEG C.
3. composite lithium battery membrane as claimed in claim 1, it is characterized in that, described temperature control is 50 ~ 230 DEG C to roller temperature.
4. the composite lithium battery membrane as described in claim 1 or 2 or 3, is characterized in that, described solution electrostatic spinning, specifically comprises the steps:
(1) solution preparation: by the polymeric material of upper strata nano fibrous membrane, intermediate layer micrometer fibers film and lower floor's nano fibrous membrane, be dissolved in respective solvent respectively, preparation quality concentration is the polymer solution of 5-40%;
(2) electrode system: adopt needle-less electrode system, it is made up of high voltage source, electrode, control system three part, the positive pole receiving electrode of high voltage source, negative pole connects collection silk device, forms electric field between electrode and collection silk device;
(3) preparation of tunica fibrosa: the polymer solution that step (1) prepares is transported in reservoir, the electrode contact of the polymer solution in reservoir and needle-less electrode system, polymer solution under the effect of electric field force in reservoir formed taylor cone before this on electrode, then become jet directive collection silk device, form tunica fibrosa.
5. composite lithium battery membrane as claimed in claim 4, it is characterized in that, the solvent of the polymeric material of described upper strata nano fibrous membrane and lower floor's nano fibrous membrane is selected from the mixture of one or more arbitrary proportions in dimethylacetylamide, Hexafluoro acetone, dimethylformamide, oxolane, hexamethyl-phosphoramide or 1-METHYLPYRROLIDONE.
6. composite lithium battery membrane as claimed in claim 4, it is characterized in that, the solvent of the polymeric material of described intermediate layer micrometer fibers film is selected from the mixture of one or more arbitrary proportions in hexafluoroisopropanol, trifluoroacetic acid, dimethylformamide, carbon disulfide or oxolane.
7. composite lithium battery membrane as claimed in claim 4, is characterized in that, in step (2), electrode is 8 ~ 600mm with the distance of collection silk device.
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Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1744348A (en) * | 2004-08-30 | 2006-03-08 | 北京东皋膜技术有限公司 | Composite diaphragm for lithium ion secondary cell and lithium ion secondary cell therewith |
| CN1758463A (en) * | 2004-10-10 | 2006-04-12 | 西安迪纳斯科技有限责任公司 | Compound diaphragm used for lithium-ion secondary battery and lithium-ion secondary battery using the diaphragm |
| CN101656306B (en) * | 2008-08-22 | 2012-07-04 | 比亚迪股份有限公司 | Composite membrane and preparation method thereof and battery comprising composite membrane |
| CN101997102B (en) * | 2009-08-26 | 2013-11-06 | 比亚迪股份有限公司 | Lithium ion battery diaphragm and manufacturing method thereof |
| CN102140762B (en) * | 2011-01-10 | 2012-06-27 | 武汉理工大学 | Reinforced nanofiber porous membrane and preparation method thereof |
| CN102231431B (en) * | 2011-05-06 | 2013-06-05 | 浙江大东南集团有限公司 | Compound nanofiber diaphragm for lithium ion power battery and manufacturing method |
| CN102299287B (en) * | 2011-08-12 | 2013-05-29 | 沧州明珠塑料股份有限公司 | Composite nanometer fiber lithium ion battery diaphragm and preparation method thereof |
| CN102629679B (en) * | 2012-04-28 | 2018-04-20 | 中国科学院理化技术研究所 | Nanofiber lithium ion battery separator material with composite construction and preparation method thereof |
| CN203277533U (en) * | 2013-04-27 | 2013-11-06 | 中材科技股份有限公司 | Composite lithium battery diaphragm |
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