CN106601964A - Nanofiber composite membrane and preparation method thereof and lithium-ion battery - Google Patents
Nanofiber composite membrane and preparation method thereof and lithium-ion battery Download PDFInfo
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- CN106601964A CN106601964A CN201611052800.3A CN201611052800A CN106601964A CN 106601964 A CN106601964 A CN 106601964A CN 201611052800 A CN201611052800 A CN 201611052800A CN 106601964 A CN106601964 A CN 106601964A
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- hexafluoropropene
- kynoar
- nanofiber composite
- composite diaphragm
- nanofiber
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
-
- 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
- H01M10/058—Construction or manufacture
- H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/44—Fibrous material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Composite Materials (AREA)
- Cell Separators (AREA)
Abstract
The invention discloses a nanofiber composite membrane and a preparation method thereof and a lithium-ion battery. The nanofiber composite membrane comprises a base material and a composite layer, wherein the composite layer is formed on the base material through an electrostatic spinning process; the composite layer comprises the following raw materials: a polyvinylidene fluoride-hexafluoropropylene spinning solution and a zirconium oxide; and the amount of the zirconium oxide is 2%-4% of total mass of the polyvinylidene fluoride-hexafluoropropylene spinning solution. The nanofiber composite membrane is prepared by the zirconium oxide matched with the polyvinylidene fluoride-hexafluoropropylene spinning solution, so that the nanofiber composite membrane has good thermal conductivity and high heat resistance. After the battery of using the membrane is needled, the needled part is not further expanded; and due to the high thermal conductivity of the nanofiber composite membrane, terrestrial heat generated from a short circuit part can be sufficiently diffused and the needling resistance of the battery is improved.
Description
Technical field
Invent and be related to technical field of lithium ion, more particularly to a kind of nanofiber composite diaphragm and preparation method thereof,
Using the lithium ion battery of the nanofiber composite diaphragm.
Background technology
At present, under the support of national policy, lithium battery is widelyd popularize on electric automobile, the safety quilt of battery
It is considered one of key factor of restriction Development of Electric Vehicles, safety also becomes following electric automobile needs the technology captured difficult
Topic.In order to promote the development of each battery production enterprise technology, National Industrial and informationization portion to issue GB/T in May, 2015
31485-2015《Power accumulator safety requirements used for electric vehicle and experimental technique》, implement from May 15th, 2015.
At present the problem of lithium battery is mainly shown as battery catches fire, blast, and its immediate cause locally occurs for inside battery
Short circuit, short dot carries out heavy-current discharge, and producing amount of heat cannot spread in time, and battery core local temperature moment is too high to cause electricity
Solution liquid, barrier film burning, battery cathode SEI film decomposes, positive electrode decomposes, and produces a large amount of gases, battery core failure.Cause in battery core
The reason for portion's short circuit have extruding, rush again, overcharge, cross put, short circuit, vibrate, fall, burning, heating, acupuncture etc., wherein acupuncture item
Mesh test and comparison difficulty passes through, lancing test operational approach be using certain diameter draw point, regulation speed under, from perpendicular to
The direction of battery pole plates is run through, and is battery core center through position.The method for improving acupuncture is more, such as from electrolysis additive, just
The aspects such as pole material, negative material, but improvement is little.
The content of the invention
The invention technical problem to be solved is, there is provided a kind of heat conductivity is good, improves the Nanowire of the anti-acupuncture performance of battery
Dimension composite diaphragm and preparation method thereof, using the lithium ion battery of the nanofiber composite diaphragm.
Invention solves the technical scheme that adopted of its technical problem：A kind of nanofiber composite diaphragm is provided, for lithium
Ion battery, including base material, the composite bed by electrostatic spinning process formation on the substrate；The composite bed includes raw material
It is as follows：Kynoar-hexafluoropropene spinning liquid and zirconium oxide；The zirconic consumption is the Kynoar-hexafluoro
The 2-4% of propylene spinning liquid gross mass.
Preferably, the composite bed is formed at least one side of the base material opposing sides.
Preferably, the zirconic particle diameter is 10～20nm.
Preferably, the Kynoar-hexafluoropropene spinning liquid mixes system with solvent by Kynoar-hexafluoropropene
Into.
Preferably, in the Kynoar-hexafluoropropene spinning liquid, the Kynoar-hexafluoropropene and solvent
Mass ratio be 11-21：79-89.
Preferably, the thickness of the nanofiber composite diaphragm is 14-20 μm.
The present invention also provides a kind of preparation method of nanofiber composite diaphragm, comprises the following steps：
S1, preparation composite bed solution：The zirconium oxide of the 2-4% of Kynoar-hexafluoropropene spinning liquid gross mass will be accounted for
In being distributed to the Kynoar-hexafluoropropene spinning liquid；
S2, the composite bed solution is ejected on base material by electrospinning device, it is multiple to be formed on the substrate
Close layer；
S3, the base material for being formed with composite bed is carried out into vacuum bakeout, nanofiber composite diaphragm is obtained.
Preferably, in step S1, the Kynoar-hexafluoropropene spinning liquid by Kynoar-hexafluoropropene with
Solvent is mixed；Kynoar-the hexafluoropropene is 11-21 with the mass ratio of solvent：79-89.
Preferably, in step S2, composite bed thickness on the substrate is controlled, so that thickness is obtained as 14-20 μm
Nanofiber composite diaphragm；
In step S3, the temperature of the vacuum bakeout is 100-120 DEG C.
The present invention also provides a kind of lithium ion battery, including battery core, and the battery core includes the nanometer described in any of the above-described
Nanofiber obtained in the preparation method of the nanofiber composite diaphragm described in fiber composite barrier film or any of the above-described it is compound every
Film.
The beneficial effect of the invention：Coordinate Kynoar-hexafluoropropene spinning liquid to prepare nanofiber with zirconium oxide to be combined
Barrier film, improves the chemical property and security performance of barrier film；The nanofiber composite diaphragm heat conductivity is good, with high-fire resistance.
After battery acupuncture using the barrier film, darted section does not further expand, due to the height of wherein nanofiber composite diaphragm
Heat conductivity so that the generation geothermal flow at short circuit can spread enough, improves the anti-acupuncture ability of battery.Battery lancing test leads to
It is relatively low that the rate of mistake can reach battery battery core internal temperature after 100%, and acupuncture.
Description of the drawings
Invention is described further below in conjunction with drawings and Examples, in accompanying drawing：
Fig. 1 is the cross-sectional view of the nanofiber composite diaphragm for inventing an embodiment；
Fig. 2 is the preparation method flow chart of the nanofiber composite diaphragm for inventing an embodiment；
Fig. 3 is the SEM figures of the nanofiber composite diaphragm of the present invention；
Fig. 4 is that the composite diaphragm of the present invention and the conventional separator of prior art are respectively prepared the AC impedance after cylindrical battery
Test curve comparison diagram；
Fig. 5 is that the composite diaphragm of the present invention and the conventional separator of prior art are respectively prepared the charge and discharge electrical measurement after cylindrical battery
Examination curve comparison figure.
Specific embodiment
In order to be more clearly understood to the technical characteristic invented, purpose and effect, now compare accompanying drawing detailed description and send out
Bright specific embodiment.
As shown in figure 1, the nanofiber composite diaphragm of one embodiment of the invention, for lithium ion battery.Nanofiber is answered
Closing barrier film includes base material 10, the composite bed 20 being formed in by electrostatic spinning process on base material 10.Composite bed 20 is formed in base material
In at least one side of 10 opposing sides.
The thickness of nanofiber composite diaphragm is 14-20 μm.
Wherein, composite bed 20 includes that raw material is as follows：Kynoar-hexafluoropropene spinning liquid and zirconium oxide；It is zirconic
Consumption is the 2-4% of Kynoar-hexafluoropropene spinning liquid gross mass.
Preferably, zirconic particle diameter is 10～20nm.
The Kynoar-hexafluoropropene spinning liquid is mixed by Kynoar-hexafluoropropene and solvent.Gather inclined fluorine
Ethylene-hexafluoropropene is 11-21 with the mass ratio of solvent：79-89；Preferably, the matter of Kynoar-hexafluoropropene and solvent
Amount is than being 16：84.
Base material can select the barrier film base material used in the prior arts such as polyethylene.
With reference to Fig. 2, and Fig. 1 is combined, the preparation method of the nanofiber composite diaphragm of one embodiment of the invention, it may include with
Lower step：
S1, preparation composite bed solution：The zirconium oxide of the 2-4% of Kynoar-hexafluoropropene spinning liquid gross mass will be accounted for
In being distributed to Kynoar-hexafluoropropene spinning liquid.
Wherein, Kynoar-hexafluoropropene spinning liquid is mixed by Kynoar-hexafluoropropene and solvent；It is poly-
Biasfluoroethylene-hexafluoropropylene is 11-21 with the mass ratio of solvent：79-89.
S2, composite bed solution is ejected on base material 10 by electrospinning device, to form composite bed on base material 10
20。
The parameter setting of electrospinning device is as follows：15 ± 5KV of electrostatic potential, metering flow rate pump be 0.5-1mL/h, spray webbing
Reception distance between head and take-up reel is 20cm.
Wherein, control thickness of the composite bed 20 on base material 10, be obtained thickness as 14-20 μm of nanofiber it is compound every
Film.Composite bed 20 may be formed in the one side of base material 10, or in opposing sides.
S3, the base material 10 for being formed with composite bed 20 is carried out into vacuum bakeout, nanofiber composite diaphragm is obtained.
The temperature of vacuum bakeout is 100-120 DEG C, and the vacuum bakeout time can be 10-12h.
The lithium ion battery of the present invention, including battery core, battery core includes above-mentioned nanofiber composite diaphragm.Battery core makes
When, by nanofiber composite diaphragm and positive plate and negative plate superposition, it is wound into battery core.Battery core is placed in battery case, is noted
Enter electrolyte, you can make lithium ion battery.
Below with specific embodiment, the present invention will be described.
Embodiment 1
Preparation method according to the present invention is obtained respectively nanofiber composite diaphragm, and wherein zirconium oxide accounts for respectively polyvinylidene fluoride
The 2% of alkene-hexafluoropropene spinning liquid gross mass.The electronic scanner microscope SEM figures of the nanofiber composite diaphragm of the embodiment
In piece such as Fig. 3 shown in e.PH-2 samples.
Embodiment 2
Preparation method according to the present invention is obtained respectively nanofiber composite diaphragm, wherein zirconium oxide account for Kynoar-
The 4% of hexafluoropropene spinning liquid gross mass.The electronic scanner microscope SEM pictures of the nanofiber composite diaphragm of the embodiment are such as
In Fig. 3 shown in e.PH-4 samples.
Using without zirconic nanofiber composite diaphragm as comparative example.The nanofiber composite diaphragm of comparative example
In electronic scanner microscope SEM pictures such as Fig. 3 shown in e.PH-0 samples.
Knowable to contrasting on Fig. 3, the composite diaphragm of embodiment 1,2 is respectively provided with fiber IPN 3 D stereo microcellular structure, has
Beneficial to rapid absorption and conduction electrolyte to barrier film.The surface of composite diaphragm sample is smooth, illustrates to be aoxidized in spinning liquid
Zirconium is dispersed preferably, and as the resistance to shrinkage factor of the increase barrier film of zirconia content is improved, this is due to filling in composite diaphragm
There is heat-resisting excellent zirconium oxide, the change in size of barrier film when can effectively hinder heat treatment, composite diaphragm is this excellent heat-resisting
Shrinkage so as to which serious thermal contraction even crimp will not occur in use, can be prevented effectively from positive and negative very big
The appearance of area short circuit, improves the security performance under battery high-temperature environment.
First, security performance test
1) nanofiber composite diaphragm and the conventional separator of prior art respectively from the present invention makes battery, each sampling
10pcs, using 1C charging currents, is charged the battery core of battery using constant current constant voltage method full electric, by voltage 4.2V, electric current
0.01C。
2) with the high temperature resistant draw point of Ф 5, (cone angle of needle point is 45-60 °, any surface finish of pin, rustless turbid, oxide layer
And greasy dirt), with the speed of (25 ± 5) mm/s, from running through perpendicular to the direction of battery core pole plate, through position preferably near piercing face
Geometric center, draw point is rested in battery core.
3) 1h is observed；When cell batteries carry out pin prick test, should not explode, it is not on fire.
4) test result is shown in Table 1, and conventional separator makes battery, tests 10 battery cores, has 6 to pass through, and 4 on fire；Use
Nanofiber composite diaphragm makes battery, tests 10 battery cores, all not on fire, passes through.
Table 1.
From the point of view of two kinds of membrane contrasts, when carrying out acupuncture experiment using conventional separator, battery has 40% generation phenomenon on fire,
Battery temperature not on fire is between 104-126 DEG C；By contrast, when carrying out lancing test using composite diaphragm of the present invention, electricity
Pond 0% is on fire, and battery temperature not on fire is between 74-98 DEG C, can see from data, using composite diaphragm of the present invention
Method for designing battery core lancing test percent of pass is obviously improved, and battery core internal temperature is relatively low when testing, and battery core safety obtains bright
It is aobvious to improve, therefore after acupuncture, darted section does not further expand, simultaneously because composite diaphragm heat conductivity of the present invention is good, because
This enables the generation geothermal flow at short circuit to spread enough, therefore lifts the safety of battery.
2nd, ac impedance measurement
18650 type cylindrical batteries are fabricated to respectively using the conventional separator of prior art and the composite diaphragm of the present invention, are entered
Row ac impedance measurement.Test comparison as shown in figure 4, wherein transverse axis be frequency Hz, the longitudinal axis be voltage V；Curve 1 is conventional separator
Test curve, curve 2 for composite diaphragm of the present invention test curve.Test result：The composite diaphragm of the present invention is in high frequency region
With lower impedance and lower the area specific impedance.
2nd, charge-discharge test
18650 type cylindrical batteries are fabricated to respectively using the conventional separator of prior art and the composite diaphragm of the present invention, are entered
Row charge-discharge test.Test comparison as shown in figure 5, wherein transverse axis be capacity, the longitudinal axis is voltage；Curve 1 is the survey of conventional separator
Examination curve, curve 2 is the test curve of composite diaphragm of the present invention.Test result：The battery tool that the composite diaphragm of the present invention makes
There is higher charge/discharge capacity.
Inventive embodiment is the foregoing is only, the scope of the claims of invention, every utilization invention description is not thereby limited
Equivalent structure or equivalent flow conversion that book and accompanying drawing content are made, or directly or indirectly it is used in other related technology necks
Domain, is included in the same manner in the scope of patent protection of invention.
Claims (10)
1. a kind of nanofiber composite diaphragm, for lithium ion battery, it is characterised in that including base material, by electrostatic spinning work
Skill forms composite bed on the substrate；The composite bed includes that raw material is as follows：Kynoar-hexafluoropropene spinning liquid and
Zirconium oxide；The zirconic consumption is the 2-4% of the Kynoar-hexafluoropropene spinning liquid gross mass.
2. nanofiber composite diaphragm according to claim 1, it is characterised in that the composite bed is formed in the base material
In at least one side of opposing sides.
3. nanofiber composite diaphragm according to claim 1, it is characterised in that the zirconic particle diameter is 10～
20nm。
4. nanofiber composite diaphragm according to claim 1, it is characterised in that the Kynoar-hexafluoropropene
Spinning liquid is mixed by Kynoar-hexafluoropropene and solvent.
5. nanofiber composite diaphragm according to claim 4, it is characterised in that the Kynoar-hexafluoropropene
In spinning liquid, the Kynoar-hexafluoropropene is 11-21 with the mass ratio of solvent：79-89.
6. the nanofiber composite diaphragm according to any one of claim 1-5, it is characterised in that the nanofiber is combined
The thickness of barrier film is 14-20 μm.
7. a kind of preparation method of nanofiber composite diaphragm, it is characterised in that comprise the following steps：
S1, preparation composite bed solution：The zirconium oxide for accounting for the 2-4% of Kynoar-hexafluoropropene spinning liquid gross mass is distributed to
In the Kynoar-hexafluoropropene spinning liquid；
S2, the composite bed solution is ejected on base material by electrospinning device, to form composite bed on the substrate；
S3, the base material for being formed with composite bed is carried out into vacuum bakeout, nanofiber composite diaphragm is obtained.
8. the preparation method of nanofiber composite diaphragm according to claim 7, it is characterised in that described in step S1
Kynoar-hexafluoropropene spinning liquid is mixed by Kynoar-hexafluoropropene and solvent；The Kynoar-
Hexafluoropropene is 11-21 with the mass ratio of solvent：79-89.
9. the preparation method of nanofiber composite diaphragm according to claim 7, it is characterised in that in step S2, control
Composite bed thickness on the substrate, so that the nanofiber composite diaphragm that thickness is as 14-20 μm is obtained；
In step S3, the temperature of the vacuum bakeout is 100-120 DEG C.
10. a kind of lithium ion battery, it is characterised in that including battery core, the battery core is included described in any one of claim 1-6
Nanometer obtained in the preparation method of the nanofiber composite diaphragm described in nanofiber composite diaphragm or any one of claim 7-9
Fiber composite barrier film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611052800.3A CN106601964A (en) | 2016-11-25 | 2016-11-25 | Nanofiber composite membrane and preparation method thereof and lithium-ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611052800.3A CN106601964A (en) | 2016-11-25 | 2016-11-25 | Nanofiber composite membrane and preparation method thereof and lithium-ion battery |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102629679A (en) * | 2012-04-28 | 2012-08-08 | 中国科学院理化技术研究所 | Nanometer fiber lithium ion battery diaphragm material with composite structure and preparation method of nanometer fiber lithium ion battery diaphragm material |
| CN102779964A (en) * | 2012-08-08 | 2012-11-14 | 龙能科技（苏州）有限公司 | Method for preparing multilayer composite membrane for secondary battery by using electrostatic spinning coating method |
| CN104681764A (en) * | 2015-02-10 | 2015-06-03 | 龙岩紫荆创新研究院 | Composite lithium ion battery ceramic diaphragm and preparation method thereof |
-
2016
- 2016-11-25 CN CN201611052800.3A patent/CN106601964A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102629679A (en) * | 2012-04-28 | 2012-08-08 | 中国科学院理化技术研究所 | Nanometer fiber lithium ion battery diaphragm material with composite structure and preparation method of nanometer fiber lithium ion battery diaphragm material |
| CN102779964A (en) * | 2012-08-08 | 2012-11-14 | 龙能科技（苏州）有限公司 | Method for preparing multilayer composite membrane for secondary battery by using electrostatic spinning coating method |
| CN104681764A (en) * | 2015-02-10 | 2015-06-03 | 龙岩紫荆创新研究院 | Composite lithium ion battery ceramic diaphragm and preparation method thereof |
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