CN111041709A - PVDF nanofiber membrane with through hole structure and preparation method and application thereof - Google Patents
PVDF nanofiber membrane with through hole structure and preparation method and application thereof Download PDFInfo
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- CN111041709A CN111041709A CN201911319496.8A CN201911319496A CN111041709A CN 111041709 A CN111041709 A CN 111041709A CN 201911319496 A CN201911319496 A CN 201911319496A CN 111041709 A CN111041709 A CN 111041709A
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4282—Addition polymers
- D04H1/4318—Fluorine series
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
- D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
- D01D5/0046—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion the fibre formed by coagulation, i.e. wet electro-spinning
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0092—Electro-spinning characterised by the electro-spinning apparatus characterised by the electrical field, e.g. combined with a magnetic fields, using biased or alternating fields
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
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Abstract
The invention belongs to the technical field of nanofiber membranes, and particularly relates to a PVDF nanofiber membrane with a through hole structure, and a preparation method and application thereof. The preparation method of the PVDF nanofiber membrane with the through hole structure comprises the following steps: dissolving PVDF in a solvent to obtain a PVDF solution, performing electrostatic spinning on the PVDF solution, and collecting in an aqueous medium to obtain a PVDF nanofiber membrane with a through hole structure; wherein the solvent is a mixture of dimethylformamide and acetone, and the volume ratio of the dimethylformamide to the acetone is 4: 6. The PVDF solution is subjected to electrostatic spinning and then collected in an aqueous medium, the PVDF nanofiber membrane with the through-hole structure is obtained through the combined effect of the electrostatic spinning and thermally induced phase separation on a dimethylformamide/acetone solvent system in the aqueous medium, the solvent uptake of the obtained PVDF nanofiber membrane with the through-hole structure is high, the PVDF nanofiber membrane with the through-hole structure is applied to a lithium ion battery diaphragm, and the discharge capacity of a lithium ion battery is high.
Description
Technical Field
The invention belongs to the technical field of nanofiber membranes, and particularly relates to a PVDF nanofiber membrane with a through hole structure, and a preparation method and application thereof.
Background
The battery diaphragm is a layer of diaphragm material between the positive electrode and the negative electrode of the battery, is a very critical part in the battery, has direct influence on the safety and the cost of the battery, and has the main functions of: the positive electrode and the negative electrode are separated, electrons in the battery cannot freely pass through the battery, and ions in the electrolyte freely pass between the positive electrode and the negative electrode.
For the lithium ion battery, because the electrolyte is an organic solvent system, the battery diaphragm needs to be resistant to the organic solvent, and needs to have good wettability to the electrolyte and enough liquid absorption and moisture retention capacity. However, the PVDF nanofiber membrane is used as a lithium ion battery separator, and the liquid absorption and moisture retention capacity is still to be improved.
Disclosure of Invention
In view of the above, the invention provides a through-hole polyvinylidene fluoride (PVDF) nanofiber membrane, and a preparation method and an application thereof, which are used for solving the problem that the liquid absorption and moisture retention capacity of the existing PVDF nanofiber membrane as a lithium ion battery diaphragm is still to be improved.
The specific technical scheme of the invention is as follows:
a preparation method of a PVDF nanofiber membrane with a through hole structure comprises the following steps:
dissolving PVDF in a solvent to obtain a PVDF solution, performing electrostatic spinning on the PVDF solution, and collecting in an aqueous medium to obtain a PVDF nanofiber membrane with a through hole structure;
wherein the solvent is a mixture of Dimethylformamide (DMF) and Acetone (Acetone), and the volume ratio of the dimethylformamide to the Acetone is 4: 6.
In the invention, the PVDF solution is subjected to electrostatic spinning and then collected in an aqueous medium, the PVDF nanofiber membrane with the through hole structure is obtained through the combined effect of the electrostatic spinning and thermally induced phase separation on a dimethylformamide/acetone solvent system in the aqueous medium, the solvent uptake of the obtained PVDF nanofiber membrane with the through hole structure is high, and the PVDF nanofiber membrane with the through hole structure is applied to a lithium ion battery diaphragm and has high discharge capacity. Moreover, the preparation method is simple and easy to popularize.
The experimental results show that the fiber in the PVDF nanofiber membrane prepared when the volume ratio of the dimethylformamide to the acetone is 4:6 has a through hole structure, and the solvent uptake percentage (540%) of the PVDF nanofiber membrane is remarkably higher than that of the commercial polyethylene (190%).
Preferably, the mass fraction of the PVDF solution is 10% to 20%, more preferably 12% to 18%, and still more preferably 18%;
the average molecular weight of the PVDF is 100,000-1,000,000, more preferably 150,000-800,000, and still more preferably 300,000.
Preferably, the temperature of the electrostatic spinning is 10-100 ℃, more preferably 15-80 ℃, and further preferably 25 ℃;
the spinning voltage of the electrostatic spinning is 10kV to 300kV, more preferably 12kV to 250kV, and further preferably 18 kV.
Preferably, the flow rate of the PVDF solution for electrostatic spinning is 1 mL/h-20 mL/h, more preferably 3 mL/h-15 mL/h;
the distance between the needle of the electrostatic spinning and the collector is 5cm to 100cm, more preferably 8cm to 80 cm, and still more preferably 10 cm.
The invention also provides a PVDF nanofiber membrane with a through hole structure, which is prepared by the preparation method of the technical scheme.
Preferably, the specific surface area of the PVDF nanofiber membrane with the through hole structure is 10m2/g~100m2/g;
The average fiber diameter of the PVDF nanofiber membrane with the through hole structure is 0.2-1 mu m.
Preferably, the aperture of the through hole is 0-0.35 μm.
Preferably, the solvent uptake of the PVDF nanofiber membrane with the through hole structure is 50-1000%.
The thickness of the PVDF nanofiber membrane with the through hole structure is 0.01 mm-10 mm.
The invention also provides the PVDF nanofiber membrane with the through hole structure prepared by the preparation method in the technical scheme and/or the application of the PVDF nanofiber membrane with the through hole structure in the technical scheme as a lithium ion battery diaphragm.
The invention also provides a lithium ion battery, which comprises the PVDF nanofiber membrane with the through hole structure prepared by the preparation method in the technical scheme and/or the PVDF nanofiber membrane with the through hole structure in the technical scheme.
In summary, the invention provides a preparation method of a PVDF nanofiber membrane with a through hole structure, which comprises the following steps: dissolving PVDF in a solvent to obtain a PVDF solution, performing electrostatic spinning on the PVDF solution, and collecting in an aqueous medium to obtain a PVDF nanofiber membrane with a through hole structure; wherein the solvent is a mixture of dimethylformamide and acetone, and the volume ratio of the dimethylformamide to the acetone is 4: 6. In the invention, PVDF solution is subjected to electrostatic spinning and then collected in an aqueous medium, and the PVDF nanofiber membrane with the through hole structure is obtained through the combined effect of the electrostatic spinning and thermally induced phase separation on a dimethylformamide/acetone solvent system in the aqueous medium, the obtained PVDF nanofiber membrane with the through hole structure has high solvent uptake, and the PVDF nanofiber membrane with the through hole structure is applied to a lithium ion battery diaphragm, so that the discharge capacity of a lithium ion battery is high.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.
FIG. 1 is a surface scanning electron micrograph, a mean diameter distribution plot, and a viscosity plot of PVDF solutions with different solvent mixtures of the PVDF nanofiber membrane obtained in example 1, wherein (a), (b), (c), (d), (e) are PVDF nanofiber membranes collected in an aqueous medium, (a '), (b '), (c '), (d '), (e ') are PVDF nanofiber membranes collected in an air medium, (a) - (e) or (a ') - (e ') are obtained with different volume ratios of DMF/acetone solvent mixtures, the volume ratios of DMF and acetone are 3:7, 4:6, 5:5, 6:4 and 7:3, respectively, (f) is the mean diameter distribution plot of PVDF nanofiber membranes, and (g) is the viscosity plot of PVDF solutions with different solvent mixtures;
FIG. 2 is an SEM image of another surface of the PVDF nanofiber membrane prepared in the example 1, wherein the volume ratio of DMF to acetone is 4:6, and the PVDF nanofiber membrane is collected in an aqueous medium;
FIG. 3 is a SEM image of the cross-section of the PVDF nanofiber membrane prepared in the example 1 and collected in an aqueous medium at a volume ratio of DMF to acetone of 4: 6;
FIG. 4 is a distribution diagram of the hole diameter of the PVDF nanofiber membrane 1 of the present example 1;
FIG. 5 is the percent solvent uptake of the PVDF nanofiber membrane obtained from electrospinning according to example 1;
fig. 6 shows a method for preparing a composite material by mixing 4: electrochemical properties of cells of PVDF membrane prepared by 6 (DMF/acetone) system, wherein (a) initial charge/discharge curve of cycle 3; (b) discharge capacity and cycle number.
Detailed Description
The PVDF nanofiber membrane with the through hole structure prepared by the preparation method is high in solvent uptake, and can enable the membrane separator to be high in discharge capacity when being applied to the membrane separator.
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
In a specific example, the PVDF is commercially available as polyvinylidene fluoride 741, available from arkema, having an average molecular weight of 300000; DMF was purchased from Dalochi chemical reagent works, Tianjin, AR grade; diethyl carbonate (DEC) was purchased from shanghai mclin biochemistry science and technology limited, AR grade; electrospinning was carried out using 22G metal needles with an inner diameter of 0.4 mm, available from alatin reagents (shanghai) ltd.
Example 1
This example carried out the preparation of a PVDF nanofiber membrane, comprising the following steps:
1) weighing PVDF powder, placing the PVDF powder in a beaker, adding DMF/acetone solvent mixtures with different volume ratios respectively, magnetically stirring the mixture for 5 hours at 40 ℃, and then ultrasonically dispersing the mixture for 30 minutes to obtain a PVDF solution with 18 weight percent. Wherein the volume ratio of the dimethyl formamide to the acetone in the solvent is 3:7, 4:6, 5:5, 6:4 and 7:3 in sequence.
2) Absorbing 20mL of PVDF solution by using a needle tube, then carrying out electrostatic spinning at 25 ℃ and 18kV, wherein the flow rate of the electrostatic spinning is 1mL/h, the distance between a needle head of the electrostatic spinning and a collector is 10cm, placing or not placing 20mm deep water in the collector, collecting the electrostatic spinning in an aqueous medium or an air medium, washing the collected membrane twice by using water, and then drying in an oven at 60 ℃ for 7h to obtain ten PVDF nanofiber membranes.
Example 2
The surface morphology of the PVDF nanofiber membrane prepared in example 1 was detected by the following method: the surface morphology of the PVDF nanofiber membrane was examined using an ultra-high resolution scanning electron microscope (HITACHI UHR FE-SEM SU8010, Japan), and the PVDF nanofiber membrane was sputtered with gold (40s, 0.1mA) as a conductive electrode.
Referring to fig. 1(a) - (e'), fig. 1(b) shows that the PVDF nanofiber membrane collected in the aqueous medium under the DMF/acetone solvent mixture of 4:6 has a through-hole structure, fig. 2 and fig. 3 respectively show another surface SEM image and a cross-sectional SEM image of the PVDF nanofiber membrane (denoted as PVDF nanofiber membrane 1) collected in the aqueous medium with the DMF/acetone volume ratio of 4:6 in example 1, and further show that the PVDF nanofiber membrane collected in the aqueous medium has a through-hole structure under the condition that the PVDF nanofiber membrane prepared is dense and porous, the pores are spherical, and the distribution is uniform, while the PVDF nanofiber membrane prepared under other conditions has no through-hole structure.
Example 1 formation of a through-hole structure in PVDF nanofiber membrane 1 the fibers were thermally quenched together with the solvent before reaching the collector, possibly due to the action of an aqueous medium present between the metal tips and the collector acting as a quenching agent, and after heating of the formed film, the residual solvent was evaporated and through-holes were formed.
Example 3
The PVDF nanofiber membrane prepared in example 1 was subjected to fiber diameter measurement, and the measurement method was: the average fiber diameter was calculated by using ImageJ software based on the scanning electron micrographs of example 2, at least 20 membrane fiber diameters were first calculated and averaged. The results, see FIG. 1(f), show that the PVDF nanofiber membranes collected in aqueous medium initially increased in average diameter from 0.7 μm to 1.27 μm, and gradually decreased in diameter to 0.4 μm as the volume ratio of DMF to acetone in the DMF/acetone solvent mixture increased from 4:6 to 7: 3; the resulting PVDF nanofiber membranes collected in air media increased the average fiber diameter from 0.63 μm to 1.15 μm as the volume ratio of DMF to acetone in the DMF/acetone solvent mixture increased from 3:7 to 5:5, and further decreased the average diameter to 0.40 μm and 0.55 μm as the volume ratio of DMF to acetone in the DMF/acetone solvent mixture further increased to 6:4 and 7:3, respectively. The PVDF nanofiber membrane prepared by collecting in an aqueous medium at a volume ratio of DMF to acetone of 4:6 had an average fiber diameter of 0.974 μm.
The PVDF solution of example 1 was subjected to a viscosity measurement by the following method: the viscosity of the PVDF solution before spinning was measured using a digital rotational viscometer (model No. NDJ-5S) with operating conditions using rotor type 1 and a spindle speed of 12rpm measured at ambient conditions, and the results are shown in fig. 1(g), which shows that the PVDF solution viscosity is directly dependent on the DMF content in the DMF/acetone solvent mixture, which increases from 188.mPa · S to 292mPa · S when the volume ratio of DMF to acetone in the DMF/acetone solvent mixture increases from 3:7 to 7: 3.
Referring to FIG. 4, a distribution diagram of the hole diameters of the PVDF nanofiber membrane 1 of example 1 is shown, wherein the average hole diameter is about 0.1 μm. Through detection, in the embodiment 1, the volume ratio of DMF to acetone is 4:6, and the specific surface area of the PVDF nanofiber membrane prepared by collecting in the aqueous medium is 11.631618m2/g。
Example 4
Lithium ion batteries generally comprise a lithium metal anode, a cathode, a polymer separator, and an electrolyte. Li+Ions passing through the polymer during charging and dischargingThe membrane diffuses from one electrode to the other. The solvent is a major part of the electrolyte, and thus the uptake of the solvent through the polymer separator greatly affects the adsorption and penetration of the electrolyte, thereby affecting the performance of the battery.
In this example, the PVDF nanofiber membrane prepared in example 1 is subjected to solvent uptake detection, specifically: PVDF nanofiber membrane prepared in example 1 and commercial PE membrane ((II))X160, Celanese corp., usa) was immersed in diethyl carbonate (DEC) solvent for 24h, and after removing from the solvent, the membrane was cleaned with a tissue paper and each sample was weighed. The percent solvent uptake was calculated by using the following equation and averaged, the results are shown in fig. 2.
The results show that the percentage of solvent uptake of the PVDF nanofiber membrane collected in the aqueous medium initially increases with the DMF content in the DMF/acetone solvent mixture, with the percentage of solvent uptake being greatest at a 4:6 DMF to acetone volume and subsequently decreasing with the DMF content in the DMF/acetone solvent mixture. According to fig. 1(b), in an aqueous medium at 4: the PVDF nanofiber membrane prepared by the 6 (DMF/acetone) system has a through-hole structure, so that the solvent uptake is remarkably increased.
The PVDF nanofiber membrane collected in aqueous medium under a 4:6 DMF/acetone solvent mixture showed a higher percent solvent uptake (540%) than the other conditions and the commercial PE membrane (190%). According to fig. 1(b), in an aqueous medium at 4: the PVDF nanofiber membrane prepared by the 6 (DMF/acetone) system has a through-hole structure that can be processed to take up more solvent, so the uptake percentage is significantly increased. Therefore, collection in aqueous medium under a 4:6 DMF/acetone solvent mixture is the best condition for preparing PVDF nanofiber membranes.
Example 5
Fixing the lithium plate as an anode, and preparing 0.6LiFePO4·0.1LiMnPO4·0.3Li3V2(PO4)3The powder was mixed with 10 wt.% acetylene black and 10 wt.% PVDF powder on an aluminum current collector as a cathode by mixing 1M LiPF6The electrolyte was prepared by dissolving in a mixture of dimethyl carbonate (DMC) and Ethylene Carbonate (EC) (volume ratio 1: 1), and PVDF nanofiber membrane was used as a separator. Electrochemical studies of PVDF nanofiber membranes were performed by forming coin cells (CR2025), the PVDF nanofiber membrane in this example was a membrane formed in a ratio of 4:6 (DMF/acetone) system.
The electrochemical research specifically comprises the following steps: the charge and discharge capacity of button cells was evaluated by a multichannel cell test system (CT2001A, Wuhan) with 2.4V-4.2V and Li+A constant current charge and discharge per Li. Constant current charging is carried out on the button cell on a multi-channel cell test system and is 2.4V-4.2V relative to Li+The results are shown in FIG. 6 for 30 cycles of/Li discharge. In fig. 6(a), the current is 0.1C, the voltage plateau is changed from 2.1V to 4.1-4.2V, and the battery adopting the PVDF nanofiber membrane prepared by the aqueous medium has a larger energy storage density. In FIG. 6(b), it is evident that the discharge capacity (98 mAhg) of the battery using PVDF nanofiber membrane prepared in air medium-1) Almost constant, with multiple cycles. Whereas the discharge capacity of the battery using the PVDF nanofiber membrane prepared in an aqueous medium was initially low and fluctuated for 20 cycles, eventually increasing to 120mAhg-1And it remains constant for 30 cycles. The increased discharge capacity of the cells using PVDF nanofiber membranes prepared in aqueous media rather than air media may be due to the presence of additional via structures on the fibers.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of a PVDF nanofiber membrane with a through hole structure is characterized by comprising the following steps:
dissolving PVDF in a solvent to obtain a PVDF solution, performing electrostatic spinning on the PVDF solution, and collecting in an aqueous medium to obtain a PVDF nanofiber membrane with a through hole structure;
wherein the solvent is a mixture of dimethylformamide and acetone, and the volume ratio of the dimethylformamide to the acetone is 4: 6.
2. The preparation method according to claim 1, wherein the mass fraction of the PVDF solution is 10-20%;
the average molecular weight of the PVDF is 100,000-1,000,000.
3. The method for preparing the fiber according to claim 1, wherein the temperature of the electrostatic spinning is 10-100 ℃;
the spinning voltage of the electrostatic spinning is 10 kV-300 kV.
4. The method according to claim 1, wherein the PVDF solution is electrospun at a flow rate of 1-20 mL/h;
the distance between the needle head of the electrostatic spinning and the collector is 5 cm-100 cm.
5. A PVDF nanofiber membrane having a through-hole structure, which is prepared by the preparation method of any one of claims 1 to 4.
6. The PVDF nanofiber membrane with a through hole structure as claimed in claim 5, wherein the specific surface area of the PVDF nanofiber membrane with a through hole structure is 10m2/g~100m2/g;
The average fiber diameter of the PVDF nanofiber membrane with the through hole structure is 0.2-1 mu m.
7. The PVDF nanofiber membrane with a through hole structure as claimed in claim 5, wherein the aperture of the through hole is 0-0.35 μm.
8. The PVDF nanofiber membrane with a through hole structure as claimed in claim 5, wherein the solvent uptake of the PVDF nanofiber membrane with a through hole structure is 50% -1000%.
9. Use of the PVDF nanofiber membrane having a through-hole structure prepared by the preparation method according to any one of claims 1 to 4 and/or the PVDF nanofiber membrane having a through-hole structure according to any one of claims 5 to 8 as a lithium ion battery separator.
10. A lithium ion battery, characterized by comprising the PVDF nanofiber membrane with a through-hole structure prepared by the preparation method of any one of claims 1 to 4 and/or the PVDF nanofiber membrane with a through-hole structure of any one of claims 5 to 8.
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CN114225106A (en) * | 2021-12-23 | 2022-03-25 | 广东工业大学 | Porous nanofiber biological membrane and preparation method and application thereof |
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CN102517673A (en) * | 2011-11-23 | 2012-06-27 | 浙江大学 | Method for preparing polymer porous nanofiber through mixed phase separation |
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