CN104746239A - Soft phase macromolecule/polyimide gradient type composite nanometer fiber membrane and preparation method thereof - Google Patents
Soft phase macromolecule/polyimide gradient type composite nanometer fiber membrane and preparation method thereof Download PDFInfo
- Publication number
- CN104746239A CN104746239A CN201310726446.8A CN201310726446A CN104746239A CN 104746239 A CN104746239 A CN 104746239A CN 201310726446 A CN201310726446 A CN 201310726446A CN 104746239 A CN104746239 A CN 104746239A
- Authority
- CN
- China
- Prior art keywords
- soft polymer
- polymer phase
- polyimide
- internal layer
- fiber membrane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention discloses a soft phase macromolecule/polyimide gradient type composite nanometer fiber membrane and a preparation method thereof. The soft phase macromolecule/polyimide gradient type composite nanometer fiber membrane comprises an obverse membrane, a middle inner layer and a reverse membrane, which are sequentially arranged from the top down, wherein the middle inner layer is formed by polyimide nanometer fibers, or the polyimide nanometer fibers and soft phase macromolecule nanometer fibers, each of the obverse membrane and the reverse membrane includes one or more than one composite layer, each composite layer is formed by the soft phase macromolecule nanometer fibers, or the polyimide nanometer fibers and the soft phase macromolecule nanometer fibers, and in the middle inner layers and all the composite layers, contents of the polyimide nanometer fibers are decreased progressively and contents of the soft phase macromolecule nanometer fibers are increased progressively from the middle inner layer outwards. By using the preparation method of the soft phase macromolecule/polyimide gradient type composite nanometer fiber membrane, not only are mechanical properties of the soft phase macromolecule/polyimide gradient type composite nanometer fiber membrane improved, but also functionality of a gel electrolyte is endowed to the soft phase macromolecule/polyimide gradient type composite nanometer fiber membrane, and therefore integration of the soft phase macromolecule/polyimide gradient type composite nanometer fiber membrane and the gel electrolyte is achieved.
Description
Technical field
The present invention relates to a kind of soft polymer phase/polyimide gradient type composite nano-fiber membrane and preparation method thereof, particularly, the present invention relates to a kind of soft polymer phase/polyimide gradient type composite nano-fiber membrane adopting double needle electrostatic spinning technique to prepare and preparation method thereof.
Background technology
Method of electrostatic spinning is a kind of important method preparing superfine fibre, and as far back as 1934, Formhals just described the technology utilizing electrostatic repulsion to obtain polymer filaments first in U.S. Patent application 1975504 [P].In recent years, along with the development of nanosecond science and technology, this technology obtains the extensive concern of people again.The appearance of double needle electrostatic spinning technique can be described as the result further furtherd investigate electrostatic spinning technique.
PI(polyimides) be a kind of special engineering plastics, can not decompose by resistance to 500 DEG C of high temperature, almost thermal deformation is not had at 150 DEG C, the film mechanicalness made is good, generally 200-300MPa can be reached, PI excellent stability in organic solvent, lower with electrolyte sympathy in lithium ion battery, it can be used as the barrier film of lithium ion battery.Therefore PI is the splendid hard phase material of a kind of performance.
Soft polymer phase generally can think homopolymers and the copolymer of esters of acrylic acid, such as, PMMA(polymethyl methacrylate), he is a kind of homopolymers that monomethyl methacrylate monomer is polymerized.PMMA hardness is not high, and mechanical strength is comparatively general, between about TENSILE STRENGTH 60MPa, vitrification point 80-100 DEG C.But PMMA spinning film and compatibility of electrolyte good, absorbency is strong, and it is good to protect fluidity, and ionic conductivity, apparently higher than PI film, is a kind of soft phase material well.PMMA is the one in numerous soft polymer phase, represents the general character of soft polymer phase.
In conjunction with the material behavior of PI and soft polymer phase, pass through electrostatic spinning technique, we can prepare the blend film of PI and soft phase, the soft mutually integrated barrier film of PI-is prepared again by blend film, although PI fiber and soft polymer phase fiber are uniformly distributed in film system, PI fiber plays mechanics skeleton function, and soft phase fiber is as the transmission gel electrolyte of lithium ion.But the drawback of the method is, soft phase fiber appears in the innermost layer of film, affects the mechanical property of whole film, and PI fiber appears at the outermost layer of film, plays certain retardation to the fast transport of lithium ion, affects the ionic conductivity of barrier film to a certain extent.
Therefore, how to prepare mechanical property and improve and the effect can giving the functional i.e. gel electrolyte of barrier film, the film reaching the integration of barrier film-gel electrolyte needs to study further and urgently develop.
Summary of the invention
The object of the invention is to overcome the poor mechanical property of the composite nano-fiber membrane for lithium ion battery of the prior art and the low shortcoming of electrical conductivity, provide a kind of soft polymer phase/polyimide gradient type composite nano-fiber membrane and preparation method thereof.
The invention provides a kind of soft polymer phase/polyimide gradient type composite nano-fiber membrane, described soft polymer phase/polyimide gradient type composite nano-fiber membrane comprises front side films, middle internal layer and reverse side film from top to bottom successively, wherein:
Described middle internal layer is formed by polyimide nano-fiber or polyimide nano-fiber and soft polymer phase nanofiber; And
Described front side films and described reverse side film comprise one or more composite bed separately, and each described composite bed is formed by soft polymer phase nanofiber or polyimide nano-fiber and soft polymer phase nanofiber;
Wherein, in described middle internal layer and each described composite bed, outside from described middle internal layer, in each layer, the content of polyimide nano-fiber successively decreases from inside to outside, and the content of soft polymer phase nanofiber increases progressively from inside to outside.
Present invention also offers the preparation method of a kind of soft polymer phase/polyimide gradient type composite nano-fiber membrane, wherein, the method comprises the following steps:
(1a) adopt the organic solution of polyamic acid or the organic solution of polyamic acid and soft polymer phase solution by forming middle internal layer with the double needle electrostatic spinning apparatus of metal needle A and metal needle B;
(2a) polyamic acid solution and soft polymer phase solution is adopted to form front side films by the double needle electrostatic spinning apparatus with metal needle A and metal needle B in the side of described middle internal layer;
(3a) then form reverse side film at the opposite side of described middle internal layer, then carry out drying to remove solvent, obtain soft polymer phase/polyimide gradient type composite nano-fiber membrane; Or
(1b) organic solution of polyamic acid and soft polymer phase solution is adopted to form front side films by the double needle electrostatic spinning apparatus with metal needle A and metal needle B;
(2b) adopt the organic solution of polyamic acid or the organic solution of polyamic acid and soft polymer phase solution by forming middle internal layer with the double needle electrostatic spinning apparatus of metal needle A and metal needle B in the side of described front side films;
(3b) then form reverse side film in the side relative with described front side films of described middle internal layer, then carry out drying to remove solvent, obtain soft polymer phase/polyimide gradient type composite nano-fiber membrane;
Wherein, described polyamic acid solution carries out spray silk by metal needle A, and described soft polymer phase solution carries out spray silk by metal needle B;
Wherein, described front side films and described reverse side film are formed as one or more composite bed separately, each described composite bed is formed by soft polymer phase nanofiber or polyimide nano-fiber and soft polymer phase nanofiber, described polyimide nano-fiber adopts polyamic acid solution carry out spray silk and formed, and described soft polymer phase nanofiber adopts soft polymer phase solution carry out spray silk and formed;
Wherein, the consumption of described polyamic acid makes in described middle internal layer and each described composite bed, outside from described middle internal layer, in each layer, the content of polyimide nano-fiber successively decreases from inside to outside, the consumption of described soft polymer phase solution makes in described middle internal layer and each described composite bed, outside from described middle internal layer, in each layer, the content of soft polymer phase nanofiber increases progressively from inside to outside.
The present invention is by the double needle electrostatic spinning technique with metallized metal syringe needle A and metal needle B, by controlling the fltting speed of the first boost motor and the second boost motor and then controlling the consumption of organic solution and the consumption of soft polymer phase solution of polyamic acid, prepare soft polymer phase/polyimide gradient type composite nano-fiber membrane, polyimides (PI) is embedded the middle internal layer of film as mechanics skeletal support material, from innermost layer to outermost layer, PI fiber content ratio successively gradient reduces, soft polymer phase fiber content ratio successively gradient increases, the method not only can improve the mechanical property of film, and the functional of barrier film can be given, the i.e. effect of gel electrolyte, reach the integration of barrier film-gel electrolyte.
Other features and advantages of the present invention are described in detail in detailed description of the invention part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for description, is used from explanation the present invention, but is not construed as limiting the invention with detailed description of the invention one below.In the accompanying drawings:
Fig. 1 is the schematic diagram that the double needle electrostatic spinning adopted according to the present invention prepares gradient type composite nano fiber;
Fig. 2 is the design sketch according to the present invention's gradient type composite nano fiber prepared as n=4;
Fig. 3 is the scanning electron microscope (SEM) photograph of amplification of the gradient type composite nano fiber prepared according to the embodiment of the present invention 1;
Fig. 4 is the scanning electron microscope (SEM) photograph of the gradient type composite nano fiber according to the embodiment of the present invention 1 preparation.
Description of reference numerals
The syringe with the first boost motor of 1 splendid attire polyamic acid solution
The syringe with the second boost motor of 2 splendid attire soft polymer phase solution
3 high-pressure electrostatic 4 metal needle A and metal needle B
The dull and stereotyped wire drawing device of 5 composite nano fiber 6 ground connection
Detailed description of the invention
Below the specific embodiment of the present invention is described in detail.Should be understood that, detailed description of the invention described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of soft polymer phase/polyimide gradient type composite nano-fiber membrane, described soft polymer phase/polyimide gradient type composite nano-fiber membrane can comprise front side films, middle internal layer and reverse side film from top to bottom successively, wherein:
Described middle internal layer can be formed by polyimide nano-fiber or polyimide nano-fiber and soft polymer phase nanofiber; And
Described front side films and described reverse side film can comprise one or more composite bed separately, and each described composite bed can be formed by soft polymer phase nanofiber or polyimide nano-fiber and soft polymer phase nanofiber;
Wherein, in middle internal layer and each described composite bed, outside from described middle internal layer, in each layer, the content of polyimide nano-fiber successively decreases from inside to outside, and the content of soft polymer phase nanofiber increases progressively from inside to outside.
According to the present invention, described front side films and described reverse side film can comprise 2-20 composite bed separately.
According to the present invention, in described middle internal layer and each described composite bed, outside from described middle internal layer, in adjacent two layers, the difference of the percentage by weight of the content of polyimide nano-fiber can be 5-50%, and in adjacent two layers, the difference of the percentage by weight of the content of soft polymer phase nanofiber can be 5-50%.
According to the present invention, described soft polymer phase can be selected from polyethylene glycol oxide, polymethyl methacrylate, PLA and polyglycolic acid one or more, be preferably polymethyl methacrylate.
According to the present invention, the diameter of described soft polymer phase nanofiber and described polyimide nano-fiber is 500-600nm, be preferably 545-570nm, the thickness of described soft polymer phase/polyimide gradient type composite nano-fiber membrane can be 15-35 μm, is preferably 18-30 μm.
According to the present invention, the pick up of described soft polymer phase/polyimide gradient type composite nano-fiber membrane can be 430-500%.
Present invention also offers the preparation method of a kind of soft polymer phase/polyimide gradient type composite nano-fiber membrane, wherein, the method can comprise the following steps:
(1a) adopt the organic solution of polyamic acid or the organic solution of polyamic acid and soft polymer phase solution by forming middle internal layer with the double needle electrostatic spinning apparatus of metal needle A and metal needle B;
(2a) organic solution of polyamic acid and soft polymer phase solution is adopted to form front side films by the double needle electrostatic spinning apparatus with metal needle A and metal needle B in the side of described middle internal layer;
(3a) then form reverse side film at the opposite side of described middle internal layer, then carry out drying to remove solvent, obtain soft polymer phase/polyimide gradient type composite nano-fiber membrane; Or
(1b) organic solution of polyamic acid and soft polymer phase solution is adopted to form front side films by the double needle electrostatic spinning apparatus with metal needle A and metal needle B;
(2b) adopt the organic solution of polyamic acid or the organic solution of polyamic acid and soft polymer phase solution by forming middle internal layer with the double needle electrostatic spinning apparatus of metal needle A and metal needle B in the side of described front side films;
(3b) then form reverse side film in the side relative with described front side films of described middle internal layer, then carry out drying to remove solvent, obtain soft polymer phase/polyimide gradient type composite nano-fiber membrane;
Wherein, the organic solution of described polyamic acid carries out spray silk by metal needle A, and described soft polymer phase solution carries out spray silk by metal needle B;
Wherein, described front side films and described reverse side film are formed as one or more composite bed separately, each described composite bed is formed by soft polymer phase nanofiber or polyimide nano-fiber and soft polymer phase nanofiber, described polyimide nano-fiber adopts polyamic acid solution carry out spray silk and formed, and described soft polymer phase nanofiber adopts soft polymer phase solution carry out spray silk and formed;
Wherein, the consumption of described polyamic acid makes in described middle internal layer and each described composite bed, outside from described middle internal layer, in each layer, the content of polyimide nano-fiber successively decreases from inside to outside, the consumption of described soft polymer phase solution makes in described middle internal layer and each described composite bed, outside from described middle internal layer, in each layer, the content of soft polymer phase nanofiber increases progressively from inside to outside.
According to the present invention, described method can also first form middle internal layer, then reverse side film is formed in the side of middle internal layer, front side films is formed again in the side relative with described front side films of middle internal layer, or, described method can also first form reverse side film, then middle internal layer is formed in the side of reverse side film, front side films is formed again at the opposite side (not forming that side of reverse side film) of middle internal layer, in a word, in the present invention, the sequencing forming front side films, middle internal layer or reverse side film is not particularly limited.
According to the present invention, described front side films and described reverse side film can be formed as 2-20 composite bed separately.
According to the present invention, the consumption of described polyamic acid solution can be controlled with the fltting speed of the first boost motor, and the consumption of described soft polymer phase organic solution can be controlled with the fltting speed of the second boost motor, in the present invention, make in described middle internal layer and each described composite bed according to the consumption of described polyamic acid solution, outside from described middle internal layer, in each layer, the content of polyimide nano-fiber successively decreases from inside to outside, the consumption of described soft polymer phase solution makes in described middle internal layer and each described composite bed, outside from described middle internal layer, in each layer, the content of soft polymer phase nanofiber increases progressively from inside to outside, the fltting speed of the first boost motor is 0.2-1.6ml/h, be preferably 0.2-0.6ml/h, the fltting speed of the second boost motor is 0.2-1.6ml/h, be preferably 0.4-1ml/h, the ratio of the fltting speed of the first boost motor and the fltting speed of the second boost motor is not particularly limited, preferably, the fltting speed V of described first boost motor
awith the fltting speed V of the second boost motor
bratio meet the relational expression shown in table 1.
According to the present invention, the present invention is by the fltting speed V to control first boost motor of its interim gradient
awith the fltting speed V of the second boost motor
bratio, thus obtain a kind of from fiber nexine to the tunica fibrosa of outer distribution gradient, speed V
awith V
bcontrol as shown in table 1, n is adjustable, and n is larger, and the exponent number of gradient is larger; In the present invention, the time between twice speed is regulated to be not particularly limited, and the time of carrying out electrostatic spinning when the velocity ratio of each setting is also not particularly limited, preferably, the time of carrying out spinning under the speed of each setting can be 20 minutes-1 hour.
According to the present invention, the consumption of described polyamic acid solution can be controlled with the fltting speed of the first boost motor, and the consumption of described soft polymer phase organic solution can be controlled with the fltting speed of the second boost motor, in the present invention, the consumption of described polyamic acid solution makes in described middle internal layer and each described composite bed, outside from described middle internal layer, in adjacent two layers, the difference of the percentage by weight of the content of polyimide nano-fiber can be 5-50%, the consumption of described soft polymer phase solution makes in described middle internal layer and each described composite bed, outside from described middle internal layer, in adjacent two layers, the difference of the percentage by weight of the content of soft polymer phase nanofiber can be 5-50%.
Table 1
Wherein, n is the number of plies of composite bed.
Fig. 2 is the design sketch according to the present invention's gradient type composite nano fiber prepared as n=4; As can be known from Fig. 2: work as PI:PMMA=100:0, upward direction, ground floor is from the inside to the outside to the 4th layer, in the ratio of the content of PI:PMMA, PI reduces gradually, and PMMA increases gradually, in like manner, in downward direction, ground floor is from the inside to the outside to the 4th layer, and in the ratio of the content of PI:PMMA, PI reduces gradually, PMMA increases gradually, and namely described middle internal layer is pure polyimide layer and it is only formed by polyimide nano-fiber; And described front side films and described reverse side film all with internal layer in the middle of described pure polyimides for boundary from the inside to the outside, also include ground floor, the second layer, third layer successively until the 4th layer, every one deck is formed by containing polyimide nano-fiber and/or soft polymer phase nanofiber, and with the gross weight of described front side films or described reverse side film for benchmark, the content of described polyimides is from ground floor until the 4th layer is successively decreased successively, and the content of described soft polymer phase is from ground floor until the 4th layer increases progressively successively.
According to the present invention, described soft polymer phase can be selected from polyethylene glycol oxide, polymethyl methacrylate, PLA and polyglycolic acid one or more, be preferably polymethyl methacrylate.
According to the present invention, described polyamic acid solution is prepared from for being dissolved in organic solvent by polyamic acid, and described organic solvent can be N, N-dimethylacetylamide, N, one or more in dinethylformamide, acetonitrile and methyl pyrrolidone, are preferably DMA.
According to the present invention, described soft polymer phase solution is prepared from for being dissolved in organic solvent by soft polymer phase, described organic solvent can be N, N-dimethylacetylamide, N, one or more in dinethylformamide, 1-METHYLPYRROLIDONE, oxolane and dimethyl sulfoxide (DMSO), be preferably DMA.
According to the present invention, in step (3a) and (3b), the condition of described oven dry comprises separately respectively: the temperature of oven dry can be 40-60 DEG C, and the time of oven dry can be 23-25 hour.
According to the present invention, the method also comprises carries out mechanical stitch process by the soft polymer phase of preparation/polyimide gradient type composite nano-fiber membrane.
According to the present invention, the condition of described mechanical stitch process comprises: pressure can be 5-10MPa, and the time can be 3-5 minute, and preferably, the time can be 3 minutes.
According to the present invention, first-selected, on described cylinder wire drawing device or on dull and stereotyped wire drawing device, prepare gradient type composite nano fiber by double needle (metal needle A and metal needle B) electrostatic spinning apparatus.The device for double needle electrostatic spinning in the present invention generally comprises high voltage source, on cylinder wire drawing device or dull and stereotyped wire drawing device, for splendid attire polyamic acid solution and with the syringe of the first boost motor and for splendid attire soft polymer phase solution (such as polymethyl methacrylate solution) and with the syringe of the second boost motor, wherein, for splendid attire polyamic acid organic solution and with one end of the syringe of the first boost motor with the metal needle A of 0.1-0.5mm, be preferably the metal needle A of 0.2-0.4mm, the other end can be the first boost motor, in like manner, for splendid attire soft polymer phase solution (such as polymethyl methacrylate solution) and with one end of the syringe of the second boost motor with the metal needle B of 0.2-1.6ml/h, be preferably the metal needle B of 0.4-1ml/h, the other end can be the second boost motor, the positive pole of described high-pressure electrostatic is electrically connected with metal needle A and metal needle B, the negative pole of described high-pressure electrostatic with on cylinder wire drawing device or dull and stereotyped wire drawing device be electrically connected.
According to the present invention, described dull and stereotyped wire drawing device is not particularly limited, as long as the conductive materials being easy to be formed film that can conduct electricity.
Fig. 1 shows the schematic diagram that the double needle electrostatic spinning apparatus adopted according to the present invention prepares gradient type composite nano fiber; As shown in Figure 1:
This double needle electrospinning process comprises and is placed in the syringe of the first boost motor and the syringe with the second boost motor by polyamic acid solution and soft phase high score solution (such as polymethyl methacrylate solution) respectively, again the positive pole of high-pressure electrostatic is electrically connected with metal needle A and metal needle B respectively, negative pole with on cylinder wire drawing device or dull and stereotyped wire drawing device be electrically connected, open high-pressure electrostatic and start double needle electrostatic spinning apparatus, regulate the speed of the first boost motor and the second boost motor, like this, high voltage electric field is formed between metal needle A in the syringe with the first boost motor and the syringe with the second boost motor and metal needle B and cylinder wire drawing device or dull and stereotyped wire drawing device, the organic solution of the polyamic acid in the syringe with the first boost motor and the syringe with the second boost motor and soft polymer phase solution are ejected by metal needle A and metal needle B and form unordered and/or orderly gradient type composite nano fiber, under the traction of electric field force, to be suspended in cylinder wire drawing device or dull and stereotyped wire drawing device and in this cylinder wire drawing device or dull and stereotyped wire drawing device, to form the gradient type composite nano-fiber membrane be made up of gradient type composite nano fiber, wherein, the condition of described double needle electrostatic spinning can comprise: the voltage of high voltage source is 5-20kV, the fltting speed of the first boost motor is 0.2-1.6ml/h, be preferably 0.2-0.6ml/h, the fltting speed of the second boost motor is 0.2-1.6ml/h, be preferably 0.4-1ml/h, the internal diameter of metal needle A is 0.1-0.5mm, be preferably 0.2-0.4mm, the internal diameter of metal needle B is 0.1-1.5mm, be preferably 0.1-0.4mm, distance between described dull and stereotyped wire drawing device and metal needle A and metal needle B is 10-20cm,
And then the soft polymer phase prepared through double needle electrostatic spinning technique/polyimide gradient type composite nano-fiber membrane oven dry is made removal of solvents, adopt chemical imines method, polyamic acid (PAA) is converted into polyimides (PI), obtains soft polymer phase/polyimide gradient type composite nano-fiber membrane; Wherein, the instrument of described oven dry adopts vacuum drying oven well-known to those skilled in the art, and the condition of described oven dry is not particularly limited, and preferably, the condition of described oven dry comprises: the temperature of oven dry can be 40-60 DEG C, and the time of oven dry can be 23-25 hour; More preferably, the temperature of oven dry can be 50 DEG C, and the time of oven dry can be 24 hours;
Preferably, more prepared soft polymer phase/polyimide gradient type composite nano-fiber membrane is carried out mechanical stitch process, wherein, the condition of described mechanical stitch process comprises: pressure can be 5-10MPa, and the time can be 3-5 minute.
According to the present invention, environment temperature and the humidity of carrying out electrostatic spinning are not particularly limited, the temperature and humidity that can be well known to those skilled in the art, and preferably, the environment temperature of carrying out electrostatic spinning is 20-80 DEG C, and humidity is 1-80%.
According to a kind of detailed description of the invention of the present invention, this preparation method can specifically comprise the following steps:
(1) polyamic acid solution is configured: be that the polyamic acid (PAA) of 10-30 % by weight is dissolved in preferred N by concentration, in N-dimethylacetylamide (DMAc), preferably, a certain amount of imidization catalyst and dehydrating agent can be added, load in the syringe with the first boost motor, stand-by;
(2) soft polymer phase solution (preferred polymethyl methacrylate solution) is configured: be that the soft polymer phase solution (preferred polymethyl methacrylate solution) of 5-20 % by weight is dissolved in preferred N by concentration, in N-dimethylacetylamide (DMAc), load in the syringe with the second boost motor, stand-by;
(3) select, metal needle A and metal needle B is installed, electrospinning parameters is set: the voltage of high voltage source is 5-20kV, the fltting speed of the first boost motor is 0.2-1.6ml/h, be preferably 0.2-0.6ml/h, the fltting speed of the second boost motor is 0.2-1.6ml/h, be preferably 0.4-1ml/h, the internal diameter of metal needle A is 0.1-0.5mm, be preferably 0.2-0.4mm, the internal diameter of metal needle B is 0.1-1.5mm, be preferably 0.1-0.4mm, described cylinder wire drawing device or the distance between dull and stereotyped wire drawing device and metal needle A and metal needle B are 5-20cm,
(4) velocity ratio of the first boost motor and the second boost motor is regulated according to table 1;
(5) metal needle A and metal needle B is connected with the positive pole of high voltage source, cylinder wire drawing device or dull and stereotyped wire drawing device are connected with the negative pole of high voltage source;
(6) middle internal layer is formed by polyamic acid solution or by polyamic acid solution and soft polymer phase solution respectively by double needle electrostatic spinning;
(7) soft polymer phase (preferred the polymethyl methacrylate solution)/polyamic acid gradient type composite nano-fiber membrane formed by unordered and/or orderly gradient type composite nano fiber of preparation is collected in the side of described middle internal layer, preparation front side films;
(8) collect soft polymer phase (preferred the polymethyl methacrylate solution)/polyamic acid gradient type composite nano-fiber membrane formed by unordered and/or orderly gradient type composite nano fiber prepared in the side relative with described front side films of described middle internal layer, prepare reverse side film;
(9) be dry process 23-25 hour in the baking oven of 40-60 DEG C in temperature by this soft polymer phase (preferred polymethyl methacrylate solution)/polyamic acid gradient type composite nano-fiber membrane, make polyamic acid wherein be converted into polyimides by chemical imines method;
(10) this polyimides/polymethyl methacrylate gradient type composite nano-fiber membrane is processed 3-5 minute under pressure is 5-10MPa.
Present invention also offers a kind of soft polymer phase/polyimide gradient type composite nano-fiber membrane prepared by preparation method of the present invention.
Below will describe the present invention by executing example.
In the following Examples and Comparative Examples, polyimides is that the present inventor is made by oneself by the method for chemical imines PAA.
In the following Examples and Comparative Examples, polyamic acid is purchased from Hangzhou Su Mengte Co., Ltd, and number-average molecular weight is 100,000; Polyethylene glycol oxide, polymethyl methacrylate, PLA and polyglycolic acid are all purchased from acros organics, lark prestige, and number-average molecular weight is between 50,000-60 ten thousand.
In the following Examples and Comparative Examples, high-pressure electrostatic is purchased from Shenzhen concerted effort micro-nano Co., Ltd, and model is NEU011; ESEM is purchased from Japanese JEOL, and model is JSM-7600FE.
In the following Examples and Comparative Examples, the pick up of this soft polymer phase/polyimide gradient type composite nano-fiber membrane is tested: (lithium salts is LiPF6 to be immersed in electrolyte after weighing up the quality of this soft polymer phase/polyimide gradient type composite nano-fiber membrane, concentration is 1mol/L, solvent is EC, EMC, DEC, mass concentration ratio is 2:3:1) middle 24h, then taking-up filter paper blots the liquid on this soft polymer phase/polyimide gradient type composite nano-fiber membrane surface, obtain corresponding gel polymer electrolyte, weigh the quality of the gel polymer electrolyte of now this correspondence, operation is all carried out in the glove box being full of argon gas.According to formulae discovery:
Pick up %=(Wi-W)/W × 100%;
Wherein, W is the quality of dry film; Wi is the quality after dry film has soaked 24h in the electrolytic solution.
In the following Examples and Comparative Examples, the electrical conductivity of this soft polymer phase/polyimide gradient type composite nano-fiber membrane is tested: this soft polymer phase/polyimide gradient type composite nano-fiber membrane is placed between two stainless steel substrates, (lithium salts is LiPF6 to the electrolyte of absorption q.s, concentration is 1M/L, solvent is EC, EMC, DEC, mass concentration ratio is 2:3:1), obtain corresponding gel polymer electrolyte, after being sealed in 2016 type button cells, carry out AC impedance experiment, intersection point that is linear and real axis is the bulk resistance of gel polymer electrolyte, the ionic conductivity obtaining gel polymer electrolyte thus can according to formulae discovery:
Conductivityσ=L/ (AR),
Wherein, L represents the thickness of gel polymer electrolyte, and A is the contact area of corrosion resistant plate and film, and R is the bulk resistance of polymer dielectric.
In the following Examples and Comparative Examples, Mechanics Performance Testing to this soft polymer phase/polyimide gradient type composite nano-fiber membrane: adopt conventional pull test instrument purchased from Shenzhen Jun Rui Instrument Ltd., sample is dumbbell shaped, it is of a size of 4mm × 10mm, and the strain rate of instrument is 20mm/min.
Embodiment 1
(1) by dissolved for PAA in purity to be 98% concentration be 15% N, N-dimethylacetylamide, soft polymer phase PMMA being dissolved in purity 98% concentration is the N of 15%, N-dimethylacetylamide, is respectively charged in electrostatic spinning apparatus with in the syringe of the first boost motor and the syringe with the second boost motor;
(2) electrospinning conditions (except fltting speed) arranges as follows: with the syringe of the first boost motor be 0.4mm with the internal diameter of the syringe of the second boost motor, receiving range is 15cm, the environment temperature of carrying out electrostatic spinning is 40 DEG C, and humidity is 30%;
(3) be used alone PAA solution-polymerized SBR 1 hour, form the middle internal layer formed by polyamic acid solution;
(4) spinning of double needle electrostatic spinning apparatus is passed through, spinning totally 9 hours, the fltting speed V of the first boost motor in the side of the middle internal layer formed and opposite side respectively
awith the fltting speed V of the second boost motor
b(n=4) as shown in table 2 below, the consumption of described polyamic acid solution is controlled with the fltting speed of the first boost motor, and the consumption of described soft polymer phase organic solution is controlled with the fltting speed of the second boost motor, in the present embodiment, the consumption of described polyamic acid solution makes in described middle internal layer and each described composite bed, outside from described middle internal layer, in adjacent two layers, the difference of the percentage by weight of the content of polyimide nano-fiber can be 25%, the consumption of described soft polymer phase solution makes in described middle internal layer and each described composite bed, outside from described middle internal layer, in adjacent two layers, the difference of the percentage by weight of the content of soft polymer phase nanofiber can be 25%, the each spinning 3.2ml of solution of PAA and PMMA, after spinning terminates, take off film, adopt chemical imines method, by the method adding catalyst and dehydrating agent, the soft phase film of PI-is become to its imidization, temperature is dry 24 hours at 50 DEG C in an oven,
And adopt the pressure of 10MPa to the film roll extrusion 3 minutes of above-mentioned formation (5).
Result obtains the PMMA/ polyimide gradient type composite nano-fiber membrane that thickness is 18 μm.As the scanning electron microscope (SEM) photograph of gradient type composite nano fiber prepared as can be seen from Fig. 3 and Fig. 4 embodiment 1, PMMA nanofiber prepared by the present invention and the diameter of polyimide nano-fiber are about 500nm.
The horizontal and vertical TENSILE STRENGTH being recorded this PMMA/ polyimide gradient type composite nano-fiber membrane by universal testing machine is respectively 40MPa and 35MPa, and puncture strength is 0.342kgf.
In glove box atmosphere, soaked in the electrolytic solution by this PMMA/ polyimide gradient type composite nano-fiber membrane, abundant imbibition, the pick up recording this film is 510%, after placing 24h, can keep the pick up of 460%, after placing 48h, can keep the pick up of 430%.
By electrochemical workstation, the ionic conductivity recording this PMMA/ polyimide gradient type composite nano-fiber membrane is 1.05 × 10
-3s/cm.
Table 2
Embodiment 2
(1) by dissolved for PAA in purity to be 98% concentration be 15% N, N-dimethylacetylamide, soft polymer phase PEO to be dissolved in purity be 98% concentration be 15% N, N-dimethylacetylamide, is respectively charged in electrostatic spinning apparatus with in the syringe of the first boost motor and the syringe with the second boost motor;
(2) electrospinning conditions (except fltting speed) arranges as follows: with the syringe of the first boost motor be 0.4mm with the internal diameter of the syringe of the second boost motor, receiving range is 15cm, the environment temperature of carrying out electrostatic spinning is 40 DEG C, and humidity is 30%.
(3) be used alone PAA solution-polymerized SBR 40 minutes, form the middle internal layer formed by polyamic acid solution;
(4) pass through the spinning of double needle electrostatic spinning apparatus in the side of the middle internal layer formed and opposite side respectively, spinning is 7h20min, the fltting speed V of the first boost motor altogether
awith the fltting speed V of the second boost motor
b(n=5) as shown in table 3 below, the consumption of described polyamic acid solution is controlled with the fltting speed of the first boost motor, and the consumption of described soft polymer phase organic solution is controlled with the fltting speed of the second boost motor, in the present embodiment, the consumption of described polyamic acid solution makes in described middle internal layer and each described composite bed, outside from described middle internal layer, in adjacent two layers, the difference of the percentage by weight of the content of polyimide nano-fiber can be 20%, the consumption of described soft polymer phase solution makes in described middle internal layer and each described composite bed, outside from described middle internal layer, in adjacent two layers, the difference of the percentage by weight of the content of soft polymer phase nanofiber can be 20%, the each spinning 3.33ml of solution of PAA and PEO, after spinning terminates, take off film, chemical imines method is adopted to become the soft phase film of PI-by the method adding catalyst and dehydrating agent to its imidization, temperature is dry 24 hours at 50 DEG C in an oven,
And adopt the pressure of 10MPa to the film roll extrusion 3 minutes of above-mentioned formation (5).
Result obtains the PEO/ polyimide gradient type composite nano-fiber membrane that thickness is 21 μm.
By scanning electron microscope (SEM) photograph, we can find out that the diameter of this PEO nanofiber and polyimide nano-fiber is all about 490nm.
The horizontal and vertical TENSILE STRENGTH being recorded this PEO/ polyimide gradient type composite nano-fiber membrane by universal testing machine is respectively 48MPa and 47MPa, and puncture strength is 0.422kgf.
In glove box atmosphere, soaked in the electrolytic solution by this PEO/ polyimide gradient type composite nano-fiber membrane, abundant imbibition, the pick up recording this film is 550%, after placing 24h, can keep the pick up of 480%, after placing 48h, can keep the pick up of 440%.
By electrochemical workstation, the ionic conductivity recording this PEO/ polyimide gradient type composite nano-fiber membrane is 1.34 × 10
-3s/cm.
Table 3
Embodiment 3
(1) be the N of 15% by dissolved for the PAA concentration being 98% in purity, N-dimethylacetylamide, soft polymer phase PLA is dissolved in purity be 98% concentration be the N of 15%, N-dimethylacetylamide, is respectively charged in electrostatic spinning apparatus with in the syringe of the first boost motor and the syringe with the second boost motor;
(2) electrospinning conditions (except fltting speed) arranges as follows: with the syringe of the first boost motor be 0.4mm with the internal diameter of the syringe of the second boost motor, receiving range is 15cm, the environment temperature of carrying out electrostatic spinning is 40 DEG C, and humidity is 30%;
(3) be used alone PAA solution-polymerized SBR 30 minutes, form the middle internal layer formed by the organic solution of polyamic acid;
(4) pass through the spinning of double needle electrostatic spinning apparatus in the side of the middle internal layer formed and opposite side respectively, spinning is 6.3h, the fltting speed V of the first boost motor altogether
awith the fltting speed V of the second boost motor
b(n=6) as shown in table 4 below, controls the consumption of described polyamic acid solution with the fltting speed of the first boost motor, and controls the consumption of described soft polymer phase organic solution with the fltting speed of the second boost motor;
In the present embodiment, the consumption of described polyamic acid solution makes in described middle internal layer and each described composite bed, outside from described middle internal layer, in adjacent two layers, the difference of the percentage by weight of the content of polyimide nano-fiber can be 16.7%, the consumption of described soft polymer phase solution makes in described middle internal layer and each described composite bed, outside from described middle internal layer, in adjacent two layers, the difference of the percentage by weight of the content of soft polymer phase nanofiber can be 16.7%;
The each spinning 3.6ml of solution of PAA and PLA.After spinning terminates, take off film, adopt chemical imines method, become the soft phase film of PI-by the method adding catalyst and dehydrating agent to its imidization, temperature is dry 24 hours at 50 DEG C in an oven;
And adopt the pressure of 10MPa to the film roll extrusion 3 minutes of above-mentioned formation (5).
Result obtains the PLA/ polyimide gradient type composite nano-fiber membrane that thickness is 22 μm.
By scanning electron microscope (SEM) photograph, we can find out that the diameter of this PLA nanofiber and polyimide nano-fiber is all about 545nm.
By universal testing machine, the horizontal and vertical TENSILE STRENGTH recording this PLA/ polyimide gradient type composite nano-fiber membrane is respectively 55MPa and 51MPa, and puncture strength is 0.445kgf.
In glove box atmosphere, soaked in the electrolytic solution by this PLA/ polyimide gradient type composite nano-fiber membrane, abundant imbibition, the pick up recording film is 600%, after placing 24h, can keep the pick up of 500%, after placing 48h, can keep the pick up of 470%.
By electrochemical workstation, the ionic conductivity recording this PLA/ polyimide gradient type composite nano-fiber membrane is 1.51 × 10
-3s/cm.
Table 4
Embodiment 4
(1) by dissolved for PAA in purity to be 98% concentration be 15% N, N-dimethylacetylamide, soft polymer phase PGA being dissolved in purity 98% concentration is the N of 15%, N-dimethylacetylamide, is respectively charged in electrostatic spinning apparatus with in the syringe of the first boost motor and the syringe with the second boost motor;
(2) electrospinning conditions (except fltting speed) arranges as follows: with the syringe of the first boost motor be 0.4mm with the internal diameter of the syringe of the second boost motor, receiving range is 15cm, the environment temperature of carrying out electrostatic spinning is 40 DEG C, and humidity is 30%;
(3) be used alone PAA solution-polymerized SBR 1 hour, form the middle internal layer formed by the organic solution of polyamic acid;
(4) pass through the spinning of double needle electrostatic spinning apparatus in the side of the middle internal layer formed and opposite side respectively, spinning needs 15 hours consuming time altogether, the fltting speed V of the first boost motor
awith the fltting speed V of the second boost motor
b(n=7) as shown in table 5 below, the consumption of described polyamic acid solution is controlled with the fltting speed of the first boost motor, and the consumption of described soft polymer phase organic solution is controlled with the fltting speed of the second boost motor, in the present embodiment, the consumption of described polyamic acid solution makes in described middle internal layer and each described composite bed, outside from described middle internal layer, in adjacent two layers, the difference of the percentage by weight of the content of polyimide nano-fiber can be 14.3%, the consumption of described soft polymer phase solution makes in described middle internal layer and each described composite bed, outside from described middle internal layer, in adjacent two layers, the difference of the percentage by weight of the content of soft polymer phase nanofiber can be 14.3%, the each spinning 4.9ml of solution of PAA and PGA.After spinning terminates, take off film, adopt chemical imines method, become the soft phase film of PI-by the method adding catalyst and dehydrating agent to its imidization, temperature is dry 24 hours at 50 DEG C in an oven;
And adopt the pressure of 10MPa to the film roll extrusion 3 minutes of above-mentioned formation (5).
Result obtains the PGA/ polyimide gradient type composite nano-fiber membrane that thickness is 30 μm.
By scanning electron microscope (SEM) photograph, we can find out that the diameter of this PGA nanofiber and polyimide nano-fiber is all about 570nm.
By universal testing machine, the horizontal and vertical TENSILE STRENGTH recording this PGA/ polyimide gradient type composite nano-fiber membrane is respectively 57MPa and 52MPa, and puncture strength is 0.564kgf.
In glove box atmosphere, soaked in the electrolytic solution by this PGA/ polyimide gradient type composite nano-fiber membrane, abundant imbibition, the pick up recording this film is 620%, after placing 24h, can keep the pick up of 540%, after placing 48h, can keep the pick up of 500%.
By electrochemical workstation, the ionic conductivity recording this PGA/ polyimide gradient type composite nano-fiber membrane is 1.85 × 10
-3s/cm.
Table 5
Comparative example 1
According to prepare the method for soft polymer phase/polyimide gradient type composite nano-fiber membrane identical with embodiment 1, institute's difference is, the fltting speed V of the first boost motor
awith the fltting speed V of the second boost motor
b(n=7) as shown in table 6 below.
Result obtains the PMMA/ polyimides phase blending type composite nano-fiber membrane that thickness is 20 μm.
By scanning electron microscope (SEM) photograph, we can find out that the diameter of this PMMA nanofiber and polyimides phase blending type composite nano fiber is all about 535nm.
By universal testing machine, the horizontal and vertical TENSILE STRENGTH recording this PMMA/ polyimides phase blending type composite nano-fiber membrane is respectively 27MPa and 24MPa, and puncture strength is 0.187kgf.
In glove box atmosphere, soaked in the electrolytic solution by this PMMA/ polyimides phase blending type composite nano-fiber membrane, abundant imbibition, the pick up recording film is 430%, after placing 24h, can keep the pick up of 350%, after placing 48h, can keep the pick up of 290%.
By electrochemical workstation, the ionic conductivity recording this PMMA/ polyimides phase blending type composite nano-fiber membrane is 6.25 × 10
-4s/cm.
Table 6
| Time period | V A | V B |
| 0-5h | 0.7ml/h | 0.7ml/h |
Comparative example 2
According to prepare the method for soft polymer phase/polyimide gradient type composite nano-fiber membrane identical with embodiment 1, institute's difference is, does not have to form the middle internal layer formed by PAA solution, the fltting speed V of the first boost motor
awith the fltting speed V of the second boost motor
b(n=7) as shown in table 7 below.
Result obtains the PMMA/ polyimides phase blending type composite nano-fiber membrane that thickness is 22 μm.
By scanning electron microscope (SEM) photograph, we can find out that the diameter of this PMMA nanofiber and polyimides phase blending type composite nano fiber is all about 555nm.
By universal testing machine, the horizontal and vertical TENSILE STRENGTH recording this PMMA/ polyimides phase blending type composite nano-fiber membrane is respectively 26MPa and 30MPa, and puncture strength is 0.198kgf.
In glove box atmosphere, soaked in the electrolytic solution by this PMMA/ polyimides phase blending type composite nano-fiber membrane, abundant imbibition, the pick up recording film is 450%, after placing 24h, can keep the pick up of 312%, after placing 48h, can keep the pick up of 270%.
By electrochemical workstation, the ionic conductivity recording this PMMA/ polyimides phase blending type composite nano-fiber membrane is 4.35 × 10
-4s/cm.
Table 7
| Time period | V A | V B |
| 0-6h | 0.6ml/h | 0.6ml/h |
By the data of above embodiment 1-4 and comparative example 1-2, we can find out, adopt gradient type film prepared by method of the present invention, by forming the middle internal layer formed by the organic solution of polyamic acid, and pass through the velocity ratio of control first boost motor and the second boost motor, effectively can improve the mechanical strength of this gradient type film, imbibition water retainability and room-temperature conductivity; And the gradient type film adopting method of the present invention to prepare is expected to alternative barrier film, play barrier film and the effect of two kinds, electrolyte, this lifting for GPE battery performance and dimensional energy density provide strong technical support.In addition, the method is easy and simple to handle, and the mode disjunction of microcomputer can be adopted to control the flow velocity of two kinds of polymer, unattended operation.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characteristic described in above-mentioned detailed description of the invention, in reconcilable situation, can be combined by any suitable mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible combination.
In addition, also can be combined between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (17)
1. soft polymer phase/polyimide gradient type composite nano-fiber membrane, described soft polymer phase/polyimide gradient type composite nano-fiber membrane comprises front side films, middle internal layer and reverse side film from top to bottom successively, wherein:
Described middle internal layer is formed by polyimide nano-fiber or polyimide nano-fiber and soft polymer phase nanofiber; And
Described front side films and described reverse side film comprise one or more composite bed separately, and each described composite bed is formed by soft polymer phase nanofiber or polyimide nano-fiber and soft polymer phase nanofiber;
Wherein, in described middle internal layer and each described composite bed, outside from described middle internal layer, in each layer, the content of polyimide nano-fiber successively decreases from inside to outside, and the content of soft polymer phase nanofiber increases progressively from inside to outside.
2. soft polymer phase according to claim 1/polyimide gradient type composite nano-fiber membrane, wherein, described front side films and described reverse side film comprise 2-20 composite bed separately.
3. soft polymer phase according to claim 1/polyimide gradient type composite nano-fiber membrane, wherein, in described middle internal layer and each described composite bed, outside from described middle internal layer, in adjacent two layers, the difference of the percentage by weight of the content of polyimide nano-fiber is 5-50%, and in adjacent two layers, the difference of the percentage by weight of the content of soft polymer phase nanofiber is 5-50%.
4. according to the soft polymer phase in claim 1-3 described in any one/polyimide gradient type composite nano-fiber membrane, wherein, soft polymer phase be selected from polyethylene glycol oxide, polymethyl methacrylate, PLA and polyglycolic acid one or more, be preferably polymethyl methacrylate.
5. according to the soft polymer phase in claim 1-4 described in any one/polyimide gradient type composite nano-fiber membrane, wherein, the diameter of described soft polymer phase nanofiber and described polyimide nano-fiber is 500-600nm, be preferably 545-570nm, the thickness of described soft polymer phase/polyimide gradient type composite nano-fiber membrane is 15-35 μm, is preferably 18-30 μm.
6. according to the soft polymer phase in claim 1-5 described in any one/polyimide gradient type composite nano-fiber membrane, wherein, the pick up of described soft polymer phase/polyimide gradient type composite nano-fiber membrane is 430-500%.
7. a preparation method for soft polymer phase/polyimide gradient type composite nano-fiber membrane, it is characterized in that, the method comprises the following steps:
(1a) adopt the organic solution of polyamic acid or the organic solution of polyamic acid and soft polymer phase solution by forming middle internal layer with the double needle electrostatic spinning apparatus of metal needle A and metal needle B;
(2a) organic solution of polyamic acid and soft polymer phase solution is adopted to form front side films by the double needle electrostatic spinning apparatus with metal needle A and metal needle B in the side of described middle internal layer;
(3a) then form reverse side film at the opposite side of described middle internal layer, then carry out drying to remove solvent, obtain soft polymer phase/polyimide gradient type composite nano-fiber membrane; Or
(1b) organic solution of polyamic acid and soft polymer phase solution is adopted to form front side films by the double needle electrostatic spinning apparatus with metal needle A and metal needle B;
(2b) adopt the organic solution of polyamic acid or the organic solution of polyamic acid and soft polymer phase solution by forming middle internal layer with the double needle electrostatic spinning apparatus of metal needle A and metal needle B in the side of described front side films;
(3b) then form reverse side film in the side relative with described front side films of described middle internal layer, then carry out drying to remove solvent, obtain soft polymer phase/polyimide gradient type composite nano-fiber membrane;
Wherein, the organic solution of described polyamic acid carries out spray silk by metal needle A, and described soft polymer phase solution carries out spray silk by metal needle B;
Wherein, described front side films and described reverse side film are formed as one or more composite bed separately, each described composite bed is formed by soft polymer phase nanofiber or polyimide nano-fiber and soft polymer phase nanofiber, described polyimide nano-fiber adopts polyamic acid solution carry out spray silk and formed, and described soft polymer phase nanofiber adopts soft polymer phase solution carry out spray silk and formed;
Wherein, the consumption of described polyamic acid makes in described middle internal layer and each described composite bed, outside from described middle internal layer, in each layer, the content of polyimide nano-fiber successively decreases from inside to outside, the consumption of described soft polymer phase solution makes in described middle internal layer and each described composite bed, outside from described middle internal layer, in each layer, the content of soft polymer phase nanofiber increases progressively from inside to outside.
8. preparation method according to claim 7, wherein, described front side films and described reverse side film are formed as 2-20 composite bed separately.
9. preparation method according to claim 7, wherein, the consumption of described polyamic acid makes in described middle internal layer and each described composite bed, outside from described middle internal layer, in adjacent two layers, the difference of the percentage by weight of the content of polyimide nano-fiber is 5-50%, the consumption of described soft polymer phase solution makes in described middle internal layer and each described composite bed, outside from described middle internal layer, in adjacent two layers, the difference of the percentage by weight of the content of soft polymer phase nanofiber is 5-50%.
10. the preparation method according to claim 7 or 9, wherein, described soft polymer phase be selected from polyethylene glycol oxide, polymethyl methacrylate, PLA and polyglycolic acid one or more, be preferably polymethyl methacrylate.
11. preparation methods according to claim 7 or 9, wherein, the organic solution of described polyamic acid is prepared from for being dissolved in organic solvent by polyamic acid, described organic solvent is N, N-dimethylacetylamide, N, one or more in dinethylformamide, acetonitrile and methyl pyrrolidone, are preferably DMA.
12. preparation methods according to any one of claims of claim 7-10, wherein, described soft polymer phase solution is prepared from for being dissolved in organic solvent by soft polymer phase, described organic solvent is N, N-dimethylacetylamide, N, one or more in dinethylformamide, 1-METHYLPYRROLIDONE, oxolane and dimethyl sulfoxide (DMSO), are preferably DMA.
13. preparation methods according to claim 7, wherein, described double needle electrostatic spinning apparatus comprises high voltage source, with the syringe of the first boost motor and metal needle A, with the syringe of the second boost motor and metal needle B, metal needle A, metal needle B and cylinder wire drawing device or dull and stereotyped wire drawing device, wherein, the condition of described double needle electrostatic spinning comprises: the voltage of high voltage source is 5-20kV, the fltting speed of the first boost motor is 0.2ml/h-1.6ml/h, be preferably 0.2ml/h-0.6ml/h, the fltting speed of the second boost motor is 0.2ml/h-1.6ml/h, be preferably 0.4ml/h-1ml/h, the internal diameter of metal needle A is 0.1-0.5mm, be preferably 0.2-0.4mm, the internal diameter of metal needle B is 0.1-1.5mm, be preferably 0.1-0.4mm, described cylinder wire drawing device or the distance between dull and stereotyped wire drawing device and metal needle A and metal needle B are 10-20cm.
14. methods according to claim 7, wherein, in step (3a) and (3b), the condition of described oven dry comprises separately respectively: the temperature of oven dry is 40-60 DEG C, and the time of oven dry is 23-25 hour.
15. preparation methods according to claim 7, wherein, the method also comprises carries out mechanical stitch process by the soft polymer phase of preparation/polyimide gradient type composite nano-fiber membrane.
16. methods according to claim 15, wherein, the condition of described mechanical stitch process comprises: pressure is 5-10MPa, and the time is 3-5 minute.
17. soft polymer phases prepared by the method in claim 7-16 described in any one/polyimide gradient type composite nano-fiber membrane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310726446.8A CN104746239B (en) | 2013-12-25 | 2013-12-25 | A kind of soft polymer phase/polyimide gradient type composite nano-fiber membrane and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310726446.8A CN104746239B (en) | 2013-12-25 | 2013-12-25 | A kind of soft polymer phase/polyimide gradient type composite nano-fiber membrane and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104746239A true CN104746239A (en) | 2015-07-01 |
| CN104746239B CN104746239B (en) | 2017-03-15 |
Family
ID=53586459
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310726446.8A Active CN104746239B (en) | 2013-12-25 | 2013-12-25 | A kind of soft polymer phase/polyimide gradient type composite nano-fiber membrane and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104746239B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107059251A (en) * | 2017-06-09 | 2017-08-18 | 东华大学 | The preparation method of one-way wet-guide nanofiber multilayer complex films with wetting gradient |
| CN110791727A (en) * | 2019-11-29 | 2020-02-14 | 无锡创彩光学材料有限公司 | Wear-resistant coating for polyimide film stretcher and preparation method thereof |
| CN111575916A (en) * | 2020-05-13 | 2020-08-25 | 贵州大学 | Preparation method of electrostatic spinning fiber membrane with continuous gradient |
| CN112481831A (en) * | 2020-12-11 | 2021-03-12 | 江苏三丰特种材料科技有限公司 | Preparation method of multi-stage structure one-way moisture-conducting waterproof breathable film |
| CN114316637A (en) * | 2021-12-28 | 2022-04-12 | 南开大学 | Controllable preparation method of gradient composite membrane |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20030000746A (en) * | 2001-06-27 | 2003-01-06 | (주)대한솔루션 | a sound absorbing and insulation material for automobile |
| CN102035043A (en) * | 2009-09-25 | 2011-04-27 | 上海比亚迪有限公司 | Polymer porous membrane, preparation method thereof, polymer electrolyte, polymer battery and preparation method of battery |
| CN102230257A (en) * | 2011-05-30 | 2011-11-02 | 中国科学院青岛生物能源与过程研究所 | Coaxial compound nanometre fibre film as well as preparation method and application thereof |
| CN102427141A (en) * | 2011-12-01 | 2012-04-25 | 中山大学 | Composite proton exchange membrane and preparation method thereof |
| CN103147253A (en) * | 2013-03-05 | 2013-06-12 | 中国科学院理化技术研究所 | High-strength polyimide nano fiber porous membrane, and preparation method and application thereof |
-
2013
- 2013-12-25 CN CN201310726446.8A patent/CN104746239B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20030000746A (en) * | 2001-06-27 | 2003-01-06 | (주)대한솔루션 | a sound absorbing and insulation material for automobile |
| CN102035043A (en) * | 2009-09-25 | 2011-04-27 | 上海比亚迪有限公司 | Polymer porous membrane, preparation method thereof, polymer electrolyte, polymer battery and preparation method of battery |
| CN102230257A (en) * | 2011-05-30 | 2011-11-02 | 中国科学院青岛生物能源与过程研究所 | Coaxial compound nanometre fibre film as well as preparation method and application thereof |
| CN102427141A (en) * | 2011-12-01 | 2012-04-25 | 中山大学 | Composite proton exchange membrane and preparation method thereof |
| CN103147253A (en) * | 2013-03-05 | 2013-06-12 | 中国科学院理化技术研究所 | High-strength polyimide nano fiber porous membrane, and preparation method and application thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107059251A (en) * | 2017-06-09 | 2017-08-18 | 东华大学 | The preparation method of one-way wet-guide nanofiber multilayer complex films with wetting gradient |
| CN107059251B (en) * | 2017-06-09 | 2019-11-08 | 东华大学 | The preparation method of one-way wet-guide nanofiber multilayer complex films with wetting gradient |
| CN110791727A (en) * | 2019-11-29 | 2020-02-14 | 无锡创彩光学材料有限公司 | Wear-resistant coating for polyimide film stretcher and preparation method thereof |
| CN111575916A (en) * | 2020-05-13 | 2020-08-25 | 贵州大学 | Preparation method of electrostatic spinning fiber membrane with continuous gradient |
| CN112481831A (en) * | 2020-12-11 | 2021-03-12 | 江苏三丰特种材料科技有限公司 | Preparation method of multi-stage structure one-way moisture-conducting waterproof breathable film |
| CN114316637A (en) * | 2021-12-28 | 2022-04-12 | 南开大学 | Controllable preparation method of gradient composite membrane |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104746239B (en) | 2017-03-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Bavatharani et al. | Electrospinning technique for production of polyaniline nanocomposites/nanofibres for multi-functional applications: A review | |
| Liu et al. | Electrospun PU@ GO separators for advanced lithium ion batteries | |
| Raghavan et al. | Electrospun polymer nanofibers: The booming cutting edge technology | |
| Mansouri et al. | Investigation on the electrospun PVDF/NP-ZnO nanofibers for application in environmental energy harvesting | |
| Joshi et al. | Progress and potential of electrospinning-derived substrate-free and binder-free lithium-ion battery electrodes | |
| Dong et al. | Surface-modified electrospun polyacrylonitrile nano-membrane for a lithium-ion battery separator based on phase separation mechanism | |
| WO2021114321A1 (en) | Flexible conductive fiber membrane material and preparation method therefor | |
| CN104746239A (en) | Soft phase macromolecule/polyimide gradient type composite nanometer fiber membrane and preparation method thereof | |
| Liang et al. | Continuous and integrated PEDOT@ Bacterial cellulose/CNT hybrid helical fiber with “reinforced cement-sand” structure for self-stretchable solid supercapacitor | |
| CN104392845A (en) | Stretchable linear supercapacitor and lithium ion battery preparation method | |
| CN106784856A (en) | A kind of carbon nano-fiber/metal foil double-layer composite material and preparation method thereof | |
| Kimura et al. | Fabrication and characterization of reinforced electrospun poly (vinylidene fluoride-co-hexafluoropropylene) nanofiber membranes | |
| CN103469488A (en) | Preparation method of reinforced electrostatic spinning nano-fiber lithium-ion battery separator | |
| CN106159173A (en) | Composite membrane of polymer prepared by a kind of composite membrane of polymer and preparation method thereof, the method, gel electrolyte, lithium ion battery | |
| CN106409525B (en) | Graphene, conducting fibre composite material and its with the preparation method of multi-stage porous carbon composite material, its product and application | |
| Xu et al. | Eco-friendly and thermally stable cellulose film prepared by phase inversion as supercapacitor separator | |
| Wang et al. | Facile production of natural silk nanofibers for electronic device applications | |
| CN104638294B (en) | A kind of mixed nanometer lattice method for preparing gel polymer electrolyte | |
| CN105907009A (en) | Preparation of conductive high polymer composite material and application of conductive high polymer composite material in strain sensor | |
| Kianfar et al. | Electrospinning of fluorinated polymers: current state of the art on processes and applications | |
| Duan et al. | Core effect on mechanical properties of one dimensional electrospun core-sheath composite fibers | |
| CN104746236B (en) | A kind of polyimides/polyethylene glycol oxide cable-type composite nano-fiber membrane and preparation method thereof | |
| Zhu et al. | Physical characterization of electrospun nanofibers | |
| Ning et al. | Tailoring the morphologies of PVDF nanofibers by interfacial diffusion during coaxial electrospinning | |
| CN105679555A (en) | Preparation method for three-dimensional aminated carbon nanotube array/stretchable textile fiber electrode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |