CN104746236B - A kind of polyimides/polyethylene glycol oxide cable-type composite nano-fiber membrane and preparation method thereof - Google Patents
A kind of polyimides/polyethylene glycol oxide cable-type composite nano-fiber membrane and preparation method thereof Download PDFInfo
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- CN104746236B CN104746236B CN201310726479.2A CN201310726479A CN104746236B CN 104746236 B CN104746236 B CN 104746236B CN 201310726479 A CN201310726479 A CN 201310726479A CN 104746236 B CN104746236 B CN 104746236B
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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
- D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
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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
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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
- D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
- D01D5/30—Conjugate filaments; Spinnerette packs therefor
- D01D5/34—Core-skin structure; Spinnerette packs therefor
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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
Abstract
The invention discloses a kind of polyimides/polyethylene glycol oxide cable-type composite nano-fiber membranes and preparation method thereof, wherein, the polyimides/polyethylene glycol oxide cable-type composite nano-fiber membrane is formed by the cable-type composite nano fiber of sandwich layer containing polyimides and polyethylene glycol oxide cortex.The present invention is enclosed in the outer layer of polyimides using polyethylene glycol oxide as shell, the advantages that not only possessing the mechanical property and high-temperature stable method of polyimides, the advantage that imbibition and the liquid-keeping property for more having had both polyethylene glycol oxide are strong, conductivity is high is a kind of up-and-coming gel polymer electrolyte for lithium ion battery.
Description
Technical field
The present invention relates to a kind of polyimides/polyethylene glycol oxide cable-type composite nano-fiber membrane and preparation method thereof, tools
Body, the present invention relates to a kind of polyimides/polyoxygenateds that can be used for lithium ion battery using coaxial electrostatic spinning technology preparation
Ethylene cable-type composite nano-fiber membrane and preparation method thereof.
Background technique
Method of electrostatic spinning is a kind of important method for preparing superfine fibre, and early in 1934, Formhals was just special in the U.S.
The technology that polymer filaments are obtained using electrostatic repulsion is described for the first time in 1975504 [P] of benefit application.In recent years, with nanometer
The development of science and technology, this technology obtain the extensive concern of people again.The appearance of coaxial electrostatic spinning technology can be described as pair
The result that electrostatic spinning technique is further furtherd investigate.
Coaxial electrostatic spinning technology prepares the process of fiber: two kinds of immiscible spinning solutions are respectively placed in inside and outside note
In emitter, under electric field force effect, the polymeric liquid of spinning nozzle capillary tip forms coaxial Taylor cone.When field strength reaches
When to thousands of or even tens of thousands of volts, charged liquid overcomes its surface tension and forms coaxial jet.As solvent volatilization, jet stream are solid
Change, form superfine fibre film on the receiving screen with opposite electrode.Under certain condition, by electrostatic repulsion, Coulomb force and surface
The collective effect of tension, polymer jet stream can be drafted thousand along unstable helical trajectory bending motion within a few tens of milliseconds
Wan Bei, to form submicron order to the coaxial fiber of nano level superfine.
In recent years, preparing the document of composite nano fiber and patent application using coaxial electrostatic spinning technology has very much, example
Such as: in document [Tao Song et al.Chemical Physics Letters [J], 2005,415:317], Song etc. is adopted
FePt magnetic particle/PCL coaxial nano cable has been prepared with coaxial electrostatic spinning technology.In patent application CN103088442A
Shi Lijun et al. discloses the method for preparing doughnut using coaxial electrostatic spinning technology.In patent application CN103102067A
Middle Liu Li et al., which is disclosed, a kind of prepares rough surface SiO using coaxial electrostatic spinning technology2The method of fiber.In patent application
Mo Xiumei et al. discloses that a kind of using coaxial electrostatic spinning technology to prepare core -shell structure medicament nano fine in CN101509153
The method of dimension.
Wherein, a kind of coaxial compound nanometre fibre film is disclosed in patent application CN102230257A and preparation method is answered
With in the disclosure in this patent using fluoropolymer, there is pollute.
Therefore, how the cable-type composite nano-fiber membrane that a kind of new green environment protection is pollution-free and conductivity is high is provided
It needs further to study and urgently develop.
Summary of the invention
It is an object of the invention to the cable-type composite nano-fiber membranes in the prior art for lithium ion battery to have
Fluorine-containing equal poisonous polymers and the low disadvantage of conductivity provide a kind of polyimides/polyethylene glycol oxide cable-type is compound and receive
Rice tunica fibrosa and preparation method thereof.
The present invention provides a kind of polyimides/polyethylene glycol oxide cable-type composite nano-fiber membranes, wherein the polyamides is sub-
Amine/polyethylene glycol oxide cable-type composite nano-fiber membrane is compound by the cable-type of sandwich layer containing polyimides and polyethylene glycol oxide cortex
Nanofiber is formed.
The present invention also provides a kind of polyimides/polyethylene glycol oxide cable-type composite nano-fiber membrane preparation method,
Wherein, method includes the following steps:
(1) polyamic acid solution as interior fluid and the polyethylene oxide solutions as outer fluid are passed through into coaxial electrostatic
Polyamic acid/polyethylene glycol oxide cable-type composite nano fiber of device for spinning preparation, and by polyamic acid/polyoxygenated of preparation
Ethylene cable-type composite nano fiber is collected on plate wire drawing device；
(2) it removes solvent the film formed on plate wire drawing device drying, obtains polyimides/polyethylene glycol oxide cable-type
Composite nano-fiber membrane.
The present invention makes precursor polyamic acid (PAA) solution of polyimides (PI) as interior fluid, polyethylene glycol oxide
(PEO) it is used as outer fluid, using coaxial electrostatic spinning technology, then by chemical imines method, so that PAA is converted into PI, and then make to gather
Acid imide is as the sandwich layer ingredient for mutually serving as the construction of cable firmly, it is ensured that the gelatin polymer electricity being made of the polyimide fiber
Solve the mechanical stability and thermomechanical stability of matter (GPE) membrane structure；Polyethylene glycol oxide is set to serve as the construction of cable as soft phase
The advantages of shell sections, polyethylene glycol oxide is that imbibition and water retainability are good, and the imbibition rate of pure PEO can reach 400% or more, due to
There are C-O-C keys in molecular weight, usually have flexibility, can form associated matter with electron acceptor or certain inorganic electrolytes, make
For the transmission channel of lithium ion.Therefore PEO is enclosed in the outer layer of PI as shell, and the cable-type nanofiber of composition is not only gathered around
There are the mechanical property of PI and high-temperature stable method, it is excellent that imbibition and the liquid-keeping property for more having had both PEO are strong, conductivity is high
Point is a kind of up-and-coming gel polymer electrolyte for lithium ion battery, and in the present invention, dissolves the molten of PEO
Agent is pure water, more meets environmentally protective requirement.In addition, preparation method of the invention is easy to operate, reaction condition is mild, cost
It is low, it is good in economic efficiency.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is the schematic diagram that the coaxial electrostatic spinning used according to the present invention prepares cable-type composite nano fiber；
Fig. 2 is the effect picture of cable-type composite nano fiber prepared in accordance with the present invention；
Fig. 3 is the scanning electron microscope (SEM) photograph of the cable-type composite nano fiber of 1 preparation according to embodiments of the present invention.
Description of symbols
1 second syringe, 2 first syringe
3 high-pressure electrostatic, 4 cable-type composite nano fiber
The plate wire drawing device of 5 ground connection
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The present invention provides a kind of polyimides/polyethylene glycol oxide cable-type composite nano-fiber membranes, wherein the polyamides is sub-
Amine/polyethylene glycol oxide cable-type composite nano-fiber membrane is compound by the cable-type of sandwich layer containing polyimides and polyethylene glycol oxide cortex
Nanofiber is formed.
According to the present invention, on the basis of the total weight of the cable-type composite nano fiber, the polyimides sandwich layer
Content can be 20-80 weight %, and the content of the polyethylene glycol oxide cortex can be 20-80 weight %；Preferably, with the electricity
On the basis of the total weight of cable type composite nano fiber, the content of the polyimides sandwich layer can be 30-60 weight %, described poly-
The content of ethylene oxide cortex can be 40-70 weight %.
According to the present invention, the polyimides/polyethylene glycol oxide cable-type composite nano fiber diameter can be 500-
1000nm, preferably 550-900nm, the outer diameter ratio of the outer diameter of the polyimides sandwich layer and the polyethylene glycol oxide cortex can be with
For 1:1.4-5, preferably 1:1.4-3.5, the polyimides/polyethylene glycol oxide cable-type composite nano-fiber membrane thickness
Can be 10-30 μm, preferably 17-22 μm, the polyimides/polyethylene glycol oxide cable-type composite nano-fiber membrane hole
Gap rate can be 70-90%, and imbibition rate can be 500-800%；Wherein, in the present invention, the outer diameter of the polyimides sandwich layer refers to
Be the polyimides sandwich layer overall diameter, the outer diameter of the polyethylene glycol oxide cortex refers to the face of the polyethylene glycol oxide
The overall diameter of the cortex of packet round.
The present invention also provides a kind of polyimides/polyethylene glycol oxide cable-type composite nano-fiber membrane preparation method,
Wherein, method includes the following steps:
(1) polyamic acid solution as interior fluid and the polyethylene oxide solutions as outer fluid are passed through into coaxial electrostatic
Polyamic acid/polyethylene glycol oxide cable-type composite nano fiber of device for spinning preparation, and by polyamic acid/polyoxygenated of preparation
Ethylene cable-type composite nano fiber is collected on plate wire drawing device；
(2) it removes solvent the film formed on plate wire drawing device drying, obtains polyimides/polyethylene glycol oxide cable-type
Composite nano-fiber membrane.
According to the present invention, the polyamic acid solution can be prepared for polyamic acid to be dissolved in organic solvent,
The organic solvent can for DMAC N,N' dimethyl acetamide, N,N-dimethylformamide, N-Methyl pyrrolidone, tetrahydrofuran and
One of dimethyl sulfoxide is a variety of, preferably n,N-dimethylacetamide.
According to the present invention, the concentration of the polyamic acid solution can be 10-30 weight %, preferably 15-20 weight %.
According to the present invention, the polyethylene oxide solutions can prepare for polyethylene glycol oxide to be dissolved in deionized water and
At, wherein the deionized water is not particularly limited, it is preferable that the conductivity of the deionized water is 1 × 10-14S/cm。
According to the present invention, the concentration of the polyethylene oxide solutions can be 10-30 weight %, preferably 15-20 weight %.
According to the present invention, the dosage of the polyamic acid and the polyethylene glycol oxide make prepared polyimides/
It can preferably contain containing the polyimides sandwich layer of 20-80 weight % in the total weight of polyethylene glycol oxide cable-type composite nano fiber
There is the polyimides sandwich layer of 30-60 weight %, and 40- can be preferably comprised containing the polyethylene glycol oxide cortex of 20-80 weight %
The polyethylene glycol oxide cortex of 70 weight %.
According to the present invention, firstly, preparing cable-type composite Nano on the plate wire drawing device by coaxial electrostatic spinning
Fiber.The electrostatic spinning apparatus for coaxial electrostatic spinning in the present invention generally comprises high-pressure electrostatic, plate wire drawing device, is used for
The first syringe with the first boost motor of fluid and have the second boost motor for containing outer fluid in containing
Two syringes, wherein one end for containing the first syringe with the first boost motor of interior fluid has in 0.1-1mm
Core metal syringe needle, the inner core metal needle of preferably 0.1-0.6mm, the other end can be the first boost motor, similarly, for containing
One end of the second syringe with the second boost motor of outer fluid has the outer cover metal syringe needle of 0.3-1.5mm, preferably 1-
The outer cover metal syringe needle of 1.5mm, the other end can be the second boost motor；The high-pressure electrostatic anode with outer cover metal syringe needle with
And the electrical connection of inner core metal needle, the cathode of the high-pressure electrostatic are electrically connected with plate wire drawing device.
According to the present invention, the plate wire drawing device is not particularly limited, and conductive is easily formed leading for film as long as capableing of
Isoelectric substance.
Fig. 1 shows the schematic diagram that the coaxial electrostatic spinning used according to the present invention prepares cable-type composite nano fiber；
As shown in Figure 1:
The coaxial electrostatic spinning method includes respectively will be as the polyamic acid solution of interior fluid and as the poly- of outer fluid
Ethylene oxide solution is placed in the first syringe and the second syringe, then by high-pressure electrostatic anode respectively with inner core metal needle
And the electrical connection of outer cover metal syringe needle, cathode are electrically connected with plate wire drawing device, are opened the supply voltage of high-pressure electrostatic and are started same
Axis electrostatic spinning apparatus, in this way, inner core metal needle and outer cover metal syringe needle in the first syringe and the second syringe
High voltage electric field is formed between plate wire drawing device, the polyamic acid of fluid as in the first syringe and the second syringe is molten
Liquid and polyethylene oxide solutions as outer fluid eject by inner core metal needle and outer cover metal syringe needle and to form nothing
Sequence and/or orderly cable-type composite nano fiber are suspended under the traction of electric field force in plate wire drawing device and in the plate
The cable-type composite nano-fiber membrane being made of cable-type composite nano fiber is formed in wire drawing device, wherein the coaxial electrostatic
The condition of spinning includes: that the supply voltage of high-pressure electrostatic is 5-20kV, and the fltting speed of the first boost motor is 0.2-1.6ml/h,
Preferably 0.2-0.6ml/h, the fltting speed of the second boost motor are 0.2-1.6ml/h, preferably 0.4-1ml/h, interior core metal
The internal diameter of syringe needle is 0.1-1mm, and preferably 0.1-0.6mm, the internal diameter of outer cover metal syringe needle is 0.3-1.5mm, preferably 1-
1.5mm, the plate wire drawing device and the distance between inner core metal needle and outer cover metal syringe needle are 5-20cm.
Then again by the polyamic acid prepared through coaxial electrostatic spinning technology/polyethylene glycol oxide cable-type composite nano fiber
Film drying removes solvent, using chemical imines method, converts polyimides (PI) for polyamic acid (PAA), obtains polyamides Asia
Amine/polyethylene glycol oxide cable-type composite nano-fiber membrane；Wherein, the instrument of the drying is using well known to those skilled in the art
Vacuum drying oven, the condition of the drying is not particularly limited, it is preferable that the condition of the drying includes: the temperature of drying can
Think 40-60 DEG C, the time of drying can be 23-25 hours；It is highly preferred that drying temperature can be 50 DEG C, drying when
Between can be 24 hours.
It according to the present invention, can also be by prepared polyimides/polyethylene glycol oxide cable after by above-mentioned steps
Type composite nano-fiber membrane carries out mechanical stitch processing, wherein it can be 5- that the condition of the mechanical stitch processing, which includes: pressure,
10MPa, time can be 3-5 minutes, it is preferable that the time can be 3 minutes.
The effect picture of cable-type composite nano fiber prepared in accordance with the present invention is as shown in Fig. 2, in the Fig. 2, in this hair
In bright, " soft phase A " indicates the polyethylene oxide solutions as outer fluid, and " soft phase B " indicates that the polyamic acid as interior fluid is molten
Liquid, the two prepare cable-type composite nano fiber by coaxial electrostatic spinning, wherein alphabetical " A " indicates prepared cable
The cortex of type composite nano fiber, alphabetical " B " indicate the sandwich layer of prepared cable-type composite nano fiber.
According to the present invention, it carries out the environment temperature of electrostatic spinning and humidity is not particularly limited, can be art technology
Temperature and humidity known to personnel, it is preferable that carry out 25 DEG C of environment temperature of electrostatic spinning, humidity 40%.
A kind of specific embodiment according to the present invention, the preparation method specifically includes the following steps:
(1) polyamic acid solution (sandwich layer solution) of the configuration as interior fluid: the polyamide for being 10-30 weight % by concentration
Sour (PAA) is dissolved in preferred n,N-dimethylacetamide (DMAc), can be preferably added a certain amount of imidization catalysis
Agent and dehydrating agent are fitted into the syringe for injecting interior fluid with the first boost motor, for use；
(2) polyethylene oxide solutions (cortex solution) of the configuration as outer fluid: the polyoxy for being 10-30 weight % by concentration
Ethylene (PEO) is dissolved in deionized water, is fitted into the syringe for injecting outer fluid with the second boost motor, for use；
(3) dosage of polyamic acid and polyethylene glycol oxide is determined: the polyamic acid and the polyethylene glycol oxide
Dosage to contain 20-80 weight % in prepared polyimides/polyethylene glycol oxide cable-type composite nano fiber total weight
Polyimides sandwich layer, preferably comprise the polyimides sandwich layer of 30-60 weight %, and the polyoxyethylene containing 20-80 weight %
Alkene cortex preferably comprises the polyethylene glycol oxide cortex of 40-70 weight %；
(4) it selects, inner core metal needle and outer cover metal syringe needle is installed, electrospinning parameters are set: high-pressure electrostatic
Supply voltage is 5-20kV, and the fltting speed of the first boost motor is 0.2-1.6ml/h, preferably 0.2-0.6ml/h, the second boosting
The fltting speed of device is 0.2-1.6ml/h, and preferably 0.4-1ml/h, the internal diameter of inner core metal needle is 0.1-1mm, preferably
0.1-0.6mm, the internal diameter of outer cover metal syringe needle are 0.3-1.5mm, preferably 1-1.5mm, and the plate wire drawing device and inner core are golden
Belonging to the distance between syringe needle and outer cover metal syringe needle is 5-20cm；
(5) anode of inner core metal needle and outer cover metal syringe needle and high-pressure electrostatic is connected, by plate wire drawing device with
The cathode of high-pressure electrostatic connects；
(6) being formed by unordered and/or orderly cable-type composite nano fiber for preparation is collected on plate wire drawing device
Polyamic acid/polyethylene glycol oxide cable-type composite nano-fiber membrane；
(7) by the polyamic acid/polyethylene glycol oxide cable-type composite nano-fiber membrane in the baking oven that temperature is 40-60 DEG C
It is dried 23-25 hours, polyamic acid therein is made to be converted into polyimides by chemical imines method；
(8) polyimides/polyethylene glycol oxide cable-type composite nano-fiber membrane is handled into 3- in the case where pressure is 5-10MPa
5 minutes.
The present invention also provides a kind of polyimides by above method preparation/polyethylene glycol oxide cable-type composite Nano is fine
Tie up film, wherein the diameter of the cable-type composite nano fiber is 500-1000nm, preferably 550-900nm, and the polyamides is sub-
The outer diameter ratio of the outer diameter of amine cortex and the polyethylene glycol oxide sandwich layer is 1:1.4-5, preferably 1:1.4-3.5, the polyamides
Imines/polyethylene glycol oxide cable-type composite nano-fiber membrane is with a thickness of 10-30 μm, and preferably 17-22 μm, the polyamides is sub-
Amine/polyethylene glycol oxide cable-type composite nano-fiber membrane porosity can be 75-86%, and imbibition rate can be 480-720%.
The present invention will be described in detail by way of examples below.
In the following Examples and Comparative Examples, polyimides is the method that the present inventor passes through chemical imines PAA
Self-control；Polyamic acid is purchased from Hangzhou Su Mengte Co., Ltd, and number-average molecular weight is 100,000；Polyethylene glycol oxide is purchased from acros
Organics, number-average molecular weight are 150,000.
In the following Examples and Comparative Examples, high-voltage electrostatic spinning machine is purchased from Shenzhen concerted effort micro-nano Co., Ltd, model
NEU011；Scanning electron microscope is purchased from Japan JEOL, model JSM-7600FE.
In the following Examples and Comparative Examples, to the polyimides/polyethylene glycol oxide cable-type composite nano-fiber membrane
Imbibition rate is tested: being dipped in after weighing up the polyimides/polyethylene glycol oxide cable-type composite nano-fiber membrane quality
For 24 hours in electrolyte (lithium salts LiPF6, concentration 1mol/L, solvent EC, EMC, DEC, mass concentration ratio 2:3:1), so
Taking-up blots the polyimides/polyethylene glycol oxide cable-type composite nano-fiber membrane surface liquid with filter paper afterwards, is corresponded to
Gel polymer electrolyte, weigh the quality of the corresponding gel polymer electrolyte at this time, operation is all being full of argon gas
Glove box in carry out.It is calculated according to formula: imbibition rate %=(Wi-W)/W × 100%；
Wherein, W is the quality of dry film；Wi is the quality after dry film has impregnated for 24 hours in the electrolytic solution.
In the following Examples and Comparative Examples, to the polyimides/polyethylene glycol oxide cable-type composite nano-fiber membrane
(Wd) porosity tested: by the polyimides weighed/polyethylene glycol oxide cable-type composite nano-fiber membrane in positive fourth
It takes out, is gently blotted the liquid on its surface with filter paper, then (the W that weighed after impregnating 2h in alcoholw), nanofiber can be obtained
The quality W of the absorbed n-butanol of filmb=Ww- WdThe pore volume of nano fibrous membrane can be by the quality (W of n-butanolb) and n-butanol
Density (ρb) be divided by obtain, the ratio between this volume and dry film volume are porosity P%=(W of nano fibrous membranew- Wd)/(ρbVp)。
In the following Examples and Comparative Examples, to the polyimides/polyethylene glycol oxide cable-type composite nano-fiber membrane
Conductivity test: the polyimides/polyethylene glycol oxide cable-type composite nano-fiber membrane is placed between two stainless steel substrates, is inhaled
The electrolyte (lithium salts LiPF6, concentration 1M/L, solvent EC, EMC, DEC, mass concentration ratio 2:3:1) of sufficient amount is received,
Obtain corresponding gel polymer electrolyte, be sealed against after 2016 type button cells, carry out AC impedance experiment, linearly with
The intersection point of real axis is the bulk resistance of gel polymer electrolyte, thus obtains the ionic conductivity of gel polymer electrolyte
It can be calculated according to formula:
Conductivityσ=L/ (AR),
Wherein, L indicates that the thickness of gel polymer electrolyte, A are the contact area of stainless steel plate and film, and R is polymer
The bulk resistance of electrolyte.
Embodiment 1
(1) it is in DMAC N,N' dimethyl acetamide that 98% concentration is 15 weight % as sandwich layer that purity will be dissolved under PAA room temperature
Solution is fitted into the first syringe of coaxial electrostatic spinning silk device；It is 1 × 10 that by PEO, to be dissolved in concentration, which be 15 weight % conductivity,- 14In the deionized water of S/cm, it is fitted into the second syringe of coaxial electrostatic spinning silk device；
(2) coaxial electrostatic spinning condition (in addition to fltting speed) is provided that the supply voltage of high-pressure electrostatic is 20kV, interior
The internal diameter of core metal syringe needle is 0.8mm, and the internal diameter of outer cover metal syringe needle is 1.2mm, the plate wire drawing device and inner core metal needle
The distance between head and outer cover metal syringe needle are 15cm, and the environment temperature for carrying out electrostatic spinning is 25 DEG C, humidity 40%,
The fltting speed of PAA and PEO is respectively 0.2ml/h and 0.8ml/h.
(3) spinning terminates after 6 hours, removes film, and using chemical imines method, temperature is small for drying 24 at 50 DEG C in an oven
When, PI is converted by PAA, and roll to it 3 minutes using the pressure of 10MPa.
As a result the polyimides with a thickness of 17 μm/polyethylene glycol oxide cable-type composite nano fiber is obtained, is such as implemented from Fig. 3
The scanning electron microscope (SEM) photograph of cable-type composite nano fiber prepared by example 1 can be seen that polyimides/polyoxyethylene prepared by the present invention
The diameter of alkene cable-type composite nano fiber is about 550nm, and center core layer diameter is about 130nm or so.
Testing the polyimides/polyethylene glycol oxide cable-type composite nano-fiber membrane tensile strength is 34MPa, porosity
It is 86%, the imbibition rate of corresponding gel polymer electrolyte is 720%, and conductivity is 2.0 × 10-3S/cm。
Embodiment 2
(1) purity will be dissolved under PAA room temperature is that the DMAC N,N' dimethyl acetamide that 98% concentration is 20 weight % is molten as sandwich layer
Liquid is fitted into the first syringe of coaxial electrostatic spinning silk device；It is 1 × 10 that PEO, which is dissolved in the conductivity that concentration is 15 weight %,- 14In the deionized water of S/cm, it is fitted into the second syringe of electrostatic spinning apparatus；
(2) coaxial electrostatic spinning condition (in addition to fltting speed) is provided that the supply voltage of high-pressure electrostatic is 20kV, interior
The internal diameter of core metal syringe needle is 0.8mm, and the internal diameter of outer cover metal syringe needle is 1.2mm, the plate wire drawing device and inner core metal needle
The distance between head and outer cover metal syringe needle are 18cm, and the environment temperature for carrying out electrostatic spinning is 25 DEG C, humidity 40%,
The fltting speed of PAA and PEO is respectively 0.3ml/h and 1.0ml/h；
(3) spinning terminates after 6 hours, removes film, and using chemical imines method, temperature is small for drying 24 at 50 DEG C in an oven
When, PI is converted by PAA, and roll to it 3 minutes using the pressure of 10MPa.
As a result the polyimides with a thickness of 22 μm/polyethylene glycol oxide cable-type composite nano-fiber membrane is obtained.
After testing, the polyimides/polyethylene glycol oxide cable-type composite nano fiber diameter is about 700nm, wherein
Sandwich layer diameter is about 190nm or so.
Testing the polyimides/polyethylene glycol oxide cable-type composite nano-fiber membrane tensile strength is 38MPa, porosity
It is 81%, the imbibition rate of corresponding gel polymer electrolyte is 680%, and conductivity is 1.7 × 10-3S/cm。
Embodiment 3
(1) purity will be dissolved under PAA room temperature is that the DMAC N,N' dimethyl acetamide that 98% concentration is 15 weight % is molten as sandwich layer
Liquid is fitted into the first syringe of electrostatic spinning apparatus；It is 1 × 10 that by PEO, to be dissolved in concentration, which be 20 weight % conductivity,-14S/cm's
In deionized water, it is fitted into the second syringe of electrostatic spinning apparatus；
(2) coaxial electrostatic spinning condition (in addition to fltting speed) is provided that the supply voltage of high-pressure electrostatic is 20kV, interior
The internal diameter of core metal syringe needle is 0.8mm, and the internal diameter of outer cover metal syringe needle is 1.2mm, the plate wire drawing device and inner core metal needle
The distance between head and outer cover metal syringe needle are 15cm, and the environment temperature for carrying out electrostatic spinning is 30 DEG C, humidity 20%,
The fltting speed of PAA and PEO is respectively 0.5ml/h and 0.5ml/h；
(3) spinning terminates after 6 hours, removes film, and using chemical imines method, temperature is small for drying 24 at 50 DEG C in an oven
When, PI is converted by PAA, and roll to it 3 minutes using the pressure of 15MPa.
As a result the polyimides with a thickness of 18 μm/polyethylene glycol oxide cable-type composite nano-fiber membrane is obtained.
After testing, the polyimides/polyethylene glycol oxide cable-type composite nano fiber diameter is about 770nm, wherein
Sandwich layer diameter is about 320nm or so.
Testing the polyimides/polyethylene glycol oxide cable-type composite nano-fiber membrane tensile strength is 47MPa, porosity
It is 79%, the imbibition rate of corresponding gel polymer electrolyte is 645%, and conductivity is 1.3 × 10-3S/cm。
Embodiment 4
(1) using PAA room temperature under be dissolved in n,N-dimethylacetamide that concentration is 20 weight % as sandwich layer solution, loading
In first syringe of electrostatic spinning apparatus；It is 1 × 10 that concentration is 20 weight % that PEO, which is dissolved in conductivity,-14S/cm go from
In sub- water, it is fitted into the second syringe of electrostatic spinning apparatus；
(2) coaxial electrostatic spinning condition (in addition to fltting speed) is provided that the supply voltage of high-pressure electrostatic is 20kV, interior
The internal diameter of core metal syringe needle is 0.8mm, and the internal diameter of outer cover metal syringe needle is 1.2mm, the plate wire drawing device and inner core metal needle
The distance between head and outer cover metal syringe needle are 10cm, and the environment temperature for carrying out electrostatic spinning is 25 DEG C, humidity 40%,
The fltting speed of PAA and PEO is respectively 0.6ml/h and 0.4ml/h；
(3) spinning terminates after 6 hours, removes film, and using chemical imines method, temperature is small for drying 24 at 50 DEG C in an oven
When, PI is converted by PAA, and roll to it 3 minutes using the pressure of 10MPa.
As a result the polyimides with a thickness of 17 μm/polyethylene glycol oxide cable-type composite nano-fiber membrane is obtained.
After testing, the polyimides/polyethylene glycol oxide cable-type composite nano fiber diameter is about 900nm, wherein
Sandwich layer diameter is about 570nm or so；
Testing the polyimides/polyethylene glycol oxide cable-type composite nano-fiber membrane tensile strength is 53MPa, porosity
It is 75%, the imbibition rate of corresponding gel polymer electrolyte is 480%, and conductivity is 1.1 × 10-3S/cm。
Comparative example 1
Polyimides/Kynoar cable-type composite nano-fiber membrane, institute are prepared in the same manner as shown in Example 1
The difference is that the polyethylene glycol oxide in embodiment 1 is replaced with the Kynoar (PVDF) that molecular weight is 60.
As a result the polyimides with a thickness of 17 μm/Kynoar cable-type composite nano-fiber membrane film is obtained.
After testing, the polyimides/Kynoar cable-type composite nano fiber diameter is about 900nm, wherein
Sandwich layer diameter is about 810nm or so.
Testing the polyimides/Kynoar cable-type composite nano-fiber membrane tensile strength is 30MPa, porosity
It is 76%, the imbibition rate of corresponding gel polymer electrolyte is 43%, and conductivity is 1.9 × 10-4S/cm。
By the result of above-described embodiment 1-4 and comparative example 1 it can be seen that the polyamides Asia prepared using method of the invention
The polyimides that amine/polyethylene glycol oxide cable-type composite nano-fiber membrane is prepared relative to comparative example/Kynoar cable-type
The sandwich layer diameter of composite nano-fiber membrane is small, tensile strength is high, the imbibition rate of corresponding gel polymer electrolyte and electricity
Conductance significantly improves.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (21)
1. a kind of polyimides of the gel polymer electrolyte for lithium ion battery/polyethylene glycol oxide cable-type composite Nano
Tunica fibrosa, which is characterized in that the polyimides/polyethylene glycol oxide cable-type composite nano-fiber membrane by sandwich layer containing polyimides and
The cable-type composite nano fiber of polyethylene glycol oxide cortex is formed,
Wherein, the polyimides/polyethylene glycol oxide cable-type composite nano-fiber membrane porosity is 75-86%, imbibition rate
For 480-720%.
2. polyimides according to claim 1/polyethylene glycol oxide cable-type composite nano-fiber membrane, wherein with described
On the basis of the total weight of cable-type composite nano fiber, the content of the polyimides sandwich layer is 20-80 weight %, the polyoxy
The content for changing ethylene cortex is 20-80 weight %.
3. polyimides according to claim 2/polyethylene glycol oxide cable-type composite nano-fiber membrane, wherein with described
On the basis of the total weight of cable-type composite nano fiber, the content of the polyimides sandwich layer is 30-60 weight %, the polyoxy
The content for changing ethylene cortex is 40-70 weight %.
4. polyimides according to claim 1/polyethylene glycol oxide cable-type composite nano-fiber membrane, wherein the electricity
The diameter of cable type composite nano fiber is 500-1000nm, the outer diameter of the polyimides sandwich layer and the polyethylene glycol oxide cortex
Outer diameter ratio be 1:1.4-5, the polyimides/polyethylene glycol oxide cable-type composite nano-fiber membrane is with a thickness of 10-30 μm.
5. polyimides according to claim 4/polyethylene glycol oxide cable-type composite nano-fiber membrane, wherein the electricity
The diameter of cable type composite nano fiber is 550-900nm, the outer diameter of the polyimides sandwich layer and the polyethylene glycol oxide cortex
Outer diameter ratio be 1:1.4-3.5, the polyimides/polyethylene glycol oxide cable-type composite nano-fiber membrane is with a thickness of 17-22 μ
m。
6. described in any one of claim 1-5 for lithium ion battery gel polymer electrolyte polyimides/
The preparation method of polyethylene glycol oxide cable-type composite nano-fiber membrane, which is characterized in that method includes the following steps:
(1) polyamic acid solution as interior fluid and the polyethylene oxide solutions as outer fluid are passed through into coaxial electrostatic spinning
Device prepares polyamic acid/polyethylene glycol oxide cable-type composite nano fiber, and the polyamic acid of preparation/polyethylene glycol oxide is electric
Cable type composite nano fiber is collected on plate wire drawing device；
(2) it removes solvent the film formed on plate wire drawing device drying, it is compound to obtain polyimides/polyethylene glycol oxide cable-type
Nano fibrous membrane.
7. according to the method described in claim 6, wherein, the polyamic acid solution is that polyamic acid is dissolved in organic solvent
In be prepared, the organic solvent be n,N-dimethylacetamide, n,N-Dimethylformamide, N-Methyl pyrrolidone, four
One of hydrogen furans and dimethyl sulfoxide are a variety of.
8. according to the method described in claim 7, wherein, the organic solvent is n,N-dimethylacetamide.
9. according to the method described in claim 6, wherein, the polyethylene oxide solutions be polyethylene glycol oxide is dissolved in from
It is prepared in sub- water.
10. the method according to any one of claim 6-9, wherein the concentration of the polyamic acid solution is 10-30
Weight %, the concentration of the polyethylene oxide solutions are 10-30 weight %.
11. according to the method described in claim 10, wherein, the concentration of the polyamic acid solution is 15-20 weight %, described
The concentration of polyethylene oxide solutions is 15-20 weight %.
12. according to the method described in claim 10, wherein, the dosage of the polyamic acid and the polyethylene glycol oxide makes
Polyamides containing 20-80 weight % in prepared polyimides/polyethylene glycol oxide cable-type composite nano fiber total weight
Imines sandwich layer, and the polyethylene glycol oxide cortex containing 20-80 weight %.
13. according to the method for claim 12, wherein the dosage of the polyamic acid and the polyethylene glycol oxide makes
Polyamides containing 30-60 weight % in prepared polyimides/polyethylene glycol oxide cable-type composite nano fiber total weight
Imines sandwich layer, and the polyethylene glycol oxide cortex containing 40-70 weight %.
14. according to the method for claim 11, wherein the dosage of the polyamic acid and the polyethylene glycol oxide makes
Polyamides containing 20-80 weight % in prepared polyimides/polyethylene glycol oxide cable-type composite nano fiber total weight
Imines sandwich layer, and the polyethylene glycol oxide cortex containing 20-80 weight %.
15. according to the method for claim 14, wherein the dosage of the polyamic acid and the polyethylene glycol oxide makes
Polyamides containing 30-60 weight % in prepared polyimides/polyethylene glycol oxide cable-type composite nano fiber total weight
Imines sandwich layer, and the polyethylene glycol oxide cortex containing 40-70 weight %.
16. according to the method described in claim 6, wherein, in step (1), the coaxial electrostatic spinning silk device includes high pressure
Power supply, the syringe for injecting interior fluid with the first boost motor are used to inject outer fluid with the second boost motor
Syringe, inner core metal needle, outer cover metal syringe needle and plate wire drawing device, wherein the condition of coaxial electrostatic spinning includes: height
Voltage source voltage is 5-20kV, and the fltting speed of the first boost motor is 0.2-1.6ml/h, and the fltting speed of the second boost motor is equal
For 0.2-1.6ml/h, the internal diameter of inner core metal needle is 0.1-1mm, and the internal diameter of outer cover metal syringe needle is 0.3-1.5mm, described
Plate wire drawing device and the distance between inner core metal needle and outer cover metal syringe needle are 5-20cm.
17. according to the method for claim 16, wherein the condition of coaxial electrostatic spinning includes: the propulsion of the first boost motor
Speed is 0.2-0.6ml/h, and the fltting speed of the second boost motor is 0.4-1ml/h, and the internal diameter of inner core metal needle is
0.1-0.6mm, the internal diameter of outer cover metal syringe needle are 1-1.5mm.
18. according to the method described in claim 6, wherein, in step (2), the condition of the drying includes: the temperature of drying
It is 40-60 DEG C, the time of drying is 23-25 hours.
19. according to the method described in claim 6, wherein, this method further includes the polyimides/polyoxy for preparing step (2)
Change ethylene cable-type composite nano-fiber membrane and carries out mechanical stitch processing.
20. according to the method for claim 19, wherein it is 5- that the condition of the mechanical stitch processing, which includes: pressure,
10MPa, time are 3-5 minutes.
21. polyimides/polyethylene glycol oxide cable-type of the preparation of the method as described in any one of claim 6-20 is compound
Nano fibrous membrane.
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| CN107630294B (en) * | 2017-10-27 | 2020-08-07 | 长沙新材料产业研究院有限公司 | Polyimide nanofiber membrane |
| CN107675274B (en) * | 2017-10-27 | 2020-06-16 | 长沙新材料产业研究院有限公司 | Polyimide nanofiber membrane and preparation method thereof |
| CN110233287A (en) * | 2019-04-08 | 2019-09-13 | 南京工业大学 | A kind of nylon base composite gel polymer electrolyte and preparation method thereof |
| CN110707357B (en) * | 2019-10-23 | 2021-05-07 | 北京卫蓝新能源科技有限公司 | Gel polymer electrolyte with core-shell structure and preparation method and application thereof |
| CN114079081A (en) * | 2020-08-18 | 2022-02-22 | 厦门大学 | Polymer electrolyte and preparation method thereof |
| CN117457996B (en) * | 2023-12-25 | 2024-03-19 | 安徽盟维新能源科技有限公司 | Double-crosslinking composite electrolyte membrane and preparation method and application thereof |
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