CN109065816A - A kind of polyurethane-nano material composite diaphragm and Preparation method and use - Google Patents
A kind of polyurethane-nano material composite diaphragm and Preparation method and use Download PDFInfo
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- CN109065816A CN109065816A CN201810922771.4A CN201810922771A CN109065816A CN 109065816 A CN109065816 A CN 109065816A CN 201810922771 A CN201810922771 A CN 201810922771A CN 109065816 A CN109065816 A CN 109065816A
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- polyurethane
- nano material
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- composite diaphragm
- material composite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of polyurethane-nano material composite diaphragm and Preparation method and use, the polyurethane/nano Material cladding diaphragm after nanomaterial-filled polyurethane solutions by solidifying.Polyurethane/nano Material cladding diaphragm with a thickness of 20~200 μm, porosity is 30%~80%.Advantages of the present invention are as follows: first is that polyurethane/nano Material cladding method for manufacturing thin film is simple, prepare that environment is mild and preparation process is environmentally protective；Second is that the content of nano material can be filled with Effective Regulation, closed and the safety issues such as fire-retardant with solving its heat；Third is that the present invention only needs its i.e. controllable porosity of common inorganic salt or solvent adding proportion, and aperture is small, ion penetration and electrochemical stability with higher compared with needing the method for special pore creating material and remover to prepare diaphragm；Fourth is that energy storage device short circuit and dendrite can be effectively prevent to puncture since the mechanical performance of polyurethane and nano material itself is more excellent.
Description
Technical field
The present invention relates to a kind of polyurethane-nano material composite diaphragm Preparation method and uses, belong to new energy materials
Technical field.
Background technique
In recent years, lithium ion battery is the new electrochmical power source system developed rapidly, with traditional ni-Cd or ni-mh electricity
Pond is compared, it has many advantages, such as high-energy density, memory-less effect, long circulation life and faster charge and discharge.It can be widely used for
Various portable electronic products are such as: mobile phone, camera, laptop need the product of rechargeable battery, are alternatively arranged as electronic vapour
Electrical source of power needed for vehicle and hybrid electric vehicle etc..In general, energy storage device is mainly by electrode, electrolyte, diaphragm and battery case
Packaging material composition.Important component of the battery diaphragm as battery directly affects the capacity, cycle performance and peace of battery
Characteristics, physics, chemistry and the mechanical performances such as full property determine the interfacial characteristics of battery, internal resistance etc., directly affect battery
The characteristics such as capacity, circulation and safety, the good diaphragm of performance play an important role the comprehensive performance for improving battery.Diaphragm is used
In high energy battery, it is important that the current loop in battery must be in giving when there are battery failures and with overheat
It is disconnected, avoid causing diaphragm that battery large area internal short-circuit occurs due to melting because battery continues heating so that on fire or even explosion and
Destroy battery.Therefore, the safety that lithium ion battery is improved by improving the performance of lithium ion battery separator receives increasingly
More concerns, various lithium ion battery separators emerge one after another.Currently, secondary battery membrane material be mainly polyolefin every
Film such as single-layer polypropylene (PP) microporous barrier, monolayer polyethylene (PE) microporous barrier and three layers of PP/PE/PP composite membrane, such diaphragm
Preparation method is mainly dry method tension pore method and wet process phase separation method.Polyalkene diaphragm drawback is: one, polyalkene diaphragm by
Re Shiyi is shunk, and it is unstable to will cause diaphragm size, and positive and negative anodes directly contact and short-circuit；Two, closed pore temperature and broken film temperature compared with
Low, when the situations such as battery puncture occur, inside battery is highly exothermic, and diaphragm is caused to melt contraction completely, and battery short circuit generates
High temperature is until battery disintegrates or explodes.Currently used capacitor diaphragm has polypropylene diaphragm and cellulosic separator two major classes.This
A little material thermal stability are poor, and porosity is low and absorbent is poor.On the one hand cause the chemical property of capacitor undesirable, separately
On the one hand its hot operation is caused to be easy to happen danger.
China Patent Publication No. is CN105591056A, and publication date is on May 18th, 2016, entitled " a kind of
Uniform dry method simple tension diaphragm of pore-forming and preparation method thereof ", polyolefin particles are plasticized to form polyolefin by extruder
Then melt squeezes out, chill roll slab from die head low temperature, obtain sheet polyolefin base membrane after setting roll sizing annealing, will move back
Fire treated polyolefin base membrane drawn, high-temperature shaping, it is cooling after obtain the uniform dry method simple tension diaphragm of pore-forming.The hair
Although bright diaphragm pore-forming is uniform, the diaphragm is cumbersome due to there is the presence of the techniques such as melting, roller casting, annealing and stretching
And energy consumption, and heat resistance is bad；China Patent Publication No. is CN104037377A, and publication date is on September 10th, 2014, hair
Bright entitled " preparation method of lithium battery diaphragm ", mLLDPE non-woven fibre is first prepared using method of electrostatic spinning, then equally adopt
Pvdf membrane is obtained in mLLDPE non-woven fibre with method of electrostatic spinning, it is compound both to obtain lithium electric separator.Although this method has its advantage,
But using method of electrostatic spinning twice, operating cost is high, and low efficiency is unfavorable for industrialization.
Summary of the invention
The object of the present invention is to provide a kind of polyurethane-nano material composite diaphragm Preparation method and uses.
The technical scheme is that a kind of polyurethane-nano material composite diaphragm, the polyurethane/nano material is multiple
Diaphragm is closed by solidifying after nanomaterial-filled polyurethane solutions；Polyurethane/nano Material cladding diaphragm with a thickness of 20~
200 μm, porosity is 30%~80%.
The nano material is silica, titanium dioxide, zinc oxide or graphene inorganic nano material.
The nano material is one-dimensional, two-dimentional or three-dimensional nanometer material, having a size of 1~500nm.
Ratio shared by nano material is 0~80% in the polyurethane-nano material composite diaphragm.
A kind of preparation method of polyurethane-nano material composite diaphragm:
(a) take urethane raw to be dissolved in volatile organic solvent, gel presoma be made, wherein polyurethane with
The mass ratio of organic solvent is controlled in 1:60~1:5；
(b) under rapid stirring, inorganic nano material and soluble inorganic salt are added into gel presoma,
Continue 30~60min of stirring, obtains mixed solution, wherein the mass ratio of soluble-salt and urethane raw is controlled in 0~1:1,
Mixing speed is controlled in 50~500r/min；
(c) obtained mixed solution is ultrasonically treated 1~3h, got a uniform mixture, supersonic frequency is controlled in 45KHz
~80KHz；
(d) by obtained homogeneous mixture solotion on the smooth vessel in surface plastic film mulch, later by vessel uniformly slowly as
In deionized water, after film forming to be solidified, removing is washed with deionized, and removes soluble inorganic salt, is placed in baking oven and is done
It is dry, obtain polyurethane-nano material composite diaphragm.
The urethane raw is one of polyurethane powder or polyurethane transparent particle.
The volatile organic solvent is one or both of N,N-dimethylformamide, tetrahydrofuran or acetone.
The soluble inorganic salt is one or both of sodium chloride, iron chloride or copper chloride.
The smooth vessel in the surface are glass plate, metal plate or plastic plate.
A kind of purposes of polyurethane-nano material composite diaphragm: battery diaphragm or capacitor diaphragm are used for.
The present invention be inorganic nano material is dispersed in the polyurethane precursor solution for having dissolved inorganic salts, and
Plastic film mulch on the smooth vessel in surface is formed a film using the characteristic that polyurethane meets water cure.It is mechanical due to polyurethane stable structure itself
It has excellent performance, adds the diaphragm of inorganic nano material preparation on its basis, not only remain its stable structure and mechanical performance
Excellent characteristic, and the performance of its hydrophilic and oleophilic and high-temperature stable is improved, improve the security performance of battery, inorganic nano
Material also all greatly improves the safety of battery there are also good chemical corrosion resistance, high voltage withstanding property and insulating properties.By
It is added to soluble inorganic salt in presoma, after removing inorganic salts, so that the porosity of diaphragm is higher, imbibition rate is higher.With
The prior art is compared, advantages of the present invention are as follows: first is that polyurethane/nano Material cladding method for manufacturing thin film is simple, prepares environment
Mild and preparation process is environmentally protective；Second is that the content of nano material can be filled with Effective Regulation, to solve its heat closing and resistance
The safety issues such as combustion；Third is that the present invention only needs compared with needing the method for special pore creating material and remover to prepare diaphragm
Common inorganic salt or solvent adding proportion, that is, its controllable porosity, and aperture is small, ion penetration with higher and
Electrochemical stability；Fourth is that energy storage can be effectively prevent to fill since the mechanical performance of polyurethane and nano material itself is more excellent
It sets short circuit and dendrite punctures.
Detailed description of the invention
Fig. 1 is the SEM scanning figure on composite diaphragm surface of the present invention.
Fig. 2 is the digital image of polyurethane-silica composite diaphragm of the present invention.
Fig. 3 is polyurethane of the present invention-graphene diaphragm digital image.
Fig. 4 is circulating effect figure of the composite diaphragm of the present invention in battery applications.
Fig. 5 is multiplying power effect picture of the composite diaphragm of the present invention in battery applications.
Fig. 6 is circulating effect figure of the composite diaphragm of the present invention in capacitor application.
Specific embodiment
As shown in Figure 1, Figure 2, Figure 3 shows, a kind of polyurethane-nano material composite diaphragm, the polyurethane/nano Material cladding
Diaphragm after nanomaterial-filled polyurethane solutions by solidifying.Polyurethane/nano Material cladding diaphragm with a thickness of 20~200
μm, porosity is 30%~80%.
The nano material is silica, titanium dioxide, zinc oxide or graphene inorganic nano material.
The nano material is one-dimensional, two-dimentional or three-dimensional nanometer material, having a size of 1~500nm.
Ratio shared by nano material is 0~80% in the polyurethane-nano material composite diaphragm.
A kind of preparation method of polyurethane-nano material composite diaphragm:
Embodiment 1
A takes 0.3g urethane raw to be dissolved in the mixed solution of 10mL N,N-dimethylformamide and 10mL tetrahydrofuran
In, gel presoma is made；
B adds 0.3g nanometer grade silica and 0.3g into gel presoma under the stirring condition of 300r/min
Iron chloride after the completion of addition, continues to stir 30min, obtains mixed solution；
C ultrasound 2h under conditions of frequency is 45KHz by obtained mixed solution, gets a uniform mixture；
D plastic film mulch on the smooth glass plate in surface by obtained homogeneous mixture solotion, later by glass plate uniformly slowly extremely
In deionized water, to urethane cures, removes composite membrane and be washed with deionized 5 times, remove iron chloride, be placed in later
It dries in baking oven to get polyurethane-nano silica composite diaphragm.
Embodiment 2
A takes 0.3g urethane raw to be dissolved in 20mL n,N-Dimethylformamide solution, and gel presoma is made；
B adds 0.3g nanometer grade silica and 0.3g into gel presoma under the stirring condition of 300r/min
Iron chloride after the completion of addition, continues to stir 30min, obtains mixed solution；
C ultrasound 2h under conditions of frequency is 45KHz by obtained mixed solution, gets a uniform mixture；
D plastic film mulch on the smooth glass plate in surface by obtained homogeneous mixture solotion, later by glass plate uniformly slowly extremely
In deionized water, to urethane cures, removes composite membrane and be washed with deionized 5 times, remove iron chloride, be placed in later
It dries in baking oven to get polyurethane-nano silica composite diaphragm.
Embodiment 3
A takes 0.3g urethane raw to be dissolved in 20mL tetrahydrofuran solution, and gel presoma is made；
B adds 0.3g nanometer grade silica and 0.3g into gel presoma under the stirring condition of 300r/min
Iron chloride after the completion of addition, continues to stir 30min, obtains mixed solution；
C ultrasound 2h under conditions of frequency is 45KHz by obtained mixed solution, gets a uniform mixture；
D plastic film mulch on the smooth glass plate in surface by obtained homogeneous mixture solotion, later by glass plate uniformly slowly extremely
In deionized water, to urethane cures, removes composite membrane and be washed with deionized 5 times, remove iron chloride, be placed in later
It dries in baking oven to get polyurethane-nano silica composite diaphragm.
Embodiment 4
A takes 0.3g urethane raw to be dissolved in the mixed solution of 10mL n,N-Dimethylformamide and 10mL acetone, system
Gelled presoma；
B adds 0.3g nanometer grade silica and 0.3g into gel presoma under the stirring condition of 300r/min
Iron chloride after the completion of addition, continues to stir 30min, obtains mixed solution；
C ultrasound 2h under conditions of frequency is 45KHz by obtained mixed solution, gets a uniform mixture；
D plastic film mulch on the smooth glass plate in surface by obtained homogeneous mixture solotion, later by glass plate uniformly slowly extremely
In deionized water, to urethane cures, removes composite membrane and be washed with deionized 5 times, remove iron chloride, be placed in later
It dries in baking oven to get polyurethane-nano silica composite diaphragm.
Embodiment 5
A takes 0.3g urethane raw to be dissolved in the mixed solution of 10mL acetone and 10mL tetrahydrofuran, and gel is made
Presoma；
B adds 0.3g nanometer grade silica and 0.3g into gel presoma under the stirring condition of 300r/min
Iron chloride after the completion of addition, continues to stir 30min, obtains mixed solution；
C ultrasound 2h under conditions of frequency is 45KHz by obtained mixed solution, gets a uniform mixture；
D plastic film mulch on the smooth glass plate in surface by obtained homogeneous mixture solotion, later by glass plate uniformly slowly extremely
In deionized water, to urethane cures, removes composite membrane and be washed with deionized 5 times, remove iron chloride, be placed in later
It dries in baking oven to get polyurethane-nano silica composite diaphragm.
Embodiment 6
A takes 0.3g urethane raw to be dissolved in 20mL acetone soln, and gel presoma is made；
B adds 0.3g nanometer grade silica and 0.3g into gel presoma under the stirring condition of 300r/min
Iron chloride after the completion of addition, continues to stir 30min, obtains mixed solution；
C ultrasound 2h under conditions of frequency is 45KHz by obtained mixed solution, gets a uniform mixture；
D plastic film mulch on the smooth glass plate in surface by obtained homogeneous mixture solotion, later by glass plate uniformly slowly extremely
In deionized water, to urethane cures, removes composite membrane and be washed with deionized 5 times, remove iron chloride, be placed in later
It dries in baking oven to get polyurethane-nano silica composite diaphragm.
Embodiment 7
A takes 0.3g urethane raw to be dissolved in the mixed solution of 10mL N,N-dimethylformamide and 10mL tetrahydrofuran
In, gel presoma is made；
B adds 0.3g Nano titanium dioxide and 0.3g into gel presoma under the stirring condition of 300r/min
Iron chloride after the completion of addition, continues to stir 30min, obtains mixed solution；
C ultrasound 2h under conditions of frequency is 45KHz by obtained mixed solution, gets a uniform mixture；
D plastic film mulch on the smooth glass plate in surface by obtained homogeneous mixture solotion, later by glass plate uniformly slowly extremely
In deionized water, to urethane cures, removes composite membrane and be washed with deionized 5 times, remove iron chloride, be placed in later
It dries in baking oven to get polyurethane-nano-titanium dioxide composite diaphragm.
Embodiment 8
A takes 0.3g urethane raw to be dissolved in the mixed solution of 10mL N,N-dimethylformamide and 10mL tetrahydrofuran
In, gel presoma is made；
B adds 0.3g Nano-class zinc oxide and 0.3g chlorine into gel presoma under the stirring condition of 300r/min
Change iron, after the completion of addition, continues to stir 30min, obtain mixed solution；
C ultrasound 2h under conditions of frequency is 45KHz by obtained mixed solution, gets a uniform mixture；
D plastic film mulch on the smooth glass plate in surface by obtained homogeneous mixture solotion, later by glass plate uniformly slowly extremely
In deionized water, to urethane cures, removes composite membrane and be washed with deionized 5 times, remove iron chloride, be placed in later
It dries in baking oven to get polyurethane-nano zine oxide composite diaphragm.
Embodiment 9
A takes 0.3g urethane raw to be dissolved in the mixed solution of 10mL N,N-dimethylformamide and 10mL tetrahydrofuran
In, gel presoma is made；
B adds 0.3g graphene and 0.3g iron chloride into gel presoma, adds under the stirring condition of 300r/min
After the completion of adding, continues to stir 30min, obtain mixed solution；
C ultrasound 2h under conditions of frequency is 45KHz by obtained mixed solution, gets a uniform mixture；
D plastic film mulch on the smooth glass plate in surface by obtained homogeneous mixture solotion, later by glass plate uniformly slowly extremely
In deionized water, to urethane cures, removes composite membrane and be washed with deionized 5 times, remove iron chloride, be placed in later
It dries in baking oven to get polyurethane-graphene composite diaphragm.
Embodiment 10
A takes 0.3g urethane raw to be dissolved in the mixed solution of 10mL N,N-dimethylformamide and 10mL tetrahydrofuran
In, gel presoma is made；
B adds 0.3g nanometer grade silica and 0.3g into gel presoma under the stirring condition of 300r/min
Sodium chloride after the completion of addition, continues to stir 30min, obtains mixed solution；
C ultrasound 2h under conditions of frequency is 45KHz by obtained mixed solution, gets a uniform mixture；
D plastic film mulch on the smooth glass plate in surface by obtained homogeneous mixture solotion, later by glass plate uniformly slowly extremely
In deionized water, to urethane cures, removes composite membrane and be washed with deionized 5 times, remove sodium chloride, be placed in later
It dries in baking oven to get polyurethane-nano silica composite diaphragm.
Embodiment 11
A takes 0.3g urethane raw to be dissolved in the mixed solution of 10mL N,N-dimethylformamide and 10mL tetrahydrofuran
In, gel presoma is made；
B adds 0.3g nanometer grade silica and 0.3g into gel presoma under the stirring condition of 300r/min
Copper chloride after the completion of addition, continues to stir 30min, obtains mixed solution；
C ultrasound 2h under conditions of frequency is 45KHz by obtained mixed solution, gets a uniform mixture；
D plastic film mulch on the smooth glass plate in surface by obtained homogeneous mixture solotion, later by glass plate uniformly slowly extremely
In deionized water, to urethane cures, removes composite membrane and be washed with deionized 5 times, remove copper chloride, be placed in later
It dries in baking oven to get polyurethane-nano silica composite diaphragm.
Embodiment 12
A takes 0.3g urethane raw to be dissolved in the mixed solution of 10mL N,N-dimethylformamide and 10mL tetrahydrofuran
In, gel presoma is made；
B adds 0.3g nanometer grade silica and 0.3g into gel presoma under the stirring condition of 300r/min
Iron chloride after the completion of addition, continues to stir 30min, obtains mixed solution；
C ultrasound 2h under conditions of frequency is 45KHz by obtained mixed solution, gets a uniform mixture；
D plastic film mulch on the smooth steel plate in surface by obtained homogeneous mixture solotion, later by steel plate uniformly slowly as going
In ionized water, to urethane cures, removes composite membrane and be washed with deionized 5 times, remove iron chloride, be placed in baking oven later
Middle drying is to get polyurethane-nano silica composite diaphragm.
Embodiment 13
A takes 0.3g urethane raw to be dissolved in the mixed solution of 10mL N,N-dimethylformamide and 10mL tetrahydrofuran
In, gel presoma is made；
B adds 0.3g nanometer grade silica and 0.3g into gel presoma under the stirring condition of 300r/min
Iron chloride after the completion of addition, continues to stir 30min, obtains mixed solution；
C ultrasound 2h under conditions of frequency is 45KHz by obtained mixed solution, gets a uniform mixture；
D plastic film mulch on the smooth aluminium sheet in surface by obtained homogeneous mixture solotion, later by aluminium sheet uniformly slowly as going
In ionized water, to urethane cures, removes composite membrane and be washed with deionized 5 times, remove iron chloride, be placed in baking oven later
Middle drying is to get polyurethane-nano silica composite diaphragm.
Embodiment 14
A takes 0.3g urethane raw to be dissolved in the mixed solution of 10mL N,N-dimethylformamide and 10mL tetrahydrofuran
In, gel presoma is made；
B adds 0.3g nanometer grade silica and 0.3g into gel presoma under the stirring condition of 300r/min
Iron chloride after the completion of addition, continues to stir 30min, obtains mixed solution；
C ultrasound 2h under conditions of frequency is 45KHz by obtained mixed solution, gets a uniform mixture；
D plastic film mulch on the smooth copper sheet in surface by obtained homogeneous mixture solotion, later by copper sheet uniformly slowly as going
In ionized water, to urethane cures, removes composite membrane and be washed with deionized 5 times, remove iron chloride, be placed in baking oven later
Middle drying is to get polyurethane-nano silica composite diaphragm.
Embodiment 15
A takes 0.3g urethane raw to be dissolved in the mixed solution of 10mL N,N-dimethylformamide and 10mL tetrahydrofuran
In, gel presoma is made；
B adds 0.3g nanometer grade silica and 0.3g into gel presoma under the stirring condition of 300r/min
Iron chloride after the completion of addition, continues to stir 30min, obtains mixed solution；
C ultrasound 2h under conditions of frequency is 45KHz by obtained mixed solution, gets a uniform mixture；
D plastic film mulch on the smooth polyfluortetraethylene plate in surface by obtained homogeneous mixture solotion, later by polytetrafluoroethylene (PTFE)
Plate uniformly slowly as in deionized water, to urethane cures, is removed composite membrane and is washed with deionized 5 times, remove chlorination
Iron is placed in baking oven later and dries to get polyurethane-nano silica composite diaphragm.
Embodiment 16
A takes 0.3g urethane raw to be dissolved in the mixed solution of 10mL N,N-dimethylformamide and 10mL tetrahydrofuran
In, gel presoma is made；
B adds 0.3g nanometer grade silica and 0.3g into gel presoma under the stirring condition of 300r/min
Iron chloride after the completion of addition, continues to stir 30min, obtains mixed solution；
C ultrasound 2h under conditions of frequency is 45KHz by obtained mixed solution, gets a uniform mixture；
D plastic film mulch on the smooth polypropylene board in surface by obtained homogeneous mixture solotion, later uniformly delays polypropylene board
Slowly it as in deionized water, to urethane cures, removes composite membrane and is washed with deionized 5 times, remove iron chloride, Zhi Houfang
It is placed in baking oven and dries to get polyurethane-nano silica composite diaphragm.
Embodiment 17
A takes 0.2g urethane raw to be dissolved in the mixed solution of 10mL N,N-dimethylformamide and 10mL tetrahydrofuran
In, gel presoma is made；
B adds 0.3g nanometer grade silica and 0.3g into gel presoma under the stirring condition of 300r/min
Iron chloride after the completion of addition, continues to stir 30min, obtains mixed solution；
C ultrasound 2h under conditions of frequency is 45KHz by obtained mixed solution, gets a uniform mixture；
D plastic film mulch on the smooth glass plate in surface by obtained homogeneous mixture solotion, later by glass plate uniformly slowly extremely
In deionized water, to urethane cures, removes composite membrane and be washed with deionized 5 times, remove iron chloride, be placed in later
It dries in baking oven to get polyurethane-nano silica composite diaphragm.
Embodiment 18
A takes 0.3g urethane raw to be dissolved in the mixed solution of 10mL N,N-dimethylformamide and 10mL tetrahydrofuran
In, gel presoma is made；
B adds 0.3g nanometer grade silica and 0.6g into gel presoma under the stirring condition of 300r/min
Iron chloride after the completion of addition, continues to stir 30min, obtains mixed solution；
C ultrasound 2h under conditions of frequency is 45KHz by obtained mixed solution, gets a uniform mixture；
D plastic film mulch on the smooth glass plate in surface by obtained homogeneous mixture solotion, later by glass plate uniformly slowly extremely
In deionized water, to urethane cures, removes composite membrane and be washed with deionized 5 times, remove iron chloride, be placed in later
It dries in baking oven to get polyurethane-nano silica composite diaphragm.
Embodiment 19
With LiFePO4It is positive and negative electrode, composite diaphragm and carga moral (Celgard) prepared by the present invention with lithium metal
The business diaphragm of company's production is as battery diaphragm, 1M LiPF6EC/EMC solution (mass ratio 1:1) be electrolyte assembling
Battery carries out charge-discharge test, and cycle performance is as shown in figure 4, high rate performance is as shown in Figure 5.Made using composite diaphragm of the present invention
For battery diaphragm, specific discharge capacity, cycle performance are superior to the business diaphragm of carga moral company production.
Embodiment 20
It is active material assembling electrode slice, composite diaphragm and commercial polypropylene microporous barrier prepared by the present invention with active carbon
As capacitor diaphragm, 1.5M NaOH solution is electrolyte group capacitor, carries out charge-discharge test, cycle performance such as Fig. 6 institute
Show.Using composite diaphragm of the present invention as battery diaphragm, capacity and cycle performance are superior to the microporous polypropylene membrane of business.
Claims (10)
1. a kind of polyurethane-nano material composite diaphragm, it is characterised in that: the polyurethane/nano Material cladding diaphragm is by receiving
It is solidified after rice material filled polyurethane solution；Polyurethane/nano Material cladding diaphragm with a thickness of 20~200 μm, hole
Rate is 30%~80%.
2. a kind of polyurethane-nano material composite diaphragm according to claim 1, it is characterised in that: the nano material
For silica, titanium dioxide, zinc oxide or graphene inorganic nano material.
3. a kind of polyurethane-nano material composite diaphragm according to claim 1 or 2, it is characterised in that: described inorganic to receive
Rice material is one-dimensional, two-dimentional or three-dimensional nanometer material, having a size of 1~500nm.
4. a kind of polyurethane-nano material composite diaphragm according to claim 1, it is characterised in that: the polyurethane-is received
Ratio shared by inorganic nano material is 0~80% in rice Material cladding diaphragm.
5. a kind of polyurethane-nano material composite diaphragm preparation method, it is characterised in that:
(a) take urethane raw to be dissolved in volatile organic solvent, gel presoma be made, wherein polyurethane with it is organic
The mass ratio of solvent is controlled in 1:60~1:5；
(b) under rapid stirring, inorganic nano material and soluble inorganic salt are added into gel presoma, are continued
30~60min is stirred, mixed solution is obtained, wherein the mass ratio control of soluble-salt urethane raw is in 0~1:1, stirring speed
Degree control is in 50~500r/min；
(c) by obtained mixed solution be ultrasonically treated 1~3h, get a uniform mixture, supersonic frequency control 45KHz~
80KHz；
(d) by obtained homogeneous mixture solotion on the smooth vessel in surface plastic film mulch, by vessel uniformly slowly as deionized water
In, after film-forming, removing is washed with deionized, and removes soluble inorganic salt, is placed in drying in baking oven, is obtained poly- ammonia
Ester-nano material composite diaphragm.
6. a kind of preparation method of polyurethane-nano material composite diaphragm according to claim 5, it is characterised in that: institute
Stating urethane raw is one of polyurethane powder or polyurethane transparent particle.
7. a kind of preparation method of polyurethane-nano material composite diaphragm according to claim 5, it is characterised in that: institute
Stating volatile organic solvent is one or both of N,N-dimethylformamide, tetrahydrofuran or acetone.
8. a kind of preparation method of polyurethane-nano material composite diaphragm according to claim 5, it is characterised in that: institute
Stating soluble inorganic salt is one or both of sodium chloride, iron chloride or copper chloride.
9. a kind of preparation method of polyurethane-nano material composite diaphragm according to claim 5, it is characterised in that: institute
The smooth vessel in the surface stated are glass plate, metal plate or plastic plate.
10. a kind of purposes of polyurethane-nano material composite diaphragm according to claim 1, it is characterised in that: for electricity
Pond diaphragm or capacitor diaphragm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810922771.4A CN109065816A (en) | 2018-08-14 | 2018-08-14 | A kind of polyurethane-nano material composite diaphragm and Preparation method and use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810922771.4A CN109065816A (en) | 2018-08-14 | 2018-08-14 | A kind of polyurethane-nano material composite diaphragm and Preparation method and use |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109065816A true CN109065816A (en) | 2018-12-21 |
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| CN109326821A (en) * | 2018-09-14 | 2019-02-12 | 湘潭大学 | A kind of nanometer-material-modified rubber-gel electrolyte film and Preparation method and use |
| CN109786624A (en) * | 2019-01-16 | 2019-05-21 | 北京卫蓝新能源科技有限公司 | A kind of preparation method and ion battery of ion battery porous septum |
| CN112076631A (en) * | 2019-06-14 | 2020-12-15 | 厦门大学 | Energy-saving anti-fouling graphene oxide/elastomer liquid composite membrane and application thereof |
| CN114447522A (en) * | 2021-12-30 | 2022-05-06 | 广东粤港澳大湾区黄埔材料研究院 | Polyurethane diaphragm and preparation method and application thereof |
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Application publication date: 20181221 |