CN105304849B - Compound many curved hole membrane material that aluminum nitride particle is filled and its preparation method and application - Google Patents
Compound many curved hole membrane material that aluminum nitride particle is filled and its preparation method and application Download PDFInfo
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- CN105304849B CN105304849B CN201510575921.5A CN201510575921A CN105304849B CN 105304849 B CN105304849 B CN 105304849B CN 201510575921 A CN201510575921 A CN 201510575921A CN 105304849 B CN105304849 B CN 105304849B
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- 239000000463 material Substances 0.000 title claims abstract description 54
- 239000012528 membrane Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 title claims description 85
- 150000001875 compounds Chemical class 0.000 title claims description 6
- 239000002245 particle Substances 0.000 title abstract description 7
- 239000004642 Polyimide Substances 0.000 claims abstract description 90
- 229920001721 polyimide Polymers 0.000 claims abstract description 90
- 239000002121 nanofiber Substances 0.000 claims abstract description 68
- 238000004519 manufacturing process Methods 0.000 claims abstract description 42
- 239000011148 porous material Substances 0.000 claims abstract description 16
- 239000000758 substrate Substances 0.000 claims abstract description 7
- 239000000725 suspension Substances 0.000 claims description 62
- 239000002105 nanoparticle Substances 0.000 claims description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- 239000004744 fabric Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 15
- 239000011230 binding agent Substances 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 13
- 238000010792 warming Methods 0.000 claims description 11
- 239000008187 granular material Substances 0.000 claims description 10
- 239000002270 dispersing agent Substances 0.000 claims description 9
- 229920000058 polyacrylate Polymers 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 230000008595 infiltration Effects 0.000 claims description 7
- 238000001764 infiltration Methods 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- BPOZNMOEPOHHSC-UHFFFAOYSA-N butyl prop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCCCOC(=O)C=C BPOZNMOEPOHHSC-UHFFFAOYSA-N 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 4
- 239000003814 drug Substances 0.000 claims description 4
- 229940079593 drug Drugs 0.000 claims description 4
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 claims description 3
- 238000003618 dip coating Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 2
- 239000002070 nanowire Substances 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 claims 2
- 230000001070 adhesive effect Effects 0.000 claims 2
- 239000003292 glue Substances 0.000 claims 1
- 230000004888 barrier function Effects 0.000 abstract description 22
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052744 lithium Inorganic materials 0.000 abstract description 5
- 229910052581 Si3N4 Inorganic materials 0.000 abstract description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 3
- 239000005543 nano-size silicon particle Substances 0.000 abstract description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 abstract description 3
- 239000010408 film Substances 0.000 description 46
- 238000001523 electrospinning Methods 0.000 description 15
- 230000015556 catabolic process Effects 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 8
- -1 AlN Compound Chemical class 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- 229920002125 Sokalan® Polymers 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000009940 knitting Methods 0.000 description 4
- 238000005457 optimization Methods 0.000 description 4
- 239000004584 polyacrylic acid Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- 239000003658 microfiber Substances 0.000 description 2
- 239000012716 precipitator Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000009941 weaving Methods 0.000 description 2
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- 229910017083 AlN Inorganic materials 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 230000035508 accumulation Effects 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000002498 deadly effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005596 polymer binder Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/44—Fibrous material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- 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
- H01M50/431—Inorganic material
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Materials Engineering (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Nonwoven Fabrics (AREA)
- Porous Artificial Stone Or Porous Ceramic Products (AREA)
Abstract
The invention discloses a kind of nano combined many curved hole membrane material, it as base material, is filled with nano silicon nitride alumina particles with polyimides (PI) nano-fiber for production of non-woven in substrate pores；Described nano silicon nitride alumina particles, its diameter, between 50 100nm, accounts for the 30 60% of nano combined many curved hole membrane material gross weight；Described PI nano-fiber for production of non-woven thickness is between 9 38 μm, and porosity is between 60 80%.Nano combined many curved hole membrane material that the present invention provides is high temperature resistant, heat resistanceheat resistant is shunk, high voltage withstanding and high rush of current, resistance to mechanical is clashed into, it is adapted for use as safety battery barrier film and safe diaphragm of supercapacitor, manufactures various high power capacity and high dynamic lithium battery or ultracapacitor.The present invention also provides for the preparation method of described nano combined many curved hole membrane material, and the application as battery diaphragm.
Description
Technical field
The invention belongs to battery diaphragm field, relate to a kind of porous film material, be specifically related to a kind of containing AlN
Compound many curved hole membrane material of nano-particle, and preparation method thereof and as the application of battery diaphragm.
Background technology
Lithium ion battery is developed rapidly as the electrokinetic cell of new-energy automobile, and will become the mankind can not
The articles for daily use lacked.But owing to currently used lithium battery diaphragm belongs to the TPO that heat resistance is poor
Porous film material, at relatively high temperatures, or crosses at over-charging of battery and puts and in the case of mechanical damage, lithium ion
The hidden danger that battery easily occurs smoldering, catches fire, even blast etc. jeopardizes user safety.Therefore, lithium is improved
The safety of ion battery is the key promoting lithium ion battery in field application such as automobile powers.
For the safety in utilization of lithium battery, people utilize the high-fire resistance of PI material, develop a kind of high hole
The electrospinning PI nanofiber battery diaphragm of gap rate.This high porosity PI nano fiber diaphragm is at 300 DEG C of high temperature
Under do not shrink, and have overcharging resisting cross put, the feature such as high rate capability and high cycle performance, make lithium-ion electric
The chemical property in pond is increased substantially.But, owing to this electro spinning nano fiber barrier film is a kind of
By the non-weaving cloth of fiber accumulations, there is too high porosity and excessive surface apertures, cause the lotus of battery
Electricity conservation rate is relatively low, micro-short circuit phenomenon often occurs, especially when battery diaphragm thickness is relatively low, as less than 30
Micron, the probability that this situation occurs is at a relatively high.Therefore, be highly desirable to create a kind of new have relatively low
Porosity and the high temperature resistant highly secure lithium ion battery barrier film of less surface apertures.
Summary of the invention
An object of the present invention is: provides a kind of and has compared with low porosity and the heatproof of less surface apertures
Many curved hole membrane material of high safety.
The two of the purpose of the present invention are: the method for the many curved hole membrane material described in offer preparation.
The three of the purpose of the present invention are: the application in battery diaphragm of the many curved hole membrane material described in offer.
The above-mentioned purpose of the present invention is achieved through the following technical solutions:
First, it is provided that a kind of nano combined many curved hole membrane material, it is with polyimides (PI) micro/nano-fibre non-woven
Cloth is base material, is filled with nano aluminum nitride (AlN) granule in substrate pores；Described nano-aluminum nitride granule, its
Diameter, between 50-100nm, accounts for the 30-60% of nano combined many curved hole membrane material gross weight；Described PI
Nano-fiber for production of non-woven thickness is between 9-38 μm, and porosity is between 60-80%.
In preferred embodiments of the present invention, described nano combined many curved hole membrane material porosity between 30-50%,
Surface average pore size is between 50-150nm, and thickness is between 10-40 μm.
Currently preferred nano combined many curved hole membrane material, described PI nano-fiber for production of non-woven is the most electric
The PI nano-fiber for production of non-woven spun.
Currently preferred nano combined many curved hole membrane material, preferably by receiving with the AlN containing 15-30%wt
The water based suspension of rice grain is coated or impregnated with PI nano-fiber for production of non-woven, makes suspension infiltration fill up PI
The hole of nano-fiber for production of non-woven, then dry prepared through 100-200 DEG C of high temperature.
Described water based suspension preferably further contain account for suspension gross weight 1.0%～5.0% binding agent,
Account for dispersant and the water of surplus of suspension gross weight 0.1%～1.0%；More preferably account for suspension gross weight 1.5～
The binding agent of 2.0%, the dispersant accounting for suspension gross weight 0.1%～0.3% and the water of surplus.
Described binding agent optimization polypropylene esters of gallic acid binding agent, the more preferably different monooctyl ester of butylacrylate-acrylic acid
Copolymer.
Described dispersant optimization polypropylene acid ammonium.
The absolute viscosity of described water based suspension is preferably 10～30mPa S, more preferably 18～28
mPa·S。
On this basis, the present invention also provides for a kind of method preparing described nano combined many curved hole membrane material,
It is with low viscosity AlN nano-particle water based suspension and PI nano-fiber for production of non-woven as raw material, passes through table
Topcoating applies infiltration or the method for dip coating infiltration, and AlN nano-particle is filled into PI nano-fiber for production of non-woven
Hole in, lower temperature dry after, be warming up to higher temperature make binding agent between AlN nano-particle and
Bond between granule and PI nanofiber.
The method of the nano combined many curved hole membrane material described in currently preferred preparation, specifically includes following step
Rapid:
1) preparation water based suspension:
By weight percentage, by the AlN nano-particle of 15-30%, the dispersant of 0.1%-1.0%, 1.0-5.0%
Binding agent and the water of surplus be mixed to get mixed liquor, by mixed liquor 8000-10000 turn/rotating speed of min under
Emulsifying, forms the absolute viscosity water based suspension at 10-30mPa S；
2) nano-particle is filled:
By step 1) water based suspension prepared paves the certain thickness suspension liquid and membrane of formation, so on horizontal plate
After by PI nano-fiber for production of non-woven cover in described suspension liquid and membrane, it is non-that suspension infilters PI nanofiber
In woven cloths, treat that nano-fiber cloth upper strata drenches, uncover PI nano-fiber for production of non-woven；
3) it is dried molding bonded
By step 2) the PI nano-fiber for production of non-woven that obtains first baking the affected part after applying some drugs 8～12min at 80～100 DEG C,
It is warming up to 160～200 DEG C of heat treatments 3～6min again, makes between AlN nano-particle and they and PI Nanowire
Because of the melted and well-bonded formation of binding agent nano combined many curved hole membrane material of the present invention between dimension.
In the method for the nano combined many curved hole membrane material described in currently preferred preparation, step 1) described in
AlN nano-particle accounts for the 15-21% of water based suspension weight.
In the method for the nano combined many curved hole membrane material described in currently preferred preparation, step 1) described in
Binding agent optimization polypropylene acid esters, more preferably butylacrylate-acrylic acid different monooctyl ester copolymer；Described dispersion
Agent optimization polypropylene acid ammonium.
In the method for the nano combined many curved hole membrane material described in currently preferred preparation, step 1) described in
Water based suspension absolute viscosity is preferably at 18～28mPa S.
In the method for the nano combined many curved hole membrane material described in currently preferred preparation, step 2) described in
The electrospinning that the preferred thickness of PI nano-fiber for production of non-woven is between 9-38 μm, porosity is between 60-80%
PI nano-fiber for production of non-woven.
In the method for the nano combined many curved hole membrane material described in currently preferred preparation, step 3) preferably will
Step 2) the PI nano-fiber for production of non-woven that obtains first baking the affected part after applying some drugs 10min at 100 DEG C, then be warming up to
160-200 DEG C of heat treatment 3-5min.
It is non-less than PI nanofiber that the present invention utilizes aluminum nitride nanometer granule to have high temperature resistant, high rigidity and diameter
The characteristics such as the surface apertures of woven cloths, are filled with in the hole of PI nano-fiber for production of non-woven, reduce PI
The porosity of nano-fiber for production of non-woven and reduce its surface apertures, improve the electric breakdown strength of barrier film, improvement
The spray charging precipitator of battery and the short circuit phenomenon stopping battery；Improve the performance that battery diaphragm heat resistanceheat resistant is shunk simultaneously.
The preparation method of the present invention is with low viscosity nano-aluminum nitride water based suspension and electrospinning PI micro/nano-fibre non-woven
Cloth is raw material, by surface coating infiltration or the method for dip coating infiltration, is filled into by AlN nano-particle
In the hole of PI nano-fiber for production of non-woven, after lower temperature is dried, it is warming up to higher temperature and makes polypropylene
Acid esters binding agent carries out bonding between AlN nano-particle and between AlN granule and PI nanofiber and forms more aperture
Many curved hole membrane structure that the organic/inorganic nano of gap is compound.In the structure of gained film product, PI nanofiber is non-
Nanofiber Network structure for support effect in woven cloths, AlN nano-particle plays filling and constructs nano-pore
The effect of gap, thus give this organic/inorganic nano be combined many curved hole membrane material have good pore structure,
The characteristics such as surface apertures is little, duct is tortuous, electric breakdown strength is high, high-fire resistance energy and very good mechanical properties,
Overcome the too high porosity of simple electrospinning PI nano-fiber for production of non-woven, excessive surface apertures and electric shock
Wear the deadly defect as safety battery barrier film such as low strength.Therefore, many curved hole film of the present invention is a kind of
It is very suitable as the membrane material of high temperature resistant high safety battery barrier film.
When the nano-particle of Selective filling, present inventors studied the usage ratio of AlN nano-particle for
The impact of material property, have been found that AlN nano-particle consumption in water based suspension less than 15%, then
Being difficult to effectively fill the hole of PI fiber non-woven, the spray charging precipitator causing battery is relatively low, easily occurs
Micro-short circuit phenomenon；And if AlN nano-particle consumption is higher than 30%, then granule dispersion is made to become difficulty,
Hinder filling effect, it is difficult to realize the pore structure that surface apertures is little, duct is tortuous, eventually pass through a large amount of
Experiment obtain the optimum amount scope of AlN nano-particle, make the overall performance of compound many curved hole membrane material
It is issued to optimum in described optimum proportioning scope.When selecting binding agent and dispersant, the present inventor needs root
Carry out multifactor in multiple binding agent and dispersant according to the characteristic of AlN nano-particle and the needs of fill process
Comprehensive screening, finally found that: polyacrylate binding agent, especially butylacrylate-acrylic acid are different pungent
Ester copolymer, it is possible to provide just right viscosity for composite aqueous suspension, for further applying infiltration
Preferable basis is provided with granule bonding；The addition of ammonium polyacrylate relatively other dispersants are easier in nanometer
Electric double layer is formed, it is possible to the dispersion to ultrafine particle plays a significant role, and can reduce on particle surface
Slurry viscosity, prevent particle agglomeration, make organic and inorganic nanoparticles dispersion in water based suspension reach
Ideal state.Additionally, the preparation method that the present invention provides compares doctor blade process of the prior art
It is more suitable for industrialized production.
Finally, the AlN of the present invention nano combined many curved hole membrane material obtains following characteristic: thickness is at 10-40
Between μm, porosity between 30-50%, surface apertures between 50-300nm, hot strength is 35～50
Between MPa, heat shrink temperature more than 350 DEG C, electric breakdown strength is between 35-50V/ μm, ionic conductance
Rate is in 1.0-8.0 × 10-3S·cm-1Between.The nano composite membrane with this characteristic is high temperature resistant, heat resistanceheat resistant is shunk,
High voltage withstanding and high rush of current, resistance to mechanical is clashed into, and is adapted for use as safety battery barrier film and the super electricity of safety
Container barrier film, manufactures various high power capacity and high dynamic lithium battery or ultracapacitor.
The present invention also provides for the described nano combined many curved hole membrane material electricity as rechargeable nonaqueous electrolytic battery
Pond barrier film or the application of capacitor diaphragm.
Detailed description of the invention
Following example will assist in those of ordinary skill in the art and are further appreciated by the present invention, but not to appoint
What form limits the present invention.
Embodiment 1:
A kind of composite film material containing AlN nano-particle, it is knitted so that electrospinning polyimides (PI) nanofiber is non-
Making cloth is base material, is filled with AlN nano-particle (AlN-NP) in substrate pores；
Its preparation method is as follows:
(1) nano aluminum nitride powder water based suspension (AlN/H2O-1) configuration: nano aluminum nitride powder
(diameter is mainly distributed on 30nm) 80.0 grams, polyacrylic acid 1.0 grams, butyl polyacrylate-different monooctyl ester
8.0 grams, distilled water 300.0 grams, disposably put in beaker, emulsified at the rotating speed of 8000 turns per minute,
Form nano aluminum nitride powder water based suspension (the AlN AlN/H that absolute viscosity is 28mPa S2O-1)。
(2) preparation of the nano combined high temperature resistant high safety battery barrier film of AlN/PI: the AlN that will be configured above
/H2O-1 nano aluminum nitride powder water based suspension is paved on a glass and is formed the suspension that thickness is 30 μm
Film, then covers the electrospinning PI nano-fiber for production of non-woven that thickness is 9 μm at AlN/H2O-1 suspension
On film, suspension infilters in PI nano-fiber for production of non-woven, treats that nano-fiber cloth upper strata drenches, shows non-knitting
Make and the hole of cloth has been fully filled with suspension, uncover PI nano-fiber for production of non-woven, heat at 100 DEG C
Dry 10min, be warming up to 160 DEG C of heat treatment 5min, make between AlN nano-particle and nano-particle and PI nanometer
By organic/inorganic nano combined many curved hole film of the melted and well-bonded formation of polyacrylate between fiber.
(3) performance characterization: the thickness of the nano combined high temperature resistant high safety battery barrier film of prepared AlN/PI
Be 10 μm, hot strength be 50MPa, elongation at break be 50%, puncture strength be 6.0N, at 350 DEG C
Under percent thermal shrinkage be 0, the porosity of many curved hole film be 30%, surface average pore size be 55nm, 0.24
Breathability under bar pressure is 120S, electric breakdown strength is 50V/ μm, and ionic conductivity is 1.0 × 10-3
S·cm-1。
Embodiment 2:
A kind of composite film material containing AlN nano-particle, it is knitted so that electrospinning polyimides (PI) nanofiber is non-
Making cloth is base material, is filled with AlN nano-particle (AlN-NP) in substrate pores；
Its preparation method is as follows:
(1) AlN water based suspension (AlN/H2O-2) configuration: (diameter is main for nano aluminum nitride powder
It is distributed in 100nm) 80.0 grams, polyacrylic acid 0.5 gram, butyl polyacrylate-different monooctyl ester 8.0 grams, steams
Distilled water 433.0 grams, disposably puts in beaker, emulsified at the rotating speed of 8000 turns per minute, is formed definitely
Viscosity is the crosslinked polystyrene Nano microsphere water based suspension (AlN/H of 18mPa S2O-2)。
(2) preparation of the nano combined high temperature resistant high safety battery barrier film of AlN/PI: the AlN that will be configured above
/H2O-2 nano silicon nitride alumina particles water based suspension is paved on a glass and is formed the suspension that thickness is 60 μm
Film, then covers the electrospinning PI nano-fiber for production of non-woven that thickness is 38 μm at AlN/H2O-2 suspension
On film, suspension infilters in PI nano-fiber for production of non-woven, treats that nano-fiber cloth upper strata drenches, shows non-knitting
Make and the hole of cloth has been fully filled with suspension, uncover PI nano-fiber for production of non-woven, heat at 100 DEG C
Dry 10min, be warming up to 200 DEG C of heat treatment 3min, make between AlN nano-particle and nano-particle and PI nanometer
By organic/inorganic nano combined many curved hole film of the melted and well-bonded formation of polyacrylate between fiber.
(3) performance characterization: the nano combined high temperature resistant high safety battery of prepared AlN/PI every film thickness
Be 40 μm, hot strength be 35MPa, elongation at break be 30%, puncture strength be 12N, at 350 DEG C
Under percent thermal shrinkage be 0, the porosity of many curved hole film be 50%, surface average pore size be 150nm, 0.12
Breathability under bar pressure is 125S, electric breakdown strength is 35V/ μm, ionic conductivity is 8.0 × 10-3
S·cm-1。
Embodiment 3:
A kind of composite film material containing AlN nano-particle, it is knitted so that electrospinning polyimides (PI) nanofiber is non-
Making cloth is base material, is filled with AlN nano-particle (AlN-NP) in substrate pores；
Its preparation method is as follows:
(1) nano-aluminum nitride water based suspension (AlN/H2O-3) configuration: nano aluminum nitride powder (diameter
It is mainly distributed on 50nm) 80.0 grams, polyacrylic acid 0.8 gram, butyl polyacrylate-different monooctyl ester 8.0 grams,
Distilled water 300.0 grams, disposably puts in beaker, emulsified at the rotating speed of 8000 turns per minute, is formed absolutely
Nano aluminum nitride powder water based suspension (AlN/H poly-to the crosslinking that viscosity is 24mPa S2O-3)。
(2) preparation of the nano combined high temperature resistant high safety battery barrier film of AlN/PI: the AlN that will be configured above
/H2O-3 nano aluminum nitride powder water based suspension is paved on a glass and is formed the suspension that thickness is 50 μm
Film, then covers the electrospinning PI nano-fiber for production of non-woven that thickness is 24 μm at AlN/H2O-3 suspension
On film, suspension infilters in PI nano-fiber for production of non-woven, treats that nano-fiber cloth upper strata drenches, shows non-knitting
Make and the hole of cloth has been fully filled with suspension, uncover PI nano-fiber for production of non-woven, heat at 100 DEG C
Dry 10min, be warming up to 200 DEG C of heat treatment 3min, make between AlN nano-particle and nano-particle and PI nanometer
By organic/inorganic nano combined many curved hole film of the melted and well-bonded formation of polyacrylate between fiber.
(3) performance characterization: the nano combined high temperature resistant high safety battery of prepared AlN/PI every film thickness
Be 25 μm, hot strength be 47MPa, elongation at break be 38%, puncture strength be 10.0N, at 350 DEG C
Under percent thermal shrinkage be 0, the porosity of perforated membrane be 48%, surface average pore size be 70nm, at 0.24bar
Breathability under pressure is 65S, electric breakdown strength is 45V/ μm, ionic conductivity is 3.0 × 10-3S·cm-1。
Embodiment 4:
A kind of composite film material containing AlN nano-particle, it is knitted so that electrospinning polyimides (PI) nanofiber is non-
Making cloth is base material, is filled with AlN nano-particle (AlN-NP) in substrate pores；
Its preparation method is as follows:
(1) AlN water based suspension (AlN/H2O-4) configuration: (diameter mainly divides nano aluminum nitride powder
Cloth is at 80nm) 80.0 grams, polyacrylic acid 0.6 gram, butyl polyacrylate-different monooctyl ester 8.0 grams, distilled water
433.0 grams, disposably put in beaker, emulsified at the rotating speed of 8000 turns per minute, form absolute viscosity
Nano aluminium nitride powder water based suspension (AlN/H for 20mPa S2O-4)。
(2) preparation of the nano combined high temperature resistant high safety battery barrier film of AlN/PI: the AlN that will be configured above
/H2O-4 nano aluminum nitride powder water based suspension is paved on a glass and is formed the suspension that thickness is 30 μm
Film, then covers the electrospinning PI nano-fiber for production of non-woven that thickness is 14 μm at AlN/H2O-4 suspension
On film, suspension infilters in PI nano-fiber for production of non-woven, treats that nano-fiber cloth upper strata drenches, shows non-knitting
Make and the hole of cloth has been fully filled with suspension, uncover PI nano-fiber for production of non-woven, heat at 100 DEG C
Dry 10min, be warming up to 200 DEG C of heat treatment 5min, make between AlN nano-particle and nano-particle and PI nanometer
By organic/inorganic nano combined many curved hole film of the melted and well-bonded formation of polyacrylate between fiber.
(3) performance characterization: the thickness of the nano combined high temperature resistant high safety battery barrier film of prepared AlN/PI
Be 15 μm, hot strength be 48MPa, elongation at break be 42%, puncture strength be 7.3N, at 350 DEG C
Under percent thermal shrinkage be 0, the porosity of perforated membrane be 45%, surface average pore size be 120nm, at 0.12bar
Breathability under pressure is 160S, electric breakdown strength is 48V/ μm, ionic conductivity is 7.4 × 10-3S·cm-1。
Above experiment material and result test description of equipment:
(1) experiment material:
In 4 experiment embodiments of the present invention use inorganic micro-nano powder, PI nano-fiber for production of non-woven,
Macromolecule dispersing agent and polymer binder etc. are all commercially available by commercial channel.
1) nano aluminum nitride powder, purchased from Beijing Deco Dao Jin Science and Technology Ltd.；
2) electrospinning polyimide nano-fiber non-weaving cloth, is produced by Jiangxi Xiancai Nano Fiber Technology Co., Ltd.；
3) ammonium polyacrylate, purchased from Shandong Zibo capital and dye chemical industry company limited；
(2) experimental result test and sign
In the present invention experimental result of 4 experiment embodiments be tested routinely by following instrument and equipment and
Characterize.
1) polymer solution and spinning liquid absolute viscosity are with NDJ-8S viscometer (Shanghai precision scientific instrument company)
Measure；
2) diameter of electro spinning nano fiber is with scanning electron microscope VEGA 3 SBU (Czech Republic)
Measure；
3) the heat decomposition temperature WRT-3P thermal weight loss of the nano combined high temperature resistant high safety battery barrier film of AlN/PI
Analyser (TGA) (Shanghai Precision Scientific Apparatus Co., Ltd) measures；
4) engineering properties (intensity, extension at break etc.) of the nano combined high temperature resistant high safety battery barrier film of AlN/PI
Measure with CMT8102 miniature control electronic universal tester (Shenzhen SANS material tests company limited)；
5) vitrification point of the nano combined high temperature resistant high safety battery barrier film of AlN/PI is to use Diamond to move
State mechanical analyzer (DMA) (Perkin-Elmer, the U.S.) measures；
6) porosity of the nano combined high temperature resistant high safety battery barrier film of AlN/PI is to be calculated by following formula
Arrive:
Porosity β=[1-(ρ/ρ o)] × 100
Wherein ρ be AlN/PI nano compound stephanoporate film density (gram/cm3), ρ o is the nano combined reality of AlN/PI
The density of body thin film (being prepared by solution casting method) (gram/cm3)；
7) breathability and the surface apertures of the nano combined high temperature resistant high safety battery barrier film of AlN/PI is to use the U.S.
Porometer 3G air permeability tester measure；
8) ionic conductivity of the nano combined high temperature resistant high safety battery barrier film of AlN/PI is to use electrochemical operation
The CHI 660D (morning China's instrument, Chinese Shanghai) that stands measures；
9) electric breakdown strength of the nano combined high temperature resistant high safety battery barrier film of AlN/PI is beautiful electrically with Shanghai henry
The ZHZ8 type Hi-pot Tester of company limited measures.
Claims (5)
1. nano combined many curved hole membrane material, it is characterised in that: it is non-with polyimides (PI) nanofiber
Woven cloths is base material, is filled with nano aluminum nitride (AlN) granule in substrate pores；Described nano-aluminum nitride granule,
Its diameter, between 50-100nm, accounts for the 30-60% of nano combined many curved hole membrane material gross weight；Described
PI nano-fiber for production of non-woven thickness is between 9-38 μm, and porosity is between 60-80%；Described nanometer
Compound many curved hole membrane material is by impregnating PI with the water based suspension of the AlN nano-particle containing 15-30%wt
Nano-fiber for production of non-woven, makes suspension infiltration fill up the hole of PI nano-fiber for production of non-woven, then warp
100-200 DEG C of high temperature is dried and is prepared；Described water based suspension contain further account for suspension gross weight 1.0%～
The butylacrylate-acrylic acid different monooctyl ester copolymer adhesive of 5.0%, account for suspension gross weight 0.1%～1.0%
Ammonium polyacrylate dispersant and the water of surplus；The absolute viscosity of described water based suspension is 10～30mPa S.
2. the material described in claim 1, it is characterised in that: described nano combined many curved hole membrane material,
Its porosity between 30-50%, surface average pore size between 50-150nm, thickness 10-40 μm it
Between.
3. the material described in claim 1, it is characterised in that: the absolute viscosity of described water based suspension is
18～28mPa S.
4. the method preparing nano combined many curved hole membrane material described in claim 1, is with low viscosity
AlN nano-particle water based suspension and PI nano-fiber for production of non-woven are raw material, are permeated by dip coating
Method, AlN nano-particle is filled in the hole of PI nano-fiber for production of non-woven, lower temperature dry
After, it is warming up to higher temperature and makes binding agent glue between AlN nano-particle and between granule and PI nanofiber
Close；Specifically include following steps:
1) preparation water based suspension:
By weight percentage, the AlN nano-particle of 15-30%, the ammonium polyacrylate of 0.1%-1.0% are divided
The water of powder, the butylacrylate-acrylic acid different monooctyl ester copolymer adhesive of 1.0-5.0% and surplus is mixed to get
Mixed liquor, by mixed liquor 8000-10000 turn/rotating speed of min is emulsified, forms absolute viscosity at 10-30
The water based suspension of mPa S；
2) nano-particle is filled:
By step 1) water based suspension prepared paves the certain thickness suspension liquid and membrane of formation, so on horizontal plate
After by PI nano-fiber for production of non-woven cover in described suspension liquid and membrane, it is non-that suspension infilters PI nanofiber
In woven cloths, treat that nano-fiber cloth upper strata drenches, uncover PI nano-fiber for production of non-woven；
3) it is dried molding bonded
By step 2) the PI nano-fiber for production of non-woven that obtains first baking the affected part after applying some drugs 8～12min at 80～100 DEG C,
It is warming up to 160～200 DEG C of heat treatments 3～6min again, makes between AlN nano-particle and they and PI Nanowire
Because of the nano combined many curved hole membrane material described in the melted and well-bonded formation of binding agent between dimension.
5. the method described in claim 4, it is characterised in that: step 3) be by step 2) PI that obtains
Nano-fiber for production of non-woven first baking the affected part after applying some drugs 10min at 100 DEG C, then it is warming up to 160-200 DEG C of heat treatment 3-5min.
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