CN105304849A - Aluminum nitride particle-filled composite multi-arc-hole membrane material as well as preparation method and application thereof - Google Patents
Aluminum nitride particle-filled composite multi-arc-hole membrane material as well as preparation method and application thereof Download PDFInfo
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- CN105304849A CN105304849A CN201510575921.5A CN201510575921A CN105304849A CN 105304849 A CN105304849 A CN 105304849A CN 201510575921 A CN201510575921 A CN 201510575921A CN 105304849 A CN105304849 A CN 105304849A
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- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 title claims abstract description 87
- 239000000463 material Substances 0.000 title claims abstract description 58
- 239000012528 membrane Substances 0.000 title claims abstract description 50
- 239000002245 particle Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 239000002131 composite material Substances 0.000 title description 7
- 239000004642 Polyimide Substances 0.000 claims abstract description 91
- 229920001721 polyimide Polymers 0.000 claims abstract description 91
- 239000002121 nanofiber Substances 0.000 claims abstract description 75
- 238000004519 manufacturing process Methods 0.000 claims abstract description 52
- 239000011148 porous material Substances 0.000 claims abstract description 16
- 239000000725 suspension Substances 0.000 claims description 60
- 239000002105 nanoparticle Substances 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- 239000000853 adhesive Substances 0.000 claims description 18
- 230000001070 adhesive effect Effects 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 229920000058 polyacrylate Polymers 0.000 claims description 15
- 239000002270 dispersing agent Substances 0.000 claims description 13
- 239000004744 fabric Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 238000010792 warming Methods 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 239000000758 substrate Substances 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
- 229920001577 copolymer Polymers 0.000 claims description 5
- 238000011049 filling Methods 0.000 claims description 5
- 230000008595 infiltration Effects 0.000 claims description 4
- 238000001764 infiltration Methods 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
- 206010020843 Hyperthermia Diseases 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 230000036031 hyperthermia Effects 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 239000012466 permeate Substances 0.000 claims description 2
- 239000002114 nanocomposite Substances 0.000 abstract description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052744 lithium Inorganic materials 0.000 abstract description 4
- 239000004745 nonwoven fabric Substances 0.000 abstract 3
- 230000035939 shock Effects 0.000 abstract 1
- 230000004888 barrier function Effects 0.000 description 19
- 238000001523 electrospinning Methods 0.000 description 16
- 239000000843 powder Substances 0.000 description 12
- 230000015556 catabolic process Effects 0.000 description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 230000035699 permeability Effects 0.000 description 6
- 238000009941 weaving Methods 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 239000004743 Polypropylene 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
- 239000012153 distilled water Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000005457 optimization Methods 0.000 description 4
- -1 polypropylene Polymers 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000012716 precipitator Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000835 fiber Substances 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
- 230000008569 process Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910017083 AlN Inorganic materials 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000005266 casting 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
- 229940074391 gallic acid Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 239000011858 nanopowder Substances 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
- 239000000047 product Substances 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 238000004017 vitrification Methods 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
- H01M50/44—Fibrous 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
- H01M50/411—Organic 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 nanocomposite multi-arc-hole membrane material which takes polyimide (PI) nanofiber nonwoven fabric as a base material, wherein pores of the base material are filled with nano aluminum nitride particles; the diameters of the nano aluminum nitride particles are between 5nnm and 100nm; the nano aluminum nitride particles account for 30 to 60 percent of total weight of the nanocomposite multi-arc-hole membrane material; the thickness of the PI nanofiber nonwoven fabric is between 9 micrometers and 38 micrometers, and the porosity of the PI nanofiber nonwoven fabric is between 60 percent and 80 percent. The nanocomposite multi-arc-hole membrane material provided by the invention has the advantages of high temperature resistance, thermal shrinkage resistance, high voltage resistance, high current shock resistance and mechanical impact resistance, and is suitable for being used as a safe battery diaphragm and a safe supercapacitor diaphragm and for manufacturing various high-capacity and high-power lithium batteries or supercapacitors. The invention also provides a preparation method of the nanocomposite multi-arc-hole membrane material and application of the nanocomposite multi-arc-hole membrane material serving as a 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 compound many curved hole membrane material containing AlN nano particle, and preparation method thereof and as the application of battery diaphragm.
Background technology
Lithium ion battery obtains as the electrokinetic cell of new-energy automobile and develops rapidly, will become the indispensable daily necessities of the mankind.But because the lithium battery diaphragm used at present belongs to the poor TPO porous film material of heat resistance, at relatively high temperatures, or when over-charging of battery cross put and mechanical damage, the hidden danger that smoldering easily appears in lithium ion battery, catch fire, even blast etc. jeopardizes user's safety.Therefore, the key of lithium ion battery in field application such as automobile powers is promoted in the fail safe improving lithium ion battery.
For the safety in utilization of lithium battery, people utilize the high-fire resistance of PI material, develop a kind of electrospinning PI nanofiber battery diaphragm of high porosity.This high porosity PI nano fiber diaphragm does not shrink under 300 DEG C of high temperature, and have overcharging resisting cross put, the feature such as high rate capability and high cycle performance, the chemical property of lithium ion battery is obtained and increases substantially.But, because this electro spinning nano fiber barrier film is a kind of non-weaving cloth by fiber accumulations, there is too high porosity and excessive surface apertures, cause the spray charging precipitator of battery lower, often there is micro-short circuit phenomenon, especially when battery diaphragm thickness is lower, as lower than 30 microns, the probability that this situation occurs is quite high.Therefore, be necessary very much to create a kind of high temperature resistant highly secure lithium ion battery barrier film had compared with low porosity and less surface apertures newly.
Summary of the invention
An object of the present invention is: provide a kind of high safe many curved hole membrane material of heatproof had compared with low porosity and less surface apertures.
Two of object of the present invention is: the method providing the many curved hole membrane material described in preparation.
Three of object of the present invention is: provide the described application of many curved hole membrane material in battery diaphragm.
Above-mentioned purpose of the present invention is achieved through the following technical solutions:
First, provide a kind of nano combined many curved hole membrane material, it for base material, is filled with nano aluminum nitride (AlN) particle with polyimides (PI) nano-fiber for production of non-woven in substrate pores; Described nano-aluminum nitride particle, its diameter, between 50-100nm, accounts for the 30-60% of nano combined many curved hole membrane material total 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 is between 30-50%, and surperficial average pore size is between 50-150nm, and thickness is between 10-40 μm.
The preferred nano combined many curved hole membrane material of the present invention, the PI nano-fiber for production of non-woven of the described preferred electrospinning of PI nano-fiber for production of non-woven.
The preferred nano combined many curved hole membrane material of the present invention, preferably by being coated with the water based suspension of the AlN nano particle containing 15-30%wt or dipping PI nano-fiber for production of non-woven, make suspension permeate the hole filling up PI nano-fiber for production of non-woven, then obtain through 100-200 DEG C of hyperthermia drying.
Described water based suspension preferably further containing account for suspension total weight 1.0% ~ 5.0% adhesive, account for the dispersant of suspension total weight 0.1% ~ 1.0% and the water of surplus; More preferably account for the adhesive of suspension total weight 1.5 ~ 2.0%, account for the dispersant of suspension total weight 0.1% ~ 0.3% and the water of surplus.
Described adhesive optimization polypropylene esters of gallic acid adhesive, the more preferably different monooctyl ester copolymer of butylacrylate-acrylic acid.
Described dispersant optimization polypropylene acid ammonium.
The absolute viscosity of described water based suspension is preferably 10 ~ 30mPaS, is more preferably 18 ~ 28mPaS.
On this basis, the present invention also provides a kind of method preparing described nano combined many curved hole membrane material, for raw material with low viscosity AlN nano particle water based suspension and PI nano-fiber for production of non-woven, permeated by surface application or dip coating infiltration method, AlN nano particle is filled in the hole of PI nano-fiber for production of non-woven, after lower temperature is dried, be warming up to higher temperature and adhesive is bonded between AlN nano particle and between particle and PI nanofiber.
The present invention preferably prepares the method for described nano combined many curved hole membrane material, specifically comprises the following steps:
1) water based suspension is prepared:
By weight percentage, the water of the AlN nano particle of 15-30%, the dispersant of 0.1%-1.0%, the 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 the water based suspension of absolute viscosity at 10-30mPaS;
2) nano particle is filled:
By step 1) water based suspension prepared paves and forms certain thickness suspension liquid and membrane on level board, then PI nano-fiber for production of non-woven is covered in described suspension liquid and membrane, suspension infilters in PI nano-fiber for production of non-woven, treat that nano-fiber cloth upper strata drenches, uncover PI nano-fiber for production of non-woven;
3) dry molding bonded
By step 2) the PI nano-fiber for production of non-woven that obtains first at 80 ~ 100 DEG C heat dry 8 ~ 12min, be warming up to 160 ~ 200 DEG C of heat treatment 3 ~ 6min again, to make between AlN nano particle and between they and PI nanofiber because of the melting of adhesive well-bonded formation nano combined many curved hole membrane material of the present invention.
The present invention preferably prepares in the method for described nano combined many curved hole membrane material, step 1) described in AlN nano particle account for the 15-21% of water based suspension weight.
The present invention preferably prepares in the method for described nano combined many curved hole membrane material, step 1) described in adhesive optimization polypropylene acid esters, the more preferably different monooctyl ester copolymer of butylacrylate-acrylic acid; Described dispersant optimization polypropylene acid ammonium.
The present invention preferably prepares in the method for described nano combined many curved hole membrane material, step 1) described in water based suspension absolute viscosity preferably at 18 ~ 28mPaS.
The present invention preferably prepares in the method for described nano combined many curved hole membrane material, step 2) described in the preferred thickness of PI nano-fiber for production of non-woven between 9-38 μm, the electrospinning PI nano-fiber for production of non-woven of porosity between 60-80%.
The present invention preferably prepares in the method for described nano combined many curved hole membrane material, step 3) preferably by step 2) the PI nano-fiber for production of non-woven that obtains first at 100 DEG C heat dry 10min, then be warming up to 160-200 DEG C of heat treatment 3-5min.
The present invention utilizes aluminum nitride nanometer particle to have high temperature resistant, high rigidity and diameter is less than the characteristics such as the surface apertures of PI nano-fiber for production of non-woven, be filled in the hole of PI nano-fiber for production of non-woven, reduce the porosity of PI nano-fiber for production of non-woven and reduce its surface apertures, improve the electric breakdown strength of barrier film, improve the spray charging precipitator of battery and stop the short circuit phenomenon of battery; Improve the performance that battery diaphragm heat resistanceheat resistant is shunk simultaneously.
Preparation method of the present invention with low viscosity nano-aluminum nitride water based suspension and electrospinning PI nano-fiber for production of non-woven for raw material, permeated by surface application or dip coating infiltration method, AlN nano particle is filled in the hole of PI nano-fiber for production of non-woven, after lower temperature is dried, be warming up to higher temperature and make palyacrylate binder between AlN nano particle and between AlN particle and PI nanofiber, carry out bonding many curved hole membrane structure of the organic/inorganic nano compound forming more fine pore.In the structure of gained film product, nanofiber network structure for support effect in PI nano-fiber for production of non-woven, AlN nano particle plays a part fill and construct nanoaperture, thus give that this organic/inorganic nano compound many curved hole membrane material has good pore structure, surface apertures is little, duct is tortuous, electric breakdown strength is high, the characteristic such as 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 the electric breakdown strength deadly defect as safety battery barrier film such as on the low side.Therefore, many curved hole film of the present invention is a kind of membrane material being very suitable for being used as high temperature resistant high safety battery barrier film.
When the nano particle of Selective filling, present inventors studied the impact of usage ratio for material property of AlN nano particle, if find that the consumption of AlN nano particle in water based suspension is lower than 15%, then be difficult to the hole of effectively filling PI fiber non-woven, cause the spray charging precipitator of battery lower, easily occur micro-short circuit phenomenon; And if AlN nano particle consumption is higher than 30%, Granular composite is then made to become difficulty, hinder filling effect, be difficult to realize the pore structure that surface apertures is little, duct is tortuous, eventually pass through the optimum amount scope that a large amount of experiments obtains AlN nano particle, make the overall performance of compound many curved hole membrane material be issued to optimum in described optimum proportioning scope.When selecting adhesive and dispersant, the present inventor needs in multiple adhesive and dispersant, to carry out multifactorial comprehensive screening according to the characteristic of AlN nano particle and the needs of fill process, final discovery: polyacrylate adhesive, especially the different monooctyl ester copolymer of butylacrylate-acrylic acid, just right viscosity can be provided for composite aqueous suspension, for further apply infiltration and particle bond provide desirable basis; Adding of ammonium polyacrylate easilier compared with other dispersants forms electric double layer on nano grain surface, can play a significant role to the dispersion of ultrafine particle, slurry viscosity can be reduced, prevent particle agglomeration, make the organic and dispersion of inorganic nanoparticles in water based suspension reach ideal state.In addition, preparation method provided by the invention compares doctor blade process of the prior art and is more suitable for suitability for industrialized production.
Finally, AlN of the present invention nano combined many curved hole membrane material obtains following characteristic: thickness between 10-40 μm, porosity between 30-50%, surface apertures between 50-300nm, hot strength between 35 ~ 50MPa, heat shrink temperature be greater than 350 DEG C, electric breakdown strength between 35-50V/ μm, ionic conductivity is in 1.0-8.0 × 10
-3scm
-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, and resistance to mechanical is clashed into, and is suitable for being used 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 the described battery diaphragm of nano combined many curved hole membrane material as rechargeable nonaqueous electrolytic battery or the application of capacitor diaphragm.
Embodiment
Following examples will contribute to those of ordinary skill in the art and understand the present invention further, but not limit the present invention in any form.
embodiment 1:
A composite film material containing AlN nano particle, it for base material, is filled with AlN nano particle (AlN-NP) with electrospinning polyimides (PI) nano-fiber for production of non-woven in substrate pores;
Its preparation method is as follows:
(1) nano aluminum nitride powder water based suspension (AlN/H
2o-1) configuration: nano aluminum nitride powder (diameter is mainly distributed in 30nm) 80.0 grams, ammonium polyacrylate 1.0 grams, butyl polyacrylate-different monooctyl ester 8.0 grams, distilled water 300.0 grams, disposablely put into beaker, emulsified at the rotating speed of 8000 turns per minute, form the nano aluminum nitride powder water based suspension (AlNAlN/H that absolute viscosity is 28mPaS
2o-1).
(2) preparation of the nano combined high temperature resistant high safety battery barrier film of AlN/PI: by AlN/H configured above
2o-1 nano aluminum nitride powder water based suspension is paved on a glass and is formed the suspension liquid and membrane that thickness is 30 μm, is then that the electrospinning PI nano-fiber for production of non-woven of 9 μm covers AlN/H by thickness
2in O-1 suspension liquid and membrane, suspension infilters in PI nano-fiber for production of non-woven, treat that nano-fiber cloth upper strata drenches, show to be filled with suspension completely in the hole of non-weaving cloth, uncover PI nano-fiber for production of non-woven, at 100 DEG C, heat dries 10min, is warming up to 160 DEG C of heat treatment 5min, to make between AlN nano particle and between nano particle and PI nanofiber by polyacrylate melting organic/inorganic nano combined many curved hole film of well-bonded formation.
(3) performance characterization: the thickness of the nano combined high temperature resistant high safety battery barrier film of prepared AlN/PI is 10 μm, hot strength is 50MPa, elongation at break is 50%, puncture strength is 6.0N, percent thermal shrinkage at 350 DEG C is 0, the porosity of many curved hole film is 30%, surperficial average pore size is 55nm, gas permeability under 0.24bar pressure is 120S, electric breakdown strength is 50V/ μm, and ionic conductivity is 1.0 × 10
-3scm
-1.
embodiment 2:
A composite film material containing AlN nano particle, it for base material, is filled with AlN nano particle (AlN-NP) with electrospinning polyimides (PI) nano-fiber for production of non-woven in substrate pores;
Its preparation method is as follows:
(1) AlN water based suspension (AlN/H
2o-2) configuration: nano aluminum nitride powder (diameter is mainly distributed in 100nm) 80.0 grams, ammonium polyacrylate 0.5 gram, butyl polyacrylate-different monooctyl ester 8.0 grams, distilled water 433.0 grams, disposablely put into beaker, emulsified at the rotating speed of 8000 turns per minute, form the crosslinked polystyrene Nano microsphere water based suspension (AlN/H that absolute viscosity is 18mPaS
2o-2).
(2) preparation of the nano combined high temperature resistant high safety battery barrier film of AlN/PI: by AlN/H configured above
2o-2 nano silicon nitride alumina particles water based suspension is paved on a glass and is formed the suspension liquid and membrane that thickness is 60 μm, is then that the electrospinning PI nano-fiber for production of non-woven of 38 μm covers AlN/H by thickness
2in O-2 suspension liquid and membrane, suspension infilters in PI nano-fiber for production of non-woven, treat that nano-fiber cloth upper strata drenches, show to be filled with suspension completely in the hole of non-weaving cloth, uncover PI nano-fiber for production of non-woven, at 100 DEG C, heat dries 10min, is warming up to 200 DEG C of heat treatment 3min, to make between AlN nano particle and between nano particle and PI nanofiber by polyacrylate melting organic/inorganic nano combined many curved hole film of well-bonded formation.
(3) performance characterization: the nano combined high temperature resistant high safety battery of prepared AlN/PI every film thickness be 40 μm, hot strength is 35MPa, elongation at break is 30%, puncture strength is 12N, percent thermal shrinkage at 350 DEG C is 0, the porosity of many curved hole film is 50%, surperficial average pore size is 150nm, gas permeability under 0.12bar pressure is 125S, electric breakdown strength is 35V/ μm, ionic conductivity is 8.0 × 10
-3scm
-1.
embodiment 3:
A composite film material containing AlN nano particle, it for base material, is filled with AlN nano particle (AlN-NP) with electrospinning polyimides (PI) nano-fiber for production of non-woven in substrate pores;
Its preparation method is as follows:
(1) nano-aluminum nitride water based suspension (AlN/H
2o-3) configuration: nano aluminum nitride powder (diameter is mainly distributed in 50nm) 80.0 grams, ammonium polyacrylate 0.8 gram, butyl polyacrylate-different monooctyl ester 8.0 grams, distilled water 300.0 grams, disposablely put into beaker, emulsified at the rotating speed of 8000 turns per minute, form the crosslinked poly-nano aluminum nitride powder water based suspension (AlN/H that absolute viscosity is 24mPaS
2o-3).
(2) preparation of the nano combined high temperature resistant high safety battery barrier film of AlN/PI: by AlN/H configured above
2o-3 nano aluminum nitride powder water based suspension is paved on a glass and is formed the suspension liquid and membrane that thickness is 50 μm, is then that the electrospinning PI nano-fiber for production of non-woven of 24 μm covers AlN/H by thickness
2in O-3 suspension liquid and membrane, suspension infilters in PI nano-fiber for production of non-woven, treat that nano-fiber cloth upper strata drenches, show to be filled with suspension completely in the hole of non-weaving cloth, uncover PI nano-fiber for production of non-woven, at 100 DEG C, heat dries 10min, is warming up to 200 DEG C of heat treatment 3min, to make between AlN nano particle and between nano particle and PI nanofiber by polyacrylate melting organic/inorganic nano combined many curved hole film of well-bonded formation.
(3) performance characterization: the nano combined high temperature resistant high safety battery of prepared AlN/PI every film thickness be 25 μm, hot strength is 47MPa, elongation at break is 38%, puncture strength is 10.0N, percent thermal shrinkage at 350 DEG C is 0, the porosity of perforated membrane is 48%, surperficial average pore size is 70nm, gas permeability under 0.24bar pressure is 65S, electric breakdown strength is 45V/ μm, ionic conductivity is 3.0 × 10
-3scm
-1.
embodiment 4:
A composite film material containing AlN nano particle, it for base material, is filled with AlN nano particle (AlN-NP) with electrospinning polyimides (PI) nano-fiber for production of non-woven in substrate pores;
Its preparation method is as follows:
(1) AlN water based suspension (AlN/H
2o-4) configure: nano aluminum nitride powder (diameter is mainly distributed in 80nm) 80.0 grams, ammonium polyacrylate 0.6 gram, butyl polyacrylate-different monooctyl ester 8.0 grams, distilled water 433.0 grams, disposablely put into beaker, emulsified at the rotating speed of 8000 turns per minute, form the nano aluminium nitride powder water based suspension (AlN/H that absolute viscosity is 20mPaS
2o-4).
(2) preparation of the nano combined high temperature resistant high safety battery barrier film of AlN/PI: by AlN/H configured above
2o-4 nano aluminum nitride powder water based suspension is paved on a glass and is formed the suspension liquid and membrane that thickness is 30 μm, is then that the electrospinning PI nano-fiber for production of non-woven of 14 μm covers AlN/H by thickness
2in O-4 suspension liquid and membrane, suspension infilters in PI nano-fiber for production of non-woven, treat that nano-fiber cloth upper strata drenches, show to be filled with suspension completely in the hole of non-weaving cloth, uncover PI nano-fiber for production of non-woven, at 100 DEG C, heat dries 10min, is warming up to 200 DEG C of heat treatment 5min, to make between AlN nano particle and between nano particle and PI nanofiber by polyacrylate melting organic/inorganic nano combined many curved hole film of well-bonded formation.
(3) performance characterization: the thickness of the nano combined high temperature resistant high safety battery barrier film of prepared AlN/PI is 15 μm, hot strength is 48MPa, elongation at break is 42%, puncture strength is 7.3N, percent thermal shrinkage at 350 DEG C is 0, the porosity of perforated membrane is 45%, surperficial average pore size is 120nm, gas permeability under 0.12bar pressure is 160S, electric breakdown strength is 48V/ μm, ionic conductivity is 7.4 × 10
-3scm
-1.Above experiment material and result testing equipment illustrate:
(1) experiment material:
Inorganic micro-nano powder, PI nano-fiber for production of non-woven, macromolecule dispersing agent and the polymer binder etc. that use in 4 experiment embodiments of the present invention are all bought by commercial channel and are obtained.
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 Co., Ltd;
(2) experimental result testing and characterization
In the present invention, the experimental result of 4 experiment embodiments is tested routinely by following instrument and equipment and characterizes.
1) polymer solution and spinning solution absolute viscosity NDJ-8S viscosimeter (Shanghai precision scientific instrument company) measure;
2) diameter of electro spinning nano fiber measures with scanning electron microscopy VEGA3SBU (Czech Republic);
3) heat decomposition temperature WRT-3P thermal gravimetric analyzer (TGA) (Shanghai Precision Scientific Apparatus Co., Ltd) of the nano combined high temperature resistant high safety battery barrier film of AlN/PI measures;
4) engineering properties (intensity, extension at break etc.) of the nano combined high temperature resistant high safety battery barrier film of AlN/PI measures with the miniature control electronic universal tester of CMT8102 (Shenzhen SANS material tests Co., Ltd);
5) vitrification point of the nano combined high temperature resistant high safety battery barrier film of AlN/PI uses Diamond Dynamic Mechanical Analyzer (DMA) (Perkin-Elmer, the U.S.) to measure;
6) porosity of the nano combined high temperature resistant high safety battery barrier film of AlN/PI is calculated by following formula:
Porosity β=[1-(ρ/ρ o)] × 100
Wherein ρ be AlN/PI nano compound stephanoporate film density (gram/cm
3), ρ o be the nano combined solid film of AlN/PI (being prepared by solution casting method) density (gram/cm
3);
7) gas permeability of the nano combined high temperature resistant high safety battery barrier film of AlN/PI and surface apertures use the Porometer3G air permeability tester of the U.S. to measure;
8) ionic conductivity of the nano combined high temperature resistant high safety battery barrier film of AlN/PI uses electrochemical workstation CHI660D (morning China's instrument, Chinese Shanghai) to measure;
9) electric breakdown strength of the nano combined high temperature resistant high safety battery barrier film of AlN/PI measures with the ZHZ8 type Hi-pot Tester of Shanghai Heng Mei Electric Applicance Co., Ltd.
Claims (10)
1. nano combined many curved hole membrane material, is characterized in that: it for base material, is filled with nano aluminum nitride (AlN) particle with polyimides (PI) nano-fiber for production of non-woven in substrate pores; Described nano-aluminum nitride particle, its diameter, between 50-100nm, accounts for the 30-60% of nano combined many curved hole membrane material total weight; Described PI nano-fiber for production of non-woven thickness is between 9-38 μm, and porosity is between 60-80%.
2. material according to claim 1, is characterized in that: described nano combined many curved hole membrane material, and its porosity is between 30-50%, and surperficial average pore size is between 50-150nm, and thickness is between 10-40 μm.
3. material according to claim 1, it is characterized in that: by being coated with the water based suspension of the AlN nano particle containing 15-30%wt or dipping PI nano-fiber for production of non-woven, make suspension permeate the hole filling up PI nano-fiber for production of non-woven, then obtain through 100-200 DEG C of hyperthermia drying.
4. material according to claim 3, is characterized in that: further containing account for suspension total weight 1.0% ~ 5.0% adhesive, account for the dispersant of suspension total weight 0.1% ~ 1.0% and the water of surplus.
5. material according to claim 4, is characterized in that: described adhesive is selected from polyacrylate adhesive, the different monooctyl ester copolymer of preferred butylacrylate-acrylic acid; Described dispersant is ammonium polyacrylate.
6. material according to claim 4, is characterized in that: the absolute viscosity of described water based suspension is 10 ~ 30mPaS, is preferably 18 ~ 28mPaS.
7. prepare the method for nano combined many curved hole membrane material according to claim 1 for one kind, for raw material with low viscosity AlN nano particle water based suspension and PI nano-fiber for production of non-woven, permeated by surface application or dip coating infiltration method, AlN nano particle is filled in the hole of PI nano-fiber for production of non-woven, after lower temperature is dried, be warming up to higher temperature and adhesive is bonded between AlN nano particle and between particle and PI nanofiber.
8. method according to claim 7, is characterized in that, specifically comprises the following steps:
1) water based suspension is prepared:
By weight percentage, the water of the AlN nano particle of 15-30%, the dispersant of 0.1%-1.0%, the 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 the water based suspension of absolute viscosity at 10-30mPaS;
2) nano particle is filled:
By step 1) water based suspension prepared paves and forms certain thickness suspension liquid and membrane on level board, then PI nano-fiber for production of non-woven is covered in described suspension liquid and membrane, suspension infilters in PI nano-fiber for production of non-woven, treat that nano-fiber cloth upper strata drenches, uncover PI nano-fiber for production of non-woven;
3) dry molding bonded
By step 2) the PI nano-fiber for production of non-woven that obtains first at 80 ~ 100 DEG C heat dry 8 ~ 12min, be warming up to 160 ~ 200 DEG C of heat treatment 3 ~ 6min again, make the nano combined many curved hole membrane material between AlN nano particle and between they and PI nanofiber because of the melting of adhesive described in well-bonded formation.
9. method according to claim 8, is characterized in that: step 1) described in adhesive be polyacrylate, the different monooctyl ester copolymer of preferred butylacrylate-acrylic acid; Described dispersant is ammonium polyacrylate.
10. method according to claim 8, is characterized in that: be rapid 3) by step 2) the PI nano-fiber for production of non-woven that obtains first at 100 DEG C heat dry 10min, then be warming up to 160-200 DEG C of heat treatment 3-5min.
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| CN104064713A (en) * | 2014-07-10 | 2014-09-24 | 厦门大学 | Composite diaphragm as well as preparation method and application thereof |
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| WO2010049478A1 (en) * | 2008-10-29 | 2010-05-06 | Ceramtec Ag | Separation layer for separating anode and cathode in lithium ion accumulators or batteries |
| CN104064713A (en) * | 2014-07-10 | 2014-09-24 | 厦门大学 | Composite diaphragm as well as preparation method and application thereof |
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