CN105226218B - PI‑PTEF‑Al2O3Ternary nano is combined many curved hole membrane materials and its preparation method and application - Google Patents
PI‑PTEF‑Al2O3Ternary nano is combined many curved hole membrane materials and its preparation method and application Download PDFInfo
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- CN105226218B CN105226218B CN201510575855.1A CN201510575855A CN105226218B CN 105226218 B CN105226218 B CN 105226218B CN 201510575855 A CN201510575855 A CN 201510575855A CN 105226218 B CN105226218 B CN 105226218B
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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
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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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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- 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
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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
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
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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 nano combined many curved hole membrane materials, it is filled with composite nanometer particle with polyimides (PI) nano-fiber for production of non-woven as base material, in substrate pores；It is characterized in that：Described composite nanometer particle is by polytetrafluorethylenano nano-microsphere (PTFE NP) and aluminum oxide nanoparticles (Al2O3NP) constituted than mixing with the weight of (7 12)/(8 13).Nano combined many curved hole membrane materials that the present invention is provided have high temperature resistant, moderate porosity, moderate surface density, good ion transporting and excellent mechanical performance, in lithium ion battery, pure polyimide nano-fiber barrier film can be overcome to cause the problem of battery micro-short circuit as porosity is too high；Power lithium-ion battery can be solved because mechanical collision causes the serious problems of thermal runaway.
Description
Technical field
The invention belongs to battery diaphragm field, is related to a kind of many curved hole membrane materials, and in particular to a kind of organic/inorganic ternary
Nano composite material, 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, will become the mankind indispensable
The articles for daily use.But as the lithium battery diaphragm for using at present belongs to the poor TPO porous film material of heat resistance, compared with
Under high-temperature, or over-charging of battery cross put and mechanical damage in the case of, lithium ion battery easily occurs smoldering, catches fire, even
Blast etc. jeopardizes the hidden danger of user safety.Therefore, the safety for improving lithium ion battery is to promote lithium ion battery in automobile
The key of the fields such as power application.
For the safety in utilization of lithium battery, people develop a kind of high porosity using the high-fire resistance of PI materials
Electrospinning PI nanofiber battery diaphragm.This high porosity PI nano fiber diaphragms are not shunk under 300 DEG C of high temperature, and are had resistance to
The features such as super-charge super-discharge, high rate capability and high circulation performance, the chemical property of lithium ion battery is made to have obtained significantly carrying
It is high.However, as this electro spinning nano fiber barrier film is a kind of non-weaving cloth by fiber accumulations, with too high porosity and
Excessive surface apertures, cause the spray charging precipitator of battery relatively low, micro-short circuit phenomenon often occur, especially when battery diaphragm thickness
When relatively low, 30 microns are less than such as, the probability that such case occurs is at a relatively high.Therefore, it is highly desirable to create and a kind of new has
Compared with the high temperature resistant highly secure lithium ion battery barrier film of low porosity and less surface apertures.
The content of the invention
An object of the present invention is：A kind of heatproof high safety with compared with low porosity and less surface apertures is provided
Many curved hole membrane materials.
The second object of the present invention is：The method that many curved hole membrane materials for preparing described are provided.
The third object of the present invention is：Application of the described many curved hole membrane materials in battery diaphragm is provided.
The above-mentioned purpose of the present invention is achieved through the following technical solutions：
First, there is provided a kind of nano combined many curved hole membrane materials, it with polyimides (PI) nano-fiber for production of non-woven is
Base material, is filled with composite nanometer particle in substrate pores；Described composite nanometer particle is by polytetrafluorethylenano nano-microsphere
And aluminum oxide nanoparticles (Al (PTFE-NP)2O3- NP) constituted than mixing with the weight of (7-12)/(8-13).
In currently preferred nano combined many curved hole membrane materials, described composite nanometer particle is by PTFE-NP and Al2O3-
NP is constituted than mixing with the weight of (30-42)/(38-50)；The most preferably PTFE-NP and Al2O3The weight ratio of-NP includes
42/38th, 30/50 or 36/44.
In currently preferred nano combined many curved hole membrane materials, the diameter of described PTFE-NP is preferably in 80-300nm
Between；Al2O3The diameter of-NP is preferably between 50-800nm.
Described PTFE-NP and Al2O3The ratio that-NP accounts for described nano combined many curved hole membrane material gross weights altogether is preferred
Between 30-60%.
The thickness of currently preferred nano combined many curved hole membrane materials is between 10-40 μm.
Currently preferred nano combined many curved hole membrane materials are by using the weight ratio containing (7-12)/(8-13)
PTFE-NP and Al2O3The water base mixing suspension of-NP is coated or impregnated with PI nano-fiber for production of non-woven, permeates suspension and fills up
The hole of PI nano-fiber for production of non-woven, then Jing 100-200 DEG C high temperature drying be obtained.
Described water base mixing suspension is preferably further containing the binding agent for accounting for suspension gross weight 1.0%～2.5%
With the dispersant for accounting for suspension gross weight 0.05%～0.15%.
The different monooctyl ester copolymer of the preferred polyacrylate of described binding agent, more preferably butylacrylate-acrylic acid.
The preferred ammonium polyacrylate of described dispersant.
Described is 20～30mPaS containing the preferred absolute viscosity of water base mixing suspension.
On this basis, the present invention also provides a kind of method for preparing described nano combined many curved hole membrane materials, be with
Low viscosity PTFE-NP and Al2O3The water base mixing suspensions of-NP and PI nano-fiber for production of non-woven are raw material, are applied by surface
Infiltration or the method for dip coating infiltration, by PTFE-NP and Al2O3- NP is filled in the hole of PI nano-fiber for production of non-woven,
After lower temperature drying, being warming up to higher temperature makes binding agent in PTFE-NP and Al2O3Between-NP and Nano microsphere and nano-particle
Bonded between PI nanofibers.
The method of the nano combined many curved hole membrane materials described in currently preferred preparation, specifically includes following steps：
1) prepare water base mixing suspension：
By weight percentage, by the Al of PTFE-NP, 8-13% of 7-12%2O3- NP, the dispersant of 0.05-0.15%,
The water of the binding agent and surplus of 1.0-2.5% is mixed to get mixed liquor, by mixed liquor in the rotating speed of 8000 turns/min emulsified, shape
Into absolute viscosity 20～30mPaS water base mixing suspension；
2) nano combined many curved hole membrane materials are prepared：
By step 1) the water base mixing suspension prepared in horizontal plate upper berth flat shape into certain thickness suspension liquid and membrane, then
PI nano-fiber for production of non-woven is covered in described suspension liquid and membrane, suspension is infiltered in PI nano-fiber for production of non-woven, is treated
Nano-fiber cloth upper strata drenches, and uncovers PI nano-fiber for production of non-woven；
3) by step 2) the first 8～12min of baking the affected part after applying some drugs at 100～120 DEG C of the PI nano-fiber for production of non-woven that obtains, then heat up
To 180～200 DEG C of 3～6min of heat treatment, PTFE-NP and Al is made2O3Between-NP and they and between PI nanofibers because of binding agent
Melting and well-bonded formation ternary nano of the present invention is combined many curved hole films.
The method of the nano combined many curved hole membrane materials described in currently preferred preparation, step 1) described in binding agent it is excellent
Select polyacrylate, the more preferably different monooctyl ester copolymer of butylacrylate-acrylic acid；The preferred ammonium polyacrylate of described dispersant.
The method of the nano combined many curved hole membrane materials described in currently preferred preparation, step 2) described in PI Nanowires
Dimension non-weaving cloth preferred thickness is between 9-38 μm, electrospinning PI micro/nano-fibre non-woven of the porosity preferably between 60-90%
Cloth.
The method of the nano combined many curved hole membrane materials described in currently preferred preparation, step 3) preferably by step 2)
The first baking the affected part after applying some drugs 10min at 100 DEG C of PI nano-fiber for production of non-woven for arriving, then it is warming up to 200 DEG C of heat treatment 5min.
The present invention has heatproof, relatively low density, nano level diameter using PTFE-NP；Al2O3- NP has superior resistance to
Warm nature, the characteristics such as the surface apertures of the high rigidity and diameter of diamond less than PI nano-fiber for production of non-woven are close to, they are mixed
Conjunction is filled in the hole of PI nano-fiber for production of non-woven, is reduced the porosity of PI nano-fiber for production of non-woven and is reduced its surface
Aperture, improve barrier film electric breakdown strength, improve the spray charging precipitator of battery and prevent the micro-short circuit phenomenon of battery；Change simultaneously
The performance that kind battery diaphragm heat resistanceheat resistant is shunk, and the surface density of barrier film will not be increased considerably.Therefore, PTFE-NP/ of the invention
Al2O3It is a kind of membrane material for being very suitable as high temperature resistant high safety battery diaphragm that-NP/PI ternary nanos are combined many curved hole films
Material.
Nano combined many curved hole membrane materials of the present invention are selected by specific material and prepared by technique, are formed with than existing
The compound many curved hole membrane structures of the organic/inorganic ternary nano of some PI nano-fiber for production of non-woven more fine pores.In its structure,
Nanofiber Network structure for support effect in PI nano-fiber for production of non-woven, PTFE-NP and Al2O3- NP plays filling and constructs
The effect of nanoaperture, has good hole knot so as to giving this organic/inorganic ternary nano and being combined many curved hole membrane materials
The characteristics such as structure, little surface apertures, high breakdown strength, heat resistance and very good mechanical properties, overcome electrospinning PI nanofiber non-
The low deadly defect as safety battery barrier film of the too high porosity of woven cloths, excessive surface apertures and electric breakdown strength；
Meanwhile, surface density increase is also unlikely to excessive.In the composite nanometer particle of Selective filling, present inventors studied organic nano
For the impact of material property, ratio between microsphere and inorganic nanoparticles finds that when composite nanometer particle ratio be higher than 60%
When, by causing, the total body density of many curved hole films of nano-particle filling is too high, the holes filling to PI nano-fiber for production of non-woven
Excessively, cause porosity low, average pore size compound many curved hole films less than normal；When composite nanometer particle ratio is less than 30%,
Compound many curved hole film insulating properties decline, and micro-short circuit risk is larger, while between two type nano granulars in composite particles
Need to control suitable ratio, make the respective high-quality characteristic of two kinds of microgranules be able to balanced performance.The present inventor is through substantial amounts of reality
The optimum proportioning scope obtained between two kinds of particles is tested, and the overall performance for being combined many curved hole membrane materials is made in the optimum proportioning model
Enclose and be issued to optimum.When selecting binding agent with dispersant, the present inventor needs characteristic and the filling according to composite nanometer particle
The needs of technique carry out multifactorial comprehensive screening in various binding agents and dispersant, finally found that：Polyacrylate glues
The different monooctyl ester copolymer of mixture, especially butylacrylate-acrylic acid, can provide just right sticking for composite aqueous suspension
Degree, provides preferably basis for further infiltration and the granule bonding of applying；The addition of ammonium polyacrylate is compared with other dispersants
Easily electric double layer is formed on nano grain surface, the dispersion of ultrafine particle can be played a significant role, can be dropped
Low slurry viscosity, particle agglomeration is prevented, reached organic and dispersion of the inorganic nanoparticles in water based suspension and more manage
The state thought.Additionally, the preparation method that the present invention is provided is compared doctor blade process of the prior art and is more suitable for industrialized production.
Finally, PTFE-NP/Al of the invention2O3- NP/PI ternary nanos are combined many curved hole membrane materials and obtain following spy
Property：Thickness is between 10-40 μm, porosity between 30-50%, surface apertures between 50-800nm, surface density is in 18-
24g/m2, tensile strength between 30～50MPa, heat shrink temperature more than 350 DEG C, electric breakdown strength between 35-50V/ μm,
Ionic conductivity is in 1.0-8.0 × 10-3S·cm-1Between.The resistance to height of organic/inorganic ternary nano composite membrane with this characteristic
Temperature, heat resistanceheat resistant are shunk, the impact of high voltage withstanding and high current, and resistance to mechanical is clashed into, and be adapted for use as safety battery barrier film and safety is super
Capacitor diaphragm, manufactures various high power capacity and high dynamic lithium battery or ultracapacitor.
The present invention also provide described nano combined many curved hole membrane materials as rechargeable nonaqueous electrolytic battery battery every
The application of film or capacitor diaphragm.
Specific embodiment
Following examples will be helpful to one of ordinary skill in the art and further understand the present invention, but not in any form
Limit the present invention.
Embodiment 1：
A kind of organic/inorganic ternary nano composite film material, it is with electrospinning polyimides (PI) nano-fiber for production of non-woven
For base material, polytetrafluorethylenano nano-microsphere (PTFE-NP) and aluminum oxide nanoparticles (Al in substrate pores, are filled with2O3-
NP), both weight ratios are 42/38；
Its preparation method is as follows：
(1) polytetrafluorethylenano nano-microsphere and the water base mixing suspension (PTFE-NP/Al of aluminum oxide nanoparticle2O3-NP/
H2O-1 configuration)：70.0 grams of polytetrafluorethylenano nano-microsphere (diameter is mainly distributed on 300nm) emulsion (solid content 60wt%),
38.0 grams of aluminum oxide nanoparticles (primary particle size is distributed in 200nm), 0.3 gram of ammonium polyacrylate, butyl acrylate-propylene
8.7 grams of the different monooctyl ester copolymer of acid, 328.0 grams of distilled water is disposably put in beaker, in 8000 turns per minute of rotating speed stimulating milk secretion
Change, form polytetrafluorethylenano nano-microsphere and the water base mix suspending of aluminum oxide nanoparticles that absolute viscosity is 28mPaS
Liquid (PTFE-NP/Al2O3-NP/H2O-1)。
(2)PTFE-NP/Al2O3The preparation of-NP/PI ternary nano complex fire resistant high safety battery diaphragms：To institute above
The PTFE-NP/Al of configuration2O3-NP/H2O-1 polytetrafluorethylenano nano-microspheres and the water base mixing suspension of aluminum oxide nanoparticle exist
Glass plate upper berth flat shape into the suspension liquid and membrane that thickness is 40 μm, then by electrospinning PI nano-fiber for production of non-woven that thickness is 9 μm
It is covered in PTFE-NP/Al2O3-NP/H2In O-1 suspension liquid and membranes, suspension is infiltered in PI nano-fiber for production of non-woven, treats Nanowire
Dimension cloth upper strata drenches, and has been fully filled with suspension, uncovers PI nano-fiber for production of non-woven in showing the hole of non-weaving cloth,
Baking the affected part after applying some drugs 10min at 100 DEG C, is warming up to 200 DEG C of heat treatment 5min, makes PTFE-NP Nano microspheres and aluminum oxide nanoparticles
Between and they and between PI nanofibers by acrylate copolymer melt and it is well-bonded formation organic/inorganic ternary receive
The many curved hole films of meter Fu He.
(3) performance characterization：Prepared PTFE-NP/Al2O3- NP/PI ternary nanos complex fire resistant high safety battery every
The thickness of film is 11 μm, tensile strength be 50MPa, elongation at break be 40%, puncture strength is 5.0N, the heat at 350 DEG C
It is that 35%, surface average pore size is 150nm, the breathability under 0.48bar pressure that shrinkage factor is the 0, porosity of many curved hole films
It it is 40V/ μm for 260S, electric breakdown strength, ionic conductivity is 3.0 × 10-3S·cm-1。
Embodiment 2：
A kind of organic/inorganic ternary nano composite film material, it is with electrospinning polyimides (PI) nano-fiber for production of non-woven
For base material, polytetrafluorethylenano nano-microsphere (PTFE-NP) and aluminum oxide nanoparticles (Al in substrate pores, are filled with2O3-
NP), both weight ratios are 30/50；
Its preparation method is as follows：
(1) polytetrafluorethylenano nano-microsphere and the water base mixing suspension (PTFE-NP/Al of aluminum oxide nanoparticle2O3-NP/
H2O-2 configuration)：50.0 grams of polytetrafluorethylenano nano-microsphere (diameter is mainly distributed on 300nm) emulsion (solid content 60wt%),
50.0 grams of aluminum oxide nanoparticles (primary particle size is distributed in 100nm), 0.4 gram of ammonium polyacrylate, butyl acrylate-propylene
8.6 grams of the different monooctyl ester copolymer of acid, 570.0 grams of distilled water is disposably put in beaker, in 8000 turns per minute of rotating speed stimulating milk secretion
Change, form polytetrafluorethylenano nano-microsphere and the water base mix suspending of aluminum oxide nanoparticles that absolute viscosity is 20mPaS
Liquid (PTFE-NP/Al2O3-NP/H2O-2)。
(2)PTFE-NP/Al2O3The preparation of-NP/PI ternary nano complex fire resistant high safety battery diaphragms：To institute above
The PTFE-NP/Al of configuration2O3-NP/H2O-2 polytetrafluorethylenano nano-microspheres and the water base mixing suspension of aluminum oxide nanoparticle exist
Glass plate upper berth flat shape into the suspension liquid and membrane that thickness is 60 μm, then by electrospinning PI nano-fiber for production of non-woven that thickness is 39 μm
It is covered in PTFE-NP/Al2O3-NP/H2In O-2 suspension liquid and membranes, suspension is infiltered in PI nano-fiber for production of non-woven, treats Nanowire
Dimension cloth upper strata drenches, and has been fully filled with suspension, uncovers PI nano-fiber for production of non-woven in showing the hole of non-weaving cloth,
Baking the affected part after applying some drugs 10min at 100 DEG C, is warming up to 200 DEG C of heat treatment 5min, makes PTFE-NP Nano microspheres and aluminum oxide nanoparticles
Between and they and between PI nanofibers by polyacrylate melt and it is well-bonded formation organic/inorganic ternary it is nano combined
Many curved hole films.
(3) performance characterization：Prepared PTFE-NP/Al2O3- NP/PI ternary nanos complex fire resistant high safety battery every
The thickness of film is 40 μm, tensile strength be 30MPa, elongation at break be 45%, puncture strength is 8.0N, the heat at 350 DEG C
It is that 46%, surface average pore size is 100nm, the breathability under 0.48bar pressure that shrinkage factor is the 0, porosity of many curved hole films
It it is 37V/ μm for 120S, electric breakdown strength, ionic conductivity is 5.0 × 10-3S·cm-1。
Embodiment 3：
A kind of organic/inorganic ternary nano composite film material, it is with electrospinning polyimides (PI) nano-fiber for production of non-woven
For base material, polytetrafluorethylenano nano-microsphere (PTFE-NP) and aluminum oxide nanoparticles (Al in substrate pores, are filled with2O3-
NP), both weight ratios are 30/50；
Its preparation method is as follows：
(1) polytetrafluorethylenano nano-microsphere and the water base mixing suspension (PTFE-NP/Al of aluminum oxide nanoparticle2O3-NP/
H2O-3 configuration)：50.0 grams of polytetrafluorethylenano nano-microsphere (diameter is mainly distributed on 300nm) emulsion (solid content 60wt%),
50.0 grams of aluminum oxide nanoparticles (primary particle size is distributed in 500nm), 0.5 gram of ammonium polyacrylate, butyl acrylate-propylene
8.5 grams of the different monooctyl ester copolymer of acid, 415.0 grams of distilled water is disposably put in beaker, in 8000 turns per minute of rotating speed stimulating milk secretion
Change, form polytetrafluorethylenano nano-microsphere and the water base mix suspending of aluminum oxide nanoparticles that absolute viscosity is 23mPaS
Liquid (PTFE-NP/Al2O3-NP/H2O-3)。
(2)PTFE-NP/Al2O3The preparation of-NP/PI ternary nano complex fire resistant high safety battery diaphragms：To institute above
The PTFE-NP/Al of configuration2O3-NP/H2O-3 polytetrafluorethylenano nano-microspheres and the water base mixing suspension of aluminum oxide nanoparticle exist
Glass plate upper berth flat shape into the suspension liquid and membrane that thickness is 50 μm, then by electrospinning PI nano-fiber for production of non-woven that thickness is 23 μm
It is covered in PTFE-NP/Al2O3-NP/H2In O-2 suspension liquid and membranes, suspension is infiltered in PI nano-fiber for production of non-woven, treats Nanowire
Dimension cloth upper strata drenches, and has been fully filled with suspension, uncovers PI nano-fiber for production of non-woven in showing the hole of non-weaving cloth,
Baking the affected part after applying some drugs 10min at 100 DEG C, is warming up to 200 DEG C of heat treatment 5min, makes PTFE-NP Nano microspheres and aluminum oxide nanoparticles
Between and they and between PI nanofibers by polyacrylate melt and it is well-bonded formation organic/inorganic ternary it is nano combined
Many curved hole films.
(3) performance characterization：Prepared PTFE-NP/Al2O3- NP/PI ternary nanos complex fire resistant high safety battery every
The thickness of film is 25 μm, tensile strength be 36MPa, elongation at break be 42%, puncture strength is 6.0N, the heat at 350 DEG C
It is that 43%, surface average pore size is 600nm, the breathability under 0.48bar pressure that shrinkage factor is the 0, porosity of many curved hole films
It it is 35V/ μm for 80S, electric breakdown strength, ionic conductivity is 6.0 × 10-3S·cm-1。
Embodiment 4：
A kind of organic/inorganic ternary nano composite film material, it is with electrospinning polyimides (PI) nano-fiber for production of non-woven
For base material, polytetrafluorethylenano nano-microsphere (PTFE-NP) and aluminum oxide nanoparticles (Al in substrate pores, are filled with2O3-
NP), both weight ratios are 36/44；
Its preparation method is as follows：
(1) polytetrafluorethylenano nano-microsphere and the water base mixing suspension (PTFE-NP/Al of aluminum oxide nanoparticle2O3-NP/
H2O-4 configuration)：60.0 grams of polytetrafluorethylenano nano-microsphere (diameter is mainly distributed on 300nm) emulsion (solid content 60wt%),
44.0 grams of aluminum oxide nanoparticles (primary particle size is distributed in 800nm), 0.4 gram of ammonium polyacrylate, butyl acrylate-propylene
8.6 grams of the different monooctyl ester copolymer of acid, 273.0 grams of distilled water is disposably put in beaker, in 8000 turns per minute of rotating speed stimulating milk secretion
Change, form polytetrafluorethylenano nano-microsphere and the water base mix suspending of aluminum oxide nanoparticles that absolute viscosity is 26mPaS
Liquid (PTFE-NP/Al2O3-NP/H2O-4)。
(2)PTFE-NP/Al2O3The preparation of-NP/PI ternary nano complex fire resistant high safety battery diaphragms：To institute above
The PTFE-NP/Al of configuration2O3-NP/H2O-4 polytetrafluorethylenano nano-microspheres and the water base mixing suspension of aluminum oxide nanoparticle exist
Glass plate upper berth flat shape into the suspension liquid and membrane that thickness is 35 μm, then by electrospinning PI nano-fiber for production of non-woven that thickness is 19 μm
It is covered in PTFE-NP/Al2O3-NP/H2In O-4 suspension liquid and membranes, suspension is infiltered in PI nano-fiber for production of non-woven, treats Nanowire
Dimension cloth upper strata drenches, and has been fully filled with suspension, uncovers PI nano-fiber for production of non-woven in showing the hole of non-weaving cloth,
Baking the affected part after applying some drugs 10min at 100 DEG C, is warming up to 200 DEG C of heat treatment 5min, makes PTFE-NP Nano microspheres and aluminum oxide nanoparticles
Between and they and between PI nanofibers by polyacrylate melt and it is well-bonded formation organic/inorganic ternary it is nano combined
Many curved hole films.
(3) performance characterization：Prepared PTFE-NP/Al2O3- NP/PI ternary nanos complex fire resistant high safety battery every
The thickness of film is 20 μm, tensile strength be 40MPa, elongation at break be 38%, puncture strength is 7.0N, the heat at 350 DEG C
It is that 45%, surface average pore size is 750nm, the breathability under 0.48bar pressure that shrinkage factor is the 0, porosity of many curved hole films
It it is 40V/ μm for 40S, electric breakdown strength, ionic conductivity is 8.0 × 10-3S·cm-1。
Above experiment material and result test equipment explanation：
Experiment material：
Inorganic nano powder, PI nano-fiber for production of non-woven, macromolecule dispersion used in 4 experiment embodiments of the present invention
The raw material such as agent and polymer binder is commercially available by commercial channel.
Polytetrafluorethylenano nano-microsphere emulsion, aluminium sesquioxide nanopowder system pass through Alibaba's sales platform and Shandong
Jing Xin crystal Science and Technology Ltd. and the purchase of Beijing Deco Dao Jin Science and Technology Ltd.s；
Electrospinning polyimide nano-fiber non-weaving cloth, is produced by Jiangxi Xiancai Nano Fiber Technology Co., Ltd.；
Ammonium polyacrylate, purchased from Shandong Zibo capital and dye chemical industry company limited；
(2) experimental result test and sign
In the present invention, the experimental result of 4 experiment embodiments is routinely tested and is characterized by following instrument and equipment.
Polymer solution and spinning liquid absolute viscosity are determined with NDJ-8S viscometers (Shanghai precision scientific instrument company)；
The diameter of electro spinning nano fiber is determined with 3 SBU of scanning electron microscope VEGA (Czech Republic)；
PTFE-NP/Al2O3The thermal decomposition temperature of-NP/PI organic/inorganic ternary nano complex fire resistant high safety battery diaphragms
Degree is determined with WRT-3P thermal gravimetric analyzers (TGA) (Shanghai Precision Scientific Apparatus Co., Ltd)；
PTFE-NP/Al2O3The engineering propertiess of-NP/PI organic/inorganic ternary nano complex fire resistant high safety battery diaphragms
(intensity, extension at break etc.) is surveyed with the miniature control electronic universal testers of CMT8102 (Shenzhen SANS material tests company limited)
It is fixed；
PTFE-NP/Al2O3The vitrification temperature of-NP/PI organic/inorganic ternary nano complex fire resistant high safety battery diaphragms
Degree is determined using Diamond Dynamic Mechanical Analyzers (DMA) (Perkin-Elmer, the U.S.)；
PTFE-NP/Al2O3The porosity of-NP/PI organic/inorganic ternary nano complex fire resistant high safety battery diaphragms is
It is calculated by following formula：
Porosity β=[1- (ρ/ρo)]×100
Wherein ρ is PTFE-NP/Al2O3- NP/PI organic/inorganic ternary nanos be combined many curved hole films density (gram/cm3),
ρoFor PTFE-NP/Al2O3The density of-NP/PI organic/inorganic ternary nano solid polymer composite thin film (being prepared by solution casting method)
(gram/cm3)；
PTFE-NP/Al2O3The breathability of-NP/PI organic/inorganic ternary nano complex fire resistant high safety battery diaphragms and
Surface apertures are determined using the Porometer 3G air permeability testers in the U.S.；
PTFE-NP/Al2O3The ionic conductance of-NP/PI organic/inorganic ternary nano complex fire resistant high safety battery diaphragms
Rate is determined using electrochemical workstation CHI 660D (morning China's instrument, Chinese Shanghai)；
PTFE-NP/Al2O3The electrical breakdown of-NP/PI organic/inorganic ternary nano complex fire resistant high safety battery diaphragms is strong
Degree is determined with the 8 type Hi-pot Testers of ZHZ of Shanghai Heng Mei Electric Applicance Co., Ltd.
Claims (1)
1. a kind of method for preparing nano combined many curved hole membrane materials, is with low viscosity polytetrafluorethylenano nano-microsphere and three oxidations
The water base mixing suspension of two aluminum nanoparticles and PI nano-fiber for production of non-woven are raw material, by the side of dip coating infiltration
Method, polytetrafluorethylenano nano-microsphere and aluminum oxide nanoparticles are filled in the hole of PI nano-fiber for production of non-woven,
After lower temperature drying, being warming up to higher temperature makes binding agent in polytetrafluorethylenano nano-microsphere and aluminum oxide nanoparticles
Between and Nano microsphere and nano-particle and PI nanofibers between bonded；
Characterized in that, specifically including following steps：
1) prepare water base mixing suspension：
By weight percentage, by the polytetrafluorethylenano nano-microsphere of 7-12%, the aluminum oxide nanoparticles of 8-13%,
The different monooctyl ester copolymer adhesive of the ammonium polyacrylate dispersant of 0.05-0.15%, the butylacrylate-acrylic acid of 1.0-2.5%
Mixed liquor is mixed to get with the water of surplus, mixed liquor is emulsified in the rotating speed of 8000 turns/min, formed absolute viscosity 20～
The water base mixing suspension of 30mPaS；
2) nano combined many curved hole membrane materials are prepared：
By step 1) the water base mixing suspension prepared in horizontal plate upper berth flat shape into certain thickness suspension liquid and membrane, then by thickness
Spend between 9-38 μm, electrospinning PI nano-fiber for production of non-woven of the porosity between 60-90% is covered in described suspension
On film, suspension is infiltered in PI nano-fiber for production of non-woven, is treated that PI nano-fiber for production of non-woven upper strata drenches, is uncovered PI Nanowires
Dimension non-weaving cloth；
3) by step 2) the first baking the affected part after applying some drugs 10min at 100 DEG C of the PI nano-fiber for production of non-woven that obtains, then be warming up to 200 DEG C it is hot at
Reason 5min, make between polytetrafluorethylenano nano-microsphere and aluminum oxide nanoparticles and they and between PI nanofibers because bonding
The melting of agent and the nano combined many curved hole films described in well-bonded formation.
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| CN201510575855.1A CN105226218B (en) | 2015-09-11 | 2015-09-11 | PI‑PTEF‑Al2O3Ternary nano is combined many curved hole membrane materials and its preparation method and application |
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| CN201510575855.1A CN105226218B (en) | 2015-09-11 | 2015-09-11 | PI‑PTEF‑Al2O3Ternary nano is combined many curved hole membrane materials and its preparation method and application |
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| CN105226218B true CN105226218B (en) | 2017-04-05 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103026530A (en) * | 2010-08-11 | 2013-04-03 | 科德宝两合公司 | Separator with increased puncture resistance |
| CN103078077A (en) * | 2013-01-17 | 2013-05-01 | 中国科学院金属研究所 | Lithium ion battery diaphragm with special structure and preparation method thereof |
| CN103199209A (en) * | 2013-04-01 | 2013-07-10 | 中国海诚工程科技股份有限公司 | Non-woven ceramic membrane with excellent closed-pore performance for lithium ion battery and technology |
| CN103887464A (en) * | 2012-12-19 | 2014-06-25 | 华为技术有限公司 | Diaphragm used for lithium ion battery, preparation method thereof, and lithium ion battery |
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2015
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103026530A (en) * | 2010-08-11 | 2013-04-03 | 科德宝两合公司 | Separator with increased puncture resistance |
| CN103887464A (en) * | 2012-12-19 | 2014-06-25 | 华为技术有限公司 | Diaphragm used for lithium ion battery, preparation method thereof, and lithium ion battery |
| CN103078077A (en) * | 2013-01-17 | 2013-05-01 | 中国科学院金属研究所 | Lithium ion battery diaphragm with special structure and preparation method thereof |
| CN103199209A (en) * | 2013-04-01 | 2013-07-10 | 中国海诚工程科技股份有限公司 | Non-woven ceramic membrane with excellent closed-pore performance for lithium ion battery and technology |
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