CN105064001B - Compound many curved hole membrane materials of silicon nitride particle filling and its preparation method and application - Google Patents
Compound many curved hole membrane materials of silicon nitride particle filling and its preparation method and application Download PDFInfo
- Publication number
- CN105064001B CN105064001B CN201510586950.1A CN201510586950A CN105064001B CN 105064001 B CN105064001 B CN 105064001B CN 201510586950 A CN201510586950 A CN 201510586950A CN 105064001 B CN105064001 B CN 105064001B
- Authority
- CN
- China
- Prior art keywords
- nano
- fiber
- woven
- production
- many curved
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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 the nano combined many curved hole membrane materials of one kind, it is filled with nano silicon nitride silicon grain using polyimides (PI) nano-fiber for production of non-woven as base material in substrate pores；Described nano silicon nitride silicon grain, its diameter accounts for the 30 60% of nano combined many curved hole membrane material gross weights between 50 100nm；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 high temperature resistants that the present invention is provided, heat resistanceheat resistant are shunk, the impact of high voltage withstanding and high current, resistance to mechanical is hit, safety battery barrier film and safe diaphragm of supercapacitor are adapted for use as, various high power capacity and high dynamic lithium battery or ultracapacitor is manufactured.The present invention also provides the preparation method of described nano combined many curved hole membrane materials, and its is used as the application of battery diaphragm.
Description
Technical field
The invention belongs to battery diaphragm field, it is related to a kind of porous film material, and in particular to one kind contains Si3N4Nanometer
Compound many curved hole membrane materials of grain, and preparation method thereof and be used as the application of battery diaphragm.
Background technology
Lithium ion battery is developed rapidly as the electrokinetic cell of new-energy automobile, will turn into the mankind indispensable
Daily necessities.But because the lithium battery diaphragm used 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, caught fire, even
Blast etc. jeopardizes the hidden danger of user's safety.Therefore, the security 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 utilize the high-fire resistance of PI materials, develop a kind of high porosity
Electrospinning PI nanofiber battery diaphragms.This high porosity PI nano fiber diaphragms do not shrink under 300 DEG C of high temperature, and with 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 set to have obtained significantly carrying
It is high.However, because 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, such as it is less than 30 microns, the probability that such case occurs is at a relatively high.Therefore, being highly desirable to create a kind of new has
Compared with low porosity and the high temperature resistant highly secure lithium ion battery barrier film of smaller surface apertures.
The content of the invention
An object of the present invention is：A kind of heatproof high safety having compared with low porosity and smaller 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 described in preparation 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 the nano combined many curved hole membrane materials of one kind, it using polyimides (PI) nano-fiber for production of non-woven as
Nano silicon nitride silicon grain is filled with base material, substrate pores；Described nano silicon nitride silicon grain, its diameter 50-100nm it
Between, account for the 30-60% of nano combined many curved hole membrane material gross weights；Described PI nano-fiber for production of non-woven thickness is at 9-38 μm
Between, porosity is between 60-80%.
In preferred embodiments of the present invention, described nano combined many curved hole membrane material porositys are 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 materials, the PI of the described preferred electrospinning of PI nano-fiber for production of non-woven
Nano-fiber for production of non-woven.
Currently preferred nano combined many curved hole membrane materials, preferably by using the Si containing 15-30%wt3N4Nanometer
The water based suspension of grain is coated or impregnated with PI nano-fiber for production of non-woven, suspension infiltration is filled up PI nano-fiber for production of non-woven
Hole, then dry and be made through 100-200 DEG C of high temperature.
Described water based suspension, which preferably further contains, to be accounted for the adhesive of suspension gross weight 1.0%~5.0%, accounts for outstanding
The dispersant of supernatant liquid gross weight 0.1%~1.0% and the water of surplus；More preferably account for the bonding of suspension gross weight 1.5~2.0%
The water of agent, the dispersant for accounting for suspension gross weight 0.1%~0.3% and surplus.
The preferred polyacrylate adhesive of described adhesive, the more preferably different monooctyl ester copolymerization of butylacrylate-acrylic acid
Thing.
The preferred ammonium polyacrylate of described dispersant.
The absolute viscosity of described water based suspension is preferably 10~30mPaS, more preferably 19~28mPaS.
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 Si3N4Nano particle water based suspension and PI nano-fiber for production of non-woven are raw material, are applied by surface and permeate or soak
The method of stain coating infiltration, by Si3N4Nano particle is filled into the hole of PI nano-fiber for production of non-woven, in lower temperature drying
Afterwards, being warming up to higher temperature makes adhesive in Si3N4Bonded between nano particle and between particle and PI nanofibers.
The method of nano combined many curved hole membrane materials described in currently preferred preparation, specifically includes following steps：
1) water based suspension is prepared：
By weight percentage, by 15-30% Si3N4Nano particle, 0.1%-1.0% dispersant, 1.0-5.0%
Adhesive and the water of surplus be mixed to get mixed liquor, mixed liquor is turned in 8000-10000/min rotating speed is emulsified, formed
Water based suspension of the absolute viscosity in 10-30mPaS；
2) nano particle is filled：
By step 1) prepare water based suspension in level board upper berth flat shape into certain thickness suspension liquid and membrane, then by PI
Nano-fiber for production of non-woven is covered in described suspension liquid and membrane, and suspension is infiltered in PI nano-fiber for production of non-woven, treats nanometer
Fiber cloth upper strata drenches, and uncovers PI nano-fiber for production of non-woven；
3) molding bonded is dried
By step 2) first heat dries 8~12min at 80~100 DEG C for obtained PI nano-fiber for production of non-woven, then be warming up to
180~200 DEG C of 3~6min of heat treatment, make Si3N4Between nano particle and they between PI nanofibers because of the melting of adhesive
And well-bonded formation nano combined many curved hole membrane materials of the present invention.
In the method for nano combined many curved hole membrane materials described in currently preferred preparation, step 1) described in Si3N4Receive
Rice grain accounts for the 15-21% of water based suspension weight.
In the method for nano combined many curved hole membrane materials described in currently preferred preparation, step 1) described in adhesive
It is preferred that the different monooctyl ester copolymer of polyacrylate, more preferably butylacrylate-acrylic acid；The preferred polyacrylic acid of described dispersant
Ammonium.
In the method for nano combined many curved hole membrane materials described in currently preferred preparation, step 1) described in it is water base outstanding
Supernatant liquid absolute viscosity is preferably in 19~28mPaS.
In the method for nano combined many curved hole membrane materials described in currently preferred preparation, step 2) described in PI nanometers
The preferred thickness of fiber non-woven is between 9-38 μm, electrospinning PI micro/nano-fibre non-woven of the porosity between 60-80%
Cloth.
In the method for nano combined many curved hole membrane materials described in currently preferred preparation, step 3) preferably by step 2)
First the heat at 100 DEG C dries 10min to obtained PI nano-fiber for production of non-woven, then is warming up to 200 DEG C of heat treatment 5min.
The present invention using silicon nitride nano particles there is high temperature resistant, high rigidity and diameter to be less than PI nano-fiber for production of non-woven
The characteristic such as surface apertures, be filled with into the hole of PI nano-fiber for production of non-woven, reduce PI nano-fiber for production of non-woven
Porosity and reduce its surface apertures, improve barrier film electric breakdown strength, improve battery spray charging precipitator and prevent battery
Short circuit phenomenon；Improve the performance that battery diaphragm heat resistanceheat resistant is shunk simultaneously.
The preparation method of the present invention is with low viscosity nano Si3N4Water based suspension and electrospinning PI nano-fiber for production of non-woven are
Raw material, apply the method that infiltration or dip coating are permeated, by Si by surface3N4Nano particle is filled into that PI nanofibers are non-to be knitted
Make in the hole of cloth, after lower temperature drying, being warming up to higher temperature makes palyacrylate binder in Si3N4Nano particle
Between and Si3N4Bonding is carried out between particle and PI nanofibers and forms many curved hole film knots that the organic/inorganic nano of more fine pore is combined
Structure.In the structure of gained film product, the Nanofiber Network structure for support effect in PI nano-fiber for production of non-woven, Si3N4Receive
Rice grain plays a part of to fill and construct nanoaperture, so that assigning this organic/inorganic nano is combined many curved hole membrane material tools
Have that good pore structure, surface apertures are small, duct is tortuous, electric breakdown strength is high, high-fire resistance energy and very good mechanical properties etc.
Characteristic, overcomes the too high porosity of simple electrospinning PI nano-fiber for production of non-woven, excessive surface apertures and electrical breakdown strong
Spend deadly defect of the relatively low grade as safety battery barrier film.Therefore, many curved hole films of the invention are that one kind is very suitable as
The membrane material of high temperature resistant high safety battery diaphragm.
In the nano particle of Selective filling, present inventors studied Si3N4The usage ratio of nano particle is for material
The influence of energy, has been found that Si3N4Consumption of the nano particle in water based suspension is less than 15%, then is difficult to effectively fill PI fibres
The hole of non-weaving cloth is tieed up, causes the spray charging precipitator of battery relatively low, micro-short circuit phenomenon easily occurs；And if Si3N4Nanometer
Grain consumption is higher than 30%, then make it that particle is scattered becomes difficult, hinders filling effect, it is difficult to realize that surface apertures are small, duct
Tortuous pore structure, eventually passes through substantial amounts of experiment and obtains Si3N4The optimum amount scope of nano particle, makes compound more bent
The overall performance of porous membrane material is issued to optimal in the optimum proportioning scope.When selecting adhesive with dispersant, the present invention
People is needed according to Si3N4Carried out the need for the characteristic and fill process of nano particle in a variety of adhesives and dispersant multifactor
Comprehensive screening, finally found that：The different monooctyl ester copolymer of polyacrylate adhesive, especially butylacrylate-acrylic acid, energy
Just right viscosity is enough provided for composite aqueous suspension, is that further coating infiltration and particle are bonded and provided preferably
Basis；The addition of ammonium polyacrylate is easier to form electric double layer on nano grain surface compared with other dispersants, can be to ultra-fine
The scattered of solid particle plays a significant role, and can reduce slurry viscosity, prevent particle agglomeration, make organic and inorganic nanoparticles
Scattered in water based suspension has reached ideal state.In addition, the preparation method that the present invention is provided compares existing skill
Doctor blade process in art is more suitable for industrialized production.
Finally, Si of the invention3N4Nano combined many curved hole membrane materials obtain following characteristic：Thickness 10-40 μm it
Between, porosity between 30-50%, surface apertures between 50-150nm, tensile strength is between 30~50MPa, thermal contraction
Temperature be more than 350 DEG C, electric breakdown strength between 35-50V/ μm, ionic conductivity is in 1.0-8.0 × 10-3S·cm-1Between.
Nano composite membrane high temperature resistant with this characteristic, heat resistanceheat resistant are shunk, the impact of high voltage withstanding and high current, and resistance to mechanical is hit, is adapted to
In as safety battery barrier film and safe diaphragm of supercapacitor, various high power capacity and high dynamic lithium battery or super capacitor are manufactured
Device.
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.
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
The limitation present invention.
Embodiment 1：
One kind contains Si3N4The composite film material of nano particle, it is with electrospinning polyimides (PI) nano-fiber for production of non-woven
For base material, Si is filled with substrate pores3N4Nano particle (Si3N4-NP)；
Its preparation method is as follows：
(1) nano Si3N4Water based suspension (Si3N4/H2O-1 configuration)：(diameter is mainly distributed on nano-silicon nitride powder
30nm) 80.0 grams, 1.0 grams of ammonium polyacrylate, 8.0 grams of the different monooctyl ester copolymer of butylacrylate-acrylic acid, 300.0 grams of distilled water,
Disposably it is put into beaker, it is emulsified in 8000 turns per minute of rotating speeds, form the nano silicon nitride that absolute viscosity is 28mPaS
Silicon water based suspension (Si3N4/H2O-1)。
(2)Si3N4The preparation of the nano combined high temperature resistant high safety battery diaphragms of/PI：By the Si configured above3N4/H2O-1
It is 30 μm of suspension liquid and membrane that Silicon Nitride Suspensions, which are paved to form thickness on a glass, then by electrospinning that thickness is 9 μm
PI nano-fiber for production of non-woven is covered in Si3N4/H2In O-1 suspension liquid and membranes, suspension is infiltered in PI nano-fiber for production of non-woven,
Treat that nano-fiber cloth upper strata drenches, be fully filled with suspension in the hole for showing non-weaving cloth, uncovered PI nanofibers non-
Woven cloths, heat dries 10min at 100 DEG C, is warming up to 200 DEG C of heat treatment 5min, makes Si3N4Between nano particle and nano particle with
Melted and well-bonded organic/inorganic nano combined many curved hole films of formation by polyacrylate between PI nanofibers.
(3) performance characterization：Prepared Si3N4The thickness of the nano combined high temperature resistant high safety battery diaphragms of/PI be 10 μm,
Tensile strength is that 50MPa, elongation at break are that 50%, puncture strength is that 6.0N, the percent thermal shrinkage at 350 DEG C are 0, perforated membrane
Porosity be that 30%, surface average pore size is that 50nm, the gas permeability under 0.48bar pressure are that 180S, electric breakdown strength are
50V/ μm, ionic conductivity is 1.0 × 10-3S·cm-1
Embodiment 2：
One kind contains Si3N4The composite film material of nano particle, it is with electrospinning polyimides (PI) nano-fiber for production of non-woven
For base material, Si is filled with substrate pores3N4Nano particle (Si3N4-NP)；
Its preparation method is as follows：
(1) nano Si3N4Water based suspension (Si3N4/H2O-2 configuration)：(diameter is mainly distributed on alpha-silicon nitride powders
100nm) 80.0 grams, 0.5 gram of ammonium polyacrylate, 8.0 grams of the different monooctyl ester copolymer of butylacrylate-acrylic acid, distilled water 433.0
Gram, disposably it is put into beaker, it is emulsified in 8000 turns per minute of rotating speeds, form the nanometer nitrogen that absolute viscosity is 19mPaS
SiClx water based suspension (Si3N4/H2O-2)。
(2)Si3N4The preparation of the micro-nano complex fire resistant high safety battery diaphragms of/PI：By the Si configured above3N4/
H2O-2 Silicon Nitride Suspensions pave the suspension liquid and membrane to form that thickness is 60 μm on a glass, are then 38 μm by thickness
Electrospinning PI nano-fiber for production of non-woven be covered in Si3N4/H2In O-2 suspension liquid and membranes, suspension infilters PI micro/nano-fibre non-wovens
In cloth, treat that nano-fiber cloth upper strata drenches, be fully filled with suspension in the hole for showing non-weaving cloth, uncovered PI Nanowires
Non-weaving cloth is tieed up, heat dries 10min at 100 DEG C, be warming up to 200 DEG C of heat treatment 3min, make Si3N4Between nano particle and sub-micron
Melted and well-bonded organic/inorganic nano combined many curved hole films of formation by polyacrylate between particle and PI nanofibers.
(3) performance characterization：Prepared Si3N4The nano combined high temperature resistant high safety batteries of/PI every film thickness for 40 μm,
Tensile strength be 35MPa, elongation at break be 30%, puncture strength be 12.0N, the percent thermal shrinkage at 350 DEG C be 0, it is porous
The porosity of film is that 50%, surface average pore size is that 150nm, the gas permeability under 0.12bar pressure are 85S, electric breakdown strength
It is 8.0 × 10 for 35V/ μm, ionic conductivity-3S·cm-1。
Embodiment 3：
One kind contains Si3N4The composite film material of nano particle, it is with electrospinning polyimides (PI) nano-fiber for production of non-woven
For base material, Si is filled with substrate pores3N4Nano particle (Si3N4-NP)；
Its preparation method is as follows：
(1) nano Si3N4Water based suspension (Si3N4/H2O-3 configuration)：(diameter is mainly distributed on alpha-silicon nitride powders
50nm) 80.0 grams, 0.7 gram of ammonium polyacrylate, 8.0 grams of the different monooctyl ester copolymer of butylacrylate-acrylic acid, 300.0 grams of distilled water,
Disposably it is put into beaker, it is emulsified in 8000 turns per minute of rotating speeds, form the micron that absolute viscosity is 24mPaS and nitrogenize
Silicon water based suspension (Si3N4/H2O-3)。
(2)Si3N4The preparation of the nano combined high temperature resistant high safety battery diaphragms of/PI：By the Si configured above3N4/H2O-3
It is 50 μm of suspension liquid and membrane that Silicon Nitride Suspensions, which are paved to form thickness on a glass, then by electrospinning that thickness is 24 μm
PI nano-fiber for production of non-woven is covered in Si3N4/H2In O-3 suspension liquid and membranes, suspension is infiltered in PI nano-fiber for production of non-woven,
Treat that nano-fiber cloth upper strata drenches, be fully filled with suspension in the hole for showing non-weaving cloth, uncovered PI nanofibers non-
Woven cloths, heat dries 10min at 100 DEG C, is warming up to 200 DEG C of heat treatment 3min, makes Si3N4Between nano particle and nano particle with
Melted and well-bonded organic/inorganic nano combined many curved hole films of formation by polyacrylate between PI nanofibers.
(3) performance characterization：Prepared Si3N4The nano combined high temperature resistant high safety batteries of/PI every film thickness for 25 μm,
Tensile strength be 45MPa, elongation at break be 38%, puncture strength be 10.0N, the percent thermal shrinkage at 350 DEG C be 0, it is porous
The porosity of film is that 40%, surface average pore size is that 68nm, the gas permeability under 0.48bar pressure are that 15S, electric breakdown strength are
50V/ μm, ionic conductivity be 3.0 × 10-3S·cm-1。
Embodiment 4：
One kind contains Si3N4The composite film material of nano particle, it is with electrospinning polyimides (PI) nano-fiber for production of non-woven
For base material, Si is filled with substrate pores3N4Nano particle (Si3N4-NP)；
Its preparation method is as follows：
(1) nano Si3N4Water based suspension (Si3N4/H2O-4) configure：Alpha-silicon nitride powders (diameter is mainly distributed on 80nm)
80.0 grams, 0.6 gram of ammonium polyacrylate, 8.0 grams of the different monooctyl ester copolymer of butylacrylate-acrylic acid, 433.0 grams of distilled water, once
Property be put into beaker, it is emulsified in 8000 turns per minute of rotating speeds, formed absolute viscosity be 20mPaS nano-silicon nitride water
Base suspension (Si3N4/H2O-4)。
(2)Si3N4The preparation of the nano combined high temperature resistant high safety battery diaphragms of/PI：By the Si configured above3N4/H2O-4
It is 30 μm of suspension liquid and membrane that Silicon Nitride Suspensions, which are paved to form thickness on a glass, then by electrospinning that thickness is 14 μm
PI nano-fiber for production of non-woven is covered in Si3N4/H2In O-4 suspension liquid and membranes, suspension is infiltered in PI nano-fiber for production of non-woven,
Treat that nano-fiber cloth upper strata drenches, be fully filled with suspension in the hole for showing non-weaving cloth, uncovered PI nanofibers non-
Woven cloths, heat dries 10min at 100 DEG C, is warming up to 200 DEG C of heat treatment 5min, makes Si3N4Between nano particle and nano particle with
Melted and well-bonded organic/inorganic nano combined many curved hole films of formation by polyacrylate between PI nanofibers.
(3) performance characterization：Prepared Si3N4The thickness of the nano combined high temperature resistant high safety battery diaphragms of/PI be 15 μm,
Tensile strength is that 48MPa, elongation at break are that 37%, puncture strength is that 7.5N, the percent thermal shrinkage at 350 DEG C are 0, perforated membrane
Porosity be that 40%, surface average pore size is that 120nm, the gas permeability under 0.24bar pressure are that 100S, electric breakdown strength are
48V/ μm, ionic conductivity be 6.2 × 10-3S·cm-1.Above experiment material and result test equipment explanation：
(1) experiment material：
The inorganic micro-nano powder that is used in 4 experiment embodiments of the present invention, PI nano-fiber for production of non-woven, macromolecule point
Powder and polymer binder etc. are commercially available by commercial channel.
1) silicon nitride nanopowder, purchased from Shandong Jing Xin crystal Science and Technology Ltd., the scientific and technological limited public affairs of Beijing Deco island gold
Department；
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 test is with characterizing
The experimental result of 4 experiment embodiments is to carry out routinely testing and characterizing by following instrument and equipment in the present invention.
1) polymer solution and spinning solution absolute viscosity are determined with NDJ-8S viscosimeters (Shanghai precision scientific instrument company)；
2) diameter of electro spinning nano fiber is determined with the SBU of SEM VEGA 3 (Czech Republic)；
3)Si3N4The heat decomposition temperature WRT-3P thermal gravimetric analyzers of the nano combined high temperature resistant high safety battery diaphragms of/PI
(TGA) (Shanghai Precision Scientific Apparatus Co., Ltd) determines；
4)Si3N4The engineering properties (intensity, extension at break etc.) of the nano combined high temperature resistant high safety battery diaphragms of/PI is used
The miniature control electronic universal testers of CMT8102 (Shenzhen SANS material tests Co., Ltd) are determined；
5)Si3N4The glass transition temperature of the nano combined high temperature resistant high safety battery diaphragms of/PI is using the dynamic machines of Diamond
Tool analyzer (DMA) (Perkin-Elmer, the U.S.) is determined；
6)Si3N4The porosity of the nano combined high temperature resistant high safety battery diaphragms of/PI is to calculate to obtain by following formula：
Porosity β=[1- (ρ/ρ o)] × 100
Wherein ρ is Si3N4/ PI nano compound stephanoporate films density (gram/cm3), ρ o are Si3N4The nano combined entities of/PI are thin
Film (being prepared by solution casting method) density (gram/cm3)；
7)Si3N4The gas permeability and surface apertures of the nano combined high temperature resistant high safety battery diaphragms of/PI use the U.S.
Porometer 3G air permeability testers are determined；
8)Si3N4The ionic conductivity of the nano combined high temperature resistant high safety battery diaphragms of/PI is to use electrochemical workstation
CHI 660D (morning China's instrument, Chinese Shanghai) are determined；
9)Si3N4The electric breakdown strength of the nano combined high temperature resistant high safety battery diaphragms of/PI is prosperous beautiful electrically limited with Shanghai
The ZHZ8 types Hi-pot Tester of company is determined.
Claims (5)
1. a kind of nano combined many curved hole membrane materials, it is characterised in that：It using polyimides (PI) nano-fiber for production of non-woven as
Nano-silicon nitride (Si is filled with base material, substrate pores3N4) particle；Described nano Si3N4Particle, its diameter is in 50-
Between 100nm, the 30-60% of nano combined many curved hole membrane material gross weights is accounted for；Described PI nano-fiber for production of non-woven thickness
Between 9-38 μm, porosity is between 60-80%；Described nano combined many curved hole membrane materials are by using containing 15-30%
Wt Si3N4The water based suspension dipping PI nano-fiber for production of non-woven of nano particle, makes suspension infiltration fill up PI nanofibers
The hole of non-weaving cloth, then be made through 100-200 DEG C of high temperature drying；Described water based suspension is further total containing suspension is accounted for
The water of the adhesive of weight 1.0%~5.0%, the dispersant for accounting for suspension gross weight 0.1%~1.0% and surplus；Described
Adhesive is the different monooctyl ester copolymer of butylacrylate-acrylic acid；Described dispersant is ammonium polyacrylate；Described water-based suspension
The absolute viscosity of liquid is 10~30mPaS.
2. the material described in claim 1, it is characterised in that：Described nano combined many curved hole membrane materials, its porosity is in 30-
Between 50%, surface average pore size is between 50-150nm, and thickness is between 10-40 μm.
3. the material described in claim 1, it is characterised in that：The absolute viscosity of described water based suspension is 19~28mPa
S。
4. a kind of method of the nano combined many curved hole membrane materials prepared described in claim 1, is with low viscosity Si3N4Nanometer
Grain water based suspension and PI nano-fiber for production of non-woven are raw material, the method by impregnating infiltration, by Si3N4Nano particle is filled out
In the hole for entering PI nano-fiber for production of non-woven, after lower temperature drying, being warming up to higher temperature makes adhesive in Si3N4Receive
Bonded between rice grain and between particle and PI nanofibers；
Specifically include following steps：
1) water based suspension is prepared：
By weight percentage, by 15-30% Si3N4Nano particle, 0.1%-1.0% dispersant, 1.0-5.0% it is viscous
Mixture and the water of surplus are mixed to get mixed liquor, and mixed liquor is emulsified in 8000-10000 turns/min rotating speed, form absolute
Water based suspension of the viscosity in 10-30mPaS；Described adhesive is the different monooctyl ester copolymer of butylacrylate-acrylic acid；Institute
The dispersant stated is ammonium polyacrylate；
2) nano particle is filled：
By step 1) prepare water based suspension in level board upper berth flat shape into certain thickness suspension liquid and membrane, then by PI nanometers
Fiber non-woven is covered in described suspension liquid and membrane, and suspension is infiltered in PI nano-fiber for production of non-woven, treats nanofiber
Cloth upper strata drenches, and uncovers PI nano-fiber for production of non-woven；
3) molding bonded is dried
By step 2) first the heat at 80~100 DEG C dries 8~12min for obtained PI nano-fiber for production of non-woven, then it is warming up to 180~
200 DEG C of 3~6min of heat treatment, make Si3N4Between nano particle and they are abundant because of the melting of adhesive between PI nanofibers
Bond nano combined many curved hole membrane materials described in formation.
5. the method described in claim 4, it is characterised in that：Step 3) be by step 2) obtained PI nano-fiber for production of non-woven
First heat dries 10min at 100 DEG C, then is warming up to 200 DEG C of heat treatment 5min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510586950.1A CN105064001B (en) | 2015-09-11 | 2015-09-11 | Compound many curved hole membrane materials of silicon nitride particle filling and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510586950.1A CN105064001B (en) | 2015-09-11 | 2015-09-11 | Compound many curved hole membrane materials of silicon nitride particle filling and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105064001A CN105064001A (en) | 2015-11-18 |
| CN105064001B true CN105064001B (en) | 2017-07-11 |
Family
ID=54493489
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510586950.1A Active CN105064001B (en) | 2015-09-11 | 2015-09-11 | Compound many curved hole membrane materials of silicon nitride particle filling and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105064001B (en) |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10208280A1 (en) * | 2002-02-26 | 2003-09-04 | Creavis Tech & Innovation Gmbh | Ceramic membrane based on a polymer or natural fiber substrate, process for its production and use |
| JP5924540B2 (en) * | 2009-11-03 | 2016-06-01 | アモグリーンテク カンパニー，リミテッド | Heat resistance, high-strength ultrafine fiber separation membrane, method for producing the same, and secondary battery using the same |
| CN102931370B (en) * | 2012-10-24 | 2016-04-06 | 江苏大学 | Nanofiber composite nano-fiber membrane and preparation method thereof |
| CN103029395B (en) * | 2012-12-21 | 2015-05-13 | 深圳瑞华泰薄膜科技有限公司 | Corona-resistant polyimide film material and preparation method thereof |
| CN103107301B (en) * | 2013-01-17 | 2015-04-08 | 中国科学院金属研究所 | Novel lithium ion battery diaphragm with inorganic coating and preparation method thereof |
| KR101298340B1 (en) * | 2013-02-12 | 2013-08-20 | 삼성토탈 주식회사 | A coated porous separator and a secondary battery using the same |
| CN103647034A (en) * | 2013-12-04 | 2014-03-19 | 合肥国轩高科动力能源股份公司 | Method for preparing nitride ceramic coating applied to lithium ion battery |
| CN103915594B (en) * | 2014-04-21 | 2017-09-26 | 上海顶皓新材料科技有限公司 | A kind of low ionic resistance high-temperature-reslithium lithium battery coated separator |
| CN104409674B (en) * | 2014-12-08 | 2017-03-29 | 清华大学 | Composite diaphragm material and preparation method and application |
-
2015
- 2015-09-11 CN CN201510586950.1A patent/CN105064001B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN105064001A (en) | 2015-11-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105098125B (en) | Compound many curved hole membrane materials of alumina particle filling and its preparation method and application | |
| CN107170942B (en) | High-temperature-resistant aramid fiber lithium ion battery composite diaphragm and preparation method thereof | |
| CN104409674B (en) | Composite diaphragm material and preparation method and application | |
| CN103296240A (en) | High-performance flexible composite nonwoven fabric membrane for lithium ion battery, as well as preparation method and application of membrane | |
| KR20170014009A (en) | Separator | |
| CN108149343B (en) | Composite nanofiber with silicon nanoparticles coated with nitrogen-doped porous carbon and preparation method thereof | |
| CN105568555B (en) | A kind of preparation method of air filtration graphene fiber film | |
| CN108807791B (en) | Composite diaphragm for lithium battery and preparation method thereof | |
| Wang et al. | A novel three-dimensional boehmite nanowhiskers network-coated polyethylene separator for lithium-ion batteries | |
| CN105244466B (en) | Compound many curved hole membrane materials of silica dioxide granule filling and its preparation method and application | |
| CN109728233A (en) | Ceramic slurry, ceramic diaphragm and lithium ion battery | |
| JP2013115031A (en) | Coating liquid for lithium ion battery separator use, and lithium ion battery separator | |
| KR101827321B1 (en) | Washable and flexible textile fiber electrode and manufacturing method thereof | |
| CN105161659B (en) | Compound many curved hole membrane materials of politef microsphere filling and its preparation method and application | |
| CN105064007B (en) | PI‑SiO2PTFE ternary nanos are combined many curved hole membrane materials and its preparation method and application | |
| CN105226219B (en) | Compound many curved hole membrane materials of zirconia particles filling and its preparation method and application | |
| CN105047847B (en) | PI AlN PTFE ternary nanos are combined many curved hole membrane materials and its preparation method and application | |
| JP6347690B2 (en) | Electrochemical element separator | |
| CN105070871B (en) | Compound many curved hole membrane material that crosslinked polystyrene microsphere is filled and its preparation method and application | |
| CN105064001B (en) | Compound many curved hole membrane materials of silicon nitride particle filling and its preparation method and application | |
| CN105206783B (en) | Compound many curved hole membrane material that boron nitride particle is filled and its preparation method and application | |
| CN106702504A (en) | Lithium battery isolation membrane coating system and coating method | |
| CN105070869B (en) | PI-BN-PTFE ternary nano is combined many curved hole membrane material and its preparation method and application | |
| CN105226218B (en) | PI‑PTEF‑Al2O3Ternary nano is combined many curved hole membrane materials and its preparation method and application | |
| CN105304849B (en) | Compound many curved hole membrane material that aluminum nitride particle is filled and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |