CN108649172A - A kind of high temperature shutoff protection mechanism battery diaphragm and preparation method thereof - Google Patents
A kind of high temperature shutoff protection mechanism battery diaphragm and preparation method thereof Download PDFInfo
- Publication number
- CN108649172A CN108649172A CN201810473561.1A CN201810473561A CN108649172A CN 108649172 A CN108649172 A CN 108649172A CN 201810473561 A CN201810473561 A CN 201810473561A CN 108649172 A CN108649172 A CN 108649172A
- Authority
- CN
- China
- Prior art keywords
- high temperature
- protection mechanism
- pvp
- battery diaphragm
- titanium dioxide
- 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.)
- Granted
Links
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
- H01M50/403—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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
-
- 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
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/572—Means for preventing undesired use or discharge
- H01M50/574—Devices or arrangements for the interruption of current
- H01M50/581—Devices or arrangements for the interruption of current in response to temperature
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Nonwoven Fabrics (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of high temperature shutoff protection mechanism battery diaphragms and preparation method thereof; the high temperature shutoff protection mechanism battery diaphragm is collected by titanium dioxide and PVP nanometers of one-dimentional structures by electrostatic spinning; the thickness of high temperature shutoff protection mechanism battery diaphragm is 20~200 μm, and porosity is 45%~85%.The features of the present invention is：First, having inorganic constituents and micro-nano tubular structure, excellent wet performance has preferable imbibition and liquid-keeping property to electrolyte；Second is that having unique high temperature shutoff protection mechanism, when operating temperature reaches 60 DEG C, battery can be prevented to charge, temperature turns again to room temperature, and can work under the conditions of relatively low pressure；Third, porosity is high, aperture is small, and there is higher ion penetration and electrochemical stability, excellent mechanical performance energy storage device short circuit and dendrite can be effectively prevent to puncture；Fourth, high-temperature shrinkage rate is low, there is preferable high temperature bearing performance and safety.
Description
Technical field
The present invention relates to a kind of high temperature shutoff protection mechanism battery diaphragms and preparation method thereof, belong to novel energy resource material technology
Field.
Background technology
In recent years, the application with electric vehicle and energy-storage system in different environments has high-energy density and height
The research and development of the lithium ion battery of safety are gradually paid attention to.In general, lithium ion battery mainly by positive/negative material, electrolyte,
Diaphragm and battery case packaging material composition.Wherein, diaphragm is the important component of lithium ion battery, and it is positive and negative to play separation
Pole, prevent electronics by while for lithium ion provide channel, to complete the effect of charge and discharge.Its physics, chemistry and machine
Tool performance determines the interfacial characteristics of battery, internal resistance etc., directly affects the characteristics such as capacity, cycle and the safety of battery, performance
Good diaphragm plays an important role the comprehensive performance for improving battery.
Currently, lithium ion battery separator material is mainly that polyalkene diaphragm such as single-layer polypropylene (PP) microporous barrier, single layer are poly-
Ethylene (PE) microporous barrier and three layers of PP/PE/PP composite membranes, such diaphragm preparation method are mainly dry method tension pore method and wet
Method phase separation method.Polyalkene diaphragm drawback is：One, it is easily shunk when polyalkene diaphragm is heated, diaphragm size can be caused unstable,
Positive and negative anodes are in direct contact and short-circuit；Two, closed pore temperature and broken film temperature are relatively low, when the situations such as battery puncture occur, in battery
Portion is highly exothermic, and diaphragm is caused to melt contraction completely, and battery short circuit generates high temperature until battery disintegrates or explodes.These drawbacks are
It is determined by polypropylene material self-characteristic, PE fusing points are 128~135 DEG C, and PP fusing points are 150~166 DEG C.It is currently used
Capacitor diaphragm has polypropylene diaphragm and cellulosic separator two major classes.These material thermal stability are poor, and porosity is low and imbibition
Poor performance.On the one hand cause the chemical property of capacitor undesirable, its hot operation is on the other hand caused to be easy to happen danger.
China Patent Publication No. is CN106252568A, and publication date is on December 21st, 2016, entitled " a kind of
High temp resistance lithium ion cell diaphragm and preparation method thereof " is formed using non-woven fabrics as base material by metal ion and nanofiber
Chemical bond is connected with silane coupling agent, is coated to non-woven fabrics base material using technologies such as spraying, dipping or blade coatings, and resistance to height is obtained
The battery diaphragm of temperature.But the diaphragm due to have the presence of non-woven fabrics and binder, its do not have high temperature shutoff protection mechanism；China
Patent publication No. is CN104037377A, and publication date is September in 2014 10, the entitled " preparation of lithium battery diaphragm
Method " first prepares mLLDPE non-woven fibres using method of electrostatic spinning, then equally fine in mLLDPE nonwovens using method of electrostatic spinning
Dimension obtains pvdf membrane, compound both to obtain lithium electric separator.Although this method has its advantage, using method of electrostatic spinning twice, operation
Of high cost, efficiency is low, is unfavorable for industrialization, while also not having high temperature shutoff protection mechanism.
Invention content
The object of the present invention is to provide a kind of high temperature shutoff protection mechanism battery diaphragms and preparation method thereof.
The technical scheme is that a kind of high temperature shutoff protection mechanism battery diaphragm, the high temperature shutoff protection mechanism
Battery diaphragm is collected by titanium dioxide and PVP (polyvinylpyrrolidone) nano-tube material by electrostatic spinning, and high temperature is opened
The thickness for closing protection mechanism battery diaphragm is 20~200 μm, and porosity is 45%~85%.
It is 100~500nm that the titanium dioxide, which is received with the outer diameter of PVP nanometers of one-dimentional structure material nano pipes, internal diameter 40
~200nm.
The mass ratio that titanium dioxide accounts in the high temperature shutoff protection mechanism battery diaphragm is 20%~80%, PVP
The mass ratio that nanometer one-dimentional structure material accounts for is 20%~80%.
A kind of preparation method of high temperature shutoff protection mechanism battery diaphragm：
Titanium dioxide is dispersed in the solution for having dissolved PVP nanometers of one-dimentional structure materials and titanium dioxide is made
Titanium/PVP nanometers of one-dimentional structure material precursor is electrospinning external solution, using oily matter as liquid in electrospinning, on electrospinning device
Dispersion relation is carried out, obtained electrospun film is disposed into oily matter with molten oil solvent, a kind of high temperature is obtained after dry
Switch protection mechanism battery diaphragm.
The preparation of the titanium dioxide/PVP nanometers of one-dimentional structure material precursor：
(a) take PVP powder to be dissolved in volatile organic solvent, be made gel presoma, wherein PVP with it is organic molten
The mass ratio of agent is controlled 1:50~1:5, PVP molecular weight 8000~1300000；
(b) effumability acid is added into gel presoma, the Yishui River is then slowly added dropwise under rapid stirring
Solution continues to stir at the solvent of titanium dioxide after being added dropwise to complete, and the specific gravity control of effumability acid and organic solvent is 1:10~
3:5, acetic acid and facile hydrolysis are at the specific gravity control of the solvent of titanium dioxide 1:1~3:1, rate of addition control 30~120 drip/
Min, to mixing speed control in 50~100r/min, mixing time controls in 5~120r/min, obtains titanium dioxide/PVP and receive
Rice one-dimentional structure material precursor.
The oily matter is the mixture of one or both of mineral oil or dimethicone.
Electrostatic spinning Dispersion relation operation is carried out on electrospinning device, liquid speed control is in 0.01~1ml/ in electrospinning
Min, for electrospinning external solution speed control in 0.02~2ml/h, inside and outside liquid speed ratio is 1:2, electrospinning positive voltage is controlled in 10~20kV,
Negative voltage control in 0~5kV, electrospinning time control 5~for 24 hours, receive distance controlling in 10~30cm, obtain electrospun film.
The molten oil solvent is the one or more in normal octane or n-hexane or hexane, impregnates the molten oily time
Control was at 12 hours or more.
The facile hydrolysis at the reagent of titanium dioxide be one kind in isopropyl titanate or tetra-n-butyl titanate or it is a kind of with
On.
The effumability acid is in hydrochloric acid, acetic acid, nitric acid, hydrofluoric acid, hydrobromic acid, hydroiodic acid, sulfurous acid or hydrosulphuric acid
One or more.
The volatile organic solvent is that one kind or one or more in methanol, ethyl alcohol, ethyl acetate or carbon tetrachloride is planted.
The present invention is dispersed in titanium dioxide in the solution for having dissolved PVP nanometers of one-dimentional structure materials, system
It is electrospinning external solution at titanium dioxide/PVP nanometers of one-dimentional structure material precursor, using oily matter as liquid in electrospinning, in Static Spinning
Dispersion relation is carried out in silk equipment, obtained electrospun film is disposed into oily matter with molten oil solvent, is obtained after dry
A kind of high temperature shutoff protection mechanism battery diaphragm.Due to the interlaced braiding between the one-dimensional tubular structure of nanometer, make its structure
Stablize, mechanical performance is excellent, and ordinary titanium dioxide itself is hydrophilic and oleophilic and high-temperature stable, to by titanium dioxide and PVP
Nanometer one-dimentional structure material cospinning at tubular diaphragm, porosity is higher, and imbibition rate is higher, thermal stability than more prominent, even if
Being shunk at a high temperature of 200 degree can almost ignore, and will not more melt brokenly, improve the security performance of battery.And due to this
Special structure so that this diaphragm has high temperature shutoff protection mechanism.Compared with prior art, advantages of the present invention is：One
It is high temperature shutoff protection mechanism battery diaphragm because itself has inorganic constituents and micro-nano tubular structure, has excellent wet
Lubricant nature energy has preferable imbibition and liquid-keeping property compared with most of pure organic barrier film to electrolyte；Second is that with common quotient
Industry diaphragm is compared, and is had unique high temperature shutoff protection mechanism, when diaphragm operating temperature reaches 60 DEG C, battery can be prevented to fill
Electricity, temperature turn again to room temperature, and diaphragm can work under the conditions of relatively low pressure again；Third, porosity is high, aperture is small, tool
There are higher ion penetration and electrochemical stability, and there is excellent mechanical performance, energy storage device can be effectively prevent short
Road and dendrite puncture；Fourth, with compared with polyalkene diaphragm, high temperature resistance is improved, PE and PP microporous barriers are at 180 DEG C
Significant shrinkage, and gradually melt, and after diaphragm of the present invention is handled at 200 DEG C, it still can work on, have at normal temperatures
Preferable high temperature bearing performance and safety.
Description of the drawings
Fig. 1 is the SEM scanning figures of switch diaphragm of the present invention.
Fig. 2 is the pipe structure TEM figures of switch diaphragm of the present invention.
Fig. 3 is the digital image of switch diaphragm of the present invention.
Fig. 4 is the TGA and DSC curve of switch diaphragm of the present invention.
Fig. 5 is the application effect figure of switch diaphragm of the present invention in the battery.
Fig. 6 is the switch performance application effect figure of switch diaphragm of the present invention in the battery.
Fig. 7 is protection voltage of the switch diaphragm of the present invention at 60 DEG C.
Specific implementation mode
The principles and features of the present invention are described below, and the given examples are served only to explain the present invention, is not intended to limit
Determine the scope of the present invention.
As shown in Figure 1, Figure 2, Figure 3 shows, a kind of high temperature shutoff protection mechanism battery diaphragm, the high temperature shutoff protection mechanism electricity
Pond diaphragm is collected by titanium dioxide and PVP nano-tube materials by electrostatic spinning, high temperature shutoff protection mechanism battery diaphragm
Thickness be 20~200 μm, porosity be 45%~85%.
The outer diameter of the titanium dioxide and PVP nanometers of one-dimentional structures is 100~500nm, internal diameter is 40~200nm.
The mass ratio that the titanium dioxide accounts for is 20%~80%.
A kind of preparation method of high temperature shutoff protection mechanism battery diaphragm：
Embodiment 1
A. 0.3g polyvinylpyrrolidones (PVP, molecular weight are taken：1300000) it is dissolved in 10ml ethanol solutions, is formed with
Conducive to the gel presoma of electrostatic spinning；
B. 3ml acetic acid is added to the gel presoma obtained by a steps, then under conditions of 60r/min is quickly stirred
Isopropyl titanate is slowly added dropwise, continues to stir 30min after being added dropwise to complete；Before titanium dioxide/PVP nanometers of one-dimentional structure material is made
Drive body；
C. using titanium dioxide/PVP nanometers of one-dimentional structure material precursor as electrospinning external solution, mineral oil is liquid in electrospinning, and
With the interior liquid speed degree of the external solution speed of 0.1ml/h and 0.05ml/h distance is received in the positive voltage of 15kV and the negative voltage of 1kV
Control carries out Dispersion relation 12h under conditions of 20cm；Obtain electrospun film；
D. electrospun film is immersed in normal octane and disposes intermediate oily matter for 24 hours, it is to obtain the final product a kind of high after dry
Warm switch protection mechanism battery diaphragm.
As shown in figure 4, prepared high-temperature-resistant membrane still keeps good thermal stability until 200 DEG C.It is hot operation
The good diaphragm material of secondary cell.
Embodiment 2
A. 0.3g polyvinylpyrrolidones (PVP, molecular weight are taken：1300000) it is dissolved in 10ml methanol solutions, is formed with
Conducive to the gel presoma of electrostatic spinning；
B. 3ml acetic acid is added to gel presoma, metatitanic acid then is slowly added dropwise under conditions of 60r/min is quickly stirred
Isopropyl ester continues to stir 30min after being added dropwise to complete；Titanium dioxide/PVP nanometers of one-dimentional structure material precursor is made；
C. using titanium dioxide/PVP nanometers of one-dimentional structure material precursor as electrospinning external solution, mineral oil is liquid in electrospinning, and
With the interior liquid speed degree of the external solution speed of 0.1ml/h and 0.05ml/h distance is received in the positive voltage of 15kV and the negative voltage of 1kV
Control carries out Dispersion relation 12h under conditions of 20cm；Obtain electrospun film；
D. electrospun film is immersed in normal octane and disposes intermediate oily matter for 24 hours, it is to obtain the final product a kind of high after dry
Warm switch protection mechanism battery diaphragm.
Embodiment 3
A. 0.3g polyvinylpyrrolidones (PVP, molecular weight are taken：1300000) it is dissolved in 10ml ethyl acetate solutions, makes
At the gel presoma for being conducive to electrostatic spinning；
B. 3ml acetic acid is added to gel presoma, metatitanic acid then is slowly added dropwise under conditions of 60r/min is quickly stirred
Isopropyl ester continues to stir 30min after being added dropwise to complete, titanium dioxide/PVP nanometers of one-dimentional structure material precursor is made；
C. using titanium dioxide/PVP nanometers of one-dimentional structure material precursor as electrospinning external solution, mineral oil is liquid in electrospinning, and
With the interior liquid speed degree of the external solution speed of 0.1ml/h and 0.05ml/h distance is received in the positive voltage of 15kV and the negative voltage of 1kV
Control carries out Dispersion relation 12h under conditions of 20cm, obtains electrospun film；
D. electrospun film will be obtained and be immersed in normal octane the oily matter for disposing centre for 24 hours, it is dry later up to one
Kind high temperature shutoff protection mechanism battery diaphragm.
Embodiment 4
A. 0.3g polyvinylpyrrolidones (PVP, molecular weight are taken：1300000) it is dissolved in 10ml carbon tetrachloride solutions, makes
At the gel presoma for being conducive to electrostatic spinning；
B. 3ml acetic acid is added to gel presoma, metatitanic acid then is slowly added dropwise under conditions of 60r/min is quickly stirred
Isopropyl ester continues to stir 30min after being added dropwise to complete, titanium dioxide/PVP nanometers of one-dimentional structure material precursor is made；
C. using titanium dioxide/PVP nanometers of one-dimentional structure material precursor as electrospinning external solution, mineral oil is liquid in electrospinning, and
With the interior liquid speed degree of the external solution speed of 0.1ml/h and 0.05ml/h distance is received in the positive voltage of 15kV and the negative voltage of 1kV
Control carries out Dispersion relation 12h under conditions of 20cm, obtains electrospun film；
D. electrospun film will be obtained and be immersed in normal octane the oily matter for disposing centre for 24 hours, it is dry later up to one
Kind high temperature shutoff protection mechanism battery diaphragm.
Embodiment 5
A. 0.3g polyvinylpyrrolidones (PVP, molecular weight are taken：1300000) it is dissolved in 10ml ethanol solutions, is formed with
Conducive to the gel presoma of electrostatic spinning；
B. 3ml hydrochloric acid is added to gel presoma, metatitanic acid then is slowly added dropwise under conditions of 60r/min is quickly stirred
Isopropyl ester continues to stir 30min after being added dropwise to complete, titanium dioxide/PVP nanometers of one-dimentional structure material precursor is made；
C. using titanium dioxide/PVP nanometers of one-dimentional structure material precursor as electrospinning external solution, mineral oil is liquid in electrospinning, and
With the interior liquid speed degree of the external solution speed of 0.1ml/h and 0.05ml/h distance is received in the positive voltage of 15kV and the negative voltage of 1kV
Control carries out Dispersion relation 12h under conditions of 20cm, obtains electrospun film；
D. electrospun film will be obtained and be immersed in normal octane the oily matter for disposing centre for 24 hours, it is dry later up to one
Kind high temperature shutoff protection mechanism battery diaphragm.
Embodiment 6
A. 0.3g polyvinylpyrrolidones (PVP, molecular weight are taken：1300000) it is dissolved in 10ml ethanol solutions, is formed with
Conducive to the gel presoma of electrostatic spinning；
B. 3ml acetic acid is added to gel presoma, metatitanic acid then is slowly added dropwise under conditions of 60r/min is quickly stirred
Four N-butyls continue to stir 30min after being added dropwise to complete, titanium dioxide/PVP nanometers of one-dimentional structure material precursor are made；
C. titanium dioxide/PVP nanometers of one-dimentional structure material precursor is made as electrospinning external solution, mineral oil is in electrospinning
Liquid, and received in the positive voltage of 15kV and the negative voltage of 1kV with the interior liquid speed degree of the external solution speed of 0.1ml/h and 0.05ml/h
Distance controlling carries out Dispersion relation 12h under conditions of 20cm, obtains electrospun film；
D will obtain electrospun film and be immersed in normal octane the oily matter for disposing centre for 24 hours, dry later up to one
Kind high temperature shutoff protection mechanism battery diaphragm.
Embodiment 7
A. 0.3g polyvinylpyrrolidones (PVP, molecular weight are taken：1300000) it is dissolved in 10ml ethanol solutions, is formed with
Conducive to the gel presoma of electrostatic spinning；
B. 3ml acetic acid is added to the gel presoma obtained by a steps, then under conditions of 60r/min is quickly stirred
Isopropyl titanate is slowly added dropwise, continues to stir 30min after being added dropwise to complete, before titanium dioxide/PVP nanometers of one-dimentional structure material is made
Drive body；
C. titanium dioxide/PVP nanometers of one-dimentional structure material precursor is made as electrospinning external solution, dimethicone is electrospinning
Interior liquid, and connect in the positive voltage of 15kV and the negative voltage of 1kV with the interior liquid speed degree of the external solution speed of 0.1ml/h and 0.05ml/h
It receives distance controlling and carries out Dispersion relation 12h under conditions of 20cm, obtain electrospun film；
D. electrospun film will be obtained and be immersed in normal octane the oily matter for disposing centre for 24 hours, it is dry later up to one
Kind high temperature shutoff protection mechanism battery diaphragm.
Embodiment 8
A. 0.3g polyvinylpyrrolidones (PVP, molecular weight are taken：1300000) it is dissolved in 10ml ethanol solutions, is formed with
Conducive to the gel presoma of electrostatic spinning；
B. 3ml acetic acid is added to gel presoma, metatitanic acid then is slowly added dropwise under conditions of 60r/min is quickly stirred
Isopropyl ester continues to stir 30min after being added dropwise to complete, titanium dioxide/PVP nanometers of one-dimentional structure material precursor is made；
C. titanium dioxide/PVP nanometers of one-dimentional structure material precursor is made as electrospinning external solution, mineral oil is in electrospinning
Liquid, and received in the positive voltage of 15kV and the negative voltage of 1kV with the interior liquid speed degree of the external solution speed of 0.1ml/h and 0.05ml/h
Distance controlling carries out Dispersion relation 12h under conditions of 20cm, obtains electrospun film；
D. electrospun film will be obtained and be immersed in n-hexane the oily matter for disposing centre for 24 hours, it is dry later up to one
Kind high temperature shutoff protection mechanism battery diaphragm.
Embodiment 9
A. 0.3g polyvinylpyrrolidones (PVP, molecular weight are taken：1300000) it is dissolved in 10ml ethanol solutions, is formed with
Conducive to the gel presoma of electrostatic spinning；
B. 3ml acetic acid is added to gel presoma, metatitanic acid then is slowly added dropwise under conditions of 60r/min is quickly stirred
Isopropyl ester continues to stir 30min after being added dropwise to complete, titanium dioxide/PVP nanometers of one-dimentional structure material precursor is made；
C. titanium dioxide/PVP nanometers of one-dimentional structure material precursor is made as electrospinning external solution, mineral oil is in electrospinning
Liquid, and received in the positive voltage of 15kV and the negative voltage of 1kV with the interior liquid speed degree of the external solution speed of 0.1ml/h and 0.05ml/h
Distance controlling carries out Dispersion relation 12h under conditions of 20cm, obtains electrospun film；
D. electrospun film will be obtained and be immersed in hexane the oily matter for disposing centre for 24 hours, it is dry later up to one
Kind high temperature shutoff protection mechanism battery diaphragm.
Embodiment 10
A. 0.4g polyvinylpyrrolidones (PVP, molecular weight are taken：1300000) it is dissolved in 10ml ethanol solutions, is formed with
Conducive to the gel presoma of electrostatic spinning；
B. 3ml acetic acid is added to gel presoma, metatitanic acid then is slowly added dropwise under conditions of 60r/min is quickly stirred
Isopropyl ester continues to stir 30min after being added dropwise to complete, titanium dioxide/PVP nanometers of one-dimentional structure material precursor is made；
C. titanium dioxide/PVP nanometers of one-dimentional structure material precursor is made as electrospinning external solution, mineral oil is in electrospinning
Liquid, and received in the positive voltage of 15kV and the negative voltage of 1kV with the interior liquid speed degree of the external solution speed of 0.1ml/h and 0.05ml/h
Distance controlling carries out Dispersion relation 12h under conditions of 20cm, obtains electrospun film；
D. electrospun film will be obtained and be immersed in normal octane the oily matter for disposing centre for 24 hours, it is dry later up to one
Kind high temperature shutoff protection mechanism battery diaphragm.
Embodiment 11
A. 0.2g polyvinylpyrrolidones (PVP, molecular weight are taken：1300000) it is dissolved in 10ml ethanol solutions, is formed with
Conducive to the gel presoma of electrostatic spinning；
B. 3ml acetic acid is added to gel presoma, metatitanic acid then is slowly added dropwise under conditions of 60r/min is quickly stirred
Isopropyl ester continues to stir 30min after being added dropwise to complete, titanium dioxide/PVP nanometers of one-dimentional structure material precursor is made；
C. titanium dioxide/PVP nanometers of one-dimentional structure material precursor is made as electrospinning external solution, mineral oil is in electrospinning
Liquid, and received in the positive voltage of 15kV and the negative voltage of 1kV with the interior liquid speed degree of the external solution speed of 0.1ml/h and 0.05ml/h
Distance controlling carries out Dispersion relation 12h under conditions of 20cm, obtains electrospun film；
D. electrospun film will be obtained and be immersed in normal octane the oily matter for disposing centre for 24 hours, it is dry later up to one
Kind high temperature shutoff protection mechanism battery diaphragm.
Embodiment 12
A. 0.3g polyvinylpyrrolidones (PVP, molecular weight are taken：1300000) it is dissolved in 10ml ethanol solutions, is formed with
Conducive to the gel presoma of electrostatic spinning；
B. 3ml acetic acid is added to gel presoma, metatitanic acid then is slowly added dropwise under conditions of 60r/min is quickly stirred
Isopropyl ester continues to stir 30min after being added dropwise to complete, titanium dioxide/PVP nanometers of one-dimentional structure material precursor is made；
C. titanium dioxide/PVP nanometers of one-dimentional structure material precursor is made as electrospinning external solution, mineral oil is in electrospinning
Liquid, and received in the positive voltage of 15kV and the negative voltage of 1kV with the interior liquid speed degree of the external solution speed of 0.1ml/h and 0.05ml/h
Distance controlling carries out Dispersion relation 12h under conditions of 10cm, obtains electrospun film；
D. electrospun film will be obtained and be immersed in normal octane the oily matter for disposing centre for 24 hours, it is dry later up to one
Kind high temperature shutoff protection mechanism battery diaphragm.
Embodiment 13
A. 0.3g polyvinylpyrrolidones (PVP, molecular weight are taken：1300000) it is dissolved in 10ml ethanol solutions, is formed with
Conducive to the gel presoma of electrostatic spinning；
B. 3ml acetic acid is added to gel presoma, metatitanic acid then is slowly added dropwise under conditions of 60r/min is quickly stirred
Isopropyl ester continues to stir 30min after being added dropwise to complete, titanium dioxide/PVP nanometers of one-dimentional structure material precursor is made；
C. titanium dioxide/PVP nanometers of one-dimentional structure material precursor is made as electrospinning external solution, mineral oil is in electrospinning
Liquid, and received in the positive voltage of 15kV and the negative voltage of 1kV with the interior liquid speed degree of the external solution speed of 0.1ml/h and 0.05ml/h
Distance controlling carries out Dispersion relation 16h under conditions of 20cm, obtains electrospun film；
D. electrospun film will be obtained and be immersed in normal octane the oily matter for disposing centre for 24 hours, it is dry later up to one
Kind high temperature shutoff protection mechanism battery diaphragm.
Embodiment 14
A. 0.3g polyvinylpyrrolidones (PVP, molecular weight are taken：1300000) it is dissolved in 10ml ethanol solutions, is formed with
Conducive to the gel presoma of electrostatic spinning；
B. 3ml acetic acid is added to gel presoma, metatitanic acid then is slowly added dropwise under conditions of 60r/min is quickly stirred
Isopropyl ester continues to stir 30min after being added dropwise to complete, titanium dioxide/PVP nanometers of one-dimentional structure material precursor is made；
C. titanium dioxide/PVP nanometers of one-dimentional structure material precursor is made as electrospinning external solution, mineral oil is in electrospinning
Liquid, and received in the positive voltage of 15kV and the negative voltage of 1kV with the interior liquid speed degree of the external solution speed of 0.1ml/h and 0.05ml/h
Distance controlling carries out Dispersion relation 8h under conditions of 20cm, obtains electrospun film；
D. electrospun film will be obtained and be immersed in normal octane the oily matter for disposing centre for 24 hours, it is dry later up to one
Kind high temperature shutoff protection mechanism battery diaphragm.
Embodiment 15
A. 50g polyvinylpyrrolidones molten (PVP, molecular weight are taken：8000) solution is formed with being conducive in 10ml ethanol solutions
The gel presoma of electrostatic spinning；
B. 3ml acetic acid is added to gel presoma, metatitanic acid then is slowly added dropwise under conditions of 60r/min is quickly stirred
Isopropyl ester continues to stir 30min after being added dropwise to complete；Titanium dioxide/PVP nanometers of one-dimentional structure material precursor is made；
C. using titanium dioxide/PVP nanometers of one-dimentional structure material precursor as electrospinning external solution, mineral oil is liquid in electrospinning, and
With the interior liquid speed degree of the external solution speed of 0.1ml/h and 0.05ml/h distance is received in the positive voltage of 15kV and the negative voltage of 1kV
Control carries out Dispersion relation 12h under conditions of 20cm；Obtain electrospun film；
Electrospun film is immersed in normal octane and disposes intermediate oily matter for 24 hours by d, to obtain the final product a kind of high after dry
Warm switch protection mechanism battery diaphragm.
Embodiment 16
A. 10g polyvinylpyrrolidones molten (PVP, molecular weight are taken：40000) solution is made advantageous in 10ml ethanol solutions
In the gel presoma of electrostatic spinning；
B. 3ml acetic acid is added to gel presoma, metatitanic acid then is slowly added dropwise under conditions of 60r/min is quickly stirred
Isopropyl ester continues to stir 30min after being added dropwise to complete；Titanium dioxide/PVP nanometers of one-dimentional structure material precursor is made；
C. using titanium dioxide/PVP nanometers of one-dimentional structure material precursor as electrospinning external solution, mineral oil is liquid in electrospinning, and
With the interior liquid speed degree of the external solution speed of 0.1ml/h and 0.05ml/h distance is received in the positive voltage of 15kV and the negative voltage of 1kV
Control carries out Dispersion relation 12h under conditions of 20cm；Obtain electrospun film；
D. electrospun film is immersed in normal octane and disposes intermediate oily matter for 24 hours, it is to obtain the final product a kind of high after dry
Warm switch protection mechanism battery diaphragm.
Embodiment 17
With LiFePO4It is positive and negative electrode, the high-temperature-resistant membrane prepared by the present invention and carga moral with lithium metal
(Celgard) the business diaphragm of company's production is as battery diaphragm, 1M LiPF6EC/EMC/DMC solution (mass ratio 1:1:
1) it is electrolyte assembled battery, carries out charge-discharge test, cycle performance is as shown in Figure 5.Machine is protected using high temperature shutoff of the present invention
For diaphragm processed as battery diaphragm, specific discharge capacity, cycle performance are superior to the business diaphragm of carga moral company production.
Embodiment 18
With LiFePO4It is positive and negative electrode, the high-temperature-resistant membrane prepared by the present invention and carga moral with lithium metal
(Celgard) the business diaphragm of company's production is as battery diaphragm, 1M LiPF6EC/EMC/DMC solution (mass ratio 1:1:
1) it is electrolyte assembled battery, carries out charge-discharge test, protection mechanism is as shown in Figure 6 and Figure 7.It is protected using high temperature shutoff of the present invention
Protection mechanism diaphragm has sensibility as battery diaphragm, to temperature, and forms protection voltage.
Claims (11)
1. a kind of high temperature shutoff protection mechanism battery diaphragm, it is characterised in that：The high temperature shutoff protection mechanism battery diaphragm by
Titanium dioxide and PVP nano-tube materials are collected by electrostatic spinning, and the thickness of high temperature shutoff protection mechanism battery diaphragm is
20~200 μm, porosity is 45%~85%.
2. a kind of high temperature shutoff protection mechanism battery diaphragm according to claim 1, it is characterised in that：The titanium dioxide
It is 100~500nm to receive with the outer diameter of PVP nano-tube materials, internal diameter is 40~200nm.
3. according to claim 1 or a kind of high temperature shutoff protection mechanism battery diaphragm, it is characterised in that：In the height
The mass ratio that titanium dioxide accounts in warm switch protection mechanism battery diaphragm is that 20%~80%, PVP nanometers of one-dimentional structure materials account for
Mass ratio be 20%~80%.
4. a kind of preparation method of high temperature shutoff protection mechanism battery diaphragm, it is characterised in that：
Titanium dioxide is dispersed in the solution for having dissolved PVP nanometers of one-dimentional structure materials, be made titanium dioxide/
PVP nanometers of one-dimentional structure material precursors are that electrospinning external solution is carried out using oily matter as liquid in electrospinning on electrospinning device
Obtained electrospun film is disposed oily matter with molten oil solvent, a kind of high temperature shutoff is obtained after dry by Dispersion relation
Protection mechanism battery diaphragm.
5. a kind of preparation method of high temperature shutoff protection mechanism battery diaphragm according to claim 4, it is characterised in that：Institute
State the preparation of titanium dioxide/PVP nanometers of one-dimentional structure material precursor：
(a) it takes PVP powder to be dissolved in volatile organic solvent, is made gel presoma, wherein PVP and organic solvent
Mass ratio is controlled 1:50~1:5, PVP molecular weight 8000~1300000；
(b) into gel presoma be added effumability acid, be then slowly added dropwise under rapid stirring facile hydrolysis at
The solvent of titanium dioxide continues to stir after being added dropwise to complete, and the specific gravity control of effumability acid and organic solvent is 1:10~3:5,
Acetic acid and facile hydrolysis are at the specific gravity control of the solvent of titanium dioxide 1:1~3:1, rate of addition is controlled in 30~120 drops/min,
To mixing speed control in 50~100r/min, mixing time is controlled in 5~120r/min, obtains titanium dioxide/PVP nanometers one
Tie up structural material presoma.
6. a kind of preparation method of high temperature shutoff protection mechanism battery diaphragm according to claim 4, it is characterised in that：Institute
State the mixture that oily matter is one or both of mineral oil or dimethicone.
7. a kind of preparation method of high temperature shutoff protection mechanism battery diaphragm according to claim 4, it is characterised in that：
Electrostatic spinning Dispersion relation operation is carried out on electrospinning device, liquid speed control is outside 0.01~1ml/min, electrospinning in electrospinning
For liquid speed control in 0.02~2ml/h, inside and outside liquid speed ratio is 1:2, the control of electrospinning positive voltage is in 10~20kV, negative voltage control
In 0~5kV, electrospinning time control 5~for 24 hours, receive distance controlling in 10~30cm, obtain electrospun film.
8. a kind of preparation method of high temperature shutoff protection mechanism battery diaphragm according to claim 4, it is characterised in that：Institute
The molten oil solvent stated is the one or more in normal octane or n-hexane or hexane, and it is small 12 to impregnate molten oily time control
When more than.
9. a kind of preparation method of high temperature shutoff protection mechanism battery diaphragm according to claim 4, it is characterised in that：Institute
It is the one or more in isopropyl titanate or tetra-n-butyl titanate that facile hydrolysis, which is stated, into the reagent of titanium dioxide.
10. a kind of preparation method of high temperature shutoff protection mechanism battery diaphragm according to claim 5, it is characterised in that：
The effumability acid be hydrochloric acid, acetic acid, nitric acid, hydrofluoric acid, hydrobromic acid, hydroiodic acid, sulfurous acid or hydrosulphuric acid in one kind or
More than one.
11. a kind of preparation method of high temperature shutoff protection mechanism battery diaphragm according to claim 5, it is characterised in that：
The volatile organic solvent is that one kind or one or more in methanol, ethyl alcohol, ethyl acetate or carbon tetrachloride is planted.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810473561.1A CN108649172B (en) | 2018-05-17 | 2018-05-17 | High-temperature switch protection mechanism battery diaphragm and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810473561.1A CN108649172B (en) | 2018-05-17 | 2018-05-17 | High-temperature switch protection mechanism battery diaphragm and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108649172A true CN108649172A (en) | 2018-10-12 |
| CN108649172B CN108649172B (en) | 2021-03-26 |
Family
ID=63756483
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810473561.1A Active CN108649172B (en) | 2018-05-17 | 2018-05-17 | High-temperature switch protection mechanism battery diaphragm and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108649172B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112941725A (en) * | 2021-01-28 | 2021-06-11 | 浙江理工大学 | Durable polyvinylidene fluoride three-layer composite hydrophilic membrane and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104022248A (en) * | 2014-06-24 | 2014-09-03 | 中国第一汽车股份有限公司 | Preparation method of high-performance lithium ion conduction membrane |
| CN105552279A (en) * | 2016-01-29 | 2016-05-04 | 常州达奥新材料科技有限公司 | Method for preparing overcharge protection battery separator with high heat stability by electrospinning method |
-
2018
- 2018-05-17 CN CN201810473561.1A patent/CN108649172B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104022248A (en) * | 2014-06-24 | 2014-09-03 | 中国第一汽车股份有限公司 | Preparation method of high-performance lithium ion conduction membrane |
| CN105552279A (en) * | 2016-01-29 | 2016-05-04 | 常州达奥新材料科技有限公司 | Method for preparing overcharge protection battery separator with high heat stability by electrospinning method |
Non-Patent Citations (1)
| Title |
|---|
| 丁军: "静电纺丝制备有机—无机复合纳米纤维锂离子电池隔膜研究", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112941725A (en) * | 2021-01-28 | 2021-06-11 | 浙江理工大学 | Durable polyvinylidene fluoride three-layer composite hydrophilic membrane and preparation method thereof |
| CN112941725B (en) * | 2021-01-28 | 2022-08-26 | 浙江理工大学 | Durable polyvinylidene fluoride three-layer composite hydrophilic membrane and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108649172B (en) | 2021-03-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR102119801B1 (en) | Flexible current collector and secondary battery using the same | |
| EP2052426B1 (en) | Heat resisting ultrafine fibrous separator and secondary battery using the same | |
| JP4574627B2 (en) | Electrode with presence / absence composite porous coating layer and electrochemical device including the same | |
| CN104466231B (en) | A kind of lithium rechargeable battery and preparation method thereof | |
| US20160351876A1 (en) | Heat resisting separator having ultrafine fibrous layer and secondary battery having the same | |
| CN107316965A (en) | Lithium lanthanum zirconium oxygen nanofiber, preparation method of composite film and solid state battery application | |
| CN106784558A (en) | Ceramic diaphragm with aeroge as powder and its application in lithium ion battery | |
| KR20050006540A (en) | Lithium secondary battery comprising fine fibrous porous polymer separator and preparation method thereof | |
| CN101222055B (en) | Co-polymer based polymer electrolyte material for lithium battery, compound electrolyte film and its preparation method | |
| CN115104222B (en) | Electrode assembly, electrochemical device and electronic device comprising same | |
| JP2015069957A (en) | Separator for lithium ion secondary battery and method for manufacturing the same, and lithium ion secondary battery and method for manufacturing the same | |
| JP2006092829A (en) | Separator for lithium ion secondary battery, its manufacturing method and lithium ion secondary battery | |
| CN105552279A (en) | Method for preparing overcharge protection battery separator with high heat stability by electrospinning method | |
| JP4828688B2 (en) | Positive electrode and non-aqueous electrolyte secondary battery | |
| Asghar et al. | Cellulose/Poly (vinylidene fluoride hexafluoropropylene) composite membrane with titania nanoparticles for lithium-ion batteries | |
| CN107068975A (en) | Positive electrode active compound composition and the lithium secondary battery comprising said composition | |
| KR20220151707A (en) | Electrochemical device and electronic device including the electrochemical device | |
| CN103000378A (en) | Preparation method of cathode active material and preparation method of capacitor | |
| JP2009123399A (en) | Separator for lithium-ion secondary battery, and lithium-ion secondary battery | |
| CN114725616A (en) | Inorganic hybrid aramid nanofiber membrane, preparation method and application of inorganic hybrid aramid nanofiber membrane in lithium battery | |
| JP5504456B2 (en) | Lithium ion secondary battery | |
| CN108649172A (en) | A kind of high temperature shutoff protection mechanism battery diaphragm and preparation method thereof | |
| WO2023179550A1 (en) | Composite oil-based separator and preparation method therefor, and secondary battery | |
| CN108258172A (en) | A kind of titanate high-temperature-resistant membrane and its preparation method and application | |
| CN101527370A (en) | Power lithium ion battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |