CN108649172B - High-temperature switch protection mechanism battery diaphragm and preparation method thereof - Google Patents

High-temperature switch protection mechanism battery diaphragm and preparation method thereof Download PDF

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CN108649172B
CN108649172B CN201810473561.1A CN201810473561A CN108649172B CN 108649172 B CN108649172 B CN 108649172B CN 201810473561 A CN201810473561 A CN 201810473561A CN 108649172 B CN108649172 B CN 108649172B
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protection mechanism
switch protection
temperature switch
pvp
titanium dioxide
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CN108649172A (en
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张平
蒋运鸿
丁燕怀
姜勇
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Xiangtan University
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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
    • 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

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  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
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Abstract

The invention discloses a high-temperature switch protection mechanism battery diaphragm and a preparation method thereof, wherein the high-temperature switch protection mechanism battery diaphragm is formed by collecting titanium dioxide and PVP nanometer one-dimensional structures through electrostatic spinning, the thickness of the high-temperature switch protection mechanism battery diaphragm is 20-200 mu m, and the porosity is 45-85%. The invention has the characteristics that: the electrolyte has inorganic components, a micro-nano tubular structure, excellent wetting performance and better liquid absorption and retention capacity for the electrolyte; secondly, a unique high-temperature switch protection mechanism is provided, when the working temperature reaches 60 ℃, the battery can be prevented from being charged, the temperature returns to the normal temperature again, and the battery can continue to work under the condition of relatively low voltage; thirdly, the porous material has high porosity, small aperture, higher ion penetrability, electrochemical stability and excellent mechanical property, and can effectively prevent the short circuit and the dendrite puncture of the energy storage device; fourthly, the high-temperature shrinkage rate is low, and the high-temperature bearing performance and the safety are better.

Description

High-temperature switch protection mechanism battery diaphragm and preparation method thereof
Technical Field
The invention relates to a high-temperature switch protection mechanism battery diaphragm and a preparation method thereof, belonging to the technical field of new energy materials.
Background
In recent years, with the application of electric vehicles and energy storage systems in different environments, the development of lithium ion batteries with high energy density and high safety has been emphasized gradually. Generally, a lithium ion battery is mainly composed of a positive/negative electrode material, an electrolyte, a separator, and a battery case packaging material. The diaphragm is an important component of the lithium ion battery, and plays a role in separating a positive electrode from a negative electrode, preventing electrons from passing through and providing a channel for lithium ions, thereby completing charge and discharge. The physical, chemical and mechanical properties of the diaphragm determine the interfacial properties, internal resistance and the like of the battery, the characteristics of the battery such as capacity, circulation, safety and the like are directly influenced, and the diaphragm with good performance plays an important role in improving the comprehensive performance of the battery.
At present, the lithium ion battery diaphragm materials are mainly polyolefin diaphragms such as single-layer polypropylene (PP) microporous membranes, single-layer Polyethylene (PE) microporous membranes and three-layer PP/PE/PP composite membranes, and the preparation methods of the diaphragms mainly comprise a dry-method stretching pore-forming method and a wet-method phase separation method. Polyolefin diaphragms have the disadvantages that: firstly, the polyolefin diaphragm is easy to shrink when being heated, so that the size of the diaphragm is unstable, and the positive electrode and the negative electrode are in direct contact and are in short circuit; and secondly, the closed pore temperature and the rupture temperature are low, when the battery is pierced and the like, a large amount of heat is released inside the battery, so that the diaphragm is completely melted and shrunk, and the battery is short-circuited to generate high temperature until the battery is decomposed or exploded. The disadvantages are determined by the characteristics of the polypropylene material, the melting point of PE is 128-135 ℃, and the melting point of PP is 150-166 ℃. The current commonly used capacitor diaphragm comprises a polypropylene diaphragm and a cellulose diaphragm. These materials have poor thermal stability, low porosity and poor liquid absorption properties. On the one hand, leads to non-ideal electrochemical properties of the capacitor and, on the other hand, to the danger of high-temperature operation thereof.
The invention discloses a high-temperature-resistant lithium ion battery diaphragm and a preparation method thereof, wherein the Chinese patent publication number is CN106252568A, the publication date is 2016, 12, and 21, the name of the invention is 'a high-temperature-resistant lithium ion battery diaphragm and a preparation method thereof', a non-woven fabric is taken as a base material, the non-woven fabric is connected with a silane coupling agent through a chemical bond formed by metal ions and nano fibers, and the non-woven fabric base material is coated by the technologies of spraying, dipping or blade coating and the like, so that. But the diaphragm does not have a high-temperature switch protection mechanism due to the existence of non-woven fabrics and a binder; the invention discloses a preparation method of a lithium battery diaphragm, which is characterized in that Chinese patent publication No. CN104037377A, the publication date is 9/10/2014, mLLDPE nonwoven fibers are prepared by an electrostatic spinning method, a PVDF film is obtained from the mLLDPE nonwoven fibers by the electrostatic spinning method, and the lithium battery diaphragm is obtained by compounding. Although the method has the advantages, the method adopts the twice electrostatic spinning method, has high operation cost and low efficiency, is not beneficial to industrialization, and does not have a high-temperature switch protection mechanism.
Disclosure of Invention
The invention aims to provide a battery diaphragm of a high-temperature switch protection mechanism and a preparation method thereof.
The technical scheme includes that the high-temperature switch protection mechanism battery diaphragm is formed by collecting titanium dioxide and PVP (polyvinylpyrrolidone) nanotube materials through electrostatic spinning, the thickness of the high-temperature switch protection mechanism battery diaphragm is 20-200 mu m, and the porosity is 45-85%.
The outer diameter of the titanium dioxide nano and PVP nano one-dimensional structure material nano tube is 100-500 nm, and the inner diameter of the nano tube is 40-200 nm.
In the high-temperature switch protection mechanism battery diaphragm, the mass ratio of titanium dioxide is 20-80%, and the mass ratio of PVP nano one-dimensional structure material is 20-80%.
A preparation method of a battery diaphragm of a high-temperature switch protection mechanism comprises the following steps:
uniformly dispersing titanium dioxide in a solution in which a PVP nano one-dimensional structure material is dissolved to prepare a titanium dioxide/PVP nano one-dimensional structure material precursor as an electrospinning external liquid, taking an oily substance as an electrospinning internal liquid, coaxially co-spinning on an electrostatic spinning device, treating the oily substance of the obtained electrospinning film by using an oil-dissolving solvent, and drying to obtain the battery diaphragm with the high-temperature switch protection mechanism.
The preparation of the titanium dioxide/PVP nano one-dimensional structure material precursor comprises the following steps:
(a) dissolving PVP powder in a volatile organic solvent to prepare a gel-like precursor, wherein the mass ratio of the PVP to the organic solvent is controlled to be 1: 50-1: 5, and the molecular weight of the PVP is 8000-1300000;
(b) adding volatile acid into the gel-like precursor, slowly dropwise adding a solvent which is easily hydrolyzed into titanium dioxide under the condition of rapid stirring, continuously stirring after dropwise adding, controlling the specific gravity of the volatile acid and the organic solvent to be 1: 10-3: 5, controlling the specific gravity of the acetic acid and the solvent which is easily hydrolyzed into the titanium dioxide to be 1: 1-3: 1, controlling the dropwise adding speed to be 30-120 drops/min, controlling the stirring speed to be 50-100 r/min, and controlling the stirring time to be 5-120 r/min to obtain the precursor of the titanium dioxide/PVP nano one-dimensional structure material.
The oily substance is one or a mixture of mineral oil and simethicone.
Carrying out electrostatic spinning coaxial co-spinning operation on electrostatic spinning equipment, controlling the speed of an electrospinning inner liquid to be 0.01-1 ml/min, controlling the speed of an electrospinning outer liquid to be 0.02-2 ml/h, controlling the speed ratio of the inner liquid to the outer liquid to be 1:2, controlling the electrospinning positive voltage to be 10-20 kV, controlling the negative voltage to be 0-5 kV, controlling the electrospinning time to be 5-24 h, and controlling the receiving distance to be 10-30 cm, so as to obtain the electrospun film.
The oil-dissolving solvent is one or more of n-octane, n-hexane or n-ethane, and the soaking time is controlled to be more than 12 hours.
The reagent which is easy to hydrolyze into titanium dioxide is one or more of isopropyl titanate or tetra-n-butyl titanate.
The volatile acid is one or more of hydrochloric acid, acetic acid, nitric acid, hydrofluoric acid, hydrobromic acid, hydroiodic acid, sulfurous acid or hydrosulfuric acid.
The volatile organic solvent is one or more of methanol, ethanol, ethyl acetate or carbon tetrachloride.
The invention uniformly disperses titanium dioxide in a solution in which a PVP nano one-dimensional structure material is dissolved to prepare a precursor of the titanium dioxide/PVP nano one-dimensional structure material as an electrospinning external liquid, an oily substance is used as an electrospinning internal liquid, coaxial co-spinning is carried out on electrostatic spinning equipment, the oily substance is removed from an obtained electrospinning film by using an oil-dissolving solvent, and the battery diaphragm with the high-temperature switch protection mechanism is obtained after drying. The nanometer one-dimensional tubular structures are interwoven with one another, so that the structure of the nanometer one-dimensional tubular structure is stable, the mechanical property is excellent, and common titanium dioxide is hydrophilic, oleophilic and stable at high temperature, so that the tubular diaphragm spun by titanium dioxide and PVP nanometer one-dimensional structural materials has higher porosity, higher liquid absorption rate and more outstanding thermal stability, almost negligible shrinkage even at the high temperature of 200 ℃, and is not easy to melt, and the safety performance of the battery is improved. And due to the special structure, the diaphragm has a high-temperature switch protection mechanism. Compared with the prior art, the invention has the advantages that: the high-temperature switch protection mechanism battery diaphragm has excellent wetting performance due to the fact that the diaphragm has inorganic components and a micro-nano tubular structure, and has better liquid absorption and retention capacity on electrolyte compared with most pure organic diaphragms; secondly, compared with the common commercial diaphragm, the diaphragm has a unique high-temperature switch protection mechanism, when the working temperature of the diaphragm reaches 60 ℃, the battery can be prevented from being charged, the temperature returns to the normal temperature again, and the diaphragm can continue to work under the condition of relatively low pressure; thirdly, the porous material has high porosity, small aperture, higher ion penetrability, electrochemical stability and excellent mechanical property, and can effectively prevent the short circuit and the dendrite puncture of the energy storage device; and fourthly, compared with the polyolefin diaphragm, the high temperature resistance is improved, the PE and PP microporous membranes are seriously shrunk and gradually melted at 180 ℃, and the diaphragm can still continuously work at normal temperature after being treated at 200 ℃, so that the high temperature resistance and safety are better.
Drawings
FIG. 1 is an SEM scan of a switching diaphragm of the present invention.
Fig. 2 is a TEM image of the tube structure of the switching diaphragm of the present invention.
Fig. 3 is a digital image of a switch diaphragm of the present invention.
Fig. 4 is a TGA and DSC trace of a switching diaphragm of the present invention.
Fig. 5 is a diagram showing the effect of the application of the switch diaphragm in the battery.
Fig. 6 is a graph showing the effect of the switch performance application of the switch diaphragm of the present invention in a battery.
Fig. 7 shows the protection voltage of the inventive switching diaphragm at 60 c.
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
As shown in fig. 1, 2 and 3, the high-temperature switch protection mechanism battery diaphragm is formed by collecting titanium dioxide and a PVP nanotube material through electrostatic spinning, the thickness of the high-temperature switch protection mechanism battery diaphragm is 20-200 μm, and the porosity is 45-85%.
The titanium dioxide and PVP nanometer one-dimensional structure has an outer diameter of 100-500 nm and an inner diameter of 40-200 nm.
The mass ratio of the titanium dioxide is 20-80%.
A preparation method of a battery diaphragm of a high-temperature switch protection mechanism comprises the following steps:
example 1
a. Dissolving 0.3g polyvinylpyrrolidone (PVP, molecular weight: 1300000) in 10ml ethanol solution to obtain gel precursor beneficial for electrostatic spinning;
b. adding 3ml of acetic acid into the gel precursor obtained in the step a, then slowly dripping isopropyl titanate under the condition of fast stirring at 60r/min, and continuing stirring for 30min after dripping is finished; preparing a precursor of the titanium dioxide/PVP nano one-dimensional structure material;
c. taking a titanium dioxide/PVP nano one-dimensional structure material precursor as an electrospinning external liquid and mineral oil as an electrospinning internal liquid, and carrying out coaxial co-spinning for 12 hours under the conditions of an external liquid speed of 0.1ml/h and an internal liquid speed of 0.05ml/h, a positive voltage of 15kV and a negative voltage of 1kV, and a receiving distance of 20 cm; obtaining an electro-spinning film;
d. and (3) soaking the electrospun film in n-octane for 24h, treating the middle oily substances, and drying to obtain the high-temperature switch protection mechanism battery diaphragm.
As shown in fig. 4, the prepared high temperature resistant separator maintains excellent thermal stability up to 200 ℃. Is a good diaphragm material of a secondary battery working at high temperature.
Example 2
a. 0.3g of polyvinylpyrrolidone (PVP, molecular weight: 1300000) is dissolved in 10ml of methanol solution to prepare a gel precursor which is beneficial to electrostatic spinning;
b. adding 3ml of acetic acid into the gel-like precursor, then slowly dripping isopropyl titanate under the condition of fast stirring at 60r/min, and continuing stirring for 30min after dripping is finished; preparing a precursor of the titanium dioxide/PVP nano one-dimensional structure material;
c. taking a titanium dioxide/PVP nano one-dimensional structure material precursor as an electrospinning external liquid and mineral oil as an electrospinning internal liquid, and carrying out coaxial co-spinning for 12 hours under the conditions of an external liquid speed of 0.1ml/h and an internal liquid speed of 0.05ml/h, a positive voltage of 15kV and a negative voltage of 1kV, and a receiving distance of 20 cm; obtaining an electro-spinning film;
d. and (3) soaking the electrospun film in n-octane for 24h, treating the middle oily substances, and drying to obtain the high-temperature switch protection mechanism battery diaphragm.
Example 3
a. 0.3g of polyvinylpyrrolidone (PVP, molecular weight: 1300000) is dissolved in 10ml of ethyl acetate solution to prepare a gel precursor which is beneficial to electrostatic spinning;
b. adding 3ml of acetic acid into the gel-like precursor, slowly dripping isopropyl titanate under the condition of rapid stirring at 60r/min, and continuously stirring for 30min after dripping is finished to prepare a precursor of the titanium dioxide/PVP nano one-dimensional structure material;
c. taking a titanium dioxide/PVP nano one-dimensional structure material precursor as an electrospinning external liquid and mineral oil as an electrospinning internal liquid, and carrying out coaxial co-spinning for 12 hours under the conditions of an external liquid speed of 0.1ml/h and an internal liquid speed of 0.05ml/h, a positive voltage of 15kV and a negative voltage of 1kV, and a receiving distance of 20cm to obtain an electrospinning film;
d. and soaking the obtained electrospun film in n-octane for 24h, treating the middle oily substances, and drying to obtain the high-temperature switch protection mechanism battery diaphragm.
Example 4
a. Dissolving 0.3g polyvinylpyrrolidone (PVP, molecular weight: 1300000) in 10ml carbon tetrachloride solution to obtain gel precursor favorable for electrostatic spinning;
b. adding 3ml of acetic acid into the gel-like precursor, slowly dripping isopropyl titanate under the condition of rapid stirring at 60r/min, and continuously stirring for 30min after dripping is finished to prepare a precursor of the titanium dioxide/PVP nano one-dimensional structure material;
c. taking a titanium dioxide/PVP nano one-dimensional structure material precursor as an electrospinning external liquid and mineral oil as an electrospinning internal liquid, and carrying out coaxial co-spinning for 12 hours under the conditions of an external liquid speed of 0.1ml/h and an internal liquid speed of 0.05ml/h, a positive voltage of 15kV and a negative voltage of 1kV, and a receiving distance of 20cm to obtain an electrospinning film;
d. and soaking the obtained electrospun film in n-octane for 24h, treating the middle oily substances, and drying to obtain the high-temperature switch protection mechanism battery diaphragm.
Example 5
a. Dissolving 0.3g polyvinylpyrrolidone (PVP, molecular weight: 1300000) in 10ml ethanol solution to obtain gel precursor beneficial for electrostatic spinning;
b. adding 3ml of hydrochloric acid into the gel-like precursor, slowly dripping isopropyl titanate under the condition of rapid stirring at 60r/min, and continuously stirring for 30min after dripping is finished to prepare a precursor of the titanium dioxide/PVP nano one-dimensional structure material;
c. taking a titanium dioxide/PVP nano one-dimensional structure material precursor as an electrospinning external liquid and mineral oil as an electrospinning internal liquid, and carrying out coaxial co-spinning for 12 hours under the conditions of an external liquid speed of 0.1ml/h and an internal liquid speed of 0.05ml/h, a positive voltage of 15kV and a negative voltage of 1kV, and a receiving distance of 20cm to obtain an electrospinning film;
d. and soaking the obtained electrospun film in n-octane for 24h, treating the middle oily substances, and drying to obtain the high-temperature switch protection mechanism battery diaphragm.
Example 6
a. Dissolving 0.3g polyvinylpyrrolidone (PVP, molecular weight: 1300000) in 10ml ethanol solution to obtain gel precursor beneficial for electrostatic spinning;
b. adding 3ml of acetic acid into the gel-like precursor, slowly dropwise adding tetra-n-butyl titanate under the condition of rapid stirring at 60r/min, and continuously stirring for 30min after dropwise adding is finished to prepare a precursor of the titanium dioxide/PVP nano one-dimensional structure material;
c. taking a precursor of the prepared titanium dioxide/PVP nano one-dimensional structure material as an electrospinning external liquid, taking mineral oil as an electrospinning internal liquid, and carrying out coaxial co-spinning for 12 hours under the conditions of an external liquid speed of 0.1ml/h and an internal liquid speed of 0.05ml/h, a positive voltage of 15kV and a negative voltage of 1kV, and a receiving distance of 20cm to obtain an electrospinning film;
and d, soaking the obtained electrospun film in n-octane for 24 hours, treating the middle oily substances, and drying to obtain the high-temperature switch protection mechanism battery diaphragm.
Example 7
a. Dissolving 0.3g polyvinylpyrrolidone (PVP, molecular weight: 1300000) in 10ml ethanol solution to obtain gel precursor beneficial for electrostatic spinning;
b. adding 3ml of acetic acid into the gel precursor obtained in the step a, then slowly dripping isopropyl titanate under the condition of rapid stirring at 60r/min, and continuing stirring for 30min after dripping is finished to prepare a precursor of the titanium dioxide/PVP nano one-dimensional structure material;
c. taking a precursor of the prepared titanium dioxide/PVP nano one-dimensional structure material as an electrospinning external liquid, taking dimethyl silicone oil as an electrospinning internal liquid, and carrying out coaxial co-spinning for 12 hours under the conditions of an external liquid speed of 0.1ml/h and an internal liquid speed of 0.05ml/h, a positive voltage of 15kV and a negative voltage of 1kV, and a receiving distance of 20cm, so as to obtain an electrospinning film;
d. and soaking the obtained electrospun film in n-octane for 24h, treating the middle oily substances, and drying to obtain the high-temperature switch protection mechanism battery diaphragm.
Example 8
a. Dissolving 0.3g polyvinylpyrrolidone (PVP, molecular weight: 1300000) in 10ml ethanol solution to obtain gel precursor beneficial for electrostatic spinning;
b. adding 3ml of acetic acid into the gel-like precursor, slowly dripping isopropyl titanate under the condition of rapid stirring at 60r/min, and continuously stirring for 30min after dripping is finished to prepare a precursor of the titanium dioxide/PVP nano one-dimensional structure material;
c. taking a precursor of the prepared titanium dioxide/PVP nano one-dimensional structure material as an electrospinning external liquid, taking mineral oil as an electrospinning internal liquid, and carrying out coaxial co-spinning for 12 hours under the conditions of an external liquid speed of 0.1ml/h and an internal liquid speed of 0.05ml/h, a positive voltage of 15kV and a negative voltage of 1kV, and a receiving distance of 20cm to obtain an electrospinning film;
d. and soaking the obtained electrospun film in n-hexane for 24h, treating the middle oily substances, and drying to obtain the high-temperature switch protection mechanism battery diaphragm.
Example 9
a. Dissolving 0.3g polyvinylpyrrolidone (PVP, molecular weight: 1300000) in 10ml ethanol solution to obtain gel precursor beneficial for electrostatic spinning;
b. adding 3ml of acetic acid into the gel-like precursor, slowly dripping isopropyl titanate under the condition of rapid stirring at 60r/min, and continuously stirring for 30min after dripping is finished to prepare a precursor of the titanium dioxide/PVP nano one-dimensional structure material;
c. taking a precursor of the prepared titanium dioxide/PVP nano one-dimensional structure material as an electrospinning external liquid, taking mineral oil as an electrospinning internal liquid, and carrying out coaxial co-spinning for 12 hours under the conditions of an external liquid speed of 0.1ml/h and an internal liquid speed of 0.05ml/h, a positive voltage of 15kV and a negative voltage of 1kV, and a receiving distance of 20cm to obtain an electrospinning film;
d. and soaking the obtained electrospun film in n-ethane for 24h, treating the middle oily substances, and drying to obtain the high-temperature switch protection mechanism battery diaphragm.
Example 10
a. 0.4g of polyvinylpyrrolidone (PVP, molecular weight: 1300000) is dissolved in 10ml of ethanol solution to prepare a gel precursor which is beneficial to electrostatic spinning;
b. adding 3ml of acetic acid into the gel-like precursor, slowly dripping isopropyl titanate under the condition of rapid stirring at 60r/min, and continuously stirring for 30min after dripping is finished to prepare a precursor of the titanium dioxide/PVP nano one-dimensional structure material;
c. taking a precursor of the prepared titanium dioxide/PVP nano one-dimensional structure material as an electrospinning external liquid, taking mineral oil as an electrospinning internal liquid, and carrying out coaxial co-spinning for 12 hours under the conditions of an external liquid speed of 0.1ml/h and an internal liquid speed of 0.05ml/h, a positive voltage of 15kV and a negative voltage of 1kV, and a receiving distance of 20cm to obtain an electrospinning film;
d. and soaking the obtained electrospun film in n-octane for 24h, treating the middle oily substances, and drying to obtain the high-temperature switch protection mechanism battery diaphragm.
Example 11
a. Dissolving 0.2g polyvinylpyrrolidone (PVP, molecular weight: 1300000) in 10ml ethanol solution to obtain gel precursor beneficial to electrostatic spinning;
b. adding 3ml of acetic acid into the gel-like precursor, slowly dripping isopropyl titanate under the condition of rapid stirring at 60r/min, and continuously stirring for 30min after dripping is finished to prepare a precursor of the titanium dioxide/PVP nano one-dimensional structure material;
c. taking a precursor of the prepared titanium dioxide/PVP nano one-dimensional structure material as an electrospinning external liquid, taking mineral oil as an electrospinning internal liquid, and carrying out coaxial co-spinning for 12 hours under the conditions of an external liquid speed of 0.1ml/h and an internal liquid speed of 0.05ml/h, a positive voltage of 15kV and a negative voltage of 1kV, and a receiving distance of 20cm to obtain an electrospinning film;
d. and soaking the obtained electrospun film in n-octane for 24h, treating the middle oily substances, and drying to obtain the high-temperature switch protection mechanism battery diaphragm.
Example 12
a. Dissolving 0.3g polyvinylpyrrolidone (PVP, molecular weight: 1300000) in 10ml ethanol solution to obtain gel precursor beneficial for electrostatic spinning;
b. adding 3ml of acetic acid into the gel-like precursor, slowly dripping isopropyl titanate under the condition of rapid stirring at 60r/min, and continuously stirring for 30min after dripping is finished to prepare a precursor of the titanium dioxide/PVP nano one-dimensional structure material;
c. taking a precursor of the prepared titanium dioxide/PVP nano one-dimensional structure material as an electrospinning external liquid, taking mineral oil as an electrospinning internal liquid, and carrying out coaxial co-spinning for 12 hours under the conditions of an external liquid speed of 0.1ml/h and an internal liquid speed of 0.05ml/h, a positive voltage of 15kV and a negative voltage of 1kV, and a receiving distance controlled at 10cm to obtain an electrospinning film;
d. and soaking the obtained electrospun film in n-octane for 24h, treating the middle oily substances, and drying to obtain the high-temperature switch protection mechanism battery diaphragm.
Example 13
a. Dissolving 0.3g polyvinylpyrrolidone (PVP, molecular weight: 1300000) in 10ml ethanol solution to obtain gel precursor beneficial for electrostatic spinning;
b. adding 3ml of acetic acid into the gel-like precursor, slowly dripping isopropyl titanate under the condition of rapid stirring at 60r/min, and continuously stirring for 30min after dripping is finished to prepare a precursor of the titanium dioxide/PVP nano one-dimensional structure material;
c. taking a precursor of the prepared titanium dioxide/PVP nano one-dimensional structure material as an electrospinning external liquid, taking mineral oil as an electrospinning internal liquid, and carrying out coaxial co-spinning for 16h under the conditions of an external liquid speed of 0.1ml/h and an internal liquid speed of 0.05ml/h, a positive voltage of 15kV and a negative voltage of 1kV, and a receiving distance of 20cm to obtain an electrospinning film;
d. and soaking the obtained electrospun film in n-octane for 24h, treating the middle oily substances, and drying to obtain the high-temperature switch protection mechanism battery diaphragm.
Example 14
a. Dissolving 0.3g polyvinylpyrrolidone (PVP, molecular weight: 1300000) in 10ml ethanol solution to obtain gel precursor beneficial for electrostatic spinning;
b. adding 3ml of acetic acid into the gel-like precursor, slowly dripping isopropyl titanate under the condition of rapid stirring at 60r/min, and continuously stirring for 30min after dripping is finished to prepare a precursor of the titanium dioxide/PVP nano one-dimensional structure material;
c. taking a precursor of the prepared titanium dioxide/PVP nano one-dimensional structure material as an electrospinning external liquid, taking mineral oil as an electrospinning internal liquid, and carrying out coaxial co-spinning for 8 hours under the conditions of an external liquid speed of 0.1ml/h and an internal liquid speed of 0.05ml/h, a positive voltage of 15kV and a negative voltage of 1kV, and a receiving distance of 20cm to obtain an electrospinning film;
d. and soaking the obtained electrospun film in n-octane for 24h, treating the middle oily substances, and drying to obtain the high-temperature switch protection mechanism battery diaphragm.
Example 15
a. Dissolving 50g polyvinylpyrrolidone solution (PVP, molecular weight: 8000) in 10ml ethanol solution to obtain gel precursor beneficial for electrostatic spinning;
b. adding 3ml of acetic acid into the gel-like precursor, then slowly dripping isopropyl titanate under the condition of fast stirring at 60r/min, and continuing stirring for 30min after dripping is finished; preparing a precursor of the titanium dioxide/PVP nano one-dimensional structure material;
c. taking a titanium dioxide/PVP nano one-dimensional structure material precursor as an electrospinning external liquid and mineral oil as an electrospinning internal liquid, and carrying out coaxial co-spinning for 12 hours under the conditions of an external liquid speed of 0.1ml/h and an internal liquid speed of 0.05ml/h, a positive voltage of 15kV and a negative voltage of 1kV, and a receiving distance of 20 cm; obtaining an electro-spinning film;
and d, soaking the electrospun film in n-octane for 24 hours, treating the middle oily substances, and drying to obtain the high-temperature switch protection mechanism battery diaphragm.
Example 16
a. Dissolving 10g of polyvinylpyrrolidone (PVP, molecular weight: 40000) in 10ml of ethanol solution to obtain a gel precursor beneficial to electrostatic spinning;
b. adding 3ml of acetic acid into the gel-like precursor, then slowly dripping isopropyl titanate under the condition of fast stirring at 60r/min, and continuing stirring for 30min after dripping is finished; preparing a precursor of the titanium dioxide/PVP nano one-dimensional structure material;
c. taking a titanium dioxide/PVP nano one-dimensional structure material precursor as an electrospinning external liquid and mineral oil as an electrospinning internal liquid, and carrying out coaxial co-spinning for 12 hours under the conditions of an external liquid speed of 0.1ml/h and an internal liquid speed of 0.05ml/h, a positive voltage of 15kV and a negative voltage of 1kV, and a receiving distance of 20 cm; obtaining an electro-spinning film;
d. and (3) soaking the electrospun film in n-octane for 24h, treating the middle oily substances, and drying to obtain the high-temperature switch protection mechanism battery diaphragm.
Example 17
With LiFePO4And metallic lithium as positive and negative electrodes, the high temperature resistant separator prepared by the present invention and a commercial separator manufactured by Karlerd (Celgard) as a battery separator, 1M LiPF6The EC/EMC/DMC solution (mass ratio of 1:1:1) of (A) was used as an electrolyte to assemble a battery, and a charge-discharge test was performed, wherein the cycle performance is shown in FIG. 5. High temperature switch protection using the inventionThe mechanical diaphragm is used as a battery diaphragm, and the discharge specific capacity and the cycle performance of the mechanical diaphragm are superior to those of commercial diaphragms produced by the Karl-Ge company.
Example 18
With LiFePO4And metallic lithium as positive and negative electrodes, the high temperature resistant separator prepared by the present invention and a commercial separator manufactured by Karlerd (Celgard) as a battery separator, 1M LiPF6The battery was assembled with the EC/EMC/DMC solution (mass ratio 1:1:1) as an electrolyte, and charge and discharge tests were performed, and the protection mechanism was as shown in fig. 6 and 7. The high-temperature switch protection mechanism diaphragm is used as a battery diaphragm, is sensitive to temperature and forms protection voltage.

Claims (10)

1. A preparation method of a battery diaphragm of a high-temperature switch protection mechanism is characterized by comprising the following steps:
(a) dissolving PVP powder in a volatile organic solvent to prepare a solution, wherein the mass ratio of the PVP to the organic solvent is controlled to be 1: 50-1: 5, and the molecular weight of the PVP is 8000-1300000;
(b) adding volatile acid into the solution, slowly dropwise adding a reagent which is easily hydrolyzed into titanium dioxide under the condition of rapid stirring, continuously stirring after dropwise adding, controlling the specific gravity of the volatile acid and an organic solvent to be 1: 10-3: 5, controlling the specific gravity of the solvent which is easily hydrolyzed into the titanium dioxide to be 1: 1-3: 1, controlling the dropwise adding speed to be 30-120 drops/min, controlling the stirring speed to be 50-100 r/min, and controlling the stirring time to be 5-120 min to obtain a titanium dioxide/PVP nano precursor;
(C) and (2) taking a titanium dioxide/PVP nano precursor as an electrospinning external liquid and an oily substance as an electrospinning internal liquid, carrying out coaxial co-spinning on electrostatic spinning equipment to obtain a titanium dioxide/PVP nanotube film, treating the oily substance of the obtained titanium dioxide/PVP nanotube film with an oil-dissolving solvent, and drying to obtain the battery diaphragm with the high-temperature switch protection mechanism.
2. The method for preparing the battery diaphragm of the high-temperature switch protection mechanism according to claim 1, wherein the method comprises the following steps: the oily substance is one or a mixture of mineral oil and simethicone.
3. The method for preparing the battery diaphragm of the high-temperature switch protection mechanism according to claim 1, wherein the method comprises the following steps: carrying out electrostatic spinning coaxial co-spinning operation on electrostatic spinning equipment, controlling the speed of an electrospinning inner liquid to be 0.01-1 ml/min, controlling the speed of an electrospinning outer liquid to be 0.02-2 ml/h, controlling the speed ratio of the inner liquid to the outer liquid to be 1:2, controlling the electrospinning positive voltage to be 10-20 kV, controlling the negative voltage to be 0-5 kV, controlling the electrospinning time to be 5-24 h, and controlling the receiving distance to be 10-30 cm.
4. The method for preparing the battery diaphragm of the high-temperature switch protection mechanism according to claim 1, wherein the method comprises the following steps: the oil-dissolving solvent is one or more than two of n-octane, n-hexane or n-ethane, and the soaking time is controlled to be more than 12 hours.
5. The method for preparing the battery diaphragm of the high-temperature switch protection mechanism according to claim 1, wherein the method comprises the following steps: the reagent which is easy to hydrolyze into titanium dioxide is one or more than two of isopropyl titanate or tetra-n-butyl titanate.
6. The method for preparing the battery diaphragm of the high-temperature switch protection mechanism according to claim 1, wherein the method comprises the following steps: the volatile acid is one or more of hydrochloric acid, acetic acid, nitric acid, hydrofluoric acid, hydrobromic acid, hydroiodic acid, sulfurous acid or hydrosulfuric acid.
7. The method for preparing the battery diaphragm of the high-temperature switch protection mechanism according to claim 1, wherein the method comprises the following steps: the volatile organic solvent is one or more of methanol, ethanol, ethyl acetate or carbon tetrachloride.
8. A high temperature switch protection mechanism battery diaphragm characterized in that: the high-temperature switch protection mechanism battery diaphragm is a titanium dioxide/PVP nanotube film prepared by the preparation method of claim 1, the thickness of the film is 20-200 μm, and the porosity is 45-85%.
9. A high temperature switch protection mechanism battery separator as claimed in claim 8, wherein: the titanium dioxide/PVP nano tube has an outer diameter of 100-500 nm and an inner diameter of 40-200 nm.
10. A high temperature switch protection mechanism battery separator as claimed in claim 8, wherein: the titanium dioxide/PVP nanotube film comprises 20-80% of titanium dioxide and 20-80% of PVP.
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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

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