CN104485437A - Composite nanofibre diaphragm with thermal pore-closing function, preparation method and energy storage device - Google Patents
Composite nanofibre diaphragm with thermal pore-closing function, preparation method and energy storage device Download PDFInfo
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- CN104485437A CN104485437A CN201410798500.4A CN201410798500A CN104485437A CN 104485437 A CN104485437 A CN 104485437A CN 201410798500 A CN201410798500 A CN 201410798500A CN 104485437 A CN104485437 A CN 104485437A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/44—Fibrous material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/52—Separators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses a composite nanofibre diaphragm with a thermal pore-closing function, a preparation method and an energy storage device, and relates to lithium ion batteries, lithium-sulphur batteries, supercapacitors, lead-acid batteries, alkaline batteries, zinc air batteries, sodium-ion batteries and fibre diaphragms thereof. The composite nanofibre diaphragm with the thermal pore-closing function is of a non-woven fabric structure, and formed by mutually crosslinking and compounding fibrillated cellulose nanofibres and at least one low-melting-point polymer nanofibres; the low-melting-point polymer nanofibres are nanofibres containing polyolefin and polyesters. The thickness of the composite nanofibre diaphragm with the thermal pore-closing function can be 10-80 mu m, the pore-closing temperature is 130-170 DEG C, the fibre film does not shrink after pore-closing, and the thermal shrinkage rate in case of heating for 30min at high temperature of 200 DEG C is less than 2%. The composite nanofibre diaphragm is capable of realizing the thermal pore-closing function, thus avoiding the direct contact of the positive electrode and the negative electrode of a battery due to the action of thermal inertia, and remarkably improving the safety of the energy storage devices above-mentioned.
Description
Technical field
The invention belongs to cell art, described battery lithium ion battery, lithium-sulfur cell, ultracapacitor, lead-acid battery, alkaline battery, zinc-air cell, sodium-ion battery.Relate to a kind of composite nano fiber barrier film with closed pore function and preparation method thereof.The invention still further relates to the application as battery diaphragm of the production of this film and this film.
Background technology
Composite nano fiber barrier film can be used as diaphragm application in battery as lithium ion battery, lithium-sulfur cell, ultracapacitor, lead-acid battery, zinc-air cell, sodium-ion battery.At present, lithium ion battery because of its have higher energy density, longer cycle life, can the advantage such as fast charging and discharging, pollution-free and memory-less effect, be widely used in portable type electronic product as: the rechargeable battery that mobile phone, notebook computer, video camera etc. are required, also expands to electric automobile, space flight and aviation, energy storage and other field gradually.
Battery diaphragm is as the critical component concerning battery safety, its Main Function is isolation both positive and negative polarity and electronics can not be passed freely through, ion can be allowed freely to pass through, its performance determines the interfacial structure, internal resistance etc. of battery, is directly connected to the overall performance of lithium battery simultaneously.When lithium battery isolation both positive and negative polarity, there is battery and overcharge or short circuit, or incorrect link, produce abnormal electric current, and use during, capacity height large at power, temperature in battery all can be caused sharply to raise, and battery diaphragm should have enough resistance to temperature functions; Because battery temperature raises, cause membrane pore size to reduce, lithium ion can not be normal through, causes battery temperature to raise, reach the fusing point of lithium or electrolytical point of ignition, by the generation of the burning and explosion accident that cause battery.
Lithium battery safety problem is very urgent problems, particularly power lithium-ion battery, has entered the numerous areas such as automobile, robot, electric tool, Aero-Space at present, dynamic lithium battery due to the magnitude of current larger, the possibility be exposed under high temperature is higher, and its fail safe receives much concern.So the security performance of barrier film should mention higher level (when battery temperature is too high, barrier film intercepts the conduction of electric current by closed pore, prevent blast, and closed pore metacneme dimensionally stable does not shrink).
The main product of current lithium ion battery separator is polypropylene and polyethylene porous membrane and the composite membrane with porous ceramic coating thereof.Its distinct issues are that wetability is poor, imbibition ability is weak, are difficult to realize high power charging-discharging, easily form dendrite and are subject to thermal deformation large, there is serious potential safety hazard under high temperature circulation condition.
In order to improve the thermal endurance of barrier film, scientific research personnel mainly takes following several method: one is by sol-gel in-situ preparation or adds nano particle or coating to improve nano fiber diaphragm thermal endurance containing the mode of solution of nano particle, as CN200810244343.7, CN201110434221.6, these method complicated process of preparation, generally need the operations such as coating processes, hot-pressing processing or extraction, simultaneously during diaphragm closed pore along with volume contraction, membrane area reduces, make barrier film lose partition effect between both positive and negative polarity, cause hidden danger; Two is use the polymer solution of high-fire resistance to carry out electrostatic spinning, as CN201210486465.3, CN201210425855.X, CN201010166400.1 and CN201210169182.6, tunica fibrosa function singleness prepared by the method, and preparation process is loaded down with trivial details, cost is high.Three is nonwoven fabrics barrier film uses in lithium ion battery separator field of nano-fiber material, is one of important topic of the high-end lithium ion battery separator of exploitation at present.Nano based battery diaphragm obviously can improve the wettability of diaphragm material, effectively improves thermal endurance and the ionic conduction performance of barrier film.The patent CN103688387A of Dreamweave company of the U.S. discloses many microporous polymers battery diaphragm, by high shear treatment, polymer nanocomposite is combined in polymer microfibers matrix, make the nanometer fiber net that pore-size effect is good, in thermal endurance, dimensional stability and good imbibition ability, wettability etc.Equally, also have patent CN103270639A, CN103943806A etc., but the thermal dimensional stability of the excellence that diaphragm material should have and good self closing performance can not be met simultaneously, the potential hazards such as battery burns, blast can be made.
Summary of the invention
Technical problem to be solved by this invention is for above defect, provides that a kind of manufacturing process is simple, low cost and composite nano fiber barrier film of excellent performance and preparation method thereof.
For solving the problems of the technologies described above, first the present invention provides a kind of nano fiber diaphragm with hot closure function, its raw material comprises fibrillating fibre element nanofiber and low melting point polymer nanofiber, combine mainly through hydrogen bond, intermolecular force between described fibrillating fibre element nanofiber, described fibrillating fibre element nanofiber is combined by the intermolecular crosslinked action of major diameter between described low melting point polymer nanofiber; Described composite nano fiber barrier film has hole so that electrolyte ion passes and stops electronics to pass; Under 130 ~ 170 DEG C of temperature environments, the closing of pores of described composite nano fiber barrier film, passes through to prevent the excessive and less desirable ion after battery damage.
Under described composite nano fiber barrier film hole closure state, the dimensionally stable of described composite nano fiber barrier film, heat 30min under 200 DEG C of high temperature within, percent thermal shrinkage is less than 2%.
The described thickness with the composite nano fiber barrier film of closed pore function is 10 ~ 80 μm,
An above-mentioned composite nano fiber barrier film preparation method with closed pore function is 1:9 ~ 9:1 fibrillating fibre element nanofiber and low melting point polymer nanofiber with mass ratio is raw material, prepares with paper technology.
The described preparation method with the composite nano fiber barrier film of closed pore function, comprises following concrete steps:
I, be that 1:9 ~ 9:1 takes fibrillating fibre element nanofiber and at least one low melting point polymer nanofiber disperses in a solvent respectively by mass ratio, rapid stirring forms slurry;
II, in the slurry of step I, binding agent is added; Add binding agent and can increase its mechanical strength, the selectable range of binding agent is more wide in range, as polyethylene glycol, polyvinyl alcohol, butadiene and cinnamic polymer, polymer, Kynoar and epoxy resin etc. that propylene is fine.
III, be 0.01% ~ 0.05% by the pulp dilution after step II to concentration;
IV, the slurry after dilution, through online dehydration forming, squeezing, drying, hot-roll forming, has the composite nano fiber barrier film of closed pore function described in namely obtaining.
Preferably, the diameter of described fibrillating fibre element nanofiber is 10-1000nm, and length is 10-3000 μm.
Described fibrillating fibre element nanofiber comprise from nano-scale wood materials be separated cellulose nano-fibrous, alginate fibre element nanofiber, and by cultivating the bacteria cellulose nanofiber that bacterial strain obtains.
Preferably, the diameter of described low melting point polymer nanofiber is 10-1000nm.
Described low melting point polymer nanofiber be polymethyl methacrylate, vinylidene based polyalcohol, polyurethane, polyvinyl chloride, polyolefin, EVA copolymer, polyethylene glycol succinate one or more combination.
Described solvent is low-molecular-weight alcohols, deionized water, or the mixed liquor of low-molecular-weight alcohol and deionized water.
The energy storage device that another aspect of the present invention is to provide the composite nano fiber barrier film described in a kind of application with closed pore function to prepare, comprises lithium ion battery, lithium-sulfur cell, alkaline battery, ultracapacitor, lead-acid battery, zinc-air cell, sodium-ion battery.
Preparation method's cost of the present invention is low, production process simply, conveniently shifts and suitable for mass production.
Closed pore function and service nano fiber diaphragm prepared by the present invention shows excellent physical property, comprising: closed pore, thermal endurance, dimensional stability, gas permeability, and relative to the feature such as good wettability and high pick up of electrolyte.Closed pore temperature is 130 ~ 170 DEG C, and after closed pore, tunica fibrosa does not shrink, and heats 30min percent thermal shrinkage and be less than 2% under 200 DEG C of high temperature.
Accompanying drawing explanation
Fig. 1 is the SEM photo of the polyolefin-based separator of comparative example;
Fig. 2 is the SEM photo of the closed pore function and service nano fiber diaphragm of embodiment 5;
Fig. 3 be the closed pore function and service nano fiber diaphragm of embodiment 5 at 200 DEG C, the SEM photo after 2h heat treatment;
Fig. 4 is the heat-shrinkable photo of closed pore function and service nano fiber diaphragm at 150 DEG C and 200 DEG C of comparative example and embodiment 3;
Fig. 5 is the closed pore function and service nano fiber diaphragm electrolyte wettability photo of comparative example and embodiment 3.
Embodiment
At this, according to Figure of description, the present invention is described in further detail, but the present invention is not limited to embodiment discussed below in conjunction with the embodiments, can implements in different forms.Following embodiment is used for those skilled in the art and embodies and implement the present invention.
According to the preparation of the closed pore function and service nano fiber diaphragm of the use fibrillating fibre of embodiment of the present invention element nanofiber and low melting point polymer nanofiber.
Use comprise fibrillation fibrillating fibre element nanofiber and low melting point polymer nanofiber slurries to prepare barrier film.At this, fibrillating fibre element nanofiber can have the diameter of 10-1000nm.
When the diameter of fibrillating fibre element nanofiber is less than 10nm, very difficult formation fibrillating fibre element nanofiber, but, when the diameter of fibrillating fibre element nanofiber is more than 1000nm, barrier film has coarse surface, and this makes electrode and barrier film not have good contact.
Equally, when the diameter of fibrillating fibre element nanofiber is more than 200nm, can not adequate relief pore-forming.Therefore, the value diameter of fibrillating fibre element nanofiber is more preferably between 10-200nm.
Use comprise fibrillation fibrillating fibre element nanofiber and low melting point polymer nanofiber slurries to prepare barrier film.At this, low melting point polymer nanofiber can have the diameter of 10-1000nm.
This fibrillating fibre element nanofiber can be selected from and comprise: the fibrillating fibre element nanofiber be separated from nano-scale wood materials, marine alga fibrillating fibre element nanofiber, and planted by one of them of cultivating in the bacterium fibrillating fibre element nanofiber of bacterial strain acquisition.
The kind of this low melting point polymer nanofiber can all use without restriction, as long as low-melting nanofiber, and comprise so a kind of slurry, low melting point polymer nanofiber in this slurry can mix with fibrillating fibre element nanofiber equably, and cannot dissolve in slurry production process.
This low melting point polymer nanofiber is selected from and comprises: low melting point polymer nanofiber for polymethyl methacrylate, vinylidene based polyalcohol, polyurethane, polyvinyl chloride, polyolefin, one or more combinations of EVA copolymer, polyethylene glycol succinate.
The solvent of wherein fibrillating fibre element nanofiber and low melting point polymer nanofiber stable dispersion can be used as solvent.Such as, deionized water, low-molecular-weight alcohol and low-molecular-weight alcohol and deionized water mixed liquor can be selected as solvent.
Relative to fibrillating fibre element nanofiber in the middle of preparation method, when fibrillating fibre element nanofiber and the mixed proportion of low melting point polymer nanofiber are less than 1:9, barrier film is heated and does not reach the effect of closed pore.On the other hand, when fibrillating fibre element nanofiber and the mixed proportion of low melting point polymer nanofiber are more than 9:1, thermal endurance and the dimensional stability of barrier film are had a strong impact on, and more difficult transfer.
Solution wherein containing fibrillating fibre element nanofiber and low melting point polymer nanofiber prepares slurry by high-speed stirred, and this slurry makes barrier film of the present invention through paper process.
In this case, according to one embodiment of present invention, a kind of method preparing barrier film is used, such as: fibrillating fibre element nanofiber is prepared into non-woven fabrics fabric by the conventional method preparing paper.But the ownership can be used for for the method for barrier film the barrier film preparing lithium ion battery.
The thickness of barrier film can close in the scope of 10-80 μm.When the thickness of barrier film is more than 80 μm, the efficiency for charge-discharge of battery will be subject to serious impact.When the thickness of barrier film is lower than 10 μm, the self discharge of battery and short circuit ratio can improve greatly.
The advantage of fibrillating fibre element nanofiber is, when using binding agent in the preparation process of barrier film, can reduce in functional group and occur-OH base, this is the reason because hydrogen bond increases, when fibrillating fibre element nanofiber is used for lithium secondary battery barrier film, therefore reaction in fibrillating fibre element nanofiber between Li ion and-OH base no longer occurs, and this causes the increase of stability.
Because binding agent end has-OH base.Therefore, binding agent can mix with fibrillating fibre element nanofiber equably.
It will be appreciated by those skilled in the art that, apply energy storage device prepared by the above-mentioned composite nano fiber barrier film with closed pore function, comprise lithium ion battery, lithium-sulfur cell, alkaline battery, ultracapacitor, lead-acid battery, zinc-air cell, sodium-ion battery, effectively must improve the safety and reliability of energy storage device.
Embodiment 1
By fibrillating fibre element nanofiber: the cellulose nano-fibrous and low melting point polymer nanofiber (polymethyl methacrylate and polyethylene glycol succinate) be separated from nano-scale wood materials of low melting point polymer nanofiber=9:1 disperse in a solvent, and subsequently by high speed machine stir make solution reach entirety evenly prepare slurry.Add solvent by pulp dilution to 0.01%, by the slurry that diluted through online dehydration forming; Squeezing, drying; Be 100 DEG C at forming temperature, linear pressure is carry out hot-roll forming under 100kg/cm condition, then through coil paper, rewinding, cut and pack, obtained battery diaphragm.
Above-mentioned closed pore composite diaphragm shows excellent characteristic, and such as, 200 DEG C, before and after 2h heat treatment, porosity is respectively 56% and 55%; At 200 DEG C, 30min is almost the percent thermal shrinkage of 0; The absorptivity of 313%; 200 DEG C, the Gurley value (s/100cc) before and after 2h heat treatment is 23 and 23.
Embodiment 2
By fibrillating fibre element nanofiber: the alginate fibre element nanofiber of low melting point polymer nanofiber=7:3 and low melting point polymer nanofiber (vinylidene based polyalcohol) dispersion in a solvent, and are stirred by high speed machine subsequently and made solution reach overall evenly to prepare slurry.Add solvent by pulp dilution to 0.01%, by the slurry that diluted through online dehydration forming; Squeezing, drying; Be 100 DEG C at forming temperature, linear pressure is carry out hot-roll forming under 100kg/cm condition, then through coil paper, rewinding, cut and pack, obtained battery diaphragm.
Above-mentioned closed pore composite diaphragm shows excellent characteristic, and such as, 200 DEG C, before and after 2h heat treatment, porosity is respectively 56% and 30%; At 200 DEG C, during 30min, be almost the percent thermal shrinkage of 1%; The imbibition percentage of 300%; 200 DEG C, the Gurley value (s/100cc) before and after 2h heat treatment is 23 and 800.
Embodiment 3
By fibrillating fibre element nanofiber: bacteria cellulose nanofiber and the low melting point polymer nanofiber (polyurethane by cultivating bacterial strain acquisition of low melting point polymer nanofiber=5:5, polyvinyl chloride and polyolefin) dispersion in a solvent, and stirred by high speed machine subsequently and makes solution reach overall evenly to prepare slurry.Add solvent by pulp dilution to 0.01%, by the slurry that diluted through online dehydration forming; Squeezing, drying; Be 100 DEG C at forming temperature, linear pressure is carry out hot-roll forming under 100kg/cm condition, then through coil paper, rewinding, cut and pack, obtained battery diaphragm.
Above-mentioned closed pore composite diaphragm shows excellent characteristic, and such as, 200 DEG C, before and after 2h heat treatment, porosity is respectively 54% and 18%; At 200 DEG C, during 30min 1.4% percent thermal shrinkage; The imbibition percentage of 285%; 200 DEG C, before and after 2h heat treatment, Gurley value (s/100cc) is 23 and 2020.
Embodiment 4
By fibrillating fibre element nanofiber: the alginate fibre element nanofiber of low melting point polymer nanofiber=3:7 and low melting point polymer nanofiber (EVA copolymer) dispersion in a solvent, and are stirred by high speed machine subsequently and made solution reach overall evenly to carry out prepared slarry.Add solvent by pulp dilution to 0.01%, by the slurry that diluted through online dehydration forming; Squeezing, drying; Be 100 DEG C at forming temperature, linear pressure is carry out hot-roll forming under 100kg/cm condition, then through coil paper, rewinding, cut and pack, obtained battery diaphragm.
Above-mentioned closed pore composite diaphragm shows excellent closed pore characteristic, and such as, 200 DEG C, before and after 2h heat treatment, porosity is respectively 58% and 5%; At 200 DEG C, during 30min 5% percent thermal shrinkage; The imbibition percentage of 260%; 200 DEG C, before and after 2h heat treatment, Gurley value (s/100cc) is 25 and 3867.
Embodiment 5
By fibrillating fibre element nanofiber: cellulose nano-fibrous and low melting point polymer nanofiber (polyurethane) dispersion be separated from nano-scale wood materials of low melting point polymer nanofiber=1:9 in a solvent, and is stirred by high speed machine subsequently and made solution reach overall evenly to carry out prepared slarry.Add solvent by pulp dilution to 0.01%, by the slurry that diluted through online dehydration forming; Squeezing, drying; Be 100 DEG C at forming temperature, linear pressure is carry out hot-roll forming under 100kg/cm condition, then through coil paper, rewinding, cut and pack, obtained battery diaphragm.
Above-mentioned closed pore composite diaphragm shows excellent characteristic, and such as, 200 DEG C, before and after 2h heat treatment, porosity is respectively 57% and 1%; At 200 DEG C, during 30min 18% percent thermal shrinkage; The imbibition percentage of 235%; 200 DEG C, before and after 2h heat treatment, Gurley value (s/100cc) is 23 and basic stuffiness.
According to the present invention, the advantage that the method that preparation has the composite nano fiber barrier film of closed pore function has is the competitive price because its simple preparation process and preparation cost bring, and is suitable for large batch of production.
Equally, can prepare and there is desirable physical feature, such as, closed pore, gas permeability, thermal stability, dimensional stability, thickness can be in harmonious proportion dipping characteristic barrier film.
When illustrating by specific embodiment and show of the present invention, for it is apparent to those skilled in the art that when not departing from the field of the invention that claim limits, the change of different forms can be carried out.
Comparative example:
Commercialization PE barrier film, without any process, directly tests.
The parameter of comparative example barrier film is as shown in table 1.
Below to the institutional performance test of closed pore nanofiber composite diaphragm that embodiment prepares.Method of testing is as follows:
1. structural characterization
Adopt scanning electron microscopy to comparative example 1, the barrier film of embodiment 4 is at 200 DEG C, and 2h front and rear surfaces carries out structural characterization, and SEM picture as shown in Figure 1, 2, 3.
2. porosity test
Take out after the barrier film of having weighed (Wd) is soaked 2h in n-butanol, blot gently with the liquid of filter paper by its surface, carrying out weigh (Ww), can obtain barrier film absorb the quality Wb=Ww-Wd of n-butanol.The pore volume of barrier film can have the density (ρ b) of the quality of n-butanol (Wb) and n-butanol, and being divided by obtains, the porosity of the when barrier film of this volume and dry barrier film volume (Vp).Computing formula is:
In formula, Wd is the quality of barrier film, and Ww is the diaphragm quality after soaking, and Wb is the n-butanol quality that barrier film absorbs, and Vp is the volume of dry barrier film, and ρ b is the density of n-butanol.
3. air penetrability (with the statement of Gurley value)
In room temperature, under the static pressure of 1.22KPa, Gurley densimeter measurement 100mL air is the gas permeability value (at least 5 parallel test) of the time (sec) required for sample as film of 1.0Sqinch (0.01,0.25Sqinch is free) by Validity Test area.
4. heat-shrinkable
By the closed pore composite diaphragm that obtains in embodiment at 200 DEG C of heat treatment 0.5h, observe the change in size (at least 5 parallel tests) of statistics barrier film.
5. the lyophily test of barrier film
Electrolyte solution (the 1.0M LiPF6 electrolyte of vinylcarbonates (EC) and dimethyl carbonate (DMC) (v/v=1:1)) 1h is placed in by obtaining composite diaphragm in embodiment, after taking-up, rapid filter paper washes out unnecessary electrolyte solution, mass change before and after test compound diaphragm adsorption, calculate imbibition percentage, its computing formula is as follows:
Structural analysis:
Comparative example 1, the barrier film of embodiment 5 is at 200 DEG C, and the SEM photo figure of 2h front and rear surfaces compares, and Fig. 1 is the SEM photo of the PE barrier film of comparative example, and its pore structure is the hole be evenly distributed formed by stretching.Fig. 2 be closed pore composite diaphragm at the SEM photo before not heating, can find out, crosslinkedly between nanofiber present three-D pore structure.Fig. 3 is the SEM photo of closed pore barrier film after 200 DEG C of heating 2h, substantially cannot see pore structure and exists, and the hole formed that is cross-linked with each other between fiber occurs closed.
Closed pore nanofiber composite diaphragm prepared in table 1 embodiment and the performance of comparative example
Fig. 4 is the photo of the alkylene barrier film of comparative example and the porous septum of embodiment 3, and this photo is before barrier film is exposed to high temperature, and is exposed to 150 DEG C, and captured after 30min at 200 DEG C.
Because the alkylene barrier film of comparative example has lower fusing point, when this alkylene barrier film is exposed at the temperature of 200 DEG C, the framework of this alkylene barrier film completely loses.Therefore, when the alkylene barrier film of comparative example 1 is used as the barrier film of lithium ion battery, its fail safe can not be guaranteed.
Meanwhile, the thermal stability due to the porous septum of embodiment 3 lasts till 250 DEG C, visible, and the nano combined barrier film of this closed pore is suitable as the barrier film of lithium secondary battery in dimensional stability and thermal contraction.
The measurement of the lyophily of porous septum of the present invention.
In order to determine the infiltration feature of the electrolyte according to porous septum of the present invention, the barrier film of preparation comparative example and embodiment 3, instilled in the barrier film of comparative example and embodiment 3 by electrolyte with microsyringe, result obtains after 2s and 15min, as shown in Figure 5.
Propene carbonate is not a bit impregnated on the barrier film in comparative example.But, be impregnated into immediately on the barrier film of embodiment 3 after this electrolytical instillation barrier film.
Suppose that the battery Wettability of the closed pore function and service nano fiber diaphragm of lithium secondary battery has a lot of impact to battery productive rate and efficiency, the nano combined barrier film being suitable for lithium secondary battery of the closed pore in visible embodiment 3.
Above-described embodiment is only for illustration of the present invention; not scope of the present invention is limited; under not departing from the present invention and designing the prerequisite of spirit; the change of the various proportioning that those of ordinary skill in the art make technical scheme of the present invention and parameter; modify, substitute, combination, to simplify, the displacement of equivalence all should fall in the protection range that claims of the present invention determines.
Claims (10)
1. one kind has the composite nano fiber barrier film of closed pore function, it is characterized in that, its raw material comprises fibrillating fibre element nanofiber and low melting point polymer nanofiber, combine mainly through hydrogen bond, intermolecular force between described fibrillating fibre element nanofiber, described fibrillating fibre element nanofiber is combined by the intermolecular crosslinked action of major diameter between described low melting point polymer nanofiber; Described composite nano fiber barrier film has hole so that electrolyte ion passes and stops electronics to pass; Under 130 ~ 170 DEG C of temperature environments, the closing of pores of described composite nano fiber barrier film, passes through to prevent the excessive and less desirable ion after battery damage.
2. the composite nano fiber barrier film with closed pore function according to claim 1, it is characterized in that, under described composite nano fiber barrier film hole closure state, the dimensionally stable of described composite nano fiber barrier film, heat 30min under 200 DEG C of high temperature within, percent thermal shrinkage is less than 2%.
3. the composite nano fiber barrier film with closed pore function according to claim 1, is characterized in that, described in there is the composite nano fiber barrier film of closed pore function thickness be 10 ~ 80 μm.
4. a composite nano fiber barrier film preparation method with closed pore function according to claim 1, is characterized in that, with mass ratio be 1:9 ~ 9:1 fibrillating fibre element nanofiber and low melting point polymer nanofiber be raw material, prepare with paper technology.
5. the preparation method with the composite nano fiber barrier film of closed pore function according to claim 4, is characterized in that, comprise following concrete steps:
I, be that 1:9 ~ 9:1 takes fibrillating fibre element nanofiber and at least one low melting point polymer nanofiber disperses in a solvent respectively by mass ratio, rapid stirring forms slurry;
II, in the slurry of step I, binding agent is added;
III, be 0.01% ~ 0.05% by the pulp dilution after step II to concentration;
IV, the slurry after dilution, through online dehydration forming, squeezing, drying, hot-roll forming, has the composite nano fiber barrier film of closed pore function described in namely obtaining.
6. have the preparation method of the composite nano fiber barrier film of closed pore function according to claim 4, it is characterized in that, the diameter of described fibrillating fibre element nanofiber is 10-1000nm, and length is 10-3000 μm.
7. there is the preparation method of the composite nano fiber barrier film of closed pore function according to claim 4,5 or 6, it is characterized in that, described fibrillating fibre element nanofiber comprise from nano-scale wood materials be separated cellulose nano-fibrous, alginate fibre element nanofiber, and by cultivating the bacteria cellulose nanofiber that bacterial strain obtains.
8. have the preparation method of the composite nano fiber barrier film of closed pore function according to claim 4, it is characterized in that, the diameter of described low melting point polymer nanofiber is 10-1000nm.
9. there is the preparation method of the composite nano fiber barrier film of closed pore function according to claim 4,5 or 8, it is characterized in that, described low melting point polymer nanofiber be polymethyl methacrylate, vinylidene based polyalcohol, polyurethane, polyvinyl chloride, polyolefin, one or more combinations of EVA copolymer, polyethylene glycol succinate.
10. an energy storage device prepared by the composite nano fiber barrier film having closed pore function described in one of application rights requirement 1 to 3, comprises lithium ion battery, lithium-sulfur cell, alkaline battery, ultracapacitor, lead-acid battery, zinc-air cell, sodium-ion battery.
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| CN201410798500.4A CN104485437B (en) | 2014-12-19 | 2014-12-19 | With hot closed pore function and service nano fiber diaphragm, preparation method and energy storage device |
| PCT/CN2015/097248 WO2016095771A1 (en) | 2014-12-19 | 2015-12-14 | Composite nanofiber separator with thermal shutdown function, preparation method therefor and energy storage components |
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| CN201410798500.4A CN104485437B (en) | 2014-12-19 | 2014-12-19 | With hot closed pore function and service nano fiber diaphragm, preparation method and energy storage device |
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| WO2016095771A1 (en) | 2016-06-23 |
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