CN103855348A - Electrochemical power source diaphragm, preparation method thereof and electrochemical power source - Google Patents
Electrochemical power source diaphragm, preparation method thereof and electrochemical power source Download PDFInfo
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- CN103855348A CN103855348A CN201210504993.7A CN201210504993A CN103855348A CN 103855348 A CN103855348 A CN 103855348A CN 201210504993 A CN201210504993 A CN 201210504993A CN 103855348 A CN103855348 A CN 103855348A
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- 230000004888 barrier function Effects 0.000 claims description 91
- 239000010954 inorganic particle Substances 0.000 claims description 37
- -1 polyethylene Polymers 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003365 glass fiber Substances 0.000 claims description 7
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- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- 229920003366 poly(p-phenylene terephthalamide) Polymers 0.000 claims description 2
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- 229920002635 polyurethane Polymers 0.000 claims description 2
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 23
- 229910001416 lithium ion Inorganic materials 0.000 description 23
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
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- 238000011056 performance test Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- 238000011161 development Methods 0.000 description 2
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- 150000002641 lithium Chemical class 0.000 description 2
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- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
-
- 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
- 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
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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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
- 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
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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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- Inorganic Chemistry (AREA)
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Abstract
The invention provides an electrochemical power source diaphragm and its preparation method and an electrochemical power source. The electrochemical power source includes a fiber composite layer and an organic binder and inorganic powder composite layer coating the fiber composite layer surface, the fiber composite layer includes mixed organic and inorganic fibers, and the weight ratio of organic fiber to inorganic fiber is 1:99-99:1. The preparation method of the electrochemical power source diaphragm includes the steps of fiber composite layer formation, preparation of an organic-inorganic suspension and film forming treatment of the organic-inorganic suspension on the fiber composite layer surface. The electrochemical power source includes the electrochemical power source diaphragm. The electrochemical power source diaphragm uses the fiber composite layer as a matrix, and uses the inorganic powder containing composite layer as a coating, the resistance temperature of the electrochemical power source diaphragm can be effectively improved, the electrochemical power source diaphragm has excellent permeability, and the power source security performance and high rate capability are improved. The preparation method has the advantages of simple process, high production efficiency and low production cost.
Description
Technical field
The invention belongs to electrochemical power source technical field, be specifically related to a kind of battery diaphragm and preparation method thereof and electrochemical power source.
Background technology
Along with the development of human being's production power, increasing running car is in city, streets and lanes, rural.Popularizing to people's life of automobile brings great convenience.But incident problem is also more and more serious.The consumption of the non-renewable energy resources such as oil is constantly accelerated, and the impact that the discharge of vehicle exhaust causes to environment also constantly expands.At present, people are in order to address these problems proposition Development of EV, to replacing orthodox car.And whether key is to have energy density, power density enough large, cycle life long enough, safe and reliable electrical source of power replace internal combustion engine.Wherein, the fail safe of power supply is the most important thing.
For electrochemical power source (power supply lithium ion battery and ultracapacitor), thereby important potential safety hazard is exactly to put or short circuit causes the temperature of power supply inside sharply to raise causing burning or blast because overcharge or cross.If power supply itself has good thermal conductivity, can fast heat be distributed, just can effectively reduce this potential safety hazard.And the key that determines electrokinetic cell fail safe is barrier film wherein.
At present, the barrier film generally adopting as lithium ion battery at electrochemical power source is porous polyolefin barrier film.Because porous polyolefin barrier film is polymer, its thermal conductivity is very poor, the heat producing can not be derived in time in charge and discharge process, can cause temperature in power supply sharply to raise.Again because porous polyolefin barrier film is polymer, itself poor heat resistance, in the time that temperature acquires a certain degree, this barrier film will shrink even and break, thus make power supply inside likely occur positive and negative between directly contact and short circuit, cause battery security hidden danger, as phenomenons such as burning, blasts, in addition, this porous polyolefin barrier film also exist wettability and high rate capability poor, therefore, this porous polyolefin barrier film is difficult to meet the requirement of electrokinetic cell to security performance and high rate capability.Therefore,, in order to meet higher requirement, need the research can better barrier film.
Summary of the invention
The object of the embodiment of the present invention is to overcome the above-mentioned deficiency of prior art, and electrochemical power source barrier film of a kind of thermal endurance and good permeability and preparation method thereof is provided.
Another object of the embodiment of the present invention is to provide a kind of fail safe and forthright high electrochemical power source doubly.
In order to realize foregoing invention object, technical scheme of the present invention is as follows:
A kind of electrochemical power source barrier film, comprise fiber composite layer and be coated with the organic binder-inorganic particle composite bed that is located at described fiber composite layer surface, described fiber composite layer comprises organic fiber and the inorfil of mixing, and the weight ratio of organic fiber and inorfil is 1:99～99:1.
And a kind of preparation method of above-mentioned electrochemical power source barrier film, comprises the steps:
Tiling after described organic fiber, inorfil are mixed, forms fiber composite layer;
After organic binder is dissolved in to organic solvent, add inorganic particle, be mixed with suspension;
Described suspension is coated in to fiber composite layer surface, and dry processing, obtains described electrochemical power source barrier film.
And, a kind of electrochemical power source, it comprises above-mentioned electrochemical power source barrier film.
It is matrix that above-mentioned electrochemical power source barrier film adopts organic fiber and inorfil to mix the fiber composite layer forming, and to contain inorganic particle composite bed as coating, effectively improve the tolerable temperature of this electrochemical power source barrier film, made this electrochemical power source every thering is excellent air penetrability.
The slurry of organic and inorganic composite bed is directly coated in the surface that fiber composite layer is matrix by above-mentioned electrochemical power source barrier film preparation method, and dry, technique is simple, and condition is easily controlled, low for equipment requirements, production efficiency, and production cost is low, is suitable for suitability for industrialized production.
Above-mentioned electrochemical power source is because comprising above-mentioned electrochemical power source barrier film, because this electrochemical power source barrier film has excellent air penetrability, effectively reduce the internal resistance of this electrochemical power source in the time of high power charging-discharging, not only improve energy density, more be conducive to reduce hot generation, due to the high tolerable temperature of this electrochemical power source barrier film, effectively improve the security performance of electrochemical power source again, extended its life-span.
Brief description of the drawings
Below in conjunction with drawings and Examples, the invention will be further described, in accompanying drawing:
Fig. 1 is embodiment of the present invention electrochemical power source membrane configuration figure;
Fig. 2 is the electrochemical power source barrier film preparation method's of the embodiment of the present invention process chart.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
Example of the present invention provides that a kind of thermal diffusivity is good, the electrochemical power source barrier film of dimensionally stable, and its structure as shown in Figure 1.This electrochemical power source barrier film comprises fiber composite layer 1 and is coated with the organic binder-inorganic particle composite bed 2 that is located at fiber composite layer 1 surface.
Wherein, above-mentioned fiber composite layer 1 is equivalent to be the sandwich layer of stratiform, it is the composite fibre that contains organic fiber and inorfil to be elaborated to stratiform form, concrete preparation method refers to the below preparation method about this electrochemical power source barrier film, wherein, the weight ratio of organic fiber and inorfil is 1:99～99:1.This fiber composite layer 1 forms the matrix of electrochemical power source barrier film, has strengthened the mechanical strength of this electrochemical power source barrier film, simultaneously due to itself characteristic, has improved the tolerable temperature of this electrochemical power source barrier film.
As the specific embodiment of the invention, the diameter of the organic fiber in this fiber composite layer 1 is preferably 5～40 μ m, and it is preferably at least one in PET fiber, superhigh molecular weight polyethylene fibers, polyethylene fibre, polypropylene fibre, PPTA fiber.It is 5～40 μ m that inorfil is preferably diameter, and it is preferably at least one in glass fibre, quartz glass fibre, ceramic fibre.This preferred organic fiber and inorganicly have good mechanical strength and a tolerable temperature, wherein, inorfil also has excellent heat conductivility, can effectively improve heat conduction and the heat dispersion of electrochemical power source barrier film.
Organic binder in above-mentioned organic binder-inorganic particle composite bed 2 and the weight ratio of inorganic particle are preferably (1～5): 1.These both preferred proportions, can make this electrochemical power source barrier film there is good electrolyte wettability, the intensity that simultaneously strengthens this organic binder-inorganic particle composite bed 2 and 1 combination of fiber composite layer, makes this electrochemical power source barrier film have good mechanical strength.
As the specific embodiment of the invention, the organic substance in this organic binder-inorganic particle composite bed 2 is that organic binder is at least one in polyvinyl alcohol, polytetrafluoroethylene, Kynoar, modified styrene butadiene rubber, Viton, polyurethane; Inorganic particle is hollow alumina and/or hollow silica, and inorganic particle particle diameter is preferably 3～1000nm, as particle diameter be 3～1000nm hollow alumina and/or hollow silica.This preferred organic binder has higher tolerable temperature and adhesion strength, thereby increase the mechanical strength of organic binder-inorganic particle composite bed 2 and 1 combination of fiber composite layer, prevent coming off of organic binder-inorganic particle composite bed 2, extend the useful life of electrochemical power source barrier film, thereby extended electrochemical power source service life cycle.This preferred inorganic particle has excellent heat conductivility, and this inorganic particle forms skeleton in organic and inorganic composite bed 2, thereby make embodiment of the present invention electrochemical power source barrier film there is excellent heat dispersion, can also improve the broken film temperature of electrochemical power source barrier film, improve the security performance of chemical power source barrier film.Because inorganic particle is preferably hollowly, can reduces significantly like this weight of electrochemical power source barrier film, thereby improve electrochemical power source energy density again.Therefore, this organic binder and inorganic particle acting in conjunction, can effectively regulate the pore of this electrochemical power source barrier film, improved tolerable temperature and the gas permeability of electrochemical power source barrier film.
As the preferred embodiment of the present invention, by controlling thickness or the weight ratio of above-mentioned fiber composite layer 1 and organic binder-inorganic particle composite bed 2, it is 10%～90% that the air penetrability of the electrochemical power source barrier film in above-described embodiment is preferably controlled, more preferably 40%～60%.By regulating thickness or the weight ratio of fiber composite layer 1 and organic binder-inorganic particle composite bed 2, realize mechanical strength to this electrochemical power source barrier film and the adjusting of gas permeability, improve electrochemical power source barrier film wettability, to improve the chemical property of electrochemical power source simultaneously.
From the above mentioned, it is matrix that above-mentioned electrochemical power source barrier film adopts organic fiber and inorfil to mix the fiber composite layer 1 forming, and taking organic binder-inorganic particle composite bed 2 of containing inorganic particle as coating, effectively improve the tolerable temperature of this electrochemical power source barrier film, made this electrochemical power source every thering is excellent air penetrability.And by the adjusting to the selecting of organic fiber and inorfil, organic binder and inorganic particle kind, mixing ratio, realize the adjusting of gas permeability, thermal endurance, thermal diffusivity and mechanical strength to electrochemical power source barrier film, obtain the high electrochemical power source barrier film of combination property.
Correspondingly, the embodiment of the present invention also provides a kind of method of preparing above-mentioned electrochemical power source barrier film, and the method process chart as shown in Figure 2, refers to Fig. 1 simultaneously.This preparation method comprises the steps:
The formation of step S01. fiber composite layer: tiling after organic fiber, inorfil are mixed, forms fiber composite layer 1;
Step S02. preparation organic and inorganic suspension: add inorganic particle after organic binder is dissolved in to organic solvent, be mixed with suspension;
Step S03. organic and inorganic suspension is in the processing of fiber composite layer surface filming: suspension prepared by step S02 is coated in fiber composite layer 1 surface, and dry processing, obtains described electrochemical power source barrier film.
Particularly, in above-mentioned steps S01, the kind that organic fiber, inorfil are selected and content as described above, in order to save length, do not repeat them here.After this organic fiber, inorfil mix, the method for tiling can be carried out as follows:
Organic fiber, inorfil are elaborated on guipure at random and uniformly by above-mentioned proportion, form fiber composite layer 1.Certainly, organic fiber, inorfil can also be elaborated on other carrier, as long as can realize organic fiber, inorfil is elaborated, this carrier has gone out outside guipure, can also be with conventional other the carrier in this area.
In above-mentioned steps S02, the kind that organic binder, inorganic particle are selected and content as described above, in order to save length, do not repeat them here.Organic solvent can be selected ether, pentane, carrene, carbon disulfide, acetone, chloroform, methyl alcohol, hexane, three fluoro acetic acid, 1,1, at least one in 1-trichloroethanes, carbon tetrachloride.In the process of the preparation of formulated suspension, preferably first organic binder is joined in organic solvent, after organic binder is dissolved completely, then add inorganic particle to stir until each component is uniformly dispersed.The concentration of this suspension is adjusted flexibly according to the mode applying, and in addition, if when suspension concentration is lower, can take repeatedly to apply, to realize the thickness of control organic binder-inorganic particle composite bed 2 and the air penetrability of this electrochemical power source barrier film.Particularly, the concentration of formulated suspension can be that the quality of inorganic particle accounts for 0.5%～25% of suspension gross mass.
In above-mentioned steps S03, the mode that suspension is coated in fiber composite layer 1 surface is preferably the combination of one or more modes in dip coated, scraper for coating, scraper coating, spraying.This preferred coating method can be dispersed in suspension fiber composite layer 1 surface uniformly, thereby makes to form on fiber composite layer 1 surface organic binder-inorganic particle composite bed 2 of even thickness.The amount that this suspension is coated in fiber composite layer 1 surface is preferably 10%～90% by the air penetrability control of this electrochemical power source barrier film, more preferably 40%～60%, and to make this electrochemical power source barrier film there is good gas permeability.
In this step S03, for the suspension that is coated in fiber composite layer 1 surface does not change in dry run, being dried in this step is preferably dry under the condition of anaerobic, removes organic solvent, organic and inorganic suspension is solidified dry, form organic binder-inorganic particle composite bed 2.Preferably, the condition of this anaerobic is at least one dry gas or the vacuum in hydrogen, nitrogen, inert gas.Dry temperature is preferably 40 DEG C～200 DEG C, and can regulate drying time according to temperature, as long as it is dry that organic binder-inorganic particle composite bed 2 is solidified completely.
From the above mentioned, the slurry of organic and inorganic composite bed 2 is directly coated in fiber composite layer matrix surface by the preparation method of above-described embodiment electrochemical power source barrier film, dry through solidifying.Its preparation method technique is simple, and condition is easily controlled, low for equipment requirements, and production efficiency is high, and production cost is low, is suitable for suitability for industrialized production.
The embodiment of the present invention has also improved a kind of fail safe and forthright high electrochemical power source doubly, this electrochemical power source comprise above-mentioned electrochemical power source barrier film and other necessity as the associated components such as power shell, electrolyte.Particularly, this electrochemical power source is lithium ion battery or ultracapacitor.
As the embodiment of the present invention, in the time that electrochemical power source is lithium ion battery, this lithium ion battery comprises positive pole, barrier film and the negative pole and battery container and the electrolyte that stack gradually.Wherein, positive pole, battery diaphragm and negative pole are reeled after stacking gradually and superposeing, and pack in battery container, and electrolyte injects battery container interior also submergence electrode and battery diaphragm.Battery diaphragm directly adopts above-mentioned electrochemical power source barrier film or utilizes the preparation method embodiment of above-mentioned electrochemical power source barrier film to prepare, and anodal and negative pole is to adopt this area conventional.Because the battery diaphragm of lithium ion battery in this embodiment adopts above-described embodiment electrochemical power source barrier film.And this electrochemical power source barrier film is as mentioned above, to mix the fiber composite layer forming as matrix and the organic binder-inorganic particle composite bed formation that contains inorganic particle taking organic fiber and inorfil, because this electrochemical power source barrier film has excellent air penetrability, effectively reduce the internal resistance of this lithium ion battery in the time of high power charging-discharging, not only improve its energy density, more be conducive to reduce hot generation, again due to the high tolerable temperature of this electrochemical power source barrier film, effectively improve the security performance of lithium ion battery, extended its life-span.
In the time that electrochemical power source is ultracapacitor, this ultracapacitor comprises electrode, barrier film, electrode and the battery container and the electrolyte that stack gradually.Wherein, electrode/barrier film/electrode is reeled after stacking gradually stack, and packs in capacitor casing, and electrolyte injects in capacitor casing and submergence electrode and barrier film.This barrier film directly adopts above-mentioned electrochemical power source barrier film or utilizes the preparation method embodiment of above-mentioned electrochemical power source barrier film to prepare, and electrode is to adopt this area conventional.
Just because of above-mentioned electrochemical power source because comprising above-mentioned electrochemical power source barrier film, because this electrochemical power source barrier film has excellent air penetrability, effectively reduce the internal resistance of this electrochemical power source in the time of high power charging-discharging, not only improve energy density, more be conducive to reduce hot generation, the high tolerable temperature performance of this electrochemical power source barrier film has effectively improved the security performance of electrochemical power source, has extended its life-span.This electrochemical power source has the performance of above-mentioned excellence.This electrochemical power source can be applied to the application in mobile terminal product, electric automobile, electrical network, communication equipment and/or electric tool.As when electrochemical power source being lithium ion battery during for communication equipment, this communication equipment comprises operational module and supply module.Wherein, supply module provides electric energy for operational module, and it comprises lithium battery mentioned above, and this lithium battery can be one or more lithium battery.When putting supply module and comprising plural lithium battery, this lithium battery can be according to the needs of the required electric energy of operational module, with in parallel or series connection or and series connection.The electric energy operation that this operational module uses supply module to provide, for example, carry out the task such as acceptance, exchange, processing, storage, transmitting of relevant information.This communication equipment can make mobile phone, notebook computer etc., and any one needs the electronic equipment of electric energy.
Illustrate above-mentioned battery isolation preparation method by multiple embodiment below, with and the aspect such as performance.
Embodiment 1
A kind of battery diaphragm and preparation method thereof and lithium ion battery, the preparation method of this battery diaphragm comprises the steps:
S11: the glass fibre of 10 microns of 10 microns of PET fibers of 50 weight portions and 50 weight portions is elaborated on guipure at random and uniformly, form fiber composite sandwich layer;
S12: to the polytetrafluoroethylene that adds 40 weight portions in the container that contains acetone, do not stop to stir, form organic solution until dissolve completely, then be the hollow alumina powder of 50 nanometers to adding the average grain diameter of 10 weight portions in this organic solution, and stir, obtain organic and inorganic suspension; Wherein, the mass percentage concentration of hollow alumina powder in organic and inorganic suspension is 10%;
S13: execute in the mode of dip coated that the organic and inorganic suspension of step S12 preparation is coated in to fiber composite sandwich layer prepared by step S11 with above-mentioned organic and inorganic suspension is two-sided, the air dryings of 100 DEG C 24 hours, obtain electrochemical power source barrier film.
Electrochemical power source barrier film prepared by the present embodiment 1 is for the preparation of lithium ion battery: electrochemical power source barrier film prepared by anodal, the present embodiment 1 and negative pole are reeled after stacking gradually stack, and pack in capacitor casing, then in battery container, inject electrolyte, finally encapsulation.
Electrochemical power source barrier film and lithium ion battery prepared by the present embodiment carry out correlated performance test, learn after tested, and the porosity of this electrochemical power source barrier film is 50%, and aperture is 50 nanometers, and thickness is 20 microns, and air penetrability is 150s/100cc.Broken film temperature is higher than 200 DEG C.The energy density of lithium ion battery is 100wh/kg.
Embodiment 2
A kind of battery diaphragm and preparation method thereof and lithium ion battery, the preparation method of this battery diaphragm comprises the steps:
S21: the glass fibre of 10 microns of 10 microns of PET fibers of 20 weight portions and 80 weight portions is elaborated on guipure at random and uniformly, form fiber composite sandwich layer;
S22: to the PVDF that adds 50 weight portions in the container that contains acetone, do not stop to stir, form organic solution until dissolve completely, then be the hollow alumina powder of 200 nanometers to adding the average grain diameter of 50 weight portions in this organic solution, and stir, obtain organic and inorganic suspension; Wherein, the mass percentage concentration of hollow alumina powder in organic and inorganic suspension is 0.5%;
S23: execute in the mode of dip coated that the organic and inorganic suspension of step S22 preparation is coated in to fiber composite sandwich layer prepared by step S21 with above-mentioned organic and inorganic suspension is two-sided, the air dryings of 100 DEG C 12 hours, obtain electrochemical power source barrier film.
Battery diaphragm prepared by the present embodiment 2 is for the preparation of lithium ion battery, and concrete preparation method is as the preparation method of the lithium ion battery in embodiment 1.
Electrochemical power source barrier film and lithium ion battery prepared by the present embodiment carry out correlated performance test, learn after tested, and the porosity of the chemical power source barrier film of the present embodiment is 50%, and aperture is 50 nanometers, and thickness is 30 microns, and air penetrability is 200s/100cc.Broken film temperature is higher than 250 DEG C.The energy density of lithium ion battery is 110wh/kg.
Embodiment 3
A kind of battery diaphragm and preparation method thereof and lithium ion battery, the preparation method of this battery diaphragm comprises the steps:
S31: the glass fibre of 5 microns of 10 microns of PET fibers of 50 weight portions and 50 weight portions is elaborated on guipure at random and uniformly, form fiber composite sandwich layer;
S32: to the PVDF that adds 40 weight portions in the container that contains acetone, do not stop to stir, form organic solution until dissolve completely, then be the hollow alumina powder of 100 nanometers to adding the average grain diameter of 30 weight portions in this organic solution, and stir, obtain organic and inorganic suspension; Wherein, the mass percentage concentration of hollow alumina powder in organic and inorganic suspension is 25%;
S33: execute in the mode of dip coated that the organic and inorganic suspension of step S32 preparation is coated in to fiber composite sandwich layer prepared by step S31 with above-mentioned organic and inorganic suspension is two-sided, the air dryings of 100 DEG C 12 hours, obtain electrochemical power source barrier film.
Battery diaphragm prepared by the present embodiment 3 is for the preparation of lithium ion battery, and concrete preparation method is as the preparation method of the lithium ion battery in embodiment 1.
Electrochemical power source barrier film and lithium ion battery prepared by the present embodiment carry out correlated performance test, learn after tested, and the porosity of the chemical power source barrier film of the present embodiment is 60%, and aperture is 40 nanometers, and thickness is 25 microns, and air penetrability is 150s/100cc.Broken film temperature is higher than 200 DEG C.The energy density of lithium ion battery is
120wh/kg。
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (10)
1. an electrochemical power source barrier film, it is characterized in that: comprise fiber composite layer and be coated with the organic binder-inorganic particle composite bed that is located at described fiber composite layer surface, described fiber composite layer comprises organic fiber and the inorfil of mixing, and the weight ratio of organic fiber and inorfil is 1:99～99:1.
2. electrochemical power source barrier film as claimed in claim 1, is characterized in that: the air penetrability of described electrochemical power source barrier film is 10～90%.
3. electrochemical power source barrier film as claimed in claim 1 or 2, is characterized in that: described organic fiber is that diameter is at least one in the PET fiber, superhigh molecular weight polyethylene fibers, polyethylene fibre, polypropylene fibre, PPTA fiber of 5～40 μ m.
4. electrochemical power source barrier film as claimed in claim 1 or 2, is characterized in that: described inorfil is that diameter is at least one in the glass fibre, quartz glass fibre, ceramic fibre of 5～40 μ m.
5. electrochemical power source barrier film as claimed in claim 1, is characterized in that: in described organic binder-inorganic particle composite bed, the weight ratio of described organic binder and inorganic particle is (1～5): 1.
6. the electrochemical power source barrier film as described in claim 1 or 4, is characterized in that: described organic substance is that organic binder is at least one in polyvinyl alcohol, polytetrafluoroethylene, Kynoar, modified styrene butadiene rubber, Viton, polyurethane.
7. the electrochemical power source barrier film as described in claim 1 or 4, is characterized in that: described inorganic particle is hollow alumina and/or hollow silica.
8. the electrochemical power source barrier film as described in claim 1 or 4, is characterized in that: the particle diameter of described inorganic particle is 3～1000nm.
9. the electrochemical power source barrier film preparation method as described in claim 1～8 any one, comprises the steps:
Tiling after described organic fiber, inorfil are mixed, forms fiber composite layer;
After organic binder is dissolved in to organic solvent, add inorganic particle, be mixed with suspension;
Described suspension is coated in to fiber composite layer surface, and dry processing, obtains described electrochemical power source barrier film.
10. an electrochemical power source, is characterized in that, comprises the arbitrary described electrochemical power source barrier film of claim 1～7.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105514328A (en) * | 2016-01-13 | 2016-04-20 | 浙江天能能源科技有限公司 | Ceramic diaphragm for lithium ion battery and preparation method of ceramic diaphragm |
| CN107768579A (en) * | 2017-08-30 | 2018-03-06 | 天能电池集团有限公司 | A kind of lead accumulator dividing plate, preparation method and lead accumulator |
| CN110289384A (en) * | 2019-06-24 | 2019-09-27 | 天能电池(芜湖)有限公司 | A kind of NEW TYPE OF COMPOSITE AGM partition preventing high current short circuit |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6200706B1 (en) * | 1995-03-31 | 2001-03-13 | Mitsubishi Paper Mills Limited | Nonwoven fabric for separator of non-aqueous electrolyte battery and non-aqueous electrolyte battery using the same |
| CN101707242A (en) * | 2009-10-14 | 2010-05-12 | 东莞新能源科技有限公司 | Organic/inorganic composite porous isolating membrane |
| CN102522514A (en) * | 2011-12-21 | 2012-06-27 | 莱州联友金浩新型材料有限公司 | High-temperature resistant micropore thin film material and application thereof |
| CN103515557A (en) * | 2012-06-18 | 2014-01-15 | 海洋王照明科技股份有限公司 | Electrochemical power source separation membrane and preparation method thereof |
-
2012
- 2012-11-30 CN CN201210504993.7A patent/CN103855348A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6200706B1 (en) * | 1995-03-31 | 2001-03-13 | Mitsubishi Paper Mills Limited | Nonwoven fabric for separator of non-aqueous electrolyte battery and non-aqueous electrolyte battery using the same |
| CN101707242A (en) * | 2009-10-14 | 2010-05-12 | 东莞新能源科技有限公司 | Organic/inorganic composite porous isolating membrane |
| CN102522514A (en) * | 2011-12-21 | 2012-06-27 | 莱州联友金浩新型材料有限公司 | High-temperature resistant micropore thin film material and application thereof |
| CN103515557A (en) * | 2012-06-18 | 2014-01-15 | 海洋王照明科技股份有限公司 | Electrochemical power source separation membrane and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105514328A (en) * | 2016-01-13 | 2016-04-20 | 浙江天能能源科技有限公司 | Ceramic diaphragm for lithium ion battery and preparation method of ceramic diaphragm |
| CN107768579A (en) * | 2017-08-30 | 2018-03-06 | 天能电池集团有限公司 | A kind of lead accumulator dividing plate, preparation method and lead accumulator |
| CN107768579B (en) * | 2017-08-30 | 2020-08-11 | 天能电池集团股份有限公司 | Lead storage battery separator, preparation method and lead storage battery |
| CN110289384A (en) * | 2019-06-24 | 2019-09-27 | 天能电池(芜湖)有限公司 | A kind of NEW TYPE OF COMPOSITE AGM partition preventing high current short circuit |
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Application publication date: 20140611 |