CN103531733A - Electrochemical separation membrane structure and manufacturing method thereof - Google Patents
Electrochemical separation membrane structure and manufacturing method thereof Download PDFInfo
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Images
Classifications
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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
- H01M50/411—Organic 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
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/44—Fibrous 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
- H01M50/40—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
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
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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
Abstract
The invention discloses an electrochemical separation membrane structure and a manufacturing method of the electrochemical separation membrane structure. The electrochemical separation membrane structure comprises a base phase polymer part, a fiber supporting part and multiple inorganic particles, wherein the base phase polymer part is in a continuous phase structure; the fiber supporting part is distributed in the base phase polymer part in a strip mode so as to provide mechanical strength; the multiple inorganic particles are uniformly distributed in the base phase polymer part and account for 0.1-50 weight percent of the whole; the fiber supporting part is in a porous structure and is provided with pores, so that the base phase polymer part is filled in the pores. Therefore, the electrochemical separation membrane structure has high connectivity, a shrinkage phenomenon of the separation membrane is effectively reduced through the inorganic particles, and the safety performance at high temperature is improved. Moreover, the electrochemical separation membrane structure is applied to a lithium battery, a resistance value of the whole component can be effectively reduced, the component has high charge and discharge capacity, and the service life of the whole component is prolonged.
Description
Technical field
The present invention relates to a kind of electrochemistry barrier film structure and preparation method thereof, be mainly used in lithium battery, the security performance when improving shrinkage phenomenon and high temperature.
Background technology
Secondary lithium battery has that energy density is high, the advantage such as have extended cycle life, the status that has replaced rapidly the traditional secondary batteries such as NI-G, ni-mh since coming out, from 1991, Japanese Sony company took the lead in after its commercialization, occupation rate of market continues to increase, only more than ten years, the global output value just surpassed the summation of NI-G and Ni-MH battery.Along with to current material and the improvement of battery design technology and the appearance of new material, the application of lithium ion battery is constantly expanded, and 3C electronic product hammers at light, thin, short and smallization especially in recent years, and lithium ion battery has become best selection.
In consumer electronics or electric motor car application market, the security requirement of lithium battery is most important Product evaluation project, therefore in battery design as barrier film etc. promote most key of material that fail safe is relevant and design work.Wherein the effect of barrier film is mainly insulating electron and avoids between positive and negative electrode short circuit and ion can freely be passed through; When battery abnormal temperature rises in addition, also need barrier film to be used for closing original pore as ion channel, avoid temperature to continue to raise and cause heat cruelly walk (thermal runaway) and then produce burning or explode.Therefore also the intensity of barrier film product itself, thickness, micropore distribute and the quality pointer such as warm start, the factors such as battery capacity, battery cycle life, fail safe have been determined, also make the market development of lithium battery isolation membrane be attracted attention, especially barrier film price accounts for the more than 20% of whole lithium battery cost, also makes the exploitation of barrier film get over fractal key.
Just it seems at present, nearly all business-like lithium ion battery is all to adopt the porous polymer film of TPO (polyolefin) as barrier film, includes PP, PE, and even PP/PE/PP tri-laminated.The barrier film of TPO is lower cost not only, and has good mechanical strength and chemically stability.
About the producer rule of barrier film, can be divided into two kinds of dry type and wet types.The processing procedure of dry type as No. 5952120,6207053 and 6368742, United States Patent (USP) case disclose and adopt TPO (polyolefin) as the materials and methods of porous isolating membrane, mainly use polyethylene (polyethylene; PE), polypropylene (polypropylene; PP) be main component, or be combined into one so that PP/PE/PP tri-is stacking.Its manufacture method is for first by material melting film extrusion, carry out again unidirectional or two-way stretching, in the process stretching, hard elastics material vertical is opened formation micropore in extruding the lamellar structure that direction is arranged in parallel, finally by fixed this microcellular structure by thermal finalization processing procedure.The lower cost for material that this method is used; but for meeting the required of lithium battery specification; process conditions is strict; cause barrier film terminal price high; and its pore space structure is straight; at cathode of lithium battery end, easily form Li dendrite and pierce through barrier film formation short circuit, therefore conventionally can make thermoresistance layer or add inorganic particulate and reduce the safety problem that short circuit causes.
For lithium battery system, because of the polarity of TPO material low, and the electrolyte using in lithium battery is to contain lithium salts to be dissolved in high-dielectric coefficient wherein, the organic solvent of high polarity mostly, affinity is between the two conventionally desirable not to the utmost, impact in one's power, electrolyte is bad to the wetting effect of barrier film, thereby whole ionic conductance is by the ionic conductance far below electrolyte itself.In order to improve both affinitys, improve degree of wetting, part Study is aimed at TPO material and carries out surfaction, improves wetting effect, as No. 6322923, United States Patent (USP) case on a polyolefin porous membrane coating one deck colloidal condition macromolecule to strengthen its wetability; The opposing party's rule is directly to change barrier material, be changed to and electrolyte between the higher material of affinity, even can and cathode-anode plate between also have higher affinity.
As previously described, if battery is overheated because of exothermic reaction, or while being subject to outside high heat damage, the hole on barrier film can be closed, and interelectrode ion cannot be conducted, and then reaches the function of cutting off battery current.Substantially the startup of closed pore (Shutdown) mechanism is that while arriving the fusing point of material, barrier film can be from the solid-state liquid state that converts to, and with polyethylene (Polyethylene) material, its fusing point is greatly about 130 ℃ of left and right.Yet in molten state, for fear of positive and negative electrode, directly contact, before fusing, all must maintain its integrality.Along with internal temperature of battery continues to rise, barrier film finally can melt break (Meltdown), causes both positive and negative polarity contact short circuit, and then causes blast.The difference of fusing break temperature and closed pore temperature is the dead line of barrier film, at tradition or general polyolefin (Polyolefin; PO) barrier film, its temperature difference is quite little, is approximately at 30～50 ℃, and depends on the molecular weight of raw material.The shortcoming of the cognitive traditional barrier film of barrier film production firm (being mainly polyethylene) in recent years, and attempt certain methods and promote its fail safe.Wherein inorganic compounding barrier film technology will be that following high energy battery develops required crucial barrier material technology.
The inorganic compounding barrier film of most utilizes individual layer PE barrier film to form as the basic material of inorganic compounding barrier film, object is in order to maintain inorganic compounding barrier film thickness, can take into account again film mechanical strength and high thermal impedance function, inorganic compounding layer mainly comprise Polyamide with how rice oxide (Al2O3 or SiO2), the basic material of inorganic compounding barrier film is individual layer porous PE film (14～16 μ m), inorganic compounding layer (4 μ m) has concurrently to be strengthened individual layer porous PE film mechanical strength and improves the inhomogeneity function of heat conduction, therefore the thickness of composite isolated film is about (18～20 μ m), the porosity of ceramic thin film (60～65%) is higher than the porosity (30～35%) of individual layer porous PE film, therefore can not affect wetability and the lithium ion penetrating power of barrier film.
As U.S. Patent number the 7959011st for a kind of by pet polymer adhesive-bonded fabric that aluminium oxide, zirconia and silica mixed, after continuous dipping and drying and sintering, owing to having produced inorganic layer between metal oxide and PET, make this film there is higher thermal stability, be heated not yielding, at 200 ℃, do not shrink and melting phenomenon, can improve the fail safe of electrokinetic cell.But between composite bed and matrix membrane, there is equally the problem that bonding strength is inadequate, membrane stability is poor.
Chinese patent CN 101481855A discloses the how preparation method of rice composite cellulosic membrane of a kind of silicon dioxide/Kynoar.This method is prepared how rice silicon dioxide of modification by collosol and gel principle one-step method, and itself and Kynoar are carried out to blend, utilizes electrostatic spinning technique to prepare composite nano rice tunica fibrosa.Chinese patent CN 101826606A discloses a kind of polytetrafluoroethyllithium lithium-ion battery barrier film and preparation method.It is to take polytetrafluoroethylporous porous membrane as base material, and at one or two surface impregnation, coating or the spraying one layer of polymeric of polytetrafluoroethylporous porous membrane, dry thermocompression forming forms composite membrane.This battery isolating film, because of its good chemical stability, thermal stability and non-oxidizability, can improve useful life and the fail safe (the self-closing temperature 100-150 ℃ of fenestra) of battery.
The same preparation of US Patent No. 2010/0316903 A1 one composite isolated film, first at the substrate surface of a porous, coat and link agent and ceramic particle, wherein linking agent is a bridging property macromolecule, therefore slurry completes after coating, can make macromolecule link agent again and carry out cross-linking reaction with the adhesive force between enhancing and porous substrate.US Patent No. 2012/0015254 A1 adds strong adhesive force in different mode, by comprising link agent and dielectric constant, at the slurry of more than 5 ceramic particles, be coated on porous substrate, recycling electrochemical means is coated in skin by Polymer Solution, form the second coating layer and be coated agent structure, increase membrane stability.Though but use macromolecule secondary cross-linking technology or electrochemistry is coated with coated mode, all will make the complicated difficultyization of processing procedure.
In sum, in high power lithium battery application scenario, for avoiding barrier film torsional deformation under lithium battery high temperature, and then affect product fail safe, barrier film need increase by the lifting of high temperature and mechanical performance stability the fail safe of battery; Most prior aries is all used and is added the both sides formation protective layer that ceramic particle is coated script film, and this mode is the accuracy of wayward film thickness not only, and can connect hypodynamic problem, thereby affects its performance.
Summary of the invention
Main purpose of the present invention is to provide a kind of electrochemistry barrier film structure, this electrochemistry barrier film structure comprises a base phase polymer moiety, one fiber support part and inorganic particulate, fiber support part is distributed in this base phase polymer moiety in strip mode, so that mechanical strength to be provided, prop up the base phase polymer moiety of support integral, inorganic particulate is distributed in base phase polymer moiety equably with 0.1wt%～50wt%, base phase polymer moiety presents the periphery that continuous structure forms fiber support part, there is porousness, and the thickness range of whole electrochemistry barrier film structure is 10～60um.
Fiber support part is made by polyolefine fiber, and this fiber support is partly a cellular structure, and has hole, and base phase polymer moiety can be filled among hole, and closely combination.Inorganic particulate be metal oxide, metal carbides, metal nitride, Titanium acid compound, metal tripolyphosphate compound at least one of them, its particle size range is 0.01～30um, there is high burning-point, high cracking temperature, in order to prevent that excessive temperature rises when the electrochemical reaction, also provide a supporting simultaneously, prevent that electrochemistry barrier film structure from significantly shrinking.
Another object of the present invention is to provide a kind of manufacture method of electrochemistry barrier film structure, the method comprises high molecule size preparation process, application step and drying steps, high molecule size preparation process is to prepare a polymer-based phase material solution, this polymer-based phase material solution comprises solvent, polymer-based phase material and inorganic particulate, polymer-based phase material is dissolved in solvent, and inorganic particulate is with 0.1wt%～50wt%, be scattered in equably in this polymer-based phase material solution, this polymer-based phase material solution further comprises an adhesive.
The mode that application step is put, is coated with to soak, polymer-based phase material solution coat is filled to part and be formed at the periphery that a porous fiber supports part, make polymer-based phase material insert porous fiber simultaneously and support in hole partly, and form an electrochemistry barrier film structure.Drying steps is with standing, air-dry or mode of heating, and this polymer-based phase material solution is dry, thereby formation has the electrochemistry barrier film structure of base phase polymer moiety, fiber support part and inorganic particulate.
The feature of electrochemistry barrier film structure of the present invention and preparation method thereof is, in electrochemistry barrier film structure of the present invention, polymer-based phase material solution can be inserted in the hole of fiber support part, and see through the mechanical strength of fiber support part, so there is preferably connectivity, and see through the shrinkage phenomenon that inorganic particulate effectively reduces barrier film, and then the security performance while improving high temperature, and then, by electrochemistry barrier film structure applications in lithium battery, can effectively reduce the resistance value of black box, not only there is higher charge and discharge capacitance amount, also promoted the life-span of black box.
Accompanying drawing explanation
Fig. 1 be electrochemistry barrier film structure micro-structural on look schematic diagram.
Fig. 2 is the partial enlarged drawing of base phase polymer moiety in Fig. 1.
Fig. 3 is the flow chart of the manufacture method of electrochemistry barrier film structure of the present invention.
Fig. 4 A to Fig. 4 C is the comparison diagram that the battery of application experiment example 1 and the battery of existing business Celgard 2320 barrier films compare fast charging and discharging test and durability analysis.
Fig. 4 D is the electrochemical source of current density of battery of electrochemistry barrier film of application experiment example 1 and the graph of a relation of electric capacity.
Fig. 5 is the result figure that the lithium battery of the electrochemistry barrier film of application experiment example 2 carries out the charge-discharge test of 1C and 3C speed.
Fig. 6 A and Fig. 6 B are respectively the battery of application experiment example 4 and the battery of existing business Celgard 2320 barrier films carries out the charge-discharge test of 0.2C and 3C speed and the comparison diagrams of 55 ℃ of high temperature performance analyses.
Wherein, description of reference numerals is as follows:
1 electrochemistry barrier film structure
10 base phase polymer moieties
15 holes
20 fiber support parts
30 inorganic particulates
The manufacture method of S1 electrochemistry barrier film structure
S10 high molecule size preparation process
S20 application step
S30 drying steps
Embodiment
Below coordinate accompanying drawing and Reference numeral to do more detailed description to embodiments of the present invention, make to have the knack of those skilled in the art and can implement according to this after studying this specification carefully.
With reference to figure 1, in the micro-structural of electrochemistry barrier film structure of the present invention, look schematic diagram.As shown in Figure 1, electrochemistry barrier film structure 1 of the present invention, comprise a base phase polymer moiety 10, one fiber support part 20 and inorganic particulate 30, fiber support part 20 is strip, in strip mode, be distributed in this base phase polymer moiety 10, so that mechanical strength to be provided, prop up the base phase polymer moiety 10 of support integral, inorganic particulate 30 is distributed in base phase polymer moiety 10 equably with 0.1wt%～50wt%, base phase polymer moiety 10 presents the periphery that continuous structure forms fiber support part 20, there is porousness, and the thickness range of whole electrochemistry barrier film structure 1 is 10～60um.
Base phase polymer moiety 10 is with Kynoar (polyvinylidene fluoride), poly terephthalic acid vinyl acetate (polyethylene terephthalate), polyurethane (polyurethane), polyethylene glycol oxide (polyethylene oxide), PPOX (polypropylene oxide), polyacrylonitrile (polyacrylonitrile), polyacrylamide (polyacrylamide), polymethyl acrylate (polymethyl acrylate), polymethyl methacrylate (polymethyl methacrylate), polyvinyl acetate (polyvinylacetate), polyvinylpyrrolidone (polyvinylpyrroidone), poly-tetraethylene glycol diacrylate (polytetraethylene glycol diacrylate), and polyimides (polyimide) at least one of them is made, when contacting with electrolyte, can form colloidal state.
Fiber support part 20 by polyethylene fibre, polypropylene fibre, polybutene fiber, poly-penta rare fiber, poly terephthalic acid vinyl acetate fiber at least one of them is made, the diameter range of this fiber support part 20 is 0.5～30um, it is a cellular structure, and there is hole, the size of hole is about 0.1～20um, and base phase polymer moiety 10 can be filled among hole, and closely combination.
Inorganic particulate be metal oxide, metal carbides, metal nitride, Titanium acid compound, metal tripolyphosphate compound at least one of them, its particle size range is 0.01～30um, be preferably aluminium oxide, silicon dioxide, titanium dioxide, calcium titanate copper (CaCu3Ti4O12), lithium titanate, calcium carbonate, zirconia, calcium oxide, iron lithium phosphate etc., there is high burning-point, high cracking temperature, in order to prevent that excessive temperature rises when the electrochemical reaction, also provide a supporting simultaneously, prevent that electrochemistry barrier film structure 1 from significantly shrinking.
With reference to figure 2, the partial enlarged drawing of base phase polymer moiety in Fig. 1.As shown in Figure 2, this base phase polymer moiety 10, except inorganic particulate 30, also comprises equally distributed a plurality of hole 15, and the scope of hole 15 sizes is about 0.1 μ m～5um, and the porosity of phase polymer moiety 10 is 40 to 75%.
With reference to the 3rd figure, the flow chart of the manufacture method of electrochemistry barrier film structure of the present invention.As shown in Figure 3, the manufacture method S1 of electrochemistry barrier film structure of the present invention comprises high molecule size preparation process S10, application step S20 and drying steps S30, high molecule size preparation process S10 prepares a polymer-based phase material solution, this polymer-based phase material solution comprises polymer-based phase material, solvent and inorganic particulate, polymer-based phase material is dissolved in this solvent, inorganic particulate accounts for 0.1wt%～50wt%, be scattered in equably in this polymer-based phase material solution, this polymer-based phase material solution further comprises an adhesive, this polymer-based phase material comprises Kynoar, poly terephthalic acid vinyl acetate, polyurethane, polyethylene glycol oxide, PPOX, polyacrylonitrile, polyacrylamide, polymethyl acrylate, polymethyl methacrylate, polyvinyl acetate, polyvinylpyrrolidone, poly-tetraethylene glycol diacrylate, and polyimides at least one of them.This solvent be acetone, butanone, N-methyl pyrrolidone, oxolane, dimethyl formamide, dimethylacetylamide, tetramethylurea at least one of them.
Adhesive be cellulose acetate (cellulose acetate), acetylbutyrylcellulose (cellulose acetate butyrate), cellulose acetate propionate (cellulose acetate propionate), ethyl cellulose (ethyl cellulose), cyanethyl cellulose (cyanoethyl cellulose), cyanoethyl polyvinyl alcohol (cyanoehyl polyvinyl alcohol) and carboxymethyl cellulose (carboxymethyl cellulose) at least one of them, account for 0.1～20wt% of described a plurality of inorganic particulates.
The mode that application step S20 puts, is coated with to soak, polymer-based phase material solution coat is filled to part and be formed at the periphery that a porous fiber supports part, make polymer-based phase material insert porous fiber simultaneously and support in hole partly, and form an electrochemistry barrier film structure.
Drying steps S30 is with standing, air-dry or mode of heating, make solvent, from polymer-based phase material solution evaporation, and this polymer-based phase material solution is dry, thereby form the electrochemistry barrier film structure 1 with a base phase polymer moiety 10, a fiber support part 20 and inorganic particulate 30 as shown in Figure 1.
Below will illustrate electrochemistry barrier film structure of the present invention and preparation method thereof with four experimental example, these experimental example, only as example, are not limited to.
<experimental example 1>
Experimental example 1, by Kynoar, is dissolved in acetone, and adding percentage by weight is the silicon dioxide SiO2 particle (particle diameter is 5 microns) of 0.7wt%, stirs loose approximately 16 hours or more for a long time to form slurry, as polymer-based phase material solution.Subsequently polymer-based phase material solution is coated on polypropylene fibre base material with dipping formula coating (dip coating).
The electrochemistry barrier film of gained after experimental example 1 is dry, and using iron lithium phosphate as positive electrode, lithium paper tinsel is as negative material, electrolyte is hexafluoro phosphorus lithium, and be assembled into button cell with prior art, and compare fast charging and discharging test and durability analysis with existing Celgard 2320 barrier films, its result is as shown in Fig. 4 A to Fig. 4 C, result shows that this electrochemistry barrier film is all close with the usefulness of business barrier film under different discharge rates, and resistance value also approaches, more effectively improve assembly life-span, fully show that the present invention can be used as the barrier film of electrochemical appliance.
After experimental example 1 is dry, the electrochemistry barrier film of gained, is assembled into button type super capacitor by prior art, and with active carbon, as positive and negative pole material, electrolyte is hexafluoro phosphorus lithium, and carries out the charge-discharge test of different current densities.As shown in Figure 4 D, this result is same shows that electrochemistry barrier film of the present invention can be applicable to supercapacitor device for the electrochemical source of current density of the battery of the electrochemistry barrier film of application experiment example 1 and the relation of electric capacity.
In addition gained laminated film is carried out to the test of high temperature heat-shrinkable, and compare with Celgard 2320 barrier films.Barrier film two ends are fixed in glass support plate, put into 130 ℃ of baking oven heating after 2 hours, commercial Celgard 2320 barrier film contraction distortions surpass 20%, and the electrochemistry barrier film shrinkage of experimental example 1 is less than 1%, deducibility is owing to using macromolecule as continuous phase filling and adding the shrinkage phenomenon that inorganic particulate effectively reduces barrier film, the security performance while also having promoted high temperature.
<experimental example 2>
Experimental example 2 explanation is usingd flat high-density fiber material as framework supporting structure, makes the polymer-based phase material solution of colloidal state and the hole inside that inorganic particulate infiltrates porous fibrous material completely, to form electrochemical appliance barrier film.Its execution mode is identical with embodiment 1 step, adopts Kynoar/acetone soln, adds 1.5% silicon dioxide SiO2 particle, stirs loose approximately 8 hours or more for a long time to form slurry, as polymer-based phase material solution.To with dipping formula coating (dip coating), be coated on flat polypropylene fibre base material as polymer-based phase material solution subsequently.
The electrochemistry barrier film that experimental example 2 is obtained is as lithium battery isolation membrane, using iron lithium phosphate as positive electrode, and lithium paper tinsel is as negative material, and electrolyte is hexafluoro phosphorus lithium, and by prior art, being assembled into the charge-discharge test that carries out 1C and 3C speed after button cell, its result is as shown in Figure 5.
<experimental example 3>
Experimental example 3 is aforementioned Kynoar Polymer Solutions, adds the calcium titanate copper (CaCu3Ti4O12, CCTO) of 0.7wt%, fully stirs loose to form slurry, as polymer-based phase material solution.Calcium titanate copper product is a perovskite cubic crystal structure, can in certain temperature range, keep a huge dielectric constant.Add ethyl cellulose (ethyl cellulose) as adhesive simultaneously, continue to stir loose 4 hours or to form slurry, with dipping formula coating (dip coating), be coated on polypropylene fibre base material more for a long time.With normal temperature, by the solution bone dry of coating, can obtain the film that a thickness is 30-40um, be a fiber material as framework supporting structure and include Kynoar/calcium titanate copper and be filled in the middle of framework supporting structure as a continuous phase.
<experimental example 4>
Experimental example 4 explanations are usingd high-density porous polyethylene film as framework supporting structure, and get aforementioned Kynoar Polymer Solution, the silicon dioxide SiO2 particle that adds 0.7wt%, with dipping formula coating (dip coating), be coated on porous polyethylene film base material, to form electrochemical appliance barrier film.
Get the electrochemistry barrier film of experimental example 4 as lithium battery isolation membrane, using iron lithium phosphate as positive electrode, lithium paper tinsel is as negative material, electrolyte is hexafluoro phosphorus lithium, and by prior art, be assembled into charge-discharge test and the 55 ℃ of high temperature performance analyses of carrying out 0.2C and 3C speed after button cell, and compare with Celgard2320,2400 business barrier films, result as shown in Fig. 6 A and Fig. 6 B, shows that barrier film of the present invention has equally higher stability and performance performance under high temperature running respectively.
The feature of electrochemistry barrier film structure of the present invention and preparation method thereof is, in electrochemistry barrier film structure of the present invention, polymer-based phase material solution can be inserted in the hole of fiber support part, and see through the mechanical strength of fiber support part, so there is preferably connectivity, and see through the shrinkage phenomenon that inorganic particulate effectively reduces barrier film, and then the security performance while improving high temperature, and then, by electrochemistry barrier film structure applications in lithium battery, can effectively reduce the resistance value of black box, not only there is higher charge and discharge capacitance amount, also promoted the life-span of black box.
Above said content is only in order to explain preferred embodiment of the present invention; not attempt is done any pro forma restriction to the present invention according to this; therefore, all have under identical invention spirit, do relevant any modification of the present invention or change, all must be included in the category that the invention is intended to protection.
Claims (13)
1. an electrochemistry barrier film structure, is characterized in that, comprises:
One base phase polymer moiety is a continuous phase structure;
One fiber support part, is distributed in this base phase polymer moiety, so that mechanical strength to be provided in strip mode; And
A plurality of inorganic particulates, are distributed in this base phase polymer moiety equably, account for whole 0.1wt%～50wt%,
Wherein this fiber support is partly a cellular structure, and has a plurality of holes, and this base phase polymer moiety is filled among described a plurality of hole.
2. structure as claimed in claim 1, it is characterized in that, this base phase polymer moiety is with Kynoar, poly terephthalic acid vinyl acetate, polyurethane, polyethylene glycol oxide, polyacrylonitrile, polyacrylamide, polymethyl acrylate, polymethyl methacrylate, polyvinyl acetate, polyvinylpyrrolidone, poly-tetraethylene glycol diacrylate, and polyimides at least one of them is made.
3. structure as claimed in claim 1, is characterized in that, this base phase polymer moiety, when contacting with an electrolyte, can form colloidal state.
4. structure as claimed in claim 1, is characterized in that, the thickness range of this electrochemistry barrier film structure is 10～60um.
5. structure as claimed in claim 1, it is characterized in that, this fiber support part with polyethylene fibre, polypropylene fibre, polybutene fiber, poly-penta rare fiber, poly terephthalic acid vinyl acetate fiber at least one of them is made, and the diameter range of this fiber support part is 0.5～30um, and the size of described a plurality of holes of this fiber support part is about 0.1～20um.
6. structure as claimed in claim 1, it is characterized in that, described a plurality of inorganic particulate be metal oxide, metal carbides, metal nitride, Titanium acid compound, metal tripolyphosphate compound at least one of them, and the particle size range of described a plurality of inorganic particulates is 0.01～30um.
7. structure as claimed in claim 1, is characterized in that, this base phase polymer moiety also comprises equally distributed a plurality of hole, and the scope of pore size is about 0.1 μ m～5um, and the porosity of this base phase polymer moiety is 40 to 75%.
8. a manufacture method for electrochemistry barrier film structure, is characterized in that, comprises:
One high molecule size preparation process, to prepare a polymer-based phase material solution, this polymer-based phase material solution comprises a polymer-based phase material, a solvent and a plurality of inorganic particulate, this macromolecule ground term material is dissolved in this solvent, described a plurality of inorganic particulate accounts for 0.1wt%～50wt%, is scattered in equably in this polymer-based phase material solution;
One application step, fills part by polymer-based phase material solution coat and is formed at the periphery that a porous fiber supports part, makes this polymer-based phase material insert porous fiber simultaneously and supports in hole partly, and form an electrochemistry barrier film structure; And
One drying steps is to make this electrochemistry barrier film structure dry with standing, air-dry or mode of heating.
9. method as claimed in claim 8, it is characterized in that, this polymer-based phase material is Kynoar, poly terephthalic acid vinyl acetate, polyurethane, polyethylene glycol oxide, polypropylene, polyacrylonitrile, polyacrylamide, polymethyl acrylate, polymethyl methacrylate, polyvinyl acetate, polyvinylpyrrolidone, poly-tetraethylene glycol diacrylate, and polyimides at least one of them.
10. method as claimed in claim 8, it is characterized in that, this porous fiber support part with polyethylene fibre, polypropylene fibre, polybutene fiber, poly-penta rare fiber, poly terephthalic acid vinyl acetate fiber at least one of them is made, and the diameter range of this fiber support part is 0.5～30um, and the size of a plurality of holes in this fiber support part is about 0.1～20um.
11. methods as claimed in claim 8, it is characterized in that, described a plurality of inorganic particulate be metal oxide, metal carbides, metal nitride, Titanium acid compound, metal tripolyphosphate compound at least one of them, and the particle size range of described a plurality of inorganic particulates is 0.01～30um.
12. methods as claimed in claim 8, it is characterized in that, this polymer-based phase material solution further comprises a solvent, this solvent be acetone, butanone, N-methyl pyrrolidone, oxolane, dimethyl formamide, dimethylacetylamide, tetramethylurea at least one of them.
13. methods as claimed in claim 8, it is characterized in that, this polymer-based phase material solution further comprises an adhesive, this adhesive be cellulose acetate, acetylbutyrylcellulose, cellulose acetate propionate, ethyl cellulose, cyanethyl cellulose, cyanoethyl polyvinyl alcohol and carboxymethyl cellulose at least one of them, account for 0.1～20wt% of described a plurality of inorganic particulates.
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