CN104064707A - Inorganic/organic composite membrane, preparation method of inorganic/organic composite membrane and lithium ion secondary battery containing membrane - Google Patents
Inorganic/organic composite membrane, preparation method of inorganic/organic composite membrane and lithium ion secondary battery containing membrane Download PDFInfo
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- CN104064707A CN104064707A CN201410251930.4A CN201410251930A CN104064707A CN 104064707 A CN104064707 A CN 104064707A CN 201410251930 A CN201410251930 A CN 201410251930A CN 104064707 A CN104064707 A CN 104064707A
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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
- 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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- 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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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses an inorganic/organic composite membrane which comprises a porous substrate and a porous insulating layer, wherein the porous insulating layer is attached to the porous substrate, and at least one surface of the porous substrate is coated with the porous insulating layer; the porous insulating layer comprises inorganic particles and a binding agent, wherein the inorganic particles are composed of n particles with different average particle diameters, n is large than or equal to 2, and the average particle diameters from the first type of inorganic particles to the nth type of inorganic particles are changed in a gradient manner. The invention further discloses a preparation method of the inorganic/organic composite membrane. The preparation method comprises the following steps: firstly, dissolving the binding agent into a solvent to form a polymer solution, then adding the inorganic particles, mixing to prepare the porous insulating layer, and then coating at least one surface of the porous substrate with the porous insulating layer. The invention further discloses a lithium ion secondary battery containing the membrane. The inorganic/organic composite membrane disclosed by the invention has the advantages of high stacking density, low thermal shrinkage rate, high puncture strength, simple preparation process and proper cost, and the lithium ion secondary battery containing the membrane has the advantages of good conservation rate of circulating volume and excellent safety performance and electrochemical performance.
Description
Technical field
The present invention relates to technical field of lithium ion secondary, especially relate to a kind of inorganic/organic composite barrier film, its preparation method and containing the lithium rechargeable battery of this barrier film.
Background technology
The features such as lithium rechargeable battery is because energy density is large, and operating voltage is high, and quality is light, at consumption electronic product, as mobile phone, notebook computer, panel computer, bluetooth earphone, the fields such as MP3 and digital camera are widely used.Increasingly serious along with environmental pollution and problem of energy crisis, lithium rechargeable battery is also more and more universal in the use in the fields such as electrokinetic cell and stationary electric power plant, but the safety issue of lithium rechargeable battery is the focus that people pay close attention to always.
The barrier film of lithium rechargeable battery, as the isolation of both positive and negative polarity, have higher ion permeability and good mechanical strength, is clipped between both positive and negative polarity, and Main Function is to prevent that both positive and negative polarity from directly contacting and being short-circuited, but can make electrolyte see through.Barrier film is mainly by polyethylene at present, the porous media that the TPO such as polypropylene form, polyalkene diaphragm has 200 ℃ of following fusing points, when lithium rechargeable battery is because inside or external factor cause being short-circuited heating and temperature while raising, very easily there is thermal contraction and cause the short circuit that both positive and negative polarity is larger to produce in barrier film, causes the thermal runaway of battery to cause accident on fire.
In order to address the above problem, industry applies at membrane surface the porous dielectric layer that one deck contains inorganic particulate, because inorganic particulate has good thermal stability, this porous dielectric layer can stop both positive and negative polarity directly to contact as supporting layer when barrier film thermal contraction, thereby avoids occurring problem on fire.
The compactness of the porous dielectric layer that membrane surface applies is larger on whole thermal contraction impact, the not high enough compactness extent of coating that causes of porous dielectric layer bulk density that the inorganic particulate of single particle size forms is also limited, the porous dielectric layer that the inorganic particulate of two or more variable grain size forms size particles accumulation composition can obtain higher bulk density, coating compactness extent is higher, and the thermal contraction meeting of barrier film is less.The patent CN101301586B that wins Chuan Degusai Co., Ltd discloses ceramic membrane and their preparation and the application that polymer carrier materials that a kind of plasma processes is improved viscosity, the patent CN100438140C of Samsung SDI Co., Ltd discloses a kind of for having the barrier film and preparation method thereof of the winding-type lithium secondary battery of gel-type polymer electrolyte, the patent CN102244223A of Dongguan New Energy Technology Co discloses a kind of electrochemical appliance and inorganic/organic composite porous membrane thereof, but they are all the inorganic particulates that uses single size, bulk density is limited, barrier film poor heat resistance.Although the patent CN102412377A of Biyadi Co Ltd has been used the inorganic particulate of two kinds of sizes, a kind of inorganic particulate average grain diameter is 0.4 ~ 1.5 micron, the second inorganic particulate average grain diameter is 1.6 ~ 5.0 microns, but the coating for 1 ~ 10 micron, the granular size of these two kinds of inorganic particulates is a bit bigger than normal, the bulk density of porous dielectric layer is fine and close not, causes barrier film thermal contraction to improve limited; On the other hand, the second inorganic particulate particle in this patent is larger, after coating, in barrier film performance, can form larger roughness, laminating defective tightness after assembling with pole piece in battery, having an obvious interface exists, it is large that lithium ion transport resistance becomes, and the chemical property of battery can be affected.
Summary of the invention
The first aspect of task of the present invention is by applying the inorganic particle of at least two or more different average grain diameters that change in gradient and the porous dielectric layer that binding agent forms at least one surface of perforated substrate, the surface roughness that a kind of compactness is good, less is provided, and the high and organic/inorganic composite diaphragm with ultralow heat-shrinkable of puncture intensity is with the deficiency of the barrier film poor heat resistance that solves barrier film bulk density and cause not.
The second aspect of task of the present invention is to provide the preparation method of organic/inorganic composite diaphragm.
The third aspect of task of the present invention is to provide the lithium rechargeable battery containing this barrier film, and described barrier film has as the characteristic described in the first aspect of invention task.
The present invention is achieved through the following technical solutions goal of the invention:
A kind of organic/inorganic composite diaphragm, comprise perforated substrate and be attached to the porous dielectric layer on perforated substrate, porous dielectric layer is coated at least one surface of perforated substrate, porous dielectric layer comprises inorganic particle and binding agent, inorganic particle is comprised of the different sized particles of n kind, n >=2, the 1st kind of inorganic particle forms graded between the average grain diameter of n kind inorganic particle.Thus, the average grain diameter of this graded forms the dense accumulation between inorganic particle, thereby reach thermal stability and puncture intensity that high-compactness degree improves barrier film, at battery because inside or external factor cause being short-circuited temperature while raising, keep barrier film primary morphology not shrink, prevent the further generation of short circuit, stop the thermal runaway of battery to cause accident on fire; On the other hand, the selection of the granular size of organic/inorganic composite diaphragm of the present invention by inorganic particulate and tightly packed, forms less surface roughness, tight with pole piece laminating in battery assembling, effectively reduced the transmission resistance of lithium ion, the chemical property of the battery of raising.
The average grain diameter excursion of described inorganic particle is 0.2 ~ 1.4 μ m, and particle size distribution is 0.05 ~ 5.0 μ m.
Further, described the 1st kind of inorganic particle average grain diameter is 0.2 ~ 0.35 μ m, and the average grain diameter of n kind inorganic particle is 0.4 ~ 1.4 μ m, and the content of every kind of inorganic particle changes from 10 ~ 90%.
As preferably, described different the 1st kind of inorganic particle and the 2nd kind of inorganic particles of particle diameter that is 10:90 ~ 90:10 by mass ratio without particle forms, the average grain diameter of the 1st kind of inorganic particle is 0.2 ~ 0.35 μ m, particle size distribution is 0.05 ~ 2.0 μ m, the average grain diameter of the 2nd kind of inorganic particle is 0.4 ~ 1.4 μ m, and particle size distribution is 0.1 ~ 5.0 μ m.
Described porous insulation layer thickness is 1 ~ 10 μ m, is preferably 2 ~ 6 μ m.
Further, the mass ratio of described inorganic particle and binding agent is 50:50 ~ 99.9:0.1.
As preferably, the mass ratio of described inorganic particle and binding agent is 70:30 ~ 99:1.
Inorganic particle of the present invention has no particular limits, only otherwise oxidation can occur in lithium rechargeable battery or reduce to there is good insulating properties simultaneously, further, described inorganic particle is at least one in calcium oxide, zinc oxide, magnesium oxide, titanium dioxide, silicon dioxide, zirconium dioxide, tin ash, ceria, alundum (Al2O3), calcium carbonate or barium titanate.
Further, described binding agent is at least one in styrene-butadiene polymer, Kynoar, Kynoar-hexafluoropropylene, polyacrylic acid, polymethylacrylic acid, polyacrylate, polymethyl methacrylate, polyacrylonitrile, sodium carboxymethylcellulose, butadiene-acrylonitrile polymer, polyvinylpyrrolidone or polyacrylic acid-styrene.
A preparation method for organic/inorganic composite diaphragm as above, comprises the following steps:
(1) preparation of porous dielectric layer
First binding agent is dissolved in and in solvent, forms polymer solution and stir, then add the inorganic particle dispersed with stirring of variable grain size even, prepare slurry, solid content is 20 ~ 70%;
(2) at perforated substrate surface-coated porous dielectric layer
At least one mode of using dip-coating, die head painting, roller coat, comma to shift in painting or intaglio plate painting prepares the slurry uniform fold preparing on a surface of polyethylene or polypropylene perforated substrate, and coating layer thickness is for being 1 ~ 10 μ m.
Further, described solvent is at least one in oxolane, methylethylketone, dimethyl formamide, dimethylacetylamide, tetramethylurea, tetramethyl phosphate, acetone, carrene, chloroform, dimethylformamide, 1-METHYLPYRROLIDONE, cyclohexane, water or alcohol.Thus, these solvents can dissolved adhesive and dispersed inorganic particle be easy to remove applying in dry.
A lithium rechargeable battery, it comprises positive plate, negative plate, electrolyte and the barrier film between positive plate and negative plate, described barrier film is above-mentioned organic/inorganic composite diaphragm.
Organic/inorganic composite diaphragm provided by the invention, on the surface of perforated substrate, apply porous dielectric layer, thereby the inorganic particle containing in porous dielectric layer is formed and is made to pile up and can reach thermal stability and the puncture intensity that high-compactness improves barrier film between inorganic particle by least two or more different average grain diameters that change in gradient, at battery because inside or external factor cause being short-circuited temperature while raising, keep barrier film primary morphology not shrink, prevent the further generation of short circuit, stop the thermal runaway of battery to cause fire incident, improved the security and stability of lithium rechargeable battery, the surface roughness of organic/inorganic composite diaphragm is less in addition, form and fit tightly with pole piece, effectively reduce the resistance of lithium ion battery transmission, improved the chemical property of battery.
Accompanying drawing explanation
Fig. 1 is the structural representation of organic/inorganic composite diaphragm embodiment 1 of the present invention;
Wherein, g1-perforated substrate, g2-porous dielectric layer, the 1st kind of inorganic particle of g21-, the 2nd kind of inorganic particle of g22-.
Embodiment
Below in conjunction with embodiment, the present invention is further detailed explanation.
comparative example 1
The preparation of positive plate: by cobalt acid lithium, conductive carbon, binding agent Kynoar in mass ratio 96:2.2:1.8 in 1-METHYLPYRROLIDONE solvent, mix and make anode sizing agent, then be coated on aluminium foil and at 110 ℃ after drying cold pressing, itemize, cutting edge, tab welding, make positive plate.
The preparation of negative plate: by graphite, conductive carbon, thickener sodium carboxymethylcellulose, binding agent butadiene-styrene rubber in mass ratio 95:1.5:1.5:2.0 in deionized water, mix and make cathode size, then be coated on Copper Foil and at 85 ℃ after drying cold pressing, itemize, cutting edge, tab welding, make negative plate.
The preparation of barrier film: get thickness and be the polyethylene micropore film of 9 μ m as perforated substrate g1.
The preparation of lithium rechargeable battery: above-mentioned positive plate, perforated substrate g1, negative plate are wound into battery core, then this battery core is placed in to aluminium plastic packaging bag, inject electrolyte (ethylene carbonate: dimethyl carbonate: methyl ethyl carbonate=1:2:1, comprise 1M lithium hexafluoro phosphate), through encapsulating, change into, the operation such as capacity, make battery.
comparative example 2
The preparation method of positive plate, negative plate and lithium rechargeable battery is all identical with comparative example 1.
The preparation of barrier film:
(1) preparation of porous dielectric layer g2
In deionized water, first add the polyacrylate dispersion (content in the aqueous solution is 40%) of 15wt% to stir 1h, then add the Al of 85wt%
2o
3particle (average grain diameter is 0.3 μ m, and particle size distribution is 0.05 ~ 2.5 μ m) stirs after 2h, in grinding in ball grinder 1h, prepares slurry, and solid content is 30%.
(2) at perforated substrate g1 surface-coated porous dielectric layer g2
Get thickness and be the polyethylene micropore film of 9 μ m as perforated substrate g1, then use intaglio plate coating that the above-mentioned slurry of system is covered on surface of perforated substrate g1 uniformly, coating layer thickness is for being 4 μ m, and then pole piece carries out itemize, cutting edge.
comparative example 3
The preparation method of positive plate, negative plate and lithium rechargeable battery is all identical with comparative example 1.
The preparation of barrier film:
(1) preparation of porous dielectric layer g2
First in deionized water, add the polyacrylate dispersion (content in the aqueous solution is 40%) of 15wt% to stir 1h, then add the Al of 85wt%
2o
3particle (average grain diameter is 2.0 μ m, and particle size distribution is 0.3 ~ 5.0 μ m) stirs after 2h, in grinding in ball grinder 1h, prepares slurry, and solid content is 30%.
(2) at perforated substrate g1 surface-coated porous dielectric layer g2
Get thickness and be the polyethylene micropore film of 9 μ m as perforated substrate g1, then use intaglio plate coating that the above-mentioned slurry of system is covered on a surface of perforated substrate g1 uniformly, coating layer thickness is 4 μ m, and then pole piece carries out itemize, cutting edge.
embodiment 1
The preparation method of positive plate, negative plate and lithium rechargeable battery is all identical with comparative example 1.
As shown in Figure 1; on the perforated substrate g1 of organic/inorganic composite diaphragm, applied one deck porous insulation g2 layer; in porous dielectric layer g2, inorganic particle comprises the 1st kind of inorganic particle g21 and the 2nd kind of inorganic particle g22 of two kinds of different-grain diameters; binding agent sticks to the surface of inorganic particle after mixing with inorganic particle, fail in the drawings to show.
The preparation of barrier film:
(1) porous dielectric layer g2 preparation
In deionized water, first add the polyacrylate dispersion (content in the aqueous solution is 40%) of 15wt% to stir 1h, then add respectively 40% the 1st kind of Al
2o
3the 2nd kind of Al of particle (average grain diameter is 0.3 μ m, and particle size distribution is 0.05 ~ 2.0 μ m) and 45wt%
2o
3particle (average grain diameter is 1.0 μ m, and particle size distribution is 0.1 ~ 3.0 μ m) stirs after 2h, in grinding in ball grinder 1h, prepares slurry, and solid content is 40%.
(2) at perforated substrate g1 surface-coated porous dielectric layer g2
Get thickness and be the polyethylene micropore film of 9 μ m as perforated substrate g1, then use intaglio plate coating that the above-mentioned slurry of system is covered on a surface of perforated substrate g1 uniformly, coating layer thickness is for being 4 μ m, and then pole piece carries out itemize, cutting edge.
embodiment 2
The preparation method of positive plate, negative plate and lithium rechargeable battery is all identical with comparative example 1.
The preparation of barrier film:
(1) porous dielectric layer g2 preparation
In deionized water, first add the polyacrylate dispersion (content in the aqueous solution is 40%) of 15wt% to stir 1h, then add respectively 25% the 1st kind of Al
2o
3inorganic particle (its average grain diameter is 0.3 μ m, and particle size distribution is 0.08 ~ 2 μ m), 30% the 2nd kind of Al
2o
3the 3rd kind of Al of inorganic particle (average grain diameter is 0.6 μ m, and particle size distribution is 0.1 ~ 3.0 μ m) and 30wt%
2o
3particle (average grain diameter is 1.0 μ m, and particle size distribution is 0.1 ~ 4.5 μ m) stirs after 2h, in grinding in ball grinder 1h, prepares slurry, and solid content is 40%.
(2) at perforated substrate g1 surface-coated porous dielectric layer g2
Get thickness and be the polyethylene micropore film of 9 μ m as perforated substrate g1, then use intaglio plate coating that the above-mentioned slurry of system is covered on a surface of perforated substrate g1 uniformly, coating layer thickness is for being 4 μ m, and then pole piece carries out itemize, cutting edge.
embodiment 3
(1) porous dielectric layer g2 preparation
In 1-METHYLPYRROLIDONE, first add the Kynoar of 3wt% to stir 1h at 45 ℃, then add respectively 40% the 1st kind of TiO
2particle (its average grain diameter is 0.25 μ m, and particle size distribution is 0.08 ~ 1.8 μ m), 30% the 2nd kind of TiO
2the 3rd kind of TiO of particle (average grain diameter is 0.7 μ m, and particle size distribution is 0.1 ~ 3.5 μ m) and 27wt%
2particle (average grain diameter is 1.2 μ m, and particle size distribution is 0.1 ~ 5 μ m) stirs after 2h, in grinding in ball grinder 1h, prepares slurry, and solid content is 65%.
(2) at perforated substrate g1 surface-coated porous dielectric layer g2
Get thickness and be the polypropylene microporous film of 12 μ m as perforated substrate g1, then use intaglio plate coating that the above-mentioned slurry of system is covered on a surface of perforated substrate g1 uniformly, coating layer thickness is 2 μ m, and then pole piece carries out itemize, cutting edge.
embodiment 4
The preparation method of positive plate, negative plate and lithium rechargeable battery is all identical with comparative example 1.
The preparation of barrier film:
(1) porous dielectric layer g2 preparation
In deionized water, first add the styrene-butadiene polymer of 30wt% to stir 1h, then add respectively 30% the 1st kind of Al
2o
3particle (its average grain diameter is 0.3 μ m, and particle size distribution is 0.08 ~ 2 μ m), 20% the 2nd kind of Al
2o
3the 3rd kind of Al of particle (average grain diameter is 0.6 μ m, and particle size distribution is 0.1 ~ 3.0 μ m) and 20wt%
2o
3particle (average grain diameter is 1.0 μ m, and particle size distribution is 0.1 ~ 4.5 μ m) stirs after 2h, in grinding in ball grinder 1h, prepares slurry, and solid content is 25%.
(2) at perforated substrate g1 surface-coated porous dielectric layer g2
Get thickness and be the polypropylene microporous film of 12 μ m as perforated substrate g1, then use dip-coating that the above-mentioned slurry of system is covered on two surfaces of perforated substrate g1 uniformly, coating layer thickness is 10 μ m, and then pole piece carries out itemize, cutting edge.
For the barrier film in above-mentioned comparative example 1 ~ 3 and embodiment 1 ~ 4, carry out thermal contraction test, puncture strength test, roughness test, the test of battery high rate performance, cycle performance test and drift bolt test experiments.
(1) thermal contraction test: the square sample that barrier film is die-cut into 100 * 100mm, indicate MD(longitudinal) and TD(horizontal) direction, measure initial MD and the length of TD, put it in the baking oven of 130 ℃ and toast 2h, the length of the rear MD of test baking and TD direction after taking out, calculate percent thermal shrinkage=[(size after the size-baking before baking)/baking size before examination] * 100%, acquired results is in Table 1:
Table 1 barrier film percent thermal shrinkage
As known from Table 1, the thermal contraction of the comparative example 2,3 after membrane surface coating one deck porous dielectric layer g2 and the barrier film of embodiment 1 ~ 4 obviously improves, use the comparative example 2 of single inorganic particle to compare with comparative example 3, owing to comparing in 2, use inorganic particle particle diameter less, the bulk density of barrier film is higher, percent thermal shrinkage is lower, and use the porous dielectric layer g2 percent thermal shrinkage of the embodiment 1 ~ 4 of two or more variable grain size to reduce at double, the more thermal contractions of particle of different gradients improve more obvious.
(2) puncture strength test
According to GB/T 23318-2009, to the strength test of puncturing of the barrier film in comparative example and embodiment, the syringe needle of test is the push rod category-B type in GB/T 23318-2009.Test result is as follows:
Table 2 barrier film puncture intensity
As known from Table 2, the puncture intensity of the comparative example 2,3 after membrane surface coating one deck porous dielectric layer g2 and the barrier film of embodiment 1 ~ 4 is obviously improved, use the puncture intensity of porous dielectric layer g2 of the embodiment 1 ~ 4 of two or more variable grain size to improve more obvious, and different gradient particles are more, puncture improved strength is more obvious.
(3) surface roughness test
Use surface roughometer to test the barrier film in comparative example and embodiment, acquired results is as listed in table 3:
Table 3 membrane surface roughness
As known from Table 3, use the surface roughness of embodiment 1 ~ 4 of two kinds and above inorganic particle than using the comparative example 2,3 of single particle to improve obviously, and the inorganic particulate of different gradients is more, surface roughness is improved more obvious.
(4) battery multiplying power test
Lithium ion battery is first adopted at 25 ℃ the multiplying power of 0.5C charge, 0.2C multiplying power discharging, records discharge capacity; Then carry out the charging of 0.5C multiplying power, 0.5C multiplying power discharging, records discharge capacity; Then carry out the charging of 0.5C multiplying power, 1.0C multiplying power discharging, records discharge capacity; Then carry out the charging of 0.5C multiplying power, 1.5C multiplying power discharging, records discharge capacity again; Finally carry out the charging of 0.5C multiplying power, 2.0C multiplying power discharging, records discharge capacity.Capability retention under variant discharge-rate=(discharge capacity under the discharge capacity/0.2C multiplying power under each multiplying power) * 100%.Acquired results is in Table 4
Capability retention under table 4 comparative example discharge-rates different from embodiment
As known from Table 4, the high rate performance that uses the embodiment 1 ~ 4 of at least two kinds of gradient inorganic particulates to compare comparative example 1,2,3 obviously promotes, the gradient inorganic particulate using is more, multiplying power promotes more obvious, this is because embodiment 1 ~ 4 has less surface roughness, better with pole piece laminating degree, reduced the transmission resistance of lithium ion, high rate performance promotes.
(5) cycle performance test
Cycle performance test: lithium ion battery is adopted at 25 ℃ to the multiplying power charging of 0.5C, the multiplying power discharging of 0.5C, carry out successively 500 circulations, battery capacity under each loop test 0.5C multiplying power, and with circulation before capacity at 25 ℃, battery compare, capability retention after computation cycles, capability retention=(capacity before the capacity/circulation after circulation under 0.5C multiplying power under battery 25 degree) * 100%.
Table 5 comparative example and embodiment circulation volume conservation rate
As known from Table 5, after membrane surface applies one deck porous dielectric layer g2, the capability retention of battery can not be affected.
(6) drift bolt test: first battery is completely filled, then establishing criteria UL1642 tests, and nail diameter is 2.5mm, and drift bolt speed is 100mm/s, respectively the battery before circulation and the battery after 500 circulations are carried out to drift bolt safety test, test result is in Table 6:
The drift bolt test result of battery before and after table 6 circulation
As known from Table 6, only have the battery of the comparative example 1 of uncoated porous dielectric layer g2 to pass through to count minimum, compare with comparative example 1, at the comparative example 2,3 of perforated substrate g1 surface-coated one deck porous dielectric layer g2 and the security performance of embodiment 1 ~ 4, obviously improve, and only contain the comparative example 2 of single size inorganic particle and the barrier film lithium secondary battery of comparative example 3 security performance after 500 circulations, decline, the battery of embodiments of the invention 1 ~ 4 battery before circulation and after 500 circulations has all kept 100% drift bolt percent of pass, has excellent security performance.
Binding agent of the present invention, solvent and inorganic particle are except being used the material of mentioning in above-mentioned comparative example and embodiment, binding agent can also be used Kynoar-hexafluoropropylene, polyacrylic acid, methyl methacrylate, polyacrylonitrile, sodium carboxymethylcellulose, butadiene-acrylonitrile polymer, polyvinylpyrrolidone or polyacrylic acid-styrene, can be also the mixture of any several materials wherein; Solvent can also be used oxolane, methylethylketone, dimethyl formamide, dimethylacetylamide, tetramethylurea, tetramethyl phosphate, acetone, carrene, chloroform, dimethylformamide, cyclohexane or alcohol, can be also the mixture of any several materials wherein; Inorganic particle can be calcium oxide, zinc oxide, magnesium oxide, silicon dioxide, zirconium dioxide, tin ash, ceria, calcium carbonate or barium titanate, can be also the mixture of any several materials wherein.
Above-described is only some embodiments of the present invention, for the person of ordinary skill of the art, without departing from the concept of the premise of the invention, can also make some distortion and improvement, and these all belong to protection scope of the present invention.
Claims (10)
1. an organic/inorganic composite diaphragm, it is characterized in that: comprise perforated substrate and be attached to the porous dielectric layer on perforated substrate, porous dielectric layer is coated at least one surface of perforated substrate, porous dielectric layer comprises inorganic particle and binding agent, inorganic particle is comprised of the different average grain diameter particles of n kind, n >=2, the 1st kind of inorganic particle forms graded between the average grain diameter of n kind inorganic particle.
2. organic/inorganic composite diaphragm according to claim 1, is characterized in that: the average grain diameter excursion of described inorganic particle is 0.2 ~ 1.4 μ m, and particle size distribution is 0.05 ~ 5.0 μ m.
3. organic/inorganic composite diaphragm according to claim 1, it is characterized in that: described the 1st kind of inorganic particle average grain diameter is 0.2 ~ 0.35 μ m, particle size distribution is 0.05 ~ 2.0 μ m, the average grain diameter of n kind inorganic particle is 0.4 ~ 1.4 μ m, particle size distribution is 0.1 ~ 5.0 μ m, and the content of every kind of inorganic particle changes from 10 ~ 90%.
4. organic/inorganic composite diaphragm according to claim 1, is characterized in that: the mass ratio of described inorganic particle and binding agent is 50:50 ~ 99.9:0.1.
5. organic/inorganic composite diaphragm according to claim 4, is characterized in that: the mass ratio of described inorganic particle and binding agent is 70:30 ~ 99:1.
6. organic/inorganic composite diaphragm according to claim 1, is characterized in that: described inorganic particle is at least one in calcium oxide, zinc oxide, magnesium oxide, titanium dioxide, silicon dioxide, zirconium dioxide, tin ash, ceria, alundum (Al2O3), calcium carbonate or barium titanate.
7. organic/inorganic composite diaphragm according to claim 1, is characterized in that: described binding agent is at least one in styrene-butadiene polymer, Kynoar, Kynoar-hexafluoropropylene, polyacrylic acid, polyacrylate, polymethyl methacrylate, polyacrylonitrile, sodium carboxymethylcellulose, butadiene-acrylonitrile polymer, polyvinylpyrrolidone or polyacrylic acid-styrene.
8. a preparation method for organic/inorganic composite diaphragm as claimed in claim 1, is characterized in that comprising the following steps:
(1) preparation of porous dielectric layer
First binding agent is dissolved in solvent and forms polymer solution, then add inorganic particle dispersed with stirring even, prepare slurry, solid content is 20 ~ 70%;
(2) at perforated substrate surface-coated porous dielectric layer
At least one mode during use dip-coating, die head painting, roller coat, comma transfer painting or intaglio plate are coated with is by the slurry uniform fold preparing at least one surface of polyethylene or polypropylene perforated substrate, and coating layer thickness is for being 1 ~ 10 μ m.
9. the preparation method of organic/inorganic composite diaphragm according to claim 8, is characterized in that:
Described solvent is at least one in oxolane, methylethylketone, dimethyl formamide, dimethylacetylamide, tetramethylurea, tetramethyl phosphate, acetone, carrene, chloroform, dimethylformamide, 1-METHYLPYRROLIDONE, cyclohexane, water or alcohol.
10. a lithium rechargeable battery, comprises positive plate, negative plate, electrolyte and the barrier film between positive plate and negative plate, it is characterized in that: described barrier film is the organic/inorganic composite diaphragm described in any one claim in claim 1 ~ 7.
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| CN201410251930.4A CN104064707B (en) | 2014-06-09 | 2014-06-09 | Inorganic/organic composite membrane, preparation method of inorganic/organic composite membrane and lithium ion secondary battery containing membrane |
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