CN104064707B - 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 PDF

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CN104064707B
CN104064707B CN201410251930.4A CN201410251930A CN104064707B CN 104064707 B CN104064707 B CN 104064707B CN 201410251930 A CN201410251930 A CN 201410251930A CN 104064707 B CN104064707 B CN 104064707B
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inorganic
inorganic particle
particle
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CN104064707A (en
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蒋中林
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Dongguan City Magic Square New Energy Technology Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
    • 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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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Inorganic Chemistry (AREA)
  • Cell Separators (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

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

Inorganic/organic composite barrier film, its preparation method and the lithium ion secondary containing this barrier film Battery
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 system Preparation Method and the lithium rechargeable battery containing this barrier film.
Background technology
Lithium rechargeable battery is big due to energy density, and running voltage is high, the features such as light weight, in consumption electronic product, As mobile phone, notebook computer, panel computer, bluetooth earphone, the field such as MP3 and digital camera has been obtained for being widely applied. Increasingly serious with environmental pollution and problem of energy crisis, lithium rechargeable battery is in the field such as electrokinetic cell and stationary electric power plant Using also increasingly popularizing, but the safety issue of lithium rechargeable battery is always focus of concern.
The barrier film of lithium rechargeable battery, as the isolation of both positive and negative polarity, will have higher ion permeability and preferable machine Tool intensity, is clipped between both positive and negative polarity, and Main Function is to prevent both positive and negative polarity directly contact to be short-circuited, but electrolyte can be made saturating Cross.At present barrier film is mainly by polyethylene, the porous media of the TPO such as polypropylene composition, polyalkene diaphragm have 200 DEG C with Under fusing point, when because internal or external factor leads to be short-circuited heating, temperature raises lithium rechargeable battery, barrier film Easily occur thermal contraction to lead to the bigger short circuit generation of both positive and negative polarity, lead to the thermal runaway of battery to cause fire accident.
In order to solve the above problems, industry coats one layer of porous dielectric layer containing inorganic particulate in membrane surface, Because inorganic particulate has excellent heat stability, this porous dielectric layer just can stop as supporting layer in barrier film thermal contraction Negative pole directly contact, thus avoid problem on fire.
The compactness of the porous dielectric layer of membrane surface coating is larger on overall thermal contraction impact, single particle size The not high enough compactness extent leading to coating of porous dielectric layer bulk density of inorganic particulate composition is also limited, two or more The porous dielectric layer that the inorganic particulate of variable grain size forms size particles accumulation composition can obtain higher bulk density, applies Layer compactness extent is higher, and the thermal contraction of barrier film can be less.Patent CN101301586B winning Chuan Degusai Co., Ltd is public Having opened a kind of polymer carrier materials of plasma process has the ceramic membrane improving viscosity and their preparation and application, Patent CN100438140C of Samsung SDI Co., Ltd discloses a kind of winding-type for having gel-type polymer electrolyte Barrier film of lithium secondary battery and preparation method thereof, patent CN102244223A of Dongguan New Energy Technology Co discloses one Plant electrochemical appliance and its inorganic/organic composite porous membrane, but they are all the inorganic particulates using single size, heap Long-pending density is limited, barrier film poor heat resistance.Although patent CN102412377A of Biyadi Co Ltd employs two kinds of chis Very little inorganic particulate, a kind of inorganic particulate mean diameter be 0.4 ~ 1.5 micron, second inorganic particulate mean diameter be 1.6 ~ 5.0 microns, but for 1 ~ 10 micron of coating, the granular size of both inorganic particulates is a bit bigger than normal, the heap of porous dielectric layer Long-pending density is not fine and close, leads to barrier film thermal contraction to improve limited；On the other hand, the second inorganic particulate granule ratio in this patent Larger, the larger roughness of ratio can be formed in barrier film performance after coating, in the battery with defective tightness of fitting after pole piece assembling, meeting With the presence of an obvious interface, lithium ion transport resistance becomes big, and the chemical property of battery can be affected.
Content of the invention
The first aspect of task of the present invention is to pass through to coat more than at least two at least one surface of perforated substrate The inorganic particle of different mean diameters changing in gradient and binding agent composition porous dielectric layer, provide a kind of compactness good, Less surface roughness, puncture strength is high and has the organic/inorganic composite diaphragm of ultra-low thermal contraction to solve barrier film heap The deficiency of the barrier film poor heat resistance that long-pending density not causes.
The second aspect of task of the present invention is the preparation method providing organic/inorganic composite separator.
The third aspect of task of the present invention is the lithium rechargeable battery providing containing this barrier film, and described barrier film has as invention Characteristic described in the first aspect of task.
The present invention is achieved through the following technical solutions goal of the invention：
A kind of organic/inorganic composite diaphragm, including perforated substrate and the porous dielectric layer being attached on perforated substrate, porous Insulating barrier is coated at least one surface of perforated substrate, and porous dielectric layer includes inorganic particle and binding agent, inorganic particle It is made up of n kind different size particle, n >=2, the 1st kind of inorganic particle forms ladder between the mean diameter of n inorganic particle Degree change.Thus, this graded mean diameter formed inorganic particle between dense accumulation, reach high-compactness degree from And improve heat stability and the puncture strength of barrier film, in battery because the internal or external factor temperature that leads to be short-circuited raises When, keep barrier film primary morphology not shrink, prevent the generation further of short circuit, stop the thermal runaway of battery from causing fire accident； On the other hand, the organic/inorganic composite diaphragm of the present invention passes through the selection of granular size of inorganic particulate and tightly packed, shape Become less surface roughness, fit closely with pole piece in battery assembling, be effectively reduced the transmission resistance of lithium ion, carry The chemical property of high battery.
The mean diameter excursion of described inorganic particle is 0.2 ~ 1.4 μm, and particle size distribution is 0.05 ~ 5.0 μm.
Further, described 1st kind of inorganic particle mean diameter is 0.2 ~ 0.35 μm, the average grain of n inorganic particle Footpath is 0.4 ~ 1.4 μm, and the content of every kind of inorganic particle is from 10 ~ 90% changes.
Preferably, described no granule is 10 by mass ratio：90~90：Different the 1st kind of inorganic particles and of 10 particle diameter 2 kinds of inorganic particle compositions, the mean diameter of the 1st kind of inorganic particle is 0.2 ~ 0.35 μm, and particle size distribution is 0.05 ~ 2.0 μm, the 2nd The mean diameter planting inorganic particle is 0.4 ~ 1.4 μm, and particle size distribution is 0.1 ~ 5.0 μm.
Described porous dielectric layer thickness is 1 ~ 10 μm, preferably 2 ~ 6 μm.
Further, described inorganic particle and the mass ratio of binding agent are 50：50~99.9：0.1.
Preferably, described inorganic particle is 70 with the mass ratio of binding agent：30~99：1.
The inorganic particle of the present invention has no particular limits, as long as will not occurring to aoxidize in lithium rechargeable battery or going back Former have excellent insulating properties simultaneously, and further, described inorganic particle is calcium oxide, zinc oxide, magnesium oxide, titanium dioxide At least one in titanium, silicon dioxide, zirconium dioxide, tin ash, ceria, aluminium sesquioxide, Calcium Carbonate or Barium metatitanate..
Further, described binding agent is styrene-butadiene, Kynoar, Kynoar-hexafluoro third Alkene, polyacrylic acid, polymethylacrylic acid, polyacrylate, polymethyl methacrylate, polyacrylonitrile, sodium carboxymethyl cellulose, At least one in butadiene-acrylonitrile polymer, Polyvinylpyrrolidone or polyacrylic acid-styrene.
A kind of preparation method of organic/inorganic composite diaphragm as above, comprises the following steps：
（1）The preparation of porous dielectric layer
First binding agent is dissolved in formation polymer solution in solvent to stir, is subsequently adding the nothing of variable grain size Machine granule dispersed with stirring uniformly, prepares slurry, and solid content is 20 ~ 70%；
（2）In perforated substrate surface-coated porous dielectric layer
Applied using dip-coating, die head painting, roller coat, comma transfer or intaglio plate apply at least one mode by the slurry preparing Material uniform fold prepares on a surface of polyethylene or polypropylene perforated substrate, and coating layer thickness is 1 ~ 10 μm.
Further, described solvent is oxolane, butanone, dimethylformamide, dimethyl acetylamide, tetramethyl Urea, tetramethyl based phosphates, acetone, dichloromethane, chloroform, dimethylformamide, N-Methyl pyrrolidone, hexamethylene, water or ethanol In at least one.Thus, these solvents can be held with dissolved adhesive and dispersed inorganic particle and coating in drying very much Easily remove.
A kind of lithium rechargeable battery, it includes positive plate, negative plate, electrolyte and is located between positive plate and negative plate Barrier film, described barrier film is above-mentioned organic/inorganic composite diaphragm.
The organic/inorganic composite diaphragm that the present invention provides, coats porous dielectric layer on the surface of perforated substrate, and porous is exhausted The inorganic particle containing in edge layer is made up of the different mean diameters that more than at least two change in gradient to be made between inorganic particle Accumulation can reach high-compactness thus improving heat stability and the puncture strength of barrier film, in battery due to internal or external factor When the temperature that leads to be short-circuited raises, keep barrier film primary morphology not shrink, prevent the generation further of short circuit, stop battery Thermal runaway has caused fire incident, improve the security and stability of lithium rechargeable battery, in addition organic/inorganic composite diaphragm Surface roughness is less, is formed with pole piece and fits tightly, and effectively reduces the resistance of lithium ion battery transmission, improves battery Chemical property.
Brief description
Fig. 1 is the structural representation of the 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-.
Specific embodiment
With reference to 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 N- first In base pyrrolidinone solvent, mix homogeneously makes anode sizing agent, carries out cold after being then coated on aluminium foil and drying at 110 DEG C Pressure, article points, cutting edge, tab welding, make positive plate.
The preparation of negative plate：Graphite, conductive carbon, thickening agent sodium carboxymethyl cellulose, binding agent butadiene-styrene rubber are pressed quality Ratio 95：1.5：1.5：2.0 in deionized water mix homogeneously make cathode size, be then coated on Copper Foil and at 85 DEG C dry Carry out after dry colding pressing, article points, cutting edge, tab welding, make negative plate.
The preparation of barrier film：Take the polyethylene micropore thin film that thickness is 9 μm 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 will This battery core is placed in aluminium plastic packaging bag, injects electrolyte（Ethylene carbonate：Dimethyl carbonate：Ethyl methyl carbonate=1：2：1, bag Lithium hexafluoro phosphate containing 1M）, the operation such as encapsulated, chemical conversion, 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）The preparation of porous dielectric layer g2
It is initially charged the polyacrylate dispersion of 15wt% in deionized water（Content in aqueous solution is 40%）Stirring 1h, so Add the Al of 85wt% afterwards2O3Granule（Mean diameter is 0.3 μm, and particle size distribution is 0.05 ~ 2.5 μm）After stirring 2h, in ball mill Middle grinding 1h, prepares slurry, and solid content is 30%.
（2）In perforated substrate g1 surface-coated porous dielectric layer g2
Take the polyethylene micropore thin film that thickness is 9 μm as perforated substrate g1, then above-mentioned by make using intaglio plate coating Slurry uniformly covers on mono- surface of perforated substrate g1, and coating layer thickness is 4 μm, and then pole piece carries out article points, 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）The preparation of porous dielectric layer g2
Add the polyacrylate dispersion of 15wt% first in deionized water（Content in aqueous solution is 40%）Stirring 1h, It is subsequently adding the Al of 85wt%2O3Granule（Mean diameter is 2.0 μm, and particle size distribution is 0.3 ~ 5.0 μm）After stirring 2h, in ball mill Middle grinding 1h, prepares slurry, and solid content is 30%.
（2）In perforated substrate g1 surface-coated porous dielectric layer g2
Take the polyethylene micropore thin film that thickness is 9 μm as perforated substrate g1, then above-mentioned by make using intaglio plate coating Slurry is uniformly covered on a surface of perforated substrate g1, and coating layer thickness is 4 μm, and then pole piece carries out article points, 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, one layer of porous insulation g2 layer, porous are coated with the perforated substrate g1 of organic/inorganic composite diaphragm In insulating barrier g2, inorganic particle includes the 1st kind of inorganic particle g21 and the 2nd kind of inorganic particle g22 of two kinds of different-grain diameters, binding agent Stick to the surface of inorganic particle after mixing with inorganic particle, fail to show in figure.
The preparation of barrier film：
（1）Prepared by porous dielectric layer g2
It is initially charged the polyacrylate dispersion of 15wt% in deionized water（Content in aqueous solution is 40%）Stirring 1h, so It is separately added into 40% the 1st kind of Al afterwards2O3Granule（Mean diameter is 0.3 μm, and particle size distribution is 0.05 ~ 2.0 μm）With 45wt% 2 kinds of Al2O3Granule（Mean diameter is 1.0 μm, and particle size distribution is 0.1 ~ 3.0 μm）After stirring 2h, in grinding in ball grinder 1h, make For obtaining slurry, solid content is 40%.
（2）In perforated substrate g1 surface-coated porous dielectric layer g2
Take the polyethylene micropore thin film that thickness is 9 μm as perforated substrate g1, then above-mentioned by make using intaglio plate coating Slurry is uniformly covered on a surface of perforated substrate g1, and coating layer thickness is 4 μm, and then pole piece carries out article points, 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）Prepared by porous dielectric layer g2
It is initially charged the polyacrylate dispersion of 15wt% in deionized water（Content in aqueous solution is 40%）Stirring 1h, so It is separately added into 25% the 1st kind of Al afterwards2O3Inorganic particle（Its mean diameter is 0.3 μm, and particle size distribution is 0.08 ~ 2 μm）、 30% the 2nd kind of Al2O3Inorganic particle（Mean diameter is 0.6 μm, and particle size distribution is 0.1 ~ 3.0 μm）With 30wt% the 3rd kind Al2O3Granule（Mean diameter is 1.0 μm, and particle size distribution is 0.1 ~ 4.5 μm）After stirring 2h, in grinding in ball grinder 1h, make For obtaining slurry, solid content is 40%.
（2）In perforated substrate g1 surface-coated porous dielectric layer g2
Take the polyethylene micropore thin film that thickness is 9 μm as perforated substrate g1, then above-mentioned by make using intaglio plate coating Slurry is uniformly covered on a surface of perforated substrate g1, and coating layer thickness is 4 μm, and then pole piece carries out article points, cutting edge.
Embodiment 3
（1）Prepared by porous dielectric layer g2
The Kynoar being initially charged 3wt% in N-Methyl pyrrolidone stirs 1h at 45 DEG C, is then respectively adding 40% the 1st kind of TiO2Granule（Its mean diameter is 0.25 μm, and particle size distribution is 0.08 ~ 1.8 μm）, 30% the 2nd kind of TiO2 Granule（Mean diameter is 0.7 μm, and particle size distribution is 0.1 ~ 3.5 μm）The 3rd kind of TiO with 27wt%2Granule（Mean diameter For 1.2 μm, particle size distribution is 0.1 ~ 5 μm）After stirring 2h, in grinding in ball grinder 1h, prepare slurry, solid content is 65%.
（2）In perforated substrate g1 surface-coated porous dielectric layer g2
Take the polypropylene microporous film that thickness is 12 μm as perforated substrate g1, then above-mentioned by make using intaglio plate coating Slurry is uniformly covered on a surface of perforated substrate g1, and coating layer thickness is 2 μm, and then pole piece carries out article points, 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）Prepared by porous dielectric layer g2
It is initially charged the styrene-butadiene stirring 1h of 30wt% in deionized water, be then respectively adding 30% 1st kind of Al2O3Granule（Its mean diameter is 0.3 μm, and particle size distribution is 0.08 ~ 2 μm）, 20% the 2nd kind of Al2O3Granule （Mean diameter is 0.6 μm, and particle size distribution is 0.1 ~ 3.0 μm）The 3rd kind of Al with 20wt%2O3Granule（Mean diameter is 1.0 μm, particle size distribution is 0.1 ~ 4.5 μm）After stirring 2h, in grinding in ball grinder 1h, prepare slurry, solid content is 25%.
（2）In perforated substrate g1 surface-coated porous dielectric layer g2
Take the polypropylene microporous film that thickness is 12 μm as perforated substrate g1, the above-mentioned slurry that then will make using dip-coating It is uniformly covered on two surfaces of perforated substrate g1, coating layer thickness is 10 μm, then pole piece carries out article points, cutting edge.
Thermal contraction test is carried out for the barrier film in above-mentioned comparative example 1 ~ 3 and embodiment 1 ~ 4, puncture strength is tested, thick Rugosity test, the test of battery high rate performance, cycle performance test and drift bolt test experiments.
（1）Thermal contraction is tested：Barrier film is punched into the square sample of 100 × 100mm, indicates MD（Longitudinally）And TD（Horizontal To）Direction, measures the length of initial MD and TD, puts it into baking 2h in 130 DEG C of baking oven, MD after test baking after taking-up With the length in TD direction, calculate percent thermal shrinkage=[（The size after size-baking before baking）/ baking size before examination] × 100%, Acquired results are shown in Table 1：
Table 1 barrier film percent thermal shrinkage
As known from Table 1, membrane surface coat one layer of porous dielectric layer g2 after comparative example 2,3 and embodiment 1 ~ 4 every The thermal contraction of film is obviously improved, and the comparative example 2 using single inorganic particle is compared with comparative example 3, due to comparing in 2 using inorganic Grain diameter is less, and the bulk density of barrier film is higher, and percent thermal shrinkage is lower, and uses two or more variable grain size The porous dielectric layer g2 percent thermal shrinkage of embodiment 1 ~ 4 reduce at double, the more thermal contractions of granule of different gradients improve more obvious.
（2）Puncture strength is tested
Puncture strength test, the pin of test are carried out according to GB/T 23318-2009 to the barrier film in comparative example and embodiment Head is the push rod B type in GB/T 23318-2009.Test result is as follows：
Table 2 diaphragm puncture intensity
As known from Table 2, membrane surface coat one layer of porous dielectric layer g2 after comparative example 2,3 and embodiment 1 ~ 4 every The puncture strength of film is obviously improved, using the porous dielectric layer g2 of the embodiment 1 ~ 4 of two or more variable grain size Puncture strength improve and become apparent from, and different gradient particles are more, and puncture strength improves more obvious.
（3）Surface roughness is tested
Using surface roughometer, the barrier film in comparative example and embodiment is tested, acquired results are as listed in table 3：
Table 3 membrane surface roughness
As known from Table 3, using two kinds and the embodiment 1 ~ 4 of above inorganic particle surface roughness than using single The comparative example 2,3 of granule improves substantially, and the inorganic particulate of different gradient is more, and surface roughness is improved more obvious.
（4）Battery multiplying power is tested
By lithium ion battery at 25 DEG C first the multiplying power using 0.5C be charged, 0.2C multiplying power discharging, record electric discharge hold Amount；Then carry out 0.5C multiplying power charging, 0.5C multiplying power discharging, record discharge capacity；Then carry out 0.5C multiplying power charging, 1.0C times Rate is discharged, and records discharge capacity；Followed by carrying out 0.5C multiplying power charging, 1.5C multiplying power discharging, record discharge capacity；Finally carry out 0.5C multiplying power charges, 2.0C multiplying power discharging, records discharge capacity.Capability retention under variant discharge-rate=（Under each multiplying power Discharge capacity/0.2C multiplying power under discharge capacity）×100%.Acquired results are shown in Table 4
Capability retention under table 4 comparative example discharge-rate different with embodiment
As known from Table 4, compare the forthright again of comparative example 1,2,3 using the embodiment 1 ~ 4 of at least two gradient inorganic particulates Can be obviously improved, the gradient inorganic particulate of use is more, multiplying power lifting more obvious, this is because embodiment 1 ~ 4 have less Surface roughness, with pole piece laminating degree more preferably, reduces the transmission resistance of lithium ion, high rate performance is lifted.
（5）Cycle performance is tested
Cycle performance is tested：Lithium ion battery is adopted at 25 DEG C the multiplying power of 0.5C charge, the multiplying power discharging of 0.5C, Carry out 500 circulations successively, the battery capacity under each loop test 0.5C multiplying power, and with circulation before capacity at 25 DEG C of battery It is compared, the capability retention after calculating circulation, capability retention=（Battery before capacity/circulation under 0.5C multiplying power after circulation Capacity under 25 degree）×100%.
Table 5 comparative example and embodiment circulation volume conservation rate
As known from Table 5, after membrane surface coats one layer of porous dielectric layer g2, the capability retention of battery will not be subject to shadow Ring.
（6）Drift bolt is tested：First battery is completely filled, then establishing criteria UL1642 is tested, nail diameter is 2.5mm, drift bolt speed is 100mm/s, carries out drift bolt to the battery after the battery before circulation and 500 circulations respectively and surveys safely Examination, test result is shown in Table 6：
The drift bolt test result of battery before and after table 6 circulation
As known from Table 6, the battery of the comparative example 1 of only uncoated porous dielectric layer g2 is minimum, with comparative example 1 phase by number Ratio substantially carries in the comparative example 2,3 of perforated substrate one layer of porous dielectric layer g2 of g1 surface-coated and the security performance of embodiment 1 ~ 4 Height, and comprise only the comparative example 2 of single size inorganic particle and the barrier film lithium secondary battery of comparative example 3 and pacify after 500 circulations Full hydraulic performance decline, the battery of embodiments of the invention 1 ~ 4 before circulation and after 500 circulations battery all maintain 100% drift bolt Percent of pass, has excellent security performance.
The binding agent of the present invention, solvent and inorganic particle except using the material mentioned in above-mentioned comparative example and embodiment, Binding agent can also be fine using Kynoar-hexafluoropropene, polyacrylic acid, methyl methacrylate, polyacrylonitrile, carboxymethyl The plain sodium of dimension, butadiene-acrylonitrile polymer, Polyvinylpyrrolidone or polyacrylic acid-styrene or wherein arbitrarily several Plant the mixture of material；Solvent can also use oxolane, butanone, dimethylformamide, dimethyl acetylamide, tetramethyl Urea, tetramethyl based phosphates, acetone, dichloromethane, chloroform, dimethylformamide, hexamethylene or ethanol or wherein arbitrarily several Plant the mixture of material；Inorganic particle can for calcium oxide, zinc oxide, magnesium oxide, silicon dioxide, zirconium dioxide, tin ash, Ceria, Calcium Carbonate or Barium metatitanate. or the mixture of wherein arbitrarily several material.
Above-described is only some embodiments of the present invention, for the person of ordinary skill of the art, is not taking off On the premise of the invention design, some deformation can also be made and improve, these broadly fall into protection scope of the present invention.

Claims (8)

1. a kind of organic/inorganic composite diaphragm it is characterised in that：Exhausted with the porous being attached on perforated substrate including perforated substrate Edge layer, porous dielectric layer is coated at least one surface of perforated substrate, and porous dielectric layer includes inorganic particle and binding agent, Inorganic particle is made up of n kind difference mean diameter particle, n >=3, the mean diameter of the 1st kind of inorganic particle to n inorganic particle Between formed graded；The mean diameter excursion of inorganic particle is 0.2 ~ 1.4 μm, and particle size distribution is 0.05 ~ 5.0 μm, And the 1st kind of inorganic particle mean diameter is 0.2 ~ 0.35 μm, particle size distribution is 0.05 ~ 2.0 μm, n inorganic particle average Particle diameter is 0.4 ~ 1.4 μm, and particle size distribution is 0.1 ~ 5.0 μm, and the content of every kind of inorganic particle is from 10 ~ 90% changes.
2. organic/inorganic composite diaphragm according to claim 1 it is characterised in that：Described inorganic particle and binding agent Mass ratio is 50：50~99.9：0.1.
3. organic/inorganic composite diaphragm according to claim 2 it is characterised in that：Described inorganic particle and binding agent Mass ratio is 70：30~99：1.
4. organic/inorganic composite diaphragm according to claim 1 it is characterised in that：Described inorganic particle is calcium oxide, oxygen Change zinc, magnesium oxide, titanium dioxide, silicon dioxide, zirconium dioxide, tin ash, ceria, aluminium sesquioxide, Calcium Carbonate or At least one in Barium metatitanate..
5. organic/inorganic composite diaphragm according to claim 1 it is characterised in that：Described binding agent is styrene-fourth two Alkene polymer, Kynoar, Kynoar-hexafluoropropene, polyacrylic acid, polyacrylate, polymethyl methacrylate, In polyacrylonitrile, sodium carboxymethyl cellulose, butadiene-acrylonitrile polymer, Polyvinylpyrrolidone or polyacrylic acid-styrene At least one.
6. a kind of preparation method of organic/inorganic composite diaphragm as claimed in claim 1 is it is characterised in that include following walking Suddenly：
（1）The preparation of porous dielectric layer
First binding agent is dissolved in formation polymer solution in solvent, is subsequently adding inorganic particle dispersed with stirring uniformly, is prepared into To slurry, solid content is 20 ~ 70%；
（2）In perforated substrate surface-coated porous dielectric layer
At least one mode in being applied using dip-coating, die head painting, roller coat, comma transfer painting or intaglio plate will be equal for the slurry preparing On at least one surface of polyethylene or polypropylene perforated substrate, coating layer thickness is 1 ~ 10 μm for even covering.
7. organic/inorganic composite diaphragm according to claim 6 preparation method it is characterised in that：
Described solvent is oxolane, butanone, dimethylformamide, dimethyl acetylamide, tetramethylurea, tetramethyl phosphoric acid At least one in salt, acetone, dichloromethane, chloroform, dimethylformamide, N-Methyl pyrrolidone, hexamethylene, water or ethanol.
8. a kind of lithium rechargeable battery, including positive plate, negative plate, electrolyte and be located between positive plate and negative plate every Film it is characterised in that：Described barrier film is organic/inorganic composite diaphragm described in claim for any one of the claim 1 ~ 5.
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