CN102437302A - Lithium ion battery diaphragm and high temperature thermal-stable lithium ion battery - Google Patents
Lithium ion battery diaphragm and high temperature thermal-stable lithium ion battery Download PDFInfo
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- CN102437302A CN102437302A CN2011103795863A CN201110379586A CN102437302A CN 102437302 A CN102437302 A CN 102437302A CN 2011103795863 A CN2011103795863 A CN 2011103795863A CN 201110379586 A CN201110379586 A CN 201110379586A CN 102437302 A CN102437302 A CN 102437302A
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Abstract
The invention provides a lithium ion battery diaphragm and a high temperature thermal-stable lithium ion battery, which relate to lithium ion batteries. The diaphragm comprises a polyolefin microporous membrane which acts as a basic layer, wherein a nano ceramic material coating is manufactured on one side surface or two side surfaces of the polyolefin microporous membrane; and compositions of the nano ceramic material coating comprise any one of a zirconium oxide, an aluminum oxide, a silicon oxide, a titanium oxide, a silicon nitride, a boron nitride and an aluminum nitride or a combination of any oxide and any nitride, and additionally comprise binders. Since a high temperature resistant nano ceramic material is led into the surface of a conventional diaphragm, an insulating property better than the insulating property of the conventional diaphragm is provided, further internal insulating property damage brought by thermal contraction of the conventional diaphragm, which leads to thermal runaway of the lithium battery, is avoided particularly at high temperatures of 130 DEG C, 150 DEG C and 180 DEG C, and thereby the high temperature thermal stability of the lithium ion battery is improved and the safe reliability of the lithium ion battery is increased.
Description
Technical field
The present invention relates to lithium ion battery, refer to a kind of lithium ion battery separator and a kind of high-temperature thermal stability type lithium ion battery especially.
Background technology
Lithium rechargeable battery (abbreviation lithium ion battery) is made up of positive pole, negative pole, electrolyte, barrier film and packing etc.Barrier film separates positive pole and negative pole between the positive pole and negative pole of lithium ion battery, avoid the direct contact of both positive and negative polarity to cause partial short-circuit, reduces self discharge and the battery defect and the reliability safety problem that produce.The normal lithium ion battery separator material that adopts is the polyolefin microporous film, is generally the polyolefin composite membrane (Fig. 1) of individual layer or multilayer.What realize commercial applications at present is three layers of composite membrane of polypropylene porous film (PP film) and polyethylene porous membrane (PE film) and PP/PE/PP.The effect of barrier film in lithium ion battery is the electronic isolation of realizing both positive and negative polarity, simultaneously because microcellular structure and electrolyte provide the ionic conduction approach together.Lithium ion battery separator thickness at present commonly used the chances are 5-40 micron, the average pore size of micropore is the 50-200 nanometer.Porosity ranges generally is 30-70%.The thickness of the barrier film of lithium ion battery, average pore size and porosity have been confirmed the resistance of the ionic conduction of barrier film.Because ambient temperature raises when perhaps internal flaw causes the temperature of barrier film to raise, and polyolefine material can take place by softening the expansion, causes the aperture to diminish, porosity is dwindled at lithium ion battery; The barrier film that employing contains the PE material can reduce rapidly about near the aperture of 130 degree greatly; The space reduces rapidly, has promoted the impedance of the ionic conduction of barrier film rapidly, causes the resistance of battery to raise rapidly; Thereby reduce the electric current of battery, reduce because the harmful effect that the outside high temperature of external short circuit brings.This phenomenon is commonly referred to " closed pore " perhaps " heat is turn-offed ".This critical temperature so-called " closed pore temperature " is " heat is turn-offed temperature " perhaps.This characteristic has positive effect for the security performance lifting of battery.
When temperature further raises, polyolefine material can melt, and causes the dimensional contraction of porous polyolefin membrane, and hole appears in the part, distortion.This temperature is called " fusion temperature ".Fusion temperature approximately is about 150-180 ℃ for polyolefine material usually.In the time of near battery diaphragm is in fusion temperature, because dimensional contraction, hole occurs, and barrier film can not provide the basic function of electron conduction partition basically, and the accident of the combustion explosion of battery can take place usually.
Adopt the barrier film of polyolefin material about 130-150 ℃, can produce thermal contraction deformation usually, dimensional contraction causes the positive pole of battery directly to contact with negative pole.This characteristic causes the unfailing performance of battery to descend.When for example on barrier film, having local open-work defective, perhaps owing to inner metallic particles, when metallic bur power pierces through the internal short-circuit that causes battery; Short dot is because big electric current flows through, and local temperature rise or surpass 150 degree reaches the fusion temperature of polyolefin film; Because the characteristic of conventional polyolefin material; Can cause contraction, cause local short dot further to enlarge, bring higher temperature rise.Finally the battery thermal runaway be possibly cause, the burning or the blast of battery caused.
Inner temperature rise also possibly be owing under the condition of some batteries abuses, produce, for example outside acupuncture, and mechanical presses is overcharged, overdischarge or the like.Conventional polyalkene diaphragm at high temperature can not provide enough insulation guarantees.
To this problem; Conventional barrier film manufacturer also can pass through improved formulations, is improved to the material that adopts super high molecular weight from adopting single PP, PE raw material, carries out resistant to elevated temperatures material and adds; Perhaps take the technology of coextrusion composite material, can to a certain extent fusion temperature be improved.But bring equipment cost to change, the cost of raw material promotes.Other performance is reliability for example, and the electrochemistry compatibility all needs authentication.
Summary of the invention
To achieve these goals, accomplish above-mentioned task, a kind of lithium ion battery separator of the present invention and high-temperature thermal stability type lithium ion battery adopt following technical scheme:
A kind of lithium ion battery separator of the present invention; Comprise polyolefin micropore film as basic unit; Making the nano ceramic material coating on one side surface of said polyolefin micropore film or on the both side surface; The composition of said nano ceramic material coating comprises in nano level zirconia, aluminium oxide, silica, titanium oxide, silicon nitride, boron nitride, the aluminium nitride any one or any one oxide wherein and the combination of any one nitride, and the composition of said nano ceramic material coating also comprises binding agent.
Binding agent is taked lithium ion battery PVDF commonly used or SBR series, and perhaps the Sodium Polyacrylate of stable electrochemical property series binding agent mainly acts on the stable formation that provides the nano ceramic material coating, bonds with polyolefin micropore film itself simultaneously.
Be approximately the low capacity lithium ion battery of 100-5000mAh for capacity, the thickness of polyolefin micropore film is 5～20 microns; Be generally jumbo automobile power cell and the energy-storage battery of 5Ah-200Ah for capacity, the thickness of polyolefin micropore film is 10～30 microns.
For capacity is the low capacity lithium ion battery of 100-5000mAh, and the thickness of its one-sided nano ceramic material coating is 1～5um; Be generally jumbo automobile power cell and the energy-storage battery of 5Ah-200Ah for capacity, the thickness of its one-sided nano ceramic material coating is 1～10um.
Below 5um, said nano level zirconia, aluminium oxide, silica, titanium oxide, silicon nitride, boron nitride and aluminium nitride average particulate diameter separately be 300～1000 nanometers for one-sided nano ceramic material coating.One-sided nano ceramic material coating person between 5～10um, said nano level zirconia, aluminium oxide, silica, titanium oxide, silicon nitride, boron nitride and aluminium nitride average particulate diameter separately are 700～2500 nanometers.
The average grain diameter of nano ceramic material that constitutes said nano ceramic material coating is greater than the average pore size of polyolefin micropore film; Perhaps, said nano level zirconia, aluminium oxide, silica, titanium oxide, silicon nitride, boron nitride and aluminium nitride smallest particles degree (Dmin) separately is greater than the maximum diameter of hole (dmax) of polyolefin micropore film.
The flow process of making said nano ceramic material coating is following:
The first step: to the processing of polyolefin micropore film: the wetability of inspection polyolefin micropore film, the wetability of polyolefin micropore film is tested with the dyne pen, and the numerical value of measurement is represented with dyne; For the water miscible binding agent of Sodium Polyacrylate series, then to carry out corona treatment according to the surface tension of polyolefin micropore film, make the dyne numerical value of polyolefin micropore film surface more than 50; For PVDF series binding agent, adopt NMP (N methyl pyrrolidone) to make solvent, then the polyolefin micropore film surface need not carry out corona treatment.
Second step: prepare the nano ceramic material coating paste: ready deionized water, adhesive solution, solvent and ceramic powders are added mixing plant according to certain proportioning stir; Mixing plant need possess the high speed shear divergent function; The shear rate of dispersion impeller is between RPM2000-3000, and mixing time is about three hours; Mill score in case of necessity to guarantee dispersive property, not conglomeration and not sedimentation; After ball milling is accomplished, slowly stir, whether carry out the froth in vacuum operation according to the bubble situation simultaneously.As adopt the PVDF binding agent, then need use nmp solvent that PVDF is fully dissolved back adding nano ceramic material and stir.
Three steps: the nano ceramic material coating paste of preparing with scraping hymenotome, perhaps is coated on the treated polyolefin micropore film with blade applicator uniformly; Also can adopt bat printing testing stand system nano ceramic material coating;
The 4th step: 60 ℃ of fortune wind oven for drying need 30～60 minutes.Need be when adopting the PVDF binding agent according to practical situation proper extension drying time.
The 5th step: double-face nanometer ceramic coating if desired, the processing that on the another side of polyolefin micropore film, repeats the 3rd step and the 4th step gets final product.
High-temperature thermal stability type lithium ion battery of the present invention, it comprises positive pole, negative pole, electrolyte, barrier film and packing, said barrier film adopts a kind of lithium ion battery separator of the present invention.
Beneficial effect of the present invention is: because conventional membrane surface (polyolefin micropore film) has been introduced the high-temperature resistant nano ceramic material; Barrier film top layer than conventional provides better insulation property; Especially 130 ℃ of high temperature, in the time of 150 ℃ and 180 ℃, the further built-in electrical insulation performance of having avoided the thermal contraction of conventional barrier film to bring is destroyed the thermal runaway that causes lithium battery; Thereby improved the high high-temp stability of lithium ion battery, improved the security reliability of lithium ion battery.
Description of drawings
Fig. 1 is the barrier film sketch map of prior art;
Fig. 2 is a barrier film sketch map of the present invention (one of embodiment);
Fig. 3 is barrier film sketch map of the present invention (embodiment two);
Fig. 4 is barrier film thermal contraction test sketch map of the present invention;
Fig. 5 is a kind of its positive pole of high-temperature stable lithium ion battery, negative pole and diaphragm configuration sketch map (front view);
Fig. 6 is a kind of its positive pole of high-temperature stable lithium ion battery, negative pole and diaphragm configuration sketch map (side cutaway view).
Among the figure: 1, polyolefin micropore film; 2, nano ceramic material coating; 3, positive pole; 4, negative pole; 5, barrier film; 6, be heated before; 7, be heated after.
Embodiment
Below, introduce embodiment of the present invention in conjunction with accompanying drawing.
To shown in Figure 6, the present invention makes nano ceramic material coating 2 on the surface of the lithium ion battery separator polyolefine porous film 1 of routine like Fig. 1.Nano ceramic material coating 2 adopts resistant to elevated temperatures ceramic material to be generally: nanoscale zirconia, aluminium oxide, silica, titanium oxide, silicon nitride, boron nitride, other metals such as aluminium nitride and nonmetallic oxide, metal and nonmetallic nitride.Nano ceramic material coating 2 can be carried out at a side (Fig. 2) or both sides (Fig. 3) of polyolefine porous film 1.Nano ceramic material coating 2 mainly contains metal and nonmetallic oxide, nitride, binding agent and other interpolation material.Binding agent is taked lithium ion battery PVDF commonly used usually, perhaps SBR series, and the perhaps Sodium Polyacrylate of stable electrochemical property series binding agent, significant feature provides the stable formation of rete, bonds with polyolefine porous film itself simultaneously.Barrier film 5 through 2 processing of nano ceramic material coating; (Fig. 4) finds that thermal contraction performance obviously reduces when carrying out the thermal contraction test for 130 ℃, 150 ℃ and 180 ℃, and the stability of mechanical dimension is superior to the conventional barrier film of not handling through the nano ceramic material coating.Under inside lithium ion cell local defect or abuse conditions; Because the thermal stability of the barrier film that process nano ceramic material coating is handled; Stoped because barrier film shrinks the defective that causes and amplified further short circuit and the temperature rise that brings, lowered the probability of battery generation integrity problem and combustion explosion greatly.
For the low capacity lithium ion battery, capacity is approximately 100-5000mAh, and the thickness of polyolefin micropore film 1 is 5～20 microns usually; For jumbo automobile power cell and energy-storage battery, capacity is generally 5Ah-200Ah, and the thickness of polyolefin micropore film 1 is 10～30 microns usually.Thickness for the general one-sided nano ceramic material coating 2 that adopts of small-capacity cells is 1～5um, is generally 1～10um for the thickness of the one-sided nano ceramic material coating 2 of high capacity cell.Carry out the front and back that nano ceramic material coating 2 is handled, according to the porosity of polyolefin micropore film 1, can be according to the demand of practical application; For the zirconia of nano ceramic material coating 2, aluminium oxide, silica; Titanium oxide; Silicon nitride, the ratio of boron nitride and aluminium nitride particle diameter separately and binding agent is carried out different proportionings, regulates the overall porosity of the barrier film (or claiming composite diaphragm) after nano ceramic material coating 2 is accomplished.
Be used to constitute the selection of the high-temperature resistant nano ceramic material of ceramic nano material coating 2, the requirement below mainly needing to satisfy: electronic isolation, possess the characteristic of electrochemical stability in lithium ion battery, in air, preserve and be not easy oxidation and hydrolysis; It is stable that material itself can keep in the hot environment more than 200 ℃.Zirconia; Aluminium oxide; Silica; Titanium oxide, silicon nitride, boron nitride and aluminium nitride grain diameter size is separately selected to optimize according to the average pore size of polyolefin micropore film 1, nano ceramic material coating 2 thickness of expectation and average pore size and the porosity that nano ceramic material coating 2 is accomplished metacneme 5.Generally for nano ceramic material coating 2 below 5um, choose the nano material of about 300～1000 nanometers of average particulate diameter D50.The nano ceramic material coating can consider to choose the nano ceramic material that average particulate diameter is approximately 700～2500 nanometers at 5～10 um.
Said nano level zirconia, aluminium oxide, silica, titanium oxide, silicon nitride, boron nitride and aluminium nitride pattern separately have bigger influence for heat-resisting shrinkage of barrier film 5 (or claiming composite diaphragm) and the space performance accomplished after the nano ceramic material coating 2.For the porosity that makes polyolefin micropore film 1 remains unchanged before and after nano ceramic material coating 2 forms or changes less; The average grain diameter of the nano ceramic material of formation nano ceramic material coating is greater than the average pore size of polyolefin micropore film, and preferably nano level zirconia, aluminium oxide, silica, titanium oxide, silicon nitride, boron nitride and aluminium nitride minimum grain size (Dmin) separately is greater than the maximum diameter of hole (dmax) of basic alkene microporous membrane.The barrier film that has the nano ceramic material coating will be kept the size stability under the high temperature; Remain on more than 130 ℃ folk prescription to the dimensional contraction rate less than 5%; Dimensional contraction rate in the time of 150 ℃ is optimized and can satisfies for the thickness of nano ceramic material coating 2 and the pattern of nano-ceramic particle less than 10%.
Definition for the average grain diameter D50 of powder body material: the cumulative particle sizes percentile of a sample powder reaches 50% o'clock pairing particle diameter (particle diameter).To be the particle diameter diameter account for 50% greater than its particle to its physical significance, also accounts for 50% less than its particle, and D50 also is meso-position radius or median particle diameter.The diameter of Dmax and Dmin representative maximum particle correspondence in diameter of particle is measured.Grain diameter measurement for powder body material generally adopts laser method to measure, and equipment adopts the laser particle analyzer of Britain Malvern Instruments company.Also can adopt electronic scanner microscope SEM to carry out meticulous measurement for accurate measurement.
For porous material barrier film for example itself, the measurement of micropore diameter generally adopts mercury injection method to measure.Usually adopt the Poremaster equipment of U.S. Kang Ta company (Quantachrome Instruments) to measure.On behalf of the accumulative total pore-size distribution percentage in the poromerics, the d50 of poromerics reach 50% is the diameter in the hole of correspondence.Being the aperture on the physical significance accounts for 50% greater than its micropore, also accounts for 50% less than its aperture.Be also referred to as average pore size or meta aperture.Dmax and dmin represent the corresponding diameter in minimum and maximum hole in micropore size is measured respectively.
Constitute the binding agent of nano ceramic material coating 2, the binding agent that general selection is compatible with the current battery system.Lithium ion battery binding agent commonly used is a polyvinylidene fluoride resin, i.e. the PVDF resin.The PVDF resin mainly is meant the copolymer of polyvinylidene fluoride homopolymer or vinylidene and other a small amount of fluorine-containing vinyl monomers, and the latter is commonly referred to and is PVDF-HFP.A kind of in addition lithium ion battery binding agent commonly used is the butadiene-styrene rubber styrene butadiene rubber (SBR) of solvent for using deionized water.PVDF and PVDF-HFP need be dissolved in N-methyl pyrrolidone (NMP) solvent.SBR is water miscible emulsion binder.Swelling takes place with electrolyte in the binding agent of PVDF series in lithium ion battery, under the condition of heating, carry out bondingly with the PVDF series binding agent of both positive and negative polarity, and perhaps one of them carries out bonding with both positive and negative polarity thereby make the barrier film of battery.
The binding agent of in adopting lithium ion battery, using, the binding agent that can be used as the nano ceramic material coating also has polyacrylic acid (PAA) class, the resin of polymethyl methacrylate (PMMA) etc.
Conventional barrier film is generally the polyolefin composite membrane (Fig. 1) of individual layer or multilayer.In the barrier film production process of routine, polyolefin master batch material process and solvent, mixing hot melt is extruded through extruder, forms coiled material through unidirectional or two-way drawing process and cleaning again.As shown in Figure 1.The length direction of film material is called for short MD (machine direction) along machine direction.Width becomes TD (transverse direction) perpendicular to the direction of equipment.
Containing the coat composed barrier film of nano ceramic material (or composite diaphragm) when being heated; Conventional barrier film has the trend of contraction; But the exotic material layer that mainly is made up of nano-ceramic particle does not shrink itself; Stoped the contraction of substrate material, thereby the variation of keeping barrier film (or composite diaphragm) overall dimensions significantly reduces (as shown in Figure 4).
In lithium ion battery, positive pole, negative pole, the position of barrier film and size relationship such as Fig. 5 and Fig. 6. barrier film is for positive pole and negative pole are separated, and in length, the width aspect is all greater than positive pole and negative pole.Lithium ion battery negative all is greater than positive pole as the acceptor of lithium ion on length and width on the size.Simply be described as barrier film＞negative pole on the size＞positive pole.In the expression of Fig. 5 and Fig. 6, L1 and L2 are greater than zero.D1 and d2 are greater than zero.In the actual battery design and manufacture process, consider the capacity density of the integral body of battery, generally speaking, d1 is approximately 0～2mm, and d2 is approximately 0～2 mm.L1 is generally 2～15 mm, and L2 is generally 5～30mm.
In the time of battery production, generally be that barrier film length direction MD is consistent with the pole plate direction of battery, the plate width direction consistent (referring to the sign of MD among Fig. 1 and TD) of Width TD and battery.In lithium ion battery, because the surplus d1 of TD direction, the d2 representative value has only 2mm, and when external condition was heated or internal short-circuit is heated, barrier film shrank and causes the anodal internal short-circuit that directly contacts with negative pole on the TD of lithium ion battery septation direction.Short circuit causes the further contraction of barrier film in case formation can continue to produce heat at short dot, and further the vicious circle of short circuit finally causes battery failure or combustion explosion.
In the formation of nano ceramic material coating: the nanometer powder that 94% mass fraction is arranged is (like Alpha-alumina; D50 is 650nm, the about 400nm of Dmin, Dmax is about 1300nm); 5% PMMA binding agent and other 1% are used for regulating some diluents or the thickener of slurry viscosity.When making slurry, add proper amount of deionized water earlier, add binding agent then, add aluminium oxide or other ceramic powders at last.Usually in order to guarantee the globality of nano ceramic material coating 2; Nano ceramic material coating 2 is unlikely to dry linting; The component of binding agent is no less than 3%; In order to guarantee the indeformable contraction of material under the high temperature, the thickness of one-sided nano ceramic material coating 2 is not less than 3um, and the mass fraction of nano ceramic material is no less than 93%.
Contain aluminum nitride particle in the nano ceramics material coating 2, aluminum nitride particle also possesses outstanding thermal conducting function except the characteristic that possesses aluminium oxide ceramics.Outstanding a lot of times of the capacity of heat transmission of the capacity of heat transmission alumina material of aluminium nitride material.When receiving thermal contraction, localized hyperthermia's point especially is for example during internal short-circuit, because the outstanding thermal conduction characteristic of aluminum nitride particle can control to lesser extent with the thermal contraction of part.
Below, introduce the barrier film (or claiming composite diaphragm) that the present invention is had the nano ceramic material coating, the change in size of carrying out the heat test.The film of the individual layer PE material of employing wet method is as base material with reference to barrier film.Adopt aluminium oxide and aluminium nitride ceramics nano powder and PMMA polymethyl methacrylate aqueous solution as the nano ceramic material coating material respectively.The nano ceramic material coating adopts the experiment film applicator to be coated on the base material PE barrier film.About THICKNESS CONTROL 5um.Cut conventional barrier film of 10cmx10cm and composite diaphragm respectively and carry out the storage test of high temperature.Test condition is 90 ℃, 130 ℃, and 150 ℃, 180 ℃.Time is respectively 60min, 30min, 10min.130 ℃ and 150 ℃ is the closed pore and the fusion temperature of the polyethylene barrier film of routine, and 150 ℃ and 180 ℃ are respectively traditional closed pore temperature that gathers the third hydrocarbon barrier film and fusion temperature.During test, sample is clipped between the smooth sheet metal.After temperature of oven is raised to design temperature, the ready measured piece that is clipped between metallic plate is put in the baking oven.Before and after the baking oven baking, test the length and width H and the W of barrier film respectively, H1, W1.With the H * W of the H1 * W1 after the baking before divided by baking, and 1 subtract each other, just can obtain the percent thermal shrinkage S of barrier film.
S%=1-（H1×W1）/（H×W）。See that Fig. 4 is reference.Because it is more that the barrier film surplus of MD direction is reserved, when investigating shrinkage, only investigate the dimensional contraction rate of TD direction sometimes.Ｓｗ％＝ 1-?W1/W。
Experimental result proves, carries out the barrier film 5 (or claiming composite diaphragm) that the nano surface ceramic coating forms and on thermal contraction performance, has advantage, has greatly improved for the thermal stability and the security performance of battery.Following form has been listed the test result of experiment.Wet method polyethylene barrier film is selected in experiment for use.ALO representes to adopt aluminium oxide as the nano ceramic material coating material.ALN representes to adopt the material of aluminium nitride as the nano ceramic material coating.
Make the flow process of nano ceramic material coating:
The first step: to the processing of polyolefin micropore film: the wetability of inspection polyolefin micropore film, the wetability of polyolefin micropore film is tested with the dyne pen, measures numerical value and representes with dyne; For the water miscible binding agent of Sodium Polyacrylate series, then to carry out corona treatment according to the surface tension of polyolefin micropore film, make that the dyne numerical value of polyolefin micropore film surface should be more than 50; For PVDF series binding agent, adopt NMP (N methyl pyrrolidone) to make solvent, then the polyolefin micropore film surface need not carry out corona treatment.
Second step: prepare the nano ceramic material coating paste: ready deionized water, adhesive solution, solvent and ceramic powders are added mixing plant according to certain proportioning stir; Mixing plant need possess the high speed shear divergent function; The shear rate of dispersion impeller is between RPM2000-3000, and mixing time is about three hours; Mill score in case of necessity to guarantee dispersive property, not conglomeration and not sedimentation; After ball milling is accomplished, slowly stir, whether carry out the froth in vacuum operation according to the bubble situation simultaneously.As adopt PVDF series binding agent, need NMP and PVDF fully be dissolved back adding nano ceramic material.
The 3rd step: the nano ceramic material coating paste of preparing with scraping hymenotome, perhaps is coated on the treated polyolefin micropore film with blade applicator uniformly; Also can adopt bat printing testing stand system nano ceramic material coating;
The 4th step: 60 ℃ of oven for drying need 30～60 minutes.Because the boiling point of nmp solvent is higher, need the proper extension time when adopting PVDF to make binding agent.
The 5th step: double-face nanometer ceramic coating if desired, the processing that on the another side of polyolefin micropore film, repeats the 3rd step and the 4th step gets final product.
Adopt the characteristic of the barrier film 5 (or claiming composite diaphragm) that this flow process and material mixture ratio make following:
1, the description of the improving of thermal contraction performance during high temperature (90 ℃, 130 ℃, 150 ℃, 180 ℃) relatively);
2, during partial short-circuit, the thermal contraction of short dot improves (using the hot needle mould of 1mm to intend inner perforated, the vary in diameter of boring a hole on the test barrier film).
Adopt aluminium oxide, giving an example and test result of aluminium oxide aluminium nitride used in aluminium nitride and mixing.The ceramic nano coating composite diaphragm of test has been taked single face nano ceramic material coating, and the double-face nanometer ceramic coating is as comparing.In the nano ceramic material that ALN75%+ALO25% representes to adopt, the mass percent of ALN is 75%, and the mass percent of ALO is 25%.
| The nano ceramic material coating material | Base material+nano ceramic material coating (um) | Shrinkage S% (90 oC * 60 minute) | Shrinkage S% (130 oC * 30 minute) | Shrinkage S% (150 oC * 10 minute) | Shrinkage S% (180 oC * 10 minute) |
| With reference to PE | 20+0 | 1.5 | 25 | 60 | 80 |
| ALN-1 | 20+5 | ﹤1 | 4 | 5 | 9 |
| ALN-2 | 20+5+5 | ﹤1 | 3 | 3.5 | 5 |
| ALO-1 | 20+5 | ﹤1 | 6 | 7 | 15 |
| ALO-2 | 20+5+5 | ﹤1 | 3.5 | 4 | 8 |
| ALN75%+ALO25% | 20+5 | ﹤1 | 5 | 5 | 10 |
| ALN25%+ALO75% | 20+5 | ﹤1 | 5 | 9 | 16 |
| ALN50%+ALO50% | 20+5 | ﹤1 | 6 | 6 | 17 |
From the result of test, the compound PE barrier film 5 that the nano ceramic material coating of employing aluminium oxide and aluminium nitride is processed, approaching on thermal contraction performance, contrast base material barrier film 1 (not having the nano ceramic material coating), promoted the thermal stability of size greatly.Adopt the compound PE barrier film 5 of nano ceramic material coating of mixed aluminium oxides and aluminium nitride, on thermal contraction performance, distinguish not obvious with a kind of material of simple use.The composite diaphragm 5 of double-face nanometer ceramic coating is for about being doubled of the rejection ratio individual layer nano ceramic material coating of thermal contraction.
But when the inside lithium ion cell short circuit, because the excellent peroxidating aluminium of the heat conductivility nano ceramic material coating of aluminium nitride can be seen bigger difference when carrying out the short circuit of the hot pin puncture of internal short-circuit simulated interior.Test method is: will test diaphragm clip on the negative electrode film of lithium ion battery, the face up vertical diaphragm of hot pin of using 1mm then and negative electrode film of the composite diaphragm that has the nano ceramic material coating kept 5 minutes.Use the hole size on projecting apparatus or the barrier film of micrometering apparatus measures after different hot pin temperature pierces through.The temperature of hot pin is regulated through the electric heater that is connected on the hot pin.
| ? | Base material+nano ceramic material coating (um) | ? | Normal temperature | Aperture mm (150 oC） | Aperture mm (200 oC） | Aperture mm (250 oC） |
| With reference to PE | 20+0 | ? | 1 | 1.30 | 2.75 | 3.88 |
| ALN-1 | 20+5 | ? | 1 | 1.21 | 1.42 | 1.78 |
| ALO-1 | 20+5 | ? | 1 | 1.33 | 1.78 | 2.31 |
| ALN75%+ALO25% | 20+5 | ? | 1 | 1.27 | 1.46 | 1.83 |
| ALN50%+ALO50% | 20+5 | ? | 1 | 1.25 | 1.51 | 1.98 |
| ALN25%+ALO75% | 20+5 | ? | 1 | 1.30 | 1.71 | 2.22 |
Can see that from test result when the puncture of hot pin, when the temperature of hot pin was about 150C, the diameter difference of perforation was not obvious.But when temperature surpasses 200
OCDuring the left and right sides, barrier film 5 contrast that possesses the nano ceramic material coating does not have the barrier film 1 of nano ceramic material coating, for the enlarged-diameter of hot pin hole the obvious suppression effect is arranged.Because the efficient heat conductivity in surface of aluminium nitride, when carrying out hot pin puncture test, can keep the point of puncture aperture less relatively through the compound barrier film of nano ceramic material coating.Aln layer can be with the conduction of a part of heat, the temperature of puncture place with respect to handle without the nano ceramic material coating and the pure alumina treatment temperature lower, thereby the varying aperture of bringing also is less relatively.Along with the reduction of aluminium nitride mixed proportion, lower owing to form continuous efficient heat conducting chance, can increase a little for the aperture of perforation place.
The above only is preferred embodiment of the present invention, is not that technical scope of the present invention is done any restriction.The technical staff of the industry; Under the inspiration of present technique scheme; Can make some distortion and revise, every foundation technical spirit of the present invention all still belongs in the scope of technical scheme of the present invention above any modification, equivalent variations and modification that embodiment did.
Claims (8)
1. lithium ion battery separator; Comprise polyolefin micropore film as basic unit; It is characterized in that: making the nano ceramic material coating on the side surface of said polyolefin micropore film or on the both side surface; The composition of said nano ceramic material coating comprises in nano level zirconia, aluminium oxide, silica, titanium oxide, silicon nitride, boron nitride, the aluminium nitride any one or any one oxide wherein and the combination of any one nitride, and the composition of said nano ceramic material coating also comprises binding agent.
2. a kind of lithium ion battery separator according to claim 1; It is characterized in that: binding agent is taked lithium ion battery PVDF commonly used; Perhaps SBR is serial; Perhaps the Sodium Polyacrylate of stable electrochemical property series binding agent mainly acts on the stable formation that provides the nano ceramic material coating, bonds with polyolefin micropore film itself simultaneously.
3. a kind of lithium ion battery separator according to claim 1 is characterized in that: be approximately the low capacity lithium ion battery of 100-5000mAh for capacity, the thickness of polyolefin micropore film is 5～20 microns; Be generally jumbo automobile power cell and the energy-storage battery of 5Ah-200Ah for capacity, the thickness of polyolefin micropore film is 10～30 microns.
4. a kind of lithium ion battery separator according to claim 1 is characterized in that: for capacity is the low capacity lithium ion battery of 100-5000mAh, and the thickness of its one-sided nano ceramic material coating is 1～5um; Be generally jumbo automobile power cell and the energy-storage battery of 5Ah-200Ah for capacity, the thickness of its one-sided nano ceramic material coating is 1～10um.
5. a kind of lithium ion battery separator according to claim 1; It is characterized in that: below 5um, said nano level zirconia, aluminium oxide, silica, titanium oxide, silicon nitride, boron nitride and aluminium nitride average particulate diameter separately be 300～1000 nanometers for one-sided nano ceramic material coating; One-sided nano ceramic material coating is 5～10um person, and said nano level zirconia, aluminium oxide, silica, titanium oxide, silicon nitride, boron nitride and aluminium nitride average particulate diameter separately are 700～2500 nanometers.
6. a kind of lithium ion battery separator according to claim 1; It is characterized in that: the average grain diameter of nano ceramic material that constitutes said nano ceramic material coating is greater than the average pore size of polyolefin micropore film; Perhaps, said nano level zirconia, aluminium oxide, silica, titanium oxide, silicon nitride, boron nitride and aluminium nitride smallest particles degree Dmin separately is greater than the maximum diameter of hole dmax of polyolefin micropore film.
7. a kind of lithium ion battery separator according to claim 1 is characterized in that: the flow process of making said nano ceramic material coating is following:
The first step: to the processing of polyolefin micropore film: the wetability of inspection polyolefin micropore film, the wetability of polyolefin micropore film is tested with the dyne pen, and the numerical value of measurement is represented with dyne; Make the binding agent of solvent for the water-soluble of SBR and Sodium Polyacrylate series or with water, then will carry out corona treatment, make the dyne numerical value of polyolefin micropore film surface more than 50 according to the surface tension of polyolefin micropore film; For PVDF series binding agent, adopt nmp solvent, then the polyolefin micropore film surface need not carry out corona treatment;
Second step: prepare the nano ceramic material coating paste: ready deionized water, adhesive solution, solvent and ceramic powders are added mixing plant according to certain proportioning stir; Mixing plant need possess the high speed shear divergent function; The shear rate of dispersion impeller is between RPM2000-3000, and mixing time is about three hours; Mill score in case of necessity to guarantee dispersive property, not conglomeration and not sedimentation; After ball milling is accomplished, slowly stir, whether carry out the froth in vacuum operation according to the bubble situation simultaneously; As adopt the PVDF binding agent, then need use nmp solvent that PVDF is fully dissolved back adding nano ceramic material and stir;
The 3rd step: the nano ceramic material coating paste of preparing with scraping hymenotome, perhaps is coated on the treated polyolefin micropore film with blade applicator uniformly; Also can adopt bat printing testing stand system nano ceramic material coating;
The 4th step: 60 ℃ of fortune wind oven for drying need 30～60 minutes; Need be when adopting the PVDF binding agent according to practical situation proper extension drying time;
The 5th step: double-face nanometer ceramic coating if desired, the processing that on the another side of polyolefin micropore film, repeats the 3rd step and the 4th step gets final product.
8. high-temperature thermal stability type lithium ion battery comprises positive pole, negative pole, electrolyte, barrier film and packing, it is characterized in that: said barrier film adopts described any one lithium ion battery separator of claim 1 to claim 7.
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