CN100502097C - New organic/inorganic composite porous film and electrochemical device prepared thereby - Google Patents
New organic/inorganic composite porous film and electrochemical device prepared thereby Download PDFInfo
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- CN100502097C CN100502097C CNB2005800203221A CN200580020322A CN100502097C CN 100502097 C CN100502097 C CN 100502097C CN B2005800203221 A CNB2005800203221 A CN B2005800203221A CN 200580020322 A CN200580020322 A CN 200580020322A CN 100502097 C CN100502097 C CN 100502097C
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- lithium
- binder polymer
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Images
Classifications
-
- 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
-
- 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)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
- Cell Separators (AREA)
Abstract
Disclosed is an organic/inorganic composite porous film comprising: (a) a porous substrate having pores; and (b) an active layer formed by coating a surface of the substrate or a part of the pores in the substrate with a mixture of inorganic particles and a binder polymer, wherein the inorganic particles in the active layer are interconnected among themselves and are fixed by the binder polymer, and interstitial volumes among the inorganic particles form a pore structure. A method for manufacturing the same film and an electrochemical device including the same film are also disclosed. An electrochemical device comprising the organic/inorganic composite porous film shows improved safety and quality, simultaneously.
Description
Technical field
The present invention relates to novel organic, compare with conventional polyolefin-based separator, it shows excellent thermal safety and lithium-ion-conducting and high electrolyte degree of swelling, also relate to the electrochemical appliance that comprises it, this device can be guaranteed fail safe and have the quality of raising.
Background technology
Recently, the interest to the store energy technology increases day by day.Battery generally has been used as the energy in mobile phone, small-sized Portable gamma camera, notebook computer, PC and the electric motor car, causes broad research and exploitation to them.About this point, electrochemical appliance is the theme that makes us very much interest.Especially the exploitation of rechargeable secondary batteries becomes the focus of concern.
Secondary cell be for charging repeatedly and the chemical cell of discharge cycles by the reversible exchange between chemical energy and the electric energy, and can be divided into Ni-MH secondary cell and lithium secondary battery.Lithium secondary battery comprises secondary lithium metal, secondary lithium battery, secondary lithium polymer battery, secondary lithium-ion polymer battery etc.
Because lithium secondary battery has than high driving voltage and the energy density of conventional batteries (as the Ni-MH battery) of using aqueous solution electrolysis liquid, therefore many manufacturing companies commercial manufacturing they.But most of lithium secondary batteries have different security features, and this depends on several factors.The safety evaluatio of battery and assurance are the important factors that will consider.Therefore, safety standard to battery security catch fire and burning aspect strict restriction is arranged.
In order to prevent the short circuit between positive pole and the negative pole, lithium ion battery that uses and lithium ion polymer battery use polyolefin-based separator at present.But because this polyolefin-based separator has 200 ℃ or lower fusing point, so there are defective in they, and promptly when battery temperature raise because of inside and/or external factor, they can shrink or fusion, cause change in volume.Therefore, there is the very big possibility of short circuit between positive pole that contraction or fusion by barrier film cause and the negative pole, thereby causes contingency, as the battery explosion that causes by discharge.Therefore, must provide a kind of barrier film that at high temperature can not cause thermal contraction.
In order to solve the problems referred to above relevant, carried out the use inorganic material and developed electrolytical multiple trial as conventional barrier film substitute with polyolefin-based separator.This electrolyte can roughly be divided into two classes.The first kind is inorganic particle or the composite solid electrolyte by using the inorganic particle with lithium-ion-conducting mix with polymer substrate to obtain that has lithium-ion-conducting by independent use.Referring to Japanese publication No.2003-022707, [" Solid State Ionics "-vol.158, n.3, p.275, (2003)], [" Journal of Power Sources "-vol.112, n.1, p.209, (2002)], [" Electrochimica Acta "-vol.48, n.14, p.2003, (2003)] etc.But known this composite electrolyte is worthless, because compare with liquid electrolyte, they have low ionic conductivity, and when they are mixed, the interface resistance height between inorganic material and the polymer.
Second class is by making the inorganic particle with lithium-ion-conducting mix or not mix the electrolyte that obtains with the gel polymer electrolyte that is formed by polymer and liquid electrolyte.In this case, introduce the inorganic material littler, so it only has the supplementary functions of assisting the lithium-ion-conducting that is produced by liquid electrolyte than the amount of polymer and liquid electrolyte.
As mentioned above, use the electrolyte of the prior art of inorganic particle to have following concomitant problem.At first, when not using liquid electrolyte, between the inorganic particle and the interface resistance between inorganic particle and the polymer excessively increase, cause quality to descend.Secondly, when introducing excessive inorganic material, can not easily handle above-mentioned electrolyte owing to its fragility.Therefore, use this electrolyte to be difficult to assembled battery.Especially, it all is the composite electrolyte that contains inorganic material of the free-standing form of film of exploitation that the great majority that carry out are up to now made great efforts.But, because the mechanical performance of the difference of film such as high fragility and be difficult in fact and use this electrolyte in the battery.Even the content that reduces inorganic particle is with the raising mechanical performance, but mixing inorganic particle and liquid electrolyte also can cause the obvious decline of mechanical performance owing to liquid electrolyte, cause the failure of battery number of assembling steps subsequently.When injecting liquid electrolyte in battery assembling back, the dispersion of electrolyte in battery needs the oversize time, and owing to the high-load of polymer in the organic/inorganic composite film causes the actual wetability of electrolyte poor.In addition, add the problem that inorganic particle can cause that lithium-ion-conducting obviously reduces in order to improve fail safe.In addition owing to do not have the hole in the electrolyte, or if any, also just have size for several dusts (
) the hole and low porosity, so electrolyte can not be used as barrier film fully.
In addition, United States Patent (USP) 6432586 discloses a kind of laminated film, and it comprises the polyolefin-based separator that scribbles silicon dioxide etc., so that improve the fragility of mechanical performance such as organic/inorganic composite electrolyte.But because this film still uses polyolefin-based separator, so still there are defective in they, promptly can not obtain the obvious raising of fail safe, comprise at high temperature preventing thermal contraction.
Description of drawings
When in conjunction with the accompanying drawings, above-mentioned and other purposes can be clearer from following detailed of the present invention, feature and advantage, wherein:
Fig. 1 is for showing the schematic diagram of organic of the present invention;
Fig. 2 is for showing the organic (PVdF-CTFE/BaTiO of embodiment 1
3) scanning electron microscopy (SEM) photo;
Fig. 3 is for showing the SEM photo of the polyolefin-based separator of using in the comparative example 1 (PP/PE/PP);
Fig. 4 is for showing the conventional film (Al that does not use binder polymer of prior art
2O
3-SiO
2/ PET nonwoven fabrics) SEM photo;
Fig. 5 is for showing the organic (PVdF-CTFE/BaTiO of embodiment 1
3) and the PP/PE/PP barrier film of use at present and the organic (PVdF-HFP/BaTiO of comparative example 3
3) remain on 150 ℃ of relatively photos after following 1 hour, wherein organic (PVdF-HFP/BaTiO of comparative example 3 at sample separately
3) have an inorganic material layer that on the PP/PE/PP barrier film, forms;
Fig. 6 is the lithium secondary battery and the organic (PVdF-CTFE/BaTiO that comprises embodiment 1 that shows the PP/PE/PP barrier film of the present use that comprises comparative example 1
3) overcharge test result's the photo and the figure of lithium secondary battery;
Fig. 7 is the lithium secondary battery and the organic (PVdF-CTFE/BaTiO that comprises embodiment 1 that shows the PP/PE/PP barrier film of the present use that comprises comparative example 1
3) the figure of high rate discharge characteristic (C-speed) of lithium secondary battery; With
Fig. 8 is the lithium secondary battery and the organic (PVdF-CTFE/BaTiO that comprises embodiment 1 that shows the PP/PE/PP barrier film of the present use that comprises comparative example 1
3) the figure of cycle characteristics of lithium secondary battery.
Summary of the invention
The technical problem to be solved in the present invention
We find, can improve the thermal safety of the difference of conventional polyolefin-based separator by the organic of using (1) heat-resisting porous substrate, (2) inorganic particle and (3) binder polymer to form.In addition, we find, because organic has and not only is present in the porous substrate but also is present in by the pore structure that is coated in the active layer that inorganic particle on the porous substrate and binder polymer form, therefore it can provide the spatial volume that the liquid electrolyte of increase can be infiltrated, and causes the raising of lithium-ion-conducting and electrolyte degree of swelling.Therefore, organic can improve and uses its quality and fail safe as the electrochemical appliance of barrier film.
Therefore, the purpose of this invention is to provide the quality that can improve electrochemical appliance and fail safe organic, make its method and comprise its electrochemical appliance.
Technical scheme
According to an aspect of the present invention, provide the organic film, it comprises: the porous substrate that (a) has the hole; (b) active layer that forms by a part with the mixture coated substrate surface of inorganic particle and binder polymer or the hole in the base material, wherein between the inorganic particle in the active layer by binder polymer interconnection and fixing, the gap between the inorganic particle forms pore structure.The electrochemical appliance that comprises described organic (preferred lithium secondary batteries) also is provided.
According to another aspect of the present invention, provide the method for making organic, it comprises step: (a) binder polymer is dissolved in and forms polymer solution in the solvent; (b) in the polymer solution that obtains by step (a), add inorganic particle and mix them; (c) applying inorganic particle and the mixture of binder polymer, the drying then that obtains by step (b) on the surface of base material or on the part in the hole in base material with hole.
Hereinafter, will illustrate in greater detail the present invention.
The present invention is characterised in that the organic that provides novel, it enough prevents electrically contacting and ion is therefrom passed through between anode and the negative pole as barrier film, improve the thermal safety of the difference relevant, and show excellent lithium-ion-conducting and high electrolyte degree of swelling with conventional polyolefin-based separator.
Mixture by coating inorganic particle and binder polymer on the surface of porous substrate (preferred fusing point is 200 ℃ or higher resistant substrates) obtains organic.The even pore structure that is present in the hole in the base material self and is formed by the gap between the inorganic particle in active layer allows the organic film as barrier film.In addition, can be by the liquid electrolyte swelling time if use by the polymer of gelation as the binder polymer composition, then organic also can be used as electrolyte.
The concrete feature of organic is as follows.
(1) do not have pore structure by the conventional solid electrolyte that uses inorganic particle and binder polymer to form, or if any, also just having pore size is the irregular pore structure of several dusts.Therefore, the partition that they can not can pass through as lithium ion fully causes battery quality to descend.By contrast, organic according to the present invention all has uniform pore structure in porous substrate and active layer, and as illustrated in fig. 1 and 2, and pore structure allows lithium ion therefrom to pass through reposefully.Therefore, can introduce a large amount of electrolyte, thereby can obtain high electrolyte degree of swelling, cause battery quality to improve by pore structure.
(2) conventional barrier film or polymer dielectric form the shape of free-standing film, assemble with electrode then.By contrast, organic according to the present invention forms by directly applying on porose porous substrate surface, thereby the hole on porous substrate and the active layer can be fixed to one another, thereby provide firm physical bond between active layer and porous substrate.Therefore, can improve problem relevant such as fragility with mechanical performance.In addition, the interfacial adhesion power of this increase can reduce interface resistance between porous substrate and the active coating.In fact, organic according to the present invention comprises the organic/inorganic composite porous layer that organically is bonded on the porous substrate.In addition, active layer can not influence the pore structure that exists in the porous substrate, thus but retaining hole structure.In addition, active layer itself has the even pore structure (seeing Fig. 1 and 2) that is formed by inorganic particle.Because above-mentioned pore structure is full of the liquid electrolyte that is injected into subsequently, thus between the inorganic particle or the interface resistance that produces between inorganic particle and the binder polymer be greatly diminished.
(3) according to organic of the present invention because resistant substrates and inorganic particle show the thermal safety of raising.
In other words, although conventional polyolefin-based separator at high temperature causes thermal contraction, because they have 120-140 ℃ fusing point, but organic is that 200 ℃ or higher porous substrate and the thermal endurance of inorganic particle can not cause thermal contraction because of fusing point.Therefore, use above-mentioned organic to reduce, even under extreme conditions, as high temperature, overcharge etc. as the fail safe that the electrochemical appliance of barrier film can not cause being caused by the internal short-circuit between positive pole and the negative pole.Therefore, this electrochemical appliance is compared with conventional batteries and is had the excellent security characteristic.
(4) by having aluminium oxide (Al
2O
3) and silicon dioxide (SiO
2) the nonwoven web made of the PET of mixed layer be known for a person skilled in the art.But this laminated film does not use the binder polymer inorganic particle that supports and interconnect.In addition, to the particle diameter of inorganic particle and the incorrect understanding of pore structure of uniformity and inorganic particle formation.Therefore, according to this laminated film existing problems of prior art, promptly they can cause battery quality decline (see figure 4).More particularly, when inorganic particle had than major diameter, the thickness of the organic/inorganic coating that obtains under same solid content increased, and caused mechanical performance to descend.In addition, in this case, in the cell charging cyclic process, there is great internal short-circuit possibility owing to excessive pore size.In addition, owing to be not used in the adhesive of inorganic particle on the fixing substrate, the final film that forms descends in mechanical properties, and is difficult to be applied in the actual battery assembling process.For example, may not can be adapted to lamination process according to the laminated film of prior art.By contrast, we recognize that porosity and the pore size of controlling organic of the present invention are factors that influences battery quality.Therefore, we change and have optimized the mixing ratio of particle diameter or the inorganic particle and the binder polymer of inorganic particle.In addition, according to the present invention, the binder polymer that uses in the active layer can be used as adhesive be used for interconnecting and stably fix they self between, between inorganic particle and the heat-resisting porous substrate surface and the inorganic particle between inorganic particle and a part of hole of base material, thereby the mechanical performance that has prevented the organic of final formation reduces.
(5) when the inorganic particle that uses in the active layer of organic film has high dielectric constant and/or lithium-ion-conducting, inorganic particle can improve lithium-ion-conducting and thermal endurance, thereby helps battery quality to improve.
(6) when the binder polymer that uses in the organic film be when showing high electrolyte degree of swelling the sort of, the electrolyte that injects in battery assembling back can penetrate in the polymer, and the polymer that comprises infiltration electrolyte wherein that obtains has the ability of conductive electrolyte ion.Therefore, compare with conventional organic/inorganic composite electrolyte, organic of the present invention can improve the quality of electrochemical appliance.In addition, organic provides advantage, promptly compares with conventional hydrophobic polyolefin base barrier film, is improved with the wetability of battery electrolyte, and allows to use battery polarity electrolyte.
(7) last, if binder polymer is the sort of of energy gelation by the electrolyte swelling time, then polymer reacts and gelation with the electrolyte that injects subsequently, thus formation gel-type organic/inorganic composite electrolyte.Compare with conventional gel-type electrolyte, this electrolyte is easier to produce, and shows excellent ionic conductivity and high electrolyte degree of swelling, thereby helps to improve battery quality.
In organic of the present invention, the base material of the mixture that scribbles inorganic particle and binder polymer there is not particular restriction, as long as it is the porous substrate with hole.But preferably using fusing point is 200 ℃ or higher heat-resisting porous substrate.This heat-resisting porous substrate can improve organic externally and/or the thermal safety of internal heat under impacting.
The non-limitative example of spendable porous substrate comprises PETG, polybutylene terephthalate (PBT), polyester, polyacetals, polyamide, Merlon, polyimides, polyether-ether-ketone, polyether sulfone, polyphenylene oxide, polyphenylene sulfidro, polyethylene naphthalenedicarboxylate (polyethylene naphthalene) or their mixture.But, can use other heat-resistant engineering plastic, there is not particular restriction.
Although the thickness to porous substrate does not have particular restriction, porous substrate preferably has the thickness between the 1 and 100 μ m, more preferably between the 5 and 50 μ m.When porous substrate has thickness less than 1 μ m, be difficult to keep mechanical performance.When porous substrate had thickness greater than 100 μ m, it may play resistive layer.
Although pore size and porosity to porous substrate do not have particular restriction, porous substrate preferably has the porosity between 5% and 95%.Pore size (diameter) is preferably 0.01-50 μ m, more preferably 0.1-20 μ m.When pore size and porosity during respectively less than 0.01 μ m and 5%, porous substrate may play resistive layer.When pore size and porosity during, be difficult to keep mechanical performance respectively greater than 50 μ m and 95%.
Porous substrate can be the form of film or fiber.When porous substrate when being fibrous, it can be the nonwoven web (preferably including long stapled spunbonded type tablet or the molten moulding mixture sheet that blows) that forms the porous tablet.
Spunbond process is carried out continuously by series of steps, and the long fibre that forms by heating and fusion, stretching is provided, and forms tablet by hot-air again.Molten spinning of blowing over the Cheng Jinhang polymer, wherein polymer can form fiber by the spinning head with hundreds of aperture, and provides therefore that to have by diameter be the three-dimensional fiber of the cobweb structure of 10 μ m or littler microfibre interconnection generation.
In organic of the present invention, a kind of component that exists in the active layer that forms on a part of hole on the porous substrate surface or in the porous substrate is the inorganic particle that uses at present in the prior art.Inorganic particle allows to form the gap between them, the physical form when being used to form micropore whereby and keeping as partition.In addition, even, therefore use the organic of inorganic particle to have excellent thermal endurance because the physical property that inorganic particle is characterised in that them can not change under 200 ℃ or higher high temperature yet.
Selection to inorganic particle does not have particular restriction, as long as they are stable on electrochemistry.In other words, the inorganic particle that can use is not in the present invention had particular restriction, if they at the driving voltage of the battery of using it (for example based on Li/Li
+0-5V) oxidation can not take place in the scope and/or reduction gets final product.Especially, the preferred inorganic particle with high as far as possible ionic conductivity that uses is because this inorganic particle can improve the quality of ionic conductivity and electrochemical appliance.In addition, when use had highdensity inorganic particle, there was difficulties in dispersion in they in coating step, and can increase the weight of the battery of wanting manufactured.Therefore, the preferred inorganic particle that uses with alap density.In addition, when use had the inorganic particle of high-k, they can help to increase the interior electrolytic salt of liquid electrolyte such as the extent of dissociation of lithium salts, thereby improved the ionic conductivity of electrolyte.
For those reasons, the preferred use has 5 or above, preferred 10 or inorganic particle, the inorganic particle with lithium conductivity or their mixture of higher high-k.
Have 5 or the concrete non-limitative example of the inorganic particle of higher dielectric constant comprise BaTiO
3, Pb (Zr, Ti) O
3(PZT), Pb
1-xLa
xZr
1-yTiyO
3(PLZT), Pb (Mg
3Nb
2/3) O
3-PbTiO
3(PMN-PT), hafnium oxide (HfO
2), SrTiO
3, SnO
2, CeO
2, MgO, NiO, CaO, ZnO, ZrO
2, Y
2O
3, Al
2O
3, TiO
2Or their mixture.
" inorganic particle with lithium-ion-conducting " used herein is meant and comprises elemental lithium and have the conductive lithium ion and can not store the inorganic particle of the ability of lithium.Inorganic particle with lithium-ion-conducting can conduct and carries lithium ion owing to the defective that exists in their structures, therefore can improve lithium-ion-conducting and help to improve battery quality.This non-limitative example with inorganic particle of lithium-ion-conducting comprises: lithium phosphate (Li
3PO
4), titanium phosphate lithium (Li
xTi
y(PO
4)
3, 0＜x＜2,0＜y＜3), titanium phosphate aluminium lithium (Li
xAl
yTi
z(PO
4)
3, 0＜x＜2,0＜y＜1,0＜z＜3), (LiAlTiP)
xO
yType glass (0＜x＜4,0＜y＜13) is as 14Li
2O-9Al
2O
3-38TiO
2-39P
2O
5, lanthanium titanate lithium (Li
xLa
yTiO
3, 0＜x＜2,0＜y＜3), D2EHDTPA germanium lithium (Li
xGe
yP
zS
w, 0＜x＜4,0＜y＜1,0＜z＜1,0＜w＜5) and as Li
3.25Ge
0.25P
0.75S
4, lithium nitride (Li
xN
y, 0＜x＜4,0＜y＜2) and as Li
3N, SiS
2Type glass (Li
xSi
yS
z, 0＜x＜3,0＜y＜2,0＜z＜4) and as Li
3PO
4-Li
2S-SiS
2, P
2S
5Type glass (Li
xP
yS
z, 0＜x＜3,0＜y＜3,0＜z＜7) and as LiI-Li
2S-P
2S
5Or their mixture.
According to the present invention, use inorganic particle to replace there is not reactivity or have inorganic particle than low-k with high dielectric constant.In addition, the present invention also provides the new purposes of inorganic particle as barrier film.
Never as the above-mentioned inorganic particle of barrier film Pb (Zr, Ti) O for example
3(PZT), Pb
1-xLa
xZr
1-yTi
yO
3(PLZT), Pb (Mg
3Nb
2/3) O
3-PbTiO
3(PMN-PT), hafnium oxide (HfO
2) wait and have 100 or higher high-k.Inorganic particle also has piezoelectricity, thereby when they are stretched or compressed under certain pressure applies, can produce electromotive force between two surfaces because of electric charge forms.Therefore, inorganic particle can prevent two internal short-circuits between the electrode, thereby helps to improve battery security.In addition, when this inorganic particle with high-k is united with the inorganic particle with lithium-ion-conducting, can obtain cooperative effect.
By particle diameter, the content of inorganic particle and the mixing ratio of inorganic particle and binder polymer of control inorganic particle, organic of the present invention can form the hole that pore size is several dusts.Also might control hole footpath size and porosity.
Although the particle diameter to inorganic particle does not have particular restriction, inorganic particle preferably has the particle diameter of 0.001-10 μ m, so that form the film that has uniform thickness and appropriate porosity is provided.When particle diameter during less than 0.001 μ m, inorganic particle has poor dispersiveness, thereby can not easily control the physical property of organic.When particle diameter during greater than 10 μ m, the organic that obtains has the thickness of increase under identical solids content, cause mechanical performance to descend.In addition, this excessive hole may increase repeatedly the possibility that produces internal short-circuit in the charge/discharge cycle.
Total weight in mixture is 100wt%, and the amount of the inorganic particle that exists in the inorganic particle of formation organic film and the mixture of binder polymer is 50-99wt%, is more particularly 60-95wt%.When the content of inorganic particle during less than 50wt%, just there is too a large amount of binder polymers so that the gap that forms between the inorganic particle reduces, therefore reduced pore size and porosity, cause battery quality to descend.When the content of inorganic particle during greater than 99wt%, polymer content is too low so that can not provide enough bonding between inorganic particle, causes the mechanical performance of the final organic that forms to descend.
In organic of the present invention, another composition that exists in the active layer that forms on a part of hole on the porous substrate surface or in the porous substrate is the binder polymer that uses at present in this area.Binder polymer preferably has alap glass transition temperature (T
g), more preferably T
gBetween-200 ℃ and 200 ℃.Has aforesaid low T
gBinder polymer be preferred because they can improve mechanical performance such as the flexibility and the elasticity of the film of final formation.Therefore polymer has prevented that as at the interconnection between they self and the adhesive of fixed inorganic particle stably the mechanical performance of the organic of final formation from reducing.
When binder polymer had ionic conductivity, it also can further improve the quality of electrochemical appliance.But, be not to use binder polymer with ionic conductivity.Therefore, binder polymer preferably has high as far as possible dielectric constant.Because the extent of dissociation of salt in electrolyte depends on the dielectric constant of solvent for use in the electrolyte, the polymer with high dielectric constant can improve the extent of dissociation of salt in the used electrolyte of the present invention.The dielectric constant of binder polymer can be 1.0-100 (measuring) under the frequency of 1kHz, and preferred 10 or higher.
Except above-mentioned functions, the further feature of the binder polymer that uses among the present invention can be when by the liquid electrolyte swelling by gelation, therefore shows high degree of swelling.Therefore, preferably use solubility parameter 15 and 45MPa
1/2Between, more preferably 15 and 25MPa
1/2Between and 30 and 45MPa
1/2Between polymer.Therefore, the hydrophilic polymer with a large amount of polar groups than hydrophobic polymer such as polyolefin more preferably.When binder polymer has less than 15MPa
1/2Or greater than 45MPa
1/2Solubility parameter the time, be difficult to by the conventional liq electrolyte swelling of battery.
The non-limitative example of the binder polymer that can use in the present invention comprises poly-(vinylidene fluoride-co-hexafluoropropylene), poly-(vinylidene fluoride-co-trichloroethylene), polymethyl methacrylate, polyacrylonitrile, polyvinylpyrrolidone, polyvinyl acetate, poly-(ethene-co-vinyl acetate), polyethylene glycol oxide, cellulose acetate, cellulose acetate-butyrate, cellulose-acetate propionate, cyanoethyl Propiram amylopectin (pullulan), the cyanoethyl polyvinyl alcohol, cyanethyl cellulose, cyanoethyl sucrose, Propiram amylopectin (pullulan), carboxymethyl cellulose, acrylonitrile-styrene-butadiene copolymer, polyimides or their mixture.Other material can use or unite use separately, as long as they satisfy above-mentioned feature.
Organic can comprise that also additive except inorganic particle and binder polymer is as all the other components of active layer.
As mentioned above, be coated to the organic that forms on the porous substrate by mixture and have the hole that is included in the porous substrate self, and in base material and in active layer, form pore structure owing to the gap between the inorganic particle that is formed on the base material with inorganic particle and binder polymer.The pore size of organic and porosity depend primarily on the particle diameter of inorganic particle and decide.For example, when using particle diameter to be 1 μ m or lower inorganic particle, therefore the hole of formation also has 1 μ m or lower pore size.Pore structure is full of the electrolyte that injects subsequently, and used for electrolyte is in conducting ion.Therefore, the pore size in hole and porosity are the key factors of the ionic conductivity of control organic.Preferably, pore size and the porosity according to organic of the present invention is respectively 0.01-10 μ m and 5-95%.
Thickness to organic of the present invention does not have particular restriction.Can be according to the battery quality control thickness.According to the present invention, film preferably has the thickness between 1 and 100 μ m, more preferably between 2 and 30 μ m.The control of film thickness can help to improve battery quality.
Inorganic particle in the organic of the present invention there is not particular restriction to the mixing ratio of binder polymer.Can be according to the thickness and the structure control mixing ratio of the film that finally will form.
Organic can with micro-pore septum (for example polyolefin-based separator)-work to be applied on the battery, this characteristic according to the final battery that forms is decided.
Can make organic by conventional method well known by persons skilled in the art.An embodiment making the method for organic of the present invention may further comprise the steps: (a) binder polymer is dissolved in and forms polymer solution in the solvent; (b) in the polymer solution that obtains by step (a), add inorganic particle and mix them; (c) applying inorganic particle and the mixture of binder polymer, the drying then that obtains by step (b) on the surface of base material or on the part in the hole in base material with hole.
Hereinafter, the method for making according to organic of the present invention will be described in detail.
(1) at first, binder polymer is dissolved in polymer solution is provided in the appropriate organic solvent.
Preferred solvent has solubility parameter and the low boiling that is similar to used solubility parameter.This solvent can evenly mix with polymer, and can easily be removed behind coated polymer.The non-limitative example of spendable solvent comprises acetone, oxolane, carrene, chloroform, dimethyl formamide, N-N-methyl-2-2-pyrrolidone N-, cyclohexane, water or their mixture.
(2) then, in the polymer solution that obtains by above-mentioned steps, add inorganic particle and disperse them, the mixture of inorganic particle and binder polymer is provided.
Preferably after being joined binder polymer solution, pulverizes inorganic particle the step of inorganic particle.Pulverizing the required time suitably is 1-20 hour.Pulverize the back particle grain size and be preferably 0.001-10 μ m.Can use conventional breaking method, preferably use the method for ball milling.
Although the composition to the mixture that comprises inorganic particle and binder polymer does not have particular restriction, this composition can help to control thickness, pore size and the porosity of the organic of final formation.
In other words, when inorganic particle (I) increased the weight ratio (I/P) of polymer (P), the porosity of organic of the present invention increased.Therefore, the thickness of organic increases down at same solid content (weight of the weight+binder polymer of inorganic particle).In addition, the hole between pore size and the inorganic particle forms pro rata increases.When the particle diameter (particle diameter) of inorganic particle increased, the clearance distance between the inorganic particle increased, thereby has increased pore size.
(3) mixture with inorganic particle and binder polymer is coated on the heat-resisting porous substrate, and drying obtains organic then.
For the mixture with inorganic particle and binder polymer applies porous substrate, can use any method well known by persons skilled in the art.Can make in all sorts of ways, comprise that dip-coating, die head are coated with, roller coat, comma is coated with or their combination.In addition, in the time will comprising inorganic particle and mixture of polymers and be coated on the porous substrate, can apply any one or two surfaces of porous substrate.
The organic of the present invention that obtains as mentioned above can be used as the barrier film in the electrochemical appliance, preferably is used in the lithium secondary battery.If the binder polymer that uses in the film is the polymer of energy gelation by the liquid electrolyte swelling time, then therefore polymer can be formed gel-type organic/inorganic composite electrolyte by gelation by reacting with the electrolyte that injects after using barrier film assembled battery.
Compare with the gel-type polymer electrolyte of prior art, gel-type organic/inorganic composite electrolyte of the present invention can easily be prepared, and has a big space of full of liquid electrolyte owing to its microcellular structure, thereby show excellent ionic conductivity and high electrolyte degree of swelling, cause battery quality to improve.
In addition, the invention provides electrochemical appliance, comprising: (a) positive pole; (b) negative pole; (c) be inserted in organic of the present invention between positive pole and the negative pole; (d) electrolyte.
This electrochemical appliance comprises any device that electrochemical reaction takes place, and its object lesson comprises various primary cells, secondary cell, fuel cell, solar cell or capacitor.Especially, electrochemical appliance is a lithium secondary battery, comprises lithium metal secondary batteries, lithium rechargeable battery, lighium polymer secondary battery or lithium ion polymer secondary cell.
According to the present invention, the organic that comprises in the electrochemical appliance is as barrier film.If the polymer that uses in the film is the polymer of energy gelation by the liquid electrolyte swelling time, then film also can be used as electrolyte.Except above-mentioned organic, can use for example polyolefin-based separator of micro-pore septum together.
Can make electrochemical appliance by conventional method well known by persons skilled in the art.In an embodiment of the method for making electrochemical appliance, assemble electrochemical appliance by the organic that use is inserted between positive pole and the negative pole, inject electrolyte then.
Can on current collector, apply electrode active material by method known to those skilled in the art and form the electrode that to use with organic of the present invention.Especially, positive electrode active materials can comprise any conventional positive electrode active materials that uses at present in the positive pole of conventional electrochemical appliance.The concrete non-limitative example of positive electrode active materials comprises intercalation materials of li ions, as lithium manganese oxide, lithium and cobalt oxides, lithium nickel oxide, oxide/lithium ferrite or their composite oxides.In addition, negative active core-shell material can comprise any conventional negative active core-shell material that uses at present in the negative pole of conventional electrochemical appliance.The concrete non-limitative example of negative active core-shell material comprises intercalation materials of li ions, as lithium metal, lithium alloy, carbon, petroleum coke, active carbon, graphite or other carbonaceous material.The non-limitative example of cathode current collector comprises by aluminium, nickel or its paper tinsel that is combined to form.The non-limitative example of cathodal current current-collector comprises by copper, gold, nickel, copper alloy or its paper tinsel that is combined to form.
The electrolyte that can use in the present invention comprises by formula A
+B
-The salt of expression, wherein A
+Representative is selected from Li
+, Na
+, K
+With the alkali metal cation in their combination, B
-Representative is selected from PF
6 -, BF
4 -, Cl
-, Br
-, I
-, ClO
4 -, ASF
6 -, CH
3CO
2 -, CF
3SO
3 -, N (CF
3SO
2)
2 -, C (CF
2SO
2)
3 -With the anion in their combination, and the salt that in organic solvent, dissolves or dissociate, wherein organic solvent is selected from propene carbonate (PC), ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), dipropyl carbonate (DPC), dimethyl sulfoxide (DMSO), acetonitrile, dimethoxy-ethane, diethoxyethane, oxolane, N-N-methyl-2-2-pyrrolidone N-(NMP), ethylmethyl carbonate (EMC), gamma-butyrolacton and their mixture.But the electrolyte that can use in the present invention is not limited to above-mentioned example.
More particularly, according to the desired properties of manufacture method and final products, can in the manufacture process of electrochemical appliance, in suitable step, inject electrolyte.In other words, can before the assembling electrochemical appliance or in the final step of assembling electrochemical appliance, inject electrolyte.
Can be used for using organic and not only comprise the conventional method for winding of barrier film and electrode, and comprise the lamination (piling up) and the method for folding of barrier film and electrode to the method on the battery.
When organic of the present invention is applied to laminating method, can improve the thermal safety of battery significantly, because compare with the battery that forms by method for winding, the battery that forms by lamination and method for folding shows more violent barrier film thermal contraction usually.In addition, when using laminating method, there is a kind of like this advantage, promptly utilizes the excellent adhesiveness assembled battery easily of the polymer that exists in the organic of the present invention.In this case, can control adhesiveness according to the content of inorganic particle and the content and the character of polymer.More particularly, increase and during when the glass transition temperature (Tg) of polymer or fusing point (Tm) reduction, between organic and electrode, can obtain higher adhesiveness when the polarity of polymer.
Implement best mode of the present invention
To be described in detail the preferred embodiments of the invention now.It should be understood that the following examples only are illustrative, the present invention is not restricted to this.
[embodiment 1-6]
The preparation of organic and use its to make lithium secondary battery
Embodiment 1
1-1.
Organic (PVdF-CTFE/BaTiO 3 ) preparation
In acetone, add the PVdF-CTFE polymer (polyvinylidene fluoride-chlorotrifluoroethylene) of quantity, and under 50 ℃, dissolved therein about 12 hours or form polymer solution for more time for about 5wt%.Adding in solids content base concentration in the polymer solution that obtains as mentioned above is the BaTiO of 20wt%
3Powder.Then, with BaTiO
3Powder is crushed to about 300nm size, and by using ball grinding method to disperse about 12 hours or the longer time, forms slurry.Then, use dip-coating method will by the slurry that obtains as mentioned above be coated in thickness for the porous PETG base material of about 20 μ m (porosity: 80%), to coating layer thickness be about 2 μ m.After measuring, immerse and the active layer that is coated on the porous PETG base material has the pore size of 0.3 μ m and 55% porosity with porosimeter.
1-2.
The manufacturing of lithium secondary battery
(anodal manufacturing)
The lithium cobalt composite oxide (LiCO that in as the N-N-methyl-2-2-pyrrolidone N-(NMP) of solvent, adds 92wt% as positive electrode active materials
2), 4wt% as the carbon black of conductive agent and the PVDF of 4wt% (polyvinylidene fluoride) as adhesive, form the positive pole slurry.Slurry is coated on the A1 paper tinsel as cathode collector that thickness is 20 μ m, and the dry positive pole that forms.Then, positive pole is rolled (roll press).
(manufacturing of negative pole)
In as the N-N-methyl-2-2-pyrrolidone N-(NMP) of solvent, add the carbon dust as negative active core-shell material, the PVDF as adhesive (polyvinylidene fluoride) of 3wt% and the carbon black of 1wt% of 96wt%, form the negative pole mixed slurry as conductive agent.Slurry is coated on the Cu paper tinsel as anode collector that thickness is 10 μ m, and the dry negative pole that forms.Then, anticathode rolls.
(manufacturing of battery)
The organic that will described in embodiment 1-1, obtain with pile up by positive pole that obtains as mentioned above and negative pole, form assembly.Then, (ethylene carbonate (EC)/ethylmethyl carbonate (EMC)=1:2 (volume ratio) comprises 1M lithium hexafluoro phosphate (LiPF to wherein injecting electrolyte
6)), obtain lithium secondary battery.
Repeat embodiment 1 and obtain lithium secondary battery, replace BaTiO except using PMNPT (niobic acid magnesium lead-lead titanates) powder
3Powder obtains organic (PVdF-CTFE/PMNPT).After measuring, immerse and the active layer that is coated on the porous PETG base material has the pore size of 0.4 μ m and 60% porosity with porosimeter.
Embodiment 3
Repeat embodiment 1 and obtain lithium secondary battery, except using BaTiO
3And Al
2O
3(mixed-powder of weight ratio=30:70) replaces BaTiO
3Powder obtains organic (PVdF-CTFE/BaTiO
3-Al
2O
3).After measuring, immerse and the active layer that is coated on the porous PETG base material has the pore size of 0.2 μ m and 50% porosity with porosimeter.
Embodiment 4
Repeat embodiment 1 and obtain lithium secondary battery, except not using the PVdF-CTFE, but carboxymethyl cellulose (CMC) polymer that will about 2wt% is added to the water, and under 60 ℃, dissolved therein about 12 hours or the longer time forms polymer solution, and use polymer solution to obtain organic (CMC/BaTiO
3).After measuring, immerse and the active layer that is coated on the porous PETG base material has the pore size of 0.4 μ m and 58% porosity with porosimeter.
Embodiment 5
Repeat embodiment 1 and obtain lithium secondary battery, also do not use BaTiO except neither using PVdF-CTFE
3Outside the powder, use PVDF-HFP and titanium phosphate lithium (LiTi
2(PO
4)
3) powder obtains organic (PVdF-HFP/LiTi
2(PO
4)
3), it comprises that thickness is the porous PETG base material (porosity: 80%) that thickness is the active layer of about 2 μ m that scribbles of about 20 μ m.After measuring, immerse and the active layer that is coated on the porous PETG base material has the pore size of 0.4 μ m and 58% porosity with porosimeter.
Embodiment 6
Repeat embodiment 1 and obtain lithium secondary battery, also do not use BaTiO except neither using PVdF-CTFE
3Outside the powder, use PVDF-HFP and BaTiO
3And LiTi
2(PO
4)
3(mixed-powder of weight ratio=50:50) obtains organic (PVdF-HFP/LiTi
2(PO
4)
3-BaTiO
3).After measuring, immerse and the active layer that is coated on the porous PETG base material has the pore size of 0.3 μ m and 53% porosity with porosimeter.
[comparative example 1-3]
Comparative example 1
Repeat embodiment 1 and obtain lithium secondary battery, except using conventional polypropylene, polyethylene/polypropylene (PP/PE/PP) barrier film (see figure 3).Barrier film has 0.01 μ m or lower pore size and about 5% porosity.
Comparative example 2
Repeat embodiment 1 and obtain lithium secondary battery, except operating weight than being the LiTi of 10:90
2(PO
4)
3Obtain organic with PVDF-HFP.After measuring with porosimeter, organic has 0.01 μ m or lower pore size and about 5% porosity.
Comparative example 3
Repeat embodiment 1 and obtain lithium secondary battery, compare BaTiO as porous substrate and operating weight as 10:90 except using the PP/PE/PP barrier film
3Obtain organic with PVDF-HFP.After measuring with porosimeter, organic has 0.01 μ m or lower pore size and about 5% porosity.
The surface analysis of experimental example 1. organic
Carry out following test to analyze the surface of organic/inorganic composite porous material film of the present invention.
The PVdF-CTFE/BaTiO of employed sample for obtaining in this test according to embodiment 1
3In contrast, use the PP/PE/PP barrier film.
When using scanning electron microscopy (SEM) to analyze, show conventional microcellular structure (see figure 3) according to the PP/PE/PP barrier film of comparative example 1.By contrast, organic according to the present invention shows the pore structure that forms and by the porous substrate surface and scribble the pore structure (see figure 2) that a part of hole in the porous substrate of inorganic particle forms in porous substrate self.
The thermal contraction evaluation of experimental example 2. organic
Carry out following test to compare organic and conventional barrier film.
Organic (the PVdF-CTFE/BaTiO that use obtains by using heat-resisting porous substrate according to embodiment 1
3) as sample.Organic (the PVdF-HFP/BaTiO that uses conventional PP/PE/PP barrier film and obtain by using conventional polyolefin-based separator according to comparative example 3
3) in contrast.
After depositing 1 hour under 150 ℃ the high temperature, check the thermal contraction of each test piece.Test piece is providing different results after through 1 hour under 150 ℃.PP/PE/PP barrier film in contrast only stays its external shape owing to high temperature shrinks.Equally, the film that is formed with the inorganic particulate granulosa on the PP/PE/PP barrier film according to comparative example 3 obviously shrinks.This shows that even use heat-resisting inorganic particle, the conventional polyolefin-based separator itself with poor thermal stability can not provide the thermal safety of raising.By contrast, organic according to the present invention shows good result, does not have the thermal contraction (see figure 5).
As can be seen from the above, organic according to the present invention has excellent thermal safety.
Experimental example 3. safety of lithium secondary battery evaluations
Carry out following test comprises each lithium secondary battery of organic of the present invention with evaluation fail safe.
The lithium secondary battery that uses embodiment 1-6 is as sample.In contrast, use be the battery of the PP/PE/PP barrier film used at present according to the use of comparative example 1, according to the use LiTi of comparative example 2
2(PO
4)
3/ PVDF-HFP film (weight ratio=10:90 is in wt%) is formed with BaTiO as the battery of barrier film with according to the use of comparative example 3 on the PP/PE/PP barrier film of using at present
3The battery of the film of/PVDF-HFP coating (weight ratio=10:90 is in wt%).
3-1. hot case test
Under the high temperature of 150 ℃ and 160 ℃, deposited each battery 1 hour, check then.The result is presented in the following table 1.
After at high temperature depositing, when depositing 1 hour under 160 ℃, each battery of the PP/PE/PP barrier film that the use of comparative example 1 and comparative example 3 is used at present all sets off an explosion.This shows that when at high temperature depositing, polyolefin-based separator causes strong thermal contraction, fusion and breaks, and causes the internal short-circuit between two electrodes of battery (being positive pole and negative pole).By contrast, the lithium secondary battery that comprises organic of the present invention shows and can prevent the safe condition that catches fire and burn, even (see Table 1) under 160 ℃ high temperature.
Therefore, can find out, comprise that the lithium secondary battery of organic of the present invention has excellent thermal safety.
[table 1]
3-2. overcharge test
Under the condition of 6V/1A and 10V/1A, each battery is charged, check then.The result is presented in the following table 2.
Behind the battery of the PP/PE/PP barrier film that comprises present application of checking comparative example 1 and comparative example 3, their (see figure 6)s of exploding.This shows that polyolefin-based separator causes interelectrode short circuit owing to overcharging of battery shunk, and causes battery security to reduce.By contrast, each lithium secondary battery that comprises organic of the present invention all shows excellent security (see Table 2 and Fig. 6) under the condition of overcharging.
[table 2]
The quality evaluation of experimental example 4. lithium secondary batteries
Carry out following test and comprise the high rate discharge characteristic and the cycle characteristics of each lithium secondary battery of organic of the present invention with evaluation.
4-1.C-the evaluation of speed characteristic
The lithium secondary battery that uses embodiment 1-6 is as sample.In contrast, use be the battery of the PP/PE/PP barrier film used at present according to the use of comparative example 1, according to the use LiTi of comparative example 2
2(PO
4)
3/ PVDF-HFP film (weight ratio=10:90 is in wt%) is formed with BaTiO as the battery of barrier film with according to the use of comparative example 3 on the PP/PE/PP barrier film of using at present
3The battery of the film of/PVDF-HFP coating (weight ratio=10:90 is in wt%).
Under the discharge rate of 0.5C, 1C and 2C, be that each battery of 760mAh circulates to capacity.Following table 3 has shown the discharge capacity of each battery, and capacity is represented based on the C-speed characteristic.
After testing; compare as the battery of barrier film with conventional polyolefin-based separator with using organic, use the organic that the ratio (with wt%) that comprises in 10:90 contains the mixture of the inorganic particle of high-k inorganic particle or band lithium-ion-conducting and binder polymer to reveal obvious capacity with discharge rate descend (seeing Table 3) separately as the battery table of the comparative example 2 of barrier film and 3 by obtaining according to embodiment above according to the present invention.This shows, and this low amount of the inorganic particle of polymer phase ratio can reduce pore size and porosity in the pore structure that is formed by the gap between the inorganic particle, causes battery quality decline.
By contrast, comprise according to the lithium secondary battery of organic of the present invention and show the C-speed characteristic that to compare with the battery that uses conventional polyolefin-based separator (see Table 3 and Fig. 7) under the discharge rate of 2C being no more than.
[table 3]
4-2. cycle characteristics evaluation
Use the use organic (PVdF-CTFE/BaTiO of embodiment 1
3) lithium secondary battery and the lithium secondary battery of the PP/PE/PP barrier film used at present according to the use of comparative example 1.Under 23 ℃ temperature, the electric current with 0.5C under the voltage of 4.2-3V charges to each battery.Then, measure the initial capacity of each battery, and each battery is carried out charge/discharge cycle 300 times.
After testing, use organic of the present invention to show 80% or higher efficient, even after 300 circulations as the lithium secondary battery of barrier film.In other words, lithium secondary battery of the present invention shows the cycle characteristics (see figure 8) that can compare with the battery that uses conventional polyolefin-based separator.Therefore, can find out, comprise that the electrochemical appliance of organic of the present invention shows long useful life.
Industrial applicibility
As can be seen from the above, organic of the present invention is by the problem of the thermal safety difference using heat-resisting porous substrate to solve to exist in conventional polyolefin-based separator.In addition, organic of the present invention has in porous substrate self and the pore structure that forms in the active layer that is formed on by use inorganic particle and binder polymer on the base material, thereby increased the space that is full of electrolyte, caused the raising of electrolyte degree of swelling and lithium-ion-conducting.Organic of the present invention helps to improve uses its thermal safety and quality as the lithium secondary battery of barrier film.
Although described the present invention in conjunction with being considered to the most practical at present with embodiment preferred, it should be understood that the present invention is not restricted to disclosed embodiment and figure.By contrast, be intended to cover the interior various improvement and the variation of spirit and scope of accessory claim.
Claims (17)
1. organic, it comprises:
(a) has the porous substrate in hole; With
(b) active layer that forms by a part with the mixture coated substrate surface of inorganic particle and binder polymer or the hole in the base material,
Wherein between the inorganic particle in the active layer by binder polymer interconnection and fixing, and the gap between the inorganic particle forms pore structure,
Described inorganic particle has the particle diameter between 0.001 μ m and 10 μ m, and is 100wt% in the mixture of inorganic particle and binder polymer, and the content of inorganic particle in described mixture is 50-99wt%.
2. according to the film of claim 1, wherein inorganic particle be selected from following at least a: (a) dielectric constant is 5 or higher inorganic particle; (b) has the inorganic particle of lithium-ion-conducting.
3. according to the film of claim 2, its medium dielectric constant microwave medium be 5 or higher inorganic particle be BaTiO
3, Pb (Zr, Ti) O
3, Pb
1-xLa
xZr
1-yTi
yO
3, Pb (Mg
3Nb
2/3) O
3-PbTiO
3, HfO
2, SrTiO
3, SnO
2, CeO
2, MgO, NiO, CaO, ZnO, ZrO
2, Y
2O
3, Al
2O
3Or TiO
2
4. according to the film of claim 2, the inorganic particle that wherein has lithium-ion-conducting be selected from following at least a:
Li
3PO
4；
Titanium phosphate lithium Li
xTi
y(PO
4)
3, 0＜x＜2,0＜y＜3 wherein;
Titanium phosphate aluminium lithium Li
xAl
yTi
z(PO
4)
3, 0＜x＜2,0＜y＜1,0＜z＜3 wherein;
(LiAlTiP)
xO
yType glass, wherein 0＜x＜4,0＜y＜13;
Lanthanium titanate lithium Li
xLa
yTiO
3, 0＜x＜2,0＜y＜3 wherein;
D2EHDTPA germanium lithium Li
xGe
yP
zS
w, 0＜x＜4,0＜y＜1,0＜z＜1,0＜w＜5 wherein;
Lithium nitride Li
xN
y, 0＜x＜4,0＜y＜2 wherein;
SiS
2Type glass Li
xSi
yS
z, 0＜x＜3,0＜y＜2,0＜z＜4 wherein; With
P
2S
5Type glass Li
xP
yS
z, 0＜x＜3,0＜y＜3,0＜z＜7 wherein.
5. according to the film of claim 1, wherein binder polymer has the glass transition temperature between-200 ℃ and 200 ℃.
6. according to the film of claim 1, wherein binder polymer has 15 and 45MPa
1/2Between solubility parameter.
7. according to the film of claim 1, wherein binder polymer be selected from following at least a: poly-(vinylidene fluoride-altogether-hexafluoropropylene), poly-(vinylidene fluoride-altogether-trichloroethylene), polymethyl methacrylate, polyacrylonitrile, polyvinylpyrrolidone, polyvinyl acetate, poly-(ethylene-co-vinyl acetate), polyethylene glycol oxide, cellulose acetate, cellulose acetate-butyrate, cellulose-acetate propionate, cyanoethyl Propiram amylopectin, the cyanoethyl polyvinyl alcohol, cyanethyl cellulose, cyanoethyl sucrose, the Propiram amylopectin, carboxymethyl cellulose, acrylonitrile-styrene-butadiene copolymer and polyimides.
8. according to the film of claim 1, the porous substrate that wherein has the hole shows 200 ℃ or higher fusing point.
9. film according to Claim 8, wherein fusing point be 200 ℃ or higher porous substrate be selected from following at least a: PETG, polybutylene terephthalate (PBT), polyester, polyacetals, polyamide, Merlon, polyimides, polyether-ether-ketone, polyether sulfone, polyphenylene oxide, polyphenylene sulfide and polyethylene naphthalenedicarboxylate.
10. according to the film of claim 1, wherein porous substrate has the pore size between 0.01 μ m and 50 μ m, and organic has the pore size between 0.01 μ m and 10 μ m.
11. according to the film of claim 1, it has the porosity between 5% and 95%.
12. according to the film of claim 1, it has the thickness between 1 and 100 μ m.
13. electrochemical appliance comprises:
(a) positive pole;
(b) negative pole;
(c) be inserted between positive pole and the negative pole as each described organic among the claim 1-12; With
(d) electrolyte.
14. according to the electrochemical appliance of claim 13, it is a lithium secondary battery.
15. according to the electrochemical appliance of claim 13, it also comprises micro-pore septum.
16. according to the electrochemical appliance of claim 15, wherein micro-pore septum is a polyolefin-based separator.
17. make the method for organic as claimed in claim 1, it may further comprise the steps:
(a) binder polymer is dissolved in forms polymer solution in the solvent;
(b) in the polymer solution that obtains by step (a), add particle diameter between 0.001 μ m and 10 μ m inorganic particle and mix them, wherein the mixture in inorganic particle and binder polymer is 100wt%, and the content of inorganic particle in described mixture is 50-99wt%; With
(c) applying inorganic particle and the mixture of binder polymer, the drying then that obtains by step (b) on the surface of base material or on the part in the hole in base material with hole.
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| KR1020040052638A KR100749301B1 (en) | 2004-07-07 | 2004-07-07 | New organic/inorganic composite porous film and electrochemical device prepared thereby |
| KR1020040070097 | 2004-09-02 |
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-
2004
- 2004-07-07 KR KR1020040052638A patent/KR100749301B1/en active IP Right Grant
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2005
- 2005-07-05 CN CNB2005800203221A patent/CN100502097C/en active Active
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103153869A (en) * | 2010-07-23 | 2013-06-12 | 洛林大学 | Wall for separating electrolytes for the selective transfer of cations through the wall, and associated manufacturing method and transfer method |
| CN103579633A (en) * | 2012-08-09 | 2014-02-12 | 清华大学 | Anode and lithium ion battery |
| CN103579633B (en) * | 2012-08-09 | 2016-02-17 | 清华大学 | Positive pole and lithium ion battery |
Also Published As
| Publication number | Publication date |
|---|---|
| KR100749301B1 (en) | 2007-08-14 |
| KR20060003665A (en) | 2006-01-11 |
| CN1969407A (en) | 2007-05-23 |
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