CN1439666A - Heat activated microporous membrane and its application in battery - Google Patents
Heat activated microporous membrane and its application in battery Download PDFInfo
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- CN1439666A CN1439666A CN02158965A CN02158965A CN1439666A CN 1439666 A CN1439666 A CN 1439666A CN 02158965 A CN02158965 A CN 02158965A CN 02158965 A CN02158965 A CN 02158965A CN 1439666 A CN1439666 A CN 1439666A
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Abstract
A novel microporous membrane comprising a hot-melt adhesive and an engineering plastics, also selectively comprising a tackifier and a filler, The present invention stil discloses the methods of preparing such microporous membrane and the uses of the microporous membrane in, e.g., batteries, super capacitors, fuel cells, sensors, electrochromic devices or the like.
Description
The right of priority of present patent application is based on two pieces of U.S. Patent applications, and its number of patent application is 10/034,388 and 10/034,494.
The field of the invention
The present invention relates to the production method of a kind of microporous membrane and this microporous membrane.More particularly, the present invention relates to the application of this microporous membrane in battery.Under particular case of the present invention, microporous membrane just is meant the barrier film that is used for battery.
Background of invention
The locomotive that is driven by electric energy for example car, motor bus and truck does not discharge any waste gas in atmosphere, therefore can not pollute environment.The energy that is used for driving this electriclocomotive is a group storage battery.Except battery itself, this secondary battery also comprises the charger that can directly charge with common alternating-current power supply simultaneously.Yet the mileage that present this electriclocomotive can travel after charging is also very limited.Its reason is that not high and its cycle life of the energy density of battery falls short of.Thereby caused the electriclocomotive can not widespread use.In addition, the fast development of radio communication and market is to mobility and high-octane demand, and the transformation and the innovation of battery technology also proposed urgent requirement.
Lithium ion battery has been used to a lot of fields very widely.This is because compare with other rechargeable cell, and its energy density is the highest, and cycle life is the longest and do not have " memory " defective.The early 1990s in last century, release liquid lithium ion battery " LLB " product by the Sony corporation of Japan first hand.In the past during the last ten years, global liquid lithium ion battery market has had considerablely and has developed.Played for the portable electronics power supply liquid lithium ion battery first of the market share of crouching that jumped since in 1997.
The liquid lithium ion battery main products is to adopt the coiling configuration, and wherein battery diaphragm is added between positive pole and the negative plate.The battery diaphragm that is used for liquid lithium ion battery is a kind of micropore shaped polymer film, and this polymkeric substance belongs to the hydrophobic polyolefin class, for example polyethylene (PE), polypropylene (PP), or by three layers of polypropylene, polyethylene/polypropylene (PP/PE/PP) be composited (United States Patent (USP) 4,620,956; 5,667,911; 5,691,077).This three stratiforms battery diaphragm is to be produced by U.S. Celgard company, and it is widely used for producing liquid lithium ion battery for many years.
By the liquid electrolyte of the liquid lithium ion battery that replaced by solid polymer electrolyte or gelatinous polymer ionogen, a kind of battery " PLB " of polymer Li-ion that cries is succeeded in developing.And be applied on the portable electronics.The United States Patent (USP) 5,418,091 that people such as Gozdz delivered in May 23 nineteen ninety-five and in the United States Patent (USP) of delivering on March 4th, 1,997 5,607,485, told about a kind of plastic battery.This battery is to form by being placed on battery diaphragm between the positive and negative polarities and then being rolled into one earlier.This battery diaphragm is made up of polymkeric substance and softening agent, and this barrier film itself is not porose.The production process of battery is mainly as follows, and at first process roller-compaction under high temperature and certain pressure extracts softening agent with a kind of volatile organic solvent then.After softening agent was walked by solvent extraction, battery diaphragm and electrode just became porous naturally.Just because of the solvent-extracted step of this arts demand, thereby it might cause environmental pollution, has also increased the production cost of battery simultaneously.In addition, this technology also has special requirement for the current collector material of electrode.Be widely used in the aluminium foil and the Copper Foil of liquid lithium ion battery, they all can not use.And the electrode current collecting body material that this polymer Li-ion battery can adopt must be aluminium net and copper mesh.Therefore the battery cost is enhanced naturally.
Introduced another kind of solid polymer dielectric film in two pieces of United States Patent (USP)s 5,603,982 and 5,609,974 that Sun delivered on February 18th, 1997 and on March 11st, 1997.This solid polymer dielectric film is at first three kinds of polymer monomers to be mixed with lithium salts and organic solvent, makes by polymerization on the throne then.When the battery that assembles and battery case are done last Vacuum Package,, this gelatinous polymer film makes battery on the electrode slice thereby can tightly adhering to.
Yet the lithium salts of patent that is used for Sun is very sensitive to moisture.Therefore the battery production process must carried out under the exsiccant condition very much.For example in the loft drier that is full of nitrogen or argon gas or in kiln, carry out.In fact, do the production cost that nature has just increased battery like this.
In order to reduce cost, the jelly glue polymer battery technology is improved.The technology of this improved is to utilize the electrode slice identical with liquid lithium ion battery.That is to say that positive and negative electrode material separate application is on aluminium foil and Copper Foil.Simultaneously need under drying conditions, not form battery yet.SANYO GS company has developed the jelly glue polymer battery technology that a kind of improved.This production technique adopts electrode slice, barrier film and the liquid electrolyte identical with liquid lithium ion battery.Different is to add a little polymer monomer among liquid electrolyte.This monomer forms gelatin polymer at last after the polymerization in battery case.Though formed gelatin polymer can bond on the electrode, its viscosity is very low so that be easy to separate with electrode slice.Thereby in battery used, the contact interface between battery diaphragm and the electrode was easy to degenerate.
People such as Pendalwar have described another kind of gel polymer lithium ion battery technology in the United States Patent (USP) of delivering on February 10th, 1,998 5,716,421.This technology is used the liquid lithium ion battery electrode slice and the liquid electrolyte of standard.Different is replaces the membranous porous polyolefin barrier film of Celgard that resembles commonly used with the multi-layer coated battery diaphragm of a kind of process.And this multi-layer coated barrier film is to produce by coating one layer of polymeric at the tow sides of porous polyolefin membrane.Because when coating, polymkeric substance is easy to penetrate membranous micropore and this hole is blocked.Thereby this multi-layer coated porosity of protocnemes that makes reduces.So, so just cause the high electric current charge-discharge performance of battery to reduce.In addition, not this barrier film and electrode bonding not strong, so the quality of battery changes easily.Especially resemble the battery that can be used for electriclocomotive for large size, situation can be more serious.
Summary of the invention
The invention relates to a kind of microporous membrane.This microporous membrane mainly by (a) hot melt adhesive and (b) engineering plastic materials form.Also can selectively add (c) tackifier, or (d) stopping composition.
Say that from another point of view microporous membrane of the present invention is made (a) with hot melt adhesive by following method, engineering plastic materials and the alternative tackifier that add are dissolved among the organic solvent; Optionally add stopping composition then, add pore former again, obtain uniform slip after the stirring, (b) this slip is applied on the carrier back film forming, (c) vapor away solvent, obtain microporous membrane after (d) washing this film with water.The microporous membrane that makes in this way can be used to produce battery.Particularly it can be used as the barrier film of lithium ion battery.
The file content of being quoted from the patent of being quoted and the content of document and these patents and the document is all integrated with among the present patent application in the allowed band of maximum.
Description of drawings
Fig. 1 is when with different current discharge, cell voltage and the percentile relation of discharge total volume.These 11 square centimeters of batteries are with No. 2 specimen preparations of the present invention.
Total loading capacity percentage when Fig. 2 represents that three batteries discharge under different strength of current relatively.One of them battery uses No. 2 samples of the present invention (circle), and another is with No. 18 samples (square), the 3rd commercial Celgard 2300 battery diaphragms of usefulness (triangle).
Detailed Description Of The Invention
" engineering plastics " at this indication include but are not limited to: following synthesising thermoplastic copolymer: condensation polymer, polyolefin, and such as United States Patent (USP) 4,247, cited blend in 498. Engineering plastics also comprise unanimously all thermoplastic polymers repeatably also of physical property. These polymer preferably are selected from such as polyimides, poly-(acid amides-acid imide), poly-(ether-acid imide), polysulfones, polyether sulfone, polyarylsufone, polyether-ketone, polyether-ether-ketone, polyphenylene sulfide, polyacrylate, and the polyamide of modification. Here the polyamide of the modification of indication refers to through chemical modification, fill, or with other polyblend so that its physical property obtain changing, such as can film forming or can be compatible with PUR etc. At this, engineering plastics also comprise poly-terephthalic acids dibutyl ester simultaneously, polystyrene, poly-(styrene-maleic anhydride), polychlorostyrene PVF, polysulfones, Merlon, with poly-(styrene-methyl methacrylate), under particular case of the present invention, fiberglass reinforced plastics also can be used as engineering plastics.
" PUR " includes but are not limited to: gather (ethene-vinylacetate), and poly-(ethene-alkyl acrylate). For the former, the weight content of vinylacetate is between 25-75%, and the vinyl acetic acid ester content that is more suitable for is 40-70%, and optimal vinyl acetic acid ester content is 40-50%. For the latter, the weight content of alkyl acrylate is between 10-30%. Simultaneously, alkyl refers to that it is comprised of one to five carbon. PUR is also included within United States Patent (USP) 4,487, all cited PURs in 891.
Be suitable for its weight content of PUR of the present invention between 2-50%, the PUR content that is more suitable for is between 5-30%, and optimal PUR content is 10-15%.
What hot melt adhesive can preferentially be selected is poly-(ethene-vinylacetate) and poly-(ethene-alkyl acrylate).Wherein, the latter's alkyl is made up of one to five carbon.And for the former, its vinylacetate weight content is between 25-90%, and in other words, the weight content of ethene is 10-75%.[0019] close in its weight content of engineering plastics of the present invention between 20-90%, the engineering plastics content that is more suitable for is 40-70%, and optimal engineering plastics content is 50-60%.Engineering plastics preferably are selected from polysulfones, polycarbonate and poly-(vinylbenzene-methyl methacrylate), perhaps their mixture.As for poly-(vinylbenzene-methyl methacrylate), the ratio of vinylbenzene and methyl methacrylate is by 9: 1 to 1: 1, and optimal is 5: 1 to 1: 1.
Be suitable for microporous membrane of the present invention and can contain tackifier.Its weight content is 0-50%, and the tackifier levels that is more suitable for is 2-30%, and optimal tackifier levels is between 5-10%.These tackifier preferably are selected from following polymers: hydrocarbon resin for example Escorez 2000 series (through the virtue modified aliphatic hydrocarbon resin, produce by Exxon-Mobil chemical company), Escorez 5000 series (by the hydrogenate hydrocarbon resinoid of Exxon-Mobil chemical company production), with poly-(biasfluoroethylene-hexafluoropropylene) " PVdF-HFP ", and above three's mixture.And among the PVdF-HFP, the weight content of R 1216 is 5-12%.
Microporous membrane of the present invention can contain the composition of powdery stopping composition.Its weight accounts for the 0-50% of whole microporous membrane, and its content of the stopping composition that is more suitable for is 5-30%, and optimal stopping composition content is 15-25%.This stopping composition can be selected from following material, such as fumed silica, and aluminum oxide, titanium oxide, molecular sieve, lime carbonate, Calucium Silicate powder, glass, stupalith, tetrafluoroethylene, and by the mixture of above combination of materials.Above-mentioned materials is fines shape material.This stopping composition average particle size particle size is less than 50 microns, and the stopping composition average particle size particle size that is more suitable for is less than 25 microns, and optimal average particle size particle size is less than 10 microns.
Generally between 25-75%, the porosity of optimal microporous membrane is 45-70% to the porosity of microporous membrane of the present invention.Under suitable temperature and pressure, this microporous membrane is through bonding on the electrode surface of battery behind the overactivation.This temperature is normally between 35-125 ℃, and the temperature that is more suitable for is 45-120 ℃, and optimal temperature is 45-90 ℃.The time that continues heating at a certain temperature is 0.01-250 minute, and be 1-60 minute optimal heat-up time.Required pressure is 0.5-100psi, and optimal pressure is 1-30psi.Having under the common condition that exists of said temperature and pressure, microporous membrane can more effectively be adhered on the electrode surface of battery.
The use of engineering plastic materials may make the physical strength of microporous membrane of the present invention be improved.Use hot melt adhesive then may make this microporous membrane when thermal treatment, have the function that can bond on the electrode.But above-mentioned materials is not limited to above-mentioned functions.
" tackifier " or make " tackifying resin " to include but are not limited to: petroleum resin, for example Escorez 2000 series are (through the virtue modified aliphatic hydrocarbon resin, it has and as the poly-good consistency of (ethene-vinylacetate) polar materials), Escorez 5600 series (hydrogenant virtueization modification clicyclic hydrocarbon resinoid) and Escorez 5400 series (the alicyclic hydrocarbon resin of hydrogenation).Above Escorez resin is produced by Exxon-Mobil chemical company.Tackifier also comprise such as rosin resin, polyterpene resin, and some help to improve the polymkeric substance or the multipolymer of hot melt adhesive performance.Such example has poly-(vinylidene-R 1216) " PVdF-HFP ".Wherein, the weight content of R 1216 is between 5-12%.Tackifier also are included in United States Patent (USP) 5,414 in addition, all cited tackifier in 039.
At this " stopping composition " that refers in particular to or make " inert filler " to include but are not limited to: silicon-dioxide, aluminum oxide, titanium oxide, molecular sieve, lime carbonate, Calucium Silicate powder, glass, stupalith, and tetrafluoroethylene.Above material is fines shape material.This stopping composition also comprises some other micropore that helps to prevent microporous membrane material flat and that can improve the microporous membrane ionic conductivity that collapses.This class material is just like United States Patent (USP) 6,057, and 061 and 5,622,792 is described.
It is flat that the reason of using stopping composition or inert filler is that micropore that it can prevent microporous membrane collapses, and also helps to improve simultaneously the ionic conductivity of microporous membrane.Certainly do not get rid of other possible reason yet.
Another aspect of the present invention is the production method that directly relates to microporous membrane.This method is: (a) with hot melt adhesive, engineering plastic materials, the tackifier that add with alternative are dissolved among the organic solvent, optionally add stopping composition then, add pore former again, obtain uniform slip after the stirring, (b) this slip is applied to back film forming on the carrier, (c) vapor away solvent, (d) after washing, obtain microporous membrane.Here the pore former of indication is a water-soluble substances, can select the basic metal halogen compounds for use, particulate alkali metal vitriol, Polyethylene glycol dimethyl ether, perhaps dimethyl formamide " DMF ".Naturally also can use the blended pore former.The first-selection of basic metal halogen compounds then is a lithiumbromide.
Here " pore former " of indication includes but are not limited to: for example lithiumbromide of an alkali metal salt, other water-soluble salt resembles granuliform sodium sulfate, water-soluble polymerss such as Polyethylene glycol dimethyl ether, the water soluble liq of low volatility, for example dimethyl formamide " DMF " and N,N-DIMETHYLACETAMIDE " DMA " also have water-soluble organic compounds such as starch.
Here " solvent " includes but are not limited to: for example tetrahydrofuran (THF) alicyclic ethers such as " THF " of volatile organic solvent, also comprises as acetone and methylethylketone ketones such as " MEK "; Linear esters such as ethyl acetate, cyclic ester and propylene moon green grass or young crops (annotate: " month green grass or young crops " is a word) such as gamma-butyrolactone.
Another advantage of microporous membrane of the present invention is hydrophilic for it, and the wetting properties of it and polar solvent is fine.Thereby cause surface resistivity lower, final body reveals high conductivity.Compare with industrialized polyethylene or polypropylene screen, microporous membrane of the present invention has better high electric current charging and discharging capabilities.In addition, the porosity height of microporous membrane of the present invention, the aperture is also big simultaneously.And porosity and pore size size can for example select the pore former of different size and adjustment consumption to control by chemical process.The more important thing is that under without any the situation that adds tackiness agent, this microporous membrane is through bonding on the electrode of battery after the thermal activation.Thereby make and set up good interface between barrier film and the electrode.When this microporous membrane was used as battery diaphragm, prepared battery was still keeping not only low but also stable internal resistance through after repeatedly discharging and recharging.Having extended cycle life of this battery, the high-temperature behavior excellence.The security feature of battery also is improved.
Bonding between microporous membrane of the present invention and the electrode is to be melted by the hot melt adhesive in this film to realize.Therefore this bonding be permanent.Its intensity is also far above developing the gel polymer electrolyte that in the past.But, bonding other reason of also not getting rid of between microporous membrane and the electrode.
Another aspect of the present invention relates to battery.This battery is made up of following elements: (1) at least one positive pole, and optimal is the positive pole that lithium ion battery is used, (2) at least one negative pole, optimal is the negative pole that lithium ion battery is used, (3) ionogen, its first-selection is a lithium-ion electrolyte.Optimal is the liquid or solid lithium-ion electrolyte; (4) microporous membrane of the present invention, the composition of this microporous membrane have (a) hot melt adhesive, (b) engineering plastic materials, tackifier (c) and optionally, and (d) stopping composition optionally.
This paper said " battery unit battery " and " elementary cell " are equal to, and are used interchangeably." battery " then is meant an elementary cell or the series of cells of being made up of a plurality of elementary cells.
The main application of microporous membrane of the present invention is to can be used to produce rechargeable lithium ion batteries.Can directly utilize the positive and negative pole material of industrialized lithium ion battery.The compound that positive electrode material can select for use lithium and metal oxide to form, such as, cobalt acid lithium " LiCoO
2", lithium nickelate " LiNiO
2", lithium manganate " LiMn
2O
4", and by above-mentioned several mixtures of forming.Negative material can be selected unformed or graphited carbon dust for use.Developing all electrode materialss that in the past can use.
The present invention also relates to the manufacture method of microporous membrane and rechargeable cell.The invention further relates to this microporous membrane and can be applicable to such as battery, ultracapacitor is so expected battery, transmitter, electrochromic device etc.
Below cited examples of implementation be intended to be used for explaining the present invention.Unless otherwise indicated, otherwise in the following example and in the explanation hereinafter, all the components unit and percentage all are to be unit with weight.
In explanation and in each section literal, cited digital scope is intended to definitely explain each aspect of the present invention, for example sets forth one group of specific performance properties index, measuring unit, condition, physical condition or percentage ratio.Any parameter within this scope is all in each claim scope of the present invention." approximately " or " about " speech illustrates that then parameter or the scope that will explain are flexibility and changeabilities.If for parameter outside those skilled in the art's employing scope or some independent parameters, temperature for example, concentration, quantity, content contains carbon number and performance etc., also may obtain following achievement: microporous membrane and manufacture method thereof, and the battery assembled of barrier film thus.
A kind of microporous membrane prepares according to following method.Poly-(ethene-vinylacetate) " PEVA-50 " that 0.90g is contained 50% vinylacetate, 0.36g by (the Houston of Exxon-Mobil chemical company, TX) the Escorez 2596 of Sheng Chaning (through the virtue modified aliphatic hydrocarbon resin), with 4.14g by the ScientificPolymer Products (Ontario of company, NY) polysulfones of Sheng Chaning (Mw.80,000) is dissolved among the 40g tetrahydrofuran (THF) " THF ".Add 1.00g again and be fuming silicon oxide in above-mentioned solution.After stirring is spent the night, in the gained slip, add 7.00g lithiumbromide " LiBr " again.After the whole dissolvings of lithiumbromide, at room temperature slip is coated directly onto on 4 inches * 15 inches Mylar (poly-terephthalic acid diethyl ester) thin-film carrier.Coating thickness is controlled at about 200 microns.Whole pot slip can be coated with 10.At room temperature, the tetrahydrofuran (THF) light that in half hour, volatilizees greatly.After treating that tetrahydrofuran (THF) volatilizees fully, the gained film is immersed in the water 1 hour at once.Then, after falling lithiumbromide with the thorough eccysis of clear water, what obtain is exactly microporous membrane.At last, this microporous membrane is placed drying at room temperature.The thickness of this microporous membrane is 1 Mill (mil) after measured, just 0.001 inch.This microporous membrane is even, and is well-balanced, and physical strength is good.The data logging of relevant this sample is in No. 1 sample of table 1.
This sample is listed in No. 2 samples of table 1.It is according to the method for the foregoing description 1 and same recipe and basic identical material preparation.Different use just that (Houston, TX) the Escorez 5690 of Sheng Chaning (clicyclic hydrocarbon resinoid) replaces Escorez 2596 (through the virtue modified aliphatic hydrocarbon resin) by Exxon-Mobil chemical company.
Embodiment 3
No. 3 samples are to prepare with slip substantially the same manner as Example 2.Different is to replace " PEVA-50 " with poly-(ethene-vinylacetate) " PEVA-70 " that contains 70% vinylacetate.
Embodiment 4
In the present embodiment, a kind of microporous membrane prepares according to following method.Poly-(ethene-vinylacetate) " PEVA-50 " that 0.90g is contained 50% vinylacetate, 0.36g by the Solvay AdvancedPolymer (Houston of company, TX) Solef 20810 of Sheng Chaning (poly-(vinylidene-R 1216) that contain 8% R 1216) and 4.14g polysulfones are dissolved among the 40g tetrahydrofuran (THF) " THF ".Add 1.50g again and be fuming silicon oxide in above-mentioned solution.After stirring is spent the night, in the gained slip, add 7.00g lithiumbromide " LiBr " again.After the whole dissolvings of lithiumbromide, at room temperature slip is coated directly onto on 4 inches * 15 inches Mylar thin-film carriers.Coating thickness is controlled at about 200 microns.In about half an hour fully after the volatilization, the gained film is immersed in the water 1 hour at once Deng tetrahydrofuran (THF).Then, after thoroughly washing, obtain microporous membrane with clear water.At last, this microporous membrane is placed drying at room temperature.The thickness of this microporous membrane is 1.2 Mills after measured, just 0.0012 inch.This microporous membrane is even, and is well-balanced, and physical strength is good.The data logging of relevant this sample is in No. 4 samples of table 1.About its aperture size and porosity data then is recorded in the table 2.
Embodiment 5-11
As shown in table 1, No. 5-No. 11 seven samples are to prepare with slip substantially the same manner as Example 4.The different just proportioning differences of each composition.No. 6 samples are to prepare under the situation of stopping composition not having.And No. 9 samples are to prepare under the situation of tackifier not having.Embodiment 12-13
In table 1, No. 12 and No. 13 samples are with slip preparation substantially the same manner as Example 4.Different just for No. 12 samples, use that (Milwaukee, MI) aluminum oxide of Sheng Chaning (mean particle size is below 10 microns) replaces silicon oxide by Sigma-Aldrich company.Yet for No. 13 samples, different is to use the molecular sieve of being produced by Sigma-Aldrich company (mean particle size is less than 10 microns) to replace silicon oxide, simultaneously without tackifier.
Embodiment 14
In the present embodiment, No. 14 samples are to use the slip preparation identical substantially with embodiment 4.Difference is: replace PEVA-50 with PEVA-40, replace Solef 20810 with Solef 21216 (poly-(vinylidene-R 1216) that contain 12% R 1216), and gather phenol with polycarbonate " PBAC " displacement.
Embodiment 15
In table 1, No. 15 samples are to use the slip preparation identical substantially with embodiment 14.Difference is: replace lithiumbromide with dimethyl formamide " DMF ", PEVA-40 adopts different proportionings, and does not add stopping composition.
Embodiment 16
In the present embodiment, No. 16 samples are to use the slip preparation identical substantially with embodiment 14.Difference is: replace polycarbonate with polymethylmethacrylate " PMMA ", replace tetrahydrofuran (THF) with methylethylketone " MEK ", and do not add tackifier.Resulting microporous membrane is very crisp and intensity is not high yet.
Embodiment 17
In this embodiment, No. 17 samples are to prepare with slip substantially the same manner as Example 14.Different just replace polysulfones with poly-(vinylbenzene-methyl methacrylate) (its ratio is 70: 30) " PSMMA ".
Embodiment 18
No. 18 samples are to prepare with slip substantially the same manner as Example 4.Different just using (Winova, Minnesota) the 30% glass fibre enhanced polysulfones that contains of Sheng Chaning replaces pure polysulfones by RTP company.About the data logging of this sample in table 1 and table 2.
Table 1
| Sample number | The composition of microporous membrane and composition are than (gram) | Solvent (gram) | Pore former (gram) | Resulting microporous membrane | |||
| Hot melt adhesive | Tackifier | Engineering plastics | Stopping composition | ||||
| ????1 | ?PEVA-50 ?0.90 | ?Escorez2596 ?0.36 | ?PSU ?4.14 | ?Silica ?1.00 | ??THF ??40 | ??LiBr ??7.00 | Uniform films |
| ????2 | ?PEVA-50 ?0.90 | ?Escorez5690 ?0.36 | ?PSU ?4.14 | ?Silica ?1.00 | ??THF ??40 | ??LiBr ??7.00 | Uniform films |
| ????3 | ?PEVA-70 ?0.90 | ?Escorez5690 ?0.36 | ?PSU ?4.14 | ?Silica ?1.00 | ??THF ??40 | ??LiBr ??7.00 | Uniform films |
| ????4 | ?PEVA-50 ?0.90 | ?Solef20810 ?0.36 | ?PSU ?4.14 | ?Silica ?1.50 | ??THF ??40 | ??LiBr ??7.00 | Uniform films |
| ????5 | ?PEVA-50 ?0.90 | ?Solef20810 ?0.54 | ?PSU ?3.96 | ?Silica ?1.00 | ??THF ??40 | ??LiBr ??7.00 | Uniform films |
| ????6 | ?PEVA-50 ?0.90 | ?Solef20810 ?0.54 | ?PSU ?3.96 | Do not have | ??THF ??40 | ??LiBr ??7.00 | PEVA disperses uneven |
| ????7 | ?PEVA-50 ?0.90 | ?Solef20810 ?0.54 | ?PSU ?3.96 | ?Silica ?1.50 | ??THF ??40 | ??LiBr ??7.00 | Uniform films |
| ????8 | ?PEVA-50 ?0.90 | ?Solef20810 ?0.36 | ?PSU ?4.14 | ?Silica ?1.00 | ??THF ??40 | ??LiBr ??7.00 | Uniform films |
| ????9 | ?PEVA-50 ?0.90 | Do not have | ?PSU ?4.50 | ?Silica ?1.00 | ??THF ??40 | ??LiBr ??7.00 | PEVA disperses uneven |
| ????10 | ?PEVA-50 ?0.90 | ?Solef20810 ?0.36 | ?PSU ?4.14 | ?Silica ?1.50 | ??THF ??40 | ??Na 2SO 4??7.00 | Inhomogeneous |
| ????11 | ?PEVA-50 ?0.90 | ?Solef20810 ?0.36 | ?PSU ?4.14 | ?Silica ?1.50 | ??THF ??40 | ??PEGDE- ??250 ??7.00 | Uniform films |
| ????12 | ?PEVA-50 ?0.90 | ?Solef20810 ?0.36 | ?PSU ?4.14 | ?Alumina ?1.00 | ??THF ??40 | ??LiBr ??7.00 | Uniform films |
| ????13 | ?PEVA-50 ?0.63 | Do not have | ?PSU ?4.05 | ?M.Sieve ?1.00 | ??THF ??40 | ??LiBr ??7.00 | Uniform films |
| ????14 | ?PEVA-40 ?0.63 | ?Solef21216 ?2.50 | ?PBAC ?1.00 | ?Silica ?1.00 | ??THF ??40 | ??LiBr ??5.00 | Uniform films |
| ????15 | ?PEVA-40 ?1.00 | ?Solef21216 ?2.50 | ?PBAC ?2.00 | Do not have | ??THF ??40 | ??DMF ??5.00 | Uniform films |
| ????16 | ?PEVA-40 ?0.63 | Do not have | ?PMMA ?2.50 | ?Silica ?2.00 | ??MEK ??40 | ??LiBr ??5.00 | Crisp, intensity is low |
| ????17 | ?PEVA-40 ?0.63 | ?Solef21216 ?0.45 | ?PSMMA ?4.05 | ?Silica ?1.00 | ??THF ??40 | ??LiBr ??5.00 | Uniform films |
| ????18 | ?PEVA-50 ?0.90 | ?Solef20810 ?0.36 | ?RTP#905 ?4.14 | ?Silica ?1.00 | ??THF ??40 | ??LiBr ??7.00 | Uniform films |
Dummy suffix notation is as follows in the table 1: PEVA-50 contains poly-(ethene-vinylacetate) of 50% vinylacetate; PEVA-40 contains poly-(ethene-vinylacetate) of 40% vinylacetate; PEVA-70 contains poly-(ethene-vinylacetate) of 70% vinylacetate; PSU, polysulfones; PBAC, polycarbonate; PMMA, polymethylmethacrylate; PSMMA, poly-(vinylbenzene-methyl methacrylate); Silica, silicon oxide; M.Sieve, molecular sieve; THF, tetrahydrofuran (THF); MEK, methylethylketone; PEGDE-250, molecular weight are 250 Polyethylene glycol dimethyl ether; DMF, dimethyl formamide.
The sign of embodiment 19 microporous membranes
To the microporous membrane of above preparation, following sign has been carried out in sampling, as thickness, and ground mass, the intermediate value of aperture size, and porosity.The data of relevant 4,8,11 and No. 12 samples are listed in the table 2.Industrialized Celgard 2300 battery diaphragms are also listed in the same table for comparing.
The intermediate value of listed aperture size is to measure with porosity tester (porometry) in table 2.As shown in table 2, the porosity of four microporous membrane samples of the present invention is all high a lot of than Celgard 2300 battery diaphragms.Can believe that its high electric current charge-discharge performance of battery that the big microporous membrane of porosity produces is good more.
Table 2
| Sample number | Thickness (inch) | Ground mass (gram/square metre) | Aperture size (micron) | Porosity (%) |
| ??????4 | ???0.0012 | ????13.36 | ????0.43 | ????69.6 |
| ??????8 | ???0.0012 | ????16.46 | ????0.57 | ????61.0 |
| ??????11 | ???0.0009 | ????15.16 | ????0.44 | ????54.0 |
| ??????12 | ???0.0011 | ????16.33 | ????0.56 | ????64.8 |
| ??Celgard2300 | ???0.0010 | ????13.85 | ????0.46 | ????39.9 |
Compare with hydrophobic polyolefins barrier film, microporous membrane of the present invention has the advantage of following several respects at least: a) good hydrophilic property just, thereby causes surface resistivity lower with the good wetting properties of polar solvent; B) aperture of microporous membrane and porosity can be by controlling with the chemical engineering method; C) this microporous membrane is heat-activatable, so it contacts and bonding fine with interelectrode.
The preparation of embodiment 20 batteries
Lithium ion battery utilizes following elements and assembles: a carbon negative pole, a LiCoO
2No. 2 microporous membranes of positive pole and a slice the present invention.Negative pole and positive pole are the electrode that industrialized liquid lithium ion battery is used, and in other words, negative pole contains about 90% carbon material, and positive pole then contains 91% left and right sides LiCoO
2
The assembling of battery is by No. 2 specimen holders of the microporous membrane of a slice 38mm * 45mm are finished between the negative pole of the positive pole of a slice 30mm * 38mm and a slice 32mm * 40mm.That is to say that the useful area of this battery is actually 11cm
2With a kind of be that the stratified plastics packing bag of matrix comes battery pack with the aluminium foil.Seal by halves then.Next will carry out drying.Transfer to one again and be full of nitrogen and water content is lower than in the drying case of 1 ppm.Annotate about 0.4g 1.2M electrolytic solution in battery.This electrolytic solution is by a LiPF by Stella Chemifa company (Osaka, Japan) production
6Salt is dissolved in the mixed solvent of being made up of in 2: 1: 1 ratios ethylene carbonate and diethyl carbonate and methylcarbonate and makes.Next, complete sealed cell.Then, after heating 30 minutes under 85 ℃ of temperature, the pressure of adding a 5psi bonds on anodal and the negative pole microporous membrane.After being cooled to room temperature, this battery is used to do and discharges and recharges test.
Fig. 1 is when with different current discharge, cell voltage and the percentile relation of discharge total volume.The current ratio that is used for discharging is respectively 0.2C, 0.5C, 1C, 1.5C and 2C.That is to say that the current density that is used for discharging is respectively 0.6,1.5,3.0,4.5, and 6mA/cm
2The test data of relevant this battery is listed in No. 1 battery sample of table 3.
Test experiments is taken battery packages apart after finishing.The result shows that microporous membrane is bonded on anodal and the negative pole really securely.
Second battery is to prepare according to the method identical with above-mentioned No. 1 battery.Used microporous membrane is No. 18 samples.Test result is recorded in No. 2 battery samples of table 3.
For than than purpose, the 3rd battery is according to the method preparation identical with above-mentioned No. 1 battery.Different is to replace No. 2 microporous membrane samples with commercial Celgard 2300 battery diaphragms.This battery is numbered No. 3, i.e. control cell.In view of Celgard 2300 battery diaphragms can not bond on the electrode when the thermal activation.Therefore, when discharging and recharging test, this control cell is sandwiched between two flat boards to guarantee that battery diaphragm and electrode have excellent contact.The test result of relevant control cell also is recorded in No. 3 battery samples of table 3.
The charge-discharge performance performance results of these three batteries as shown in Figure 2.This figure be the total loading capacity percentage of three batteries when under different strength of current, discharging relatively.These three batteries are respectively No. 1 battery (circle) and No. 2 batteries (square) and with No. 3 control cell (triangle) of making comparisons.Obviously as seen, the high current discharge ability of No. 1 and No. 2 battery is all above control cell.
Table 3
| Battery number | Battery diaphragm number | Discharge capability when current ratio is 1C (%) | Discharge capability when current ratio is 2C (%) |
| ????1 | ??????2 | ?????97.1 | ??????77.9 |
| ????2 | ??????18 | ?????97.1 | ??????73.6 |
| 3 (control cell) | Celgard2300 | ?????96.7 | ??????71.6 |
Principle of the present invention and be applied in the front and illustrate.Because above explanation is intended to illustrate and non-limiting principle of the present invention, be not limited to the above particular content that shows so this invention is claimed.Perhaps those skilled in the art can do some variations even improvement, but this is also in claim scope of the present invention.
Claims (17)
1. a microporous membrane has at least its composition of one deck to comprise (a) hot melt adhesive, and (b) engineering plastic materials also can comprise (c) tackifier and (d) stopping composition selectively.
2. according to the described microporous membrane of claim 1, its composition comprises tackifier.
3. according to the described microporous membrane of claim 1, its composition comprises stopping composition.
4. according to the described microporous membrane of claim 1, its composition comprises (a) hot melt adhesive, (b) engineering plastic materials, (c) tackifier, (d) stopping composition.
5. according to the described microporous membrane of claim 1, when under heat-activated under 35-125 ℃ the temperature and the pressure at 0.5-100psi, this microporous membrane can bond on the electrode of battery.
6. according to the described microporous membrane of claim 1, wherein the weight content of hot melt adhesive is 2-50%.
7. according to the described microporous membrane of claim 1, wherein the weight content of engineering plastic materials is 20-90%.
8. according to the described microporous membrane of claim 1, wherein the weight content of tackifier is 0-30%.
9. according to the described microporous membrane of claim 1, wherein the weight content of stopping composition is 0-30%.
10. according to the described microporous membrane of claim 1, the porosity of this microporous membrane is between 25-75%.
11. according to the described microporous membrane of claim 1, wherein hot melt adhesive is poly-(ethene-vinylacetate), perhaps poly-(ethene-alkyl acrylate).
12. according to the described microporous membrane of claim 1, wherein engineering plastic materials is to be selected from polysulfones, polycarbonate, poly-(vinylbenzene-methyl methacrylate), perhaps their mixture.
13. according to the described microporous membrane of claim 1, wherein tackifier be selected from following material such as, through the virtue modified aliphatic hydrocarbon resin, hydrogenant virtueization modification clicyclic hydrocarbon resinoid, the alicyclic hydrocarbon resin of hydrogenation, rosin resin, polyterpene resin, poly-(vinylidene-R 1216), and their mixture.
14. according to the described microporous membrane of claim 3, wherein stopping composition is to be selected from following fines shape material: silicon-dioxide, aluminum oxide, titanium oxide, molecular sieve, lime carbonate, Calucium Silicate powder, glass, stupalith, and tetrafluoroethylene.
15. the production method of a microporous membrane, its concrete steps are as follows: (a) with hot melt adhesive, engineering plastic materials and the alternative tackifier that add are dissolved among the organic solvent.Optionally add stopping composition then, add pore former again, obtain uniform slip after the stirring, (b) this slip is applied to back film forming on the carrier, (c) vapor away solvent, (d) after washing, obtain microporous membrane.
16. in accordance with the method for claim 18, used pore former is a water-soluble substances.
17. battery, it is made up of following elements: (1) at least one positive pole, (2) at least one negative pole, (3) ionogen, (4) microporous membrane of the present invention, the composition of this microporous membrane have (a) hot melt adhesive, (b) engineering plastic materials, (c) and optionally tackifier, and (d) stopping composition optionally.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US10/034,494 | 2001-12-28 | ||
| US10/034,388 US6998193B2 (en) | 2001-12-28 | 2001-12-28 | Microporous membrane and its uses thereof |
| US10/034,494 US6527955B1 (en) | 2001-12-28 | 2001-12-28 | Heat-activatable microporous membrane and its uses in batteries |
| US10/034,388 | 2001-12-28 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1439666A true CN1439666A (en) | 2003-09-03 |
| CN1218986C CN1218986C (en) | 2005-09-14 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB021589658A Expired - Fee Related CN1218986C (en) | 2001-12-28 | 2002-12-19 | Heat activated microporous membrane and its application in battery |
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| JP (1) | JP3651609B2 (en) |
| CN (1) | CN1218986C (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1327546C (en) * | 2004-02-24 | 2007-07-18 | 株式会社巴川制纸所 | Separator for electronic component and method for producing the same |
| CN102891323A (en) * | 2011-07-22 | 2013-01-23 | 夏普株式会社 | Current collector and nonaqueous secondary cell |
| CN104332575A (en) * | 2014-09-09 | 2015-02-04 | 深圳市信宇人科技有限公司 | Cast-coated all-ceramic battery diaphragm and cast coating method thereof |
| CN109415827A (en) * | 2016-06-27 | 2019-03-01 | 西门子股份公司 | The gas barrier that inorfil for electrochemical conversion process enhances |
| CN109786624A (en) * | 2019-01-16 | 2019-05-21 | 北京卫蓝新能源科技有限公司 | A kind of preparation method and ion battery of ion battery porous septum |
| CN114667622A (en) * | 2019-09-27 | 2022-06-24 | 尼大意器株式会社 | Diaphragm for redox flow battery and method for manufacturing the diaphragm |
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| JP2006338918A (en) * | 2005-05-31 | 2006-12-14 | Tomoegawa Paper Co Ltd | Electronic component and separator therefor |
| WO2010024328A1 (en) * | 2008-08-29 | 2010-03-04 | 日本ゼオン株式会社 | Porous membrane, secondary battery electrode and lithium ion secondary battery |
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| CN117304466B (en) * | 2023-11-29 | 2024-03-26 | 中国科学院宁波材料技术与工程研究所 | Degradable polycarbonate and preparation method and application thereof |
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2002
- 2002-12-19 JP JP2002368090A patent/JP3651609B2/en not_active Expired - Fee Related
- 2002-12-19 CN CNB021589658A patent/CN1218986C/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1327546C (en) * | 2004-02-24 | 2007-07-18 | 株式会社巴川制纸所 | Separator for electronic component and method for producing the same |
| CN102891323A (en) * | 2011-07-22 | 2013-01-23 | 夏普株式会社 | Current collector and nonaqueous secondary cell |
| CN104332575A (en) * | 2014-09-09 | 2015-02-04 | 深圳市信宇人科技有限公司 | Cast-coated all-ceramic battery diaphragm and cast coating method thereof |
| CN109415827A (en) * | 2016-06-27 | 2019-03-01 | 西门子股份公司 | The gas barrier that inorfil for electrochemical conversion process enhances |
| CN109415827B (en) * | 2016-06-27 | 2021-07-02 | 西门子股份公司 | Inorganic fiber reinforced gas separator for electrochemical conversion processes |
| CN109786624A (en) * | 2019-01-16 | 2019-05-21 | 北京卫蓝新能源科技有限公司 | A kind of preparation method and ion battery of ion battery porous septum |
| CN114667622A (en) * | 2019-09-27 | 2022-06-24 | 尼大意器株式会社 | Diaphragm for redox flow battery and method for manufacturing the diaphragm |
| CN114667622B (en) * | 2019-09-27 | 2023-11-21 | 尼大意器株式会社 | Separator for redox flow battery and method for manufacturing same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3651609B2 (en) | 2005-05-25 |
| JP2004002658A (en) | 2004-01-08 |
| CN1218986C (en) | 2005-09-14 |
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