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WO2004049480A2 - Separateur a faible teneur en eau destine a une cellule electrochimique - Google Patents

Separateur a faible teneur en eau destine a une cellule electrochimique Download PDF

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Publication number
WO2004049480A2
WO2004049480A2 PCT/EP2003/012113 EP0312113W WO2004049480A2 WO 2004049480 A2 WO2004049480 A2 WO 2004049480A2 EP 0312113 W EP0312113 W EP 0312113W WO 2004049480 A2 WO2004049480 A2 WO 2004049480A2
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WO
WIPO (PCT)
Prior art keywords
separator
lithium
particles
mixture
battery
Prior art date
Application number
PCT/EP2003/012113
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German (de)
English (en)
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WO2004049480A3 (fr
Inventor
Volker Hennige
Christian Hying
Gerhard HÖRPEL
Original Assignee
Degussa Ag
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Degussa Ag filed Critical Degussa Ag
Priority to AU2003293640A priority Critical patent/AU2003293640A1/en
Publication of WO2004049480A2 publication Critical patent/WO2004049480A2/fr
Publication of WO2004049480A3 publication Critical patent/WO2004049480A3/fr

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/44—Fibrous material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/454—Separators, membranes or diaphragms characterised by the material having a layered structure comprising a non-fibrous layer and a fibrous layer superimposed on one another
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • 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

Definitions

  • the present invention relates to a method for producing a separator with a low water content for an electrochemical cell, a separator which can be produced by this method, and an electrochemical cell which comprises such a separator with a low water content.
  • electrochemical cell or battery means batteries and accumulators (secondary batteries) of any kind, in particular alkali, such as Lithium, lithium ion, lithium polymer, and alkaline earth batteries and accumulators, including in the form of high-energy or high-performance systems.
  • alkali such as Lithium, lithium ion, lithium polymer, and alkaline earth batteries and accumulators, including in the form of high-energy or high-performance systems.
  • Electrochemical cells comprise electrodes with opposite poles, which are separated from one another by a separator while maintaining ion conductivity.
  • a separator is a thin, porous, electrically insulating material with high ion permeability, good mechanical strength and long-term stability against those in the system, e.g. B. in the electrolyte of the electrochemical cell, chemicals and solvents used. It is intended to completely electronically isolate the cathode from the anode in electrochemical cells. He must also be permanently elastic and the movements in the system, for. B. in the electrode package when loading and unloading, follow.
  • the separator largely determines the life of the arrangement in which it is used, e.g. B. that of an electrochemical cell.
  • the development of rechargeable electrochemical cells or batteries is therefore influenced by the development of suitable separator materials.
  • General information about electrical separators and batteries can e.g. B. at J.O. Besenhard can be read in "Handbook of Battery Materials” (VCH Verlag, Weinheim 1999).
  • High-energy batteries are used in various applications where it is important to have the largest possible amount of electrical energy available. This is the case, for example, with traction batteries, but also with emergency power supply with batteries (Auxillary Power Systems) the case.
  • the energy density is often given in weight [Wh / kg] or volume-related [Wh / L] sizes. Energy densities of 350 to 400 Wh / L and 150 to 200 Wh / kg are currently being achieved in high-energy batteries.
  • the requested performance with such batteries is not so large, so that one can make compromises with regard to the internal resistance. This means that the conductivity of the electrolyte-filled separator, for example, does not have to be as great as that of high-performance batteries, so that other separator concepts are also possible.
  • polymer electrolytes can be used in high-energy systems, which have a very low conductivity of 0.1 to 2 mS / cm. Such polymer electrolyte cells cannot be used as high-performance batteries.
  • Separator materials for use in high-performance battery systems must have the following properties: They must be as thin as possible to ensure a small specific space requirement and to keep the internal resistance low. To ensure these low internal resistances, it is important that the separator also has a large porosity. They must also be light in order to achieve a low specific weight. In addition, the wettability must be high, otherwise dead zones that are not wetted will arise.
  • separators consist mainly of porous organic polymer films or inorganic nonwovens such as. B. fleeces of glass or
  • Ceramic materials or ceramic papers are made by different companies. Important producers are: Celgard, Tonen,nde, Asahi, Binzer, Mitsubishi, Daramic and others.
  • the separators made of inorganic nonwovens or ceramic paper are mechanically unstable and break easily. This leads to short circuits. Because the electrodes can easily come into contact due to broken points.
  • a typical organic separator is e.g. B. made of polypropylene or a polypropylene / polyethylene / polypropylene composite.
  • a major disadvantage of these organic polyolefin separators is their relatively low thermal load capacity of below 150 ° C. A short-lasting reaching of the melting point of these polymers leads to a large melting of the separator and to a short circuit in the electrochemical cell which uses such a separator. The use of such separators is therefore generally not very safe. Because when higher temperatures are reached, especially at least 150 ° C or even at least 180 ° C, these separators are destroyed.
  • the polymer-based separators have other serious disadvantages in terms of chemical resistance.
  • the polymers in the electrochemical cells are slowly but steadily attacked by contact with the electrodes, even at normal operating and storage temperatures such as room temperature.
  • the polymer is slowly attacked on the contact surface of the separator with the lithium or with the lithiated graphite.
  • the polymer separators are also attacked inside the separator by the substances formed during the operation of an electrical cell. As a result, these separators can no longer reliably protect the electrodes from a short circuit. The service life is reduced.
  • the capacity of an electrochemical cell that uses such separators decreases over time.
  • Composite structure which comprises a flat, provided with a plurality of openings, flexible substrate with a coating thereon.
  • the material of the substrate is selected from metals, alloys, plastics, glass and carbon fiber or a combination of such materials, and the coating is a continuous, porous, electrically non-conductive ceramic coating.
  • the use of the ceramic coating promises thermal and chemical resistance.
  • the separators which have a carrier or a substrate made of electrically conductive material (as indicated in the example), have proven unsuitable for lithium-ion cells, since the coating of the thickness described cannot be produced without defects over a large area. Short circuits are therefore very easy.
  • metal meshes as thin as are required for very thin separators are not commercially available.
  • the separator described in DE 101 42 622 has a very high conductivity
  • the separator described there still does not meet the requirements for a separator that can be used technically in terms of thickness and weight, as well as safety.
  • the small thickness of the separator of less than 100 ⁇ m problems arise such that the growth of dendrites is facilitated with the relatively large pores with a uniform distribution which ensure good ion conductivity. Therefore, short circuits often occur in practice if the thickness of the separators is very small.
  • the large pores allow dendrites to grow, which can easily form in the large pores. This means that short circuits often occur with these separators in practice.
  • the large particles in this document consist of Al 2 O 3 and ZrO 2 . Due to the high density of these ceramics, these separators also have a large basis weight, which reduces the mass-specific specific energy density (in Wh / g).
  • the object of the present invention was therefore to provide a method for producing an almost water-free separator for an electrochemical cell, one Separator, which can be produced by this method, and an improved electrochemical cell, which comprises such a separator.
  • step (b) comprises contacting a porous carrier having an inorganic coating with the mixture from step (a), the mixture preferably being a solution of the lithium compound in a solvent around the inner and / or outer surface to treat the porous carrier with the mixture and to create the separator intermediate.
  • the porous support having an inorganic coating preferably comprises a flat, flexible substrate provided with a plurality of openings, on and in which the inorganic coating is located.
  • the contacting and treatment of inner and / or outer surfaces of a porous carrier having an inorganic coating with a mixture can, for. B. be carried out so that the porous carrier having an inorganic coating is rolled off a roll at a speed of 1 m / h to 2 m / s, preferably at a speed of 0.5 m / min to 20 m / min and most preferably with one Speed from 1 m / min to 5 m / min through at least one apparatus which brings the mixture onto and into the carrier, such as e.g. B. a roller, and at least one other apparatus which enables the heating of the separator intermediate, such. B. an electrically heated oven, and the product thus produced is rolled up on a second roll.
  • the pre-treatment steps can also be carried out in a continuous process while maintaining the parameters mentioned.
  • the method is carried out such that the porous support having an inorganic coating has a maximum longitudinal tension of 10 N / cm, preferably 3 N / cm, during the treatment process.
  • Treatment processes are understood to mean all process steps in which a material is brought onto and into a carrier.
  • the carrier is preferably stretched during the treatment process with a maximum force of 0.01 N / cm. It can be particularly preferred if the carrier is guided untensioned in the longitudinal direction during the treatment process.
  • the porous carrier having an inorganic coating can be, for example, a separator with an inorganic composite structure, which is already known from the prior art.
  • a separator which is improved in terms of water content can advantageously be created by subsequent treatment.
  • the deficit should preferably be used not less than 0.5 times, particularly preferably not less than 0.7 times the stoichiometric amount of lithium compound in relation to the amount of OH groups.
  • the OH groups are determined using the following procedure:
  • a sample dried in a vacuum at 120 ° C. (only water but no OH groups being removed) is placed in a two-necked flask with a dropping funnel and a side outlet for gases.
  • a solution of 1 mol / L lithium aluminum hydride in tetrahydrofuran is then slowly added dropwise to this sample.
  • hydrogen is produced (in a stoichiometry of 1 mol of escaping hydrogen per 1 mol of OH groups in the sample).
  • the hydrogen produced is measured volumetrically. The amount of hydrogen produced can thus be converted into the number of OH groups.
  • Another advantage of the invention is an increase in the conductivity of a separator filled with an electrolyte achieved by the method according to the invention.
  • a separator according to the invention which is filled with an electrolyte
  • the surface positions of the lithium ion are available for the charge transport over the surface. This leads to an increased conductivity through the separator. Since this rapid charge transport takes place exclusively via lithium ions, there is an advantageous increase in the number of transfers for cations.
  • the sensitivity of an electrochemical cell equipped with such a separator to high discharge currents can advantageously be reduced. In this way, the polarization in such an electrochemical cell is advantageously reduced.
  • This has the additional advantage that the load capacity of the separators produced by the method according to the invention is increased. The electrochemical cells can thus advantageously be discharged with larger currents.
  • the mixture in step (a) is preferably a dispersion which is used as further mixture components
  • step (b) optionally fine particles, wherein step (b) comprises the following steps:
  • step (b-1) providing a flat, multi-aperture flexible substrate, (b-2) applying the dispersion in a thin layer on and into the substrate, thereby creating the separator precursor, and wherein in step (c ) by heating the separator intermediate to 50 to 350 ° C Separator is created with a porous carrier having an inorganic coating.
  • This embodiment has the advantage that fewer steps are required overall to create a separator with a low water content.
  • the substrate can consist of a nonwoven made of non-woven, non-electrically conductive polymer fibers, ceramic fibers or glass fibers.
  • the fine particles can have an average primary particle size in the range from 1 to 200 nm, preferably 2 to 100 nm, very particularly preferably 3 to 50 nm. As a result, the service life and life of the separator can be improved in an advantageous manner.
  • the fine particles contain a pyrogenic oxide of the elements silicon, zirconium and / or aluminum, such as. B. silica, in particular Aerosil or aluminum oxide.
  • the dispersion preferably has oxide particles as ceramic particles
  • the lithium compound to be used in step (a) is preferably selected from lithium nitrate, lithium chloride, lithium carbonate, lithium acetate, lithium formate, lithium azide, lithium metal hydrides, such as e.g. LiAlH, lithium alcoholates or organolithium compounds.
  • the solvent or dispersant in step (a) can be aqueous or non-aqueous, e.g. Water, an alcohol, ketone, ether, saturated and or unsaturated hydrocarbon or a mixture thereof.
  • the carrier is a flexible nonwoven with a porous inorganic coating on and in this nonwoven, the material of the nonwoven being made of nonwoven, not electrically conductive Polymer fibers can be selected. However, it can also be a nonwoven or woven fabric made of ceramic or glass fibers.
  • Such a fleece preferably has a thickness of at most 30 ⁇ m, very particularly preferably a thickness of 5 to 30 ⁇ m.
  • the porous support having an inorganic coating or the planar, flexible substrate having a plurality of openings comprises fibers, preferably selected from fibers of polyamide, polyacrylonitrile, polyester, such as e.g. Polyethylene terephthalate (PET) and / or polyolefin, e.g. Polyethylene (PE) or polypropylene (PP), glass fibers or ceramic fibers.
  • PET Polyethylene terephthalate
  • PP polypropylene
  • the carrier or the flexible substrate comprises polymer fibers, polymer fibers other than those mentioned above can be used, provided that they both have the temperature stability required for the production of the separators and are stable under the operating conditions in a lithium battery.
  • the separator according to the invention has polymer fibers which have a softening temperature of greater than 100 ° C. and a melting temperature of greater than 110 ° C.
  • the carrier or the substrate can comprise fibers and or filaments with a diameter of 1 to 150 ⁇ m, preferably 1 to 20 ⁇ m, and / or threads with a diameter of 3 to 150 ⁇ m, preferably 10 to 70 ⁇ m.
  • the substrate is a fleece with a pore size of 5 to 500 ⁇ m, preferably 10 to 200 ⁇ m.
  • the flexible nonwoven preferably has a weight per unit area of less than 20 g / m.
  • the flexible nonwoven has a porosity of more than 50%.
  • the porous inorganic coating on and in the fleece has ceramic oxide particles of the elements Si and optionally Al, and / or Zr with an average particle size of 0.1 to 10 ⁇ m, preferably 0.5 to 5 ⁇ m.
  • the porous inorganic coating located on and in the fleece very particularly preferably has aluminum oxide particles with an average particle size of 0.5 to 5 ⁇ m, which are bonded to an oxide of the elements Zr or Si.
  • the carrier preferably has a porosity of 30 to 90%.
  • the separator obtained according to the invention will have a tensile strength of more than 1 N / cm.
  • the separator or the separator intermediate product can preferably be bent to a radius down to 100 mm, preferably up to 1 mm, without damage.
  • the thickness of the separator is at most 35 ⁇ m.
  • the contact in step (b) or the application of the thin layer in step (b-2) is preferably carried out by printing, pressing, pressing, rolling, knife coating, spreading, dipping, spraying or pouring on the mixture or the dispersion.
  • the object of the invention is achieved by a separator for an electrochemical cell, which can be obtained by one of the methods described above.
  • Lithium atoms are preferably present on inner and / or outer surfaces of the separator according to the invention via an oxygen bridge on atoms of a group 3A, 4A, 3B or 4B element in the periodic table of the elements, preferably selected from one of the elements silicon, aluminum and zirconium.
  • Such structures can be detected by Raman spectroscopy.
  • the separator also has a low water content has a water content of less than 1000 ppm, preferably less than 500 ppm, very particularly preferably less than 200 ppm.
  • the separator of the present invention is outstandingly suitable for electrochemical cells with high capacity and high energy density due to its configuration according to the invention.
  • the separator according to the invention is suitable for electrochemical cells which are based on the transfer of alkali and / or alkaline earth metal ions, such as e.g. Lithium metal and lithium ion batteries. It is therefore advantageous if these separators also show the protective measures specific to these applications, such as the interruption property and short-circuit property with a high short-circuit temperature.
  • Interrupting property or "shut-down" is to be understood as a measure in which easily separable substances, such as, for example, thermoplastic plastics, can be incorporated into the separator for specific operating temperatures.
  • Short-circuit property or melt-down means that the separator melts completely at a short-circuit temperature. A contact and a short circuit can then occur between large areas of the electrodes of an electrochemical cell. For a safe operation of an electrochemical cell with a high capacity and energy density, the highest possible short-circuit temperature is desirable.
  • the separator according to the invention has a significant advantage.
  • the ceramic material which adheres to the perforated support in the separator of the present invention has a melting point which is far above the safety-relevant temperature range for electrochemical cells.
  • the separator of the present invention therefore has superior safety. It is namely stable in a preferred safe embodiment under operating conditions of at least 50 ° C. Even more preferably, it is stable at at least 100 ° C, 150 ° C, and most preferably at least 180 ° C.
  • Polymer separators bring the currently required for lithium batteries Safety by preventing any current transport through the electrolyte above a certain temperature (the shutdown temperature, which is around 120 ° C). This happens because the pore structure of the separator collapses at this temperature and all pores are closed. Because no more ions can be transported, the dangerous reaction that can lead to the explosion comes to a standstill. If the cell is heated further due to external circumstances, the breakdown temperature is exceeded at approx. 150 to 180 ° C. From this temperature, the separator melts and contracts. At many points in the battery cell there is now a direct contact between the two electrodes and thus a large internal short circuit. This leads to an uncontrolled reaction, which ends with an explosion of the cell, or the pressure that is created is often reduced by fire through a pressure relief valve (a rupture disc).
  • a pressure relief valve a rupture disc
  • the carrier of the separator comprises polymer fibers.
  • This hybrid separator which has inorganic components and polymeric carrier material, is shutdown when the high temperature causes the polymer structure of the carrier material to melt and penetrate into the pores of the inorganic material, thereby closing it.
  • meltdown breakdown
  • the separator according to the invention thus meets the requirements for a safety shutdown required by various battery manufacturers due to the shutdown in the battery cells.
  • the inorganic particles ensure that there can never be a meltdown. This ensures that there are no operating states in which a large-scale short circuit can occur.
  • the separator has an additional non-inherent shutdown mechanism.
  • This can e.g. B. can be realized in that a very thin wax or polymer particle layer of so-called shutdown particles, which melt at a desired shutdown temperature, is present on or in the separator.
  • Particularly preferred materials from which the shutdown particles can consist are, for example, natural or artificial waxes, low-melting polymers, such as. B. polyolefins, wherein the material of the shutdown particles is selected so that the particles at the desired Melt the cut-off temperature and close the pores of the separator so that further ion flow is prevented.
  • the shutdown particles preferably have an average particle size (D w ) which is greater than or equal to the average pore size (d s ) of the pores of the porous inorganic layer of the separator. This is particularly advantageous because such penetration and closure of the
  • Pores of the separator layer which reduces the pore volume and thus the
  • the thickness of the cut-off particle layer is only critical if an excessively thick layer would unnecessarily increase the resistance in the battery system. To be safe
  • the shutdown particle layer should have a thickness (z w ) that is approximately equal to the average particle size of the shutdown particles (D w ) up to 10 D w , preferably from 2 D w to D w .
  • a separator equipped in this way has a primary one
  • High-energy batteries are very important and are therefore often required.
  • the separator according to the invention is very safe.
  • the polymer separator would melt and contract at the point of penetration (a short-circuit current flows over the nail and heats it up).
  • the short circuit point becomes larger and the reaction gets out of control.
  • the polymeric substrate material melts, but not the inorganic separator material.
  • the reaction inside the battery cell after such an accident is much more moderate. This battery is therefore significantly safer than one with a polymer separator. This is particularly important in the mobile area.
  • the method for applying a dispersion as a thin layer on and into a substrate for producing a separator or separator intermediate, and the production of a porous carrier having an inorganic coating, which preferably has a flat surface comprising a plurality of openings provided, flexible substrate is known in principle from WO 99/15262. However, not all parameters or input materials can be used.
  • a dispersion can e.g. B. by printing, pressing, pressing, rolling, knife coating, spreading, dipping, spraying or pouring onto and into the flexible substrate provided with a plurality of openings.
  • the flexible substrate provided for application and introduction into the plurality of openings can have a sol of the elements Al, Zr and / or Si, and is preferably produced by dispersing ceramic particles and optionally fine particles in one of these brines.
  • the sols can be obtained by hydrolyzing at least one compound, with water or an acid, or a combination of these compounds. It may be advantageous to add the compound to be hydrolyzed to alcohol or an acid or a combination of these liquids before the hydrolysis.
  • the compound to be hydrolyzed at least one nitrate, a chloride, a carbonate, an alcoholate or an element-organic compound of the elements Al, Zr and / or Si is preferably hydrolyzed.
  • the hydrolysis is preferably carried out in the presence of water, steam, ice or an acid or a combination of these compounds.
  • particulate sols are produced by hydrolysis of the compounds to be hydrolyzed. These particulate sols are characterized by the fact that the compounds formed in the sol by hydrolysis are present in particulate form.
  • the particulate sols can be prepared as described above or as described in WO 99/15262. These brines usually have a very high water content, which is preferably greater than 50% by weight. It may be advantageous to add the compound to be hydrolyzed to alcohol or an acid or a combination of these liquids before the hydrolysis.
  • the hydrolyzed compound can be treated with at least one organic or inorganic acid, preferably with a 10 to 60% organic or inorganic acid, particularly preferably with a mineral acid selected from sulfuric acid, hydrochloric acid, perchloric acid, phosphoric acid and nitric acid or a mixture of these acids become.
  • the particulate sols thus produced can then be used to prepare dispersions, the production of dispersions for application to nonwovens pretreated with polymer sol being preferred.
  • polymeric sols are produced by hydrolysis of the compounds to be hydrolyzed.
  • the sol has a water and / or acid content of less than 50% by weight.
  • These polymeric sols are distinguished by the fact that the compounds formed in the sol by hydrolysis are polymeric (ie chain-like crosslinked over a larger space).
  • the polymeric sols usually have less than 50% by weight, preferably very much less than 20% by weight, of water and / or aqueous acid.
  • the hydrolysis is preferably carried out in such a way that the compound to be hydrolyzed with the 0.5 to 10 times molar ratio and preferably with half the molar ratio of water, steam or ice, based on the hydrolyzable group, the hydrolyzable compound, is hydrolyzed.
  • up to 10 times the amount of water can be used with very slow hydrolyzing compounds such.
  • Very rapidly hydrolyzing compounds such as zirconium tetraethylate can already form particulate sols under these conditions, which is why 0.5 times the amount of water is preferably used for the hydrolysis of such compounds.
  • Both particulate brine (high water content, low solvent content) and polymer Sols (low water content, large solvent content) can be used as sol in the process according to the invention for producing a dispersion.
  • commercially available brines such as e.g. B. zirconium nitrate sol or silica sol can be used.
  • the process for creating separator precursors by applying and solidifying a suspension on a substrate is known per se from DE 101 42 622 and in a similar form from WO 99/15262, but not all parameters or feedstocks can be referred to the production of the Separator intermediate and separators transferred.
  • sols or dispersions which has been adapted to the polymers in terms of wetting behavior completely impregnates nonwoven materials and thus flawless coatings are obtainable.
  • the method therefore preferably adjusts the wetting behavior of the sol or the dispersion.
  • This adjustment is preferably carried out by the production of sols or dispersions, these sols one or more alcohols, such as. B. methanol, ethanol or propanol or mixtures thereof, and / or have aliphatic hydrocarbons.
  • alcohols such as. B. methanol, ethanol or propanol or mixtures thereof
  • solvent mixtures are also conceivable which can be added to the sol or the dispersion in order to adapt them to the fleece used in terms of wetting behavior.
  • the mass fraction of the suspended or dispersed component (ceramic particles) in the dispersion is preferably 1 to 100 times, particularly preferably 1 to 50 times and very particularly preferably 1 to 10 times the sol used.
  • Oxide particles such as aluminum oxide particles, which preferably have an average particle size of 0.1 to 10 ⁇ m, in particular 0.5 to 5 ⁇ m, are particularly preferably used to produce the dispersion as ceramic particles.
  • Alumina particles in the area of preferred particle sizes are for example from the company Martinswerke under the designations MDS 6; DN 206, MZS 3 and MZS 1 and offered by Alcoa with the designations CL3000 SG, CT800 SG and HVA SG.
  • Ceramic particles are therefore preferably used, which by a conventional method such.
  • Air classification, centrifuging and hydroclassification were classified. Fractions in which the coarse grain fraction, which makes up up to 10% of the total amount, have been separated off by wet sieving are preferably used as ceramic particles. This disruptive coarse grain fraction, which cannot be broken up or only with great difficulty by the processes typical in the production of the slurries, such as grinding (ball mill, attritor mill, mortar mill), dispersing (Ultra-Turrax, ultrasound), grinding or chopping, B.
  • the inorganic porous layer has a very uniform pore size distribution. This is achieved in particular by using ceramic particles which have a maximum particle size of preferably 1/3 to 1/5 and particularly preferably less than or equal to 1/10 of the thickness of the nonwoven used.
  • Table 1 Typical data of ceramics depending on the type of powder used
  • adhesion promoters such as e.g. B. add organofunctional silanes.
  • compounds selected from the octylsilanes, the vinylsilanes, the amine-functionalized silanes and / or the glycidyl-functionalized silanes, such as, for. B. the Dynasilane from Degussa can be used.
  • adhesion promoters for polymer fibers such as polyethylene (PE) and polypropylene (PP) are vinyl, methyl and octylsilanes, the exclusive use of methylsilanes not being optimal; for polyamides and polyamines, it is amine-functional silanes, for polyacrylates and polyesters Glycidyl-functionalized silanes and for polyacrylonitrile it is also possible to use glycidyl-functionalized silanes.
  • Other adhesion promoters can also be used, but these have to be matched to the respective polymers.
  • the adhesion promoters are advantageously selected such that the solidification temperature is below the melting or softening point of the polymer used as the substrate and below its decomposition temperature.
  • Dispersions according to the invention preferably have very much less than 25% by weight, preferably less than 10% by weight, of compounds which can act as adhesion promoters.
  • An optimal proportion of adhesion promoter results from the coating of the fibers and / or particles with a monomolecular layer of the adhesion promoter.
  • the amount of adhesion promoter required in grams can be obtained by multiplying the amount of oxides or fibers used (in g) by the specific surface area of the materials (in m 2 g " ') and then dividing by the specific space requirement of the adhesion promoter (in m 2 g "1 ) are obtained, 1 • where the specific space requirement is often in the order of 300 to 400 mg " .
  • Table 2 below contains an exemplary overview of usable adhesion promoters based on organofunctional Si compounds for typical polymers used as nonwoven material. Table 2
  • AMEO 3-aminopropyltriethoxysilane
  • DAMO 2-aminoethyl-3-aminopropyltrimethoxysilane
  • GLYMO 3-glycidyloxytrimethoxysilane
  • MEMO 3-methacryloxypropyltrimethoxysilane
  • VTEO vinyl triethoxysilane
  • VTMO vinyltrimethoxysilane
  • VTMOEO vinyltris (2-methoxyethoxy) silane
  • the abovementioned adhesion promoters are applied in a preceding step to a flat, flexible substrate, such as a polymer fleece, which is provided with a multiplicity of openings.
  • a suitable solvent such as. B. dissolved ethanol.
  • This solution can also contain a small amount of water, preferably 0.5 to 10 times the amount based on the molar amount of the hydrolyzable group, and small amounts of an acid, such as. B. HCl or HNO, as a catalyst for the hydrolysis and condensation of the Si-OR groups.
  • an acid such as. B. HCl or HNO
  • this solution is applied to the carrier or the substrate and the adhesion promoter is fixed by a temperature treatment at 50 to a maximum of 350 ° C. on the carrier or substrate.
  • the method only takes place after the adhesion promoter has been applied the application and solidification of the dispersion.
  • the adhesive behavior of the flexible carriers or substrates can be improved, in particular with respect to aqueous, particulate sols, which is why carriers or substrates with suspensions or dispersions based on commercially available sols such as, B. zirconium nitrate sol or silica sol can be coated.
  • this procedure of applying an adhesion promoter also means that the manufacturing process of the separators according to the invention must be expanded by an intermediate or pretreatment step. This is feasible, however, also more complex than the use of adapted brines to which adhesion promoters have been added, but also has the advantage that better results are achieved even when dispersions based on commercially available brines are used.
  • the coatings according to the invention are brought into and onto the substrate by solidifying the dispersion.
  • the dispersion present on and in the substrate can be solidified by heating to 50 to 350 ° C. Since the maximum temperature is determined by the polymer fleece when using polymeric substrate materials, this must be adjusted accordingly.
  • the dispersion present on and in a substrate is solidified by heating to 100 to 350 ° C. and very particularly preferably by heating to 110 to 280 ° C. It can be advantageous if the heating is carried out for 1 second to 60 minutes at a temperature of 100 to 350 ° C.
  • the dispersion is particularly preferably heated for solidification to a temperature of 110 to 300 ° C., very particularly preferably at a temperature of 110 to 280 ° C. and preferably for 0.5 to 10 min.
  • the composite can be heated by means of heated air, hot air, infrared radiation or by other heating methods according to the prior art.
  • the method for applying a thin layer on and in the substrate or contacting a porous carrier having an inorganic coating with a mixture can, for. B. be carried out such that the flexible substrate, for example a polymer fleece, or the porous carrier having an inorganic coating is unrolled from a roll at a speed of 1 m / h to 2 m / s, preferably at a speed of 0.5 m / min. up to 20 m / min and very particularly preferably at a speed of 1 m / min to 5 m / min through at least one apparatus which brings the dispersion or the mixture onto and into the substrate or the carrier, such as, for. B.
  • a roller and at least one other apparatus which enables the dispersion to solidify on and in the carrier by heating, such as. B. passes through an electrically heated oven and the product so produced is rolled up on a second roll.
  • the pre-treatment steps can also be carried out in a continuous process while maintaining the parameters mentioned.
  • the flat, flexible substrate having a plurality of openings in particular a polymer fleece, has a maximum longitudinal tension of 10 N / cm, preferably 3 N, during the coating process / cm.
  • the coating process is understood to mean all process steps in which a material is brought onto and into a flexible substrate and is subjected to a heat treatment there, that is to say also the application of the adhesion promoter.
  • the substrate is preferably stretched during the coating process with a maximum force of 0.01 N / cm. It can be particularly preferred if the substrate is guided in the longitudinal direction without tension during the treatment process or the coating process.
  • the substrate material is deformed (also elastic).
  • the ceramic coating cannot follow the substrate material due to possible deformation (elongation) when the tensile stress is too high, which leads to the coating becoming detached from the substrate over the entire surface. The resulting product cannot then be used as intended.
  • the separator according to the invention is to be equipped with an additional automatic shutdown mechanism, this can be done e.g. B. happen that after after solidifying the dispersion applied to the substrate, a layer of particles which melt at a desired temperature and close the pores of the separator, so-called shutdown particles, is applied to the separator to produce a shutdown mechanism and fixed.
  • the layer of shutdown particles can e.g. B. by applying a suspension of wax particles with an average particle size larger than the average pore size of the separator in a sol, water, solvent or solvent mixture.
  • the suspension for applying the particles preferably contains from 1 to 50% by weight, preferably from 5 to 40% by weight and very particularly preferably from 10 to 30% by weight of shutdown particles, in particular wax particles, in the suspension.
  • the inorganic coating of the separator often has a very hydrophilic character, it has proven to be advantageous if the coating of the separator was produced using a silane in a polymeric sol as an adhesion promoter and was thus rendered hydrophobic. In order to achieve good adhesion and uniform distribution of the shutdown particles in the shutdown layer even on hydrophilic porous inorganic separator layers, several variants are possible.
  • the porous inorganic layer of the separator it has proven to be advantageous to hydrophobicize the porous inorganic layer of the separator before the shutdown particles are applied.
  • the production of hydrophobic membranes which works on the same principle, is described for example in WO 99/62624.
  • the porous inorganic coating is preferably treated by treatment with alkyl, aryl or fluoroalkylsilanes, as described, for. B. are sold under the name Dynasilan by Degussa, hydrophobized. It can z. B. the known methods of hydrophobization, which are used, inter alia, for textiles (D. Knittel; E. Schollmeyer; Melliand Textilber.
  • the coating or the separator is treated with a solution which has at least one hydrophobic substance.
  • the solution is water, which is preferably mixed with an acid, preferably acetic acid or Hydrochloric acid, has been adjusted to a pH of 1 to 3, and / or an alcohol, preferably ethanol.
  • the proportion of water treated with acid or of alcohol in the solvent can in each case be from 0 to 100% by volume.
  • the proportion of water in the solvent is preferably from 0 to 60% by volume and the proportion of alcohol from 40 to 100% by volume.
  • hydrophobic substances such as, for example, with triethoxy (3,3,4,4,5,5,6,6,7,7,8,8-tridecafluorooctyl) silane, but also one Treatment with methyltriethoxysilane or i-butyltriethoxysilane is completely sufficient to achieve the desired effect.
  • the solutions are stirred at room temperature for uniform distribution of the hydrophobic substances in the solution and then applied to the inorganic coating of the separator and dried. Drying can be accelerated by treatment at temperatures from 25 to 100 ° C.
  • the porous inorganic coating can also be treated with other adhesion promoters before the shutdown particles are applied. Treatment with one of the adhesion promoters mentioned below can then also be carried out as described above, i. H. that the porous inorganic layer is treated with a polymeric sol which has a silane as an adhesion promoter.
  • the layer of shutdown particles is preferably applied by applying a suspension of shutdown particles in a suspension medium selected from a sol, water or solvent, such as. B. alcohol, ether or ketones, or a solvent mixture on the inorganic coating of the separator and subsequent drying.
  • a suspension of shutdown particles in a suspension medium selected from a sol, water or solvent, such as. B. alcohol, ether or ketones, or a solvent mixture
  • the particle size of the shutdown particles present in the suspension is arbitrary.
  • D w average particle size
  • the shutdown particles used preferably have a average particle size (D w ) which is greater than the average pore diameter (d s ) and less than 5 d s , particularly preferably less than 2 d s .
  • Preventing cut-off particles into the pores of the porous inorganic layer consists in adjusting the viscosity of the suspension in such a way that, in the absence of external shear forces, the suspension does not penetrate into the pores of the inorganic layer of the separator.
  • Such a high viscosity of the suspension can e.g. can be achieved by the
  • Suspension auxiliaries that influence the flow behavior e.g. Silicas (Aerosil,
  • auxiliary materials such as Aerosil 200 is often a proportion of 0.1 to 50% by weight, preferably 0.5 to 10% by weight, of silica, based on the suspension, sufficient to achieve a sufficiently high viscosity of the suspension.
  • the proportion of auxiliary substances can be determined by simple preliminary tests.
  • the suspension used has shut-off particles with adhesion promoters.
  • adhesion promoter suspension can be applied directly to an inorganic layer of the separator, even if this is not before
  • a suspension having an adhesion promoter can also be applied to a hydrophobized layer or to a separator layer during its manufacture
  • Adhesion promoter was used to be applied. Silanes which are preferably used as adhesion promoters in the suspension having shutdown particles
  • adhesion promoters are e.g. B.
  • AMEO (3-aminopropyltriethoxysilane)
  • MEMO (3-methacryloxypropyltrimethoxysilane)
  • Silfin (vinylsilane + initiator + catalyst), VTEO (vinyltriethoxysilane) or VTMO
  • silane (Vinyltrimethoxysilane). Such silanes are e.g. B. from Degussa also available in aqueous solution under the name Dynasilan 2926, 2907 or 2781. A maximum share
  • Suspensions containing switch-off particles preferably contain adhesion promoters from 0.1 to 10% by weight, preferably from 1 to 7.5% by weight and very particularly preferably from 2.5 to 5% by weight, based on the suspension, of adhesion promoters ,
  • All particles that have a defined melting point can be used as shutdown particles.
  • the material of the particles is selected according to the desired switch-off temperature. Since relatively low switch-off temperatures are desired for most batteries, it is advantageous to use switch-off particles which are selected from particles of polymers, polymer mixtures, natural and or artificial waxes. Particles made of polypropylene or polyethylene wax are particularly preferably used as shutdown particles.
  • the suspension containing the shutdown particles can be applied to the porous inorganic layer of the separator by printing, pressing on, pressing in, rolling up, knife coating, spreading on, dipping, spraying or pouring on.
  • the switch-off layer is preferably obtained by drying the applied suspension at a temperature from room temperature to 100 ° C., preferably from 40 to 60 ° C.
  • the cut-off particles are fixed by heating at least once to a temperature above the glass temperature, so that the particles melt without changing the actual shape. In this way it can be achieved that the shutdown particles adhere particularly well to the porous inorganic separator layer.
  • the suspension containing the cut-off particles can be applied with subsequent drying and any heating above the glass transition temperature can be carried out continuously or quasi-continuously. If a flexible separator is used as the starting material, this can in turn be unwound from a roll, passed through a coating, drying and optionally heating apparatus and then rolled up again.
  • an electrochemical cell in particular a lithium battery, lithium ion battery or a lithium polymer battery, provided, the cell comprising one of the separators described above with a low water content.
  • the electrolyte which is used in such an electrochemical cell can be any conventional electrolyte which can be used in electrochemical cells.
  • Solutions of a soluble lithium salt in one or more organic solvents such as, for example, ethylene carbonate and dimethyl carbonate (EC-DMC) can be mentioned as examples.
  • organic solvents such as, for example, ethylene carbonate and dimethyl carbonate (EC-DMC)
  • suitable non-aqueous solvents include, for example, ⁇ -butyrolactone, tetrahydrofuran, 1,2-dimethoxyethane, propylene carbonate, diethyl carbonate, methyl ethyl carbonate, diethoxyethane, dioxolane and methyl formate.
  • Suitable soluble lithium salts are those commonly used.
  • LiPF 6 LiPF 6 , LiAsF 6 , LiBF 4 , LiClO, LiCF 3 SO 3 , LiN (CF 3 SO 2 ) 3 and LiN (C 2 F 5 SO) 3 , LiPF 6 being particularly preferred.
  • the use of one of the above-described separators with a low water content for producing an electrochemical cell, in particular a lithium battery, lithium ion battery or a lithium polymer battery, is provided, in each case preferably for high-current or high-performance applications.
  • the electrochemical cell is preferably rechargeable.
  • the porosity is to be understood as the porosity that can be determined using the known mercury porosimetry method with a Porosimeter 4000 from Carlo Erba Instruments.
  • Mercury porosimetry is based on the Washburn equation (EW Washburn, "Note on a Method of Determining the Distribution of Pore Sizes in a Porous Material", Proc. Natl. Acad. Sei., 7, 115-16 (1921) ).
  • the determination of the water content of the separators is carried out in the following way: A precisely balanced sample from a separator is heated to 180 ° C. in a tightly closed sample vessel. The amount of water released is continuously transferred over a period of more than 2 hours with a dry nitrogen stream into a (previously) anhydrous solution and there according to the method of Karl Fischer (see E. Eberius: water determination with Karl Fischer Solution, 3rd edition, Verlag Chemie, Weinheim 1968).
  • Test example 2 Lithium battery with S450PET separator from reference example 1
  • the S450PET separator produced in reference example 1 is placed in a Li-ion cell consisting of a positive mass made of LiCoO 2 , a negative mass consisting of graphite and an electrolyte made of LiPF 6.
  • a Li-ion cell consisting of a positive mass made of LiCoO 2 , a negative mass consisting of graphite and an electrolyte made of LiPF 6.
  • LiPF 6 ethylene carbonate / dimethyl carbonate
  • the battery heats up excessively and consumes significantly more electricity than its nominal capacity. No special features can be observed from the 5th cycle. However, this separator is not suitable for use in a battery due to the heating.
  • Test example 2 Lithium battery with S800PET separator from reference example 2
  • the S800PET separator produced in reference example 2 is placed in a Li-ion cell consisting of a positive mass as LiCoO 2 , a negative mass consisting of graphite and an electrolyte made of LiPF 6 in ethylene carbonate / dimethyl carbonate (EC / DMC) , built-in [LiCoO 2 // S800PET, EC / DMC 1: 1, IM LiPF 6 // graphite].
  • the charging behavior of this battery is checked. After more than 250 cycles, the battery shows only a slight decrease in capacity by a few percentage points. An increase in the charging voltage from 4.1 to 4.2 volts in the 200th charging cycle does not harm the battery. During the first cycle, the battery heats up excessively and consumes significantly more electricity than its nominal capacity. No special features can be observed from the 5th cycle. However, this separator is not suitable for use in a battery due to the heating.
  • Example 1 Production of an S100PET separator with low water content
  • Example 2 Preparation of a S240PET separator with low water content
  • Example 3 Preparation of a S450PET separator with low water content
  • a water-containing S450PET separator (0.28% by weight water content) produced according to reference example 1 is treated in a continuous impregnation process (belt speed approx. 30 m / h) with a 1% solution of LiNO 3 in water and then at 200 ° C dried in vacuo. After that, the water content in the separator is less than 200 ppm.
  • a water-containing S800PET separator (0.34% by weight water content) produced according to reference example 2 is treated in a continuous impregnation process (belt speed approx. 30 m / h) with a solution of 0.1 mol lithium ethylate in one liter of ethanol and then at 200 ° C dried in vacuo. After that, the water content in the separator is less than 200 ppm.
  • Example 3 Lithium battery with the S450PET separator according to the invention with a low water content from Example 3
  • the S450PET separator produced in Example 3 is placed in a Li-ion cell consisting of a positive mass of LiCoO 2 , a negative mass of graphite and an electrolyte of LiPF 6 in ethylene carbonate / dimethyl carbonate (EC / DMC), built-in [LiCoO 2 // S450PET, EC / DMC 1: 1, IM LiPF 6 // graphite].
  • the charging behavior of this battery is checked. After more than 500 cycles, the battery shows only a slight decrease in capacity by a few percentage points. Even an increase in the charging voltage from 4.1 to 4.2 volts in the 450th charging cycle does not harm the battery. In contrast to test examples 1 and 2, the battery does not overheat during the first cycle. The power consumption in the first cycle largely corresponds to the nominal capacity of the cell.
  • This separator is ideal for use in a battery.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Cell Separators (AREA)

Abstract

L'invention concerne un procédé de production d'un séparateur à faible teneur en eau destiné à une cellule électrochimique. Ce procédé consiste: (a) à prendre un mélange contenant (a-1) un composé de lithium et un radical qui se volatilise légèrement lorsqu'il est chauffé, (a-2) un solvant et/ou un dispersant et (a-3) éventuellement d'autres composés; (b) à produire un demi-produit séparateur avec le mélange, le composé de lithium étant au moins partiellement exposé sur la surface du demi-produit séparateur; (c) à chauffer le demi-produit séparateur à une température comprise entre 50 et 350 °C pendant un temps prédéterminé pour éliminer le radical du composé de lithium, éventuellement par voie pyrolytique, au moins partiellement de la surface du demi-produit séparateur et pour obtenir le séparateur à faible teneur en eau.
PCT/EP2003/012113 2002-11-26 2003-10-31 Separateur a faible teneur en eau destine a une cellule electrochimique WO2004049480A2 (fr)

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AU2003293640A AU2003293640A1 (en) 2002-11-26 2003-10-31 Separator having a low water content for an electrochemical cell

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DE10255123A DE10255123A1 (de) 2002-11-26 2002-11-26 Separator mit niedrigem Wassergehalt für eine elektrochemische Zelle
DE10255123.5 2002-11-26

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005038960A1 (fr) * 2003-10-14 2005-04-28 Degussa Ag Separateur electrique comportant un mecanisme de coupure, procede de fabrication et utilisation dans des piles au lithium
WO2015197428A1 (fr) * 2014-06-23 2015-12-30 Evonik Litarion Gmbh Séparateur hydrophobe et procédé de fabrication du séparateur
US9680141B2 (en) 2012-01-30 2017-06-13 Litarion GmbH Separator comprising an organic-inorganic adhesion promoter

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102016125168A1 (de) 2016-12-21 2018-06-21 Fortu New Battery Technology Gmbh Wiederaufladbare elektrochemische Zelle mit keramischer Separatorschicht und Indikatorelektrode
DE102016125177A1 (de) 2016-12-21 2018-06-21 Fortu New Battery Technology Gmbh Elektrode-Separator-Element mit einer keramischen Separatorschicht
CN116514571A (zh) * 2022-12-21 2023-08-01 咸阳陶瓷研究设计院有限公司 一种利用锂渣制备无机吸音材料的方法

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Publication number Priority date Publication date Assignee Title
US6153337A (en) * 1997-12-19 2000-11-28 Moltech Corporation Separators for electrochemical cells
WO1999057769A1 (fr) * 1998-05-06 1999-11-11 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Separateur electrique a base d'un substrat revetu de ceramique
JP3643289B2 (ja) * 1999-04-30 2005-04-27 株式会社オハラ ガラスセラミックス複合電解質、及びリチウム二次電池
DE10240032A1 (de) * 2002-08-27 2004-03-11 Creavis Gesellschaft Für Technologie Und Innovation Mbh Ionenleitender Batterieseparator für Lithiumbatterien, Verfahren zu deren Herstellung und die Verwendung derselben

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005038960A1 (fr) * 2003-10-14 2005-04-28 Degussa Ag Separateur electrique comportant un mecanisme de coupure, procede de fabrication et utilisation dans des piles au lithium
US7655360B2 (en) 2003-10-14 2010-02-02 Degussa Ag Electric separator comprising a shutdown mechanism, method for the production thereof, and use in lithium batteries
US9680141B2 (en) 2012-01-30 2017-06-13 Litarion GmbH Separator comprising an organic-inorganic adhesion promoter
WO2015197428A1 (fr) * 2014-06-23 2015-12-30 Evonik Litarion Gmbh Séparateur hydrophobe et procédé de fabrication du séparateur

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AU2003293640A8 (en) 2004-06-18
DE10255123A1 (de) 2004-06-03
WO2004049480A3 (fr) 2004-08-12
TW200418218A (en) 2004-09-16

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