EP1738424A1 - Utilisation d'un separateur ceramique dans des piles a ions lithium presentant un electrolyte contenant des liquides ioniques - Google Patents

Utilisation d'un separateur ceramique dans des piles a ions lithium presentant un electrolyte contenant des liquides ioniques

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Publication number
EP1738424A1
EP1738424A1 EP05708055A EP05708055A EP1738424A1 EP 1738424 A1 EP1738424 A1 EP 1738424A1 EP 05708055 A EP05708055 A EP 05708055A EP 05708055 A EP05708055 A EP 05708055A EP 1738424 A1 EP1738424 A1 EP 1738424A1
Authority
EP
European Patent Office
Prior art keywords
separator
substrate
separator according
coating
base component
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP05708055A
Other languages
German (de)
English (en)
Inventor
Gerhard HÖRPEL
Volker Hennige
Christian Hying
Sven Augustin
Carsten Jost
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Evonik Operations GmbH
Original Assignee
Degussa GmbH
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 GmbH filed Critical Degussa GmbH
Publication of EP1738424A1 publication Critical patent/EP1738424A1/fr
Withdrawn legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0289—Means for holding the electrolyte
    • H01M8/0293—Matrices for immobilising electrolyte solutions
    • H—ELECTRICITY
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    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
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    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
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    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H—ELECTRICITY
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    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H—ELECTRICITY
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    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
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    • H01M50/409—Separators, membranes or diaphragms characterised by the material
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    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
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    • H01M50/431—Inorganic material
    • H01M50/434—Ceramics
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    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
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    • H01M50/44—Fibrous material
    • H—ELECTRICITY
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    • 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
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    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
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    • 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
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    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/463—Separators, membranes or diaphragms characterised by their shape
    • H—ELECTRICITY
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    • H01M2300/0088—Composites
    • H01M2300/0094—Composites in the form of layered products, e.g. coatings
    • 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
    • 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
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    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Definitions

  • Veir e ⁇ ndhiiiBiP s-anes IkeF-iim-iiscI-nsiiii Sensairäatoirs mm -L l n ⁇ - ⁇ -i ° I (ii) i ⁇ ae ⁇ - ⁇ lbat-i- (Sirn (Siii-. ding e ⁇ -ag
  • the present invention relates to the use of ceramic or predominantly ceramic separators filled with electrolyte which have ionic liquids in lithium-ion batteries.
  • Lithium-ion batteries are energy storage systems that have a very high energy density (up to 180 Wh / kg). These lithium-ion batteries are mainly used in the field of portable electronics, such as in laptops, camcorders, handhelds or cell phones, so-called cell phones.
  • the negative electrode material consists mainly of graphitic carbon, carbon black and a suitable binder material. This "graphite electrode” is used due to its stable cycle properties and - compared to lithium metal (which is used in so-called “jithium-metal batteries”) - quite high handling safety, although graphitic carbon has a very low potential of approx. 100 up to 200 mV vs. Li / Li * has.
  • Lithium transition metal oxides such as LiCo0 2 , LiNi0 2 or LiMn x Ni y Co ] - ] C are mostly used as positive electrode material.
  • y O 2 are used which have a high potential (3.8-4.2 V vs. Li / Li 4 ).
  • the high energy density of the lithium-ion batteries results, among other things, from the high potential window due to the electrode combination, which can be up to 4 V.
  • This high potential difference places high demands on the electrolyte materials used, for example a combination of a polar liquid with a lithium salt is used as the electrolyte, the lithium salt taking over the ion conduction.
  • electrolytes according to the prior art are generally not permanently stable, since both the electrolyte liquid and the lithium conductive salt can be reduced at the negative electrode.
  • the technical usability of lithium-ion batteries is due to the fact that an important component of conventional electrolytes, for example ethylene carbonate, is involved in the reduction the negative electrode forms an electrolyte-insoluble film (solid electrolyte interphase layer) on the surface of the graphite, this film permitting ion conduction, but preventing a further reduction of the electrolyte.
  • an important component of conventional electrolytes for example ethylene carbonate
  • Ethylene carbonate which is solid at room temperature, is generally used as a mixture with low-viscosity solvents, such as, for example, dimethyl carbonate or ethyl methyl carbonate (EMC), in order to increase the conductivity.
  • EMC ethyl methyl carbonate
  • Blomgren et al. describe the use of ionic liquids as electrolyte materials in the lithium-ion battery (A. Webber, GE Blomgren, Advances in Lithium-Ion Batteries (2002), 185 - 232; GE Blomgren, J. Power Sources 2003, 119 - 121, 326 - 329)
  • Covalent Associates describes a non-flammable electrolyte consisting of a salt with an organic cation or of an ionic liquid (IL), an organic solvent, an acylate or fluoropolymer and a conductive salt.
  • IL ionic liquid
  • JP 2002373704 Yuasa Corp a non-aqueous electrolyte consisting of a salt melted at room temperature, a lithium salt and a cyclic ester with a ⁇ bond.
  • Ionic liquids are used as solvents in the electrolyte in the battery despite many Try not yet established. This is probably due essentially to the fact that the use of ionic liquids as solvents in the electrolyte in lithium-ion batteries is disadvantageous due to the poor wetting behavior in relation to conventional separators
  • the poor wettability of the conventional separators Due to the poor wettability of the conventional separators, it takes a relatively long time before the wound battery can be filled with electrolyte, and secondly, the poor wettability can lead to the electrolyte not being evenly distributed in the cell (e.g. due to air bubbles or unfilled pores remain in the separator), which can lead to poor long-term stability of the battery. In addition, the poor wettability can result in the load capacity of the battery becoming very poor. H. the maximum charge / discharge currents are relatively low.
  • separators which consist of ceramic or have surfaces made of ceramic are used in combination with electrolytes containing ionic liquids. Because of the ceramic nature of the separators (at least on the surfaces of the separators), they are extremely hydrophilic and are therefore very well wettable with polar electrolytes which have ionic liquids.
  • Ceramic separators the ceramic material, applied to a support, e.g. B. have a polymer fiber fleece for use in Li batteries based on conventional electrolytes are from the prior art, for. B. from WO 03/021697, WO 03/072231, WO 03/073534, WO 2004/021469, WO 2004/021474, WO 2004/021475, WO 2004/021476, WO 2004/021477 and WO 2004/021499.
  • the present invention therefore relates to the use of a ceramic separator or a separator which has a ceramic surface, in particular the use of a separator comprising a flat, flexible substrate provided with a plurality of openings and having a coating on and in this substrate, wherein the material of the substrate is selected from woven or non-woven, non-electrically conductive natural or polymer fibers and the coating is a porous, electrically insulating, ceramic coating in a battery, the separator in the battery being filled with an electrolyte composition , which has a conductive salt and a base component, the base component having at least one ionic liquid which has a melting point of less than 100 ° C. as the main component with a proportion of greater than 50% by mass
  • the present invention also relates to a separator filled with an electrolyte, comprising a flat, flexible substrate provided with a plurality of openings and having a coating on and in this substrate, the material of the substrate being selected from woven or non-woven, non-electrical conductive natural or polymer fibers and the coating is a porous, electrically insulating, ceramic coating, the separator being filled with an electrolyte composition, which is characterized in that the electrolyte composition has a conductive salt and a base component, the base component as the main component with a proportion greater than 50% by mass has at least one ionic liquid which has a melting point less than 100 ° C
  • the present invention also relates to a method for producing a separator according to the invention, in which a flat, flexible substrate provided with a plurality of openings is first applied to the substrate and by applying a suspension which has particles of at least one inorganic compound suspended in a sol by at least once heating, in which the suspension is solidified on vmd in the carrier, is provided in and on this substrate with a coating, which is characterized in that the separator thus prepared has an electrolyte composition which has a conductive salt and a base component, the Base component as the main component with a proportion of greater than 50% by mass has at least one ionic liquid which has a melting point less than 100 ° C, is impregnated.
  • the present invention also relates to the use of a separator according to the invention, in particular a separator as claimed in the claims, as a separator in batteries, in particular in lithium metal or lithium-ion batteries, and a lithium-ion battery with a separator according to the invention in particular a separator as claimed in the claims
  • the system according to the invention consisting of a partially ceramic separator and electrolyte composition, the base component of which has more than 50% by mass of ionic liquid, has the advantage that, if at all, only a small proportion of highly flammable components are present in the electrolyte. In this way, a higher level of safety is achieved for lithium-ion batteries which are equipped with the separator according to the invention
  • the separators according to the invention are themselves safer than conventional separators.
  • Polymer separators for example, provide the security currently required for lithium batteries 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 break-down temperature is exceeded at approx. 150 to 180 ° C. From this temperature, the separator melts, which contracts. At many points in the battery cell, there is now 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 separator according to the invention which has inorganic components and preferably a polymeric material as a substrate
  • meltdown breakdown
  • the separator according to the invention therefore 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.
  • shutdown mechanism is absolutely necessary for the application, this can also be achieved in that the surface and / or the pores of the ceramic or hybrid separator according to the invention are equipped with a substance which, when the Temperature limit closes the pores and prevents further ion flow. This can be achieved, for example, by an additional layer of a polymer or a wax, the melting point of which is in the range 80-150 ° C.
  • 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 hybrid separator according to the invention at most 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 from. This battery is therefore significantly safer than one with a polymer separator. This is particularly important in the mobile area.
  • the system according to the invention has the advantage that the open pores of the separator can be completely or at least almost completely filled with the electrolyte composition. This is due to the ceramic surface of the separator, which, because it is hydrophilic, can be easily wetted by a polar liquid. The good wettability ensures that the capillary forces are sufficient to absorb the electrolyte composition into the pores of the separator. This is with hydrophobic separators, such as. B. polymer separators not the case.
  • a ceramic separator or a separator which has a ceramic surface in particular the use of a separator comprising a flat, flexible substrate provided with a multiplicity of openings and having a coating on and in this substrate, the material of the substrate is selected from woven or non-woven, non-electrically conductive natural or
  • Polymer fibers and the coating is a porous, electrically insulating, ceramic coating in a battery, is characterized in that the separator in the
  • Battery is filled with an electrolyte composition, which is a conductive salt and a
  • the base component having as a main component with a proportion of greater than 50% by mass at least one ionic liquid which has a melting point less than 100 ° C.
  • the battery can in particular be a lithium metal or lithium ion battery. Separators such as are described below as separators according to the invention are preferably used.
  • the separator according to the invention comprising a planar, flexible substrate provided with a plurality of openings with a coating on and in this substrate, the material of the substrate being selected from woven or non-woven, non-electrically conductive fibers, preferably natural or polymer fibers and the coating is a porous, electrically insulating, ceramic coating, the separator being filled with an electrolyte composition, characterized in that the electrolyte composition has a conductive salt and a base component, the base component being the main component with a proportion of greater than 50% by mass has at least one ionic liquid which has a melting point less than 100 ° C.
  • the separator itself which is not filled with eleldrolyte composition, can be a separator known in the prior art, as used, for. B. in the documents WO 03/021697, WO 03/072231, WO 03/073534, WO 2004/021469, WO 2004/021474, WO 2004/021475, WO 2004/021476, WO 2004/021477 and WO 2004/021499 to which express reference is made with regard to the separator and the method for its production.
  • the separator itself preferably has a nonwoven as the flexible substrate, the material of the substrate or nonwoven preferably being selected from non-woven, non-electrically conductive polymer fibers.
  • the substrate particularly preferably has a flexible fleece with a weight per unit area of less than 20 g / m 2 , preferably from 5 to 8 g / m 2 . !
  • the separator according to the invention preferably has a substrate with a thickness of less than 30 ⁇ m, preferably with a thickness of 5 to 30 ⁇ m and particularly preferably with a thickness of 10 to 18 ⁇ m.
  • the substrate is preferably a nonwoven.
  • a particularly homogeneous pore radius distribution in the substrate is particularly advantageous for use in a separator according to the invention.
  • the substrate particularly preferably has a pore radius distribution in which at least 50% of the pores have a pore radius of
  • the substrate preferably a nonwoven, preferably has a porosity of 50 to 97%, preferably 60 to 90%, particularly preferably 70 to 85%.
  • the porosity is defined as the volume of the substrate (100%) minus the volume of the fibers of the substrate, that is, the proportion of the volume of the substrate that is not filled by material.
  • the volume of the substrate can be calculated from the dimensions of the substrate.
  • the volume of the fibers results from the measured weight of the substrate under consideration and the density of the polymer fibers.
  • the high porosity of the substrate ensures that the separator has a sufficiently high porosity and thus a sufficiently high conductivity even after the porous inorganic or ceramic coating has been applied.
  • the low thickness of the substrate used also ensures good conductivity, which also makes it possible to keep the thickness of the separator as small as possible.
  • Preferred substrates are nonwovens made of polymer fibers.
  • the substrate preferably has polymer fibers which are selected from fibers of polyacrylonitrile (PAN), polyamides, polyimides, polyacrylates, polytetrafluoroethylene, polyesters, such as, for. B. Poryethylene terephthalate (PET) and / or polyolefin, such as. B. polyethylene (PE) or polypropylene (PP) or mixtures of such polyolefins.
  • PAN polyacrylonitrile
  • PET Poryethylene terephthalate
  • polyolefin such as. B. polyethylene (PE) or polypropylene (PP) or mixtures of such polyolefins.
  • the substrate can also have two or more different fibers from different polymers. This can e.g. B. be advantageous if some of the fibers of the substrate have a relatively low melting point, such as. B. polyethylene fibers and some of the fibers have a relatively high melting point, such as. B. polyacrylonitrile fibers.
  • the polyethylene fibers will melt when the battery heats up due to the FeU function and thus lead to shutdown, while the fibers melting at higher temperatures can still ensure the stability of the separator.
  • the substrate particularly preferably has polymer fibers which have a diameter of 0.1 to 10 ⁇ m, preferably of 1 to 4 ⁇ m.
  • the separators according to the invention preferably have a thickness of less than 50 ⁇ m, preferably less than 40 ⁇ m, particularly preferably a thickness of 15 to 30 ⁇ m.
  • the thickness of the substrate has a great influence on the properties of the separator, since on the one hand the flexibility but also the surface resistance of the separator impregnated with electrolyte depends on the thickness of the substrate. Due to the small thickness, a particularly low electrical resistance of the separator is achieved when used with an electrolyte.
  • the separator itself naturally has a very high electrical resistance, since it must have insulating properties itself.
  • thinner separators allow an increased packing density in a battery stack, so that a larger amount of energy can be stored in the same volume.
  • the separator according to the invention has a porous, electrically insulating, ceramic coating on and in the substrate.
  • the coating on and in the substrate preferably has an oxide, nitride or carbide of the metals Al, Zr, Si, Sn, Ce and / or Y, or consists of one or more of these compounds.
  • the porous inorganic coating located on and in the substrate particularly preferably has oxide particles of the elements Al, Si and / or Zr, preferably with an average particle size of 0.1 to 7, preferably from 0.5 to 5 ⁇ m and very particularly preferably from 1.5 to 3 ⁇ m.
  • the separator particularly preferably has a porous inorganic coating located on and in the substrate, the aluminum oxide particles having an average particle size of 0.1 to 7 ⁇ m, preferably 0.5 to 5 ⁇ m and very particularly preferably 1.5 to 3 microns, which are glued with an oxide of the elements Zr or Si.
  • the aluminum oxide particles having an average particle size of 0.1 to 7 ⁇ m, preferably 0.5 to 5 ⁇ m and very particularly preferably 1.5 to 3 microns, which are glued with an oxide of the elements Zr or Si.
  • the preferred maximum particle size is preferably less than 1/3, preferably less than 1/5 and particularly preferably less than or equal to 1/10 of the thickness of the substrate used.
  • the separator preferably has a porosity of 30 to 80%, preferably 40 to 75% and particularly preferably 45 to 70%.
  • the porosity relates to the attainable, i.e. open, pores.
  • the porosity can be determined using the known method of mercury porosimetry or can be calculated from the volume and density of the feedstocks used if it is assumed that only open ones Pores are present.
  • the separators according to the invention are distinguished by the fact that they can have a tear strength of at least 1 N / cm, preferably at least 3 N / cm and very particularly preferably from 3 to 10 N / cm.
  • the separators according to the invention can preferably be bent down to any radius down to 100 m, preferably down to 50 mm and very particularly preferably down to 1 mm without damage.
  • the high tensile strength and the good bendability of the separator according to the invention has the advantage that changes in the geometries of the electrodes which occur during charging and discharging of a battery can be carried out by the separator without the latter being damaged.
  • the flexibility also has the advantage that this separator can be used to produce commercially standardized winding cells. In these cells, the electrode / separator layers are wound up in a spiral in standardized size and contacted
  • shutdown mechanism can be realized in that a very thin wax or polymer article layer is present on or in the separator, which melt at a desired shutdown temperature, so-called shutdown particles.
  • Particularly preferred materials from which the shutdown particles can consist are, for example, natural or artificial waxes, low-melting polymers, such as. B. polyolefins, the material of the shutdown particles being selected so that the particles melt at the desired shutdown temperature and close the pores of the separator, so that a 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 (de) of the pores of the porous inorganic layer of the separator. This is particularly advantageous because it prevents the pores of the separator layer from penetrating and closing, which would result in a reduction in the pore volume and thus in the conductivity of the separator and also in the performance of the battery.
  • the thickness of the shutdown particle layer is only critical insofar as a layer that is too thick would unnecessarily increase the resistance in the battery system.
  • the shutdown particle layer should have a thickness (z,) 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 safety feature. In contrast to the purely organic separator materials, this separator cannot melt completely and therefore there can be no meltdown.
  • the shutdown mechanism can also be implemented in that a porous shutdown layer made of a material which melts at a predetermined temperature and closes the pores of the ceramic layer is present on the ceramic coating, the shutdown layer being covered by a porous fabric, selected from a fabric, fleece, felt, knitted fabric or a porous film is formed.
  • This switch-off layer preferably has a thickness of 1 to 20, preferably 5 to 10 ⁇ m.
  • the switch-off layer can consist of a material selected from polymers, polymer mixtures, natural or artificial waxes or mixtures thereof, which has a melting temperature of less than 130 ° C
  • the electrolyte composition present in the separator has, in addition to at least one conductive salt, at least one base component which preferably consists of at least 75% by mass of ionic liquid. It can be advantageous if the base component consists entirely of ionic liquid
  • ionic liquids are understood to be salts which have a melting point of at most 100 ° C.
  • the electrolyte composition preferably has salts which have a melting temperature of below 750 ° C., preferably below 50 ° C., very particularly preferably below 20 ° C. and very particularly preferably below 0 ° C.
  • the electrolyte compositions preferably contain ionic liquids (A) which have organic cations.
  • the electrolyte compositions present in the separator according to the invention preferably contain ionic liquids (A) which have one or more cations according to the structures below,
  • R 1 R 2 , R 3, R 4, R 5 and R 6, the same or different, and hydrogen, hydroxy, alkoxy, sulfanyl (RS), NH 2 , NHR, NRR 'group, where R and R' may be the same or different, substituted or unsubstituted alkyl groups having 1 to 8 carbon atoms, or halogen, in particular F, Cl, Br or I, with one of the radicals Rl to R4, preferably all the radicals Rl to R4, preferably for cations of structure 10 and 11 are not hydrogen, a linear or branched aliphatic hydrocarbon with 1 to 20, preferably 1 to 8, preferably 1 to 4 carbon atoms, which is substituted, for example with a hydroxy, alkyl having 1 to 8, preferably 1 to 4 carbon atoms and / or halogen - Group, or may be unsubstituted, a cycloaliphatic hydrocarbon radical having 5 to 30, preferably 5 to 10, preferably 5 to 8 carbon atoms,
  • the electrolyte composition according to the invention preferably contains at least one ionic liquid (A) which has a cation based on ammonium, pyridinium, pyrrolidinium, pyrrolinium, oxazolium, oxazolinium, imidazoHum, thiazolium or phosphonium ions
  • the ionic liquids (A) contained in the electrolyte composition preferably have one or more anions selected from phosphate, halogen phosphates, in particular hexafluorophosphate, alkyl phosphates, aryl phosphates, nitrate, sulfate, hydrogen sulfate, alkyl sulfates, aryl sulfates, perfluorinated alkyl and aryl sulfates, sulfonate, alkyl sulfonates, Arylsulfonates, perfluorinated alkyl and arylsulfonates, in particular trifluoromethylsulfonate, tosylate, perchlorate, tetracoroaluminate, heptachlorodialuminate, tetrafluoroborate, alkylborates, amides, in particular perfluorinated alkyls, dicyanamide, saccharinate fluoride, preferably thi
  • the electrolyte composition preferably contains ionic liquids (A) which contain at least one salt, having as the cation an imidazoHum, a pyridinium, an ammonium or phosphonium ion with the following provisions:
  • R and R ' are identical or different, substituted, for example with a hydroxy, alkyl having 1 to 8, preferably 1 to 4 carbon atoms and / or halogen group, or unsubstituted alkyl, preferably an alkyl group having 1 to 8 Carbon atoms, or aryl groups, preferably an aryl group with 6 to 12 carbon atoms, where R and R 'preferably have different meanings, and an anion selected from tetrafluoroborate, alkyl borate, especially triethylhexyl borate, aryl borate, haiogen phosphate, especially hexafluorophosphate, nitrates, sulphonates, in particular perfluorinated alkyl and arylsulphonates, hydrogensulfate, alkyl sulfates, especially perfluorinated alkyl and aryl sulfates, thiocyanates, perfluorinated amides, dicyanamide and / or bis (
  • the electrolyte composition according to the invention preferably contains ionic liquids ( ⁇ ) selected from l-ethyl-3-memyHmida ⁇ H ⁇ m ⁇ -bis (trifluoro-ethyl-3-methylimidazoHum tetrafluoroborate, l-ethyl-3-n ⁇ mylinMdazoHum-d ⁇ cyanamide, l-ethyl- 3-methylimidazoHum-ethyl sulfate, 1-butyl-3 -memyHrmd ⁇ olium-bis (trifluo ⁇ nethan-s ⁇ dfonyl) -n ⁇ id, l-butyl-2,3-d ⁇ ethylinMdazoHum-dicyanamide and or methyl-trioctylammonium bis (trifluoromethidanesulfonyl.
  • ⁇ ionic liquids
  • the melting points of some are more suitable as ionic liquids in the electrolyte composition of the separator according to the invention ionic liquids listed
  • the salts can be prepared according to Welton (Chem. Rev. 1999, 99, 2071) and Wasserscheid et al. (Angew. Chem. 2 ⁇ , 112, 3026 - 3945), or the literature cited in these papers.
  • EMIM l-ethyl-3-memylimidazolium ion
  • BMIM ln-butyl-3-methylimidazoHum ion
  • Ts HaCC ⁇ lLSO ⁇ (tosyl)
  • Oc octyl
  • Et ethyl
  • Me methyl
  • Bu n -Butyl
  • CF 3 S0 3 triflate anion
  • Ph phenyl
  • the electrolyte composition according to the invention contains at least one ionic liquid (A) which contains a cation based on an ammonium, preferably tetraalkylammoriium and particularly preferably trimethylalkylammonium and / or triethylalkylammonium
  • A ionic liquid
  • the electrolyte composition according to the invention can also have a mixture of at least two different ionic liquids (A).
  • the electrolyte composition according to the invention can have at least two different anions and or two different cations based on the ionic liquid (A).
  • the ionic liquid (A) in the base component of the electrolyte composition is preferably from 80 to 99.5% by weight, preferably from 90 to 99% by weight, particularly preferably from 92 to 98% by weight and very particularly preferably from 94 up to 97 wt .-% based on the sum of all components of the base component.
  • the separator according to the invention has the ionic liquids as a liquid or solidified liquid at room temperature, ie as a solid.
  • the electrolyte composition present in the separator according to the invention preferably has a lithium compound, preferably LiPF ⁇ , LiCl ⁇ 4, LiAsF ⁇ , LiBF4, L-CF3SO3, LiN (CF3S ⁇ 2) 2, LiN (S0 2 CF 2 CF 3 ) 2 , LiSbF ⁇ , LiAICk, as the conductive salt (D).
  • the electrolyte salt is present in the electrolyte composition according to the invention preferably in a concentration of 0.25 mol kg up to the solubility limit of the electrolyte salt in the base component, preferably in a concentration of 0.25 to 0.75 mol / kg, preferably 0.5 mol / kg included on the base component.
  • the electrolyte composition present in the separator according to the invention can contain a film former (B) as further constituents of the base component.
  • a film former (B) as further constituents of the base component.
  • This is preferably an organic compound and can preferably be an organic carbonate compound and particularly preferably vinylene carbonate.
  • the base component as film former can be a compound selected from ethylene sulfite, (meth) acrylonitrile, halogenated ethylene carbonate, in particular chloroethylene carbonate, Contain lithium-borato complexes, in particular lithium bis (oxalato) borate or lithium bis (biphenylato) borate, maldic anhydride, pyridine, dimethylacetarnide, A-niline, pyrrole or derivatives of these compounds.
  • the base component as film former (B) has a functional ionic liquid which has organic cations according to at least one of structures 1 to 14, at least one of the substituents R1, R2, R3, R4, R5 and R6 Has a multiple bond, preferably a double bond.
  • the base component contains the film former (B) preferably in an amount of 0.5 to 10% by weight, preferably 2 to 8% by weight and very particularly preferably 3 to 6% by weight.
  • the base component can contain a viscosity modifier (C).
  • the viscosity modifier can be an organic, aprotic solvent, preferably a
  • Carbonate a flame retardant selected from chlorinated or brominated
  • Hydrocarbons from halogenated or alkyl- or aryl-substituted phosphines,
  • Phosphates, phosphonates, phosphonites and phosphites or an ionic liquid Phosphates, phosphonates, phosphonites and phosphites or an ionic liquid.
  • both viscosity modifiers and film formers are ionic liquids
  • the entire base component can consist exclusively of ionic liquids. In this way, an electrolyte composition according to the invention can be obtained which contains or contains almost no volatile components.
  • the general use of the viscosity modifier is
  • the electrolyte composition according to the invention preferably has from 0 to 10% by weight of the viscosity modifier, preferably 0 to 3% by weight.
  • the separator has an electrolyte composition which consists of a base component 80 to 99.5 parts by mass, preferably 90 to 99 parts by mass, particularly preferably 92 to 98 parts by mass and very particularly preferably 94 to 97 parts by mass of at least one ionic liquid (A) which has a melting point of less than 100 ° C., 0.5 to 20 parts by mass, preferably preferably from 1 to 10 parts by mass, particularly preferably from 2 to 8 parts by mass and very particularly preferably from 3 to 6 parts by mass of a film former (B) and 0 to 19.5 parts by mass, preferably from 0 to 9 parts by mass, preferably from 0 to 6 parts by mass, particularly preferably from 0 to 3 and very particularly preferably from 1 to 2 parts by mass of a viscosity modifier (C) and a Leitzsalz (D), the electrolyte composition from 0.25 mol / kg to the solubility limit of the Leitsalzes in the base component of a viscosity modifier (C) and a
  • the separator according to the invention is preferably obtainable by the method according to the invention for producing a separator according to the invention, with firstly a flat, flexible substrate provided with a plurality of openings by applying a
  • Suspension which has particles of at least one inorganic compound suspended in a sol, on the substrate and by at least moderate heating, in which the
  • Suspension is solidified on and in the carrier, is provided in and on this substrate with a coating, which is characterized in that the so prepared
  • 50 mass% has at least one ionic liquid that has a melting point smaller
  • Impregnation of the separator with the electrolyte composition means the filling of the open (accessible) pores of the separator with the electrolyte composition.
  • the electrolyte compositions used are those as already mentioned in the description of the separator.
  • the separator can be impregnated with the electrolyte composition at room temperature or at elevated temperature.
  • the impregnation is preferably carried out at room temperature, at which the ionic liquid is present as the liquid In In a special embodiment, the impregnation is carried out at a temperature of 50 to ICO ° C.
  • the separator can be impregnated (filled) with the electrolyte composition before or after the installation / installation of the separator in the battery.
  • the separator is preferably first installed in the battery and then the battery is filled with the electrolyte composition, as a result of which the separator is impregnated with the electrolyte composition.
  • the separator is generally impregnated after the battery cells have been produced in the form of coils or stacks of the electrodes which are mechanically separated by the separators.
  • the easiest way to do this is to evacuate the housing that contains the winding or stack and then fill it with electrolyte
  • the separators used in the process according to the invention which have not yet been filled with an electrolyte composition can, for. B. as in documents WO 03/021697, WO 03/072231, WO 03/073534, WO 2004/021469, WO 2004/021474, WO 2004/021475, WO 2004/021476, WO 2004/021477 and WO 2004/021499 described, manufactured. Reference is expressly made to these documents with regard to the procedure for producing the unfilled separator. In addition to the manufacture of the separators, however, the use of commercially available separators, such as those used for. B. may be offered by the Creavis Society for Technology and Innovation, Mari, Germany, under the product name SEPARION ® .
  • a possible embodiment of the method for producing a separator that is initially not filled with the electrolyte composition is characterized in that a porosity of more than 50%, preferably of 50 to, to and on a flexible substrate, preferably having a thickness of less than 30 ⁇ m 97% and a pore radius distribution, in which at least 50% of the pores have a pore radius of 75 to 150 ⁇ m, by applying a suspension and at least heating once, in which the suspension is on and in Is solidified substrate, a porous, inorganic coating is brought, the suspension having particles of an inorganic compound suspended in at least one sol and the material of the substrate is selected from woven or non-woven, non-electrically conductive natural or polymer fibers.
  • the substrate particularly preferably has nonwoven polymer fibers.
  • the substrate is very particularly preferably a nonwoven.
  • the suspension preferably has an oxide, nitride or carbide of the metals Al, Zr, Si, Sn, Ce and / or Y.
  • the suspension particularly preferably has metal oxide particles with an average particle diameter of 0.5 to 7 ⁇ m, preferably from 1 to 5 ⁇ m and very particularly preferably from 1.5 to 3 ⁇ m of the MetaUe Al, Zr and / or Si suspended in a sol ,
  • the method itself is known in principle from WO 99/15262, but parameters and feedstocks, in particular feedstocks which are not electrically conductive, cannot be used for the manufacture of the separator according to the invention.
  • the particles used to produce the dispersion and the nonwovens used as the substrate differ significantly from the starting materials described there.
  • the suspension can e.g. B. by printing, pressing, pressing, rolling, knife coating, painting, dipping, spraying or pouring onto and into the substrate.
  • the substrate used preferably has a thickness of less than 30 ⁇ m, preferably less than 20 ⁇ m and particularly preferably a thickness of 7.5 to 15 ⁇ m. Particularly preferred substrates are those as described in the description of the separator according to the invention.
  • the substrate used preferably has polymer fibers as described in the description of the separator according to the invention.
  • Particularly preferred substrates have polymer fibers, which are selected from polyacrylonitrile, polyester, such as. B. polyethylene terephthalate, and / or polyolefins.
  • other known polymer fibers can also 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 the lithium battery.
  • the substrate used preferably has polymer fibers which have have a softening temperature of greater than 100 ° C and a melting temperature of greater than 110 ° C. It can be advantageous if the polymer fibers have a diameter of 0.1 to 10 ⁇ m, preferably 1 to 5 ⁇ m.
  • the suspension used for coating has at least one sol of the elements Al, Zr and / or Si, and is produced by suspending particles of the inorganic compound, preferably the oxides, in at least one of these brines.
  • the brines can be hydrolyzed by 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.
  • As the compound to be hydrolyzed at least one nitrate, one chloride, one carbonate, one alcoholate 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 distinguished 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 sols 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 hydrated compound can be peptized 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 be treated.
  • the particulate sols produced in this way can then be used for the production of suspensions, the production of suspensions for application to polymer fiber devices pretreated with polymer sol being preferred
  • polymeric sols are produced by hydrolysis of the compounds to be hydrolyzed.
  • the sol has a proportion of water and / or acid of less than 50% by weight.
  • polymeric sols are distinguished by the fact that the compounds formed in the sol by hydrolysis are polymeric (i.e. 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 is based on the molar ratio of 0.5 to 10 times and preferably on half the molar ratio of water, steam or ice is hydrolyzed onto the hydrolyzable group, the hydrolyzable compound. Up to 10 times the amount of water can be used with very slowly hydrating compounds such as B.
  • sols with a desired very low proportion of water and / or acid in the sol, it can be advantageous if the compound to be hydrolyzed in an organic solvent, in particular ethanol, isopropanol, butanol, amyl alcohol, hexane, cyclohexane, ethyl acetate and or mixtures of these compounds is dissolved before the actual hydrolysis is carried out.
  • an organic solvent in particular ethanol, isopropanol, butanol, amyl alcohol, hexane, cyclohexane, ethyl acetate and or mixtures of these compounds is dissolved before the actual hydrolysis is carried out.
  • a sol produced in this way can be used to produce the suspension according to the invention.
  • Both particulate brine (large water content, low solvent content) and polymeric brine (low water content, large solvent content) can be used as sol in the Processes according to the invention can be used to produce the suspension.
  • the brines which are available as just described, in principle also commercially available brines such as e.g. B. zirconium nitrate sol or silica sol can be used. Missing the manufacture of separators by applying and solidifying a suspension to a carrier is known per se from DE 101 42 622 and in a similar form from WO 99/15262, but it is not possible to refer to the manufacture of the parameters or feedstocks transferred membrane of the invention.
  • a sol system or a suspension which has been adapted to the polymers in terms of wetting behavior completely soaks the VHesmateriaHen and thus flawless coatings are available.
  • the wetting behavior of the sol or suspension is therefore preferably adjusted in the method according to the invention. This adjustment is preferably carried out by the production of brines or suspensions, these brines containing one or more alcohols, such as. B. methanol, ethanol or propanol or mixtures thereof, and / or have aUphatic hydrocarbons.
  • alcohols such as. B. methanol, ethanol or propanol or mixtures thereof
  • other solvent mixtures are also conceivable which can be added to the sol or the suspension in order to adapt them to the VHes used in terms of crosslinking behavior.
  • the mass fraction of the suspended inorganic component (metal oxide particles) in the suspension is preferably 1 to 100 times, particularly preferably 1 to 50 times and very particularly preferably 1 to 10 times the sol used.
  • Aluminum oxide particles which preferably have an average particle size of 0.5 to 7 ⁇ m, are particularly preferably used as metal oxide particles for producing the suspension.
  • Alumina particles are in the range of preferred particle sizes 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. It has been found that the use of commercially available metal oxide particles may lead to unsatisfactory results, since there is often a very large increase in grain size.
  • metal oxide particles which by a conventional method such.
  • B. consist of aggregates, hard agglomerates, grinding ball abrasion. The aforementioned measures ensure that the inorganic porous layer has a very uniform pore size distribution. This is achieved in particular by using metal oxide particles which have a maximum particle size of preferably less than 1/3, preferably less than 1/5 and particularly preferably less than or equal to 1/10 of the thickness of the VHeses used.
  • Table 1 Typical data of ceramics depending on the powder type used
  • adhesion promoters such as e.g. B. Include SUane.
  • compounds selected from the octylsuane, the vinylsilane, the amine-functionalized suans and / or the gly dyl-functionalized suans, such as, for example, are used as adhesion promoters.
  • B. the Dynasilane from Degussa can be used.
  • adhesion promoters for polyethylene (PE) and polypropylene (PP) are vinyl-, methyl- and octylsilanes, whereby an exclusive use of methylsuane is not optimal, for polyamides and polyamines it is amiifunctional silanes, for polyacrylates and polyesters it is glycidyl-functionalized Silanes and for polyacrylonitrile one can also use glycated polyfunctionalized silanes.
  • Other adhesion promoters can also be used, but they have to be matched to the respective polymers. The adhesion promoters must be selected so that the solidification temperature is below the melting or softening point of the polymer used as the substrate and below its decomposition temperature.
  • Suspensions 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 ear 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 material (in m 2 g _1 ) and then dividing by the specific space requirement of the adhesion promoter (in m 2 g '1 ) are obtained, the specific space requirement often being in the order of 300 to 400 m 2 g "1 .
  • Table 2 below contains an exemplary overview of adhesion promoters that can be used, based on organofunctional Si compounds for typical polymers used as VHes material.
  • GLYMO 3-glycidyloxytrimethoxysUan
  • VTEO vinyltrimethoxysilane (vinyltrimethoxysilane)
  • the coatings according to the invention are brought into and onto the substrate by solidifying the suspension in and on the substrate.
  • the suspension present on and in the substrate can be solidified by heating to 50 to 350 ° C. Since the maximum temperature is determined by the substrate when using polymeric substrate materials, this must be adjusted accordingly.
  • the suspension present on and in the substrate is heated to 100 to 350 ° C. and very particularly preferably heated to 110 to 280 ° C solidified. 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 suspension 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 minutes.
  • the inventive heating of the composite can be carried out by means of heated air, hot air, mlrarotstrahlimg or by other heating methods according to the prior art.
  • the inventive method can, for. B. be carried out so that the substrate, for. B. a PolymervHes is rolled from a RoUe, 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 suspension onto and into the substrate, such as. B. a roller, and at least one other apparatus which allows the solidification of the suspension on and in the substrate by heating, such as. B. passes through an electrically heated furnace and the separator thus produced is rolled up on a second roller.
  • a PolymervHes is rolled from a RoUe, 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
  • the separator in a continuous process.
  • the pre-treatment steps can also be carried out in a continuous process while maintaining the parameters mentioned.
  • the impregnation can also be carried out in a continuous process.
  • the method is carried out such that the substrate, in particular the polymer fleece, has a maximum longitudinal tension of 10 N / cm, preferably 3 N / cm, during the coating process or the coating processes.
  • Coating processes are understood to mean all process steps in which a material is brought onto and into the substrate and is solidified there by heat treatment, that is to say also the application of the adhesion promoter.
  • the substrate is preferably stretched during the coating processes with a maximum force of 0.01 N / cm. It can be particularly preferred if the substrate during the coating process or the coating processes in the longitudinal direction is carried out untensioned.
  • the separator according to the invention can be equipped with an additional automatic shutdown mechanism, this can be done e.g. B. happen that after the solidification of the suspension applied to the substrate, a layer of particles that melt at a desired temperature and close the pores of the separator, so-called shutdown particles, is applied and fixed to produce a shutdown mechanism on the separator.
  • 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 solvent in a polymeric sol as an adhesion promoter and was thus rendered hydrophobic. In order to achieve good adhesion and even 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 before the application of the shutdown particles.
  • 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 as a solvent is water, preferably with an acid, preferably acetic acid or hydrochloric acid, to a pH of 1 to 3 has been set, and / or has 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 amount 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 below
  • Adhesion promoter can then also be carried out as described above, ie 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 articles present in the suspension is arbitrary.
  • D w average particle size
  • the shutdown particles used preferably have an 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 .
  • silicas (Aerosil, Degussa) can be added.
  • auxiliary substances such as B. Aerosü 200 is often a content of 0.1 to 10 wt .-%, preferably 0.5 to 50 wt .-% silica, based on the suspension, already sufficient to achieve a sufficiently high viscosity of the suspension.
  • the proportion of auxiliary substances can be determined by simple preliminary tests. It can be advantageous if the suspension containing shut-off particles used has adhesion promoters. Such a suspension with adhesion promoters can be applied directly to an inorganic layer of the separator, even if it has not been hydrophobicized before application.
  • a suspension having an adhesion promoter can also be applied to a hydrophobized layer or to a separator layer, in the production of which an adhesion promoter was used.
  • Silanes which have amino, vinyl or methacrylic side groups are preferably used as adhesion promoters in the suspension having shutdown particles.
  • adhesion promoters are e.g. B. AMEO (3-aminopropyltiethoxysüan), MEMO (3-methac ⁇ yloxypropyltrimethoxysUan), silfin (VinylsUan + initiator + catalyst), VTEO (vinyltriethoxysilane) or VTMO (vinyltrimethoxysüan).
  • silanes are e.g. B. also available from Degussa in aqueous solution under the name Dynasilan 2926, 2907 or 2781.
  • An anteu of n __x 10% by weight of adhesion promoter has been found to be sufficient to ensure sufficient adhesion of the switch-off particles to the porous inorganic layer.
  • Shear mediators preferably have suspensions of deactivating particles of 0.1 to 10% by weight, preferably 1 to 7.5% by weight and very particularly preferably 2.5 to 5% by weight, of adhesive, based on the suspension ,
  • 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. It may be advantageous if, after being applied to the porous inorganic layer, 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 cutoff 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, it can in turn be unwound from a roll, passed through a coating, drying and, if necessary, heating apparatus and then re-opened.
  • the switching layer is not in the form of particles but in the form of flat structures, such as, for. B. perforated foils, nonwovens, knitted fabrics or fabrics applied.
  • the application of such a fabric can by known methods z. B. done by lamination.
  • As the material for the fabric those can be selected as those listed for the shutdown particles.
  • the separator according to the invention which is filled with an electrolyte composition which has at least one ionic liquid or is only filled with the electrolyte composition in the battery, can be used as a separator in batteries.
  • the separator according to the invention can be used in a battery that is a lithium metal or lithium ion battery.
  • the separators according to the invention provide access to batteries, in particular lithium metal and / or lithium ion batteries, which have a separator according to the invention.
  • batteries can in particular be lithium high-energy or lithium high-performance batteries.
  • 1 to 4 show various graphics which are intended to explain the subject matter of the invention in more detail, without the invention being so limited.
  • FIGS. 1 to 3 show how high an ionic liquid is drawn into a separator by capillary forces within which time. 1 shows two curves, the curve labeled Separion representing the wetting behavior of a ceramic separator according to the invention and the curve labeled PO separator representing the wetting behavior of a conventional pohyolefin separator. It can be clearly seen in Fig.
  • FIG. 4 shows the charging and discharging behavior of an electrochemical half which contains the separator according to the invention
  • Example 1 Production of a ceramic separator SEPARION ® S4S0P
  • the fleece yeast then passed through an oven (length 1 m), which had the specified temperature.
  • a separator with a medium one was obtained Pore size of 450 ⁇ m and a thickness of approx. 35 ⁇ m.
  • the Gurley number was about 10.
  • the Gurley number was determined in the same apparatus as the BP. When determining the Gurley number, however, the time t was determined which required a gas volume of 100 ml to flow through an area of 6.45 cm 2 (at a pressure of 31 cm water column of the gas). The time t is the Gurley number.
  • the separator was cut to a size of 30 mm in diameter.
  • the cut separator was stored in a wetting liquid (demineralized water) for at least one day.
  • the separator thus prepared was placed in an apparatus between a round sintered metal disc with a BP of approx.
  • the apparatus above the separator had an upwardly open vessel, which had the same cross-section as the separator and was filled with 2 cm with deionized water, and below the separator had a second vessel, which also had the same cross-section as the separator had, and which was equipped with an air inlet, via which compressed air could be introduced into the vessel via a pressure reducing valve.
  • the separator was installed under the sintered metal disc, so that the sintered metal disc battened the bottom of the upper vessel and the separator closed off the lower vessel.
  • the pressure in the lower vessel was then increased in 0.1 bar steps, with half a minute between each pressure increase. After each pressure increase, the water surface in the upper vessel was observed for about half a minute. When the first small gas bubbles appeared on the water surface, the pressure of the BP was reached and the measurement was stopped.
  • the wetting of the polyolefin separator is significantly worse than that of the ceramic separator from Example 1, i.e. the rise in the height of the ceramic separator after 3 hours is higher, but the wetting speed is also significantly higher than that of the polyolefin separator.
  • Example 3 Determination of the wetting behavior of 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) amide
  • Example 4 Determination of the wetting behavior of 2-ethyl-3-methyl-2-oxazoiumium methyl sulfate of 2-ethyl-oxazoline with dimethyl sulf t) carried out.
  • a commercially available 25 ⁇ m thick PP / PE / PP separator (Celgard, type 2500) serves as the reference material for the ceramic separator from Example 1 with a thickness of 35 ⁇ m.
  • Another type of thin layer chromatography was carried out as in Example 2
  • the electrochemical cycles take place in so-called half-cell arrangements.
  • the electrolyte composition according to the invention is measured in a sandwich arrangement.
  • Working electrode - separator / electrolyte composition according to the invention - counter / reference electrode.
  • the working electrode (negative electrode) is an electrode with an electrode material consisting of 90% by weight of commercially available SFG 44 graphite from ⁇ MCAL SA, Switzerland and 10% by weight of polyvinyldenfluoride (PVdF) binder.
  • PVdF polyvinyldenfluoride
  • the potential limits are 0 and -1.55 V, this corresponds to 10 mV and 1.56 V vs. Li / Li + used.
  • the cycle speed is given with the current density per active mass of the electrode material. The value used for this is 10 mA / g graphite for the first cycle and 50 mA / g graphite for the subsequent cycles. Charging and discharging takes place with a current reduction when the voltage limit is reached below a value of 5 mA / g The use of this current reduction enables the efficiency of an electrode (part of the current that flows in constant current mode, or galvanostatic portion) to possibly irreversible damage (which results in a reduction in the total, i.e. including the capacity flowing in the potentiostatic step) separate (see H. Buqa et al. in ITE Battery Letters, 4 (2003), 38).
  • Half-products were produced with the separator and the ionic liquid l-emyl-3-memyl-imidazoHum-bis (trifluoromethanesu] fonyl) amide.
  • a 1 molar solution with LiPF 6 was prepared from a mixture of 95 g of IL 1-ethyl-3-meftyl-inncla-roHum-bis (trifl and 5 g of vinylene carbonate (VC) (composition of electrolytes).
  • VC vinylene carbonate
  • Cells with graphite were then used built as anode and Li-Titanat as cathode, using a pure glass fleece as reference for the ceramic separators.
  • the separator mechanically separates the electrodes from each other.
  • the glass fleece separator used here in the test cells is ruled out for commercial applications, since it is much too thick for Li batteries with 100 to 200 ⁇ m, which means that Energy density of the ZeUen is too low.

Abstract

L'invention concerne un séparateur rempli d'une composition électrolytique, présentant une surface céramique, la composition électrolytique présentant un liquide ionique. Le remplissage au moyen de la composition électrolytique peut par exemple est obtenu du fait que le séparateur est employé dans une pile remplie d'une composition électrolytique correspondante.
EP05708055A 2004-04-20 2005-02-24 Utilisation d'un separateur ceramique dans des piles a ions lithium presentant un electrolyte contenant des liquides ioniques Withdrawn EP1738424A1 (fr)

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DE102004018930A DE102004018930A1 (de) 2004-04-20 2004-04-20 Verwendung eines keramischen Separators in Lithium-Ionenbatterien, die einen Elektrolyten aufweisen, der ionische Flüssigkeiten enthält
PCT/EP2005/050789 WO2005104269A1 (fr) 2004-04-20 2005-02-24 Utilisation d'un separateur ceramique dans des piles a ions lithium presentant un electrolyte contenant des liquides ioniques

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WO2005104269A1 (fr) 2005-11-03
US9214659B2 (en) 2015-12-15
KR20070012833A (ko) 2007-01-29
DE102004018930A1 (de) 2005-11-17
KR101202048B1 (ko) 2012-11-15
TW200607142A (en) 2006-02-16
CN1973388A (zh) 2007-05-30

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