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WO1999057769A1 - Electrical separator on the basis of a substrate with ceramic coating - Google Patents

Electrical separator on the basis of a substrate with ceramic coating Download PDF

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Publication number
WO1999057769A1
WO1999057769A1 PCT/EP1999/003080 EP9903080W WO9957769A1 WO 1999057769 A1 WO1999057769 A1 WO 1999057769A1 EP 9903080 W EP9903080 W EP 9903080W WO 9957769 A1 WO9957769 A1 WO 9957769A1
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WO
WIPO (PCT)
Prior art keywords
oxide
coating
electrical separator
substrate
separator according
Prior art date
Application number
PCT/EP1999/003080
Other languages
German (de)
French (fr)
Inventor
Thomas Berger
Angela Piepke
Original Assignee
Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V.
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
Priority claimed from DE19838800A external-priority patent/DE19838800C1/en
Application filed by Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. filed Critical Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V.
Publication of WO1999057769A1 publication Critical patent/WO1999057769A1/en

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/02—Diaphragms; Separators
    • 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
    • H01M50/431—Inorganic material
    • H01M50/434—Ceramics
    • H01M50/437—Glass
    • 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
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • 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
    • H01M50/431—Inorganic material
    • H01M50/434—Ceramics
    • 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
    • H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/06—Lead-acid accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/24—Alkaline accumulators
    • H01M10/30—Nickel accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/34—Gastight accumulators
    • H01M10/345—Gastight metal hydride accumulators
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • 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
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • Solid or polymer electrolytes have a much lower conductivity than the electrolyte solutions used. They are therefore not suitable for the production of high-performance batteries.
  • Non-metals such as plastics, glass, carbon fiber and the like, provided that they have through openings and are flexible.
  • the substrate can be made from a 3
  • Examples are magnesium oxide, calcium oxide, strontium oxide, barium oxide, scandium oxide, yttrium oxide, titanium oxide, zirconium oxide, aluminum oxide, silicon oxide, tin oxide, cerium oxide, europium oxide, mixtures of these oxides or mixed oxides of the cations mentioned.
  • Examples of ternary oxides are: non-conductive spinels, non-conductive pyrochlores, non-conductive olivines. In contrast, electrically conductive ceramics such as (doped) semiconductor ceramics are unsuitable.
  • the electrical separator according to the invention is suitable for all arrangements in which electrodes have to be electrically insulated from one another.
  • electrodes have to be electrically insulated from one another.
  • they can also be used e.g. done in capacitors.
  • the separators are sintered in an inert gas atmosphere at 1000 to 1100 ° C for at least 15 minutes in an inert gas furnace.
  • Figures 1 and 2 show a separator according to the invention according to the example in cross section (enlargements: Figure 1: 130: 1, Figure 2: 648: 1). It can clearly be seen that the substrate is completely covered with ceramic, so that dendrites can no longer grow through. The mere presence of the open pores of the coating enables the unhindered passage of ions.

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  • Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Cell Separators (AREA)

Abstract

The invention relates to an electrical separator comprising a flat, flexible substrate having a plurality of openings and a coating thereon. The invention is characterized in that the substrate material is selected from among metals, alloys, plastic materials, glass or carbon fibres or a combination of such materials and in that the coating is a porous, ceramic coating which extends across the entire substrate surface.

Description

Elektrischer Separator auf Basis von keramisch beschichtetem TrägermaterialElectrical separator based on ceramic coated carrier material
Die vorliegende Erfindung betrifft einen elektrischen Separator. Ein elektrischer Separator ist ein Separator, der in Batterien, Brennstoffzellen und anderen Anordnungen, in denen Elektroden z.B. unter Aufrechterhaltung von Ionenleitfähigkeit voneinander separiert werden müssen, eingesetzt wird.The present invention relates to an electrical separator. An electrical separator is a separator used in batteries, fuel cells and other arrangements in which electrodes e.g. must be separated from each other while maintaining ion conductivity.
Der Separator ist ein dünner, poröser, isolierender Stoff mit hoher Ionendurchlässigkeit, guter mechanischer Festigkeit und Langzeitstabilität gegen die im System, z.B. im Elektrolyten der Batterie, verwendeten Chemikalien und Lösungsmittel. Er soll in Batterien oder Brennstoffzellen die Kathode von der Anode elektronisch völlig isolieren. Außerdem muß er dauerelastisch sein und den Bewegungen im System, z.B. im Elektrodenpaket beim Laden und Entladen, folgen.The separator is a thin, porous, insulating material with high ion permeability, good mechanical strength and long-term stability against those in the system, e.g. in the electrolyte of the battery, chemicals and solvents used. It is intended to completely electronically isolate the cathode from the anode in batteries or fuel cells. In addition, it must be permanently elastic and the movements in the system, e.g. in the electrode pack when loading and unloading.
Der Separator bestimmt maßgeblich die Lebensdauer der Anordnung, in der er verwendet wird, z.B. die von Batterie-Zellen.The separator largely determines the life of the arrangement in which it is used, e.g. that of battery cells.
Die Entwicklung einer wiederaufladbaren Batterie mit Lithium- Elektrode (negative Masse) ist wünschenswert. Hierfür eignen sich jedoch käufliche Separatoren nicht. In Batterien werden derzeit folgende Separatoren eingesetzt:The development of a rechargeable battery with a lithium electrode (negative ground) is desirable. However, commercially available separators are not suitable for this. The following separators are currently used in batteries:
- Celgard®; microporöse Folie aus PP- Celgard®; microporous film made of PP
- Vliese oder Gewebe aus PP, Glasfaser oder dergleichen- Nonwovens or fabrics made of PP, glass fiber or the like
- Fest- oder Polymerelektrolyte (mit Isoliereigenschaften) - Aluminiumoxidpapier.- Solid or polymer electrolytes (with insulating properties) - Alumina paper.
Solche Separatoren sind ungeeignet, weil sie entweder chemisch oder aber mechanisch nicht beständig sind, was zu Kurzschlüssen führt .Such separators are unsuitable because they are either not chemically or mechanically stable, which leads to short circuits.
Das System Li/LiAlCl4 x S02/LiCo02 besteht aus einer Lithiumkobaltdioxid-Elektrode (positive Masse) , in die Lithiumionen reversibel ein- und ausgelagert werden können (Interkalationselektrode) . Bei der Ladung des Systems werden die Lithiumionen aus der Interkalationselektrode ausgelagert und metallisch, im allgemeinen dendritisch, auf einem AbieiterThe Li / LiAlCl 4 x S0 2 / LiCo0 2 system consists of a lithium cobalt dioxide electrode (positive mass) into which lithium ions can be reversibly stored and removed (Intercalation electrode). When the system is charged, the lithium ions are removed from the intercalation electrode and metallic, generally dendritic, on a drain
(negative Masse) abgeschieden.(negative mass) deposited.
Als Separator für dieses System war bisher nurSo far, was only used as a separator for this system
Aluminiumoxidpapier verwendbar, da die Elektrolytlösung bzw. die bei der Überladereaktion produzierten Stoffe sehr aggressiv sind und mit den KunststoffSeparatoren reagieren.Aluminum oxide paper can be used because the electrolyte solution or the substances produced during the overloading reaction are very aggressive and react with the plastic separators.
Fest- oder Polymerelektrolyte haben eine wesentlich geringere Leitfähigkeit als die eingesetzten Elektrolytlösungen . Sie eignen sich deshalb nicht für die Herstellung von Hochleistungsbatterien.Solid or polymer electrolytes have a much lower conductivity than the electrolyte solutions used. They are therefore not suitable for the production of high-performance batteries.
Aluminiumoxidpapier ist spröde und nicht immer in der Lage, das Durchwachsen von Lithiumdendriten zu verhindern. Durch die Verwendung von Aluminiumoxidpapier ist eine flache Bauform vorgegeben, da es nicht biegbar ist.Aluminum oxide paper is brittle and is not always able to prevent lithium dendrites from growing through. The use of aluminum oxide paper dictates a flat design since it is not bendable.
Aufgabe der Erfindung ist es, einen elektrischen Separator bereitzustellen, der eine hohe Ionendurchlässigkeit, Stabilität gegenüber den eingesetzten Chemikalien sowie mechanische Stabilität und Flexibilität aufweist. Er soll das Auftreten von Kurzschlüssen beim Aufladen von Batterien wirksam verhindern, also elektrisch isolierend sein. Der Separator sollte insbesondere auch für den Einsatz in Hochleistungsbatterien geeignet sein.The object of the invention is to provide an electrical separator which has high ion permeability, stability with respect to the chemicals used, and mechanical stability and flexibility. It is intended to effectively prevent the occurrence of short circuits when charging batteries, that is, to be electrically insulating. The separator should also be particularly suitable for use in high-performance batteries.
Die Aufgabe wird durch die Bereitstellung eines elektrischen Separators gelöst, der ein flächiges, biegbares, mit einer Vielzahl durchgängiger Öffnungen versehenes Substrat und auf diesem eine die Öffnungen des Substrates schließende, poröse Beschichtung aus einem keramischen Material umfaßt. Als Substrat eignen sich vor allem Metalle und Legierungen, aber auchThe object is achieved by the provision of an electrical separator which comprises a flat, bendable substrate which is provided with a plurality of through openings and on which there is a porous coating made of a ceramic material which closes the openings of the substrate. Metals and alloys are particularly suitable, but also
Nichtmetalle wie beispielsweise Kunststoffe, Glas, Kohlefaser und dergleichen, sofern sie durchgängige Öffnungen besitzen und biegsam sind. Selbstverständlich kann das Substrat aus einer 3Non-metals such as plastics, glass, carbon fiber and the like, provided that they have through openings and are flexible. Of course, the substrate can be made from a 3
Kombination der genannten Materialien bestehen. Durchgängige Öffnungen und Biegsamkeit kann man beispielsweise dadurch erzielen, daß man textile Flachsubstrate wie Gewebe, Gewirke, Gelege (Filze, Vliese) verwendet. Unter "textil" soll hier die Verwendung von Fäden, Fasern, (ggf. sehr) dünnen, gut biegbaren Drähten oder dergleichen verstanden werden. Weiterhin können Lochbleche, Streckmetalle und dergleichen verwendet werden. Die offene Fläche des Substrats wird den Anforderungen entsprechend gewählt, ist aber im allgemeinen nicht kritisch.Combination of the materials mentioned exist. Through openings and flexibility can be achieved, for example, by using flat textile substrates such as woven fabrics, knitted fabrics, laid fabrics (felts, nonwovens). "Textile" is to be understood here to mean the use of threads, fibers, (possibly very) thin, easily bendable wires or the like. Perforated sheets, expanded metals and the like can also be used. The open area of the substrate is chosen according to the requirements, but is generally not critical.
Keramiken sind chemisch sehr widerstandsfähig, insbesondere auch gegenüber aggressiven Substanzen wie starken, auch oxidierenden Säuren oder starken Laugen. Die Erfindung schlägt deshalb vor, das genannte Substrat mit einer elektrisch isolierenden keramischen Beschichtung zu versehen. Es kann sich dabei beispielsweise um binäre Oxide oder ternäre Oxide entsprechend der Formel AxByOz handeln. Insbesondere finden Oxide der III. und IV. Haupt- und Nebengruppe und deren Mischungen Verwendung, aber auch Oxide der II. Hauptgruppe und Mischoxide aus Oxiden der genannten Gruppen können als Beschichtung eingesetzt werden. Beispiele sind Magnesiumoxid, Calciumoxid, Strontiumoxid, Bariumoxid, Scandiumoxid, Yttriumoxid, Titanoxid, Zirkonoxid, Aluminiumoxid, Siliciumoxid, Zinnoxid, Ceroxid, Europiumoxid, Mischungen dieser Oxide oder Mischoxide der genannten Kationen. Als Beispiele für ternäre Oxide seien genannt: nichtleitende Spinelle, nichtleitende Pyrochlore, nichtleitende Olivine . Elektrisch leitende Keramiken wie (dotierte) Halbleiterkeramiken sind dagegen ungeeignet.Ceramics are very chemically resistant, especially to aggressive substances such as strong, also oxidizing acids or strong alkalis. The invention therefore proposes to provide the substrate mentioned with an electrically insulating ceramic coating. These can be, for example, binary oxides or ternary oxides corresponding to the formula A x B y O z . In particular, oxides of III. and IV. main and sub-group and their mixtures use, but also oxides of the II. main group and mixed oxides of oxides of the groups mentioned can be used as a coating. Examples are magnesium oxide, calcium oxide, strontium oxide, barium oxide, scandium oxide, yttrium oxide, titanium oxide, zirconium oxide, aluminum oxide, silicon oxide, tin oxide, cerium oxide, europium oxide, mixtures of these oxides or mixed oxides of the cations mentioned. Examples of ternary oxides are: non-conductive spinels, non-conductive pyrochlores, non-conductive olivines. In contrast, electrically conductive ceramics such as (doped) semiconductor ceramics are unsuitable.
Es ist wesentlich, daß das Substrat mit einer durchgehenden Beschichtung versehen ist, und zwar bevorzugt beidseitig. Dadurch wird das Durchwachsen von Dendriten wirksam verhindert. Die Beschichtung ist daher als geschlossene Beschichtung anzusprechen, wobei dieser Ausdruck bedeuten soll, daß die Beschichtung unabhängig von der dritten Dimension der räumlichen Struktur des Substrates (z.B. Streckmetall oder gewirkte Fasern) einen 2-dimensional gesehen flächig durchgehenden Belag bildet. Der Ausdruck „geschlossen" soll dagegen nicht das Vorhandensein 4 offener Poren ausschließen, denn solche müssen vorhanden sein, um die erforderliche Ionenleitfähigkeit zu gewährleisten.It is essential that the substrate is provided with a continuous coating, preferably on both sides. This effectively prevents dendrites from growing through. The coating is therefore to be addressed as a closed coating, this expression being intended to mean that the coating forms a two-dimensionally continuous covering regardless of the third dimension of the spatial structure of the substrate (eg expanded metal or knitted fibers). The expression "closed", on the other hand, is not intended to mean the existence 4 Exclude open pores, as these must be present to ensure the required ionic conductivity.
Die Porosität der Beschichtung kann in einem breiten Bereich variieren. Sie beträgt bevorzugt 20 bis 60%, stärker bevorzugt 25 bis 50% und ganz besonders bevorzugt beträgt sie 30 bis 40%. Die Porengröße im keramischen Material kann ebenfalls variieren und liegt bevorzugt im Bereich von etwa 10 bis 100 nm.The porosity of the coating can vary within a wide range. It is preferably 20 to 60%, more preferably 25 to 50% and very particularly preferably 30 to 40%. The pore size in the ceramic material can also vary and is preferably in the range from about 10 to 100 nm.
Der erfindungsgemäße Separator ist insbesondere für sekundäreThe separator according to the invention is in particular for secondary ones
(wiederaufladbare) Lithium-Batterien geeignet. Er ist allerdings nicht auf derartige Batterien beschränkt, sondern kann auch beispielsweise in Systemen wie NiMeH / NiCd / Bleiakku / etc. eingesetzt werden.Suitable for (rechargeable) lithium batteries. However, it is not limited to such batteries, but can also be used, for example, in systems such as NiMeH / NiCd / lead acid batteries / etc.
Der erfindungsgemäße Separator genügt allen Anforderungen der genannten Systeme. Er ist flexibel, ionendurchlässig, mechanisch stabil und chemisch inert. Durch Anpassung der Ausgangsmaterialien oder durch Nachbehandlung der keramischen Schicht kann verschiedenen chemischen und technischen Ansprüchen Rechnung getragen werden. So kann beispielsweise durch Nachbehandlung oder durch Umsetzung mit entsprechenden chemischen Gruppen, die dem Fachmann bekannt sind, eine hydrophile oder hydrophobe Beschichtung erzeugt werden.The separator according to the invention meets all the requirements of the systems mentioned. It is flexible, permeable to ions, mechanically stable and chemically inert. Various chemical and technical requirements can be taken into account by adapting the starting materials or by post-treating the ceramic layer. For example, a hydrophilic or hydrophobic coating can be produced by post-treatment or by reaction with appropriate chemical groups known to the person skilled in the art.
Zur Herstellung des erfindungsgemäßen elektrischen Separators ist es vorteilhaft, das Substrat mit einer Suspension des/der gewünschten Oxids/Oxide zu beschichten und den Separator anschließend bei geeigneten Temperaturen zu sintern. Durch Auswahl einer entsprechenden Partikelgröße können dabei die Porosität und die Größe der Poren in bekannter Weise beeinflußt werden. Als Beschichtungsverfahren einsetzbar sind neben dem im untenstehenden Beispiel dargestellten Tauchverfahren auch Beschichtungen durch elektrophoretische Abscheidung, Sprühen, Aufzentrifugieren oder Spin-coaten. Das Herstellverfahren für den erfindungsgemäßen Separator ist jedoch nicht auf die genannten Verfahren beschränkt. 5To produce the electrical separator according to the invention, it is advantageous to coat the substrate with a suspension of the desired oxide (s) and then to sinter the separator at suitable temperatures. The porosity and the size of the pores can be influenced in a known manner by selecting an appropriate particle size. In addition to the immersion process shown in the example below, coatings can also be used as coatings by electrophoretic deposition, spraying, centrifuging or spin-coating. However, the manufacturing process for the separator according to the invention is not limited to the processes mentioned. 5
Der erfindungsgemäße Separator ist durch Auswahl des geeigneten Substrates und der aufzubringenden Schichtdicke (beispielsweise auch durch mehrfaches Anwenden des Beschichtungsvorgangs oder durch Einstellen der Viskosität der Suspension, z.B. beim Tauchverfahren) in der Dicke variabel herstellbar. Bevorzugt liegt die Separatordicke zwischen 100 und 500 μm. Er läßt sich einfach und in gleichmäßiger Qualität erzeugen.The separator according to the invention can be variably produced in thickness by selecting the suitable substrate and the layer thickness to be applied (for example also by repeatedly using the coating process or by adjusting the viscosity of the suspension, for example in the immersion process). The separator thickness is preferably between 100 and 500 μm. It can be produced easily and in uniform quality.
Die erfindungsgemäßen Separatoren sind widerstandsfähig gegen das Durchwachsen von Lithiumdendriten, was eine längere Lebensdauer der Batterie und mehr Sicherheit bedeutet.The separators according to the invention are resistant to the growth of lithium dendrites, which means a longer battery life and more safety.
Außerdem ist der Batteriebau nun nicht mehr auf die flache Bauweise beschränkt. Es können z.B. auch Wickelzellen hergestellt werden. Auch eine meanderförmige Bauweise ist nun möglich .In addition, battery construction is no longer limited to the flat design. For example, winding cells can also be produced. A meandering design is now also possible.
Der erfindungsgemäße elektrische Separator ist für alle Anordnungen geeignet, in denen Elektroden elektrisch voneinander isoliert werden müssen. Neben den genannten Anwendungen in Batterien, insbesondere Hochleistungsbatterien, und in Brennstoffzellen kann daher auch eine Verwendung z.B. in Kondensatoren erfolgen.The electrical separator according to the invention is suitable for all arrangements in which electrodes have to be electrically insulated from one another. In addition to the applications mentioned in batteries, in particular high-performance batteries, and in fuel cells, they can also be used e.g. done in capacitors.
Nachstehend wird die Herstellung eines erfindungsgemäßen Separators anhand eines Beispiels beschrieben. Edelstahlgewebe :The production of a separator according to the invention is described below using an example. Stainless steel mesh:
Von der Fa. Bückmann (Nr.: E 31 122) Dicke ca.: 80 bis 90 μm; Gewicht ca.: 16 mg/cm2 - zuschneiden entfetten in eine Vorrichtung einspannen 6From Bückmann (no .: E 31 122) thickness approx .: 80 to 90 μm; Weight approx .: 16 mg / cm 2 - cut to degrease, clamp in a device 6
Suspension :Suspension:
750 g Aluminiumoxid der Fa. Alcoa (Nr.: NO713-10)750 g aluminum oxide from Alcoa (no .: NO713-10)
840 ml destilliertes Wasser werden ca.: 10 min lang mit einem Ultraschallhomogenisator behandelt, um Agglomerate zu zerschlagen.840 ml of distilled water are treated with an ultrasound homogenizer for approx. 10 minutes in order to break up agglomerates.
150 μl Acetylaceton werden zugegeben, um spätere Agglomeratbildung zu unterdrücken. Diese Suspension wird vor jeder Tauchbeschichtung noch durch Siebe gegossen (160, 80 und 40 μm) , um eine möglichst agglomeratfreie Beschichtung zu erhalten.150 μl of acetylacetone are added to suppress subsequent agglomerate formation. This suspension is poured through sieves (160, 80 and 40 μm) before each dip coating in order to obtain a coating that is as agglomerate-free as possible.
Das Edelstahlgewebe wird durch Eintauchen in die Suspension beschichtet .The stainless steel mesh is coated by immersing it in the suspension.
Sintern:Sintering:
Im Schutzgasofen werden die Separatoren in Inertgasatmosphäre bei 1000 bis 1100°C mind. 15min lang gesintert.The separators are sintered in an inert gas atmosphere at 1000 to 1100 ° C for at least 15 minutes in an inert gas furnace.
Ergebnis : Die so entstandenen Separatoren sind abriebfest, flexibel und durchlässig. Sie sind ca. 150 μm dick und haben ein Flächengewicht von ca. 40 mg/cm2. Die Gesamtporosität der Separatoren beträgt ca. 35% (gemessen mit Quecksilber- Porosimetrie) , und die Hauptporengröße in der keramischen Schicht liegt im Bereich zwischen 30 und 80 nm.Result: The separators created in this way are abrasion-resistant, flexible and permeable. They are approx. 150 μm thick and have a basis weight of approx. 40 mg / cm2. The total porosity of the separators is approximately 35% (measured using mercury porosimetry), and the main pore size in the ceramic layer is in the range between 30 and 80 nm.
Die Figuren 1 und 2 zeigen einen erfindungsgemäßen Separator gemäß Beispiel im Querschliff (Vergrößerungen: Figur 1: 130:1, Figur 2: 648:1). Man erkennt deutlich, daß das Substrat vollständig mit Keramik belegt ist, so daß ein Durchwachsen von Dendriten nicht mehr möglich ist. Allein das Vorhandensein der offenen Poren der Beschichtung ermöglicht den ungehinderten Ionendurchtritt . Figures 1 and 2 show a separator according to the invention according to the example in cross section (enlargements: Figure 1: 130: 1, Figure 2: 648: 1). It can clearly be seen that the substrate is completely covered with ceramic, so that dendrites can no longer grow through. The mere presence of the open pores of the coating enables the unhindered passage of ions.

Claims

7Ansprüche : 7 Claims:
1. Elektrischer Separator, umfassend ein flächiges, mit einer Vielzahl von Öffnungen versehenes, flexibles Substrat mit einer darauf befindlichen Beschichtung, dadurch gekennzeichnet, daß das Material des Substrates ausgewählt ist unter Metallen, Legierungen, Kunststoffen, Glas und Kohlefaser oder einer Kombination solcher Materialien und die Beschichtung eine flächig durchgehende, poröse, elektrisch nicht leitende keramische Beschichtung ist.1. Electrical separator comprising a flat, provided with a plurality of openings, flexible substrate with a coating thereon, characterized in that 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 flat, porous, electrically non-conductive ceramic coating.
2. Elektrischer Separator nach Anspruch 1, dadurch' gekennzeichnet, daß das Substrat ein textiles Flachsubstrat, insbesondere ein Gewebe, Gelege, Gewirke, Filz oder Vlies, oder ein Lochblech oder ein Streckmetall ist.2. Electrical separator according to claim 1, characterized 'in that the substrate is a flat textile substrate, in particular a woven fabric, scrim, knitted fabric, felt or fleece, or a perforated plate or an expanded metal.
3. Elektrischer Separator nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die keramische Beschichtung aus mindestens einem binären Oxid und/oder einem ternären Oxid der Formel AxByOz besteht.3. Electrical separator according to claim 1 or 2, characterized in that the ceramic coating consists of at least one binary oxide and / or a ternary oxide of the formula A x B y O z .
4. Elektrischer Separator nach Anspruch 3, worin das oder die Oxide ausgewählt ist/sind unter Oxiden der II. Hauptgruppe und der III. und IV. Haupt- und Nebengruppe.4. Electrical separator according to claim 3, wherein the oxide or oxides is selected from oxides of the II. Main group and III. and IV. main and sub-group.
5. Elektrischer Separator nach einem der voranstehenden Ansprüche, dadurch gekennzeichnet, daß die keramische Beschichtung aus Aluminiumoxid besteht oder dieses enthält.5. Electrical separator according to one of the preceding claims, characterized in that the ceramic coating consists of or contains aluminum oxide.
6. Elektrischer Separator nach einem der Ansprüche 1 bis6. Electrical separator according to one of claims 1 to
4, dadurch gekennzeichnet, daß die Keramik aus einem Oxid oder einer Oxidmischung oder einem Mischoxid besteht, ausgewählt unter Magnesiumoxid, Calciumoxid, Strontiumoxid, Bariumoxid, Scandiumoxid, Yttriumoxid, Titanoxid, Zirkonoxid, Aluminiumoxid, Siliciumoxid, Zinnoxid, Ceroxid, Europiumoxid, gegebenenfalls in Mischung oder als Mischoxid mit Aluminiumoxid . 84, characterized in that the ceramic consists of an oxide or an oxide mixture or a mixed oxide, selected from magnesium oxide, calcium oxide, strontium oxide, barium oxide, scandium oxide, yttrium oxide, titanium oxide, zirconium oxide, aluminum oxide, silicon oxide, tin oxide, cerium oxide, europium oxide, optionally in a mixture or as a mixed oxide with aluminum oxide. 8th
Elektrischer Separator nach einem der voranstehenden Ansprüche, dadurch gekennzeichnet, daß die keramische Schicht auf einer oder auf beiden Seiten des Separators mit einer hydrophoben oder einer hydrophilen Beschichtung versehen ist.Electrical separator according to one of the preceding claims, characterized in that the ceramic layer is provided on one or on both sides of the separator with a hydrophobic or a hydrophilic coating.
* * * * * *
PCT/EP1999/003080 1998-05-06 1999-05-05 Electrical separator on the basis of a substrate with ceramic coating WO1999057769A1 (en)

Applications Claiming Priority (4)

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DE19820229 1998-05-06
DE19820229.6 1998-05-06
DE19838800A DE19838800C1 (en) 1998-05-06 1998-08-26 Battery separator based on ceramic-coated carrier material
DE19838800.4 1998-08-26

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WO2003021697A3 (en) * 2001-08-31 2003-12-18 Creavis Tech & Innovation Gmbh Electric separator, method for producing the same and the use thereof
WO2004049480A3 (en) * 2002-11-26 2004-08-12 Creavis Tech & Innovation Gmbh Separator having a low water content for an electrochemical cell
WO2003073534A3 (en) * 2002-02-26 2004-12-29 Creavis Tech & Innovation Gmbh Electric separator, method for the production and use thereof
WO2003073545A3 (en) * 2002-02-26 2005-01-06 Creavis Tech & Innovation Gmbh Flexible electrolyte membrane based on a carrier comprising polymer fibres, methods for the production thereof and use of the same
WO2003069711A3 (en) * 2002-02-13 2005-01-20 Creavis Tech & Innovation Gmbh Flexible electrolyte based on a glass fabric, method for the production and utilization thereof
WO2005038833A3 (en) * 2003-10-14 2005-12-08 Degussa Capacitor comprising a ceramic separating layer
WO2010124892A1 (en) * 2009-04-28 2010-11-04 Evonik Litarion Gmbh Production and use of ceramic composite materials based on a polymeric carrier film
DE10238943B4 (en) * 2002-08-24 2013-01-03 Evonik Degussa Gmbh Separator-electrode unit for lithium-ion batteries, method for their production and use in lithium batteries and a battery, comprising the separator-electrode unit
CN103972447A (en) * 2013-01-28 2014-08-06 海洋王照明科技股份有限公司 Electrochemical power diaphragm and preparation method thereof, and electrochemical battery or capacitor
CN104183805A (en) * 2013-05-25 2014-12-03 湖南省正源储能材料与器件研究所 Preparation method for ceramic coating separator
DE10347570B4 (en) * 2003-10-14 2015-07-23 Evonik Degussa Gmbh Inorganic separator-electrode unit for lithium-ion batteries, method for their production, use in lithium batteries and lithium batteries with the inorganic separator-electrode unit
EP4117060A1 (en) * 2021-07-09 2023-01-11 Hochschule Rheinmain University of Applied Sciences Wiesbaden Rüsselsheim Improved method of manufacturing a polar plate

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Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7351494B2 (en) 2001-08-31 2008-04-01 Degussa Ag Electric separator, method for producing the same and the use thereof
WO2003021697A3 (en) * 2001-08-31 2003-12-18 Creavis Tech & Innovation Gmbh Electric separator, method for producing the same and the use thereof
WO2003069711A3 (en) * 2002-02-13 2005-01-20 Creavis Tech & Innovation Gmbh Flexible electrolyte based on a glass fabric, method for the production and utilization thereof
WO2003073534A3 (en) * 2002-02-26 2004-12-29 Creavis Tech & Innovation Gmbh Electric separator, method for the production and use thereof
WO2003073545A3 (en) * 2002-02-26 2005-01-06 Creavis Tech & Innovation Gmbh Flexible electrolyte membrane based on a carrier comprising polymer fibres, methods for the production thereof and use of the same
US8053102B2 (en) 2002-02-26 2011-11-08 Evonik Degussa Gmbh Electric separator, method for the production and use thereof
US8709638B2 (en) 2002-02-26 2014-04-29 Evonik Degussa Gmbh Electric separator, method for the production and use thereof
DE10238943B4 (en) * 2002-08-24 2013-01-03 Evonik Degussa Gmbh Separator-electrode unit for lithium-ion batteries, method for their production and use in lithium batteries and a battery, comprising the separator-electrode unit
WO2004049480A3 (en) * 2002-11-26 2004-08-12 Creavis Tech & Innovation Gmbh Separator having a low water content for an electrochemical cell
DE10347570B4 (en) * 2003-10-14 2015-07-23 Evonik Degussa Gmbh Inorganic separator-electrode unit for lithium-ion batteries, method for their production, use in lithium batteries and lithium batteries with the inorganic separator-electrode unit
WO2005038833A3 (en) * 2003-10-14 2005-12-08 Degussa Capacitor comprising a ceramic separating layer
US7525788B2 (en) 2003-10-14 2009-04-28 Degussa Ag Capacitor comprising a ceramic separating layer
WO2010124892A1 (en) * 2009-04-28 2010-11-04 Evonik Litarion Gmbh Production and use of ceramic composite materials based on a polymeric carrier film
CN103972447A (en) * 2013-01-28 2014-08-06 海洋王照明科技股份有限公司 Electrochemical power diaphragm and preparation method thereof, and electrochemical battery or capacitor
CN104183805A (en) * 2013-05-25 2014-12-03 湖南省正源储能材料与器件研究所 Preparation method for ceramic coating separator
CN104183805B (en) * 2013-05-25 2017-07-25 湖南省正源储能材料与器件研究所 A kind of preparation method of ceramic coating diaphragm
EP4117060A1 (en) * 2021-07-09 2023-01-11 Hochschule Rheinmain University of Applied Sciences Wiesbaden Rüsselsheim Improved method of manufacturing a polar plate
WO2023280984A1 (en) * 2021-07-09 2023-01-12 Hochschule Rheinmain University Of Applied Sciences Wiesbaden Rüsselsheim Improved process for producing a polar plate

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