WO2007017506A1 - Electrochemical energy accumulator - Google Patents

Electrochemical energy accumulator Download PDF

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Publication number
WO2007017506A1
WO2007017506A1 PCT/EP2006/065150 EP2006065150W WO2007017506A1 WO 2007017506 A1 WO2007017506 A1 WO 2007017506A1 EP 2006065150 W EP2006065150 W EP 2006065150W WO 2007017506 A1 WO2007017506 A1 WO 2007017506A1
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WO
WIPO (PCT)
Prior art keywords
energy storage
electrodes
storage according
dlc
electrode
Prior art date
Application number
PCT/EP2006/065150
Other languages
German (de)
French (fr)
Inventor
Alexander Hahn
Manfred Waidhas
Original Assignee
Siemens Aktiengesellschaft
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Publication date
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Publication of WO2007017506A1 publication Critical patent/WO2007017506A1/en

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/04—Cells with aqueous electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/02—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof using combined reduction-oxidation reactions, e.g. redox arrangement or solion
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/04—Hybrid capacitors
    • H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/46—Metal oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/78—Cases; Housings; Encapsulations; Mountings
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M16/00—Structural combinations of different types of electrochemical generators
    • 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
    • Y02E60/13—Energy storage using capacitors

Definitions

  • the invention relates to an electrochemical energy storage, with a housing, an electrolyte, with arresters and with electrodes.
  • Electrochemical energy stores are known in the prior art in separate embodiments either as a battery or as a capacitor. Batteries are characterized by a high energy density compared to capacitors, but have a comparatively low power density. Particularly marked from ⁇ is such behavior in primary lithium thionyl batteries. But also rechargeable systems, such as the known lead-acid battery, are not in the La ⁇ ge, high pulse currents to provide. In contrast, capacitors, in particular double-layer capacitors (DLC), have a limited energy density but a very high power density.
  • DLC double-layer capacitors
  • Photoflash cameras are a specific example in which a high-energy energy store, ie, a battery, is connected to a high-pulse-capacity memory, ie, a capacitor.
  • a high-energy energy store ie, a battery
  • a high-pulse-capacity memory ie, a capacitor
  • the invention solves the problem of insufficient pulse load capacity of smaller and medium size, now compact units are formed.
  • the Dop ⁇ pel fürkondensatoren can be fully integrated into the battery structure and in the battery and the Doppeltikkon- capacitors use of the same electrolyte is made.
  • the electrodes of the battery form a redox system, wherein the DLC electrodes can be applied to the same arresters of the battery system.
  • an electrochemical energy storage is realized, which has a much higher pulse load capacity ⁇ than the corresponding pure battery systems.
  • FIG. 1 shows the schematic structure of a battery with DLC electrodes integrated therein
  • FIG. 2 shows a design especially for a coin cell
  • FIG. 3 shows the structure of a primary lithium battery with DLC electrodes in a three-layered formation
  • FIG. 4 shows such a structure in four-ply formation and FIG. 5 shows an alternative to FIG. 3.
  • FIG. 1 shows a battery structure is shown with a negative electrode 1 and a positive electrode 3, see between the one in Figure 1 is not designated in detail
  • Electrolyte and a separator 2 is arranged. 4 and 4 ', the arresters for the electrodes 1 and 3 are shown.
  • the separator 2 consists of insulating, but porous material and has the function to open the electrolyte space.
  • the electrolyte is located in the pores of the separator 2 and establishes an ionic connection between the electrodes 1, 3 of the further he can fill the remaining space in the housing enclosing the structure.
  • Such a double-layer capacitor is also generally referred to as a DLC element, wherein the English term "p_ouble L_ayer Ondenator" is used.
  • a housing 10 is further indicated, in which the combination of battery and DLC is located.
  • Suitable electrolyzer ⁇ th are available for such applications: either water-based systems SYS such. As potassium hydroxide, or organic electrolyte systems, such as those used for example for lithium-ion batteries.
  • a button cell 20 is taken as an example.
  • Such a cell consists of a negative electrode 21, which is located on an arrester 24, a separator 22 and an associated positive electrode 23 with arrester 24 '.
  • On the negative electrode 21 are now several strip-shaped electrodes 25 of a double-layer capacitor DLC.
  • the negative electrode 21 consists of Li and C segments and the positive electrode 23 of MnO 2 .
  • the housing of the button cell 20 is omitted in Figure 3 for the sake of clarity.
  • FIGS. 3 to 5 each describe differently constructed, but in principle identical, primary lithium batteries.
  • lithium-ion elements are suitable with a corresponding structure.
  • FIG 3 such a construction is shown with egg ⁇ ner three-layered electrode assembly, in Figure 4 a four-layer electrode arrangement and in Figure 5 an alternative in turn with a three-layer electrode assembly.
  • the negative electrode 11, the positive electrode 13, the separators 12, the arresters 14 and the DCL-electrode 15 be ⁇ are distinguished in Figures 3 to fifth
  • the negative electrode 11 is made of lithium or Li / C is the positive electrode of, for example, manganese oxide (MnO 2 ).
  • the DCL electrode is formed in particular by optionally modified activated carbon.
  • FIG. 4 there is centrally a negative electrode 11, which is covered on the opposite side of the arrester 12 with a DLC electrode 15 made of carbon (C).
  • a separator 12 On both sides there is a separator 12 which is followed on the lower side by a positive electrode 13 followed by a DLC electrode 15 and on the upper side by a DLC electrode 15 having a positive electrode 13.
  • This arrangement is part of a construction with m stacked individual electrodes, wherein in particular the electrode layer n and n + 1 are shown.
  • the positive electrode 13 is again formed of MnO 2 and the negative electrode is made of Li / C.
  • the arresters 14 are coated differently on the front and back.
  • FIG. 5 A basically similar construction results from FIG. 5, in which again two layers n and n + 1 of an m-layer structure are shown. The result is the above sequence of the negative electrode 11 with the DLC electrode 15 and the separator 12, followed by the positive electrode 13 with separator 12.
  • ⁇ Lich is that the negative arrester 14 is coated on both sides un ⁇ differently here.
  • the positive arrester 14 ' is coated with only one material.
  • the negative electrode 11 can also - as in a
  • Nickel (Ni) -Metallhydrid battery - consist of a hydrogen (H 2 ) - storing metal alloy and the positive electrode of a NiO / NiO (OH) 2 -redox system.
  • DLC electrode materials instead of the activated carbon (C), other suitable DLC electrode materials can be used, whereby a sufficient conductivity and a large surface must be ensured. , Also mixtures of different materials are possible.
  • ge ⁇ is respectively ensured that the combination of Faraday ' ⁇ schem energy storage and double layer capacitor has a much higher capacity than pulse corresponding pure battery elements.

Abstract

In the prior art, electrochemical energy accumulators are known as batteries or capacitors. Batteries are characterized by being compared to capacitors of a high energy density, but have a comparatively low power density. According to the invention, a faradaic energy accumulator, i.e. a battery, is combined with a double layer capacitor (DLC) and located in the same electrolytes. A common housing (10) is provided, in particular, for both partial accumulators.

Description

Elektrochemischer Energiespeieher Electrochemical energy collector
Die Erfindung bezieht sich auf einen elektrochemischen Energiespeicher, mit einem Gehäuse, einem Elektrolyten, mit Ableitern und mit Elektroden.The invention relates to an electrochemical energy storage, with a housing, an electrolyte, with arresters and with electrodes.
Elektrochemische Energiespeicher sind vom Stand der Technik in separaten Ausführungen entweder als Batterie oder als Kondensator bekannt. Batterien zeichnen sich durch eine im Vergleich zu Kondensatoren hohe Energiedichte aus, besitzen aber eine vergleichsweise geringe Leistungsdichte. Besonders aus¬ geprägt ist ein derartiges Verhalten bei primären Lithium- Thionyl-Batterien . Aber auch wieder aufladbare Systeme, wie beispielsweise der bekannte Blei-Akku, sind nicht in der La¬ ge, hohe Impulsströme bereitzustellen. Kondensatoren, insbesondere Doppelschichtkondensatoren (DLC = Double Layer Con- densator) besitzen dagegen eine eingeschränkte Energiedichte, dafür allerdings eine sehr hohe Leistungsdichte.Electrochemical energy stores are known in the prior art in separate embodiments either as a battery or as a capacitor. Batteries are characterized by a high energy density compared to capacitors, but have a comparatively low power density. Particularly marked from ¬ is such behavior in primary lithium thionyl batteries. But also rechargeable systems, such as the known lead-acid battery, are not in the La ¬ ge, high pulse currents to provide. In contrast, capacitors, in particular double-layer capacitors (DLC), have a limited energy density but a very high power density.
In der Praxis behilft man sich für den Fall, dass für technische Anwendungen eine hohe Energiedichte bei gleichzeitig ho¬ her Impulsbelastbarkeit gefordert wird, damit, dass das Bat¬ teriesystem nicht nach der erforderlichen Energiemenge, sondern nach der Leistung ausgelegt wird. Dies führt allerdings in Bezug auf die Energiemenge zu deutlich überdimensionierten Systemen mit dem Nachteil eines zu hohen Gewichtes und Volu¬ mens. Die Starterbatterien im PKW bis hin in Diesellokomoti¬ ven sind dafür entsprechende Beispiele.In practice, that a high energy density is required together with ho ¬ her impulse capacity for technical applications makes do in the event so that the bat ¬ is teriesystem not designed according to the required amount of energy, but after the performance. However, this results in terms of the amount of energy to significantly oversized systems with the disadvantage of excessive weight and Volu ¬ mens. Are ven the starter batteries in cars ranging in Diesellokomoti ¬ for appropriate examples.
Blitzlichtgeräte für die Photographie sind ein spezifisches Beispiel, bei dem ein Energiespeicher hoher Energie, d.h. eine Batterie, mit einem Speicher hoher Impulsleistung, d.h. einem Kondensator, miteinander verbunden sind. Beim Einschalten des Gerätes wird der Kondensator aus der Batterie aufge¬ laden und gibt dann in sehr kurzer Zeit seinen Energieinhalt ab. Hierbei handelt es sich aber um die Kombination zweier isolierter elektrochemischer Energiespeicher.Photoflash cameras are a specific example in which a high-energy energy store, ie, a battery, is connected to a high-pulse-capacity memory, ie, a capacitor. When the device, the capacitor load from the battery topped ¬ and then in a very short time its energy content from. But this is the combination of two isolated electrochemical energy storage.
Ausgehend von letzterem Stand der Technik ist es Aufgabe der Erfindung, einen kompakten Energiespeicher anzugeben, der die Vorteile der Batterie mit den Vorteilen des Kondensators ver¬ bindet .Based on the latter prior art, it is an object of the invention to provide a compact energy storage, which ver ¬ binds the advantages of the battery with the advantages of the capacitor.
Die Aufgabe ist erfindungsgemäß durch die Gesamtheit der Merkmale des Patentanspruches 1 gelöst. Weiterbildungen sind in den Unteransprüchen angegeben.The object is achieved by the totality of the features of claim 1. Further developments are specified in the subclaims.
Die Erfindung löst das Problem unzureichender Impulsbelastbarkeit von Batterien kleinerer und mittlerer Baugröße, wobei nun kompakte Einheiten gebildet werden.The invention solves the problem of insufficient pulse load capacity of smaller and medium size, now compact units are formed.
Vorteilhaft ist bei der Erfindung insbesondere, dass die Dop¬ pelschichtkondensatoren voll in den Batterieaufbau integriert werden können und bei der Batterie und den Doppelschichtkon- densatoren Verwendung vom gleichen Elektrolyten gemacht wird. Dabei bilden die Elektroden der Batterie ein Redoxsystem, wobei die DLC-Elektroden auf den gleichen Ableitern des Batteriesystems aufgebracht werden können.It is advantageous in the invention in particular that the Dop ¬ pelschichtkondensatoren can be fully integrated into the battery structure and in the battery and the Doppelschichtkon- capacitors use of the same electrolyte is made. The electrodes of the battery form a redox system, wherein the DLC electrodes can be applied to the same arresters of the battery system.
Mit der Erfindung ist ein elektrochemischer Energiespeicher realisiert, der eine deutlich höhere Impulsbelastbarkeit auf¬ weist als die entsprechenden reinen Batteriesysteme.With the invention, an electrochemical energy storage is realized, which has a much higher pulse load capacity ¬ than the corresponding pure battery systems.
Weitere Einzelheiten und Vorteile der Erfindung ergeben sich aus nachfolgender Figurenbeschreibung von Ausführungsbeispielen in Verbindung den Patentansprüchen. Es zeigenFurther details and advantages of the invention will become apparent from the following description of exemplary embodiments in conjunction with the claims. Show it
Figur 1 den schematischen Aufbau einer Batterie mit darin integrierten DLC-Elektroden, Figur 2 einen Aufbau speziell für eine Knopfzelle,1 shows the schematic structure of a battery with DLC electrodes integrated therein, FIG. 2 shows a design especially for a coin cell,
Figur 3 den Aufbau einer primären Lithiumbatterie mit DLC- Elektroden in dreilagiger Formation,FIG. 3 shows the structure of a primary lithium battery with DLC electrodes in a three-layered formation,
Figur 4 einen derartigen Aufbau in vierlagiger Formation und Figur 5 eine Alternative zu Figur 3.Figure 4 shows such a structure in four-ply formation and FIG. 5 shows an alternative to FIG. 3.
In der Figur 1 ist ein Batterieaufbau mit einer negativen Elektrode 1 und einer positiven Elektrode 3 dargestellt, zwi- sehen der ein in Figur 1 nicht im Einzelnen bezeichneter1 shows a battery structure is shown with a negative electrode 1 and a positive electrode 3, see between the one in Figure 1 is not designated in detail
Elektrolyt und ein Separator 2 angeordnet ist. Mit 4 bzw. 4' sind die Ableiter für die Elektroden 1 und 3 dargestellt.Electrolyte and a separator 2 is arranged. 4 and 4 ', the arresters for the electrodes 1 and 3 are shown.
Der Separator 2 besteht aus isolierendem, aber porösem Mate- rial und hat die Funktion, den Elektrolytraum aufzuspannen. Der Elektrolyt befindet sich in den Poren des Separators 2 und stellt eine ionische Verbindung zwischen den Elektroden 1, 3 her Des weitern kann er den verbleibenden Leerraum im, den Aufbau umschließenden Gehäuse füllen.The separator 2 consists of insulating, but porous material and has the function to open the electrolyte space. The electrolyte is located in the pores of the separator 2 and establishes an ionic connection between the electrodes 1, 3 of the further he can fill the remaining space in the housing enclosing the structure.
In einem Endbereich befinden sich auf den Ableitern 4 bzw. 4' Elektroden 5 bzw. 5' , die zusammen mit dem Elektrolyten und dem Separator 2 einen Doppelschichtkondensator bilden. Ein solcher Doppelschichtkondensator wird auch allgemein als DLC- Element bezeichnet, wobei auf die englische Bezeichnung „p_ouble L_ayer £ondensator" zurückgegriffen wird.In one end region are on the arresters 4 and 4 'electrodes 5 and 5', which together with the electrolyte and the separator 2 form a double-layer capacitor. Such a double-layer capacitor is also generally referred to as a DLC element, wherein the English term "p_ouble L_ayer Ondenator" is used.
In Figur 1 ist weiterhin ein Gehäuse 10 angedeutet, in dem sich die Kombination aus Batterie und DLC befindet.In Figure 1, a housing 10 is further indicated, in which the combination of battery and DLC is located.
Wesentlich ist bei der Anordnung gemäß Figur 1, dass ein gemeinsamer Elektrolytraum mit dem gleichen Elektrolyten für die Batterie und dem DLC vorhanden ist. Geeignete Elektroly¬ ten für solche Anwendungen sind: Entweder wasserbasierte Sys- teme, z. B. Kalilauge, oder organische Elektrolytsysteme, wie sie beispielsweise für Lithium-Ionen-Batterien eingesetzt werden .It is essential in the arrangement of Figure 1, that a common electrolyte space with the same electrolyte for the battery and the DLC is present. Suitable electrolyzer ¬ th are available for such applications: either water-based systems SYS such. As potassium hydroxide, or organic electrolyte systems, such as those used for example for lithium-ion batteries.
In Figur 2 ist eine Knopfzelle 20 als Beispiel herangezogen. Eine solche Zelle besteht aus einer negativen Elektrode 21, die sich auf einem Ableiter 24 befindet, einem Separator 22 und einer zugehörigen positiven Elektrode 23 mit Ableiter 24' . Auf der negativen Elektrode 21 befinden sich nun mehrere streifenförmige Elektroden 25 eines Doppelschichtkondensators DLC. Die negative Elektrode 21 besteht dabei aus Li- und C- Segmenten und die positive Elektrode 23 aus MnO2. Das Gehäuse der Knopfzelle 20 ist in Figur 3 der Übersichtlichkeit halber weggelassen.In Figure 2, a button cell 20 is taken as an example. Such a cell consists of a negative electrode 21, which is located on an arrester 24, a separator 22 and an associated positive electrode 23 with arrester 24 '. On the negative electrode 21 are now several strip-shaped electrodes 25 of a double-layer capacitor DLC. The negative electrode 21 consists of Li and C segments and the positive electrode 23 of MnO 2 . The housing of the button cell 20 is omitted in Figure 3 for the sake of clarity.
Die Figuren 3 bis 5 beschreiben jeweils unterschiedlich aufgebaute, aber prinzipiell gleiche primäre Lithiumbatterien. Alternativ sind auch Lithium-Ionenelemente mit entsprechendem Aufbau geeignet. In Figur 3 ist ein derartiger Aufbau mit ei¬ ner dreilagigen Elektroden-Anordnung dargestellt, in Figur 4 eine vierlagige Elektroden-Anordnung und in Figur 5 eine Alternative wiederum mit einer dreilagigen Elektrodenanordnung.FIGS. 3 to 5 each describe differently constructed, but in principle identical, primary lithium batteries. Alternatively, lithium-ion elements are suitable with a corresponding structure. In Figure 3, such a construction is shown with egg ¬ ner three-layered electrode assembly, in Figure 4 a four-layer electrode arrangement and in Figure 5 an alternative in turn with a three-layer electrode assembly.
Im Einzelnen sind in den Figuren 3 bis 5 die negative Elektrode mit 11, die positive Elektrode mit 13, die Separatoren mit 12, die Ableiter mit 14 und die DCL-Elektrode mit 15 be¬ zeichnet .In detail, the negative electrode 11, the positive electrode 13, the separators 12, the arresters 14 and the DCL-electrode 15 be ¬ are distinguished in Figures 3 to fifth
In den Figuren 3 bis 5 besteht die negative Elektrode 11 aus Lithium oder Li/C die positive Elektrode aus beispielsweise Manganoxid (MnO2) . Die DCL-Elektrode wird insbesondere durch ggf. modifizierte Aktivkohle gebildet.In FIGS. 3 to 5, the negative electrode 11 is made of lithium or Li / C is the positive electrode of, for example, manganese oxide (MnO 2 ). The DCL electrode is formed in particular by optionally modified activated carbon.
Speziell in Figur 4 ist zentrisch eine negative Elektrode 11 vorhanden, die auf der Gegenseite des Ableiters 12 mit einer DLC-Elektrode 15 aus Kohlenstoff (C) belegt ist. Beidseitig ist ein Separator 12 vorhanden, der an der unteren Seite von einer positiven Elektrode 13 mit anschließender DLC-Elektrode 15 und auf der Oberseite von einer DLC-Elektrode 15 mit einer positiven Elektrode 13 gefolgt wird. Diese Anordnung ist Teil eines Aufbaus mit m gestapelten Einzelelektroden, wobei speziell die Elektrodenlage n und n+1 dargestellt sind.Specifically in FIG. 4, there is centrally a negative electrode 11, which is covered on the opposite side of the arrester 12 with a DLC electrode 15 made of carbon (C). On both sides there is a separator 12 which is followed on the lower side by a positive electrode 13 followed by a DLC electrode 15 and on the upper side by a DLC electrode 15 having a positive electrode 13. This arrangement is part of a construction with m stacked individual electrodes, wherein in particular the electrode layer n and n + 1 are shown.
In Figur 4 sind die positive Elektrode 13 wiederum aus MnO2 und die negative Elektrode aus Li/C gebildet. Die Ableiter 14 sind auf Vorder- und Rückseite unterschiedlich beschichtet. Ein prinzipiell ähnlicher Aufbau ergibt sich aus Figur 5, in der wiederum zwei Lagen n und n+1 eines m-lagigen Aufbaus dargestellt sind. Es ergibt sich obige Abfolge der negativen Elektrode 11 mit der DLC-Elektrode 15 und dem Separator 12, dem die positive Elektrode 13 mit Separator 12 folgt. Wesent¬ lich ist hier, dass der negative Ableiter 14 beidseitig un¬ terschiedlich beschichtet ist. Der positive Ableiter 14' ist dagegen mit nur einem Material beschichtet.In Fig. 4, the positive electrode 13 is again formed of MnO 2 and the negative electrode is made of Li / C. The arresters 14 are coated differently on the front and back. A basically similar construction results from FIG. 5, in which again two layers n and n + 1 of an m-layer structure are shown. The result is the above sequence of the negative electrode 11 with the DLC electrode 15 and the separator 12, followed by the positive electrode 13 with separator 12. Wesent ¬ Lich, is that the negative arrester 14 is coated on both sides un ¬ differently here. The positive arrester 14 ', however, is coated with only one material.
Die negative Elektrode 11 kann auch - wie bei einerThe negative electrode 11 can also - as in a
Nickel (Ni) -Metallhydrid-Batterie - aus einer Wasserstoff (H2) - speichernden Metalllegierung bestehen und die positive Elektrode aus einem NiO/NiO (OH) 2-Redoxsystem.Nickel (Ni) -Metallhydrid battery - consist of a hydrogen (H 2 ) - storing metal alloy and the positive electrode of a NiO / NiO (OH) 2 -redox system.
Statt der Aktivkohle (C) können auch andere geeignete DLC- Elektrodenmaterialien verwendet werden, wobei eine hinreichende Leitfähigkeit und eine große Oberfläche gewährleistet sein muss. . Auch Mischungen unterschiedlicher Materialien sind möglich.Instead of the activated carbon (C), other suitable DLC electrode materials can be used, whereby a sufficient conductivity and a large surface must be ensured. , Also mixtures of different materials are possible.
Bei den vorstehend beschriebenen Beispielen ist jeweils ge¬ währleistet, dass die Kombination von Faraday' schem Energie¬ speicher und Doppelschichtkondensator eine deutlich höhere Impulsbelastbarkeit als entsprechende reine Batterieelemente aufweist . In the above examples ge ¬ is respectively ensured that the combination of Faraday '¬ schem energy storage and double layer capacitor has a much higher capacity than pulse corresponding pure battery elements.

Claims

Patentansprüche claims
1. Elektrochemischer Energiespeicher, mit einem Gehäuse, einem Elektrolyten, Ableitern und Elektroden, dadurch gekenn- zeichnet, dass ein Faraday' scher Energiespeicher (Batterie) und ein Doppelschichtkondensator (DLC) miteinander kombiniert sind und sich im gleichen Elektrolytraum befinden.1. Electrochemical energy storage, with a housing, an electrolyte, arresters and electrodes, characterized in that a Faraday 'shear energy storage (battery) and a double-layer capacitor (DLC) are combined and are in the same electrolyte space.
2. Energiespeicher nach Anspruch 1, dadurch gekennzeichnet, dass in einem einzigen Gehäuse (10) sowohl Elektroden (1, 3;2. Energy storage according to claim 1, characterized in that in a single housing (10) both electrodes (1, 3;
11, 13; 11, 23) mit einem Redoxsystem als auch Elektroden (5, 15, 25) eines Doppelschichtkondensators enthalten sind.11, 13; 11, 23) are contained with a redox system as well as electrodes (5, 15, 25) of a double-layer capacitor.
3. Energiespeicher nach Anspruch 2, dadurch gekennzeichnet, dass sich die Doppelschichtkondensator-Elektroden räumlich abgegrenzt von den Elektroden (1, 3; 11, 13; 11, 23) der Bat¬ terie auf den Batterieelektrodenableitern (4, 14, 24) befinden .3. Energy storage according to claim 2, characterized in that the double-layer capacitor electrodes are spatially delimited from the electrodes (1, 3, 11, 13, 11, 23) of the Bat ¬ terie on the Batterieelektrodenableitern (4, 14, 24).
4. Energiespeicher nach Anspruch 2 oder Anspruch 3, dadurch gekennzeichnet, dass die Elektroden mit dem Redoxsystem eine positive Elektrode (3, 13, 23) aus Nickeloxid/Nickeloxid¬ hydrid (NiO/NiO (OH)2) und eine negative Elektrode (1, 11, 23) aus einer Wasserstoff (H2) -speichernden Metalllegierung bein- halten.4. Energy storage according to claim 2 or claim 3, characterized in that the electrodes with the redox system, a positive electrode (3, 13, 23) of nickel oxide / nickel oxide ¬ hydride (NiO / NiO (OH) 2 ) and a negative electrode (1 , 11, 23) comprise a hydrogen (H 2 ) -storing metal alloy.
5. Energiespeicher nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die positive Elektrode und/oder die negative Elektrode mit einem DLC-Elektrodenmaterial ge- mischt sind.5. Energy store according to one of the preceding claims, characterized in that the positive electrode and / or the negative electrode are mixed with a DLC electrode material.
6. Energiespeicher nach Anspruch 5, dadurch gekennzeichnet, dass für eine Lithium-Primärbatterie die aus Lithium beste¬ hende negative Elektrode (21) durch Bezirke (25), beispiels- weise Streifen, eines DLC-Materials ergänzt ist.6. Energy storage according to claim 5, characterized in that for a lithium primary battery, the best of lithium existing ¬ negative electrode (21) by districts (25), for example strips, a DLC material is added.
7. Energiespeicher nach Anspruch 5 oder Anspruch 6, dadurch gekennzeichnet, dass das DLC-Material ein Material auf Koh- lenstoffbasis, vorzugsweise Aktivkohle oder anderweitig modi¬ fizierte Kohlenstoffverbindungen, ist.7. Energy storage according to claim 5 or claim 6, characterized in that the DLC material is a material on Koh- lenstoffbasis, preferably activated carbon or otherwise modi ¬ fied carbon compounds, is.
8. Energiespeicher nach einem der vorhergehenden Ansprüche, gekennzeichnet in der Realisierung als primäre Lithiumbatte¬ rie oder Lithium-Ionen-Element .8. Energy storage according to one of the preceding claims, characterized in the realization as primary Lithiumbatte ¬ rie or lithium-ion element.
9. Energiespeicher nach Anspruch 8, dadurch gekennzeichnet, dass eine dreilagige Elektroden-Anordnung vorhanden ist. (Fig. 3, Fig. 5)9. Energy storage according to claim 8, characterized in that a three-layer electrode arrangement is present. (Fig. 3, Fig. 5)
10. Energiespeicher nach Anspruch 6, dadurch gekennzeichnet, dass eine vierlagige Elektroden-Anordnung vorhanden ist.10. Energy storage according to claim 6, characterized in that a four-layer electrode arrangement is present.
(Fig. 4) (Fig. 4)
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