WO2012076328A1 - Collector for a lithium-ion cell, lithium-ion accumulator and motor vehicle comprising a lithium-ion accumulator - Google Patents

Collector for a lithium-ion cell, lithium-ion accumulator and motor vehicle comprising a lithium-ion accumulator Download PDF

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Publication number
WO2012076328A1
WO2012076328A1 PCT/EP2011/070649 EP2011070649W WO2012076328A1 WO 2012076328 A1 WO2012076328 A1 WO 2012076328A1 EP 2011070649 W EP2011070649 W EP 2011070649W WO 2012076328 A1 WO2012076328 A1 WO 2012076328A1
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WO
WIPO (PCT)
Prior art keywords
lithium
collector
ion
cell
motor vehicle
Prior art date
Application number
PCT/EP2011/070649
Other languages
German (de)
French (fr)
Inventor
Stephan Leuthner
Thomas Woehrle
Holger Fink
Joachim Fetzer
Original Assignee
Sb Limotive Company Ltd.
Sb Limotive Germany 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 Sb Limotive Company Ltd., Sb Limotive Germany Gmbh filed Critical Sb Limotive Company Ltd.
Publication of WO2012076328A1 publication Critical patent/WO2012076328A1/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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, 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

Definitions

  • the present invention relates to a collector for a negative electrode of a lithium-ion secondary battery with at least one lithium-ion cell, a lithium-ion battery and a motor vehicle with an electric drive motor for driving the motor vehicle and connected to the electric drive motor or connectable lithium-ion battery.
  • Lithium-ion cells have at least one positive and one negative electrode (cathode or anode), the lithium-ion (Li +) reversible on (intercalation) or outsource (deintercalation) can.
  • cathode or anode the lithium-ion (Li +) reversible on (intercalation) or outsource (deintercalation) can.
  • Lithium-ion cell, lithium-ion polymer cell, lithium-ion cell, battery, accumulator and system are used largely synonymously.
  • copper or nickel as the passive material in a lithium-ion cell results in higher manufacturing costs. It also uses passive materials that have a higher crystallographic density compared to aluminum. Thus, aluminum has a density of 2.7 g / cm 3 and copper and nickel have a density of 8.9 g / cm 3 . Accordingly, the use of copper or nickel as materials for collectors has a negative impact on the gravimetric energy density of the lithium-ion cell.
  • a weight-reduced aluminum-based collector for the negative electrode side of a lithium-ion cell is provided, which is at least partially provided with a metallic layer which prevents lithium-ion alloying during operation of the lithium-ion cell.
  • the metallic layer is made of copper or nickel.
  • weight advantages of aluminum can thus be utilized not only for the positive electrode, but also for the negative electrode side of the accumulator and at the same time avoid the disadvantage of the alloy by lithium.
  • the collector according to the invention is not assumed by a conventional collector for the positive electrode side made of aluminum, but it will workpieces with a smaller
  • the copper layer can be 5 ⁇ strong and that of the
  • Aluminum core 1000 ⁇ or the nickel layer is 5 ⁇ strong and the aluminum core 1000 ⁇ .
  • the metallic layer should be as thin as possible.
  • a lower weight is achieved than in the prior art.
  • the collector according to the invention is assembled by applying a thin copper foil or layer to the aluminum workpiece.
  • nickel can also be used for surface finishing.
  • Aluminum foil is preferably either a) galvanic,
  • Electrode side in a lithium-ion cell long-term stable.
  • the collectors show the same electrical performance and identical behavior in long-term cyclization and storage as a reference cell with a conventional copper or nickel collector.
  • the properties of the collector according to the invention were, inter alia, since a detachment of the copper or nickel layer from the aluminum workpiece during storage or operation of the cells a priori not
  • lithium-ion cells with a collector according to the invention which has been surface-finished by means of ion beam coating, since collectors produced in this way have achieved the best results in previously mentioned comparative experiments.
  • the present invention also provides a lithium ion accumulator equipped with this collector on the negative electrode side with at least one lithium ion cell and a motor vehicle with an electric drive motor for driving the motor vehicle and a connected or connectable with the electric drive motor
  • Lithium-ion battery Lithium-ion battery.
  • Figure 1 is a perspective view of a collector according to the invention with a conventional spatial configuration according to the prior art (US 20080107961 A1)
  • Figure 2 is a sectional side view of a collector according to the invention for the negative electrode of a lithium-ion cell.
  • a collector 10 is shown, which is connected to a terminal 11, which has a base 12.
  • the collector 10 is surrounded by a metallic layer 13 of copper or nickel and has a core of one

Abstract

The invention relates to a collector (10) for a negative electrode of a lithium-ion accumulator comprising at least one lithium-ion cell, said collector (10) consisting of an aluminum workpiece (14) and at least sections thereof being covered by a metal layer (13) consisting of copper or nickel. The invention further relates to a lithium-ion accumulator and to a motor vehicle comprising a lithium-ion accumulator.

Description

Beschreibung  description
Titel title
Kollektor für eine Lithium-Ionen-Zelle, Lithium-Ionen-Akkumulator sowie  Collector for a lithium-ion cell, lithium-ion battery as well
Kraftfahrzeug mit einem Lithium-Ionen-Akkumulator Motor vehicle with a lithium-ion battery
Die vorliegende Erfindung betrifft einen Kollektor für eine negative Elektrode eines Lithium-Ionen-Akkumulators mit mindestens einer Lithium-Ionen-Zelle, einen Lithium-Ionen-Akkumulator sowie ein Kraftfahrzeug mit einem elektrischen Antriebsmotor zum Antreiben des Kraftfahrzeugs und einer mit dem elektrischen Antriebsmotor verbundenen oder verbindbaren Lithium-Ionen-Akkumulators. The present invention relates to a collector for a negative electrode of a lithium-ion secondary battery with at least one lithium-ion cell, a lithium-ion battery and a motor vehicle with an electric drive motor for driving the motor vehicle and connected to the electric drive motor or connectable lithium-ion battery.
Stand der Technik State of the art
Lithium-Ionen-Zellen besitzen mindestens eine positive und eine negative Elektrode (Kathode bzw. Anode), die Lithium-Ionen (Li+) reversibel ein- (Interkalation) oder wieder auslagern (Deinterkalation) kann. Die Begriffe Lithium-ion cells have at least one positive and one negative electrode (cathode or anode), the lithium-ion (Li +) reversible on (intercalation) or outsource (deintercalation) can. The terms
Lithium-Ionen-Zelle, Lithium-Ionen-Polymer-Zelle, Lithium-Ionen-Zelle, -Batterie, -Akkumulator und -System werden weitgehend synonym benutzt. Lithium-ion cell, lithium-ion polymer cell, lithium-ion cell, battery, accumulator and system are used largely synonymously.
An Lithium-Ionen-Akkumulatoren werden hohe Anforderungen, insbesondere im automotiven Bereich bezüglich der gravimetrischen Energiedichte (angegeben in Wh/kg) gestellt, um beispielsweise möglicht hohe Reichweiten von mit High demands are placed on lithium-ion accumulators, in particular in the automotive sector with regard to the gravimetric energy density (given in Wh / kg), in order, for example, to achieve long ranges of
Elektromotoren angetriebenen Fahrzeugen zu erzielen. Die Nenn-Kapazität einer Lithium-Ionen-Zelle wird von den so genannten Aktivmaterialien bestimmt. Electric motors powered vehicles to achieve. The nominal capacity of a lithium-ion cell is determined by the so-called active materials.
Allerdings sind in jeder Lithium-Ionen-Zelle noch so genannte Passivmaterialien oder„Totmaterialien" vorhanden, die damit Einfluss auf die Energiedichte der Lithium-Ionen-Zelle haben. Dazu gehören beispielsweise elektrisches However, so-called passive materials or "dead materials" are present in each lithium-ion cell, which thus have an influence on the energy density of the lithium-ion cell
Leitmaterial, Elektrodenbinder, Separatoren, Ableiterfolien und das Gehäuse der Zelle bzw. des Akkumulators selbst und Kollektoren. Kollektoren dienen dazu, den Stromfluss aus und in die Elektroden der Zelle zu gewährleisten. Conductive material, electrode binders, separators, arrester foils and the housing of the cell or the accumulator itself and collectors. Collectors serve to ensure the flow of current from and into the electrodes of the cell.
Der Aufbau einer Lithium-Ionen-Zelle ist beispielhaft in der US 20080107961 A1 beschrieben, wobei der Kollektor als ein Funktionsteil beschrieben wird, das zwischen den Elektroden und dem entsprechenden Terminal konfektioniert ist. The construction of a lithium-ion cell is described by way of example in US 20080107961 A1, the collector being described as a functional part which is assembled between the electrodes and the corresponding terminal.
Üblicherweise werden in Lithium-Ionen-Zellen Kollektoren aus Aluminium zur Kontaktierung auf der positiven Elektrodenseite verwendet. Auf der negativen Elektrodenseite wird Kupfer, Nickel oder vernickeltes Kupfer eingesetzt, da es bei Verwendung von Aluminium auf der negativen Seite aufgrund des gegebenen Potentials sonst zur Legierung von Lithium und Aluminium kommen würde. In der Regel verwendet man dabei Aluminium- und Kupfer- Werkstücke mit Conventionally, in aluminum-ion cells, aluminum collectors are used for contacting on the positive electrode side. On the negative electrode side, copper, nickel or nickel-plated copper is used, since the use of aluminum on the negative side would otherwise lead to the alloying of lithium and aluminum due to the given potential. As a rule, one uses aluminum and copper workpieces with
Material-Dicken von ca. 1 bis 5 mm. Material thicknesses of approx. 1 to 5 mm.
Aus der Verwendung von Kupfer bzw. Nickel als passives Material in einer Lithium-Ionen-Zelle resultieren höhere Herstellungskosten. Zudem werden damit passive Materialien verwendet, die eine höhere kristallographische Dichte im Vergleich zu Aluminium besitzen. So weist Aluminium eine Dichte von 2,7 g/cm3 und Kupfer sowie Nickel eine von 8,9 g/cm3 auf. Dementsprechend hat die Verwendung von Kupfer bzw. Nickel als Materialien für Kollektoren einen negativen Einfluss auf die gravimetrische Energiedichte der Lithium-Ionen-Zelle. The use of copper or nickel as the passive material in a lithium-ion cell results in higher manufacturing costs. It also uses passive materials that have a higher crystallographic density compared to aluminum. Thus, aluminum has a density of 2.7 g / cm 3 and copper and nickel have a density of 8.9 g / cm 3 . Accordingly, the use of copper or nickel as materials for collectors has a negative impact on the gravimetric energy density of the lithium-ion cell.
Offenbarung der Erfindung Disclosure of the invention
Erfindungsgemäß wird ein gewichtsreduzierter aluminiumbasierter Kollektor für die negative Elektrodenseite einer Lithium-Ionen-Zelle zur Verfügung gestellt, der zumindest teilweise mit einer metallischen Schicht versehen ist, die während des Betriebes der Lithium-Ionen-Zelle eine Legierung mit Lithium-Ionen unterbindet. Die metallische Schicht besteht aus Kupfer oder aus Nickel. According to the invention, a weight-reduced aluminum-based collector for the negative electrode side of a lithium-ion cell is provided, which is at least partially provided with a metallic layer which prevents lithium-ion alloying during operation of the lithium-ion cell. The metallic layer is made of copper or nickel.
Zur Vereinfachung von Fertigungsprozessen wird der erfindungsgemäße To simplify manufacturing processes of the invention
Kollektor vollständig mit der jeweiligen äußeren metallischen Schicht umgeben. Damit wird ein Kollektor erhalten, der vorteilhafterweise bei gleichem Volumen ein geringeres Gewicht hat als herkömmliche Kupfer- oder Nickel-basierte Kollektoren. Collector completely surrounded by the respective outer metallic layer. Thus, a collector is obtained which advantageously has a lower weight for the same volume than conventional copper or nickel-based collectors.
Die Gewichtsvorteile des Aluminiums können damit nicht nur für die positive Elektrode, sondern auch für die negative Elektrodenseite des Akkumulators nutzbar gemacht und gleichzeitig der Nachteil der Legierung durch Lithium vermieden werden. The weight advantages of aluminum can thus be utilized not only for the positive electrode, but also for the negative electrode side of the accumulator and at the same time avoid the disadvantage of the alloy by lithium.
Vorzugsweise wird bei der Herstellung des erfindungsgemäßen Kollektors nicht von einem üblichen Kollektor für die positive Elektrodenseite aus Aluminium ausgegangen, sondern es werden Werkstücke mit einer geringeren Preferably, in the production of the collector according to the invention is not assumed by a conventional collector for the positive electrode side made of aluminum, but it will workpieces with a smaller
Materialstärke verwendet, so dass erst nach der Beschichtung mit Kupfer oder Nickel eine übliche Dicke von ca. 1 bis 5 mm erhalten wird. Material thickness used, so that only after the coating with copper or nickel, a usual thickness of about 1 to 5 mm is obtained.
Beispielsweise kann die Kupferschicht 5 μηι stark sein und die des For example, the copper layer can be 5 μηι strong and that of the
Aluminiumkerns 1000 μηι oder die Nickelschicht ist 5 μηι stark und die des Aluminiumkerns 1000 μηι. Aluminum core 1000 μηι or the nickel layer is 5 μηι strong and the aluminum core 1000 μηι.
Andere Dimensionierungen der Schichten bzw. der Gesamtdicke des Kollektors sind natürlich möglich, wobei die metallische Schicht möglichst dünn sein sollte. So wird bei gleicher Dimensionierung des Kollektors ein geringeres Gewicht als nach dem Stand der Technik erreicht. Other dimensions of the layers or the total thickness of the collector are of course possible, the metallic layer should be as thin as possible. Thus, with the same dimensioning of the collector, a lower weight is achieved than in the prior art.
Der erfindungsgemäße Kollektor wird konfektioniert durch das Aufbringen einer dünnen Kupferfolie bzw. Schicht auf das Aluminiumwerkstück. Alternativ kann auch Nickel für die Oberflächenveredelung verwendet werden. The collector according to the invention is assembled by applying a thin copper foil or layer to the aluminum workpiece. Alternatively, nickel can also be used for surface finishing.
Das Aufbringen der dünnen Schichten aus Kupfer oder Nickel auf die Applying the thin layers of copper or nickel on the
Aluminiumfolie erfolgt vorzugsweise entweder a) galvanisch, Aluminum foil is preferably either a) galvanic,
b) durch Walzplattieren oder b) by roll-plating or
c) mittels lonenstrahlbeschichtung. Bei allen Verfahren ist zu gewährleisten, dass die aufgebrachte Schicht keinerlei Defekte aufweist, da es sonst doch zur Einlagerung von Lithium in den c) by means of ion beam coating. In all procedures, it must be ensured that the applied layer does not show any defects, since otherwise the incorporation of lithium into the
Aluminiumkern des Kollektors kommt. Überraschenderweise sind die gewichtsreduzierten Kollektoren für die negativeAluminum core of the collector comes. Surprisingly, the weight-reduced collectors are for the negative
Elektrodenseite in einer Lithium-Ionen-Zelle langzeitstabil. Zudem zeigen die Kollektoren eine gleiche elektrische Performance und ein identisches Verhalten bei Langzeit-Zyklisierung und -Lagerung wie eine Referenzzelle mit einem herkömmlichen Kollektor aus Kupfer oder Nickel. Electrode side in a lithium-ion cell long-term stable. In addition, the collectors show the same electrical performance and identical behavior in long-term cyclization and storage as a reference cell with a conventional copper or nickel collector.
Überraschend waren die Eigenschaften des erfindungsgemäßen Kollektors u.a., da eine Ablösung der Kupfer- oder Nickelschicht von dem Aluminiumwerkstück während des Lagerns oder des Betreibens der Zellen a priori nicht Surprisingly, the properties of the collector according to the invention were, inter alia, since a detachment of the copper or nickel layer from the aluminum workpiece during storage or operation of the cells a priori not
auszuschließen gewesen war. Dies wäre für die elektrochemische Performance der Lithium-Ionen-Zelle sehr nachteilig gewesen. had been ruled out. This would have been very detrimental to the electrochemical performance of the lithium-ion cell.
Besonders bevorzugt sind Lithium-Ionen-Zellen mit einem erfindungsgemäßen Kollektor, der mittels lonenstrahlbeschichtung oberflächenveredelt wurde, da derart hergestellte Kollektoren in vorab genannten Vergleichsversuchen die besten Ergebnisse erzielt haben. Particularly preferred are lithium-ion cells with a collector according to the invention, which has been surface-finished by means of ion beam coating, since collectors produced in this way have achieved the best results in previously mentioned comparative experiments.
Gegenstand der vorliegenden Erfindung sind auch ein mit diesem Kollektor an der negativen Elektrodenseite ausgerüsteter Lithium-Ionen-Akkumulator mit mindestens einer Lithium-Ionen-Zelle sowie ein Kraftfahrzeug mit einem elektrischen Antriebsmotor zum Antreiben des Kraftfahrzeugs und einem mit dem elektrischen Antriebsmotor verbundenen oder verbindbaren The present invention also provides a lithium ion accumulator equipped with this collector on the negative electrode side with at least one lithium ion cell and a motor vehicle with an electric drive motor for driving the motor vehicle and a connected or connectable with the electric drive motor
Lithium-Ionen-Akkumulator. Lithium-ion battery.
Vorteilhafte Weiterbildungen der Erfindung sind in den Unteransprüchen angegeben und in der Beschreibung beschrieben. Advantageous developments of the invention are specified in the subclaims and described in the description.
Zeichnungen drawings
Ein Ausführungsbeispiel der Erfindung wird anhand von Zeichnungen und der nachfolgenden Beschreibung näher erläutert. Es zeigen: Figur 1 in einer perspektivischen Ansicht einen erfindungsgemäßen Kollektor mit einer üblichen räumlichen Ausgestaltung gemäß dem Stand der Technik (US 20080107961 A1), und Figur 2 in einer geschnittenen Seitenansicht einen erfindungsgemäßen Kollektor für die negative Elektrode einer Lithium-Ionen-Zelle. An embodiment of the invention will be explained in more detail with reference to drawings and the description below. Show it: Figure 1 is a perspective view of a collector according to the invention with a conventional spatial configuration according to the prior art (US 20080107961 A1), and Figure 2 is a sectional side view of a collector according to the invention for the negative electrode of a lithium-ion cell.
In Figur 1 ist ein Kollektor 10 dargestellt, der mit einem Terminal 11 , das einen Sockel 12 aufweist, verbunden ist. Der Kollektor 10 ist mit einer metallischen Schicht 13 aus Kupfer oder Nickel umgeben und weist einen Kern aus einemIn Figure 1, a collector 10 is shown, which is connected to a terminal 11, which has a base 12. The collector 10 is surrounded by a metallic layer 13 of copper or nickel and has a core of one
Aluminiumwerkstück 14 auf. Zur Verdeutlichung des Aufbaus ist in Figur 2 ein Schnitt durch den Kollektor 10 gezeigt, wobei das Aluminiumwerkstück 14 von der metallischen Schicht 13 bedeckt ist, die in Relation zum Aluminiumwerkstück 14 zur Gewichtsoptimierung sehr dünn ist. Aluminum workpiece 14 on. To clarify the structure, a section through the collector 10 is shown in Figure 2, wherein the aluminum workpiece 14 is covered by the metallic layer 13, which is very thin in relation to the aluminum workpiece 14 for weight optimization.

Claims

Ansprüche claims
1. Ein Kollektor für eine negative Elektrode eines Lithium-Ionen-Akkumulators mit mindestens einer Lithium-Ionen-Zelle, dadurch gekennzeichnet, dass der Kollektor (10) aus einem Aluminiumwerkstück (14) besteht, das zumindest im Kontaktbereich mit der negativen Elektrode der Lithium-Ionen-Zelle mit einer metallischen Schicht (13) bedeckt ist, die aus Kupfer oder Nickel besteht. 1. A collector for a negative electrode of a lithium-ion battery with at least one lithium-ion cell, characterized in that the collector (10) consists of an aluminum workpiece (14), at least in the contact region with the negative electrode of the lithium Ion cell is covered with a metallic layer (13), which consists of copper or nickel.
2. Der Kollektor nach Anspruch 1 , wobei der Kollektor (10) vollständig von der metallischen Schicht (13) umgeben ist. 2. The collector of claim 1, wherein the collector (10) is completely surrounded by the metallic layer (13).
3. Der Kollektor nach Anspruch 1 oder 2, wobei die metallische Schicht (13) galvanisch aufgebracht ist. 3. The collector of claim 1 or 2, wherein the metallic layer (13) is applied by electroplating.
4. Der Kollektor nach Anspruch 1 oder 2, wobei die metallische Schicht (13) mittels Walzplattieren aufgebracht ist. 4. The collector according to claim 1 or 2, wherein the metallic layer (13) is applied by roll cladding.
5. Der Kollektor nach Anspruch 1 oder 2, wobei die metallische Schicht (13) mittels lonenstrahlbeschichtung aufgebracht ist. 5. The collector of claim 1 or 2, wherein the metallic layer (13) is applied by ion beam coating.
6. Ein Lithium-Ionen-Akkumulator mit mindestens einer Lithium-Ionen-Zelle mit einem Kollektor (10) auf einer negativen Elektrodenseite nach einem der Ansprüche 1 bis 5. 6. A lithium-ion secondary battery with at least one lithium-ion cell with a collector (10) on a negative electrode side according to one of claims 1 to 5.
7. Ein Kraftfahrzeug mit einem elektrischen Antriebsmotor zum Antreiben des Kraftfahrzeugs und einem mit dem elektrischen Antriebsmotor verbundenen oder verbindbaren Lithium-Ionen-Akkumulator gemäß Anspruch 6. 7. A motor vehicle having an electric drive motor for driving the motor vehicle and a connected to the electric drive motor or connectable lithium-ion battery according to claim 6.
PCT/EP2011/070649 2010-12-10 2011-11-22 Collector for a lithium-ion cell, lithium-ion accumulator and motor vehicle comprising a lithium-ion accumulator WO2012076328A1 (en)

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