WO2012084570A1 - Carbon-silicon multi-layer systems - Google Patents

Carbon-silicon multi-layer systems Download PDF

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Publication number
WO2012084570A1
WO2012084570A1 PCT/EP2011/072439 EP2011072439W WO2012084570A1 WO 2012084570 A1 WO2012084570 A1 WO 2012084570A1 EP 2011072439 W EP2011072439 W EP 2011072439W WO 2012084570 A1 WO2012084570 A1 WO 2012084570A1
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carbon
silicon
multilayer system
individual layers
layers
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PCT/EP2011/072439
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German (de)
French (fr)
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Thomas KÖCK
Stefan Klein
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Sgl Carbon Se
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • 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
    • H01M4/04—Processes of manufacture in general
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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 invention relates to carbon-silicon multilayer systems, processes and their preparation and the use thereof.
  • Silicon has the "right" electrochemical activity with lithium, which has long been regarded as an interesting starting material, but its performance was actually too great, silicon absorbs enough ions to make the anode swell up to four times its original size that the material can break, and after only a few charges, silicon anodes are no longer usable ("silicon for more capacity", Technology Review,
  • J. Yang et al. (“HIGH ENERGY ANODE MATERIALS AND NOVEL ELECTRODE ARCHITECTURE FOR LITHIUM ION BATTERIES” Conference Proceedings: Annual World Conference on Carbon, (2010)) describes a Si-CNT material. rial, which is suitable as an anode material. The Si-CNTs are obtained by vapor deposition of CNTs with silicon and then processed further to the anode material.
  • the object of the present invention is therefore to provide a carbon-silicon multi-layer system which overcomes the disadvantages of the prior art and enables the production of graphite / silicon anodes.
  • the present invention is a carbon-silicon multilayer system consisting of a substrate and alternating layers of carbon and silicon, wherein the individual layers each consist of substantially amorphous carbon or of substantially amorphous silicon.
  • the substrate is selected from metallic substrates or from non-metallic metallic substrates. It is particularly preferred that the metallic substrate is selected from the group consisting of copper and copper alloys.
  • the individual layers have a thickness between 3 nm and 400 nm.
  • the individual layers have approximately the same thickness.
  • the invention is also an inventive carbon-silicon multilayer system, wherein at least one layer is doped with other elements.
  • the doping elements are selected from Sn, Pb, Al, Au, Pt, Zn, Cd, Ag, Mg, P, Ga, Ge, As.
  • An essential feature of the present invention is that the individual layers each consist of substantially amorphous carbon or substantially amorphous silicon. Amorphous structures are characterized by having no XRD diffraction peaks.
  • the measure of the amorphous state would thus be the existence of diffraction peaks or their absence. As soon as peaks are visible in an XRD diffraction pattern, the layer or the layer system is no longer amorphous.
  • XRD x-ray diffraction
  • the X-ray diffraction method makes use of the fact that X-rays interact with the crystal lattice of a solid, resulting in X-ray interference and hence diffraction patterns (Sp card, L., et al., Modern X-Ray Diffraction, BG Teubner Verlag, Wiesbaden, 2005).
  • diffraction patterns which are unique to each crystalline element, it is possible to draw conclusions about the atomic arrangement of the crystal and to bombard the samples to be examined with X-rays are limited.
  • the incident rays are diffracted by atoms in the crystal lattice and interfere with each other.
  • the carbon-silicon multilayer systems of the present invention show no diffraction peaks which would indicate a crystalline structure of silicon. Silicon is almost completely amorphous in the multilayer systems according to the invention.
  • Another object of the invention is a method for producing a carbon-silicon multi-layer system according to the invention, wherein the individual layers successively applied to the substrate by means of magnetron sputtering.
  • these layers are doped simultaneously with another element.
  • these layers are doped with another element in a further working step.
  • the doping is likewise carried out by means of magnetron sputtering
  • the present invention also relates to the use of the carbon-silicon multi-layer system according to the invention as a constituent of the anode material in Li-ion batteries or rechargeable batteries.
  • the carbon-silicon multi-layer system according to the invention has the advantage of having substantially amorphous structures.
  • the incorporation of Li-ions does not destroy the crystal lattice of the silicon. Exactly this destruction of the crystal lattice is the cause of the low cycle stability of previously known anodes for silicon-based Li-ion batteries.
  • the production of the carbon-silicon multi-layer system according to the invention takes place for example by means of magnetron sputtering. This mechanism of the sputtering effect by particle bombardment (magnetron sputtering) will be explained in more detail below.
  • the incident ion releases its energy to the solid atoms through elastic and inelastic collisions.
  • the impact cascade extends, for example, for an ion with an energy of 1 keV, to a range of 5-10 nm below the target surface.
  • the partly resulting recoil atoms are important for the sputtering process, since they can lead to a reversal of the shot impulse by further impacts. Due to the outward momentum, atoms from a depth of about 1 nm can leave the solid state (RA Haefer, surface and thin-film technology, Springer-Verlag, Berlin, Heidelberg, 1987, G. Kienel, vacuum coating 3 - plant automation, measuring and Analysis Technology; VDI-Verlag, Dusseldorf, 1994).
  • the simplest sputtering setup consists of a planar target that can be operated with both DC and AC power. In DC mode, an anomalous glow discharge is maintained between the cathode (target) and the anode (grounded substrate plate).
  • a capacitive high-frequency discharge is ignited at operating frequencies in the range from a few MHz to a few 10 MHz between two electrodes (G. Kienel and K. Röll).
  • a so-called bias voltage can additionally be applied to the substrate plate during the coating.
  • the substrates are at a negative potential, which exposes the substrates to ion bombardment (RA Haefer).
  • the method of magnetron sputtering can also be used for doping the individual layers with a wide variety of doping elements such as Sn, Pb, Al, Au, Pt, Zn, Cd, Ag, Mg, P, Ga, Ge, As and the like.
  • the method is known to the person skilled in the art and can be adapted in a simple manner to the respective requirements.
  • Figure 1 is an electron micrograph of a carbon-silicon multi-layer system according to the invention.
  • FIG. 2 shows the result of the X-ray diffraction of the carbon-silicon multi-layer system according to the invention
  • FIG. 3 shows the schematic structure of a test T cell for determining the cycle stability of the carbon-silicon multi-layer system according to the invention.
  • Figure 4 shows the result of measuring the cycle life of the carbon-silicon multi-layer system according to the invention.
  • a sputtering system from Denton Vacuum, LLC (Discovery 18) is used.
  • As sputtering targets pure silicon (purity 99.999%) and pure carbon (purity 99.999%) are used. Before coating, these targets are made by so-called ion etching cleaned to deposit very pure layers. The uniformity of the layer thickness is ensured by a rotating sample tray.
  • the substrate used is a copper foil from Schlenk (ETP copper strip E-Cu58 LTA, grade W8), which is likewise cleaned by an ion etching process before being coated on the surface.
  • the deposition parameters may vary depending on the target, i. Sputter rate of the element and desired layer thickness can be selected independently.
  • the applied powers were 600 W in the case of the carbon target and 300 W in the case of the silicon target.
  • FIG. 1 shows an example of a carbon-silicon multi-layer system.
  • FIG. 1 is an electron micrograph of the carbon-silicon multilayer system.
  • FIG. 1 shows a carbon-silicon multilayer system produced in this way.
  • the darker stripes represent the silicon layers and the lighter stripes reflect the carbon layers.
  • the substrate layer can be seen, on which a first carbon layer is applied.
  • the thickness of the respective layers is about 30 nm.
  • the lower third of Figure 1 is also a slightly narrower silicon layer can be seen. This shows that, depending on the equipment conditions, the layer thickness can be freely selected within wide limits.
  • the X-ray diffraction tests are carried out on a Siemens AG (Siemens D500) system.
  • the measuring setup of the apparatus works according to the Bragg-Brentano principle.
  • As an X-ray source the CuK alpha line was used (about 1.54 A).
  • the acceleration voltage was 40 kV. 2 shows the result of the X-ray diffraction of the carbon-silicon multi-layer system according to the invention according to Example 1.
  • the peaks shown originate from the substrate material copper. The positions where the peaks of the silicon crystal lattice are to be expected are marked. However, the superimposed spectrum does not have these peaks.
  • test T cells were constructed.
  • a schematic representation of the structure of such a T cell is shown in FIG.
  • a spring was installed for a constant contact pressure between anode and cathode.
  • the area of the cathodes (metallic lithium), the three separators and the anode (coated copper foil) is filled with an electrolyte.
  • LiPF 6 EC-DEC was used for unloading and charging cycles.
  • these cells were installed in a Maccor 4000 Series apparatus.
  • FIG. 4 shows the high cycle stability of the inventive carbon-silicon multilayer system according to Example 1.
  • the carbon-silicon multi-layer systems according to the invention can be produced in a simple manner by means of sputtering methods.
  • the carbon-silicon multi-layer systems according to the invention can be used in a simple manner with methods known in the prior art as anodes for Li-ion batteries.
  • the carbon-silicon multi-layer systems according to the invention have various advantages.
  • the carbon-silicon multi-layer systems according to the invention can be produced in virtually any desired layer thicknesses, with the respective carbon or silicon layers each having the same thickness or in each case may have different strengths.
  • the layer density can be controlled in a simple manner via the parameters of the sputtering method.
  • the substrates can be chosen almost freely. Any substrates that are known and suitable as substrates for sputtering are suitable. Substrates can be metal foils. However, glass surfaces or other non-metallic surfaces are also suitable.
  • the individual layer can also be doped in a simple manner with the desired elements. This doping can also be accomplished in a simple manner by means of the control of the sputtering method.

Abstract

The invention relates to carbon-silicon multi-layer systems, comprising a substrate and alternating layers made of carbon and silicon, wherein the individual layers are each made of substantially amorphous carbon or substantially amorphous silicon. The invention further relates to a method for producing a carbon-silicon multi-layer system, wherein the individual layers are applied to the substrate in succession by means of magnetron sputtering. The individual layers can be produced in nearly any thickness and can be optionally doped. The carbon-silicon multi-layer systems according to the invention can be used as an anode material in lithium-ion batteries and have high cycle resistance when used in such a way.

Description

Kohlenstoff-Silizium-Mehrschichtsysteme  Carbon-silicon multilayer systems
Die Erfindung betrifft Kohlenstoff-Silizium-Mehrschichtsysteme, Verfahren und deren Herstellung sowie die Verwendung derselben. The invention relates to carbon-silicon multilayer systems, processes and their preparation and the use thereof.
Silicium besitzt die„richtige" elektrochemische Aktivität zu Lithium, so dass es schon lange als interessantes Ausgangsmaterial gilt. Doch seine Leistungsfähigkeit war eigentlich zu groß. Silizium absorbiert so viele Ionen, dass die Anode bis auf das Vierfache ihrer Originalgröße anschwillt. Dies hat zur Folge, dass das Material brechen kann. Nach nur wenigen Ladevorgängen sind Siliziumanoden bislang nicht mehr zu gebrauchen („Silicium für mehr Kapazität", Technology Review, Silicon has the "right" electrochemical activity with lithium, which has long been regarded as an interesting starting material, but its performance was actually too great, silicon absorbs enough ions to make the anode swell up to four times its original size that the material can break, and after only a few charges, silicon anodes are no longer usable ("silicon for more capacity", Technology Review,
18.1 .2008). 18.1 .2008).
Eine Lösung des Problem wird von K. Evanoff et al. („Silicon-Decorated Carbon Nanotubes as High Capacity Anodes for Lithium Ion Batteries" Conference Pro- ceedings: Annual World Conference on Carbon, (2010)) beschrieben. Hierbei werden vertikal ausgerichtete Carbon-Nanotubes (VACNTs) verwendet, welche an der Innenseite mit Nanobeschichtungen aus Silizium versehen sind. Aber auch diese Systeme weisen Nachteile bei zunehmenden Entladungsraten auf. A solution to the problem is described by K. Evanoff et al. ("Silicon-Decorated Carbon Nanotubes as High Capacitance Anodes for Lithium Ion Batteries" Conference Pro- grams: Annual World Conference on Carbon, (2010)), using vertically oriented carbon nanotubes (VACNTs), which are internally coated on the inside However, these systems also have disadvantages with increasing discharge rates.
J. Y. Howe et al. ("Microstructural Characterization of Silicon/Carbon Nanofiber Composites for Use in Li-ion Batteries" Conference Proceedings: Annual World Conference on Carbon, (2010)) beschreiben die Mikrostruktur von Li-Ionenbat- terien-Anoden, die aus Silizium/Carbon-Nanofaser- (CNF) Kompositen in Sub- Nanometer-Bereich hergestellt sind. Hierbei treten jedoch wegen der unterschiedlichen Leitfähigkeit von Silizium und Kohlenstoff Probleme auf. J. Y. Howe et al. (Microstructural Characterization of Silicon / Carbon Nanofibre Composites for Use in Li-ion Batteries) Conference Proceedings: Annual World Conference on Carbon, (2010) describe the microstructure of Li-ion battery anodes made of silicon / carbon nanofibres - (CNF) composites are made in sub-nanometer range. Here, however, occur because of the different conductivity of silicon and carbon problems.
Weiterhin beschreiben J. Yang et al. ("HIGH ENERGY ANODE MATERIALS AND NOVEL ELECTRODE ARCHITECTURE FOR LITHIUM ION BATTERIES" Conference Proceedings: Annual World Conference on Carbon, (2010)) ein Si-CNT-Mate- rial, welches als Anodenmaterial geeignet ist. Die Si-CNTs werden durch Bedampfen von CNTs mit Silizium erhalten und dann zum Anodenmaterial weiterberarbei- tet. Furthermore, J. Yang et al. ("HIGH ENERGY ANODE MATERIALS AND NOVEL ELECTRODE ARCHITECTURE FOR LITHIUM ION BATTERIES" Conference Proceedings: Annual World Conference on Carbon, (2010)) describes a Si-CNT material. rial, which is suitable as an anode material. The Si-CNTs are obtained by vapor deposition of CNTs with silicon and then processed further to the anode material.
Schließlich beschreiben T.-H. Park et al. („ADDITION OF SPECIALLY DESIGNED SIO-CNF AND SI-CNF COMPOSITES TO IMPROVE CAP ACITY AND RATE PERFORMANCES OF ANODIC GRAPHITE FOR LI-ION BATTERIES" Conference Proceedings: Annual World Conference on Carbon, (2010)) die Herstellung und Verwendung von SiO-CNF- und Si-CNF-Kompositen als Anodenmaterial. Finally, T.-H. Park et al. ("ADDITION OF SPECIALLY DESIGNED SIO-CNF AND SI-CNF COMPOSITES TO IMPROVE CAP ACITY AND RATE PERFORMANCES OF ANODIC GRAPHITE FOR LI-ION BATTERIES" Conference Proceedings: Annual World Conference on Carbon, (2010)) describes the preparation and use of SiO 2. CNF and Si-CNF composites as anode material.
Bisher ist es aber nicht gelungen, geeignete Anodenmaterialien auf der Basis von CNTs oder Carbonnanofasern herzustellen. Es besteht daher weiterhin ein großer Bedarf an geeigneten Anodenmaterialien auf Siliziumbasis. So far, however, it has not been possible to produce suitable anode materials based on CNTs or carbon nanofibers. Therefore, there is still a great need for suitable silicon-based anode materials.
Aufgabe der vorliegenden Erfindung ist es daher, die Nachteile des Standes der Technik zu überwinden und ein geeignetes Anodenmaterial, welches Silizium enthält zur Verfügung zu stellen. Aufgabe der vorliegenden Erfindung ist es daher, ein Kohlenstoff-Silizium-Mehrschichtsystem zur Verfügung zu stellen, welches die Nachteile des Standes der Technik überwindet und die Herstellung von Graphit/Silizium-Anoden ermöglicht. It is therefore an object of the present invention to overcome the disadvantages of the prior art and to provide a suitable anode material containing silicon. The object of the present invention is therefore to provide a carbon-silicon multi-layer system which overcomes the disadvantages of the prior art and enables the production of graphite / silicon anodes.
Die Aufgabe wird durch die Merkmale des Hauptanspruch gelöst. Vorteilhafte Weiterbildungen der Erfindung sind in den abhängigen Ansprüchen gekennzeichnet. The object is solved by the features of the main claim. Advantageous developments of the invention are characterized in the dependent claims.
Gegenstand der vorliegenden Erfindung ist ein Kohlenstoff-Silizium-Mehrschichtsystem, bestehend aus einen Substrat und alternierenden Schichten aus Kohlenstoff und Silizium, wobei die einzelnen Schichten jeweils aus im wesentlichen amorphem Kohlenstoff oder aus im wesentlichen amorphem Silizium bestehen. The present invention is a carbon-silicon multilayer system consisting of a substrate and alternating layers of carbon and silicon, wherein the individual layers each consist of substantially amorphous carbon or of substantially amorphous silicon.
Erfindungsgemäß bevorzugt ist ein Kohlenstoff-Silizium-Mehrschichtsystem, bei dem das Substrat ausgewählt ist aus metallischen Substraten oder aus nichtmetal- lischen Substraten. Besonders bevorzugt ist es, dass das metallische Substrat ausgewählt ist aus der Gruppe bestehend aus Kupfer und Kupferlegierungen. According to the invention, preference is given to a carbon / silicon multilayer system in which the substrate is selected from metallic substrates or from non-metallic metallic substrates. It is particularly preferred that the metallic substrate is selected from the group consisting of copper and copper alloys.
Erfindungsgemäß bevorzugt ist es dabei, dass die einzelnen Schichten eine Dicke zwischen 3 nm und 400 nm aufweisen. According to the invention, it is preferred that the individual layers have a thickness between 3 nm and 400 nm.
Besonders bevorzugt ist es dabei, dass die einzelnen Schichten die annährend gleiche Dicke aufweisen. It is particularly preferred that the individual layers have approximately the same thickness.
Erfindungsgemäß ist auch ein erfindungsgemäßes Kohlenstoff-Silizium-Mehrschichtsystem, wobei mindestens eine Schicht mit anderen Elementen dotiert ist. Dabei ist es besonders bevorzugt, dass die Dotierungselemente ausgewählt sind aus Sn, Pb, AI, Au, Pt, Zn, Cd, Ag, Mg, P, Ga, Ge, As. According to the invention is also an inventive carbon-silicon multilayer system, wherein at least one layer is doped with other elements. It is particularly preferred that the doping elements are selected from Sn, Pb, Al, Au, Pt, Zn, Cd, Ag, Mg, P, Ga, Ge, As.
Ein wesentliches Merkmal der vorliegenden Erfindung ist es, dass die einzelnen Schichten jeweils aus im wesentlichen amorphem Kohlenstoff oder aus im wesentlichen amorphem Silizium bestehen. Amorphe Strukturen sind dadurch gekennzeichnet, dass diese keine XRD-Beugungspeaks aufweisen. An essential feature of the present invention is that the individual layers each consist of substantially amorphous carbon or substantially amorphous silicon. Amorphous structures are characterized by having no XRD diffraction peaks.
Die Maßzahl für den amorphen Zustand wäre somit die Existenz von Beu- gungspeaks bzw. deren Abwesenheit. Sobald in einem XRD-Beugungsbild Peaks zu erkennen sind ist die Schicht bzw. das Schichtsystem nicht mehr amorph. The measure of the amorphous state would thus be the existence of diffraction peaks or their absence. As soon as peaks are visible in an XRD diffraction pattern, the layer or the layer system is no longer amorphous.
XRD (x-ray diffraction) ist ein Röntgenbeugungsverfahren. Bei dem Verfahren der Röntgenbeugung nutzt man die Tatsache, dass Röntgenstrahlen mit dem Kristallgitter eines Festkörpers wechselwirken und es hierbei zu Interferenzen der Röntgenstrahlung und somit zu Beugungsbildern kommt (L. Spieß et al.„Moderne Röntgenbeugung"; B.G. Teubner Verlag, Wiesbaden, 2005). Wertet man diese Beugungsdiagramme, die für jedes kristalline Element einzigartig sind, aus, so lassen sich Rückschlüsse auf die atomare Anordnung des Kristalls ziehen. Die zu untersuchenden Proben werden mit Röntgenstrahlen beschossen, die durch Blenden begrenzt sind. Die einfallenden Strahlen werden an Atomen im Kristallgitter gebeugt und interferieren miteinander. XRD (x-ray diffraction) is an X-ray diffraction method. The X-ray diffraction method makes use of the fact that X-rays interact with the crystal lattice of a solid, resulting in X-ray interference and hence diffraction patterns (Spieß, L., et al., Modern X-Ray Diffraction, BG Teubner Verlag, Wiesbaden, 2005). By evaluating these diffraction patterns, which are unique to each crystalline element, it is possible to draw conclusions about the atomic arrangement of the crystal and to bombard the samples to be examined with X-rays are limited. The incident rays are diffracted by atoms in the crystal lattice and interfere with each other.
Die erfindungsgemäßen Kohlenstoff-Silizium-Mehrschichtsysteme zeigen keine Beugungspeaks, welche eine kristalline Struktur von Silizium anzeigen würden. Silizium liegt in den erfindungsgemäßen Mehrschichtsystemen nahezu vollständig amorph vor. The carbon-silicon multilayer systems of the present invention show no diffraction peaks which would indicate a crystalline structure of silicon. Silicon is almost completely amorphous in the multilayer systems according to the invention.
Ein weiterer Gegenstand der Erfindung ist ein Verfahren zur Herstellung eines erfindungsgemäßen Kohlenstoff-Silizium-Mehrschichtsystems, wobei man die einzelnen Schichten nacheinander auf das Substrat mittels Magnetron-Sputtering aufträgt. Another object of the invention is a method for producing a carbon-silicon multi-layer system according to the invention, wherein the individual layers successively applied to the substrate by means of magnetron sputtering.
Erfindungsgemäß bevorzugt ist dabei, dass man während des Auftragens der einzelnen Schichten diese Schichten gleichzeitig mit einem anderen Element dotiert. According to the invention, it is preferred that during the application of the individual layers, these layers are doped simultaneously with another element.
Bevorzugt ist ferner, dass man nach dem Auftragen der einzelnen Schichten diese Schichten in einem weiteren Arbeitsschritt mit einem anderen Element dotiert. It is further preferred that, after the application of the individual layers, these layers are doped with another element in a further working step.
Besonders bevorzugt ist dabei jeweils, dass man die Dotierung gleichfalls mittels Magnetron-Sputtering durchführt It is particularly preferred in each case that the doping is likewise carried out by means of magnetron sputtering
Gegenstand der der vorliegenden Verwendung ist ferner die Verwendung des erfindungsgemäßen Kohlenstoff-Silizium-Mehrschichtsystem als Bestandteil des A- nodenmaterials in Li-Ionen-Batterien bzw. Akkus. The present invention also relates to the use of the carbon-silicon multi-layer system according to the invention as a constituent of the anode material in Li-ion batteries or rechargeable batteries.
Das erfindungsgemäße Kohlenstoff-Silizium-Mehrschichtsystem weist den Vorteil auf, im Wesentlichen amorphe Strukturen zu besitzen. Bei der Einlagerung von Li- lonen kommt es somit nicht zu einer Zerstörung des Kristallgitters des Siliziums. Genau diese Zerstörung des Kristallgitters ist aber die Ursache für die geringe Zyklenstabilität von bisher bekannten Anoden für Li-Ionen-Akkus auf Siliziumbasis. Die Herstellung des erfindungsgemäßen Kohlenstoff-Silizium-Mehrschichtsystems erfolgt beispielsweise mittels Magnetron-Sputtering. Dieser Mechanismus des Zerstäubungseffekts durch Teilchenbeschuss (Magnetron-Sputtering) wird nachfolgend näher erläutert. The carbon-silicon multi-layer system according to the invention has the advantage of having substantially amorphous structures. Thus, the incorporation of Li-ions does not destroy the crystal lattice of the silicon. Exactly this destruction of the crystal lattice is the cause of the low cycle stability of previously known anodes for silicon-based Li-ion batteries. The production of the carbon-silicon multi-layer system according to the invention takes place for example by means of magnetron sputtering. This mechanism of the sputtering effect by particle bombardment (magnetron sputtering) will be explained in more detail below.
Das einfallende Ion gibt seine Energie durch elastische und inelastische Stöße an die Festkörperatome ab. Die Stoßkaskade erstreckt sich dabei, beispielsweise für ein Ion mit einer Energie von 1 keV, auf einen Bereich von 5-10 nm unterhalb der Targetoberfläche. Die dabei zum Teil entstehenden Rückstoßatome sind für den Zerstäubungsprozess wichtig, da sie durch weitere Stöße zu einer Umkehr des Be- schussimpulses führen können. Durch den nach außen gerichteten Impuls können Atome aus einer Tiefe von etwa 1 nm den Festkörper verlassen (R.A. Haefer; Oberflächen- und Dünnschicht-Technologie; Springer-Verlag, Berlin, Heidelberg, 1987; G. Kienel; Vakuumbeschichtung 3 - Anlagenautomatisierung, Meß- und Analysetechnik; VDI-Verlag, Düsseldorf, 1994). Während des Zerstäubungsprozesses entstehen nahezu ausschließlich neutrale Teilchen (G. Kienel und K. Röll; Vakuumbeschichtung 2 - Verfahren und Anlagen; VDI-Verlag, Düsseldorf, 1995). Nur ein geringer Anteil liegt als positiv oder negativ geladene Ionen sowie Atomcluster vor. Die Energie der zerstäubten Atome liegt, je nach Targetelement, zwischen 10 und 40 eV (R.A. Haefer). Der einfachste Sputteraufbau besteht aus einem planaren Target, das sowohl mit Gleich- (DC) als auch mit Wechselspannung (RF) betrieben werden kann. Im DC-Modus wird eine anomale Glimmentladung zwischen der Kathode (Target) und der Anode (geerdeter Substratteller) aufrechterhalten. Im RF- Modus wird zwischen zwei Elektroden eine kapazitive Hochfrequenzentladung bei Arbeitsfrequenzen im Bereich von einigen MHz bis einigen 10 MHz gezündet (G. Kienel und K. Röll). Um lose Verunreinigungen zu entfernen oder auch die Schichtstruktur positiv zu beeinflussen, kann zusätzlich während der Beschichtung eine sogenannte Bias-Spannung an den Substratteller angelegt werden. Dadurch liegen die Substrate auf einem negativen Potenzial, wodurch die Substrate einem lonen- bombardement ausgesetzt werden (R.A. Haefer ). Das Verfahren des Magnetron-Sputtering kann auch zur Dotierung der einzelnen Schichten mit unterschiedlichsten Dotierungselementen wie Sn, Pb, AI, Au, Pt, Zn, Cd, Ag, Mg, P, Ga, Ge, As und dergleichen verwendet werden. Das Verfahren ist dem Fachmann bekannt und kann in einfacher Weise an die jeweiligen Anforderungen angepasst werden. The incident ion releases its energy to the solid atoms through elastic and inelastic collisions. The impact cascade extends, for example, for an ion with an energy of 1 keV, to a range of 5-10 nm below the target surface. The partly resulting recoil atoms are important for the sputtering process, since they can lead to a reversal of the shot impulse by further impacts. Due to the outward momentum, atoms from a depth of about 1 nm can leave the solid state (RA Haefer, surface and thin-film technology, Springer-Verlag, Berlin, Heidelberg, 1987, G. Kienel, vacuum coating 3 - plant automation, measuring and Analysis Technology; VDI-Verlag, Dusseldorf, 1994). During the sputtering process almost exclusively neutral particles are formed (G. Kienel and K. Röll, Vacuum coating 2 - Processes and Systems, VDI-Verlag, Dusseldorf, 1995). Only a small proportion is present as positively or negatively charged ions and atomic clusters. Depending on the target element, the energy of the atomized atoms lies between 10 and 40 eV (RA Haefer). The simplest sputtering setup consists of a planar target that can be operated with both DC and AC power. In DC mode, an anomalous glow discharge is maintained between the cathode (target) and the anode (grounded substrate plate). In the RF mode, a capacitive high-frequency discharge is ignited at operating frequencies in the range from a few MHz to a few 10 MHz between two electrodes (G. Kienel and K. Röll). In order to remove loose impurities or to positively influence the layer structure, a so-called bias voltage can additionally be applied to the substrate plate during the coating. As a result, the substrates are at a negative potential, which exposes the substrates to ion bombardment (RA Haefer). The method of magnetron sputtering can also be used for doping the individual layers with a wide variety of doping elements such as Sn, Pb, Al, Au, Pt, Zn, Cd, Ag, Mg, P, Ga, Ge, As and the like. The method is known to the person skilled in the art and can be adapted in a simple manner to the respective requirements.
Die folgenden Beispiele erläutern die Erfindung. The following examples illustrate the invention.
Zur Erläuterung der Beispiele sind die Figuren 1 bis 4 angefügt. Es zeigt: To explain the examples, Figures 1 to 4 are added. It shows:
Figur 1 eine elektronenmikroskopische Darstellung eines erfindungsgemäßen Kohlenstoff-Silizium-Mehrschichtsystems; Figure 1 is an electron micrograph of a carbon-silicon multi-layer system according to the invention;
Figur 2 das Ergebnis der Röntgenbeugung des erfindungsgemäßen Kohlenstoff- Silizium-Mehrschichtsystems; FIG. 2 shows the result of the X-ray diffraction of the carbon-silicon multi-layer system according to the invention;
Figur 3 den schematischen Aufbau einer Test-T-Zelle zur Bestimmung er Zyklenbeständigkeit des erfindungsgemäßen Kohlenstoff-Silizium-Mehrschichtsystems; und FIG. 3 shows the schematic structure of a test T cell for determining the cycle stability of the carbon-silicon multi-layer system according to the invention; and
Figur 4 das Ergebnis der Messung der Zyklenbeständigkeit des erfindungsgemäßen Kohlenstoff-Silizium-Mehrschichtsystem. Figure 4 shows the result of measuring the cycle life of the carbon-silicon multi-layer system according to the invention.
Beispiel 1 example 1
Herstellung eines Kohlenstoff-Silizium-Mehrschichtsystems  Production of a carbon-silicon multilayer system
Für die Herstellung des Mehrschichtsystems wird eine Zerstäubungsanlage von Denton Vacuum, LLC (Discovery 18) verwendet. Als Sputtertargets werden reines Silizium (Reinheit 99.999%) sowie reiner Kohlenstoff (Reinheit 99.999%) verwendet. Vor der Beschichtung werden diese Targets durch ein sogenanntes lonenätzen gereinigt, um sehr reine Schichten abzuscheiden. Die Gleichmäßigkeit der Schichtdicke wird durch einen rotierenden Probenteller sichergestellt. For the manufacture of the multilayer system, a sputtering system from Denton Vacuum, LLC (Discovery 18) is used. As sputtering targets pure silicon (purity 99.999%) and pure carbon (purity 99.999%) are used. Before coating, these targets are made by so-called ion etching cleaned to deposit very pure layers. The uniformity of the layer thickness is ensured by a rotating sample tray.
Als Substrat wird eine Kupferfolie der Firma Schlenk (ETP Kupferband E-Cu58 LTA, Qualität W8) verwendet, das ebenfalls vor der Beschichtung an der Oberfläche durch einen lonenätzprozess gereinigt wird. The substrate used is a copper foil from Schlenk (ETP copper strip E-Cu58 LTA, grade W8), which is likewise cleaned by an ion etching process before being coated on the surface.
Die Abscheidungsparameter können je nach Target, d.h. Zerstäubungsrate des Elements und erwünschter Schichtdicke unabhängig voneinander gewählt werden. Für das beschriebene Mehrschichtsystem lagen die angelegten Leistungen im Falle des Kohlenstofftargets bei 600 W und im Falle des Siliziumtargets bei 300 W. The deposition parameters may vary depending on the target, i. Sputter rate of the element and desired layer thickness can be selected independently. For the described multilayer system, the applied powers were 600 W in the case of the carbon target and 300 W in the case of the silicon target.
In der Figur 1 ist ein Beispiel für ein Kohlenstoff-Silizium-Mehrschichtsystem gezeigt. Figur 1 ist eine elektronenmikroskopische Darstellung des Kohlenstoff-Silizium-Mehrschichtsystems. FIG. 1 shows an example of a carbon-silicon multi-layer system. FIG. 1 is an electron micrograph of the carbon-silicon multilayer system.
Figur 1 zeigt ein derart hergestelltes Kohlenstoff-Silizium-Mehrschichtsystem. In der Figur 1 geben die dunkleren Streifen die Silizium-Schichten und die helleren Streifen die Kohlenstoffschichten wieder. Im unteren Teil der Figur 1 ist die Substratschicht zu erkennen, auf welcher zunächst eine Kohlenstoffschicht aufgetragen ist. Die Dicke der jeweiligen Schichten liegt bei ca. 30 nm. In unteren Drittel der Figur 1 ist ferner eine etwas schmalere Silizium-Schicht zu erkennen. Dies zeigt, dass je nach apparativen Bedingungen die Schichtdicke in weiten Grenzen frei wählbar ist. FIG. 1 shows a carbon-silicon multilayer system produced in this way. In Figure 1, the darker stripes represent the silicon layers and the lighter stripes reflect the carbon layers. In the lower part of Figure 1, the substrate layer can be seen, on which a first carbon layer is applied. The thickness of the respective layers is about 30 nm. In the lower third of Figure 1 is also a slightly narrower silicon layer can be seen. This shows that, depending on the equipment conditions, the layer thickness can be freely selected within wide limits.
Beispiel 2 Example 2
XRD-Messung  XRD-measurement
Die Röntgenbeugungsversuche werden an einer Anlage der Siemens AG (Siemens D500) durchgeführt. Der Messaufbau der Apparatur arbeitet nach dem Bragg- Brentano Prinzip. Als Röntgenquelle wurde die CuK alpha Linie verwendet (etwa 1 ,54 A). Die Beschleunigungsspannung betrug 40 kV. In der Figur 2 ist das Ergebnis der Röntgenbeugung des erfindungsgemäßen Kohlenstoff-Silizium-Mehrschichtsystems gemäß dem Beispiel 1 dargestellt. Die dargestellten Peaks stammen vom Substratmaterial Kupfer. Die Positionen, an denen die Peaks des Siliziumkristallgitters zu erwarten sind, sind markiert. Das darüber gelegte Spektrum weist diese Peaks jedoch nicht auf. The X-ray diffraction tests are carried out on a Siemens AG (Siemens D500) system. The measuring setup of the apparatus works according to the Bragg-Brentano principle. As an X-ray source, the CuK alpha line was used (about 1.54 A). The acceleration voltage was 40 kV. 2 shows the result of the X-ray diffraction of the carbon-silicon multi-layer system according to the invention according to Example 1. The peaks shown originate from the substrate material copper. The positions where the peaks of the silicon crystal lattice are to be expected are marked. However, the superimposed spectrum does not have these peaks.
Beispiel 3 Example 3
Zyklenbeständigkeit  cycle stability
Zur Überprüfung der Zyklenbeständigkeit wurden einige Test-T-Zellen gebaut. Eine schematische Darstellung des Aufbaus einer derartigen T-Zelle ist in der Figur 3 wiedergegeben. Für einen konstanten Anpressdruck zwischen Anode und Kathode wurde eine Feder verbaut. Der Bereich der Kathoden (metallisches Lithium), der drei Separatoren und der Anode (beschichtete Kupferfolie) ist mit einem Elektrolyt gefüllt. In diesem Fall wurde LiPF6 EC-DEC verwendet. Für die Entlade- und Ladezyklen wurden diese Zellen in eine Maccor 4000 Series Apparatur verbaut. To test cycle stability, several test T cells were constructed. A schematic representation of the structure of such a T cell is shown in FIG. For a constant contact pressure between anode and cathode, a spring was installed. The area of the cathodes (metallic lithium), the three separators and the anode (coated copper foil) is filled with an electrolyte. In this case LiPF 6 EC-DEC was used. For unloading and charging cycles, these cells were installed in a Maccor 4000 Series apparatus.
Die Figur 4 zeigt die hohe Zyklenbeständigkeit des erfindungsgemäßen Kohlenstoff- Silizium-Mehrschichtsystem gemäß dem Beispiel 1 . FIG. 4 shows the high cycle stability of the inventive carbon-silicon multilayer system according to Example 1.
Es konnte gezeigt werden, dass die erfindungsgemäßen Kohlenstoff-Silizium-Mehrschichtsysteme in einfacher weise mittels Sputterverfahren herstellbar sind. Die erfindungsgemäßen Kohlenstoff-Silizium-Mehrschichtsysteme lassen sich in einfacher Weise mit im Stand der Technik bekannten Verfahren als Anoden für Li-Ionen- Akkus verwenden. It has been shown that the carbon-silicon multi-layer systems according to the invention can be produced in a simple manner by means of sputtering methods. The carbon-silicon multi-layer systems according to the invention can be used in a simple manner with methods known in the prior art as anodes for Li-ion batteries.
Die erfindungsgemäßen Kohlenstoff-Silizium-Mehrschichtsysteme weisen verschiedene Vorteile auf. So sind die erfindungsgemäßen Kohlenstoff-Silizium-Mehrschichtsysteme in nahezu beliebigen Schichtdicken herstellbar, wobei die jeweiligen Kohlenstoff- oder Siliziumschichten jeweils die gleiche Stärke oder jeweils unter- schiedliche Stärken aufweisen können. Die Schichtdichte ist in einfacher Weise über die Parameter des Sputterverfahrens steuerbar. The carbon-silicon multi-layer systems according to the invention have various advantages. Thus, the carbon-silicon multi-layer systems according to the invention can be produced in virtually any desired layer thicknesses, with the respective carbon or silicon layers each having the same thickness or in each case may have different strengths. The layer density can be controlled in a simple manner via the parameters of the sputtering method.
Ein weiterer Vorteil der erfindungsgemäßen Kohlenstoff-Silizium-Mehrschichtsysteme ist es, dass die Substrate nahezu frei gewählt werden können. Jedwede Substrate sind geeignet, die als Substrate für Sputterverfahren bekannt und geeignet sind. Substrate können Metallfolien sein. Geeignet sind aber auch Glasoberflächen oder andere nichtmetallische Oberflächen. Another advantage of the carbon-silicon multi-layer systems according to the invention is that the substrates can be chosen almost freely. Any substrates that are known and suitable as substrates for sputtering are suitable. Substrates can be metal foils. However, glass surfaces or other non-metallic surfaces are also suitable.
Ferner lassen sich die einzelnen Schicht in ebenfalls einfacher Weise mit den gewünschten Elementen dotieren. Auch diese Dotierung kann mittels der Steuerung des Sputterverfahrens in einfacher Weise bewerkstelligt werden. Furthermore, the individual layer can also be doped in a simple manner with the desired elements. This doping can also be accomplished in a simple manner by means of the control of the sputtering method.

Claims

Patentansprüche claims
1 . Kohlenstoff-Silizium-Mehrschichtsystem, bestehend aus einen Substrat und alternierenden Schichten aus Kohlenstoff und Silizium, wobei die einzelnen Schichten jeweils aus im wesentlichen amorphem Kohlenstoff oder aus im wesentlichen amorphem Silizium bestehen. 1 . Carbon-silicon multilayer system consisting of a substrate and alternating layers of carbon and silicon, wherein the individual layers each consist of substantially amorphous carbon or of substantially amorphous silicon.
2. Kohlenstoff-Silizium-Mehrschichtsystem, gemäß Anspruch 1 , dadurch gekennzeichnet, dass das Substrat ausgewählt ist aus metallischen Substraten oder aus nichtmetallischen Substraten. 2. Carbon-silicon multilayer system according to claim 1, characterized in that the substrate is selected from metallic substrates or from non-metallic substrates.
3. Kohlenstoff-Silizium-Mehrschichtsystem, gemäß Anspruch 2, dadurch gekennzeichnet, dass das metallischen Substrat ausgewählt ist aus der Gruppe bestehend aus Kupfer und Kupferlegierungen. 3. carbon-silicon multilayer system, according to claim 2, characterized in that the metallic substrate is selected from the group consisting of copper and copper alloys.
4. Kohlenstoff-Silizium-Mehrschichtsystem, gemäß Anspruch 1 , dadurch gekennzeichnet, dass die einzelnen Schichten eine Dicke zwischen 3 nm und 400 nm aufweisen. 4. carbon-silicon multilayer system, according to claim 1, characterized in that the individual layers have a thickness between 3 nm and 400 nm.
5. Kohlenstoff-Silizium-Mehrschichtsystem, gemäß Anspruch 1 , dadurch gekennzeichnet, dass die einzelnen Schichten die annährend gleiche Dicke aufweisen. 5. carbon-silicon multilayer system, according to claim 1, characterized in that the individual layers have approximately the same thickness.
6. Kohlenstoff-Silizium-Mehrschichtsystem, gemäß Anspruch 1 , dadurch gekennzeichnet, dass mindestens eine Schicht mit anderen Elementen dotiert ist. 6. carbon-silicon multilayer system, according to claim 1, characterized in that at least one layer is doped with other elements.
7. Kohlenstoff-Silizium-Mehrschichtsystem, gemäß Anspruch 6, dadurch gekennzeichnet, dass die Dotierungselemente ausgewählt sind aus Sn, Pb, AI, Au, Pt, Zn, Cd, Ag, Mg, P, Ga, Ge, As. 7. carbon-silicon multilayer system, according to claim 6, characterized in that the doping elements are selected from Sn, Pb, Al, Au, Pt, Zn, Cd, Ag, Mg, P, Ga, Ge, As.
8. Verfahren zur Herstellung eines Kohlenstoff-Silizium-Mehrschichtsystems, gemäß Anspruch 1 , wobei man die einzelnen Schichten nacheinander auf das Substrat mittels Magnetron-Sputtering aufträgt. 8. A process for producing a carbon-silicon multilayer system according to claim 1, wherein the individual layers are successively applied to the substrate by means of magnetron sputtering.
9. Verfahren, gemäß Anspruch 8, dadurch gekennzeichnet, dass man während des Auftragens der einzelnen Schichten diese Schichten gleichzeitig mit einem anderen Element dotiert. 9. The method according to claim 8, characterized in that during the application of the individual layers, these layers are doped simultaneously with another element.
10. Verfahren, gemäß Anspruch 8, dadurch gekennzeichnet, dass man nach dem Auftragen der einzelnen Schichten diese Schichten in einem weiteren Arbeitsschritt mit einem anderen Element dotiert. 10. The method according to claim 8, characterized in that doped after applying the individual layers, these layers in a further step with another element.
1 1 . Verfahren, gemäß Anspruch 8 oder 9, dadurch gekennzeichnet, dass man die Dotierung gleichfalls mittels Magnetron-Sputtering durchführt 1 1. A method according to claim 8 or 9, characterized in that the doping is likewise carried out by means of magnetron sputtering
12. Verwendung von Kohlenstoff-Silizium-Mehrschichtsystem, gemäß Anspruch 1 , als Bestandteil des Anodenmaterials in Li-Ionen-Batterien. 12. Use of carbon-silicon multilayer system, according to claim 1, as a component of the anode material in Li-ion batteries.
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