Surface-coated silicon-carbon composite material, method for producing surface-coated silicon-carbon composite material, anode electrode, and electrochemical storage device

Abstract

The present invention relates to a porous carbon support containing micropores and mesopores and having a total pore volume exceeding 0.5 cm 3 / g; a silicon content of 30% to 70% including 30% and 70%; and a surface region containing a first surface coating, at least partially coated, containing at least one element from the group of elements Li, B, Al, Si, P, Ti, Zr, Nb and / or W. Further, the present invention relates to a method for manufacturing such a surface-coated silicon-carbon composite material, an anode electrode, and an electrochemical energy storage device.

Description

Technical Field

[0001] The present disclosure relates to a surface-coated silicon-carbon composite material containing a porous carbon scaffold containing micropores and mesopores having a pore volume. Further, the present disclosure relates to a method for manufacturing a surface-coated silicon-carbon composite material, an anode electrode, and an electrochemical energy storage device.

Background Art

[0002] Lithium-ion batteries are widely used and provide stored energy to various components. In particular, in electric vehicles and hybrid electric vehicles, such lithium-ion batteries supply electrical energy to vehicle components and the drive train. In such use cases, a long electric driving range is highly desirable, which can be achieved by increasing the capacity of the battery. The capacity of the battery can be increased by increasing the surface area of the electrodes. This is achieved by a more complex surface structure.

[0003] To increase the area for reversible lithium intercalation and the amount of lithium ions involved during the charge and discharge procedures, different methods for coating at least one of the current collectors of the anode with silicon-carbon are known. Such complex surface structures and coating films may be prone to chemical reactions with environmental compounds, for example, during the manufacture of lithium-ion cells. In particular, during the electrolyte filling of a lithium-ion cell, the anode and part of its surface structure may be inadvertently exposed to harmful, for example, oxidizing substances.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] The object of the present disclosure is to provide a silicon-carbon composite material having improved chemical stability and a method for manufacturing the silicon-carbon composite material.

Means for Solving the Problems

[0006] This object is achieved by the subject matter of the independent claims. Further developments of the subject matter of the independent claims are provided in the dependent claims. According to one aspect of the present disclosure, a silicon-carbon composite material is disclosed. Such a silicon-carbon composite material can be used for an anode electrode and thus for an electrochemical energy storage device such as a lithium-ion cell or a battery.

Embodiments for Carrying Out the Invention

[0007] The silicon-carbon composite material contains a porous carbon scaffold having micropores and mesopores and a total pore volume exceeding 0.5 cm 3 / g.

[0008] Furthermore, the porous carbon scaffold silicon-carbon composite material can contain a plurality of particles in order to further adjust its chemical and mechanical properties. By providing additional particles inside the porous carbon scaffold of the silicon-carbon composite material, it becomes possible to control the kinetics of lithium ions inside the silicon-carbon composite material.

[0009] The silicon-carbon composite material has a silicon content of 30% to 70% including 30% and 70% and a surface region having a first surface coating that is at least partially applied. The surface coating of the surface region of the silicon-carbon composite material contains at least one element of the element group consisting of Li, B, Al, Si, P, Ti, Zr, Nb and / or W. The percentages mentioned in the present application can relate to weight percentages or volume percentages with respect to the silicon-carbon composite material.

[0010] In a further aspect of the present invention, an anode electrode containing a surface-coated silicon-carbon material is provided. The anode electrode can preferably contain a metal component, such as a metal foil. A silicon-carbon composite material can be applied to one or both sides of a metal part acting as a current collector to improve the electrical properties of the anode electrode.

[0011] The silicon-carbon composite material according to a further aspect of the present invention can contain, for example, at least one surface coating on a surface region not in contact with a metal component. By providing at least one surface coating, such as a first surface coating, the chemical and mechanical stability of the coated silicon-carbon composite material, and thus the anode electrode having such a material, is improved. In particular, the surface coating can be applied by chemical vapor deposition, such as an atomic layer deposition process. Such a surface coating can also be applied onto a silicon-carbon composite material having a complex or non-uniform surface shape.

[0012] Lithium ions for reversible lithium intercalation can bypass the first surface coating without a significant reduction in the corresponding kinetics when the at least partially applied first surface coating is formed as a layer having a thickness of 0.1 nm to 1 μm.

[0013] According to a further embodiment, the first surface coating contains a metal oxide from at least one or more of the element groups B, Al, Si, Zr, Nb, W, and / or Li. For example, suitable metal oxides are Al 2 O 3 and / or LiAlO 2 and can be formed as.

[0014] In another embodiment, suitable metal oxides are ZrO 2 or / and Li 2 ZrO 3 , or, Al 2 O 3 , ZrO 2 and can be formed as a mixture of mixed lithium aluminum oxide and lithium zirconium oxide.

[0015] A suitable surface coating can be applied at a temperature between 100 °C and 450 °C by atomic layer deposition (ALD) of trimethylaluminum with water or oxygen (followed by two or more ALD cycles), and, optionally, subsequently reacting the resulting aluminum oxide and aluminum hydroxide with a lithium compound such as Li-N(SiMe 3 ) 2 to form a lithiated metal oxide. Such a coating can also be applied in combination with heat exposure and / or in combination with a catalyst. In another embodiment, the surface coating layer can be applied by mixing a metal oxide compound (Al 2 O 3 , Zr(OH) 4 , ZrO(OH) 2 ) with a lithium compound and subsequently performing a heat treatment step at a temperature above 200 °C. In a further embodiment, the first surface coating covers at least 50% of the surface area of the silicon-carbon composite material. Thus, most of the surface area of the silicon-carbon composite material can be protected by the first surface coating.

[0016] The silicon-carbon composite material can contain additional protection when the surface area of the silicon-carbon composite material is at least partially covered by the first surface coating and at least partially covered by the second surface coating. Preferably, the second surface coating is applied at least partially over and / or in addition to the first surface coating. The second surface coating allows for further control of the chemical and mechanical stability of the silicon-carbon composite material.

[0017] According to one embodiment of the silicon-carbon composite material, the second surface coating film is formed as a carbon coating film. Such a second surface coating film can result in a reduction in the electrical resistance of the silicon-carbon composite material in the transition region between the second surface coating film and the current collector or metal when the silicon-carbon composite material is utilized in an electrode. Further, such a second surface coating film can increase the conductivity within the layer of the silicon-carbon composite material. In another embodiment, an additional process is applied to further passivate the surface region or the silicon-carbon composite material by flushing a dry atmosphere (O 2 , N 2 or a mixture thereof) at an elevated temperature of 120 °C to 250 °C over the silicon-carbon composite material.

[0018] In a further embodiment of the silicon-carbon composite material, the silicon-carbon composite material contains a surface area in the range of 2 m 2 / g to 30 m 2 / g, more preferably in the range of 4 m 2 / g to 10 m 2 / g. Appropriate limits of 2 m 2 / g, 30 m 2 / g, 4 m 2 / g, and 10 m 2 / g can also form part of the defined range. Accordingly, the first surface coating layer and / or the second surface coating layer can be efficiently applied onto the lithium-silicon-carbon composite material with an increased surface area due to its porous carbon scaffold.

[0019] According to a further embodiment of the silicon-carbon composite material, the silicon-carbon composite material contains lithium. Further, the first surface coating layer may contain lithium formed as a metal oxide. For example, the first surface coating may contain a metal oxide from Li, in addition to especially Al 2 O 3 . Particularly preferably, the first surface coating can act as a channel for lithium ions during reversible lithium intercalation between the electrolyte and the silicon-carbon composite material, such as Al 2 O 3 , AlO(OH) and LiAlO2 It may contain a mixture of them. Thereby, the kinetics of lithium ions passing through the first and / or second surface coating films can be improved.

[0020] According to a further aspect of the present invention, a method for manufacturing a surface-coated silicon-carbon composite material is provided. In the steps of the method, a porous carbon scaffold having micropores and mesopores is provided. At least one further compound containing Si and optionally at least one of Fe, Al, Ni, W and / or Ti is introduced into the micropores and mesopores of the porous carbon scaffold by chemical vapor infiltration to form a silicon-carbon composite. At least one surface coating film is applied onto the surface region of the silicon-carbon composite material to form the surface-coated silicon-carbon composite material, and the at least one surface coating film contains aluminum oxide or zirconium oxide and at least partially covers the surface region of the silicon-carbon composite material.

[0021] By providing a surface coating film containing aluminum oxide or zirconium oxide, the silicon-carbon composite material can be protected from unintended chemical reactions such as uncontrolled oxidation processes. In particular, during the manufacture of a battery cell or an electrochemical energy storage device, the electrode containing the surface-coated silicon-carbon composite material provides improved chemical stability and reduces the possibility of unwanted chemical reactions due to at least a partial surface coating film.

[0022] In one embodiment, at least one surface coating film of the surface region of the silicon-carbon composite material is applied by a vapor deposition method. Therefore, methods such as atomic layer deposition or molecular layer deposition can be implemented to provide a surface coating film having a controlled and uniform layer thickness.

[0023] In a further embodiment, at least one surface coating is treated with a metal alkoxide or a metal amide or an alkyl metal compound to form a treated compound surface, and the treated compound surface is treated with moisture or oxygen or ozone to form at least one layer of the surface coating. Such materials for forming the treated compound surface are widely used and can thus be provided in a cost-effective manner. For example, trimethylaluminum can be utilized to form the treated compound surface.

[0024] The surface coating and / or the silicon-carbon composite material in the surface region of the silicon-carbon composite material are formed containing lithium. Thus, the silicon-carbon composite material can be pre-charged with lithium ions for use in an electrochemical energy storage device. Further, for example, in addition to the metal oxide Al 2 O 3 compound, lithium can be provided, for example, as LiAlO 2 、Li 2 ZrO 3 or LiNbO 3 to introduce channels for faster lithium ion exchange between the electrolyte and the silicon-carbon composite material of the electrode.

[0025] According to a further embodiment, the surface coating in the surface region of the silicon-carbon composite material contains a metal oxide from at least one of the element groups B, Al, Si, Zr, Nb, W and / or Li. Thus, in the case of atomic layer deposition or molecular layer deposition, the metal oxide is utilized as a precursor. Alternative or additional precursors may be formed, for example, as ZrO 2 、TiO 2 、Al 2 O 3 、SiN x 、TaN x and the like. Further, Nb(OEt) 5 or Li-N(SiMe 3 ) 2By introducing a molecule such as , the chemical composition of at least one surface coating can be precisely controlled. Therefore, the method for manufacturing a surface-coated silicon-carbon composite material includes a plurality of possible materials for adjusting the chemical and mechanical properties of the surface coating.

[0026] In a further embodiment, during the formation of the surface coating of the surface coating region of the silicon-carbon composite material, a temperature in the range of 15 °C to 550 °C is applied to the silicon-carbon composite material and the surface coating. Therefore, methods such as thermal atomic layer or molecular layer deposition or plasma-enhanced atomic layer or molecular layer deposition are suitable for the manufacture of surface-coated silicon-carbon composite materials.

[0027] According to a further embodiment, the silicon-carbon composite material is treated with a metal alkoxide or a metal amide or an alkyl metal compound to form a treated compound surface, and the treatment with moisture or oxygen or ozone on the treated compound surface is repeated at least once. Therefore, a flat coating film of the surface region of the silicon-carbon composite material can be surely formed without leaving any undesirable traces of the treated compound, for example, AlCH 3 ,.

[0028] When a temperature in the range of 15 °C to 550 °C is applied during the treatment of the treated compound with moisture or oxygen or ozone, the manufacturing method can be accelerated.

[0029] According to a further aspect of the present invention, a method for manufacturing at least one anode electrode is provided. In the process, a silicon-carbon composite material mixture having at least one carbon is mixed. In a further process, the silicon-carbon composite material mixture is combined with at least one aqueous binder solution and / or at least one non-aqueous binder solution to form an electrode paste. Further, the electrode paste is at least partially applied on at least one surface of a conductor foil or a current collector. Next, the conductor foil coated with the electrode paste is dried at a temperature of 100 °C to 140 °C to form at least one anode electrode.

[0030] As binders, styrene-butadiene rubber / carboxymethyl cellulose (CMC / SBR) blends, polyacrylic acid (PAA) and / or lithium polyacrylate (LiPAA) or sodium polyacrylate (NaPAA) can be used. In alternative embodiments, the binder is formed as a fluoropolymer such as polytetrafluoroethylene (PTFE), perfluoroalkoxy polymer resin (PFA), fluorinated ethylene propylene (FEP), ethylene tetrafluoroethylene (ETFE), polyvinyl fluoride (PVF), ethylene chlorotrifluoroethylene (ECTFE), polyvinylidene fluoride (PCDF), polychlorotrifluoroethylene (PCTFE), trifluoroethanol, or a combination of at least one of these materials and at least one other material. In a further embodiment, the binder is a polyimide or a copolymer of polyacrylic acid and styrene-butadiene. Further possible binders can be formed as methyl methacrylate or polyvinylidene difluoride.

[0031] The surface coating step can be applied after the drying process of the electrode paste, or the silicon-carbon composite material can be provided in a pre-surface-coated form.

[0032] In a further aspect of the present invention, there is provided an electrochemical energy storage device, particularly formed as a lithium-ion battery. The electrochemical energy storage device contains at least one anode electrode of the present invention, at least one cathode electrode, a separator disposed between the cathode electrode and the anode electrode, and an electrolyte containing lithium ions. The cathode electrode preferably contains a transition metal oxide.

[0033] By using an anode electrode having a surface-coated silicon-carbon material, the requirements for the drying chamber environment for manufacturing the electrochemical energy storage device can be reduced due to the surface-protected anode electrode. Depending on the preferred application, according to a further aspect of the present invention, the manufacturing process of the anode electrode can also be carried out based on a dry or semi-dry silicon-carbon composite material mixture.

[0034] In a first step, a dry silicon-carbon composite material mixture containing graphite particles and / or carbon black particles combined with a binder powder is provided. The binder powder can be formed as PTFE powder.

[0035] Optionally, 5% to 10% ethylene carbonate can be added to the mixture.

[0036] Next, the silicon-carbon composite material mixture combined with the binder powder is at least partially applied by rolling onto at least one surface of a conductor foil or current collector. In a further step, at least one surface coating is applied to the surface area of the silicon-carbon composite material forming the surface-coated silicon-carbon composite material, where the at least one surface coating contains aluminum oxide or zirconium oxide and at least partially covers the surface area of the silicon-carbon composite material.

[0037] The conductor foil coated with the dry or semi-dry electrode paste is then dried at a temperature of, for example, 100°C to 140°C to form at least one anode electrode.

[0038] In a further aspect, the use of a silicon-carbon composite material in an anode electrode is disclosed, where the silicon-carbon composite material contains a porous carbon scaffold containing micropores and mesopores and a total pore volume of 0.5 cm 3 / g or more and a silicon content of 30% to 70%, and contains at least a partially applied surface coating layer forming a surface coating region on the surface area of the silicon-carbon composite material containing at least one element selected from the group of elements Li, B, Al, Si, P, Ti, Zr, Nb, and / or W.

[0039] In a further embodiment, the surface coating layer on the silicon-carbon composite material has a thickness in the range of 0.1 nm to 0.1 μm. In a further embodiment, the surface coating layer on the silicon-carbon composite material contains a metal oxide from at least one or more of the element groups LI, B, Al, Si, Zr, Nb, and W.

[0040] In a further embodiment, the surface coating region of at least one surface coating covers 50% or more of the surface region of the silicon-carbon composite material.

[0041] In a further embodiment, the silicon-carbon composite material contains a further surface coating or a second surface coating on the first surface coating layer, whereby the first surface coating layer and the second surface coating at least partially form a surface coating region.

[0042] In a further embodiment, the further surface coating or the second surface coating is a carbon coating.

[0043] On a further aspect, the use of the anode electrode in the electrochemical energy storage device of the present invention is provided.

[0044] The present disclosure will be described in more detail below based on the schematic embodiments shown in the accompanying drawings.

Brief Description of the Drawings

[0045]

Figure 1

[0046]

Figure 2

Figure 3

[0047] In the drawings, the same reference numbers identify like elements. The sizes and relative positions of the elements in the figures are not necessarily drawn to scale, and some of these elements are enlarged and positioned to improve the viewability of the figure. Further, the particular shapes of the drawn elements are not intended to convey any information regarding the actual shapes of the particular elements, and are selected only to facilitate recognition in the drawings.

[0048] Unless the context requires otherwise, throughout this specification and the claims, the term "comprise" and its variations such as "comprises" and "comprising" are to be construed in an open inclusive sense, i.e., "including, but not limited to." In this specification, any concentration range, percentage range, ratio range or integer range is to be understood to include any integer value within the specified range and, where appropriate, fractions thereof (such as one tenth and one hundredth of an integer), unless otherwise indicated. As used herein, the terms "about" and "approximately" mean ±20%, ±10%, ±5% or ±1% of the indicated range, value, or structure, unless otherwise indicated. The terms "a" and "an" as used herein are to be understood to refer to "one or more" of the recited components. The use of alternatives (e.g., "or") is to be understood to mean either one, both, or any combination thereof.

[0049] Throughout this specification, references to "one embodiment" or "an embodiment" mean that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment of the invention. Thus, the appearances of the phrases "in one embodiment" or "in an embodiment" in various places throughout this specification are not necessarily all referring to the same embodiment. Further, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.

[0050] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. As used in this specification and the claims, the singular forms "a", "an", and "the" include plural references unless the context clearly dictates otherwise.

[0051] The term carbon portion of the silicon-carbon composite material refers to a material or substance consisting of carbon or containing at least carbon. In this regard, the carbon material can contain high-purity, amorphous, and crystalline materials. The carbon material can be activated carbon, pyrolyzed dry polymer gel, pyrolyzed polymer cryogel, pyrolyzed polymer xerogel, pyrolyzed polymer aerogel, activated dry polymer gel, activated polymer cryogel, activated polymer xerogel, activated polymer aerogel, or a combination thereof. In a further embodiment, the carbon can be produced by pyrolysis of coconut shells or other organic waste. In this regard, a polymer is a molecule containing two or more repeating structural units. Porous carbon, also known as a porous carbon material, usually has the advantages of being easy to manufacture, usually having few impurities, and having a large pore volume. As a result, porous carbon exhibits good electrical conductivity as well as high mechanical and chemical stability. In one embodiment, the carbon material has a high micropore volume ratio. Typically, porous carbon has a pore space, also referred to as pore volume, which is a group of voids (pores) in the carbon that can be filled with gas or fluid. In this regard, the properties and manufacturing methods of porous carbon are described in the prior art, for example, Patent Document 1, the entire disclosure of which is incorporated herein by reference in its entirety for all purposes.

[0052] The Si portion of the silicon-carbon composite material may be pure silicon or a material composition containing silicon. For example, the Si portion may be at least one alloy. The alloy may be a silicon-titanium alloy (Si-Ti), a silicon-iron alloy (Si-Fe), or a silicon-nickel alloy (Si-Ni). In a further embodiment, the Si portion may consist of a P-dopant, an As-dopant, or an N-dopant. The P-dopant is usually a phosphorus-dopant, the As-dopant is usually an arsenic-dopant, and the N-dopant is usually a nitrogen-dopant.

[0053] FIG. 1 is an exemplary diagram illustrating a method 1 for manufacturing a surface-coated silicon-carbon composite material 10 according to an embodiment of the present invention.

[0054] In a first method step 2, a porous carbon scaffold having micropores and mesopores is provided. The illustrated shape and size of the porous carbon scaffold and the silicon-carbon composite material 10 are intended for the explanation of method 1. The final shape and size of the materials utilized may vary according to requirements.

[0055] In a further method step 3, at least one further compound containing Si and optionally at least one of Fe, Al, Ni, and / or Ti is introduced into the micropores and mesopores of the porous carbon scaffold by chemical vapor infiltration to form a silicon-carbon composite material.

[0056] In a further method step 4, at least one surface coating 11 is applied onto the surface region of the silicon-carbon composite material 10 to form a surface-coated silicon-carbon composite material.

[0057] The at least one surface coating 11 contains aluminum oxide or zirconium oxide and at least partially covers the surface region of the silicon-carbon composite material 10. In the illustrated example, the at least one surface coating 11, 12 covers the entire surface region of the silicon-carbon composite material 10 for the purpose of explaining the principle.

[0058] In the illustrated embodiment, the surface region of the silicon-carbon composite material 10 is covered with trimethylaluminum TMA. During the exposure of the surface region to trimethylaluminum, it dissociatively chemisorbs onto the surface region of the silicon-carbon composite material 10, and any residual trimethylaluminum in the gas phase can be easily removed.

[0059] The dissociative chemisorption of trimethylaluminum TMA results in a treated compound surface covered with AlCH 3 molecules. This surface can be treated with water H 2 O or oxygen O 2 or ozone O 3 to form at least one layer of a surface coating, which is the first surface coating 11 in the above example.

[0060] This first surface coating 11 consists of Al 3 since the CH 2 O 3 of the treated compound surface chemically reacts during the treatment. Such a coating can be provided by thermal atomic layer deposition, which also requires a temperature increase up to, for example, 450°C.

[0061] In any step 5, the first surface coating layer 11 can be modified by treatment with Li-N(SiMe 3 ) 2 in combination with heating to form a modified first surface coating layer 11', such that it contains Li in the form of LiAlO 2 O 3 in addition to Al 2 molecules. Such molecules having lithium Li can increase the kinetics of Li ions through the modified first surface coating layer 11'.

[0062] In a further step 6, a second surface coating layer 12 can be applied over the first surface coating layer 11. In the illustrated example, the second surface coating layer 12 consists of carbon C. Before performing such passivation through the second surface coating layer 12, the material can be heated to dissipate any remaining binder and / or solvent, such as ethylene or propylene.

[0063] FIG. 2 shows a cross-sectional view of an exemplary electrochemical energy storage device 100 having an electrode anode 110 containing a surface-coated silicon-carbon composite material 10 manufactured by the method shown in FIG. 1. The electrochemical energy storage device 100 is formed as a lithium-ion battery cell. The electrochemical energy storage device 100 includes at least one anode electrode 110, at least one cathode electrode 120, and a separator 130 disposed between the cathode electrode 120 and the anode electrode 110. The cathode electrode preferably contains a transition metal oxide.

[0064] Furthermore, an electrolyte 140 containing lithium ions is provided within the cell housing 150 of the electrochemical energy storage device 100. The electrochemical energy storage device 100 can be formed as a lithium-ion battery cell in pouch form. Accordingly, the cell housing 150 may be formed as an aluminum bag. The anode electrode 110, the cathode electrode 120, and the separator 130 are also disposed within the cell housing 150. Note that FIG. 2 shows a simplified cross-sectional view. The anode electrode 110, the cathode electrode 120, and the separator 130 are typically formed as multiple layers that are wound or folded in order to optimize packaging and to increase the possible surface area of the electrolyte 140. In the illustrated example, only one layer of the components is shown for purposes of illustration.

[0065] The anode electrode 110 is coated on both sides with the surface-coated silicon-carbon composite material 10. The surface coating 11 of the surface-coated silicon-carbon composite material 10 is performed on the surface region of the silicon-carbon composite material 10 that is not in contact with the current collector 111 of the anode electrode 110.

[0066] By using the anode electrode 110 having the surface-coated silicon-carbon material 10, the requirements for the dry chamber environment for manufacturing the electrochemical energy storage device 100 can be reduced. In particular, during the filling of the electrolyte 140 into the cell housing 150, the surface protection by the surface coating 11 can reduce or prevent the chemical interaction between the anode electrode and contaminants. FIG. 3 shows a further exemplary electrochemical energy storage device 100. The electrochemical energy storage device 100 contains an anode electrode 110 having a surface-coated silicon-carbon composite material 10. In contrast to the embodiment shown in FIG. 2, the surface coating 11 of the silicon-carbon composite material 10 is partially applied to the surface of the silicon-carbon composite material 10 such that some portions of the surface region of the silicon-carbon composite material 10 remain without the surface coating 11.

Claims

1. A silicon-carbon composite material (10, 11), comprising: - A porous carbon scaffold containing micropores and mesopores and having a total pore volume exceeding 0.5 cm ３ / g; - A silicon content of 30% to 70% including 30% and 70%; and - A surface region where a first surface coating (11) containing at least one of the element groups Li, B, Al, Si, P, Ti, Zr, Nb, and / or W is at least partially applied; A silicon-carbon composite material containing the above.

2. The silicon-carbon composite material according to Claim 1, wherein the at least partially applied first surface coating (11) is formed as a layer having a thickness of 0.1 nm to 1 μm.

3. The silicon-carbon composite material according to Claim 1 or 2, wherein the first surface coating (11) contains a metal oxide from at least one or more of the element groups B, Al, Si, Zr, Nb, W, and Li.

4. The first surface coating (11) contains, among other things, Al ２ O ３ In addition to that, the silicon-carbon composite material according to any one of claims 1 to 3, which contains a metal oxide derived from Li.

5. The silicon-carbon composite material according to any one of Claims 1 to 4, wherein the first surface coating (11) covers at least 50% of the surface region of the silicon-carbon composite material (10).

6. The silicon-carbon composite material according to any one of Claims 1 to 5, wherein the surface region of the silicon-carbon composite material (10) is at least partially covered by the first surface coating (11) and a second surface coating (12), and the second surface coating (12) is at least partially applied on and / or in addition to the first surface coating (11).

7. The silicon-carbon composite material according to Claim 6, wherein the second surface coating (12) is formed as a carbon coating.

8. The silicon-carbon composite material (10) has a surface area in the range of 2 m ２ / g to 30 m ２ / g, particularly in the range of 4 m ２ / g to 10 m ２ / g, and the silicon-carbon composite material according to any one of claims 1 to 7 contains such a surface area.

9. The silicon-carbon composite material according to any one of Claims 1 to 8, wherein the silicon-carbon composite material (10) contains lithium.

10. A manufacturing method (1) of the surface-coated silicon-carbon composite material (10) according to any one of Claims 1 to 9, comprising: - Preparing a porous carbon scaffold having micropores and mesopores; - Introducing at least one additional compound containing Si and, optionally, at least one of Fe, Al, Ni, W, and / or Ti into the micropores and mesopores of the porous carbon scaffold by chemical vapor infiltration to form a silicon-carbon composite material (10); - At least one surface coating (11, 12) is applied onto the surface region of the silicon-carbon composite material (10) that forms the surface-coated silicon-carbon composite material (10), where the at least one surface coating (11) contains aluminum oxide or zirconium oxide and at least partially covers the surface region of the silicon-carbon composite material (10). Manufacturing method.

11. The method according to claim 10, wherein the at least one surface coating (11, 12) on the surface region of the silicon-carbon composite material is applied by a vapor deposition method.

12. The at least one surface coating is treated with a metal alkoxide or a metal amide or an alkyl metal compound to form a treated compound surface, and the treated compound surface is treated with moisture or oxygen or ozone to form the at least one layer of the first surface coating (11). The method according to claim 10 or 11.

13. The method according to any one of claims 10 to 12, wherein the first surface coating (11) on the surface region of the silicon-carbon composite material (10) and / or the silicon-carbon composite material (10) is formed with lithium.

14. The method according to any one of claims 10 to 13, wherein the first surface coating (11) on the surface region of the silicon-carbon composite material (10) contains a metal oxide from at least one of the element groups B, Al, Si, Zr, Nb, W, and / or Li.

15. During the formation of the first surface coating (11) in the surface coating region of the silicon-carbon composite material, a temperature in the range of 15°C to 550°C is applied to the silicon-carbon composite material (10) and the first surface coating (11). The method according to any one of claims 10 to 14.

16. The method according to claim 12, wherein the silicon-carbon composite material (11) is treated with a metal alkoxide or a metal amide or an alkyl metal compound to form a treated compound surface, and the treatment of the treated compound surface with moisture or oxygen or ozone is repeated at least once.

17. The method according to any one of claims 12 to 16, wherein a temperature in the range of 15°C to 550°C is applied during the treatment of the treated compound with moisture or oxygen or ozone.

18. An anode electrode (110) containing a surface-coated silicon-carbon material (10) having at least one surface coating (11, 12) according to any one of claims 1 to 9.

19. A method for manufacturing at least one anode electrode (110) according to claim 18, comprising: - Mixing a silicon-carbon composite material mixture having at least one carbon; - Combining the silicon-carbon composite material mixture with at least one aqueous binder solution and / or at least one non-aqueous binder solution to form an electrode paste; - At least partially coating the electrode paste on at least one surface of a conductor foil (111); - Drying the conductor foil (111) coated with the electrode paste at a temperature of 100°C to 140°C to form the at least one anode electrode (110) Method.

20. A method for manufacturing at least one anode electrode (110) according to claim 18, comprising: - Mixing a dry or semi-dry silicon-carbon composite material mixture having at least one carbon; wherein the mixture is combined with a binder powder and contains graphite particles and / or carbon black particles; - Applying the silicon-carbon composite material mixture combined with the binder powder at least partially onto at least one surface of a current collector formed as a conductor foil (111) by rolling; - Drying the conductor foil (111) having the applied mixture at a temperature of 100°C to 140°C to form the at least one anode electrode (110) Method.

21. An electrochemical energy storage device (100) particularly formed as a lithium-ion battery, comprising: - At least one anode electrode (110) according to claim 18; - At least one cathode electrode (120) containing a transition metal oxide; - A separator (130) disposed between the cathode electrode (120) and the anode electrode (110); and - An electrolyte (140) containing lithium ions An electrochemical energy storage device containing the same.

Images