CN108138302B

CN108138302B - Method and device for producing a flexible layer stack, method for producing a negative electrode for a lithium battery, and negative electrode for a lithium battery

Info

Publication number: CN108138302B
Application number: CN201580083477.3A
Authority: CN
Inventors: 托马斯·德皮施
Original assignee: Applied Materials Inc
Current assignee: Applied Materials Inc
Priority date: 2015-10-02
Filing date: 2015-10-02
Publication date: 2020-12-22
Anticipated expiration: 2035-10-02
Also published as: JP2018532231A; JP7023222B2; KR102271227B1; WO2017054889A1; TWI714639B; KR20180063250A; TW201717471A; CN108138302A

Abstract

The present disclosure provides a method for manufacturing a flexible layer stack (100). The method comprises the following steps: providing (310) a flexible substrate (101); depositing (320) a first layer (110) over a flexible substrate (101), the first layer (110) comprising a first material; depositing (330) a second layer (120) over the first layer (110), the second layer (120) comprising a second material; and removing (340) the flexible substrate (101).

Description

Method and device for producing a flexible layer stack, method for producing a negative electrode for a lithium battery, and negative electrode for a lithium battery

Technical Field

Examples of the present disclosure relate to a method and apparatus for manufacturing a flexible layer stack, and to a flexible layer stack. Examples of the present disclosure relate particularly to a method and apparatus for manufacturing a negative electrode for a lithium battery, and to a negative electrode for a lithium battery.

Background

Many methods are known for depositing materials on substrates. For example, the substrate may be coated by a Physical Vapor Deposition (PVD) process, a Chemical Vapor Deposition (CVD) process, a Plasma Enhanced Chemical Vapor Deposition (PECVD) process, or the like. Generally, the process is performed in a processing apparatus or processing chamber in which the substrate to be coated is located. A deposition material is provided in the apparatus. A variety of materials, including oxides, nitrides or carbides of the materials, may be used for deposition on the substrate. In addition, non-vacuum coating methods may be used. For example, a roll-to-roll-coating process, such as slot die coating (slot die coating), may be used to fabricate lithium (Li) batteries.

The coated materials can be used in many applications and in many technical fields. For example, the coated materials may be used in the field of microelectronics, such as for the manufacture of lithium batteries. Other applications typically include thin film batteries, electrochromic windows, insulated panels, Organic Light Emitting Diode (OLED) panels, substrates with TFTs, color filters, or similar applications.

In the case of lithium batteries, it is desirable to have a high energy or storage density, which can be viewed as the amount of energy stored in a given system or region per unit volume of space (Wh/l) or mass per weight (Wh/kg). For example, the energy density can be increased by combining several cells, which are interconnected by a common anode between two adjacent cells, into a lithium battery.

In view of the above, a method for manufacturing a flexible layer stack, an apparatus for manufacturing a flexible layer stack and a flexible layer stack overcoming at least some of the problems in the art would be advantageous. The present disclosure aims to provide a flexible layer and/or a particularly thin flexible layer that enables a high energy density.

Disclosure of Invention

In view of the above, a process chamber and a method for cooling a substrate according to the independent claims are provided. Other aspects, advantages and features of the present application are apparent from the dependent claims, the description and the accompanying drawings.

According to an aspect of the present disclosure, a method for manufacturing a flexible layer stack is provided. The method includes providing a flexible substrate; depositing a first layer over the flexible substrate, the first layer comprising a first material; depositing a second layer over the first layer, the second layer comprising a second material; and removing the flexible substrate.

According to another aspect of the present disclosure, a method for manufacturing an anode of a lithium (Li) battery is provided. The method comprises the following steps: guiding the flexible substrate in the vacuum chamber using a roller arrangement (roller arrangement); depositing a first layer over the flexible substrate, the first layer comprising lithium; depositing a second layer over the first layer, the second layer comprising copper; depositing a third layer over the second layer, the third layer comprising lithium; and removing the flexible substrate.

According to another aspect of the present disclosure, an apparatus for manufacturing a flexible layer stack is provided. The apparatus comprises: a roller arrangement for guiding the flexible substrate; a first deposition source arrangement configured to deposit a first layer over a flexible substrate, the first layer comprising a first material; a second deposition source arrangement configured to deposit a second layer over the first layer, the second layer comprising a second material; and a third deposition source arrangement configured to deposit a third layer over the second layer, the third layer comprising the first material.

According to another aspect of the present disclosure, a negative electrode for a lithium battery is provided. The negative electrode is flexible and includes: a first layer comprising lithium and having a thickness equal to or greater than 5 μ ι η and/or equal to or less than 15 μ ι η; a second layer comprising copper and having a thickness equal to or less than 10 μm, preferably equal to or less than 8 μm, typically equal to or less than 7 μm, in particular equal to or less than 5 μm; and a third layer including lithium and having a thickness equal to or greater than 5 μm and/or equal to or less than 15 μm.

Examples are also directed to apparatuses for performing the disclosed methods and include apparatus components for performing the described method blocks. These method blocks may be performed by hardware components, a computer programmed by suitable software, any combination of the two, or in any other manner. Furthermore, examples according to the present application are also directed to methods of operating the described apparatus. Which comprises method blocks for performing the functions of the device.

Drawings

So that the manner in which the above recited features of the present disclosure can be understood in detail, a more particular description of the disclosure, briefly summarized above, may be had by reference to examples. The drawings relate to examples of the disclosure and are illustrated below:

fig. 1 shows a schematic view of a flexible layer stack according to examples described herein;

2A-C illustrate schematic diagrams of a flexible layer stack at different processing states according to examples described herein;

3A-D show schematic diagrams of a flexible layer stack at different processing states according to examples described herein;

4A-B illustrate schematic diagrams of removing a flexible substrate from a flexible layer stack according to examples described herein;

fig. 5 shows a schematic view of a flexible layer stack according to examples described herein;

fig. 6 shows a schematic view of an apparatus for manufacturing a flexible layer stack according to examples described herein;

fig. 7 shows a schematic view of an apparatus for manufacturing a flexible layer stack according to examples described herein; and

fig. 8 illustrates a flow diagram of a method for manufacturing a flexible layer stack according to examples described herein.

Detailed Description

Reference will now be made in detail to the various examples of the disclosure, one or more examples of which are illustrated in the figures. In the description of the figures below, like reference numerals refer to like components. In general, the description is made with respect to differences of the respective examples. Examples are provided by way of explanation of the disclosure and are not meant as limitations of the disclosure. Moreover, features illustrated or described as part of one example can be used on or in conjunction with other examples to yield yet further examples. It is intended that the present description include such modifications and variations.

Furthermore, in the following description, a roller or roller arrangement, for example being a component of a roller arrangement, is understood to be a device that provides a surface that may come into contact with a substrate (or a portion of a substrate) during its presence in a deposition arrangement, such as a deposition apparatus or a deposition chamber. At least a portion of the roller arrangement may comprise a rounded shape for contacting the substrate. In some examples, the roller device may have a substantially cylindrical shape. The substantially cylindrical shape may be formed around a straight longitudinal axis or may be formed around a curved longitudinal axis. According to some examples, the roller devices described herein may be adapted to contact a flexible substrate. The roller device referred to herein may be: guide rollers adapted to guide the substrate as it is being coated (or a portion of the substrate as it is being coated) or as it is present in the deposition apparatus; a spreader roller adapted to provide a defined tension to the substrate to be coated; a deflecting roller (deflecting roller) for deflecting the substrate according to a defined travel path or the like.

According to some examples described herein, a flexible substrate (flexible substrate may also be referred to as a film) described herein may include materials such as PET, HC-PET, PE, PI, PU, TaC, one or more metals, paper, combinations thereof, and may include Coated substrates such as Hard Coated PET (e.g., HC-PET, HC-TaC), and the like.

According to examples described herein, which may be combined with other examples, a method for manufacturing a flexible layer stack, in particular for manufacturing a negative electrode of a lithium (Li) battery, is provided. Wherein a flexible substrate is provided. A first layer comprising a first material is deposited over the flexible substrate. A second layer comprising a second material is deposited over the first layer. Next, the flexible substrate is removed. The flexible substrate may be considered a temporary carrier. According to examples described herein, one or more layers of a predetermined thickness may be deposited on the flexible substrate before the flexible substrate is removed from the layers deposited on the flexible substrate. In particular, the thickness of the individual layers can be accurately controlled. Furthermore, handling of the flexible layer stack may be improved, as the flexible layer may protect the layers deposited thereon from the environment during manufacturing.

Fig. 1 illustrates a flexible layer stack 100 according to examples described herein. The flexible layer stack 100 shown in fig. 1 includes a first layer 110, a second layer 120, and a third layer 130. Although the flexible layer stack 100 is illustrated in fig. 1 as having three layers, one of ordinary skill in the art will appreciate that the flexible layer stack 100 may include a greater or lesser number of layers that may be disposed above, below, and/or between the first layer 110, the second layer 120, and/or the third layer 130 illustrated in fig. 1.

According to some examples described herein, the first layer 110 may include a first material and/or the second layer 120 may include a second material. Further, the third layer 130 may comprise the third material or the third layer 130 may comprise the first material of the first layer 110. For example, the first material may be an alkali metal, such as lithium. The second material may be a conductive material, typically a metal, such as copper (Cu) or nickel (Ni). Further, the second layer 120 may include one or more sub-layers. According to some examples described herein, the first material is lithium and the second material is copper. For example, the second layer 120 may be a current collector layer.

According to some examples described herein, the first layer 110 may have a thickness equal to or less than about 25 μm, typically equal to or less than 20 μm, particularly equal to or less than 15 μm, and/or typically equal to or greater than 3 μm, particularly equal to or greater than 5 μm. The first layer 110 may be thick enough to provide the desired functionality, and may be thin enough to be flexible. In particular, the first layer 110 may be as thin as possible so that the first layer 110 may still provide its desired function.

According to some examples described herein, the second layer 120 may have a thickness equal to or less than 10 μm, typically equal to or less than 8 μm, advantageously equal to or less than 7 μm, in particular equal to or less than 6 μm, in particular equal to or less than 5 μm. According to some examples, the thickness of the second layer 120 may be equal to or less than 4 μm, or equal to or less than 3 μm, or equal to or less than 2 μm.

The flexible layer stack 100 shown in fig. 1 may be, for example, a negative electrode of a secondary battery (secondary cell) or a negative electrode for a secondary battery, such as a negative electrode or an anode of a lithium battery or a negative electrode or an anode for a lithium battery. According to some examples described herein, a flexible negative electrode for a lithium battery comprises a first layer 110, a second layer 120 and a third layer 130, the first layer 110 comprising lithium and having a thickness equal to or greater than 5 μ ι η and/or equal to or less than 15 μ ι η, the second layer 120 comprising copper and having a thickness equal to or less than 10 μ ι η, typically equal to or less than 8 μ ι η, advantageously equal to or less than 7 μ ι η, in particular equal to or less than 6 μ ι η, in particular equal to or less than 5 μ ι η, the third layer 130 comprising lithium and having a thickness equal to or greater than 5 μ ι η and/or equal to or less than 15 μ ι η. In the case of a lithium battery, the second layer 120 may be a current collector layer.

For example, a negative electrode for a lithium battery or a negative electrode for a lithium battery is manufactured by depositing a lithium layer on both sides of a copper foil. In order to reduce the weight of the battery to increase the energy storage density per weight (Wh/kg) or per volume (Wh/l), it may be desirable to minimize the amount of material used for the elements of the lithium battery. Copper foil having a thickness typically greater than 10 μm is generally used. However, if the layer stack is not properly pressed against a coating drum (coating drum), the copper foil and/or layer stack being manufactured may overheat during deposition of the lithium layer on the copper foil. However, since the tension can stretch the copper film, the amount of tension that can press the layer stack under manufacture against the coating drum is limited, particularly for thin copper films.

In addition, lithium may be considered unstable in the general environment because it reacts immediately with moisture. The layer(s) are typically encapsulated and/or protected while the coating system is vented (vent). The system is typically vented with dry nitrogen or argon and roll replacement can be done in a dry chamber without moisture. Generally, a drying chamber or a glove box (glove box) is used to handle or process lithium.

In addition, lithium may be coated on both sides of the copper foil. The coated lithium deposited on one side of the copper foil may be protected as the copper foil is wound over a roller arrangement to deposit lithium on the other side of the copper foil. For example, a protective layer or spacing layer (interlaf) may be placed over the deposited or coated lithium layer before the lithium layer contacts the roller or the drum of the roller arrangement to avoid damage from the roller arrangement.

In order to obtain a lithium battery having a high energy density in terms of weight per kilogram of the lithium battery, it may be necessary to minimize the amount of material used for the elements of the lithium battery while maximizing the function of the elements. In the case of the anode, it may be necessary to maximize the contact surface area of the anode in terms of maximizing the function, and it may be necessary to minimize the thickness of the anode in terms of minimizing the weight of the anode. As mentioned above, the usual approach still uses copper foil with a thickness typically greater than 10 μm. The smaller thickness of the copper foil still provides the desired function. However, at present copper foils cannot be made thinner than about 8 μm on a commercial scale.

Fig. 2A to 2C show schematic views of a flexible layer stack 100 at different processing points of a corresponding manufacturing method according to examples described herein.

Fig. 2A illustrates a flexible substrate 101. A first layer 110 comprising a first material is deposited over the flexible substrate 101. In particular, a sputtering process, an evaporation process, such as a thermal evaporation process, or a CVD process, such as a plasma enhanced CVD process, may be used to deposit a layer or thin layer, such as the first layer 110, on the flexible substrate 101. Furthermore, roll-to-roll deposition systems may also be used in, for example, the display industry and the Photovoltaic (PV) industry. For example, roll coating, slot die coating, or printing may be used.

As can be seen in fig. 2B, a second layer 120 comprising a second material may be deposited over the first layer 110. The second layer 120 may have a thickness less than the first layer 110. Additionally or alternatively, the second layer may have a thickness equal to or greater than the thickness of the first layer 110.

Next, the flexible substrate 101 may be removed from the first layer 110 with the second layer 120 deposited thereon. The resulting flexible layer stack 100 is shown in fig. 2C. That is, the flexible substrate 101 may be removed from the flexible layer stack 100. In particular, the flexible layer stack 100 may be considered to not include the flexible substrate 101. The flexible substrate 101 may be considered a temporary carrier. A "temporary carrier" may be considered a substrate or carrier that provides support for the manufacture of a layer stack, such as the flexible layer stack 100, which may be removed from the layer stack after or during processing of the layer stack. Furthermore, in the context of the present application, the flexible layer stack 100 may also be considered to comprise a flexible substrate 101.

Fig. 3A-3D show schematic views of a flexible layer stack 100 at different processing points of a corresponding manufacturing method according to other examples described herein.

Fig. 3A illustrates a flexible substrate 101. A first layer 110 comprising a first material is deposited over the flexible substrate 101. In particular, a sputtering process, an evaporation process, such as a thermal evaporation process, or a CVD process, such as a plasma enhanced CVD process, may be used to deposit a layer or thin layer, such as the first layer 110, on the flexible substrate 101. Furthermore, roll-to-roll deposition systems may also be used in, for example, the display industry and the Photovoltaic (PV) industry. For example, roll coating, slot die coating, or printing may be used.

As can be seen from fig. 3B, a second layer 120 comprising a second material may be deposited over the first layer 110. The second layer 120 may have a thickness less than the first layer 110. Additionally or alternatively, the second layer 120 may have a thickness equal to or greater than the thickness of the first layer 110.

According to fig. 3C, a third layer 130 may be deposited over the second layer 120. The third layer 130 may include a third material different from the first material and the second material. Alternatively, the third layer 130 may comprise the first material.

In particular, the third layer 130 can be formed of the same material or material composition as the first layer 110 with similar or identical structure and thickness as the first layer 110. That is, the second layer 120 may be considered to be sandwiched between two substantially identical layers, e.g., two layers comprising the same materials and/or structures.

The flexible substrate 101 may be removed from the first layer 110 on which the second layer 120 and the third layer 130 are deposited. The resulting flexible layer stack 100 is shown in fig. 3D.

For example, the flexible layer stack 100 shown in fig. 3D may be the flexible layer stack 100 shown in fig. 1. That is, by the manufacturing method described above, the flexible layer stack 100 can be obtained.

For example, the flexible layer stack 100 as shown in fig. 1 and 3D may be a negative electrode of or for a secondary battery, such as an anode of or for a lithium battery. In this case, the first material may be lithium and the second material may be copper. The first layer 110 and the third layer 130 may be formed to have a thickness equal to or greater than 5 μm and/or equal to or less than 15 μm, and/or the second layer 120 may be formed to have a thickness equal to or less than 10 μm, typically equal to or less than 8 μm, advantageously equal to or less than 7 μm, in particular equal to or less than 6, in particular equal to or less than 5 μm.

According to some examples described herein, the flexible substrate 101 may be configured to act as a protective layer for the first layer, in particular during the manufacturing of the flexible layer stack 100. That is, the flexible substrate 101 may protect layers deposited thereon, such as the first layer 110, from environmental stresses. For example, lithium is highly reactive and flammable, and lithium corrodes when exposed to moisture. The flexible substrate 101 disposed on or over the surface of the first layer 110 may protect the first layer 110 from contact and/or reaction with the environment. Furthermore, the flexible substrate 101 may be held on or over the flexible layer stack 100, for example during storage of the flexible layer stack 100, until the flexible layer stack 100 is actually used. In addition, for the case of using a coating tool that includes a deposition source without contacting the front surface, the operation of the spacer layer may be avoided because the flexible substrate 101 may act as a protective layer and/or spacer layer.

According to some examples described herein, a further protective layer may be provided and/or deposited on the third layer 130, in particular to protect the third layer 130 from environmental stresses. The further protective layer may comprise the same material as the flexible substrate 101 or another material suitable for protecting the third layer 130.

According to some examples described herein, the flexible substrate 101 and/or the further protective layer may be a barrier film or a metal film having a low water content and/or a low water vapor rate and/or oxygen transmission rate (oxygen transmission rate) to specifically protect the first layer 110 and/or the third layer 130, respectively, from reacting with the environment.

Although the anode of the secondary battery or the anode for the secondary battery and the manufacture thereof have been described, the present disclosure is not limited thereto. The present disclosure is applicable to any flexible layer stack, particularly where double-sided coating of layers in general, such as the copper layers described above, is applied. That is, the present disclosure provides a method of manufacturing a flexible layer stack by depositing a series of layers on a flexible substrate and removing the flexible substrate from the layers after deposition of the layers.

For example, the disclosed method may be used to manufacture a flexible layer stack 100 having a metal mesh as the first layer 110 and finally as the third layer 130. In this case, an insulating layer may be deposited as the second layer 120. Further, a flexible layer stack 100 can be manufactured having an Indium Tin Oxide (ITO) layer or ITO coating as the first layer 110 and finally as the third layer 130 and an insulating layer as the second layer 120. The present disclosure may be practiced to be particularly advantageous for flexible layer stacks having an intermediate layer between two similar or substantially identical or identical layers.

Fig. 4A-B show schematic views of removing a flexible substrate 101 from a flexible layer stack according to examples described herein.

According to some examples described herein, the release layer 105 may be provided over the flexible substrate 101, in particular over the flexible substrate 101. That is, the release layer 105 may be provided between the flexible substrate 101 and the first layer 110. In particular, the release layer 105 may be deposited over the flexible substrate 101, typically on the flexible substrate 101, in particular before the first layer 110 is deposited. According to examples described herein, it may be beneficial to remove the flexible substrate 101.

For example, as shown in fig. 4A, the release layer 105 may be an etch stop layer 105. According to some examples described herein, removing the flexible substrate 101 includes etching the flexible substrate 101. The flexible substrate 101 may be etched to the first layer 110. In the case where the etch stop layer 105 is provided between the flexible substrate 101 and the first layer 110, the etching may be performed until the etch stop layer 105 is reached.

In the case where the etch stop layer 105 is provided, the first material may be protected from contact with, for example, an etching solution used to etch the flexible substrate. As outlined above, it may be desirable to protect the first layer 110 from environmental stresses. By providing the etch stop layer 105, the first layer 110 may be protected from contact with, for example, an etching solution. In addition, the etch stop layer 105 or the remaining portion of the etch stop layer 105 after etching the flexible substrate 101 may serve as a protection layer for protecting the first layer 110 from environmental stress.

Etching the flexible substrate 101 may include a wet etching process or a dry etching process. The etch stop layer 105 may include a material having a lower etch rate than the material of the flexible substrate 101 in consideration of the applied etch process.

Further, as shown in fig. 4B, the release layer 105 may be a stripping layer 105. According to some examples described herein, removing the flexible substrate 101 includes peeling the flexible substrate 101 off of the first layer 110. The flexible substrate 101 may be peeled off the first layer 110. In the case where the peeling layer 105 is provided between the flexible substrate 101 and the first layer 110, the flexible substrate 101 and the peeling layer 105 may be peeled off the first layer 110.

The stripping layer 105 may provide a higher adhesion or adhesion to the flexible substrate 101 than to the first layer 110. In particular, the peeling layer 105 may have a lower adhesion or adhesion to the first layer 110 than the adhesion or adhesion of the flexible substrate 101 to the first layer 110. The stripping layer can be considered a low adhesion layer relative to the first layer 110 or the material of the first layer 110 and a high adhesion layer relative to the flexible substrate 101 or the material of the flexible substrate 101.

The stripping layer 105 may be a single layer or comprise multiple layers, e.g., bonded to each other. For example, the stripping layer 105 may include an adhesive sublayer facing the flexible substrate 101 and a non-adhesive sublayer facing the first layer 110. In this case, "non-adhesive" or "non-adhesive sub-layer" may be understood as a layer that has some adhesive properties but whose ability to adhere to its adjacent or adjoining layer may be low or lower than the ability of the "adhesive" sub-layer to adhere to its corresponding adjacent or adjoining layer.

Further, the release layer 105 may be a laser release layer. According to some examples described herein, removing the flexible substrate 101 includes laser irradiating the laser release layer. That is, the laser release layer may be an adhesive layer whose adhesive property is lost by irradiation of laser light and/or an adhesive layer damaged by irradiation of laser light. For example, the laser release layer may be irradiated with laser through the flexible substrate 101. In this case, the flexible substrate 101 may include a material transparent to laser light for irradiating the laser release layer.

Fig. 5 shows a schematic view of a flexible layer stack 100 according to examples described herein.

According to some examples described herein, the first adhesion layer 115 may be provided between the first layer 110 and the second layer 120. In particular, the first adhesion layer 115 may be deposited on or over the first layer 110, typically depositing the first adhesion layer 115 prior to depositing the second layer 120. According to some examples, the first adhesive layer 115 may have two opposing surfaces, one of the opposing surfaces contacting the first layer 110 and the other of the opposing surfaces contacting the second layer 120. Adhesion between the first layer 110 and the second layer 120 may be beneficial. The stability of the flexible layer stack 100 may be improved.

According to some examples described herein in which the third layer 130 is provided, the second adhesive layer 125 can be provided between the second layer 120 and the third layer 130. In particular, the second adhesion layer 125 may be deposited on or over the second layer 120, typically before depositing the third layer 130, the second adhesion layer 125 is deposited. According to some examples, the second adhesive layer 125 may have two opposing surfaces, one of the opposing surfaces contacting the second layer 120 and the other of the opposing surfaces contacting the third layer 130. Adhesion between the second layer 120 and the third layer 130 may be beneficial. The stability of the flexible layer stack 100 may be improved.

Fig. 6 shows a schematic view of an apparatus 200 for manufacturing a flexible layer stack 100 according to examples described herein.

The apparatus 200 comprises a roller arrangement 250 for guiding the flexible substrate 101, the apparatus 200 may also be referred to as a processing apparatus 200. One or more processing stations may be provided to process the flexible substrate 101. For example, a first deposition source arrangement 210 may be provided, the first deposition source arrangement 210 being configured to deposit a first layer 110 comprising a first material over the flexible substrate 101. Furthermore, a second deposition source arrangement 220 may be provided, the second deposition source arrangement 220 being configured to deposit a second layer 120 comprising a second material over the first layer 110. Furthermore, a third deposition source arrangement 230 may be provided, the third deposition source arrangement 230 being configured to deposit a third layer 130 comprising a third material or the first material over the second layer 120.

For example, the first deposition source arrangement 210 may be configured to deposit an alkali metal, such as lithium, over the flexible substrate 101 for forming the first layer 110. The second deposition source arrangement 220 may be configured to deposit an electrically conductive material, typically a metal such as copper, over the first layer 110 for forming the second layer 120. The third deposition source arrangement 230 may be configured to deposit an alkali metal, such as lithium, over the second layer for forming the third layer 130.

According to examples described herein, each of the first, second, and third

deposition source arrangements

210, 220, and 230 may include one or more deposition sources. In particular, the number of deposition sources per deposition source arrangement, such as the first deposition source arrangement 210, the second deposition source arrangement 220 and the third deposition source arrangement 230, may be adjusted according to the desired layer thickness formed by the individual deposition source arrangements. For example, in the case of a negative electrode for a lithium battery or a negative electrode for a lithium battery, it is desirable that the lithium layer is thicker than the copper layer interposed between the lithium layers. The first deposition source arrangement 210 and the third deposition source arrangement 230 may be configured for depositing lithium and include more deposition sources than the second deposition source arrangement 220 configured for depositing copper. As exemplarily shown in fig. 6, the first deposition source arrangement 210 and the third deposition source arrangement 230 each include two deposition sources, and the second deposition source arrangement 220 includes one deposition source.

Additional deposition source arrangements may be provided for depositing the stripping layer 105, the first adhesion layer 115, and/or the second adhesion layer 125. In particular, a deposition source arrangement for depositing the stripping layer 105 may be provided before the first deposition source arrangement 210 for depositing the first layer 110. A deposition source arrangement for depositing the first adhesion layer 115 may be provided between the first deposition source arrangement 210 and the second deposition source arrangement 220, the first deposition source arrangement 210 being for depositing the first layer 110 and the second deposition source arrangement 220 being for depositing the second layer 120. A deposition source arrangement for depositing the second adhesion layer 125 may be provided between the second deposition source arrangement 220 and the third deposition source arrangement 230, the second deposition source arrangement 220 for depositing the second layer 120 and the third deposition source arrangement 230 for depositing the third layer 130.

The apparatus 200 may include a vacuum chamber 205. According to examples described herein, the flexible substrate 101 is guided in the vacuum chamber 205 using a roller arrangement 250. The roller arrangement 250 may include a process drum 256 or a coating drum 256, and the process drum 256 or the coating drum 256 may be disposed in the vacuum chamber 205. One or more processing stations may be disposed in the vacuum chamber 205 to process the substrates as they are directed onto the process drum 256. Fig. 6 schematically shows three processing stations in the form of five deposition stations forming a first deposition source arrangement 210, a second deposition source arrangement 220 and a third deposition source arrangement 230. Illustratively, each of the processing stations or deposition source arrangements can be a rotatable sputter target or a pair of rotatable sputter targets or any desired number of rotatable sputter targets. According to examples described herein, the deposition source arrangement may comprise a linear evaporator, e.g. for lithium.

Although the vacuum chamber 205 has been described as a vacuum chamber, in the case of non-vacuum deposition techniques such as roll coating, slot die coating, and printing, a chamber 205 such as a drying chamber or glove box may be used.

As further shown in fig. 6, the coating drum 256 or the process drum 256 has a rotational axis, which is provided in the apparatus 200. The process drum 256 has a curved outer surface for guiding the flexible substrate 101 along the curved outer surface. The flexible substrate 101 is guided through a first vacuum processing zone and for example at least one second vacuum processing zone. Although deposition source arrangements are often referred to herein as processing stations, other processing stations, such as etching stations, heating stations, etc., may also be provided along the curved surface of the processing drum 256. Thus, the apparatus described herein, which may have compartments for multiple deposition sources, allows for modular combination of multiple sputtering, evaporation, CVD, PECVD and/or PVD processes in a single deposition apparatus, such as an R2R coater.

According to some examples described herein, a processing station may be modularly equipped with different processing tools. In a modular concept, all kinds of deposition sources may be used in a processing apparatus or in a deposition apparatus according to examples described herein, such as an apparatus for manufacturing a flexible layer stack. The modular concept helps to reduce the cost for depositing complex layer stacks that have to be deposited applying complex combinations of different deposition techniques or process parameters.

In general, according to some examples described herein, a plasma deposition source may be suitable for depositing a thin film on a flexible substrate, such as a web (web) or foil, a glass substrate, or a silicon substrate. In general, the plasma deposition source may be adapted and used to deposit thin films, such as the first layer 110 and/or the second layer 120 and/or the third layer 130, on the flexible substrate 101, for example, to form the flexible layer stack 100. The flexible layer stack may be used to provide or for a negative electrode of a secondary battery or TFT, a touch screen device member, or a flexible PV module.

According to examples described herein, the plasma deposition source may be provided as a PECVD (plasma enhanced chemical vapor deposition) source, having a multi-zone electrode arrangement comprising two, three or even more RF (radio frequency) electrodes arranged opposite to the moving web. According to examples described herein, a multi-zone plasma deposition source may also be provided for MF (medium frequency) deposition. According to still further examples described herein, one or more deposition sources provided in the deposition apparatus described herein may be microwave sources and/or may be sputter sources, such as sputter targets. For example, for a microwave source, the plasma is excited and sustained by microwave radiation, and the source is configured to excite and/or sustain the plasma with the microwave radiation.

As shown in fig. 6, the flexible substrate 101 may be guided from the unwind roll 251 to the process drum 256, and may be wound onto the rewind roll 257 after processing the flexible substrate 101. To guide the flexible substrate 101 through the apparatus 200, a plurality of rollers 253 may be provided. The roller 253 may provide at least one function selected from the group consisting of: guiding the flexible substrate 101, stretching (stretching) the flexible substrate 101, spreading (spreading) the flexible substrate 101, charging the flexible substrate 101, discharging the flexible substrate 101, and heating or cooling the flexible substrate 101.

According to some examples described herein, the process drum 256 may be heated or cooled to a desired process temperature. The controller may be connected to a heating or cooling device in the treatment drum 256 by a connection. According to typical examples described herein, the process drum 256 may be heated for deposition purposes and may be cooled, for example, during an etching process. Further, the process drum 256 may be cooled during deposition of, for example, a material having a low melting point, such as lithium.

According to examples described herein, a removal arrangement 260 may be provided, the removal arrangement 260 being for removing the flexible substrate 101 from the first layer 110 and/or the flexible layer stack 100. In particular, the removal arrangement 260 may be provided in the apparatus 200 after the process drum 256, typically before the rewind roll 257. While the removal arrangement 260 has been described as being provided before the rewind roll 257 in the apparatus 200, the flexible layer stack 100 may be wound onto the rewind roll 257 with the flexible substrate 101 included or having the flexible substrate 101 disposed thereon. For example, the flexible layer stack 100 may be stored with the flexible substrate 101 for protection reasons as described above. In this case, a separate removal arrangement may be provided for removing the flexible substrate 101 before the flexible layer stack is used for its intended operation and/or function. According to some examples described herein, the flexible layer stack 100 may be stored, in particular before removing the flexible substrate 101. For example, in the case of a lithium battery, the flexible substrate 101 may be removed before the battery cell is assembled.

Fig. 7 illustrates a further apparatus 200 for manufacturing a flexible layer stack 100 and/or processing a flexible substrate 101 according to examples described herein.

The apparatus 200 shown in fig. 7 is similar to the apparatus shown in fig. 6. However, the apparatus shown in FIG. 7 includes more than one treatment drum. The throughput of the apparatus can advantageously be increased.

According to examples described herein, the first process drum 256a may be configured to deposit a first material and the second process drum 256b may be configured to deposit a second material. That is, the first processing drum 256a may be provided with a first deposition source arrangement 210, the first deposition source arrangement 210 being configured to deposit a first material, and the second processing drum 256b may be provided with a second deposition source arrangement 220, the second deposition source arrangement 220 being configured to deposit a second material. For example, the first process drum 256a may be configured to deposit an alkali metal, such as lithium, on the flexible substrate 101 for forming the first layer 110 and to deposit an alkali metal, such as lithium, on the second layer 120 still to be formed for forming the third layer 130. The second process drum 256b may be configured to deposit a conductive material, typically a metal such as copper, on the first layer 110 for forming the second layer 120.

That is, the flexible substrate 101 may be unwound from the unwind roll 251, directed by the roll 253 to the first process drum 256a and the second process drum, wound onto the rewind roll 257 after processing the first layer 110 and at least a portion of the second layer 120. The flexible substrate 101 may then be directed from the rewind roll 257 back to the unwind roll 251 through the second process drum 256b and the first process drum 256a, where the last remaining portion of the second layer 120 and the third layer 130 may be deposited, respectively. Thus, the flexible substrate 101 may be rolled forward and backward through the apparatus for manufacturing the flexible layer stack 100.

As exemplarily shown in fig. 7, the first removal arrangement 260a may be arranged in close proximity to the unwind roller 251 and/or the second removal arrangement 260b may be provided in close proximity to the rewind roller 257. In particular, the removal arrangement may advantageously be provided immediately adjacent to one of the unwind and

rewind rollers

251, 257 to which the flexible layer stack 100 is wound after processing the flexible layer stack 100.

Further, process drums, such as the first process drum 256a and the second process drum 256b, may be particularly configured for the material to be deposited as the flexible layer stack 100 passes through the respective process drums. For example, the first process drum 256a may be cooled during the deposition of lithium onto the flexible substrate 101 directed over the first process drum 256 a.

According to examples described herein, one or more process drums may be arranged in separate vacuum chambers. In the example shown in fig. 7, a first process drum 256a is disposed in the first vacuum chamber 205a, and a second process drum 256b is disposed in the second vacuum chamber 205 b. That is, the processing environment in each of the vacuum chambers, such as the first vacuum chamber 205a and the second vacuum chamber 205b, may be adapted for each deposition process to be performed in the respective vacuum chambers. In the case of lithium deposition, which can be considered highly contaminated, only the vacuum chamber actually used for lithium deposition is contaminated.

In the example of FIG. 7, two

process drums

256a, 256b and two

vacuum chambers

205a, 205b are shown. However, any number of process drums and/or vacuum chambers may be provided. For example, three process drums, a first process drum, a second process drum, and a third process drum, may be provided. The first treatment drum may be provided with a first deposition source arrangement 210, the second treatment drum may be provided with a second deposition source arrangement 220, and the third treatment drum may be provided with a third deposition source arrangement 230. Each of the first, second and third

deposition source arrangements

210, 220, 230 may comprise a predetermined number of deposition sources, for example according to a desired thickness of a layer to be formed by the respective deposition source arrangement.

Furthermore, each of the first, second and third process drums may be arranged in separate vacuum chambers, i.e. in the first, second and third vacuum chambers, respectively. Furthermore, one or more process drums may be arranged in a common vacuum chamber, while other process drums are arranged in different vacuum chambers. For example, a first process drum and a third process drum, both equipped with a deposition source arrangement configured to deposit a first material (e.g., first deposition source arrangement 210 and third deposition source arrangement 230), may be disposed in a common vacuum chamber, while a second process drum, equipped with one or more deposition source arrangements configured to deposit a second material (such as second deposition source arrangement 220), may be disposed in another vacuum chamber. That is, the process drums for depositing the same material may advantageously be arranged in the same vacuum chamber. In addition, a chamber such as a dry chamber or a glove box may be used instead of the vacuum chamber, depending on the deposition process used. For example, the lithium deposition process may be performed in a chamber, such as a drying chamber, and/or the copper deposition process may be performed in a vacuum chamber.

According to some examples, one or more process drums 256, which may be considered part of the roller arrangement 250, may be heated or cooled to a desired process temperature. In particular, the temperature of the flexible substrate 101 may be adjusted by the roller arrangement 250 before the flexible substrate 101 contacts the one or more process drums 256. In the case of a cooled process drum, the adjustment control with the down-regulation amount (under-regulation) may adjust the temperature to be slightly higher than the temperature of the process drum, and the adjustment control with the over-regulation amount (over-regulation) may adjust the temperature to be slightly lower than the temperature of the process drum.

Fig. 8 shows a flow diagram of a method 300 for manufacturing a flexible layer stack 100 according to examples described herein.

The method 300 for manufacturing the flexible layer stack 100 includes providing a flexible substrate 101, according to block 310. A first layer 110 comprising a first material is deposited over the flexible substrate 101, in accordance with block 320. A second layer 120 comprising a second material is deposited over the first layer 110, according to block 330. The flexible substrate 101 is removed, per block 340. In particular, the flexible layer stack 100 may generally be stored and/or transported prior to removal of the flexible substrate 101.

According to examples described herein, a third layer 130 comprising a third material or a first material may be deposited over the second layer 120. In particular, the method 300 may include depositing other layers and/or other processing operations, such as stretching the flexible substrate 101, unrolling the flexible substrate 101, charging the flexible substrate 101, discharging the flexible substrate 101, and heating or cooling the flexible substrate 101, in accordance with the above or further blocks.

According to certain examples described herein, the method 300 may be provided as a negative electrode for manufacturing a lithium battery or a negative electrode for a lithium battery. Wherein the flexible substrate 101 can be guided in the vacuum chamber 205 using a roller arrangement 250. A first layer 110 comprising lithium may be deposited over the flexible substrate 101. In particular, the first layer 110 may be a lithium layer. A second layer 120 comprising copper may be deposited over the first layer 110. In particular, the second layer 120 may be a copper layer. A third layer 130 comprising lithium may be deposited over the second layer 120. In particular, the third layer 130 may be a lithium layer. The flexible substrate 101 may be removed.

The first layer 110 and the third layer 130 can form a thickness equal to or less than about 25 μm, preferably equal to or less than 20 μm, typically equal to or less than 15 μm, and/or preferably equal to or greater than 3 μm, typically equal to or greater than 5 μm. The second layer 120 may form a thickness equal to or less than 10 μm, typically equal to or less than 8 μm, advantageously equal to or less than 7 μm, in particular equal to or less than 6 μm, in particular equal to or less than 5 μm.

The examples described herein may provide the following benefits. The lithium may be deposited on a temporary support. And thus may facilitate temperature control and operation during manufacturing or processing. Furthermore, the thickness of the deposited layer, such as a copper layer, may be adjusted. Therefore, there is no limitation of layer thickness, such as commercially available copper foil. In the case of a secondary battery such as a lithium battery, a thin copper layer may be treated. The energy density of lithium batteries, i.e., smaller weight and volume for the same energy storage capacity, can be increased. Furthermore, work for double-sided coating at a certain layer may be omitted, such as e.g. coating the first side with lithium, protecting the coated layer with a protective film, flipping the layer stack to coat the second side with e.g. lithium. Advantageously, the coating process or the deposition process may be performed on a carrier film, such as a flexible substrate, which itself may serve as a protective or protection layer, for example for the deposited lithium.

While the foregoing is directed to examples of the present disclosure, other and further examples of the disclosure may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.

Claims

1. Method for manufacturing a flexible layer stack (100), the method comprising:

providing a flexible substrate (101);

depositing a first layer (110) over the flexible substrate (101), the first layer (110) comprising a first material, wherein the first material is an alkali metal;

depositing a second layer (120) over the first layer (110), the second layer (120) comprising a second material, wherein the second material is an electrically conductive material; and

removing the flexible substrate (101),

wherein the flexible layer stack (100) is a negative electrode for a secondary battery and the second layer is a current collector layer.

2. The method of claim 1, further comprising:

depositing a third layer (130) over the second layer (120), wherein the third layer (130) comprises the first material.

3. The method of claim 1, wherein the first material is lithium.

4. The method of claim 1, wherein the first layer (110) is formed to a thickness equal to or less than 25 μ ι η.

5. The method of claim 1 or 4, wherein the first layer (110) is formed to a thickness equal to or greater than 3 μm.

6. The method of claim 1, wherein the second material is copper.

7. The method of claim 1, further comprising:

guiding the flexible substrate (101) in a vacuum chamber (205) using a roller arrangement (250).

8. The method of claim 1, wherein the flexible substrate (101) is configured to act as a protective layer for the first layer (110).

9. The method of claim 1 or 8, wherein the flexible substrate (101) is configured to act as a protective layer for the first layer (110) during the manufacturing of the flexible layer stack (100).

10. The method of claim 1, wherein the step of removing the flexible substrate (101) comprises peeling the flexible substrate (101) off the first layer (110).

11. The method of claim 1, wherein the step of removing the flexible substrate (101) comprises etching the flexible substrate (101).

12. The method of claim 1, further comprising:

a release layer (105) is provided over the flexible substrate (101).

13. A method (300) for manufacturing a negative electrode (100) for a lithium battery, the method comprising:

guiding a flexible substrate (101) in a vacuum chamber (205) using a roller arrangement (250);

depositing a first layer (110) over the flexible substrate (101), the first layer (110) comprising lithium;

depositing a second layer (120) over the first layer (110), the second layer (120) comprising copper, wherein the second layer (120) is a current collector layer;

depositing a third layer (130) over the second layer (120), the third layer (130) comprising lithium; and

removing the flexible substrate (101).

14. Apparatus for manufacturing a flexible layer stack (100), the apparatus (200) comprising:

a roller arrangement (250) for guiding a flexible substrate (101);

a first deposition source arrangement (210) configured to deposit a first layer (110) over the flexible substrate (101), the first layer (110) comprising a first material, wherein the first material is an alkali metal;

a second deposition source arrangement (220) configured to deposit a second layer (120) over the first layer (110), the second layer (120) comprising a second material, wherein the second material is an electrically conductive material; and

a third deposition source arrangement (230) configured to deposit a third layer (130) over the second layer (120), the third layer (130) comprising the first material,

15. The apparatus of claim 14, further comprising:

a removal arrangement (260) for removing the flexible substrate (101) from the first layer (110).

16. The apparatus of claim 14 or 15, wherein the first material is lithium and the second material is copper.

17. A negative electrode for a lithium battery, the negative electrode being flexible and comprising:

a first layer (110) comprising lithium and having a thickness of at least one selected from the group consisting of: equal to or greater than 5 μm and equal to or less than 15 μm;

a second layer (120) deposited over the first layer, the second layer comprising copper and having a thickness equal to or less than 10 μm, wherein the second layer is a current collector layer; and

a third layer (130) over the second layer, the third layer comprising lithium and having a thickness selected from at least one of the group consisting of: equal to or greater than 5 μm and equal to or less than 15 μm.

18. The anode of claim 17, further comprising at least one layer selected from the group consisting of: a first adhesive layer (115) between the first layer (110) and the second layer (120) and a second adhesive layer (125) between the second layer (120) and the third layer (130).