CN110741491A - Method and processing system for forming components of an electrochemical energy storage device and oxidation chamber - Google Patents

Method and processing system for forming components of an electrochemical energy storage device and oxidation chamber Download PDF

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Publication number
CN110741491A
CN110741491A CN201780091917.9A CN201780091917A CN110741491A CN 110741491 A CN110741491 A CN 110741491A CN 201780091917 A CN201780091917 A CN 201780091917A CN 110741491 A CN110741491 A CN 110741491A
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roller
ceramic layer
flexible substrate
module
energy storage
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罗兰·特拉斯尔
托尔斯滕·布鲁诺·迪特尔
苏布拉曼亚·赫尔勒
肯特·赵
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Applied Materials Inc
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Applied Materials Inc
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)
  • Cell Separators (AREA)

Abstract

A processing system for forming a component of an electrochemical energy storage device is provided, the processing system including a deposition module (102) configured to deposit a ceramic layer (52) over a flexible substrate (111), and an oxidation module (150) configured to subject the ceramic layer (52) to an oxidizing atmosphere at an elevated temperature.

Description

Method and processing system for forming components of an electrochemical energy storage device and oxidation chamber
Technical Field
Embodiments of the present disclosure relate to methods and processing systems for forming components of electrochemical energy storage devices, and oxidation chambers. Embodiments of the present disclosure relate, inter alia, to methods and processing systems for forming cathodes, anodes, electrolytes, or separators of lithium or lithium ion (Li-ion) batteries, and oxidation chambers for post-processing cathodes, anodes, electrolytes, or separators of lithium or lithium ion batteries.
Background
Electrical separators may, for example, be described as separators used in batteries and other arrangements in which electrodes are isolated from one another while maintaining ionic conductivity.
Conventionally, separators comprise thin, porous, electrically insulating substances, have high ionic porosity, good mechanical strength, and long-term stability with respect to chemicals and solvents used in the system (e.g., in the electrolyte of the battery). In a battery, the separator typically completely electrically insulates the cathode from the anode. Furthermore, the diaphragm is usually permanently elastic and follows movements in the system not only from external loads but also from the "breathing" of the electrodes when ions are introduced and expelled.
, the separator is critical in determining the life and safety of systems using the separator for example, the development of rechargeable batteries is greatly influenced by the development of suitable separator materials.
In particular, a separator for use in a high-energy battery or a high-performance battery may be very thin to ensure low specific space conditions and minimize internal resistance, may have high porosity to ensure low internal resistance, and be lightweight to achieve low specific weight of a battery system.
The separator generally includes a ceramic layer that is porous to the ions of the battery, in the case of a lithium battery, the ceramic layer may be porous to lithium ions (Li-ion).
In view of the above, embodiments described herein are directed to methods and systems for forming components of electrochemical energy storage devices that may advantageously overcome at least problems in the art the present disclosure is directed to methods and systems for forming components of electrochemical energy storage devices that may increase the charge transport (discharge/charge rate) voltage and cycle life of electrochemical energy storage devices.
Disclosure of Invention
In view of the above, methods and processing systems for forming components of an electrochemical energy storage device, and oxidation chambers configured to oxidize ceramic layers of components of an electrochemical energy storage device according to the independent claims are provided.
According to aspect of the present disclosure, methods for forming components of an electrochemical energy storage device are provided.
According to aspect of the present disclosure, a processing system for forming a component of an electrochemical energy storage device is provided, the processing system including a deposition module configured for depositing a ceramic layer over a flexible substrate, and an oxidation module configured to subject the ceramic layer to an oxidizing atmosphere at an elevated temperature.
According to a aspect of the present disclosure, there is provided an oxidation chamber configured to oxidize ceramic layers of components of an electrochemical energy storage device, the oxidation chamber including a substrate transport mechanism, the substrate transport mechanism including a th roller and a second roller, the substrate transport mechanism configured to transport a flexible substrate from a th roller along a transport path to the second roller, wherein the ceramic layers are formed on the flexible substrate.
Several examples also pertain to apparatus 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 application also relate to a method for operating the described device. The method includes method blocks or operations 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 exemplary embodiments. The accompanying drawings are related to embodiments of the disclosure and are described below:
fig. 1 shows a schematic diagram of a processing system for forming a component of an electrochemical energy storage device, according to an embodiment;
fig. 2 shows a schematic diagram of a processing system for forming a component of an electrochemical energy storage device, according to an embodiment;
FIG. 3 shows an enlarged portion of the processing system shown in FIG. 2;
FIG. 4 shows a schematic diagram of an oxidation chamber for forming a component of an electrochemical energy storage device, according to an embodiment;
fig. 5 schematically illustrates a method for forming a component of an electrochemical energy storage device, in accordance with an embodiment; and
fig. 6 schematically illustrates a method for forming a component of an electrochemical energy storage device, in accordance with an embodiment.
Detailed Description
Reference will now be made in detail to the various embodiments of the present disclosure, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to the like elements in the following description of the drawings, in particular, differences from individual embodiments will be described.
Fig. 1 shows a processing system 100 for forming components of an electrochemical energy storage device.
In the context of the present disclosure, the term "electrochemical energy storage device" may be understood as a rechargeable or non-rechargeable electrochemical energy storage device, in this respect, the present disclosure does not distinguish between the term "battery" in the aspect of and the term "battery" in the aspect of .
generally, an electrochemical energy storage device, for example, as a basic functional unit, may include two electrodes of opposite polarity, namely a negative anode and a positive cathode, the cathode and anode may be insulated by a separator disposed between the cathode and anode to avoid short circuits between the cathode and anode.
As shown in FIG. 1, the processing system 100 may include a deposition module 102 the deposition module 102 may be configured to deposit a ceramic layer 52 on or over the flexible substrate 111 in particular, the flexible substrate may have an th side and/or a second side, the second side being opposite the th side the ceramic layer 52 may be deposited on or over at least of the th side and the second side of the flexible substrate 111.
In the context of the present disclosure, a "ceramic layer" (such as ceramic layer 52) may be understood to include a layer of or be formed from a ceramic material. "ceramic material" is understood to mean an inorganic, non-metallic, solid-state material comprising metal, non-metallic or metalloid atoms held predominantly in ionic and covalent bonds. In the context of the present disclosure, a ceramic material may particularly be understood as a dielectric material, which particularly comprises metal and oxygen atoms, such as for example aluminum oxide, aluminum nitride, etc. According to embodiments described herein, the ceramic layer 52 may be an aluminum oxide layer.
According to embodiments described herein, the ceramic material may be at least non-conductive or very poorly conductive metal oxides, the metals being aluminum, silicon, lead, zirconium, titanium, hafnium, lanthanum, magnesium, zinc, tin, cerium, yttrium, calcium, barium, strontium, and combinations thereof although silicon is often referred to as a metalloid, in the context of the present disclosure silicon should be included whenever a metal is mentioned.
The ceramic layer 52 may be porous or have porosity according to embodiments described herein. In particular, ceramic layer 52 may be porous such that certain elements may pass through ceramic layer 52.
The flexible substrate 111 may particularly comprise a flexible substrate such as a plastic film, a mesh (web), a foil, a flexible glass or a strip (strip). The term flexible substrate may also encompass other forms of flexible substrates. The flexible substrate used in embodiments described herein may be bendable. The term "flexible substrate" or "substrate" may be used synonymously with the term "foil" or the term "mesh". In particular, embodiments described herein may be used to coat any kind of flexible substrate, for example for producing a flat coating with a uniform thickness, or for producing a coating pattern or coating structure of a predetermined shape on a flexible substrate or on top of an underlying coating structure. In addition to ceramic layers, electronic devices and structures may be formed on the flexible substrate by applying masks, etching, and/or deposition.
According to embodiments described herein, the flexible substrate 111 may comprise a polymeric material selected from the group of: polyacrylonitrile (polyacrylonitrile), polyester (polyester), polyamide (polyamide), polyimide (polyimide), polyolefin (polyolefin), polytetrafluoroethylene (polytetrafluoroethylene), carboxymethylcellulose (carboxymethylcellulose), polyacrylic acid (polyacrylic acid), polyethylene (polyethylene), polyethylene terephthalate (polyethylene terephthalate), polyphenylene ether (polyphenylene ether), polyvinyl chloride (polyvinyl chloride), polyvinylidene chloride (polyvinylidene chloride), polyvinylidene fluoride (polyvinylidene fluoride), poly (vinylidene fluoride-co-hexafluoropropylene) (polytetrafluoroethylene), polylactic acid (polylactic acid), polypropylene (polybutylene), polybutylene (polybutylene terephthalate), polybutylene terephthalate (polybutylene terephthalate), polybutylene terephthalate, Polyoxymethylene (polyoxymethylene), polysulfone (polysulfone), styrene-acrylonitrile (styrene-acrylonitrile), styrene-butadiene rubber (styrene-butadiene rubber), ethylene vinyl acetate (ethylene vinyl acetate), styrene-maleic anhydride (styrene maleic anhydride), and combinations thereof. Any other polymeric material that is stable in strongly reducing conditions (strongly reducing conditions) such as found in lithium-based electrochemical energy storage devices may also be used. According to embodiments described herein, the flexible substrate 111 and/or the ceramic layer 52 may be optimized for electrochemical energy storage devices comprising strongly basic electrolytes by selecting particularly alkali resistant raw materials. For example, the flexible substrate 111 may include polyolefin or polyacrylonitrile instead of polyester.
In the case of a membrane, the flexible substrate 111 may be made of and/or include microporous polyethylene, polypropylene, polyolefin and/or laminates thereof.
In the case of a cathode, the flexible substrate 111 may be made of aluminum and/or include aluminum. In this case, the cathode layer may be formed on the flexible substrate 111. Ceramic layer 52 may be formed on the cathode layer. For example, the flexible substrate 111 may have a thickness of 5 μm to 12 μm in the case of a cathode and/or the cathode layer may have a thickness of up to 100 μm. Additionally or alternatively, the flexible substrate 111 may be or may include a polymeric material described herein, such as polyester, with an aluminum layer deposited on the flexible substrate 111. The polymer substrate may be thinner than, for example, an aluminum substrate and/or a deposited aluminum layer. The deposited aluminum layer may have a thickness of about 0.5 μm to about 1 μm. When the embodiment is practiced, the thickness of the cathode may be reduced.
In the case of an anode, the flexible substrate 111 may be made of and/or include copper. In this case, the anode layer may be formed on the flexible substrate 111. Ceramic layer 52 may be formed on the anode layer. For example, the flexible substrate 111 may have a thickness of 5 μm to 12 μm in the case of an anode and/or the anode layer may have a thickness of up to 100 μm. Additionally or alternatively, the flexible substrate 111 may be or include a polymeric material described herein, such as polyester, with a copper layer deposited on the flexible substrate 111. The polymer substrate may be thinner than, for example, a copper substrate and/or a deposited copper layer. The deposited copper layer may have a thickness of about 0.5 μm to about 1 μm. When the embodiment is practiced, the thickness of the anode may be reduced.
According to embodiments described herein, the material of the flexible substrate 111, in particular the polymer material, may have a high melting point, such as equal to or greater than 200 ℃. Components of electrochemical energy storage devices that include polymeric materials with high melting points may be useful in electrochemical energy storage devices with fast charge cycles. In practice, especially with the aid of the high thermal stability of the components comprising polymeric materials having a high melting point according to embodiments described herein, electrochemical energy storage devices equipped with such components may not be too heat sensitive and can tolerate temperature increases due to rapid charging without adversely changing the components or damaging the electrochemical energy storage device. When practicing the embodiments, faster charging cycles may be achieved, which may be beneficial for electric vehicles that may be charged in a shorter period of time.
According to embodiments described herein, the flexible substrate 111 with or without the ceramic layer 52 may have a porosity in the range from 10% to 90%, in particular in the range from 40% to 80%. The flexible substrate 111 and/or the ceramic layer 52 may provide a path for the electrolyte during application and may reduce electrolyte breakthrough time. In the context of the present disclosure, "porosity," such as the porosity of the flexible substrate 111 and/or the ceramic layer 52, may be related to the accessibility (accessibility) of the open pores. For example, porosity may be determined by common methods, such as, for example, by mercury intrusion porosimetry (mercury porosimetry) and/or may be calculated from the volume and density of the material assuming all pores are open pores.
In accordance with embodiments described herein, an electrochemical energy storage device can be a lithium ion battery, in which the flexible substrate 111 can often be made of microporous polyethylene and polyolefin, during the electrochemical reaction of charge and discharge cycles, lithium ions are transported through pores in the flexible substrate 111 and/or ceramic layer 52 between two electrodes of the lithium ion battery.
The present disclosure may provide for very thin components of an electrochemical energy storage device, such as very thin separators. When practicing the embodiments, the proportion of the composition of the electrochemical energy storage device that does not contribute to the activity (activity) of the electrochemical energy storage device may be reduced. Furthermore, the reduction in thickness may simultaneously result in an increase in ionic conductivity. Components according to embodiments described herein may allow, for example, for an increase in the density of a battery pack so that a large amount of energy may be stored in the same volume. When practicing the embodiments, the limited current density can be similarly increased by the enlargement of the electrode area.
Embodiments described herein may be used to produce a separator. The separator may be separate from the electrochemical energy storage device or integrated directly into the electrochemical energy storage device, such as, for example, a lithium ion battery with an integrated separator. In integrated separator applications, a single layer separator or a multilayer separator may be formed directly on the electrode of an electrochemical energy storage device. In addition, the ceramic layer 52 may be applied to an electrode of an electrochemical energy storage device, such as an anode or a cathode. Thus, the component of the electrochemical energy storage device may be a separator or separator, an electrolyte, an anode and/or a cathode.
According to embodiments described herein, ceramic layer 52 may be formed by evaporating a metal. In particular, the ceramic layer 52 may be formed by evaporating a metal in an inductively heated crucible. Further, a process gas such as, for example, oxygen may be provided for forming ceramic layer 52. According to embodiments described herein, ceramic layer 52 may be formed by reactive evaporation. When practicing the embodiments, very high coating speeds can be achieved compared to traditional diaphragm coating techniques, such as dip-coating. In particular, the coating speed may vary according to the thickness and type of the ceramic material to be formed on the flexible substrate 111.
According to embodiments described herein, the thickness of the ceramic layer 52 formed on the flexible substrate 111 may be equal to or greater than 25nm, particularly equal to or greater than 50nm, particularly equal to or greater than 100nm, and/or equal to or less than 1000nm, particularly equal to or less than 500nm, particularly equal to or less than 150 nm. When practicing the embodiments, very high energy densities in electrochemical energy storage devices can be achieved.
When the ceramic layer is formed by evaporation52, particularly when the ceramic layer 52 is formed by reactive evaporation, the ceramic layer 52 may not be formed at full stoichiometry, or may be formed at non-stoichiometry. In the context of the present disclosure, "stoichiometries", such as the stoichiometry of ceramic layer 52, can be understood as calculations of the relative amounts of reactants and products in a chemical reaction. Thus, "non-stoichiometric" or "incompletely stoichiometric" may mean that the product does not include all of the reactants. In the example of alumina as the material of ceramic layer 52, the fully stoichiometric reaction may be: 4Al +3O2＝2Al2O3. If the alumina is not formed in full stoichiometry or in non-stoichiometry, the product of the reaction may be, for example, Al2O2.5. Thus, AlO where x ≠ 1.5xAny of the compositions of (a) may be considered non-stoichiometric or not formed in full stoichiometry. In such non-stoichiometric ceramic layers, there may be unbound excess atoms that may react with elements of the electrochemical energy storage device, particularly during charging and/or discharging of the electrochemical energy storage device. In the example of a lithium ion battery, the unbound excess atoms may react with lithium ions that traverse the ceramic layer, such as during charging and/or discharging of the lithium ion battery. In an example of alumina as the material of the ceramic layer 52, the unbound excess atoms may be Al.
According to embodiments described herein, the processing system 100 may include an oxidation module 150. The oxidation module 150 may be configured to subject the ceramic layer 52 to an oxidizing atmosphere. According to embodiments described herein, the ceramic layer 52 may be in an oxidizing atmosphere, particularly at elevated temperatures. When practicing the embodiments, the stoichiometry of ceramic layer 52 may be improved. According to an advantageous embodiment, a virtually completely stoichiometric ceramic layer 52 can be achieved.
In the context of the present application, an "oxidizing atmosphere", such as an oxidizing atmosphere in which the ceramic layer 52 may be located, may be understood as an atmosphere that facilitates an oxidation reaction, for example, to improve the stoichiometry of the ceramic layer 52. According to embodiments described herein, the oxidizing atmosphere may comprise more than 20 volume-% oxygen.
In the presence of aluminaIn examples of materials for ceramic layer 52, alumina may oxidize when in an oxidizing atmosphere such that the amount of unbound excess Al atoms decreases and/or the alumina includes an increased amount of Al2O3. According to embodiments described herein, the aluminum oxide layer may be in an oxidizing atmosphere in a manner that improves the stoichiometry of the aluminum oxide layer. Thus, fewer elements of the electrochemical energy storage device (such as the lithium ions described above) may react with the ceramic layer 52. When practicing the embodiments, higher rates of discharge and/or recharge, higher voltages, and/or improved lifetimes may be achieved. Thus, improved charge transport, increased voltage and/or extended cycle life may be achieved in practice.
In addition, the mechanical strength of the ceramic layer 52 can be improved. When practicing the embodiments, the fabrication, post-processing, and storage of the components of the electrochemical energy storage device, as well as the electrochemical energy storage device itself, can be improved. In particular, the increased strength of the ceramic layer 52 may facilitate rolling and/or rewinding the ceramic layer 52 formed on the flexible substrate 111.
According to embodiments described herein, the ceramic layer 52 may be in an oxidizing atmosphere at an elevated temperature. In the context of the present disclosure, an "elevated temperature," such as an elevated temperature at which ceramic layer 52 may be in an oxidizing atmosphere, may be understood as an elevated, i.e., elevated, temperature relative to the ambient temperature. Thus, elevated temperature is understood to be a temperature above room or ambient temperature. There may also be means for raising the ambient temperature to an elevated temperature. For example, a heating device or heating element may be applied to achieve an elevated temperature.
According to embodiments described herein, the elevated temperature may be equal to or greater than ambient temperature, and/or equal to or greater than 23 ℃, in particular equal to or greater than 50 ℃, in particular equal to or greater than 80 ℃. Additionally or alternatively, the elevated temperature is equal to or greater than 50 ℃, in particular equal to or greater than 60 ℃, in particular equal to or greater than 80 ℃, and/or equal to or less than 180 ℃, in particular equal to or less than 120 ℃, in particular equal to or less than 100 ℃.
However, there may be steps that may provide an upper limit for the elevated temperature in electrochemical energy storage device applications, as described above, the flexible substrate 111 may deform when subjected to temperatures, although materials for the flexible substrate 111 having a melting point of about 200 ℃ may be used as described above, many flexible substrates do not have such a high melting point, further, Li has a melting point of about 180 ℃ and may also limit the temperature range of the elevated temperature.
FIG. 1 shows the oxidation module 150 disposed downstream of the deposition module 102, although this arrangement may be used according to embodiments described herein, other arrangements may be possible, for example, the oxidation module 150 may be disposed in series, i.e., in series with the deposition module 102, in which case the oxidation module 150 and the deposition module 102 may be in the same processing system or processing chamber, further, the oxidation module 150 may be disposed off-line, i.e., in a different line than the deposition module 102, in which case the oxidation module 150 and the deposition module 102 may be in different processing systems or processing chambers, for example, a separate oxidation chamber may be provided for the oxidation module 150. further, the deposition module 102 may be disposed in a th processing chamber, and the oxidation module 150 may be disposed in a second processing chamber of the same processing system.
The flexible substrate 111 may be moved during processing in a vacuum processing chamber, for example, from the deposition module 102 to the oxidation module 150. According to embodiments described herein, a substrate transport mechanism may be provided. For example, the flexible substrate 111 may be conveyed along the conveyance path P through the deposition module 102 and/or the oxidation module 150.
As shown in fig. 1, a substrate support and/or a second substrate support may be provided, the second substrate support being disposed 0 apart from the substrate support, the 1 substrate support and/or the second substrate support may also be referred to as a roller, e.g., a th roller and/or a second roller, the th roller 22 and the second roller 24 may be part of the substrate transport mechanism according to the embodiments described herein, the flexible substrate 111 may be transported from the th roller 22 to the second roller 24 according to the embodiments described herein, the flexible substrate 111 may be carried and/or transported from the th roller 22 to the second roller 24 along a transport path P (shown by a circle having a point in the center to represent the transport path P perpendicular to the plane of projection.) according to the embodiments described herein, the substrate transport mechanism may be configured to transport the flexible substrate 111 from the second roller along the transport path P to the second roller 24 according to the embodiments described herein, the deposition module 102 and/or the oxidation module 150 may be disposed from the second roller 22 to the roller 24 according to the embodiments described herein when the flexible roller 111 and the substrate transport module 52 may be disposed at a location between the th roller 22 and the second roller 24 according to the embodiments described herein.
In implementations, the flexible substrate 111 may be unwound from a storage roller, may be conveyed on the outer surface of a coating drum, and may be guided along the outer surface of other rollers.
In the context of the present disclosure, for example, "roller" or "roller device" as part of of a roller assembly may be understood as a device that provides a surface, a substrate (or portion of a substrate), such as flexible substrate 111 (or portion of flexible substrate 111), may contact the surface during its presence in a deposition arrangement, such as a deposition apparatus or a deposition chamber at least portion of the roller device may include a rounded shape for contacting the substrate.
According to embodiments described herein, the processing system may be configured to process flexible substrates 111 having a length of 500m or more, 1000m or more, or thousands of meters, the substrate width may be 100mm or more, 300mm or more, 500mm or more, or 1m or more, the substrate width may be 5m or less, particularly 2m or less, generally, the substrate thickness may be 5 μm or more and 200 μm or less, particularly from 15 μm to 20 μm.
Fig. 2 shows a schematic view of a processing system 100 for depositing a ceramic material on a surface of a flexible substrate 111. The processing system 100 may include a load/unload chamber 101. The load/unload chamber 101 may be configured to load the flexible substrate 111 into the processing system 100 and/or unload the flexible substrate 111 from the processing system 100. According to embodiments described herein, the load/unload chamber may be maintained under vacuum during processing of the flexible substrate 111. A vacuum device 190 may be provided to evacuate the load/unload chamber 101, the vacuum device 190 being, for example, a vacuum pump.
According to embodiments described herein, the load/unload chamber 101 may include an unwind module 110 and/or a rewind module 130 the unwind module 110 may include an unwind roller for unwinding the flexible substrate 111 during processing, the flexible substrate 111 may be unwound (represented by arrow 113) and/or directed to the coating drum 120 by or a plurality of guide rollers 112 after processing, the flexible substrate 111 may be wound (arrow 114) onto a rewind roller in the rewind module 130.
Additionally, the load/unload chamber 101 may include a tension module 180, e.g., including or a plurality of tension rollers, additionally or alternatively, the load/unload chamber 101 may also include a pivot device 170, such as, for example, a pivot arm, the pivot device 170 may be configured to be movable relative to the rewind module 130.
According to embodiments described herein, the unwind module 110, the rewind module 130, the guide rollers 112, the pivot device 170, and the tension module 180 may be portions of the substrate transport mechanism and/or the roller assembly.
According to embodiments described herein, the processing system 100 may include a deposition chamber 103 or an evaporation chamber 103. The deposition chamber 103 may include a deposition module 102. The deposition module 102 may be similar or identical to the deposition module 102 described with particular reference to fig. 1. The deposition chamber 103 may be evacuated by a vacuum device 190, and the vacuum device 190 may also be used to evacuate the load/unload chamber 101. Additionally or alternatively, the deposition chamber 103 may have a vacuum device separate from the vacuum device 190 that may also be used to evacuate the load/unload chamber 101.
As exemplarily shown in FIG. 2, the deposition module 102 may include an evaporation apparatus 140, the evaporation apparatus 140 may be configured to evaporate a material, particularly a metal, according to embodiments described herein, the evaporation apparatus 140 may include or a plurality of evaporation pans, the evaporation apparatus 140 may further include a or a plurality of wires (wires) to be supplied into the evaporation apparatus 140, particularly, each evaporation pan may have wires, the or the plurality of wires may include and/or may be made of a material to be evaporated, particularly, the or the plurality of wires may provide a material to be evaporated.
In accordance with embodiments described herein, the evaporation apparatus 140 may be or a plurality of inductively heated crucibles, which may be configured, for example, to evaporate metal in a vacuum environment by RF induction heating, particularly MF induction heating.
In contrast to conventional evaporation methods that use a resistance heated crucible to evaporate the metal, the use of an induction heated crucible allows the heating process to be performed inside the crucible, rather than by conduction through an external source. Induction heating crucibles have the advantage that all the walls of the crucible are heated very quickly and uniformly. The evaporation temperature of the metal can be more closely controlled than with conventional resistance heated crucibles. When using an induction heated crucible, it may not be necessary to heat the crucible above the evaporation temperature of the metal. When practicing the embodiments, more controlled and efficient metal evaporation can be provided to make the ceramic layer formed on the flexible substrate more homogeneous. By reducing the likelihood of splashing of the evaporated metal, precise control of the crucible temperature can also avoid/reduce pinhole and via defects in the ceramic layer. Pinhole and via defects in the separator can lead to short circuits in the electrochemical cell.
In accordance with embodiments described herein, the induction heating crucible may be surrounded by or a plurality of induction coils (not shown in the figures), for example.
The evaporation source may include or multiple beam sources according to embodiments described herein or multiple beam sources may provide or multiple beams to evaporate material to be evaporated.
A power supply 240 (seen in fig. 3) may be provided according to embodiments described herein. The power supply 240 may be connected to the induction coil. The power supply may be an Alternating Current (AC) power supply that may be configured to provide power having a low voltage but a high current and a high frequency. Furthermore, the reactive power may be increased, for example by including a resonant circuit. According to embodiments described herein, the induction heating crucible may, for example, comprise a ferromagnetic material in addition to or instead of the electrically conductive material. The magnetic material may, for example, improve the induction heating process and may allow better control of the evaporation temperature of the metal.
According to embodiments described herein, the coating drum 120 of the processing system 100 may separate the load/unload chamber 101 from the deposition chamber 103. the coating drum 120 may be configured to direct the flexible substrate 111 into the deposition chamber 103. generally, the coating drum 120 may be disposed in the processing chamber such that the flexible substrate 111 may pass over the evaporation module 102. according to embodiments described herein, the coating drum 120 may be cooled.
The deposition module 102 may include a plasma source 108, the plasma source 108 configured to generate a plasma between the evaporation device 140 and the coating drum 120. the plasma source 108 may be, for example, an electron beam device configured to ignite the plasma with an electron beam.
According to embodiments described herein, the deposition module 102 may include a gas source for supplying a process gas. The gas source may comprise a gas introduction device 107. The gas introduction device 107 may be arranged to controllably introduce process gases into the deposition module 102 and/or the deposition chamber 103. The gas introduction device may, for example, comprise a nozzle and a supply pipe connected to, for example, a process gas source for providing process gas into the deposition module 102 and/or the deposition chamber 103.
The process gas may be a reactive gas. In particular, the process gas may be a reaction gas that reacts with the metal evaporated by the evaporation apparatus 140. For example, the process gas can be and/or include oxygen, ozone, argon, and combinations thereof.
For the case where oxygen is included in the process gas, the oxygen gas may react with the evaporated metal, for example, to form the ceramic layer 52 on the flexible substrate 111. Components of electrochemical energy storage devices, such as separators or separators, electrolytes, cathodes, and anodes, can include AlOx. Metals such as aluminum may be heated, for example, by induction heating a crucibleThe pot is evaporated and oxygen may be provided to the evaporated metal by means of a gas introduction device.
According to embodiments described herein, the processing system may include an oxidation module 150. The oxidation module 150 may be an annealing module for annealing the ceramic layer 52. The oxidation module 150 may be similar to or the same as the oxidation module 150 described with particular reference to fig. 1. As exemplarily shown in fig. 2, the oxidation module 150 may be disposed downstream of the deposition chamber 103. The oxidation module 150 may be configured to subject the ceramic layer to an oxidizing atmosphere and/or an annealing atmosphere, in particular at an oxidizing distance and/or an annealing distance. The oxidation distance and/or the annealing distance may be long enough to achieve the desired amount of oxidation and/or annealing.
According to embodiments described herein, the oxidation module 150 may include a gas assembly 151 the gas assembly 151 may be configured to provide an oxidizing gas, such as oxygen according to embodiments described herein, the oxidation module 150 may include a heating assembly (not shown) the heating assembly may be configured to increase the temperature of at least of the supplied oxidizing gas, the flexible substrate 111, and the ceramic layer 52.
According to embodiments described herein, the oxidation module 150 may include a suction device. The pumping device 152 may be configured to pump an excessive amount of oxidizing gas, that is, oxidizing gas that is not used to oxidize the ceramic layer 52. The suction device 152 may be disposed opposite the gas assembly 151 with respect to the flexible substrate 111. Accordingly, the process gas supplied by the gas assembly 151 may be provided to the ceramic layer 52, traverse the flexible substrate 111, and be pumped by the pumping device 152. When practicing embodiments, contamination of the processing system 100 may be avoided.
The oxidation module 150 may further include a plasma source (not shown in FIG. 2, see FIG. 4.) the plasma source may be the plasma source 153 of the oxidation chamber 200 described with particular reference to FIG. 4.
FIG. 3 shows an enlarged portion of the processing system 100 shown in FIG. 2. according to embodiments described herein, the processing system 100 may include a control system 220. the control system 220 may be connected to at least of the deposition module 102, the oxidation module 150, the gas introduction device 107, the plasma source 108, and the power supply 240. according to embodiments described herein, the control system 220 may be configured to adjust at least of the power supplied to the deposition module 102, the power supplied to the plasma source 108, the amount of process gas introduced into the deposition module 102 by the gas introduction device 107, and/or the orientation of the flow of process gas.
According to embodiments described herein, the gas introduction device 107 may be arranged to provide a flow of process gas in a direction approximately parallel to the direction of evaporation 230 of the metal according to embodiments described herein, the orientation of the flow of gas provided by the gas introduction device may be adjusted according to at least of the uniformity and composition of the ceramic layer 52.
According to embodiments described herein, the plasma 210 may be directed in a direction substantially perpendicular to the evaporation direction 230 of the metal. When practicing the embodiments, splashing of evaporated metal may be avoided and/or pinhole defects of the ceramic layer may be reduced.
Although the oxidation module 150 is shown in fig. 1-3 as being arranged in series with the deposition module 102, the oxidation module 150 may be arranged off-line as described above. For example, an oxidation chamber 200 may be provided in which the oxidation module 150 is disposed. The oxidation chamber 200 may be separate from the deposition chamber 103. In addition, the oxidation chamber 200 may be separate from the processing system 100. In addition, the processing system 100 may be a multi-chamber system including a plurality of processing chambers, such as the deposition chamber 103 and/or the oxidation chamber 200. In addition, the processing system 100 may include a storage chamber in which the rewound flexible substrate 111 having the ceramic layer 52 deposited on the flexible substrate 111 may be stored before the rewound flexible substrate 111 having the ceramic layer 52 deposited on the flexible substrate 111 may be transferred to the oxidation chamber 200.
Fig. 4 shows an oxidation chamber 200 according to an embodiment. The oxidation chamber 200 may include an oxidation module 150 and/or a substrate transfer mechanism.
The substrate transfer mechanism may include the th roller 222 and/or the second roller 224. the th roller 222 and/or the second roller 224 of the oxidation chamber 200 may be similar to or the same as, for example, the th roller 22 and/or the second roller 24 of the processing system 100 described with particular reference to fig. 1. additionally, the oxidation chamber 200 may include similar or the same substrate transfer mechanism and/or roller assembly of the processing system 100 described with particular reference to fig. 2. accordingly, the substrate transfer mechanism and/or roller assembly of the oxidation chamber 200 may include the same, similar or corresponding components as the substrate transfer mechanism and/or roller assembly of the processing system 100, including, in particular, the unwind module 110, the rewind module 130, the guide roller 112, the pivot device 170, and the tension module 180. the substrate transfer mechanism may be configured to transfer the flexible substrate 111 from the th roller 222 to the second roller 224 along the transfer path P'.
According to embodiments described herein, the oxidation module 150 may be disposed in the conveyance path P' between the th roller 222 and the second roller 224 the oxidation module 150 may be configured to subject the ceramic layer 52 to an oxidizing atmosphere at an elevated temperature.
Additionally, the oxidation module 150 in the oxidation chamber 200 may further include the same or similar components described above with particular reference to FIGS. 1-3, including in particular the gas assembly 151 and/or pumping device 152. additionally, the oxidation module 150 may include a plasma source 153. the plasma source 153 may be configured to generate a plasma between the gas assembly 151 and the flexible substrate 111. the plasma source 153 may be, for example, an electron beam device configured to ignite a plasma with an electron beam.
According to embodiments described herein, the oxidation module 150 may include a heating assembly 154 the heating assembly 154 may be configured to elevate the temperature of at least of the oxidation chamber 200, the oxidizing atmosphere, the flexible substrate 111, and the ceramic layer 52.
Although the plasma source 153 and the heating assembly 154 are shown in fig. 3 as being part of the oxidation module 150 disposed in the oxidation chamber 200, the plasma source 153 and/or the heating assembly 154 may also be present in the oxidation module 150 outside of the oxidation chamber 200, such as in series with the oxidation module 150. For example, the plasma source 153 and/or the heating assembly 154 may also be part of the oxidation module 150 described herein with particular reference to fig. 1-3. In the case where the heating assembly 154 is disposed in a process chamber other than the oxidation chamber 200, the heating assembly 154 may be configured to heat the process chamber.
Fig. 5 shows a flow diagram of a method 500 for forming a component of an electrochemical energy storage device, the method may include at least of operations 510 and 520, depositing a ceramic layer 52 over a flexible substrate 111 according to operation 510, subjecting the ceramic layer 52 to an oxidizing atmosphere at an elevated temperature according to operation 520.
Fig. 6 schematically illustrates a method 300 for forming a component of an electrochemical energy storage device, according to embodiments described herein. The method 300 may include providing 310 a flexible substrate having a front side and a back side. According to embodiments described herein, providing the flexible substrate may include guiding the flexible substrate from an unwind module to a rewind module through a coating drum of an evaporation apparatus.
In accordance with embodiments described herein, the method may further include evaporating 320 metal in an induction heating crucible, in particular, evaporating aluminum and/or silicon through an induction heating crucible, in accordance with embodiments described herein, in embodiments herein, the method further includes applying 330 a ceramic layer to at least of the front and back sides of the flexible substrate.
The evaporated metal may react with the reaction gas to form a porous coating layer on the flexible substrate. The metal may be evaporated in a vacuum environment. For example, evaporated aluminum may react with oxygen to form porous AlO on a flexible substratexAnd (3) a layer.
In accordance with embodiments described herein, evaporating metal in the induction heating crucible may further include sensing 340 an evaporation temperature of the metal evaporation, and adjusting a power provided to evaporate the metal in the induction heating crucible based on the sensed evaporation temperature.
In embodiments described herein, the ceramic layer applied to the flexible substrate may have a thickness of from about 25nm to about 300nm, such as, for example, from 100nm to 200 nm.
According to embodiments described herein, vaporizing metal in an inductively heated crucible can further include providing 350 a process gas, such as, for example, oxygen, to the vaporized metal.
The method for forming a component of an electrochemical energy storage device may further include providing a plasma between the evaporated metal and the flexible substrate.
The stoichiometry of a porous layer deposited on a flexible substrate can be affected, for example, by the evaporation rate of the metal and the amount of process gas provided to the evaporated metal. A further aspect that may affect the stoichiometry of the deposited porous layer may be the pressure differential between the vacuum inside the evaporation chamber and the pressure of the surrounding atmosphere. Thus, as described herein, ceramic layer 52 may be deposited non-stoichiometrically, or not at full stoichiometry.
According to embodiments described herein, a method for forming a component of an electrochemical energy storage device may include subjecting the ceramic layer 52 to an oxidizing atmosphere at an elevated temperature 370. When practicing the embodiments, the stoichiometry of the ceramic layer may be improved. Even a completely stoichiometric ceramic layer can be achieved in practice.
This written description uses examples to disclose the disclosure, including the best mode, and also to enable practice of the described subject matter, including making and using any devices or systems and performing any incorporated methods. Embodiments described herein provide improved methods and apparatus for producing a membrane that: high porosity and good ionic conductivity; having a composite hole structure that is free of or has reduced pinhole or via defects to inhibit short circuits; has excellent thermal and mechanical stability; and can be produced at low cost. While various specific embodiments have been disclosed above, the non-mutually exclusive features of the embodiments described above may be combined with each other. The patentable scope is defined by the claims, and other embodiments are intended to be within the scope of the claims if the embodiments have structural elements that do not differ from the literal language of the claims, or if the embodiments include equivalent structural elements with insubstantial differences from the literal language of the claims.

Claims (15)

1, a method for forming a component of an electrochemical energy storage device, comprising:
depositing a ceramic layer (52) over a flexible substrate (111); and
-subjecting the ceramic layer (52) to an oxidizing atmosphere at an elevated temperature.
2. The method of claim 1, wherein the ceramic layer (52) is an aluminum oxide layer.
3. The method of claim 2, wherein the aluminum oxide layer is in the oxidizing atmosphere in a manner that improves the stoichiometry of the aluminum oxide layer.
4. The method of any of claims 1-3, wherein the electrochemical energy storage device is a lithium ion battery.
5. The method of any of claims 1-4, wherein the component is a septum.
6. The method of any of claims 1-4, wherein the component is an electrode.
7. The process of any of claims 1-6, wherein the elevated temperature is equal to or greater than 50 ℃, particularly equal to or greater than 60 ℃, particularly equal to or greater than 80 ℃, and/or equal to or less than 180 ℃, particularly equal to or less than 120 ℃, particularly equal to or less than 100 ℃.
8. The method of any of claims 1-7, wherein the oxidizing atmosphere comprises more than 20 vol% oxygen.
9. The method of any of claims 1-8, further comprising the step of :
-transferring the flexible substrate (111) from the th roller (22) to the second roller (24), -forming the ceramic layer (52) while transferring the flexible substrate (111) from the th roller (22) to the second roller (24).
10. The method of claim 9, wherein the ceramic layer (52) is in an oxidizing atmosphere as the flexible substrate (111) is transferred from the th roller (22) to the second roller (24).
11, A processing system (100) for forming a component of an electrochemical energy storage device, comprising:
a deposition module (102) configured for depositing a ceramic layer (52) over a flexible substrate (111); and
an oxidation module (150) configured to subject the ceramic layer (52) to an oxidizing atmosphere at an elevated temperature.
12. The processing system of claim 11, wherein said oxidation module (150) comprises a gas assembly (151) configured to provide an oxidizing gas and a heating assembly (154) configured to raise a temperature of at least of the supplied oxidizing gas, the flexible substrate, and the ceramic layer.
13. The processing system of claim 11 or 12, further comprising:
a substrate transport mechanism comprising an th roller (22) and a second roller (24), the substrate transport mechanism configured to transport the flexible substrate (111) from the th roller (22) to the second roller (24) along a transport path (P) along which the deposition module (102) and the oxidation module (150) are arranged.
14, an oxidation chamber configured to oxidize a ceramic layer of a component of an electrochemical energy storage device, the oxidation chamber comprising:
a substrate transfer mechanism including a th roller (222) and a second roller (224), the substrate transfer mechanism being configured to transfer a flexible substrate (111) from the th roller (222) to the second roller (224) along a transfer path (P'), a ceramic layer (52) being formed on the flexible substrate (111), and
an oxidation module (150) disposed on the transport path (P') between the th roller (222) and the second roller (224), the oxidation module (150) configured to subject the ceramic layer (52) to an oxidizing atmosphere at an elevated temperature.
15. The oxidation chamber of claim 14, further comprising:
a heating assembly (154) configured to raise a temperature of at least of the oxidation chamber (200), the oxidizing atmosphere, the flexible substrate (111), and the ceramic layer (52).
CN201780091917.9A 2017-09-20 2017-09-20 Method and processing system for forming components of an electrochemical energy storage device and oxidation chamber Pending CN110741491A (en)

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