Lithium metal layer transfer onto anode current collector

Abstract

A method for manufacturing an anode electrode includes providing a first substrate, a second substrate, and an anode current collector. The method includes forming a first lithium metal layer on a first substrate and a second lithium metal layer on a second substrate. The method includes pressing a first lithium metal layer and a second lithium metal layer into an anode current collector to form an anode electrode.

Description

Technical Field

[0001] The present disclosure relates to battery cells and, more particularly, to anode electrodes for battery cells. Background Art

[0002] The information provided in this section is intended to generally introduce the background of the present disclosure. To the extent that work currently named as inventors is described in this section, and aspects of the specification that may not have been otherwise identified as prior art at the time of filing, are not admitted, either explicitly or implicitly, as prior art to the present disclosure.

[0003] The present disclosure relates to battery cells and, more particularly, to anode electrodes for battery cells.

[0004] Electric vehicles (EVs), such as battery electric vehicles (BEVs), hybrid vehicles, and / or fuel cell vehicles, include one or more motors and a battery system including one or more battery cells, modules, and / or battery packs. A power control system is used to control the charging and / or discharging of the battery system during charging and / or driving. Summary of the invention

[0005] A method for manufacturing an anode electrode includes providing a first substrate, a second substrate, and an anode current collector; forming a first lithium metal layer on the first substrate and forming a second lithium metal layer on the second substrate; and pressing the first lithium metal layer and the second lithium metal layer into the anode current collector to form an anode electrode.

[0006] In other features, the method includes removing the first substrate and the second substrate after pressing. The first substrate includes a separator layer. The first substrate includes a polymer film.

[0007] In other features, the method includes forming a first lithium metal layer on a first substrate, comprising at least one of electroplating, vapor depositing, powder coating, or spraying the first lithium metal layer on the first substrate. The first substrate includes a solid electrolyte layer. The solid electrolyte layer is selected from a polymer electrolyte, an oxide-based electrolyte, and a sulfide-based electrolyte.

[0008] In other features, the solid electrolyte layer is selected from a solvent-free polymer electrolyte layer, a gel polymer electrolyte layer, a composite polymer electrolyte layer, a polyethylene oxide (PEO) layer, a polyacrylonitrile (PAN) layer, a polycarbonate layer, and a polysiloxane layer. The method includes disposing a protective layer on the first substrate between the first lithium metal layer and the first substrate. The protective layer includes a ceramic. The protective layer is selected from alumina, zirconium oxide, zeolite, lithiated zeolite, and combinations thereof.

[0009] In other features, the method includes adding a conductive layer to at least one surface of the first substrate before forming the first lithium metal layer on the first substrate. The anode current collector includes one of a mesh current collector, a porous metal current collector, and a perforated current collector. The anode current collector is made of a material selected from copper, stainless steel, brass, bronze, zinc, aluminum, and alloys thereof.

[0010] A method for manufacturing an anode electrode, comprising providing a first substrate, a second substrate and an anode current collector including a void. The anode current collector comprises one of a mesh current collector, a porous metal current collector and a perforated current collector. The anode current collector is made of a material selected from copper, stainless steel, brass, bronze, zinc, aluminum and / or an alloy thereof. The method comprises forming a first lithium metal layer on a first substrate and forming a second lithium metal layer on a second substrate. Forming the first lithium metal layer on the first substrate comprises at least one of the following: electroplating, vapor deposition, powder coating or spraying the first lithium metal layer on the first substrate. The method comprises pressing the first lithium metal layer and the second lithium metal layer into the void of the anode current collector to form an anode electrode.

[0011] In other features, the method includes removing the first substrate and the second substrate after pressing. The first substrate includes a solid electrolyte layer. The first substrate includes a polymer layer. The method includes disposing a protective layer on the first substrate between the first lithium metal layer and the first substrate, wherein the protective layer includes a ceramic. The method includes forming a conductive layer on the first substrate before forming the first lithium metal layer on the first substrate.

[0012] The present invention discloses the following scheme:

[0013] Scheme 1. A method for manufacturing an anode electrode, comprising:

[0014] providing a first substrate, a second substrate and an anode current collector;

[0015] forming a first lithium metal layer on the first substrate, and forming a second lithium metal layer on the second substrate; and

[0016] The first lithium metal layer and the second lithium metal layer are pressed into the anode current collector to form an anode electrode.

[0017] Option 2. The method according to Option 1 also includes removing the first substrate and the second substrate after the pressing.

[0018] Option 3. A method according to Option 1, wherein the first substrate includes an isolation layer.

[0019] Option 4. A method according to Option 1, wherein the first substrate comprises a polymer film.

[0020] Option 5. The method according to Option 1, wherein forming the first lithium metal layer on the first substrate comprises at least one of the following: electroplating, vapor deposition, powder coating or spraying the first lithium metal layer on the first substrate.

[0021] Option 6. A method according to Option 1, wherein the first substrate includes a solid electrolyte layer.

[0022] Option 7. A method according to Option 6, wherein the solid electrolyte layer is selected from a polymer electrolyte, an oxide-based electrolyte, and a sulfide-based electrolyte.

[0023] Option 8. A method according to Option 6, wherein the solid electrolyte layer is selected from a solvent-free polymer electrolyte layer, a gel polymer electrolyte layer, a composite polymer electrolyte layer, a polyethylene oxide (PEO) layer, a polyacrylonitrile (PAN) layer, a polycarbonate layer and a polysiloxane layer.

[0024] Option 9. The method according to Option 1 also includes disposing a protective layer on the first substrate between the first lithium metal layer and the first substrate.

[0025] Option 10. A method according to Option 9, wherein the protective layer comprises ceramic.

[0026] Option 11. The method according to Option 9, wherein the protective layer is selected from the group consisting of alumina, zirconium oxide, zeolite, lithiated zeolite, and combinations thereof.

[0027] Option 12. The method according to Option 1 also includes adding a conductive layer to at least one surface of the first substrate before forming the first lithium metal layer on the first substrate.

[0028] Option 13. A method according to Option 1, wherein the anode current collector comprises one of a mesh current collector, a porous metal current collector and a perforated current collector.

[0029] Option 14. The method according to Option 1, wherein the anode current collector is made of a material selected from the group consisting of copper, stainless steel, brass, bronze, zinc, aluminum and alloys thereof.

[0030] Solution 15. A method for manufacturing an anode electrode, comprising:

[0031] providing a first substrate, a second substrate, and an anode current collector including a void,

[0032] wherein the anode current collector comprises one of a mesh current collector, a porous metal current collector and a perforated current collector, and

[0033] wherein the anode current collector is made of a material selected from copper, stainless steel, brass, bronze, zinc, aluminum and / or alloys thereof;

[0034] forming a first lithium metal layer on the first substrate and forming a second lithium metal layer on the second substrate,

[0035] wherein forming the first lithium metal layer on the first substrate comprises at least one of: electroplating, vapor deposition, powder coating or spraying the first lithium metal layer on the first substrate; and

[0036] The first lithium metal layer and the second lithium metal layer are pressed into the voids of the anode current collector to form an anode electrode.

[0037] Option 16. The method according to Option 15 also includes removing the first substrate and the second substrate after the pressing.

[0038] Option 17. A method according to Option 15, wherein the first substrate includes a solid electrolyte layer.

[0039] Option 18. A method according to Option 15, wherein the first substrate comprises a polymer layer.

[0040] Option 19. The method according to Option 15 also includes disposing a protective layer on the first substrate between the first lithium metal layer and the first substrate, wherein the protective layer comprises ceramic.

[0041] Option 20. The method according to Option 15 further includes forming a conductive layer on the first substrate before forming the first lithium metal layer on the first substrate.

[0042] Further areas of applicability of the present disclosure will become apparent from the detailed description, claims and drawings.The detailed description and specific examples are intended to be illustrative only and are not intended to limit the scope of the present disclosure. BRIEF DESCRIPTION OF THE DRAWINGS

[0043] The present disclosure will be more fully understood through the detailed description and accompanying drawings, in which:

[0044] Figure 1 is a side cross-sectional view of an example of a battery cell according to the present disclosure, the battery cell including a cathode electrode, an anode electrode, and a separator disposed in a battery cell housing;

[0045] FIG. 2A to FIG. 2D is a side cross-sectional view of an example of an anode electrode according to the present disclosure;

[0046] Figure 3 is a plan view illustrating masking of a substrate before forming a lithium metal layer on the substrate according to the present disclosure; and

[0047] Figure 4 is a flow chart of an example of a method for manufacturing an anode electrode according to the present disclosure.

[0048] Among the drawings, reference numerals may be repeated to identify similar and / or identical elements. DETAILED DESCRIPTION

[0049] Although battery cells according to the present disclosure are shown in the context of an electric vehicle, the battery cells may be used in stationary applications and / or other applications.

[0050] A battery cell such as a lithium-ion battery cell comprises a cathode electrode, an anode electrode and a separator. The anode electrode comprises an anode active material layer, such as a lithium metal layer, disposed on an anode current collector. The lithium metal layer is difficult to deposit with a uniform thickness. In addition, the width of the lithium metal layer is currently limited to 100 mm.

[0051] The anode electrode according to the present disclosure includes a lithium metal layer and an anode current collector. The lithium metal layer is formed on a substrate (e.g., a separator layer, a polymer film, a solid electrolyte layer, or a discarded substrate). The lithium metal layer and the substrate are pressed (e.g., between rollers or presses) onto one or both sides of the anode current collector. The lithium metal layer is pressed into the void of the anode current collector. In some examples, the substrate is removed from the lithium metal layer and discarded after pressing. Alternatively, the substrate may correspond to a separator layer or a solid electrolyte layer of a lithium-ion battery cell.

[0052] In some examples, the anode current collector is a 3-dimensional (3D) current collector, such as a wire mesh, an expanded metal, and / or a perforated foil (including gaps between metals). The lithium metal layer is pushed into the gaps of the anode current collector. The substrate can be used to prevent the lithium metal layer from directly contacting the roller or press, which prevents sticking to the roller or press. The defects in the lithium metal layer after pressing will become homogenized due to the high strain that occurs when the lithium metal layer is pressed into the gaps of the anode current collector. Therefore, the lithium metal layer does not need to be perfectly deposited on the substrate.

[0053] In some examples, the substrate is masked prior to adding the lithium metal layer to the substrate to limit where the lithium metal layer is formed on the substrate. The mask helps define the shape of the anode electrode to be cut from the multilayer structure.

[0054] Reference now Figure 1The battery cell 10 includes C cathode electrodes 20, A anode electrodes 40, and S separators 32 arranged in a predetermined order in a battery cell stack 12 located in a housing 50, where C, S, and A are integers greater than zero. The C cathode electrodes 20-1, 20-2, ..., and 20-C include a cathode active material layer 24 arranged on one or both sides of a cathode current collector 26. The A anode electrodes 40-1, 40-2, ..., and 40-A include an anode active material layer 42 (e.g., including a lithium metal layer) arranged on one or both sides of an anode current collector 46.

[0055] In some examples, cathode active material layer 24 is a free-standing electrode that is respectively disposed adjacent to (or attached to) cathode current collector 26. In some examples, cathode active material layer 24 includes a coating comprising one or more active materials, one or more conductive fillers / additives, and / or one or more binder materials applied to a current collector.

[0056] In some instances, the cathode current collector 26 comprises a metal foil, a metal mesh and / or a porous metal. In some instances, the anode current collector 46 comprises a metal mesh, a porous metal and / or a perforated metal. In some instances, the cathode current collector 26 and / or the anode current collector 46 are made of one or more materials selected from copper, stainless steel, brass, bronze, zinc, aluminum and / or their alloys. The external tabs 28 and 48 are respectively connected to the current collectors of the cathode electrode and the anode electrode, and can be arranged on the same side or opposite sides of the battery stack 12. The external tabs 28 and 48 are connected to the terminals of the battery cells.

[0057] Reference now FIG. 2A to FIG. 2C , showing the use of a press and / or rollers to press the lithium metal layer 72 onto the anode current collector 46 ( Figure 2A ) on one or both sides of the substrate 70 and the anode active material layer (e.g., lithium metal layer 72). In some examples, the lithium metal layer 72 is electroplated, vapor deposited, powder coated and / or sprayed onto the substrate 70 before pressing.

[0058] In some examples, the substrate (s) 70, the lithium metal layer (s) 72, and the anode current collector 46 are fed through one or more sets of rollers with a predetermined gap therebetween to press the layers. After pressing, the lithium metal layer 72 is pressed into the voids in the anode current collector 46 to mechanically connect the layers.

[0059] In some examples, substrate 70 may include a separator layer ( Figure 2B). Forming the lithium metal layer on the separator layer reduces waste (e.g., relative to another substrate 70 that is temporarily used to support the lithium metal layer 72 and then discarded). Examples of substrates 70 (e.g., separator layers) include polymer films. Examples of polymer films include porous films (e.g., polyolefins, polyvinylidene fluoride (PVDF), polyethylene terephthalate, etc.).

[0060] In other examples, substrate 70 includes a ceramic layer. In some examples, the ceramic layer is selected from alumina, zirconia, zeolite, lithiated zeolite, or other suitable ceramic materials.

[0061] In other examples, the substrate 70 includes a solid electrolyte layer. When the substrate 70 includes a solid electrolyte layer, the solid electrolyte layer is not removed before assembly into a battery cell. Forming the lithium metal layer on the solid electrolyte layer reduces waste (e.g., relative to another substrate 70 that is temporarily used to support the lithium metal layer 72 and then discarded). In some examples, the solid electrolyte layer is selected from a polymer electrolyte, an oxide-based electrolyte, and / or a sulfide-based electrolyte.

[0062] In some examples, the polymer electrolyte is selected from a solvent-free polymer electrolyte layer, a gel polymer electrolyte layer, a composite polymer electrolyte layer, a polyethylene oxide (PEO) layer, a polyacrylonitrile (PAN) layer, a polycarbonate layer, and a polysiloxane layer.

[0063] Examples of oxide-based electrolytes include garnet-type (e.g. Li 7 La 3 Zr 2 O 12 ), perovskite type (such as Li 3x La 2 / 3-x TiO 3 ), NASICON type (such as Li 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 , Li 1+x Al x Ge 2-x (PO 4 ) 3 ), LISICON type (such as Li 2+2x Zn 1-x GeO 4 ) or other suitable oxide-based solid electrolytes.

[0064] Examples of sulfide-based electrolytes include xLi 2 S-(100-x)P 2 S 5 , Li 6 PS5 X (wherein X = chlorine (Cl), bromine (Br) or iodine (I)), L 10 G 2 S 12 (LGPS), or other suitable sulfide solid electrolyte materials. In some examples, oxide-based or sulfide-based solid electrolytes are prepared using powders for pressing at elevated temperatures to form thin films (eg, with or without a binder such as a fibrillating binder).

[0065] exist Figure 2C In the embodiment, the substrate 70 is optionally removed after pressing (for example, when the substrate 70 does not correspond to a separator or a solid electrolyte layer). In other words, the substrate 70 can be made of any suitable material that can be removed after the lithium metal layer is pressed or rolled onto the anode current collector 46.

[0066] exist Figure 2D In the embodiment of the present invention, the substrate 70 further includes a layer 90 disposed between the lithium metal layer 72 and the substrate 70. In some examples, the layer 90 includes a conductive layer formed on the substrate 70 (e.g., before the lithium metal layer 72 is formed). In other words, the conductive layer is formed on the substrate 70 before the lithium metal layer 72 is electroplated or powder coated on the substrate 70.

[0067] For example, a chromic acid-based solution is used to etch substrate 70. A solution containing palladium salts and tin salts is used to coat the etched surface of substrate 70. Layer 90 includes a metal layer (e.g., nickel or copper) applied to substrate 70 using an electroless plating solution. In other examples, layer 90 includes a conductive paint applied to substrate 70.

[0068] In some examples, layer 90 includes a protective layer disposed between substrate 70 and anode active material layer 42 (e.g., lithium metal). The protective layer prevents lithium metal layer 72 from entering the pores of substrate 70 (e.g., when substrate 70 corresponds to a separator). In some examples, the protective layer includes a ceramic layer. In some examples, the ceramic layer is selected from alumina, zirconium oxide, zeolite, lithiated zeolite, or other suitable ceramic materials.

[0069] Reference now Figure 3 , the substrate 70 is masked at one or more mask locations 80 to prevent the lithium metal layer 72 from being deposited in the mask locations 80. In some examples, the mask is removed after the lithium metal layer 72 is added. In some examples, the mask includes a mask base and an adhesion layer that is attached to the substrate 70 and then removed after plating. In some examples, the mask reduces or prevents the deposition of the lithium metal layer 72 on the mask locations 80.

[0070] Reference now Figure 4, a method 210 for making an anode electrode is shown. At 210, the substrate and / or layers (e.g., conductive layers or protective layers) are optionally masked. At 214, a lithium metal layer (or conductive layer or protective layer, if used) is formed on the substrate. At 218, the lithium metal layer 72 and substrate 70 are arranged on one or both sides of the anode current collector 46 (where the lithium metal layer 72 faces the anode current collector 46). At 222, the lithium metal layer(s) 72 are pressed into the anode current collector 46. At 226, the substrate 70 is optionally removed (if the substrate 70 is not a separator). At 230, the anode electrode is arranged in a battery cell.

[0071] The anode electrode according to the present disclosure combines lithium deposition on a substrate and the use of a 3-dimensional (3D) current collector. The method avoids the need to deposit a lithium metal layer 72 directly on the anode current collector 46, which can be challenging. In some instances, the substrate 70 corresponds to a separator capable of supporting a lithium metal layer while transferring the lithium layer to a 3D current collector. It is understood that the method for manufacturing an anode current collector with a lithium metal layer is not limited by width. The surface and / or internal defects of the lithium metal layer are less worthy of attention because the anode current collector is flattened when pressed into the pores of the 3D anode current collector. The substrate can also serve a dual purpose, namely being able to press the lithium metal layer onto the anode current collector and then act as a separator between the anode electrode and the cathode electrode in the battery cell. Pressing can be used to control the thickness of the lithium metal layer.

[0072] The foregoing description is essentially only exemplary and is absolutely not intended to limit the present disclosure, its application or use. The broad teachings of the present disclosure can be implemented in various forms. Therefore, although the present disclosure includes specific examples, the true scope of the present disclosure should not be limited thereto, because after studying the drawings, the specification and the following claims, other modifications will become apparent. It should be understood that one or more steps in the method may be implemented in different orders (or simultaneously) without changing the principles of the present disclosure. In addition, although each embodiment is described above as having certain features, any one or more features described with respect to any embodiment of the present disclosure may be implemented in any other embodiment and / or combined with the features of any other embodiment, even if the combination is not explicitly described. In other words, the embodiments are not mutually exclusive, and the mutual replacement of one or more embodiments is still within the scope of the present disclosure.

[0073] Various terms are used to describe the spatial and functional relationships between elements (e.g., between modules, circuit elements, semiconductor layers, etc.), including "connected," "engaged," "coupled," "adjacent," "next to," "on top of," "on," "under," and "disposed." Unless explicitly described as "directly," when describing the relationship between a first element and a second element in the above disclosure, the relationship can be a direct relationship in which there are no other intervening elements between the first element and the second element, or an indirect relationship in which there are one or more intervening elements (spatially or functionally) between the first element and the second element. The phrase "at least one of A, B, and C" as used herein should be interpreted to mean a logical (A or B or C) using a non-exclusive logical OR, and should not be interpreted to mean "at least one A, at least one B, and at least one C."

[0074] In the drawings, the direction of the arrows, as shown by arrows, generally demonstrates the flow of information (such as data or instructions) related to the diagram. For example, when component A and component B exchange various information but the information transmitted from component A to component B is related to the diagram, the arrow may point from component A to component B. Such a unidirectional arrow does not mean that no other information is transmitted from component B to component A. In addition, for the information transmitted from component A to component B, component B may send a request for the information to component A or a receipt of the information.

Claims

1. A method for manufacturing an anode electrode, comprising: providing a first substrate, a second substrate and an anode current collector; forming a first lithium metal layer on the first substrate, and forming a second lithium metal layer on the second substrate; and The first lithium metal layer and the second lithium metal layer are pressed into the anode current collector to form an anode electrode. 2 . The method of claim 1 , further comprising removing the first substrate and the second substrate after the pressing. The method of claim 1 , wherein the first substrate comprises a spacer layer. The method of claim 1 , wherein the first substrate comprises a polymer film. 5 . The method of claim 1 , wherein forming the first lithium metal layer on the first substrate comprises at least one of: electroplating, vapor depositing, powder coating, or spraying the first lithium metal layer on the first substrate. The method of claim 1 , wherein the first substrate comprises a solid electrolyte layer. 7 . The method of claim 6 , wherein the solid electrolyte layer is selected from the group consisting of a polymer electrolyte, an oxide-based electrolyte, and a sulfide-based electrolyte.

8. The method according to claim 6, wherein the solid electrolyte layer is selected from the group consisting of a solvent-free polymer electrolyte layer, a gel polymer electrolyte layer, a composite polymer electrolyte layer, a polyethylene oxide (PEO) layer, a polyacrylonitrile (PAN) layer, a polycarbonate layer, and a polysiloxane layer. 9 . The method of claim 1 , further comprising disposing a protective layer on the first substrate between the first lithium metal layer and the first substrate.

10. The method of claim 9, wherein the protective layer comprises ceramic.

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