Patent Application
20230420731
The present invention generally relates to the field of solid-state and/or thin film batteries. More specifically, embodiments of the present invention pertain to a high energy-density solid-state battery and methods of making the same.
Solid-state lithium batteries are ionic-charge storage devices that are ideally suited for wearable, IoT, and other non-EV applications due to their small size, safety, and high cyclability. Currently, they typically exist as single-cell devices, and require extrinsic packaging with relatively high area/volume overhead. These constraints limit the total charge capacity and volumetric energy density achievable. An additional disadvantage of the single-cell approach is that it generally needs to be relatively large in the x-y dimensions in order to carry sufficient charge capacity. This potentially large footprint can limit usage in area-constrained applications. To support a broader range of products and applications, a solution is desired that enables a multi-cell battery with high active battery area utilization and low packaging overhead for maximizing battery energy density.
This “Discussion of the Background” section is provided for background information only. The statements in this “Discussion of the Background” are not an admission that the subject matter disclosed in this “Discussion of the Background” section constitutes prior art to the present disclosure, and no part of this “Discussion of the Background” section may be used as an admission that any part of this application, including this “Discussion of the Background” section, constitutes prior art to the present disclosure.
The present invention relates to solid-state and thin film batteries, and more specifically to a stacked solid-state battery and method(s) of making the same. In one aspect, the present invention relates to a solid-state battery, comprising a plurality of cells and first and second terminals on opposite sides or edges of the battery. Each of the cells comprises a cathode current collector (CCC), a cathode on the cathode current collector, a solid-state electrolyte on the cathode, an anode current collector (ACC) on the electrolyte, a barrier and/or insulation film with a via or opening therein exposing the ACC, and a conductive redistribution layer in the via or opening and on the barrier and/or insulation film. The redistribution layer is also on a first sidewall of each cell. The first sidewall of each cell is on a first one of the opposite sides or edges of the battery. One of the first and second terminals is electrically connected to each ACC through the redistribution layer on the first sidewall, and the other of the first and second terminals is electrically connected to each cathode or CCC on a second one of the opposite sides or edges of the battery.
In some embodiments, the CCC comprises a metal foil, sheet or film. The metal foil may be in the form of a sheet or roll, and may also function as a mechanical substrate supporting the remainder of the battery cell and/or on which the battery cell may be formed. The metal foil may comprise stainless steel, aluminum, copper, nickel, inconel, brass, molybdenum or titanium, and the aluminum, copper, nickel, molybdenum or titanium may be alloyed with up to 10% of one or more other elements. When the CCC comprises the metal foil, it may further comprise first and second barriers on opposite major surfaces of the metal foil, the first and second barriers having a thickness effective to prevent migration of atoms or ions from the metal foil into overlying layers. Alternatively, the metal foil, sheet or film may have a single barrier on a major surface thereof, having a thickness effective to prevent migration of atoms or ions from the metal foil, sheet or film into overlying layers. The barrier(s) may comprise a glass, a ceramic, or a conductive, amorphous material.
In various embodiments, the cathode may comprise a lithium metal oxide or lithium metal phosphate. For example, the cathode may comprise lithium cobalt oxide (LiCoO2), lithium manganese oxide (LiMn2O4), or lithium iron phosphate (LiFePO4).
In other or further embodiments, the solid-state electrolyte may comprise a lithium phosphorus oxynitride (LiPON) or Li2WO4. Optionally, the LiPON electrolyte may be carbon-doped.
In yet other or further embodiments, the anode current collector may comprise a conductive metal or graphite. For example, the anode current collector may comprise nickel, zinc, copper, or an alloy thereof. In various implementations, the anode current collector has a thickness of 0.1-5 μm, and area dimensions that are 50-90% of corresponding length and width dimensions, respectively, of the corresponding cell.
In other or further embodiments, the barrier and/or insulation film may comprise a polyolefin. Optionally, the barrier and/or insulation film may have an inorganic oxide or nitride overlayer thereon. For example, the polyolefin may comprise parylene, polyethylene or polypropylene, and the overlayer may comprise Al2O3, SiO2 or Si3N4. Alternatively, the barrier/insulation film may have a polycarbonate or amorphous carbon coating thereon.
In various embodiments, the redistribution layer may comprise an air- and/or water-stable metal. For example, the redistribution layer may comprise Cu, Ni, or Al.
In other or further embodiments, the first and second terminals may comprise a conductive epoxy. For example, the conductive epoxy may comprise an Ag-filled or Ni-filled conductive epoxy paste. Alternatively, the first and second terminals comprise a noble metal such as Au, Pt, Pd or Cu, either in the conductive epoxy, or plated onto the redistribution layer and/or exposed edges of the CCC and/or cathode.
In some embodiments, the present solid-state battery may further comprise a dummy cell on an uppermost surface of a stack of the plurality of cells. The dummy cell may comprise a metal foil substrate (e.g., identical to that of the CCC, when the CCC comprises a metal foil) encapsulated with an encapsulant. The encapsulant may be identical to the barrier and/or insulation film. The dummy cell is generally configured to protect the stack of battery cells from externally-caused damage and to provide a barrier to ingress of moisture and air (e.g., into the active region[s] of the battery cells).
The present invention also relates to a method of making a solid-state battery cell, comprising forming a cathode on a substrate, forming a solid-state electrolyte on or over the cathode, forming an anode current collector on or over the solid-state electrolyte, encapsulating the substrate, the cathode, the solid-state electrolyte, and the anode current collector with an encapsulation (e.g., that is essentially the same as the barrier and/or insulation film in the present solid-state battery), forming an opening in the encapsulation exposing the anode current collector, and forming a conductive redistribution layer on the exposed anode current collector, the encapsulation, and a first sidewall of the solid-state battery cell.
Similar to the present solid-state battery, the substrate may comprise a metal foil, sheet or film that can also function as a cathode current collector. When the substrate comprises the metal foil, the method may further comprise forming a barrier on a major surface of the metal foil. The barrier generally has a thickness effective to prevent migration of atoms or ions from the metal foil into overlying layers. The barrier may comprise a glass, a ceramic, or a conductive, amorphous material.
In various embodiments, the cathode may be formed by blanket deposition and patterning. For example, blanket deposition may comprise laser deposition (e.g., pulsed laser deposition [PLD]), sputtering, chemical vapor deposition (CVD), sol-gel processing, etc. Alternatively, the cathode may be formed by selective deposition. Selective deposition may comprise screen printing, inkjet printing, spray coating, or extrusion coating (e.g., using an ink comprising one or more sol-gel precursors and one or more solvents, having a viscosity appropriate for the printing or coating technique).
In other or further embodiments, forming the electrolyte may comprise depositing a lithium phosphorus oxynitride (LiPON) layer or a tungsten oxide layer of the formula WO3+x(0≤x≤1). The LiPON layer may be deposited by RF sputtering or atomic layer deposition (ALD). The tungsten oxide layer may be deposited by sputtering, optionally using pulsed DC power, in an oxygen or oxygen-containing atmosphere. In embodiments in which the electrolyte comprises the tungsten oxide layer, forming the electrolyte may further comprise lithiating and thermally annealing the WO3+x. Lithiating may comprise wet lithiation or dry lithiation. Thermal annealing may comprise heating at a temperature of 150-500° C. for a length of time of 5-240 minutes in a conventional oven, a vacuum oven, or a furnace.
In certain embodiments, forming the cathode and forming the solid-state electrolyte may comprise blanket-depositing the cathode as a first layer and blanket-depositing the solid-state electrolyte as a second layer.
In some embodiments, forming the anode current collector may comprise selectively depositing the anode current collector in a predetermined area of the solid-state electrolyte. For example, selectively depositing the anode current collector may comprise screen printing, inkjet printing, or spray coating the anode current collector.
In other or further embodiments, the encapsulation covers all front, back and exposed side surfaces of all cells. In various examples, the encapsulation may be formed by pyrolysis, thermal CVD, ALD, inkjet printing, or screen printing. The via or opening may be formed by (i) laser ablation or (ii) photolithographic masking and etching, for example.
In various embodiments, forming the redistribution layer may comprise sputtering, thermally evaporating, or blanket-depositing the redistribution layer, photolithographically patterning a photoresist on the redistribution layer, and etching the redistribution layer. However, instead of sputtering, thermally evaporating, or blanket-depositing the redistribution layer, the redistribution layer may be deposited by ALD. Alternatively, forming the redistribution layer may comprise selectively depositing the redistribution layer, such as by inkjet printing, aerosol-jet printing or screen printing. As for the present solid-state battery, the redistribution layer comprises an air- and/or water-stable metal. For example, the air- and/or water-stable metal may comprise Cu, Ni or Al.
A further aspect of the present invention concerns a method of making a stacked solid-state battery. Such a method comprises the method of making the battery cell, conducted a plurality of times (simultaneously and/or in sequence) to form a plurality of the battery cells, stacking a subset of the plurality of the battery cells so that the first sidewall of each battery cell is on a first side of a resulting stack of the battery cells, and depositing a conductor on each of the first side and a second, opposite side of the resulting stack to form first and second terminals of the stacked solid-state battery.
In most embodiments, the plurality of battery cells forms an array of the battery cells (e.g., having a plurality of rows and/or a plurality of columns), and the method may further comprise, before encapsulating the substrate, the cathode, the solid-state electrolyte, and the anode current collector, cutting or dicing the array to form columns or rows of isolated battery cell pairs having sidewalls that fully expose the cathode, the substrate, and the solid-state electrolyte. Such embodiments may further comprise singulating the cells in the columns or rows of isolated cell pairs. For example, singulating the cells may comprise laser dicing, mechanical dicing or stamping (e.g., the array or the columns or rows of isolated cell pairs, in spaces between adjacent ones of the battery cells).
In various embodiments, stacking the subset of the plurality of the battery cells may form a multi-layer set of parallel cells with edges of the CCCs along the first side of the resulting stack, and the redistribution layers along the second, opposite side of the resulting stack. In other or further embodiments, the method may further comprise placing a dummy cell (as described for the present solid-state battery) on an uppermost surface of the resulting stack. Thus, the dummy cell may comprise a metal foil substrate encapsulated with an encapsulant, as described herein, and the dummy cell may be configured to protect the resulting stack from externally-caused damage and/or to provide a barrier to ingress of moisture and air.
The multi-cell architecture and method allow for high flexibility in customizing for specific three-dimensional (x-y-z) form factors. This and other capabilities and advantages of the present invention will become readily apparent from the detailed description of various embodiments below.
Reference will now be made in detail to various embodiments of the invention, examples of which are illustrated in the accompanying drawings. While the invention will be described in conjunction with the following embodiments, it will be understood that the descriptions are not intended to limit the invention to these embodiments. On the contrary, the invention is intended to cover alternatives, modifications and equivalents that may be included within the spirit and scope of the invention. Furthermore, in the following detailed description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. However, it will be readily apparent to one skilled in the art that the present invention may be practiced without these specific details. In other instances, well-known methods, procedures and components have not been described in detail so as not to unnecessarily obscure aspects of the present invention. Furthermore, it should be understood that the possible permutations and combinations described herein are not meant to limit the invention. Specifically, variations that are not inconsistent may be mixed and matched as desired.
The technical proposal(s) of embodiments of the present invention will be fully and clearly described in conjunction with the drawings in the following embodiments. It will be understood that the descriptions are not intended to limit the invention to these embodiments. Based on the described embodiments of the present invention, other embodiments can be obtained by one skilled in the art without creative contribution and are in the scope of legal protection given to the present invention.
Furthermore, all characteristics, measures or processes disclosed in this document, except characteristics and/or processes that are mutually exclusive, can be combined in any manner and in any combination possible. Any characteristic disclosed in the present specification, claims, Abstract and Figures can be replaced by other equivalent characteristics or characteristics with similar objectives, purposes and/or functions, unless specified otherwise.
For the sake of convenience and simplicity, the term “length” generally refers to the largest dimension of a given 3-dimensional structure or feature. The term “width” generally refers to the second largest dimension of a given 3-dimensional structure or feature. The term “thickness” generally refers to a smallest dimension of a given 3-dimensional structure or feature. The length and the width, or the width and the thickness, may be the same in some cases. A “major surface” refers to a surface defined by the two largest dimensions of a given structure or feature, which in the case of a structure or feature having a circular surface, may be defined by the radius of the circle.
In addition, for convenience and simplicity, the terms “part,” “portion,” and “region” may be used interchangeably but these terms are also generally given their art-recognized meanings. Also, unless indicated otherwise from the context of its use herein, the terms “known,” “fixed,” “given,” “certain” and “predetermined” generally refer to a value, quantity, parameter, constraint, condition, state, process, procedure, method, practice, or combination thereof that is, in theory, variable, but is typically set in advance and not varied thereafter when in use.
The present invention concerns a solid-state battery cell, a stacked solid-state battery, and methods of making the same. The present solid-state battery cell is an intrinsic anode-less battery, including a substrate, a cathode on the substrate, a solid-state electrolyte (SSE) on the cathode, and an anode current collector (ACC) on the SSE. The substrate, which generally comprises a metal foil, serves as the cathode current collector (CCC). Due to its anode-less nature, a conventional lithium anode may not be present between the SSE and ACC.
The following discussion provides examples of solid-state and/or thin film batteries, stacked solid-state batteries, and general manufacturing processes for such batteries.
An Exemplary Method of Making a Battery Stack with a Multi-Layer Solid-State Electrolyte
The barrier 115a-b comprises one or more layers of one or more materials in a thickness effective to prevent migration of atoms or ions from the metal foil, sheet or film 110 into overlying layers. The barrier material(s) may comprise a glass or ceramic, such as silicon dioxide, aluminum oxide, silicon nitride, a silicon and/or aluminum oxynitride, etc., or a (refractory) metal nitride, such as aluminum nitride, titanium nitride, titanium aluminum nitride, tungsten nitride, titanium tungsten nitride, TiW alloy, tantalum nitride, etc. In some embodiments, each of the first and second barriers 115a-b comprises alternating glass/ceramic and metal nitride layers (e.g., a first metal nitride layer, a first glass/ceramic layer, and a second metal nitride layer, which may further comprise a second glass/ceramic layer, a third metal nitride layer, etc.). Each barrier 115a or 115b may have a total thickness of 0.5-3 μm, but the barrier 115 is not limited to this range. The barriers 115a-b may be blanket-deposited onto the foil, sheet or film 110 by chemical or physical vapor deposition (e.g., sputtering, thermal evaporation, atomic layer deposition [ALD], etc.), solution-phase coating with a precursor material followed by annealing to form the glass/ceramic or metal nitride, etc. Exemplary barrier materials, structures and thicknesses and methods for their deposition are disclosed in U.S. Pat. No. 9,299,845 and U.S. patent application Ser. No. 16/659,871, filed Oct. 22, 2019 (Atty. Docket No. IDR5090), the relevant portions of each of which are incorporated by reference herein.
In some embodiments, the foil, sheet or film 110 functions as a cathode current collector. In such embodiments, at least the barrier 115a (and optionally the barrier 115b) is a conductive, amorphous material, such as the metal nitrides listed above or an amorphous metal alloy (e.g., a TiW alloy).
Forming the electrolyte 140 may comprise depositing a LiPON layer or a tungsten oxide layer of the formula WO3+x (0≤x≤1) by sputtering, optionally using pulsed DC power. When the electrolyte 130 comprises LiPON, it may be deposited by RF sputtering or ALD. The sputtering target may comprise a Li3PO4 or mixed graphite-Li3PO4 target, the latter of which may contain 1-15 wt % of graphite, when the electrolyte 130 comprises LiPON or carbon-doped LiPON, and a metallic/elemental tungsten target when the electrolyte 130 comprises a tungsten oxide. In the latter case, sputtering is performed in an oxygen or oxygen-containing atmosphere. The method of making the electrolyte 130 may further comprise lithiating and thermally annealing the WO3+x, which can transform it into Li2WO4, a good Li-ion conductor. Lithiating may comprise wet lithiation (e.g., immersing the WO3+x in a solution containing a lithium electrolyte such as LiClO4, LiPF6, LiBF4, etc., and applying an appropriate electric field) or dry lithiation (e.g., sputtering or thermally evaporating elemental lithium onto the tungsten oxide in a vacuum chamber, optionally while heating the substrate 100). Thermal annealing may comprise heating at a temperature of 150-500° C. for a length of time of 5-240 minutes, or any temperature or length of time therein (e.g., 250-450° C. for 10-120 minutes), in a conventional oven, a vacuum oven, or a furnace. To ensure substantially complete diffusion of the lithium into and/or throughout the WO3+x, the WO3+x should be annealed (preferably in air) at a temperature of at least 100° C. for at least 10 minutes (e.g., to transform it into Li2WO4).
The anode current collectors 140a-d generally comprise a conductive metal, such as nickel, zinc, copper, alloys thereof (e.g., NiV), etc., or another conductor, such as graphite. The anode current collectors 140a-d can be selectively deposited by screen printing, inkjet printing, spray coating, etc., or formed by blanket deposition (e.g., sputtering or evaporation) and patterning (e.g., low-resolution photolithography, development and etching). The anode current collectors 140a-d may have a thickness of 0.1-5 μm, although it is not limited to this range.
The anode current collectors 140a-d may have area dimensions (i.e., length and width dimensions) that are 50-95% of the corresponding length and width dimensions, respectively, of the cell (see e.g.,
The cells may further include one or more interlayers that modify the interfaces between layers. For example, a metal oxide (e.g., Nb2O5, Al2O3, Li4Ti5O12 or LiNbO3) interlayer may be formed on the cathode 120 prior to deposition of the electrolyte 130 (e.g., to reduce interfacial stress, decrease interfacial resistance, or suppress formation of a space charge layer). An amorphous (e.g., elemental silicon) interlayer may be deposited on the electrolyte 130 prior to formation of the anode current collectors 140a-d to inhibit reduction of the electrolyte. Of course, the battery cell can be made in the reverse order (i.e., the anode current collector may be first formed on the substrate, then the remaining layers deposited in reverse order thereon).
An advantage of the present method is that some/all of the active battery layers (e.g., the cathode 120 and the solid-state electrolyte 130) are deposited as blanket layers. This maximizes the active area utilization of the battery cells for high intrinsic capacity, and also results in a topographically planar or “flat” cell to facilitate formation of the uppermost layer(s) and downstream packaging due to the pattern-free blanket-deposited layers. However, if necessary or desired, the cathode 120 and the SSE 130 can be slightly pulled back from the cell edge by subtractive patterning (e.g., low-resolution photolithography, laser ablation) or selective deposition (as described herein).
Referring to
As shown in
Cell stacking may comprise a conventional pick-and-place technique. However, other stacking methods, such as strip folding, strip stacking, etc. (see, e.g., U.S. patent application Ser. No. 17/185,122, filed Feb. 25, 2021 [Attorney Docket No. IDR2020-02], the relevant portions of which are incorporated herein by reference), before or after dicing are also acceptable. A dummy cell 210 (e.g., a metal foil substrate encapsulated as described with respect to
Battery terminal dipping and plating the stacked set of cells 200 forms external electrical contacts 230a-b, as shown in
An Exemplary Stacked Solid-State Battery
In some embodiments, a thin stainless-steel (SS) substrate 110 serves as the cathode current collector. In such embodiments, there is no need for a separate CCC layer, which consumes space in the battery 250 and increases complexity of the method of making the battery. SS is mechanically strong, and therefore, its thickness can be minimized (e.g., to 3-50 μm) to maximize cell energy density. The substrate 110 can be further encapsulated by a barrier metal 115a-b to suppress diffusion between the substrate and the cathode 120 (as well as any overlying layer).
In some embodiments, the present battery 250 includes an anode-free ACC 140, which may be defined with minimal pull-back from the cell edges. This design also maximizes area utilization. Furthermore, the use of underlying blanket cathodes 120 and solid-state electrolytes 130 result in a flat or planar ACC over the other battery layers, which minimizes mechanical stresses from Li plating and/or stripping during cell cycling.
The present solid-state battery and method are unique from previous solutions, and have the following differentiation(s):
The foregoing descriptions of specific embodiments of the present invention have been presented for purposes of illustration and description. They are not intended to be exhaustive or to limit the invention to the precise forms disclosed, and obviously many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and its practical application, to thereby enable others skilled in the art to best utilize the invention and various embodiments with various modifications as are suited to the particular use contemplated.
This application claims the benefit of U.S. Provisional Pat. Appl. No. 63/343,526, filed May 18, 2022, pending, incorporated herein by reference in its entirety.
| Number | Date | Country | |
|---|---|---|---|
| 63343526 | May 2022 | US |
