Embodiments of the present disclosure relate generally to thin film batteries and methods of making the same, and more specifically, although not exclusively, to thin film batteries with the surface of one of the substrate and cathode current collector being three-dimensionally restructured by a laser process.
Thin film batteries (TFBs) may comprise a thin film stack of layers including current collectors, a cathode (positive electrode), a solid state electrolyte and an anode (negative electrode). A TFB is generally fabricated as a two dimensional (2D) device and the battery performance (e.g., rate capability and capacity utilization) is limited by the surface area of the cathode-electrolyte and anode-electrolyte interfaces through which Li must diffuse during the intercalation/deintercalation processes. Furthermore, TFBs are known to exhibit peeling/delamination at various interfaces and at various stages of fabrication and operation, such as after cathode annealing, after electrolyte deposition, after anode deposition, after encapsulation deposition, or during battery cycle testing.
Clearly, there is a need for TFB structures and methods of manufacture that induce greater adhesion strength between layers in the TFB stack, and provide a larger interfacial surface area between the cathode and the electrolyte and/or the anode and the electrolyte in order to improve battery performance.
Some embodiments of the present disclosure relate to thin film batteries (TFBs) with the surface of one of the substrate and current collector being three-dimensionally restructured by a laser process during battery thin film stack fabrication, followed by depositions of subsequent layers such that the interfacial contact area between the cathode/anode and the electrolyte is a three-dimensional surface roughly in conformity with the three-dimensionally restructured surface of the substrate/current collector. The resulting three-dimensionally structured interfaces between the cathode/anode layer(s) and the electrolyte layer are expected to improve TFB performance (e.g., rate capability and capacity utilization) and increase adhesion strength between layers within the TFB stack sufficiently to reduce peeling/delamination, when compared with a TFB stack having planar interfacial layers.
According to some embodiments, a thin film battery may comprise: a substrate comprising a substrate surface; a first current collector (FCC) layer formed on the substrate surface, the FCC layer having a first FCC surface and a second FCC surface and wherein the first FCC surface is in contact with the substrate and the second FCC surface is a first three-dimensional surface; a first electrode layer deposited on the first current collector, and an electrolyte layer deposited on the first electrode layer; wherein the interface between the first electrode layer and the electrolyte layer is a second three-dimensional surface roughly in conformity with the first three-dimensional surface. Furthermore, in embodiments, the substrate surface is a third three-dimensional surface and said first three-dimensional surface is roughly in conformity with said third three-dimensional surface.
According to some embodiments, a method of making the thin film battery may comprise: providing a substrate; three-dimensionally restructuring the surface of the substrate to form a restructured substrate surface; depositing a first current collector (FCC) layer on the restructured substrate surface; depositing an electrode layer on the FCC layer; and depositing an electrolyte layer on the electrode layer; wherein the interface between the electrode layer and the electrolyte layer is a first three-dimensional surface roughly in conformity with the restructured substrate surface.
According to some further embodiments, a method of making the thin film battery may comprise: providing a substrate; depositing a first current collector (FCC) layer on the surface of the substrate; three-dimensionally restructuring the surface of the FCC layer to form a restructured FCC surface; depositing a first electrode layer on the restructured FCC surface; and depositing an electrolyte layer on the first electrode layer; wherein the interface between the first electrode layer and the electrolyte layer is a first three-dimensional surface roughly in conformity with the restructured FCC surface.
According to some embodiments, an apparatus for manufacturing TFBs according to some embodiments may include: a first system for three-dimensionally restructuring the surface of a substrate to form a restructured substrate surface; a second system for depositing a first current collector (FCC) layer on the restructured substrate surface; a third system for depositing an electrode layer on the FCC layer; and a fourth system for depositing an electrolyte layer on the electrode layer; wherein the interface between the electrode layer and the electrolyte layer is a first three-dimensional surface roughly in conformity with the restructured substrate surface. The first system may comprise, for example, a laser ablation patterning system, in embodiments an ion sputtering system, and in embodiments a mechanical roughening system (such as a bead blaster).
According to some further embodiments, an apparatus for manufacturing TFBs according to some embodiments may include: a first system for depositing a first current collector (FCC) layer on the surface of a substrate; a second system for three-dimensionally restructuring the surface of the FCC layer to form a restructured FCC surface; a third system for depositing a first electrode layer on the restructured FCC surface; and a fourth system for depositing an electrolyte layer on the first electrode layer; wherein the interface between the first electrode layer and the electrolyte layer is a first three-dimensional surface roughly in conformity with the restructured FCC surface. The second system may comprise, for example, a laser ablation patterning system, in embodiments an ion sputtering system, and in embodiments a mechanical roughening system (such as a bead blaster).
These and other aspects and features of the present disclosure will become apparent to those ordinarily skilled in the art upon review of the following description of specific embodiments in conjunction with the accompanying figures, wherein:
Embodiments of the present disclosure will now be described in detail with reference to the drawings, which are provided as illustrative examples of the disclosure so as to enable those skilled in the art to practice the disclosure. Notably, the figures and examples below are not meant to limit the scope of the present disclosure to a single embodiment, but other embodiments are possible by way of interchange of some or all of the described or illustrated elements. Moreover, where certain elements of the present disclosure can be partially or fully implemented using known components, only those portions of such known components that are necessary for an understanding of the present disclosure will be described, and detailed descriptions of other portions of such known components will be omitted so as not to obscure the disclosure. In the present specification, an embodiment showing a singular component should not be considered limiting; rather, the disclosure is intended to encompass other embodiments including a plurality of the same component, and vice-versa, unless explicitly stated otherwise herein. Moreover, applicants do not intend for any term in the specification or claims to be ascribed an uncommon or special meaning unless explicitly set forth as such. Further, the present disclosure encompasses present and future known equivalents to the known components referred to herein by way of illustration.
Some embodiments of the present disclosure relate to thin film batteries (TFBs) with the surface of one of the substrate and cathode current collector (CCC) being three-dimensionally restructured by a laser process during battery thin film stack fabrication, followed by depositions of subsequent layers such that the interfacial contact area between the cathode and the electrolyte is a three-dimensional surface roughly in conformity with the three-dimensionally restructured surface of the substrate/CCC. Furthermore, in some embodiments the electrolyte-anode and anode-ACC interfaces may also be three dimensional surfaces roughly in conformity with the three-dimensionally restructured surface of the restructured substrate/CCC. The resulting three-dimensionally structured interfaces between the cathode layer and the electrolyte layer and the electrolyte layer and the anode layer are expected to improve TFB performance (e.g., rate capability and capacity utilization, especially at higher rates of charging/discharging) and improve interfacial adhesion of layers within the TFB stack sufficiently to reduce peeling/delamination, when compared with a TFB stack having planar interfacial layers. (Roughening of interfaces between layers induces “mechanical wrapping” at the interface for greater adhesion strength.) Moreover, the three-dimensionally structured interface between the cathode layer and the electrolyte layer is expected to increase access to the (003) planes in the polycrystalline grain structures in a LiCoO2 cathode layer at the interface, which reduces resistance to lithium intercalation/deintercalation during battery usage.
Substrate materials that strongly absorb laser energy are suitable for the process described above with reference to
The surface of the CCC may be restructured by a laser process as described in more detail herein, or another process may be used, such as mechanical roughening (e.g. bead blasting), plasma processing and ion bombardment, for example. Note that some of these other processes which are non-thermal may be suitable for three dimensionally restructuring the cathode and/or electrolyte surfaces, where the phase and crystallinity of the cathode and/or electrolyte needs to be preserved.
Cathode current collectors are typically formed of metal layers deposited to a thickness of about 0.5 microns or greater and strongly absorb laser energy and are suitable for the process described above with reference to
It should be noted that substrate and CCC surfaces can be restructured using traditional mask imaging followed by wet and/or plasma etch. However, this approach is only readily available for use with a limited number of materials, such as silicon, for example, and involves multiple steps and adds significant cost to the fabrication of TFB products, when compared to the process of the embodiments disclosed herein. Furthermore, laser restructuring of LiCoO2 cathode layers prior to electrolyte deposition has been evaluated by the inventors and it has been determined that laser restructuring of LiCoO2 cathode layers results in phase separation of the LiCoO2 layer into high temperature (HT) LCO and Co3O4, which overall negatively affects battery performance and as such is highly undesirable for thin cathode TFBs. (The impurity phase Co3O4 is detrimental to battery charge capacity and also to cycle life.)
An example of a cathode layer is a LiCoO2 layer, of an anode layer is a Li metal layer, and of an electrolyte layer is a LiPON layer. However, it is expected that a wide range of cathode materials such as NMC (NiMnCo oxide), NCA (NiCoAl oxide), LMO (LixMnO2), LFP (LixFePO4), LiMn spinel, etc. may be used, a wide range of anode materials such as Si, Sn, C, etc. may be used, and a wide range of lithium-containing electrolyte materials such as LLZO (LiLaZr oxide, such as Li7La3Zr2O12), LiSiCON, Ta2O5, etc. may be used. Deposition techniques for these layers may be any deposition technique that is capable of providing the desired composition, phase and crystallinity, and may include deposition techniques such as PVD (physical vapor deposition), reactive sputtering, non-reactive sputtering, RF (radio frequency) sputtering, multi-frequency sputtering, evaporation, CVD (chemical vapor deposition), ALD (atomic layer deposition), etc. and when non-vacuum techniques are applicable, may also include slot die coating, plasma spray, spray pyrolysis, electroplating, slurry based screening, etc.
In order to illustrate the movement of a substrate through an in-line fabrication system such as shown in
Some examples of apparatus for fabricating TFBs according to certain embodiments are as follows. An apparatus for manufacturing TFBs according to some embodiments may include: a first system for three-dimensionally restructuring the surface of a substrate to form a restructured substrate surface; a second system for depositing a first current collector (FCC) layer on the restructured substrate surface; a third system for depositing an electrode layer on the FCC layer; and a fourth system for depositing an electrolyte layer on the electrode layer; wherein the interface between the electrode layer and the electrolyte layer is a first three-dimensional surface roughly in conformity with the restructured substrate surface. The first system may comprise, for example, a laser ablation patterning system, in embodiments an ion sputtering system, and in embodiments a mechanical roughening system (such as a bead blaster). Furthermore, in embodiments the apparatus may further comprise: a fifth system for depositing a second electrode layer on the electrolyte layer; wherein the fourth system deposits the electrolyte layer, and wherein the interface between the electrolyte layer and the second electrode layer is a second three-dimensional surface roughly in conformity with the restructured substrate surface. The systems may be cluster tools, in-line tools, stand-alone tools, or a combination of one or more of the aforesaid tools. Furthermore, the systems may include some tools which are common to one or more of the other systems.
Another apparatus for manufacturing TFBs according to some embodiments may include: a first system for depositing a first current collector (FCC) layer on the surface of a substrate; a second system for three-dimensionally restructuring the surface of the FCC layer to form a restructured FCC surface; a third system for depositing a first electrode layer on the restructured FCC surface; and a fourth system for depositing an electrolyte layer on the first electrode layer; wherein the interface between the first electrode layer and the electrolyte layer is a first three-dimensional surface roughly in conformity with the restructured FCC surface. The second system may comprise, for example, a laser ablation patterning system, in embodiments an ion sputtering system, and in embodiments a mechanical roughening system (such as a bead blaster). Furthermore, in embodiments the apparatus may further comprise: a fifth system for depositing a second electrode layer on the electrolyte layer; wherein the interface between the electrolyte layer and the second electrode layer is a second three-dimensional surface roughly in conformity with the restructured FCC surface. The systems may be cluster tools, in-line tools, stand-alone tools, or a combination of one or more of the aforesaid tools. Furthermore, the systems may include some tools which are common to one or more of the other systems.
Although embodiments of the present disclosure have been particularly described with reference to restructuring of either the substrate or the CCC surface, further embodiments include applying the same approach to directly restructuring one or more of the different interfaces on the anode-side of the TFB after electrolyte deposition. (This process may also be done in combination with restructuring of substrate or CCC surfaces.) For example, the surface of the electrolyte layer may be three dimensionally restructured—this process may be suitable for crystalline electrolyte materials such as LLZO.
Although embodiments of the present disclosure have been particularly described with reference to TFB stacks with CCC deposited on the substrate followed by cathode, electrolyte, anode, and then ACC, further embodiments include using the same approach for a TFB stack in which the ACC is deposited on the substrate followed by anode, electrolyte, cathode and CCC, wherein the substrate and/or ACC is three dimensionally restructured as described above, and the surfaces of one or more subsequently deposited layers will also be three dimensional surfaces roughly in conformity with the three-dimensionally restructured substrate and/or CCC surface.
Although embodiments of the present disclosure have been particularly described with reference to TFBs, the principles and teaching of the present disclosure may be applied to other electrochemical devices, including energy storage devices generally, and also to electrochromic devices. It should be noted that in the case of electrochromic devices interface roughening may lead to undesired diffuse scattering and a device with an undesirable “hazy” appearance, although the roughened interface may improve the device speed; for certain applications the trade-off between optical quality and device speed may be worthwhile, and furthermore the interface roughness may be designed to provide an improvement in speed while not unduly degrading the optical appearance.
Although embodiments of the present disclosure have been particularly described with reference to TFBs with a first current collector layer on the surface of a substrate, the principles and teaching of the present disclosure may be applied to certain TFBs without a current collector layer on the surface of the substrate—for example, TFBs with electrically conductive substrates. In embodiments a thin film battery may comprise: a substrate comprising a substrate surface, wherein the substrate surface is a first three-dimensional surface; a first electrode layer deposited on the substrate, and an electrolyte layer deposited on the first electrode layer; wherein the interface between the first electrode layer and the electrolyte layer is a second three-dimensional surface roughly in conformity with the first three-dimensional surface. According to some embodiments, a method of making the thin film battery may comprise: providing a substrate; three-dimensionally restructuring the surface of the substrate to form a restructured substrate surface; depositing an electrode layer on the restructured substrate surface; and depositing an electrolyte layer on the electrode layer; wherein the interface between the electrode layer and the electrolyte layer is a first three-dimensional surface roughly in conformity with the restructured substrate surface. According to some embodiments, an apparatus for manufacturing TFBs according to some embodiments may include: a first system for three-dimensionally restructuring the surface of a substrate to form a restructured substrate surface; a second system for depositing an electrode layer on the restructured substrate surface; and a third system for depositing an electrolyte layer on the electrode layer; wherein the interface between the electrode layer and the electrolyte layer is a first three-dimensional surface roughly in conformity with the restructured substrate surface.
Although embodiments of the present disclosure have been particularly described with reference to certain embodiments thereof, it should be readily apparent to those of ordinary skill in the art that changes and modifications in the form and details may be made without departing from the spirit and scope of the disclosure.
This application claims the benefit of U.S. Provisional Application No. 62/042,557 filed Aug. 27, 2014.
Filing Document | Filing Date | Country | Kind |
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PCT/US15/47286 | 8/27/2015 | WO | 00 |
Number | Date | Country | |
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62042577 | Aug 2014 | US |