Embodiments of the present disclosure relate generally to electrochemical devices and more specifically, although not exclusively, to electrochemical device stacks including an interlayer for reducing the resistance and over-potential at the interfaces with an electrode and a solid state electrolyte.
Electrochemical devices such as thin film batteries (TFBs) and electrochromic devices (EC) include a thin film stack of layers including current collectors, a cathode (positive electrode), a solid state electrolyte and an anode (negative electrode).
The performance of these electrochemical devices is dependent on the ease of lithium transport through the layers of the stack, which is influenced not only by the impedance of each layer but also by the resistance/impedance at the interfaces between layers. As such, large charge transfer resistance at theses electrode/electrolyte interfaces in solid state thin film batteries has (or can have) a big impact on the overall lithium transport and therefore the battery performance, where some of the performance factors would be power capability and capacity utilization.
Clearly, there is a need for device structures and methods of manufacture that effectively reduce the interfacial resistance in these electrochemical devices in order to promote lithium transport through the interfaces.
The present disclosure relates, in general, to the introduction of interlayers between an electrode and the solid state electrolyte in electrochemical devices such as thin film batteries (TFBs), electrochromic (EC) devices, etc., in order to reduce the interfacial resistance and over-potential for promoting ion transport, such as lithium ion transport, through certain of the interfaces in the device stack.
According to some embodiments, a thin film electrochemical device may comprise: a first electrode layer comprising a first electrode material; an electrolyte layer, the electrolyte layer comprising an electrolyte material; a second electrode layer, the second electrode layer comprising a second electrode material; and at least one interlayer between and in contact with at least one of (a) the first electrode layer and the electrolyte layer and (b) the second electrode layer and the electrolyte layer; wherein the interlayer comprises an interlayer material characterized by (1) the interlayer material does not affect charge carrier intercalation/de-intercalation at interfaces between the electrolyte layer and either or both of the first and second electrode layers, (2) the interlayer material reduces resistance and over-potential at interfaces between the electrolyte layer and either or both of the electrode layers; (3) the electromotive force (emf) of the interlayer material compared with lithium metal is lower than the emf of the first or second electrode material versus lithium metal; and (4) as deposited, the interlayer material is an ion conductor, such as a lithium ion conductor.
According to some embodiments, a method of making a thin film electrochemical device may comprise: depositing a device stack comprising a first electrode layer, an electrolyte layer, a second electrode layer and at least one interlayer, the at least one interlayer being deposited on at least one of (a) the first electrode layer, wherein the electrolyte layer is deposited on the at least one interlayer, and (b) the electrolyte layer, wherein the second electrode layer is deposited on said at least one interlayer; wherein the at least one interlayer comprises an interlayer material characterized by (1) the interlayer material does not affect charge carrier intercalation/de-intercalation at interfaces between the electrolyte layer and either or both of the first and second electrode layers, (2) the interlayer material reduces resistance and over-potential at interfaces between the electrolyte layer and either or both of the electrode layers; (3) the electromotive force (emf) of the interlayer material compared with lithium metal is lower than the emf of the first or second electrode material versus lithium metal; and (4) as deposited, the interlayer material is an ion conductor, such as a lithium ion conductor.
According to further embodiments an apparatus for manufacturing electrochemical devices may comprise: a system for depositing a device stack comprising a first electrode layer, an electrolyte layer, a second electrode layer and at least one interlayer, the at least one interlayer being deposited on at least one of (a) the first electrode layer, wherein one of the at least one interlayer is between and in contact with the first electrode layer and the electrolyte layer, and (b) the electrolyte layer, wherein one of the at least one interlayer is between and in contact with the electrolyte layer and the second electrode layer; wherein the at least one interlayer comprises an interlayer material characterized by (1) the interlayer material does not affect charge carrier intercalation/de-intercalation at interfaces between the electrolyte layer and either or both of the first and second electrode layers, (2) the interlayer material reduces resistance and over-potential at interfaces between the electrolyte layer and either or both of the electrode layers; (3) the electromotive force (emf) of the interlayer material compared with lithium metal is lower than the emf of the first or second electrode material versus lithium metal; and (4) as deposited, the interlayer material is an ion conductor, such as a lithium ion conductor.
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.
The present disclosure describes electrochemical device structures and methods of fabricating the electrochemical devices including one or more thin interlayers between an electrode (positive and/or negative) and the solid state electrolyte (LiPON, for example), for reducing the resistance and over-potential at the interfaces with the electrode and the solid state electrolyte. Furthermore, the device may include an interlayer comprising a multiplicity of layers of different materials between an electrode and the electrolyte in order to create a “cascading” chemical potential through the interlayer.
According to embodiments the TFB device of
An electrochromic (EC) device 200 is represented in
According to embodiments the electrochromic device of
Furthermore, the process flow may be described as a method of making a thin film electrochemical device comprising: depositing a device stack comprising, in order, a first electrode layer, an electrolyte layer, and a second electrode layer; and depositing at least one interlayer, the interlayer being deposited in the stack either on the first electrode layer or on the electrolyte layer. As above, the process may further include depositing multiple layers of different materials on top of each other between an electrode layer and the electrolyte layer in order to create a “cascading” chemical potential through the interlayer.
An example of a cathode layer is a LiCoO2 layer, of a anode layer is a Li metal layer, 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, Al, Sn, etc. may be used, and a wide range of lithium-conducting electrolyte materials such as LLZO (LiLaZr oxide), LiSiCON, 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. The deposition method can also be non-vacuum based, such as plasma spray, spray pyrolysis, slot die coating, screen printing, etc. The materials of the interlayer can be selected from metal oxides such as TiO2, Ta2O5, ZrO2, ZnO, SnO2, Al2O3 and including cathodically active battery materials (e.g. materials with a lower chemical potential than the cathode) such as TiOx, TiS2, etc., where the interlayer materials satisfy the following criteria:
1) the interlayer material does not affect Li intercalation/de-intercalation at either interface;
2) the interlayer material reduces resistance and overpotential at interfaces between the interlayer and both the electrode layer and the electrolyte layer;
3) for an interlayer between a lithium-containing cathode layer and an electrolyte layer, the electromotive force of the interlayer material compared with lithium metal is lower than the emf of the host cathode material versus lithium metal;
4) for an interlayer between an anode layer and an electrolyte layer, the electromotive force of the interlayer material compared with lithium metal is lower than the emf of the host anode material versus lithium metal; and
5) the interlayer material as deposited is an ion conductor, such as a lithium ion conductor, and is generally an electron conductor, although in embodiments the interlayer may be electrically non-conductive when thin enough for electron tunneling.
Furthermore, it is expected that performance of a particular interlayer composition will be strongly dependent on good control over the composition, phase and crystallinity of the interlayer.
The thickness of the interlayer in embodiments may be in the range of 3 nm-200 nm, and in some embodiments the thickness may be in the range of 10 nm-50 nm. While the demonstration of the concept was with a PVD (physical vapor deposition) sputtered interlayer, it is expected that the concept is agnostic to the method of deposition—for example the deposition technique for the interlayer may be any deposition technique that is capable of providing the desired composition, phase and crystallinity, and may include deposition techniques such as PVD, reactive sputtering, non-reactive sputtering, RF (radio frequency) sputtering, multi-frequency sputtering, evaporation, CVD (chemical vapor deposition), ALD (atomic layer deposition), etc.. The deposition method can also be non-vacuum based, such as plasma spray, spray pyrolysis, slot die coating, screen printing, etc. Also, the demonstration was with a single interlayer, but one can conceive of multiple interlayers creating a “cascading” chemical potential through the interlayers between the electrode layer and the electrolyte layer—for example, between the electrode layer and the electrolyte there may be a layer of Ta2O5, then a layer of TiS2 and then a layer of TiOx.
With the addition of a TiOx interlayer, the interfacial resistance between a LiCoO2 cathode layer and a LiPON electrolyte layer, appears to be reduced, as shown in the Table below. Furthermore,
It is expected that embodiments of the present disclosure will be well suited for use with solid state batteries with higher voltage cathodes/positive electrolyte layers, such as LiCoO2 and LiPON, providing improved performance as measured by capacity utilization, rate capability and/or cycle life, for example.
In order to illustrate the movement of a substrate through an in-line fabrication system such as shown in
An apparatus for manufacturing electrochemical devices may comprise: a system for depositing a device stack comprising a first electrode layer, an electrolyte layer, a second electrode layer and at least one interlayer, the at least one interlayer being deposited on at least one of (a) the first electrode layer, wherein one of the at least one interlayer is between and in contact with the first electrode layer and the electrolyte layer, and (b) the electrolyte layer, wherein one of the at least one interlayer is between and in contact with the electrolyte layer and the second electrode layer; wherein the at least one interlayer comprises an interlayer material characterized by (1) the interlayer material does not affect charge carrier intercalation/de-intercalation at interfaces between the electrolyte layer and either or both of the first and second electrode layers, (2) the interlayer material reduces resistance and over-potential at interfaces between the electrolyte layer and either or both of the electrode layers; (3) the electromotive force (emf) of the interlayer material compared with lithium metal is lower than the emf of the first or second electrode material versus lithium metal; and (4) as deposited, the interlayer material is an ion conductor, such as a lithium ion conductor. Furthermore, in embodiments the system may further deposit current collector layers and protective coatings. The system may be a cluster tool, an in-line tool, stand-alone tools, or a combination of one or more of the aforesaid tools.
Although embodiments of the present disclosure have been particularly described with reference to lithium ion electrochemical devices, the teaching and principles of the present disclosure may also be applied to electrochemical devices based on transport of other ions, such as protons, sodium ions, etc.
Although embodiments of the present disclosure have been particularly described with reference to TFB devices, the teaching and principles of the present disclosure may also be applied to various electrochemical devices including electrochromic devices, electrochemical sensors, electrochemical capacitors, etc.
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. 62/043,261, filed Aug. 28, 2014,
Filing Document | Filing Date | Country | Kind |
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PCT/US2015/047418 | 8/28/2015 | WO | 00 |
Number | Date | Country | |
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62043261 | Aug 2014 | US |