TW201717462A - Adhesion promotion in electrochemical devices - Google Patents

Abstract

A thin film battery (TFB) may comprise: an adhesion promotion layer on a thin substrate with a substrate thickness in the range of 10 microns to 100 microns, the adhesion promotion layer comprising an electrically insulating material having a thickness in the range of 50 nm to 5,000 nm; a metal adhesion layer on the adhesion promotion layer; a current collector layer on the metal adhesion layer; a cathode layer on the current collector layer; an electrolyte layer on the cathode layer; and an anode layer on the electrolyte layer; wherein the device layers form a stack on the thin substrate; and wherein the adhesion promotion layer prevents cracking of the stack and delamination from the thin substrate of the stack during fabrication of the stack, including annealing of the cathode at a temperature in the range of 500 DEG C to 800 DEG C.

Description

Adhesion enhancement in electrochemical components

The present application claims priority to U.S. Provisional Application No. 62/222,574, filed on Sep. 23, 2015, the content of which is incorporated herein in its entirety. Embodiments of the present disclosure are generally directed to electrochemical components and methods of making such electrochemical components, and more particularly, but not exclusively, to thin film cells having an adhesion promoting layer deposited on a substrate Upper and between the substrate and the collector layer.

A thin film battery (TFB) can include a multilayer film stack comprising an anode current collector and a cathode current collector (ACC and CCC), a cathode (positive electrode), a solid electrolyte, an anode (negative electrode), and an encapsulation layer or package. During the fabrication process of a thin film battery, one of the layers, ie, the positive electrode (referred to herein as a cathode), is typically formed of a material such as lithium cobalt oxide (LCO), which needs to be annealed at a relatively high temperature to form Desirable material properties, such as electrodes having a high percentage (greater than 90%) of high temperature phase LiCoO ₂ (HT-LCO). In order to form a robust and well-functioning component structure, the stresses and (between layers and between the substrates) of the individual layers in the component stack need to be controlled and optimized, especially since the positive electrode experiences this relatively high temperature (eg in Heat treatment in the range of 500 ° C to 800 ° C).

In addition, there is a need to improve component metrics, where energy density in component metrics is one of the key metrics. In order to increase the energy density and further improve the form factor of the thin film solid state battery, the use of a thinner substrate is one of the most effective and necessary methods. However, the use of thinner (e.g., 10 micron to 100 micron thick) substrates presents many challenges in the fabrication of components with desirable operational characteristics and robustness. One of the key issues observed by the inventors of the present invention is, for example, when the elements on the thin substrate are annealed as needed for proper formation of the cathode (LCO layer), poor layer adhesion in the element stack and between the stack and the substrate. . Another problem that arises from thin substrates that are quite flexible when using manipulation is that if the component layer is poorly adhered between layers or between the layers and the substrate, it may break during various stages of component fabrication and even Delamination. This rupture and delamination is visually observable from the top side of the component, and as discussed in more detail below, for a transparent substrate, it can be viewed through the back side of the substrate. Furthermore, cracking and delamination reduce the mechanical yield of TFB at the time of fabrication, as this is due to further stress buildup with additional layers after LCO deposition and annealing. Such stress accumulation that the component does not have good adhesion to the substrate during the fabrication step can even lead to even worse conditions when the component is used in a cycle where the volume change occurs in the component that moves back and forth between the cathode and the anode. As used herein, "mechanical yield" refers to the mechanical stability of an electrochemical cell at the end of fabrication and after the minimum cycle of use.

An example of such a thin substrate is a mica substrate, which is a type of silicate having a layered or sheet-like structure and which can be easily separated into very thin layers (125 to 25 micrometers or less, down to 10 micrometers). Acid salt) mineral. Mica is chemically inert, elastic, flexible, and electrically insulating. Unless a high temperature process above about 500 ° C to 600 ° C is required, mica is a substrate suitable for thin film batteries, and the inventors have observed a tendency for the element layer to peel and delaminate from the substrate at temperatures above about 500 ° C to 600 ° C. This limits the use of mica substrates for the manufacture of high quality batteries because of the typical cathode materials (eg LCO) in order to obtain cathode materials with a purer phase and greater crystallinity (greater than 90% HT-LCO) and good cell performance. The annealing temperature may need to be higher than 600 °C. This is especially true if the LCO deposition rate is extremely high in order to reduce the cost of ownership.

Another example of a thin substrate is a polycrystalline ceramic substrate such as yttria stabilized zirconia (YSZ). Although the YSZ substrates can withstand much higher thermal budgets than mica, for example including annealing over 600 ° C, the inventors have found that the adhesion between the substrate and the component stack may not be satisfactory and results in mechanical stability. Sexual problem.

Another example of a thin substrate is a glass substrate having a relatively high glass transition temperature, such as above the annealing temperature, and in some embodiments greater than 700 °C. Examples of such glasses include aluminoborosilicate glass having a glass transition temperature of 717 ° C and an alkaline earth boroaluminosilicate glass having a glass transition temperature of about 700 ° C. On these substrates, the inventors of the present invention have found that the adhesion between the substrate and the component stack layer may also be unsatisfactory, leading to problems in component performance and mechanical stability.

Obviously, the fabrication process and the electrochemical device structure have the following requirements: reducing element layer cracking and delamination during high temperature annealing (eg, LCO annealing), and thus maintaining the functionality and integrity of the overall electrochemical device structure (by controlling components) Stress between layers and/or between the component layer stack and the substrate to avoid delamination of the component layer). Furthermore, fabrication processes and electrochemical device structures have the need to reduce component layer cracking and delamination during high temperature annealing (eg, LCO annealing) and thus allow component materials (eg, typically require higher processing rates than for low deposition rates). The annealing temperature is programmed to form a faster deposition rate of the LCO of the desired layer quality, thus allowing for higher throughput and lower cost of ownership.

According to some embodiments, a thin film battery (TFB) may include: an adhesion promoting layer on a thin substrate having a substrate thickness ranging from 10 micrometers to 100 micrometers, the adhesion promoting layer comprising an electrically insulating material, the adhesion promoting layer Having a thickness ranging from 50 nm to 5000 nm; a metal adhesion layer on the adhesion promoting layer; a collector layer on the metal adhesion layer; and a cathode layer on the current collector layer On the layer; an electrolyte layer on the cathode layer; and an anode layer on the electrolyte layer; wherein the adhesion promoting layer, the metal adhesion layer, the current collector, the cathode layer, the electrolyte layer And forming the anode layer on the thin substrate; and wherein the adhesion promoting layer prevents the stack from rupturing during fabrication of the stack and prevents delamination of the stack from the thin substrate, the stack being fabricated to include a range of 500 ° C to 800 The temperature of °C anneals the cathode.

According to some embodiments, a method for fabricating a thin film battery may include depositing an adhesion promoting layer onto a thin substrate having a substrate thickness ranging from 10 micrometers to 100 micrometers, the adhesion promoting layer comprising an electrically insulating material, the adhesion promoting layer having a thickness ranging from 50 nm to 5000 nm; depositing a metal adhesion layer on the adhesion promoting layer; depositing a collector layer on the metal adhesion layer; depositing a cathode layer on the current collector layer; in a range of 500 ° C to 800 Annealing the cathode layer; after the annealing step, depositing an electrolyte layer on the cathode layer; and depositing an anode layer on the electrolyte layer; wherein the adhesion promoting layer, the metal adhesion layer, the current collector layer, The cathode layer, the electrolyte layer and the anode layer are stacked on the thin substrate; and wherein the adhesion promoting layer prevents cracking of the stack during fabrication of the stack and prevents delamination of the stack from the thin substrate, the fabrication of the stack Including annealing the cathode layer.

According to some embodiments, an apparatus for manufacturing a thin film battery may include: a first system for depositing an adhesion promoting layer onto a thin substrate having a substrate thickness ranging from 10 micrometers to 100 micrometers, the adhesion promoting layer comprising an electrically insulating material The adhesion promoting layer has a thickness ranging from 50 nm to 5000 nm; the second system is for depositing a metal adhesion layer on the adhesion promoting layer, and depositing a collector layer on the metal adhesion layer; For depositing a cathode layer on the current collector layer; a fourth system for annealing the cathode layer at a temperature ranging from 500 ° C to 800 ° C; and a fifth system for depositing an electrolyte layer on the cathode layer And a sixth system for depositing an anode layer on the electrolyte layer; wherein the adhesion promoting layer, the metal adhesion layer, the current collector layer, the cathode layer, the electrolyte layer, and the anode layer are stacked on the thin layer And wherein the adhesion promoting layer prevents cracking of the stack during fabrication of the stack and prevents delamination of the stack from the thin substrate, the stacking comprising annealing the cathode layer.

The embodiments of the present disclosure will be described in detail with reference to the accompanying drawings. In particular, the following figures and examples are not intended to limit the scope of the disclosure to a single embodiment, but other embodiments are possible by interchangeing some or all of the illustrated or illustrated elements. Also, some of the elements of the present disclosure may be implemented in part or in whole using known components, and only those portions of the present disclosure that need to be understood by such known components will be described, and such known components will be skipped. A detailed description of the other sections to avoid confusion with this disclosure. In the present specification, an embodiment showing a single component is not considered to be limiting; rather, the disclosure is intended to include other embodiments including a plurality of identical components, and vice versa, unless otherwise explicitly indicated herein. In addition, the Applicant does not intend to imply any term in the specification or the scope of the claims as a rare or special meaning unless explicitly stated. Moreover, the present disclosure includes the present and future known equivalents of the known components referred to herein by way of illustration.

The present disclosure describes how the adhesion promoting layer is added to the top surface of the TFB substrate before the component layer is deposited onto the substrate, and the adhesion promoting layer has good adhesion to both the substrate and the collector layer (both metal adhesion layer and current collector). The adhesion promoting layer acts as a double-sided adhesive layer, and the adhesion promoting layer reduces the dependence of the CCC adhesive layer on the substrate. This increases the freedom of choice of TFB substrate material and promotes the increase in energy density of the TFB component.

The adhesion promoting layer can be a thin electrical insulation (eg, having a resistance greater than 30 MΩ) dielectric layer (eg, Al ₂ O ₃ , ZrO ₂ , SiO _{2 ,} etc., including suboxides, stoichiometry, and non-stoichiometry of the foregoing) The thin, electrically insulating dielectric layer can withstand high annealing temperatures and provide better adhesion and stress balance, as well as crystalline, amorphous, and mixed phase versions. An adhesion promoting layer is deposited between the thin substrate (eg, mica, YSZ, and glass) and the collector layer, which includes a metal adhesion layer (ADL) and a typical refractory metal current collector. The adhesion promoting layer should have good thermal stability at temperatures above 700 ° C and promote adhesion to the substrate (mica, YSZ and glass) and most of the collector metal (eg Ti, Ta, TaN, etc.) The improved adhesion of both. The thickness of the dielectric adhesion layer ranges from 50 nm to 5000 nm, in the examples from 50 nm to 500 nm, and in the examples ranges from 100 nm to 300 nm.

1 shows an example of a TFB component 100 in accordance with some embodiments of the present invention, including: a substrate 110 (eg, mica, YSZ ceramic having 2 to 8 weight percent cerium oxide and other minor additives and impurities, and glass); An adhesion promoting layer 120 over the top surface of the substrate; a metal adhesion layer 130 (eg, Ti) and a cathode current collector (CCC) 140 (eg, Au, Pt) on the top surface of the intermixed barrier layer; a cathode 150 on the CCC (eg, LCO layer); electrolyte 160 covering the cathode and part of CCC to isolate CCC from other electrodes; anode 170 (eg, Li) and anode current collector (ACC) 180 at the top surface of the partial electrolyte (eg: Au) And an encapsulation layer 190 covering the exposed surface of the anode and the electrolyte and a portion of the current collector. It is to be noted that the adhesive layer 130 is also provided between the intermixed barrier layer and the ACC if necessary, but not all embodiments are required.

Figure 1 shows an example of a TFB component in more detail as follows. The TFB of Figure 1 is typically fabricated using a shadow mask and is described below, although those of ordinary skill in the art will appreciate that the same material and layer order in the component stack can be used with only a slightly different layout. The cover manufacturing process produces TFB. Thin substrates, such as glass, ceramic, mica, metal or tantalum substrates, can have thicknesses ranging from 10 μm to 700 μm. Next, the layer deposited on the substrate will be explained. The adhesion promoting layer may include one or more of Al ₂ O ₃ , ZrO ₂ , SiO _{2 ,} etc. (including suboxides, stoichiometric and non-stoichiometric changes of the foregoing substances, and crystalline, amorphous, and mixed phases). The version) is deposited on the surface of the thin substrate in a thickness ranging from 50 nm to 5000 nm, in the embodiment ranging from 50 nm to 500 nm, and in the embodiment ranging from 100 nm to 300 nm. The metal adhesion layer (for example, Ti, Ta, TaN) has a larger area than the cathode layer region and is deposited on the adhesion promoting layer in a thickness ranging from 10 nm to 1000 nm. The cathode current collector (for example, Au, Pt) has the same area as the adhesive layer and is deposited on the top of the metal adhesive layer with a thickness ranging from 50 nm to 1000 nm. A cathode layer (e.g., LiCoO ₂ ) is deposited on top of the cathode current collector layer in a thickness ranging from 0.5 μm to 40 μm. If necessary, the stack is heat treated to anneal the cathode layer prior to a further deposition step. The solid electrolyte layer (eg, LiPON) has a larger area than the cathode and cathode current collectors and extends beyond the cathode and cathode current collectors (except for the electrical contact areas, leaving CCC uncovered in the electrical contact areas) in the range of 0.5 μm A thickness of up to 4 μm is deposited on top of the intermediate layer. The anode current collector (eg, Cu, Au, Pt) does not overlap with the cathode layer and the cathode current collector, and is deposited on the top of the solid electrolyte in a thickness ranging from 100 nm to 1000 nm; in addition, if necessary, at the anode set The electrical adhesive layer was previously deposited in a manner similar to that used for the cathode current collector layer. The anode (for example, Li metal) has a region larger than the cathode region and smaller than the electrolyte region, and is deposited on the electrolyte and a portion of the ACC in a thickness ranging from 1 μm to 15 μm, and partially overlaps the anode current collector layer. The encapsulation layer of various functions has a region larger than the anode layer region and smaller than the electrolyte layer region, and is deposited on the top of the anode layer with a thickness ranging from 400 nm to 3 μm; the encapsulation layer may be a metal layer (for example: Cu, Au) , Pt, etc.) in combination with a dielectric layer such as LiPON, Al ₂ O ₃ , ZrO ₂ , SiO ₂ , Si ₃ N ₄ , a planarized polymer layer, and the like.

As described in more detail below, in an embodiment, the adhesion promoting layer of Figure 1 is incorporated into the component stack to overcome the problems caused by delamination of the component layer by the substrate due to cracking. In order to achieve good adhesion of the component layers to the substrate, the following must be managed: (1) good adhesion strength from chemical bonding and/or mechanical (roughness) bonding between interfaces; (2) design to resist The stress built into the layers between the other layers of the stack and the stresses built into the other layers; and (3) the stresses due to thermal annealing required to achieve the desired characteristics of the cathode material. Thus, compared to the observed off and added directly promote YSZ deposited Ti / Pt (ADL / collector) between, Al ₂ O ₃ without adhesion on YSZ substrate an Al ₂ O ₃ layer enhancing adhesion promotion layer Better adhesion between YSZ and the adhesion promoting layer and between the adhesion promoting layer and Ti/Pt (ADL/current collector). This may be due to the effect of the Ar/O ₂ plasma, particularly the O ₂ content produced during the PVD deposition of the Al ₂ O ₃ layer, including the preferred chemical bonding at the YSZ-Al ₂ O ₃ interface. Further, deposited Ti ADL on the Al ₂ O ₃ generated Ti-O bond to the Al ₂ O ₃ O is formed, Ti-O bonds than the In ₂ O ₃ in the O of Al formed formed YSZ in O The Ti-O bond is strong. It is also possible that the stress in the Al ₂ O ₃ layer itself compensates for component stacking (up to full stack formation) and/or increased stress in the substrate during processing, especially considering the different coefficients of thermal expansion due to different component layers and substrates. (TEC) will increase the stress in the element during annealing of the cathode material.

The use of PVD in an argon/oxygen gas plasma environment at a higher area power density (e.g., greater than 3.5 KW/cm ² ) can be optimized for deposition with an aluminum oxide film as an adhesion promoting layer. Also, according to the logic of the previous paragraph, higher deposition power can induce better adhesion.

In order to confirm the effectiveness of the adhesion promoting layer, the following experiment was carried out. As a control group, the following stack (without the adhesion promoting layer) was produced: Ti/Au metal adhesion layer/CCC on the mica substrate, followed by LCO cathode, LiPON electrolyte, and Li anode layer. The stack was annealed at 600 ° C after LCO deposition and before LiPON deposition, and the stack exhibited poor adhesion to the mica substrate after deposition of the Li anode layer, resulting in significant delamination of the stack from the substrate. Making a second stack: According to some embodiments, an alumina adhesion promoting layer, a Ti/Au metal adhesion layer/CCC is coated on the mica substrate, followed by an LCO cathode, a LiPON electrolyte, and a Li anode layer. The stack was annealed at 600 ° C after LCO deposition, and the stack exhibited better adhesion to the mica substrate than the control group after deposition of the Li anode layer. It should be noted that cracking and delamination are most pronounced after Li anode deposition, as it is easier to see defects after lithium deposition and may also be due to further stresses that lead to more cracking and delamination of lithium metal deposition. Enhanced.

Furthermore, even in the case of YSZ (having 2 to 8 weight percent cerium oxide) and glass (alkaline earth boroaluminosilicate having a glass transition temperature of about 700 ° C), better results can be seen, adding an adhesion promoting layer to YSZ And the glass substrate appears to have eliminated all delamination, providing 100% mechanical yield of the TFB cell. It has been found that the addition of an adhesion promoting layer improves the mechanical yield of TFB (including mica, YSZ and glass) produced on all substrates tested by the inventors of the present invention.

Although the adhesion promoting layer is exemplified by PVD (physical vapor deposition) sputtering of the intermediate layer, it is expected that the concept of the deposition method is unknown, for example, the deposition technique for the adhesion promoting layer may provide the desired composition, phase and crystallization. Any deposition technique that 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) and so on. The deposition method can also be a non-vacuum system such as plasma spray, spray pyrolysis, slot die coating, screen printing, and the like.

Although the embodiments of the present disclosure have been specifically described with respect to planar TFBs (having ACC and CCC in the same plane), the principles and teachings of the present disclosure are applicable to other TFB configurations, including vertical stack configurations in which ACC is in a vertical stack configuration. And CCC are parallel, but on the opposite side of the stack.

2 is a schematic diagram of a processing system 500 for fabricating a TFB in accordance with some embodiments of the present disclosure. The processing system 500 includes a standard mechanical interface (SMIF) 501 pair cluster tool 502 equipped with a reactive plasma cleaning (RPC) chamber 503 and a process chamber C1 ‒ C4 (504, 505) that can be utilized in the above described processing steps. , 506 and 507). The glove box 508 can also be attached to a cluster tool. The glove box can store the substrate in an inert environment (eg, under a rare gas such as He, Ne or Ar), which is useful after alkali metal/alkaline earth metal deposition. If desired, an ante chamber 509 pair of glove boxes can also be used. The front chamber is a gas exchange chamber (inert gas to air and vice versa) that allows the substrate to be transported into and out of the glove box to not contaminate the glove. An inert environment in the box. (It should be noted that the glove box can be replaced by a dry room atmosphere with a low dew point, which is because the lithium foil manufacturer uses it.) The chamber C1‒C4 can be set up to make a TFB process step. As described above, the TFB can include, for example: Deposition of the alumina adhesion promoting layer on the mica, YSZ or glass substrate; deposition of the metal adhesion layer and CCC on the adhesion promoting layer; followed by deposition of the LCO cathode on the CCC to form a stack on the substrate; annealing of the stack and many more. An example of a suitable cluster tool platform includes a display cluster tool. It should be understood that while the processing system 500 has been shown in a cluster configuration, a linear system may also be employed in which the processing chambers are arranged in a row without a transfer chamber such that the substrate is continuously moved from one chamber to the next.

3 is an image of a tandem fabrication system 600 having multiple tandem tools 601 through 699 that include tools 630, 640, 650, in accordance with some embodiments. The tandem tool contains tools for depositing all TFB layers. Also, the tandem tool includes a pre-conditioning chamber and a rear adjustment chamber. For example, tool 601 can be a pump-back chamber for establishing a vacuum before the substrate moves through vacuum damper 602 into the deposition tool. Some or all of the tandem tools may be vacuum tools that are separated by a vacuum air brake. It should be noted that the particular TFB fabrication method to be used will determine the order of the process tools and the particular process tools in the process pipeline, for example, the tools specified in the process flow described above. Also, the movable substrate is passed through a tandem fabrication system oriented horizontally or vertically.

To illustrate, for example, the movement of the substrate through the tandem fabrication system shown in FIG. 3, the substrate transporter 701 and the unique tandem tool 630 in place are shown in FIG. The substrate holder 702 accommodating the substrate 703 (the substrate holder exhibits partial cut-off to make the substrate visible) is mounted on the conveyor 701 or equivalent element as indicated for moving the holder and the substrate through the tandem tool 630. In some embodiments, the tandem platform for processing tool 630 can be configured for a vertical substrate, and in some embodiments, for a horizontal substrate.

Some examples of devices for making TFBs are as follows, in accordance with certain embodiments. According to some embodiments, the first device for fabricating the TFB may comprise: a first system for ranging from 50 nm to 5000 nm, in embodiments from 50 nm to 500 nm, and in embodiments from 100 nm to 300 The thickness of the adhesion promoting layer of nm deposits the adhesion promoting layer onto the thin substrate; the second system is for depositing the metal adhesion layer on the adhesion promoting layer, and depositing the collector layer on the metal adhesion layer, and collecting the current collector The layer is patterned to form CCC and ACC; the third system is for depositing a cathode layer, such as an LCO layer, on the CCC layer to form the stack on the substrate; and a fourth system for depositing the electrolyte layer on the cathode layer a fifth system for depositing an anode, such as lithium metal, on the electrolyte layer to form the stack on the substrate; and a sixth system for the temperature in the range of 500 ° C to 800 ° C and in the range 4 to The cathode layer is annealed for 15 hours, and in the embodiment for a temperature range of 2 to 30 hours, such as the thickness of the layer to be annealed; wherein the adhesion promoting layer is included in the range of 500 ° C to 800 ° C during component processing Yin under temperature Annealing, preventing element cracking and delamination of the layer stack. Also, the apparatus can include a seventh system for depositing an encapsulation layer over the stack. Also, in some embodiments, the second system can be two or more separate systems, for example, one system for depositing a metal adhesion layer, the second system for depositing a current collector layer, and the third system In the patterned collector layer. The apparatus may also include a system for patterning the various layers, and in embodiments, a shadow mask may be used in one or more of the foregoing deposition systems. The system can be a cluster tool, a tandem tool, a stand-alone tool, or a combination of one or more of the foregoing. Also, the system can include some tools that are common to one or more of the other systems.

And, in accordance with some embodiments, the second device for fabricating the TFB can comprise: a first system for a range of 50 nm to 5000 nm, in the embodiment a range of 50 nm to 500 nm, and in an embodiment a range of 100 nm The thickness of the adhesion promoting layer to 300 nm deposits the adhesion promoting layer onto the thin substrate; the second system is used for depositing the metal adhesion layer on the adhesion promoting layer and depositing the collector layer on the metal adhesion layer; a system for depositing a cathode layer, such as an LCO layer, on the CCC layer; a fourth system for depositing an electrolyte layer on the cathode layer; and a fifth system for depositing an anode, such as lithium metal, on the electrolyte layer a sixth system for depositing ACC on the anode layer to form the stack on the substrate; and a seventh system for performing the temperature in the range of 500 ° C to 800 ° C and in the range of 4 to 15 hours, and In the example, the temperature is maintained for a period of 2 to 30 hours, for example, the thickness of the layer to be annealed, wherein the adhesion promoting layer comprises a cathodic annealing at a temperature ranging from 500 ° C to 800 ° C during component processing. Preventive component layer Stack of rupture and delamination. Also, the apparatus can include an eighth system for depositing an encapsulation layer over the stack. Also, in some embodiments, the second system can be two separate systems, one for depositing a metal bond layer and the second system for depositing CCC. The apparatus may also include a system for patterning the various layers, and in embodiments, a shadow mask may be used in one or more of the foregoing deposition systems. The system can be a cluster tool, a tandem tool, a stand-alone tool, or a combination of one or more of the foregoing. Also, the system can include some tools that are common to one or more of the other systems.

Although embodiments of the present disclosure have specifically described TFBs with LCO cathodes, the principles and teachings of the present disclosure are applicable to TFBs having other cathode materials, including LiMO ₂ (M = Co, Ni, Mn, etc.). Wherein, for example, LiMnO ₂ and LiFePO may be used in a temperature ranging from 500 ° C to 800 ° C and in a range of 4 to 15 hours, and in the embodiment, a holding time of 2 to 30 hours, for example, a thickness of a layer to be annealed. ₄ annealing.

Although the embodiments of the present disclosure have been specifically described with respect to TFB, the principles and teachings of the present disclosure can be applied to other electrochemical components, typically including energy storage components, and the principles and teachings of the present disclosure can also be applied to electrochromism. element.

Although the embodiments of the present disclosure have been specifically described with respect to a single side TFB, the principles and teachings of the present disclosure are applicable to a two-sided TFB.

While the embodiment of the present invention has been described with respect to the specific embodiments of the present invention, it is to be understood by those of ordinary skill in the art that the present invention may be modified or modified without departing from the spirit and scope of the present disclosure. Obvious.

100‧‧‧TFB components
110‧‧‧Substrate
120‧‧‧Adhesive promotion layer
130‧‧‧Adhesive layer
140‧‧‧Cathode Current Collector (CCC)
150‧‧‧ cathode
160‧‧‧ Electrolytes
170‧‧‧Anode
180‧‧‧Anode Collector (ACC)
190‧‧‧Encapsulation layer
500‧‧‧Processing system
501‧‧‧Standard Mechanical Interface (SMIF)
502‧‧‧ Cluster Tools
503‧‧‧Reactive plasma cleaning (RPC) chamber
504‧‧‧Processing chamber C1
505‧‧‧Processing chamber C2
506‧‧‧Processing chamber C3
507‧‧‧Processing chamber C4
508‧‧‧Gift box
509‧‧‧ front chamber (ante chamber)
600‧‧‧ tandem production system
601‧‧ Tools
602‧‧‧vacuum air lock
630‧‧ Tools
640‧‧‧ tools
650‧‧ Tools
699‧‧‧ tools
701‧‧‧ conveyor
702‧‧‧Substrate holder
703‧‧‧Substrate

These and other aspects and features of the present disclosure will become apparent and appreciated from the <RTIgt;

1 is a cross-sectional view of a thin film battery according to some embodiments of the present invention, the thin film battery including an adhesion promoting layer between the adhesive layer and the current collector layer and the substrate;

2 is a schematic diagram of a clustering tool for TFB production in accordance with some embodiments of the present disclosure;

3 is an image of a TFB production system having multiple tandem tools in accordance with some embodiments of the present disclosure;

4 is an image of the tandem tool of FIG. 3 in accordance with some embodiments of the present disclosure.

Domestic deposit information (please note according to the order of the depository, date, number)

Foreign deposit information (please note in the order of country, organization, date, number)

(Please change the page separately) No

100‧‧‧TFB components

110‧‧‧Substrate

120‧‧‧Adhesive promotion layer

130‧‧‧Adhesive layer

140‧‧‧Cathode Current Collector (CCC)

150‧‧‧ cathode

160‧‧‧ Electrolytes

170‧‧‧Anode

180‧‧‧Anode Collector (ACC)

190‧‧‧Encapsulation layer

Claims (20)

A thin film battery (TFB) comprising: an adhesion promoting layer on a thin substrate having a substrate thickness ranging from 10 micrometers to 100 micrometers, the adhesion promoting layer comprising an electrically insulating material, the adhesion promoting layer Having a thickness ranging from 50 nm to 5000 nm; a metal adhesion layer on the adhesion promoting layer; a current collector layer on the metal adhesion layer; a cathode layer, the cathode Laminating on the current collector layer; an electrolyte layer on the cathode layer; and an anode layer on the electrolyte layer; wherein the adhesion promoting layer, the metal adhesion layer, the current collector, The cathode layer, the electrolyte layer, and the anode layer are stacked on the thin substrate; and wherein the adhesion promoting layer prevents the stack from rupturing during fabrication of the stack and prevents delamination of the stack from the thin substrate, the stacking The fabrication comprises annealing the cathode at a temperature ranging from 500 °C to 800 °C. The TFB of claim 1, wherein the thin substrate has a thickness ranging from 20 micrometers to 40 micrometers. The TFB of claim 1, wherein the thin substrate is a mica substrate. The TFB of claim 1, wherein the thin substrate is a cerium oxide stabilized zirconia substrate. The TFB of claim 1, wherein the thin substrate is a glass substrate formed of glass having a glass transition temperature greater than 700 ° C, and wherein the cathode layer has an annealing temperature of about 600 ° C. The TFB of claim 1, wherein the cathode layer is a lithium cobalt oxide (LCO) layer having a high temperature phase LCO greater than 90% by volume. The TFB of claim 1, wherein the adhesion promoting layer has a thickness ranging from 100 nm to 300 nm. The TFB of claim 1, wherein the adhesion promoting layer is an aluminum oxide layer. A method for fabricating a thin film battery, comprising the steps of: depositing an adhesion promoting layer onto a thin substrate having a substrate thickness ranging from 10 micrometers to 100 micrometers, the adhesion promoting layer comprising an electrically insulating material, the adhesion enhancement The layer has a thickness ranging from 50 nm to 5000 nm; depositing a metal adhesion layer on the adhesion promoting layer; depositing a current collector layer on the metal adhesion layer; depositing a cathode layer on the current collector layer Annealing the cathode layer at a temperature ranging from 500 ° C to 800 ° C; after the annealing step, depositing an electrolyte layer on the cathode layer; and depositing an anode layer on the electrolyte layer; wherein the adhesion a promotion layer, the metal adhesion layer, the current collector layer, the cathode layer, the electrolyte layer, and the anode layer are stacked on the thin substrate; and wherein the adhesion promoting layer prevents the stack from rupturing during fabrication of the stack and The stack is prevented from delaminating from the thin substrate, the fabrication of the stack comprising annealing the cathode layer. The method of claim 9, wherein the thin substrate has a thickness ranging from 20 micrometers to 40 micrometers. The method of claim 9, wherein the thin substrate is a mica substrate. The method of claim 9, wherein the thin substrate is a cerium oxide stabilized zirconia substrate. The method of claim 9, wherein the thin substrate is a glass substrate formed of glass having a glass transition temperature greater than 700 ° C, and wherein the cathode layer has an annealing temperature of about 600 ° C. The method of claim 9, wherein the cathode layer is a lithium cobalt oxide (LCO) layer having a high temperature phase LCO greater than 90% by volume after the annealing step. The method of claim 14, wherein the annealing step has a temperature holding time ranging from 2 to 30 hours. The method of claim 9, wherein the adhesion promoting layer has a thickness ranging from 100 nm to 300 nm. The method of claim 9, wherein the adhesion promoting layer is an aluminum oxide layer. The method of claim 17, wherein the aluminum oxide layer is deposited by physical vapor deposition in an argon/oxygen gas plasma environment having an area power density greater than 3.5 W/cm ² . An apparatus for manufacturing a thin film battery, comprising: a first system for depositing an adhesion promoting layer onto a thin substrate having a substrate thickness ranging from 10 micrometers to 100 micrometers, the adhesion promoting layer comprising an electrical insulation a material having a thickness in the range of 50 nm to 5000 nm; a second system for depositing a metal adhesion layer on the adhesion promoting layer, and depositing a current collector layer on the metal adhesion layer a third system for depositing a cathode layer on the current collector layer; a fourth system for annealing the cathode layer at a temperature ranging from 500 ° C to 800 ° C; a fifth system, For depositing an electrolyte layer on the cathode layer; and a sixth system for depositing an anode layer on the electrolyte layer; wherein the adhesion promoting layer, the metal adhesion layer, the current collector layer, the cathode a layer, the electrolyte layer, and the anode layer are stacked on the thin substrate; and wherein the adhesion promoting layer prevents the stack from rupturing during fabrication of the stack and prevents the stack from delaminating from the thin substrate, the stack The fabrication of the stack includes annealing the cathode layer. The apparatus of claim 19, wherein the first system comprises a physical vapor deposition tool for depositing in an argon/oxygen gas plasma environment having an area power density greater than 3.5 W/cm ² Alumina adhesion promoting layer.