Patent Grant
8535396
The field of this invention is the apparatus, composition, and fabrication of lithium-based, solid-state, thin-film, secondary and primary batteries with improved capacity density, energy density, and power density, and preferably with flexible form factor and crystalline LiCoO2, LiNiO2, LiMn2O4 cathodes and derivative materials.
The following passage describes the need and evolution of the subject technology in the field of thin film batteries.
Thin-film batteries may be fabricated by sequential vacuum depositions of layered battery components onto a given substrate in, for example, the following order: positive cathode current collector, positive cathode, negative anode current collector, electrolyte (separator), negative anode, and encapsulation. A lamination process may be used instead of a deposition process step (see, for example, U.S. Pat. No. 6,916,679 versus Wang et al., 143 J. Electrochem. Soc. 3203-13 (1996) or U.S. Pat. No. 5,561,004). Optionally, the two terminals of a thin-film battery may not simply comprise extensions of the positive and the negative current collectors, but may be additionally deposited terminal contacts that make electrical contact to the respective current collector. The positive cathode material may be insufficiently crystalline in the as-deposited state and, associated with this fact, may exhibit insufficient electrochemical properties (see, for example, Wang et al., supra). For this reason, the positive cathode may be crystallized during battery fabrication, which can be achieved in a post-deposition, high-temperature (“anneal”) process (see, for example, Wang et al., supra or Bates et al., “Thin-Film Lithium Batteries” in New Trends in Electrochemical Technology: Energy Storage Systems for Electronics (T. Osaka & M. Datta eds., Gordon and Breach 2000)). The anneal process, which is applied immediately after the deposition of the positive cathode, may limit the choice of materials for the substrate and positive cathode current collector, thereby limiting, in turn, the capacity density, energy density, and power density of the thin-film battery, both per volume and weight. The affect of the substrate on those three quantities is, for example, explained in more detail below.
The intrinsic (i.e., without substrate and without encapsulation) volumetric and gravimetric densities of the capacity, the energy, and the power of lithium-based, solid-state, thin-film secondary (rechargeable) and primary (non-rechargeable) batteries are dominated by the volumetric and gravimetric densities of the capacity, the energy, and the power of the positive cathode material. Crystalline LiCoO2 may be an example of a choice for the positive cathode material for both bulk (non thin-film) and thin-film batteries in terms of volumetric and gravimetric densities of the capacity, energy, power, and cyclability, in the case of secondary batteries, followed by derivatives of crystalline LiMn2O4, crystalline LiMnO2, and crystalline LiNiO2. Doping these main parent positive cathode materials with other transition metals (leading to derivatives) such as Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru, Rh, La, Hf, Ta, W, and Re and main group elements selected from the groups 1, 2, 13, 14, 15, 16 and 17 has been found to alter the properties of LiCoO2, LiMn2O4, LiMnO2, and LiNiO2 with only little, if any, overall improvement.
According to U.S. Pat. No. 6,280,875, native titanium oxide on a Ti substrate is not inert enough to prevent adverse reactions from occurring between a Ti substrate and the battery components. This approach is severely restricted because the choice of substrate materials is limited to materials capable of forming a native surface oxide during the anneal step of the positive cathode. Apart from the present invention, metallic substrates including flexible foils that do not form a native surface oxide have not been employed successfully as thin-film battery substrates. Fabricating solid-state, thin-film secondary batteries by depositing, for example, high-temperature cathode materials directly onto metallic substrates, including flexible foils, other than Zr, and then annealing at high temperature, such as 700° C. in air for 1 hour, may result in the positive cathode and substrate materials reacting detrimentally to such an extent that the positive cathode is rendered useless. Pure Ti and Zr substrates are also relatively expensive.
Prior thin-film batteries do not disclose the use of an effective barrier layer between the substrate and the battery, and, therefore, provide potential negative observations. A need exists for the present invention such as, for example, an inventive barrier layer with sublayering attributes to overcome certain problems of prior thin film-batteries.
Various aspects and embodiments of the present invention, as described in more detail and by example below, address certain of the shortfalls of the background technology and emerging needs in the relevant industries.
The number of portable and on-board devices continues to increase rapidly while the physical dimensions available may decrease. The batteries that run these devices should keep pace with the demands of the devices served, potentially shrinking in size while, for example, delivering the same power. The thinner the batteries become, the more applications they may serve. One enabling power device is the thin-film, solid-state battery. When footprint is a limiting factor but capacity demand is still “high,” it becomes important to pack and stack as many battery cells as possible into the space (footprint×height) available.
The batteries with the highest capacity, voltage, current, power, and rechargeable cycle life may, for example, take advantage of today's most powerful positive cathode materials, LiCoO2, LiMn2O4, LiMnO2, LiNiO2, and derivatives thereof.
When vacuum deposited into thin-films, these materials may preferably include post-deposition annealing at high temperatures in order to improve their crystallinity, which is directly related to development of their full range of electrochemical properties. For an electrochemical apparatus, which employs such a thin-film battery, to become thinner, mainly the inert, electrochemically inactive part of the electrochemical apparatus should become thinner. One approach may be to build the battery on thin, metal foil substrates instead of thick, bulky ceramic ones. Metal foils are more flexible, thinner, and less expensive than ceramic substrates of the same footprint. Furthermore, they are easily available in much larger areas which translates into substantial cost savings in manufacturing.
However, LiCoO2, like other positive cathode materials, is a strong oxidizer and possesses very mobile and thus reactive lithium ions. At the high annealing temperatures necessary to crystallize the as-deposited LiCoO2 film, it reacts strongly with most metals and alloys as well as with many compounds, except for a limited number of inert ceramics. In other cases, unwanted species from the substrate may diffuse into LiCoO2 during the high annealing temperatures and contaminate the positive cathode, thereby detrimentally altering its electrochemical properties. If the annealing temperature is kept sufficiently low to prevent reactions or unwanted diffusion, then the positive cathode may not fully crystallize, and capacity, energy, current, and power capability, and, in the case of rechargeable batteries, lifetime (number of cycles) may suffer.
High-power positive cathode materials may unfold their full, desirable, electrochemical properties in their crystalline state. Because these materials may, for example, be used in the present invention in thin-film form, they may typically be deposited by one of the common vapor phase thin-film deposition methods, such as sputter deposition (RF, pulse DC, or AC), electron-beam evaporation, chemical vapor deposition, plasma enhanced chemical vapor deposition, spray pyrolysis, ion-assisted beam evaporation, electron-beam directed vapor deposition, cathodic arc deposition, etc. These vapor phase methods may not produce positive cathode films in the as-deposited state that exhibit comparable electrochemical properties to positive cathodes that are fabricated from their respective, well-crystallized powders used in bulk batteries, such as cell phone and camcorder type batteries. Thus, the inferior electrochemical properties of such positive cathodes deposited by thin-film methods may be attributed to the lack of the necessary degree of crystallinity in the as-deposited state.
The degree of crystallinity, however, may be improved by a post-deposition anneal at higher temperatures, typically between 200° C.-900° C., better between 500° C.-850° C., and even better between 650° C.-800° C. Atmospheres used in these anneals are typically air, O2, N2, Ar, He, H2, H2O, CO2, vacuum (P<1 Torr), or mixtures thereof. To achieve sufficient crystallization and hence improved electrochemical properties, annealing times should preferably, for example, be extended when reducing the annealing temperature below about 650° C. The rate of crystallization may be exponentially activated by temperature, and thus decreases significantly with decreased annealing temperature. If the anneal temperature is lowered too much, then the applied energy from the annealing temperature may not be sufficient to overcome the thermal activation energy necessary for the crystallization process to occur at all. For example, a 900° C. anneal in air for 15 minutes may yield the same degree of crystallinity in magnetron-sputtered LiCoO2 films as about a 1 hour anneal in air at 700° C. and as about a 12 hour anneal in air at 600° C. After annealing at 400° C. in air for 24 hours, the electrochemical quality of magnetron-sputter-deposited LiCoO2 cathode films may remain poor and unimproved after 72 hours at that temperature. Thus, LiCoO2 cathode films fabricated via vapor phase methods may be post-deposition annealed at 700° C. in air for about 30 minutes to 2 hours. This relatively high annealing temperature, however, may cause chemical compatibility issues, thereby rendering such an annealing step potentially undesirable in the fabrication process of thin-film batteries, as well as increasing the cost and reducing the fabrication throughput.
Post-deposition annealing conditions may severely limit the choice of substrate materials. Not only should substrates preferably be able to withstand the high annealing temperatures (T>500° C.), but they should also preferably be chemically inert against all battery film materials that are in contact with the substrate with regards to the anneal atmosphere, battery operation, and storage conditions applied. Likewise, the substrate should preferably not be a source of impurities that can diffuse into the battery film materials, neither during fabrication nor thereafter during operation and storage of the electrochemical apparatus. Such impurities may poison any of the battery film materials and diminish, severely impact or even destroy battery performance and lifetime. Certain choices of substrates may be, for example, restricted to chemically inert, high-temperature ceramics, for example, Al2O3, MgO, NaCl, SiC, and quartz glass. Two metals, Zr and Ti, for example, have demonstrated limited success as metallic substrates. The electrochemical apparatus of the present invention does not require the substrate to be Zr or Ti.
Although the above-mentioned ceramics have demonstrated their ability to withstand high temperatures without chemical reactions during the thin-film battery fabrication, there may be significant drawbacks to using them in cost-effective manufacturing of thin-film batteries. Ceramics tend to be at least 5 mil≈125 μm thick, brittle, inflexible (rigid), and relatively expensive per given footprint. Also, their sheer area size may be limited. The thinner the ceramic substrate becomes, the smaller the maximum area that can safely be handled without breaking the ceramics. For example, 12 inch×12 inch plates of ¼ inch thick Al2O3 are commercially readily available. However, thinned and polished Al2O3 ceramic substrates of 10 mil≈250 μm in thickness reduce the area that can be fabricated with reasonable yields to approximately 4 inch×4 inch boards. Thin (<20 mil or <500 μm), 4 inch×8 inch polished ceramic boards are available as custom orders, but not as a routinely stocked item at acceptable prices for large-scale manufacturing of thin-film batteries.
Due to their fragile character below about 100 μm, the use of ceramics as a substrate material for thin-film batteries may become impractical (despite the discussion in U.S. Pat. No. 6,632,563, discussing Mica substrates with thicknesses below 100 μm). One of the properties of Mica is its extremely brittle and fragile character, even at much greater thicknesses than 100 μm. Using ceramic substrates thicker than 100 μm, however, may cause the electrochemically inactive mass and volume of the substrate to make up more than 90% of the total battery weight and volume, which may be undesirable.
For all of these stated reasons, non-ceramic foils may be used as thin-film battery substrates. Under non-ceramic substrates, including, for example, metallic and polymeric substrates, silicon, and doped silicon may assume an intermediate position.
Non-ceramic foils, for example, may offer advantages as substrates for thin-film batteries, provided the substrate material is able to withstand the processing conditions, including temperature and, for example, contacting certain potentially reactive battery layers. Relative to ceramic substrates of a given footprint, non-ceramic foil substrates can be thinner, more flexible, less expensive, readily available in larger sizes, and may decrease the overall thickness of the battery or electrochemical apparatus while reducing the electrochemically inactive mass and volume of the entire battery, which in turn may increase the battery's capacity density, energy density, and power density. Non-ceramic foils are, for example, available in rolls of 0.5-5 mil≈12-125 μm thickness, up to several meters wide, and up to many meters in length. Substrates that come in long rolls present the possibility of roll-to-roll fabrication at much lower costs than the typical batch mode fabrication processes currently in practice. Fabricating a thin-film battery on a thinner, more flexible substrate without compromising battery performance, compared to a thin-film battery fabricated on a thick rigid substrate, plays a role in enabling certain applications for the thin-film battery technology.
Reducing the electrochemically inactive mass and volume of the battery by making the substrate significantly thinner may increase the capacity density, energy density, and power density of the battery per mass and volume. For example, a given application may allot a volume for the battery of 2 cm×2 cm×0.1 cm. Currently, there are no traditional button cell or jelly roll (spiral wound or prismatic) batteries available that can physically fit in that volume. In contrast, a thin-film, solid-state battery may fit that volume because even when fabricated onto a ceramic substrate of 0.05 cm, the entire battery, including an optionally protective encapsulation or encasing (see definitions further below), is much thinner than 0.1 cm. Fabricating a thin-film battery on a 2 mil≈50 μm=0.005 cm thick foil substrate with the same footprint and same battery capacity may further allow the stacking of a maximum of 20 batteries into this volume. The actual number of batteries is determined, for example, by the thickness of each battery cell including its substrate and its optional, protective encapsulation or encasing. Using a thin non-ceramic foil substrate instead of a thick ceramic one may cause a manifold increase in capacity density, energy density, and power density.
Thin-film batteries may, for example, be fabricated by sequentially depositing the individual battery component layers on top of each other. As mentioned, examples of the best positive cathodes include (but are not limited to) LiCoO2, LiMn2O4, LiMnO2, LiNiO2, and derivates thereof. The electrochemical apparatus of the present invention does not require a LixV2Oy cathode where 0<x≦100 and 0<y≦5. The positive cathodes may include a post-deposition anneal at temperatures well above 500° C. in order to crystallize completely, thereby achieving their full electrochemical properties. Because certain known solid-state lithium electrolytes may react destructively when in contact with the high-temperature positive cathodes at these high temperatures, the positive cathode can be deposited and annealed before depositing the electrolyte layer.
Positive cathode materials may generally be considered poor semi-conductors, at least over some range of their state of charge during battery operation. To get maximum power out of the battery and into the external circuit, the positive cathode layer may be deposited onto a metallic back contact, the cathode current collector (CCC) layer. This CCC also should undergo the high-temperature cathode anneal and not react with the positive cathode at the same time. For this reason, a noble metal such as, for example, gold or an alloy thereof, or equivalent may be used.
The facts outlined above suggest that for improvement in the performance of batteries, positive cathode materials may be deposited as the second layer of batteries immediately after the deposition of the CCC. The post-deposition anneal of the positive cathode layer may, therefore, accomplish its crystallization before the next fabrication step, the electrolyte deposition. Due to the close proximity of the high-temperature cathode material to the substrate, which may only be separated from each other by a relatively thin CCC (0.1-1 μm), strong detrimental interdiffusion and reaction of the positive cathode and the substrate have been observed when not using ceramic substrates, but instead high-temperature stable metallic foils, such as stainless steel. This interdiffusion may, for example, not be blocked out by the metallic CCC itself for three main reasons. First, the CCC film is relatively thin (0.1-1 μm), thereby representing only a thin pseudo-diffusion barrier. Second, the CCC exhibits a crystalline grain structure. Grain boundaries may be the usual locations for ionic and electronic diffusion and conduction so that the CCC should be viewed as inherently permeable for ions and electrons from both the adjacent positive cathode layer and the adjacent metallic foil substrate. Thus, during the cathode anneal step, the foil substrate material and cathode film material may interdiffuse. Third, the metallic CCC alloys directly into the metallic foil substrate affecting its current collecting properties.
The thickness of the CCC is determined, for example, by cost, mass, volume, and adhesion, which all may become technologically impractical when fabricating the CCC thicker than about 2 μm, especially when using a costly noble metal such as gold. Potentially, significantly thicker CCC films of about more than 5 μm may avoid interdiffusion depending, for example, on temperature and pertinent dwell time of the annealing step. However, the use of such a thick CCC may, for example, incorporate increased materials costs and potentially unreliable adhesion.
Replacing ceramic substrates with metal foil substrates introduces tremendous opportunities for enabling new technologies using thin-film batteries, in addition to reducing fabrication costs over thin-film batteries fabricated onto ceramic substrates. In contrast to ceramic plates, metallic foils are commercially readily available in thicknesses of less than 75 μm with some materials available as thin as 4 μm. These foils are much more flexible than their ceramic counterparts, contribute less structural, inactive mass to the battery, and, most importantly, substantially reduce the overall thickness of the complete thin-film battery device. It should be emphasized that minimizing the overall thickness and increasing the flexibility of the battery is critically important for most thin-film battery applications. Thinner thin-film battery devices are able to fit into new, physically smaller applications. What was once not practical with a button-cell battery now becomes possible with a thin-film battery (i.e., smart cards, etc.). The added flexibility of a foil substrate further, for example, allows conformation to new, non-planar shapes.
Furthermore, thin metal foils may generally cost less than ceramics per footprint area and come in much larger sizes such as rolls. With the availability of flexible, large area substrates, the potential exists for developing roll-to-roll fabrication methods, thereby further reducing production costs.
New applications may, for example, be enabled with a thin-film battery that provides uncompromised or improved performance relative to state-of-the-art thin-film battery that is fabricated on ceramic substrate. In this regard, the present invention may include the deposition of an interdiffusion barrier layer onto metallic foil substrates wherein the barrier layer chemically separates the battery (i.e., electrochemically active cell) part from the substrate part of the electrochemical apparatus during high and low post-deposition anneal temperatures, for example, in the range between 100° C. and up to the melting point of the substrate, as well as all operation and storage conditions of the electrochemical apparatus while not becoming a source of impurities itself. An embodiment of this aspect of the present invention is shown, for example, in
The barrier may, for example, prevent diffusion of any contaminants entering the battery from the substrate as well as, for example, block ions from escaping the battery and diffusing into the substrate during both battery fabrication and during battery operating and storage conditions. Such a barrier layer may not, for example, exhibit a grain structure at any time. That is, it may be amorphous or glassy in its as-deposited state and remain as such throughout the entire annealing and battery fabrication process as well as during battery operation and storage conditions. The absence of a grain structure in the barrier layer may avoid the detrimental grain boundary diffusion or conduction of ions and electrons. As mentioned earlier, grain boundaries are the pathways along which impurities and contaminants may travel. When certain of these conditions are met, the thin-film batteries fabricated on metallic substrates, flexible and thin or less flexible and thicker, may exhibit properties comparable to, for example, thin-film batteries fabricated on chemically inert yet thick, heavier, rigid, and expensive ceramic substrates.
Certain potentially suitable materials for the diffusion barrier layer may be poor ion conducting materials, for example, such as borides, carbides, diamond, diamond-like carbon, silicides, nitrides, phosphides, oxides, fluorides, chlorides, bromides, iodides, and any multinary compounds thereof. Of those compounds, electrically insulating materials may further prevent possible reactions between the substrate and the battery layers to occur, because for example, if these chemical reactions may include the diffusion of ions and electrons, then blocking electrons is one means of blocking these example chemical reactions. However, electrically conducting materials may be used as well, for example, ZrN, as long as they are, for example, not conducting any of the ions of the substrate or battery layer materials. In some cases metals, alloys, and/or semi-metals may serve as a sufficient barrier layer depending on the anneal temperatures applied during the battery fabrication process and substrate material used. The diffusion barrier layer may, for example, be single or multi-phase, crystalline, glassy, amorphous or any mixture thereof, although glassy and amorphous structures are usually used due to their lack of grain boundaries that would otherwise serve as locations for increased, but unwanted, ion and electron conduction.
Because certain materials block out the conduction of a wide variety of ions, they may also be used in certain non-lithium containing thin-film batteries, such as batteries whose electro-active ions are, for example, beryllium, sodium, magnesium, potassium, calcium, boron, and aluminum. The thickness of the diffusion barrier layer may, for example, range from 0.01 μm to 1 mm.
Although the barrier and/or sub-barrier layer concepts and principles for thin-film batteries of the present invention have initially been developed for metallic substrates, the same barrier layer materials may, for example, be deposited onto polymeric substrates and doped and undoped silicon substrates whose associated thin-film battery applications are also of commercial interest. The post-deposition anneal temperatures may, for example, be lower than the melting point of the silicon or polymeric substrates used, irrespective of the barrier layer applied in order to, for example, avoid melting of the substrate.
An embodiment of the present invention relates, for example, to a method for fabricating flexible, high-capacity, solid-state, thin-film batteries on thin foil substrates, for example, metallic substrates. For the purpose of the present invention, an electrochemical apparatus is defined as an apparatus comprising at least one electrochemical active cell, for example a thin-film battery, a pertinent substrate, for example a metallic substrate, and a suitable diffusion barrier layer, which in turn can be composed of a multitude of barrier sublayers, between the electrochemically active cell and the substrate (see
The success of certain embodiments of the present invention is attributed to the utilization of an appropriate, chemically inert diffusion barrier layer and sublayers between the substrate and the thin-film battery which may effectively separate these two parts of the electrochemical apparatus. The diffusion barrier layer can, preferably, be able to withstand the high annealing temperatures that may be applied to the thin-film battery part during its fabrication onto the substrate, be chemically inert to both the substrate and the thin-film battery part, not be a source of impurities, at least not for the thin-film battery part, and keep the thin-film battery part chemically separated from the substrate under the operating and storage conditions of the electrochemical apparatus after its completed fabrication. Additionally, the barrier layer should for example, preferably, prevent diffusion of any contaminants attempting to enter the thin-film battery part from the substrate, as well as block Li ions from escaping the thin-film battery part and diffusing into the substrate during both battery fabrication and all battery operating and storage conditions. As an added benefit, the barrier layer may also protect the substrate during processing from the atmosphere applied during the post-deposition anneal and from any of the thin-film battery components already present at that fabrication stage of the unfinished electrochemical apparatus.
Fabricating the diffusion barrier of a multitude of barrier sublayers allows the fine-tuning of the physical (mechanical (in particular, pinhole-freeness, flexibility, and adhesion), electrical, magnetic, acoustic, thermal, and optical) and chemical properties of the diffusion barrier layer and thus improves the performance and reliability of the electrochemical apparatus over one that is fabricated with a diffusion barrier layer that might include only one single layer of a given material, such as Si3N4, for example, or Ti84B16, for example, which thermodynamically is a two-phase system (“composite”) of almost equal amounts of TiB2 and beta-B (see Binary Alloy Phase Diagrams, 2nd Ed. (T. B. Massalski, H. Okamoto, P. R. Subramanian, and L. Kacprzak eds., ASM International 1990), incorporated herein by reference), or a TiO2—Ba0.5Sr0.5TiO3 composite material, such as described in U.S. Pat. No. 6,444,336 (incorporated herein by reference). In the simplest form, a diffusion barrier layer of the present invention may include a thin (˜1000 Å) barrier sublayer with additional adhesion improving properties, such as Ti, and one (1 μm) thicker barrier sublayer, such as Si3N4.
Barrier sublayer materials for a diffusion barrier layer of the present invention may include, but are not limited to, thin-films of amorphous Si3N4, SiC, ZrN, and TiC, among others. These are exemplary of compounds which may effectively serve as barriers due to their ion blocking properties, amorphous structure, and chemical inertness to the substrate, as well as to the battery part of the electrochemical apparatus. The pre-eminent characteristics of these barrier layer chemistries are their inherent ability to retain their amorphous, as-deposited state and their diffusion blocking properties up to substantially high temperatures, for example 700° C., and for longer periods at those temperatures, for example 2 hours, during the preferred LiCoO2 crystallization post-deposition anneal process. As a result, thin-film batteries fabricated on metal foils with such barrier layers retain good electrochemical properties for equivalently configured thin-film batteries that are fabricated onto ceramic substrates, but with the added benefits of being flexible, much thinner, and cheaper.
An embodiment of the present invention further, for example, relates to fabricating an appropriate barrier layer onto substrates in conjunction with a subsequent thin-film battery fabrication where the barrier layer may chemically separate the substrate from the battery part during the battery fabrication as well as during battery operation and storage conditions thereafter. Polymeric substrates and doped and undoped silicon substrates may be used in addition to metallic substrates.
An object of an embodiment of the present invention is to provide, for example, an electrochemical apparatus with a metallic, polymeric, or doped or undoped silicon substrate, with a battery (electrochemically active cell) on only one side of the substrate.
Another object of an embodiment of the present invention is to provide, for example, an electrochemical apparatus with a metallic, polymeric, or doped or undoped silicon substrate, with two batteries (two electrochemically active cells), one on each side of the substrate.
Another object of an embodiment of the present invention is to provide, for example, a method of fabricating an electrochemical apparatus with a metallic, polymeric, or doped or undoped silicon substrate, with a battery (electrochemically active cell) on only one side of the substrate.
A further object of an embodiment of the present invention is to provide, for example, a method of fabricating an electrochemical apparatus with a metallic, polymeric, or doped or undoped silicon substrate, with two batteries (two electrochemically active cells), one on each side of the substrate.
a illustrates a schematic of an exemplary use of an embodiment of a barrier layer that includes an electrically conductive barrier sublayer for the case in which the electrical separation between the positive and the negative part of the electrochemically active cell is accomplished through fabrication of the negative part entirely on top of the electrolyte.
b illustrates a schematic of another exemplary use of an embodiment of a barrier layer that includes an electrically conductive barrier sublayer on metallic substrate for the case in which the electrical separation between the positive and the negative part of the battery is accomplished through fabrication of the negative part entirely on top of the electrolyte.
c illustrates a schematic of an exemplary use of an embodiment of a barrier layer that includes an electrically conductive barrier sublayer on metallic substrate for the case in which the electrical separation between the positive and the negative part of the battery is accomplished through fabrication of the positive part entirely on top of the electrolyte.
a illustrates a schematic of an exemplary use of an embodiment of a barrier layer that includes electrically conductive barrier sublayers for the case in which the electrical separation between the positive and the negative part of the electrochemical active cell is not done via fabrication of the negative part entirely on top of the electrolyte.
b illustrates a schematic of another exemplary use of an embodiment of a barrier layer that includes electrically conductive barrier sublayers for the case in which the electrical separation between the positive and the negative part of the electrochemically active cell is not done via fabrication of the negative part entirely on top of the electrolyte.
c illustrates a schematic of another exemplary use of an embodiment of a barrier layer that includes electrically conductive barrier sublayers for the case in which the electrical separation between the positive and the negative part of the electrochemically active cell is not done via fabrication of the negative part entirely on top of the electrolyte while the negative anode has direct contact to a barrier sublayer.
a illustrates a schematic of an embodiment of an anode configuration of the “normal configuration” in which the negative anode is not in direct contact with the barrier layer.
b illustrates a schematic of an embodiment of an anode configuration of the “normal configuration” in which the negative anode is in direct contact with at least one of the barrier sublayers.
It should be understood that this invention is not limited to the particular methodology, protocols, etc., described herein and, as such, may vary. The terminology used herein is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the present invention, which is defined solely by the claims.
As used herein and in the claims, the singular forms “a,” “an,” and “the” include the plural reference unless the context clearly indicates otherwise.
All patents and other publications identified are incorporated herein by reference in their entirety for the purpose of describing and disclosing, for example, the methodologies, apparatuses, and compositions described in such publications that might be used in connection with the present invention. These publications are provided solely for their disclosure prior to the filing date of the present application. Nothing in this regard should be construed as an admission that the inventors are not entitled to antedate such disclosure by virtue of prior invention or for any other reason.
Unless defined otherwise, all technical terms used herein have the same meaning as those commonly understood to one of ordinary skill in the art to which this invention pertains. Although any known methods, devices, and materials may be used in the practice or testing of the invention, certain exemplary preferred methods, devices, and materials in this regard are described here.
Thin-film batteries may, for example, be fabricated in batch mode by depositing the individual battery component layers sequentially. Once a substrate material has been selected, it may be prepared by cleaning and, if desired, other pre-treatments. The barrier layer composed of its barrier sublayers, which may be 0.5-5 μm thick in total, is the key to successful fabrication of thin-film batteries on metallic and polymeric foils as well as silicon. The barrier layer should be able to withstand the annealing temperatures for the positive cathode film together with the cathode current collector, remain chemically inert, and not be a source of impurities.
Additionally, the barrier layer should prevent diffusion of any contaminants entering the positive cathode from the substrate as well as block all ions and atoms from the positive cathode and the cathode current collector from diffusing into the substrate during both the battery fabrication and all battery operating and storage conditions. The barrier layer may be deposited onto the clean substrate and typically coats the substrate everywhere with a uniform, defect-free film. The ensuing battery layers may then be deposited sequentially in batch fashion using shadow masks to demarcate the boundaries of each layer of the thin-film battery. The barrier layer may be designed and fabricated to isolate the effects of grain boundary diffusion, thereby eliminating reactions between the subsequently deposited positive cathode, such as LiCoO2, with its underlying cathode current collector and the substrate, such as for example a gold cathode current collector and a flexible stainless steel foil substrate, respectively. The following presents exemplary ways of depositing embodiments of barrier layers, including their barrier sublayers, onto substrates onto which thin-film batteries are fabricated.
1. Substrate Selection and Preparation
First, the substrate material may be chosen. The thin-film batteries may be fabricated on a variety of metallic foils and sheets with varied surface finishes. A thin foil of stainless steel may be used for the substrate. However, other, more expensive and thicker materials or lower melting materials work as well, including, but not limited to, Ti and Ti-alloys, Al and Al-alloys, Cu and Cu-alloys, and Ni and Ni-alloys, for example. Additionally, the preferred physical properties of the foil, such as type of steel alloy, surface roughness, homogeneity, and purity, are left to the user to determine the optimum manufacturing parameters for the particular device. The electrochemical apparatus of the present invention does not require the substrate to be Al coated with metals or semi-metals that include V, Mn, Mg, Fe, Ge, Cr, Ni, Zn, and Co. Moreover, the electrochemical apparatus of the present invention does not require the substrate to be a pure polymide.
Once the stainless steel foil material, for example, has been selected, it is generally cleaned in order to remove oils, particulates, and other surface contaminants that may otherwise impede chemical or mechanical adhesion of the barrier layer to the substrate. Any cleaning procedure, for example, any suitable wet chemical cleaning or plasma cleaning process that provides a sufficiently clean surface, may be used in this regard. Optionally, the cleaned foil substrate may be further pre-treated, if so desired. For example, to relieve the intrinsic stress of metallic foils, an anneal step at high temperatures (e.g., 500° C.) prior to depositing the barrier layer may be employed, provided that the anneal temperature remains below the melting point of the metallic foil.
Although substantially independent of any foil material and its thickness, several annealing strategies may further reduce or accommodate thermal and mechanical stresses on a film-by-film basis. For example, pre-annealing a cleaned foil may be performed as described above to condition an uncoated metal foil. Additionally, other annealing steps may include, for example, a post-deposition barrier layer anneal, a post-deposition cathode current collector layer anneal, or any combination of post-deposition layer anneals prior to the cathode crystallization anneal. Such steps may be preceded or followed by additional plasma treatments (see, for example, D. M. Mattox, Handbook of Physical Vapor Deposition (PVD) Processing, Society of Vacuum Coaters, Albuquerque, N. Mex. 660ff and 692ff (Noyes Publications 1998)). Analogously, silicon and polymeric substrates may be prepared.
2. Barrier Layer Deposition
Depositing a barrier layer onto substrates may be performed in conjunction with thin-film battery fabrication that, for example, chemically separates the substrate from the battery part during the battery fabrication as well as, for example, during battery operation and storage conditions thereafter.
In general, chemical reactions between potential reactants may be prevented when either their ions or their electrons are confined to each of the reactants' space or blocked at the reactants' interface so that preferably no interdiffusion of these species between the potential reactants is possible. In addition to the mere diffusion blocking properties, the materials selected for the barrier layer and its constituting barrier sublayers should take into account that the barrier layer (a) shall be able to withstand the annealing temperatures for the positive cathode film together with the cathode current collector, (b) remain chemically inert, and (c) not be a source of impurities.
An electrically conductive material, such as ZrN, for example, that possesses adequate diffusion blocking properties relative to ions so as to chemically separate the substrate from the battery part in the electrochemical apparatus, may be deposited. In this case, the conductive barrier sublayer may also serve as a current collector. Because ZrN is also stable in contact with negative anode materials, in particular metallic lithium, it may be used as the cathode current collector and/or the anode current collector.
Although constructing a barrier layer with just one single layer of a specific material is feasible in principle, for example, electrically insulating and metal ion blocking Si3N4, it has been found that a barrier layer composed of more than one suitable sublayer, in which each sublayer provides different specific properties to the barrier layer with the objective to fine-tune the barrier layer properties, achieves higher fabrication yields and consequently higher reliability in battery performance over a given thin-film battery's lifetime. For this reason, the present invention focuses on the fabrication and provision of a barrier layer that is composed of more than just one single layer and that preferably chemically separates the substrate from the battery part of the electrochemical apparatus while allowing the reliable fabrication of such apparatus.
2.1 Fabrication of a Barrier Layer Including Insulating Barrier Sublayers
A barrier layer may be directly deposited onto the substrate. A barrier layer composed of barrier sublayers wherein at least one barrier sublayer is amorphous or glassy may be designed and fabricated to avoid or minimize grain boundary diffusion of ions and electrons, thereby reducing the diffusion of unwanted species into and out of the battery layers during fabrication and during operation and storage conditions of the battery thereafter. It is preferable to prevent or minimize chemical reactions between the battery components with the substrate.
Each of the barrier sublayers may, for example, be selected from a group of materials that may block the diffusion of ions from a LiCoO2 cathode layer (lithium ions, cobalt ions, and oxygen ions), atoms and ions from the current collector (gold, platinum, nickel, copper, etc.), and ions and atoms from the stainless steel substrate (iron, chromium, nickel, other heavy metals, and main group elements of the selected stainless steel type), although it may, for example, be sufficient to use simply electrically insulating materials that are inert to the substrate, the current collector, and/or the positive cathode. Selecting a barrier layer composed of sublayers that is capable of blocking ions and electrons may be considered a preferable approach regarding obtaining a substrate part and the battery part of the electrochemical apparatus that may be chemically separated during fabrication and during operation and storage conditions of the electrochemical apparatus thereafter.
The group of binary borides, carbides, silicides, nitrides, phosphides, oxides, fluorides, chlorides, bromides, and iodides, as well as diamond, diamond-like carbon, high-temperature stable organic polymers, and high-temperature stable silicones may, for example, provide general ion blocking properties in addition to electrical insulation properties. Therefore, these materials may be used for the barrier sublayer materials. In addition to using preferably the binary compounds of these materials, the barrier sublayers may, for example, be formed of any multinary compound composed of these materials such as, but not limited to, oxy-nitrides, carbo-borides, carbo-oxy-nitrides, silico-carbo-nitrides, and oxy-fluorides. The electrochemical apparatus of the present invention does not require the barrier layer to be a pure oxide.
The above-listed binary and multinary barrier sublayer materials may be deposited by selecting one or more of the many suitable thin-film deposition methods including sputtering (RF-magnetron, AC magnetron, DC and DC pulse magnetron, diode RF or DC or AC), electron beam evaporation, thermal (resistive) evaporation, plasma enhanced chemical vapor deposition, ion beam assisted deposition, cathodic arc deposition, electrochemical deposition, spray pyrolysis, etc. A Si3N4 barrier sublayer, for instance, may be fabricated by utilizing a pure silicon target that is sputtered preferably in a RF magnetron sputter system using an Ar—N2 reactive plasma environment. SiC and TiC barrier sublayer films are usually RF magnetron sputtered from targets of the same respective composition in an inert Ar plasma environment while their nitrogen doped derivatives, SiC:N and TiC:N, are deposited from SiC and TiC targets, respectively, in a reactive Ar—N2 plasma environment using RF magnetron sputter equipment.
The formation of optimized oxy-nitrides, carbo-borides, carbo-oxy-nitrides, silico-carbo-nitrides, oxy-fluorides, and the like may be accomplished by providing sputter gas mixtures that may contain N2, O2, N2O, BF3, C2F6, B2H6, CH4, SiH4, etc. either alone or in addition to an inert carrier gas, such as argon, and/or in addition to providing the elements from a sputter target. For example, the thin-film deposition of titanium silico-carbo-nitride (or titanium silicon carbide nitride), Ti3SiC2:N, may be accomplished by RF magnetron sputtering in Ar—N2 plasma atmosphere using either a single sputter target constructed of alternating areas of TiC and SiC, in an overall area ratio of 3:1 or two separate sputter targets, one of TiC and the other one of SiC, that are operated in such a way that they deposit a mixed material layer having a TiC/SiC ratio of 3:1 at any given time onto the same substrate area (dual target sputter deposition). The barrier-layer coated substrate may or may not be post-deposition processed prior to continuing with the battery fabrication.
An example for a barrier sublayer material may be Si3N4, SiNxOy for 3x+2y=4, or oxide-gradiented Si3N4 that may reach a stoichiometry at its surface, or at both of its surfaces, of almost SiO2, if so desired. Additionally, SiC or TiC, with or without nitrogen doping, may be used as a barrier sublayer material.
A few specific derivatives of these materials may not be most preferable as ion blockers when used in a barrier layer without any further, suitable barrier sublayers, because they allow the diffusion of certain ions in the fabrication process or during battery operating and storage conditions while exhibiting only poor insulating properties, such as non-stoichiometric ZrO2, non-stoichiometric YSZ (yttrium stabilized zirconia), and non-stoichiometric LiI (lithium iodide). In contrast to their stoichiometric counterparts, the non-stoichiometry is the main reason why these materials are electrically conductive while allowing oxygen and lithium ion diffusion, respectively.
To, for example, fine-tune certain barrier properties, such as improved adhesion to the substrate and/or the battery part, mechanical flexibility, stability to adjacent layers, pinhole-freeness, electrical resistance, and chemical inertness, suitable barrier layers may be provided that comprise barrier sublayers. For example, a barrier layer on top of a stainless steel 430 substrate may be constructed from a stack of barrier sublayers of the following sequence: 500 Å SiO2 (for improved adhesion to the oxide-bonding stainless steel substrate)/2000 Å Si3N4 (electrically insulating and diffusion blocking material towards lithium ions, cobalt ions, oxygen ions, iron ions, chromium ions, and gold atoms, for example)/1000 Å SiC:N (strongly diffusion blocking layer relative to lithium ions, cobalt ions, oxygen ions, iron ions, chromium ions, and gold atoms)/2000 Å Si3N4 (electrically insulating and diffusion blocking material towards lithium ions, cobalt ions, oxygen ions, iron ions, chromium ions, and gold atoms, for example)/500 Å SiO2 (adhesion facilitator to the current collector layer) onto which 300 Å cobalt current collector adhesion layer and 3000 Å gold current collector can be deposited.
In some cases the insulating barrier sublayers may not only be in contact with the positive cathode and/or the cathode current collector but also may be in contact with the negative anode and/or the anode current collector. In any case the barrier sublayers may, for example, be preferably chemically inert to all materials with which it is in contact. This characteristic may limit, for example, the use of a pure Al2O3 or SiO2 barrier layers when in contact with a metallic lithium negative anode which otherwise might react detrimentally to Li2O, LiAlO2, and Li—Al alloys or Li2O, Li2SiO3, and Li—Si alloys.
2.2 Fabrication of a Barrier Layer of at Least One Electrically Conductive Barrier Sublayer
Conductive barrier sublayers may, for example, be equally effective if, for example, they satisfy the preferable attributes of: 1) preventing ionic diffusion into or out of the battery layers; and 2) not reacting with either the substrate or the battery layers during the fabrication process and thereafter during all battery operating and storage conditions. The barrier layer, may, for example, include electrically insulating barrier sublayers as well. Such electrically insulating and electrically conductive sublayers may, for example, not all have the same shape or area size. Therefore, a barrier layer of such a mixed stack of barrier sublayers may, for example, be electrically conductive in some areas that are in contact with the substrate part or the battery part while in other contact areas with the substrate part or the battery part the barrier layer exhibits electrically insulating properties.
The materials for the electrically conductive barrier sublayers may, for example, be selected from the group of conductive binary borides, carbides, silicides, nitrides, phosphides, and oxides, as well as from the group of any of their conductive multinary compounds, for example, but not limited to, oxy-nitrides, carbo-borides, carbo-oxy-nitrides, silico-carbo-nitrides, and oxy-fluorides. Also, high-temperature stable polymers and high-temperature stable silicones may be used that are specifically engineered to be electrically conductive. The materials selection list for the electrically insulating barrier sublayers has been provided in the previous section 2.1 above and are incorporated herein. The barrier sublayers may be formed from completely different compositions, such as a barrier layer that may be fabricated of a barrier sublayer stack of, for example, 5000 Å ZrN/4000 Å Si3N4/3000 Å WC/1000 Å MoSi2 where each of the barrier sublayers may, for example, have different area dimensions.
As a result, for example, the Si3N4 barrier sublayer may extend over the entire footprint area of, for example, the metallic substrate while the ZrN barrier sublayer only covers the area on the substrate underneath the cathode current collector while the WC and MoSi2 barrier sublayers are, for example, covering at least the entire area underneath the anode current collector while further extending into the area of ZrN. Due to its area size, the interposed Si3N4 barrier sublayer may, for example, provide electrical separation of the electrically conductive ZrN barrier sublayer from the electrically conductive WC/MoSi2 barrier sublayers and thus the electrical separation between the positive and the negative parts of the battery (see
In this embodiment, an electrically conductive barrier sublayer, such as ZrN, TiN, WC, MoSi2, TiB2, or NiP may be deposited by standard deposition methods including sputter deposition (RF-magnetron, DC and DC pulse magnetron, AC magnetron, diode RF or DC or AC), electron beam evaporation, thermal (resistive) evaporation, plasma enhanced chemical vapor deposition, ion beam assisted deposition, cathodic arc deposition, electrochemical deposition, spray pyrolysis, etc. onto the substrate. For example, a ZrN barrier sublayer may be fabricated either from a ZrN sputter target performing a DC magnetron sputter deposition in an inert Ar atmosphere or from a metallic Zr target also using DC magnetron sputter deposition but in a reactive Ar—N2 atmosphere.
Additionally, certain metals (e.g., Au, Pt, Ir, Os, Ag, Pd), semi-metals (e.g., graphitic carbon, Si), and alloys (e.g., based on Au, Pt, Ir, Os, Ag, Pd, C, and Si) may be selected as an electrically conductive barrier sublayer, preferably, but not limited to, when the post-deposition anneal temperatures necessary to crystallize the positive cathode are moderate, such as 200° C.-500° C. The electrically conductive barrier sublayer may or may not be heat processed further before continuing with the battery fabrication process.
If fabricated appropriately in terms of electrical accessibility from the positive battery terminal, a conductive barrier sublayer may have the added advantage of eliminating a separate cathode current collector, unless, for example, one chooses to optimize the electrical properties of the conductive barrier sublayer by coating it with a better conducting and inert thin layer, for example, gold. Whether or not additionally coated with such a better conducting layer, the approach of the conductive barrier sublayer may include that, at the same time, the anode current collector and negative anode be separated from the conductive barrier sublayer to which the positive cathode and/or its cathode current collector makes electrical contact. This separation may be achieved, for example, as follows:
1) By extending the electrolyte in area so that both the negative anode and its anode current collector are entirely located on top of the electronically insulating electrolyte, which in turn serves, in this case, effectively as a local barrier sublayer for the negative anode and its anode current collector (see
2) When the negative anode and/or the anode current collector are not located entirely on top of the electrolyte, then they may make contact with the barrier layer and thus with at least with one of its barrier sublayers and/or the metallic substrate. In this case, one or more of the barrier sublayers may be electrically conductive while at least one of the sublayers should be insulating (see
2.3 Barrier Layer and Substrates
One reason for providing a barrier layer is, for example, providing chemical separation between the substrate part and the battery part of an electrochemical apparatus of an embodiment of the present invention during the fabrication of the battery part, which may entail process temperatures of up to the melting point of the substrate, and thereafter, during all operation and storage conditions of the electrochemical apparatus. The same principles as detailed above may apply for at least three substrate types of the present invention, which may comprise metallic substrates, polymeric substrates, and doped or undoped silicon substrates.
Direct depositions of electrically insulating or conductive barrier sublayers may be accomplished in a straightforward manner onto the three substrate types as described above. Of course, the inherent physical and chemical limitations each substrate type possesses should be observed, and the deposition parameters for each barrier sublayer should be adjusted accordingly. For example, a sputter deposition may be performed under such high deposition rates that the resulting deposition temperature at the substrate surface may exceed the melting point of the polymeric substrate. Therefore, the deposition parameters should preferably be limited so as to observe the melting point of the substrate. In another example, a very thin Si substrate of only 10 μm may be used. In such a case, it may be relevant to adjust the stresses of the barrier sublayers during their depositions, neglecting any post-deposition anneal for the moment, to the mechanical properties of the fragile Si substrate, in order not to crack it prior to the deposition of any subsequent barrier sublayers and/or the battery layers. More specific examples could be given without limiting the scope of the invention with respect to the possible use of all three substrate types and the basic principles for the fabrication of a barrier layer, including its barrier sublayers, onto them.
3. Battery Fabrication
Once the substrate in the present invention is fabricated with a barrier layer, the subsequent fabrication steps of the electrochemical apparatus depend on whether or not a second electrochemically active cell shall be fabricated onto the second side of the substrate to accomplish a “double-sided” electrochemical apparatus, which is discussed further below. The electrochemical apparatus of the present invention does not require the first electrochemically active cell to be a solar battery.
For the case of a “single-sided” electrochemical apparatus, however, wherein only a first electrochemically active cell is fabricated onto the first side of the substrate, a second layer is optionally deposited onto the second side of the substrate prior to the fabrication of the component layers of the first electrochemically active cell. This second layer can be fabricated with the objective to protect the substrate from the ambient environment against chemical and mechanical factors during the fabrication, operation, and storage of the electrochemical apparatus. In addition, through the implementation of the second layer, the first electrochemically active cell may be protected against chemical contaminants from the ambient environment that could enter the substrate at the second, otherwise unprotected side and diffuse through the substrate, thereby potentially reaching and detrimentally reacting with the first electrochemical active cell during fabrication, operation, and/or storage of the electrochemical apparatus. This protection of the first electrochemically active cell may be in addition to the protection provided by the substrate itself and by the barrier layer between the substrate and said first electrochemically active cell, in particular for the case in which the barrier layer may not cover the entire area underneath the first electrochemically active cell. The protection of both the substrate and the first electrochemically active cell may result in an extended lifetime of the electrochemical apparatus.
The second layer may be fabricated from a material that includes a chemical compound selected, for example, from the group of metals, semi-metals, alloys, borides, carbides, diamond, diamond-like carbon, silicides, nitrides, phosphides, oxides, fluorides, chlorides, bromides, iodides, or for example, from the group of any multinary compounds composed of borides, carbides, silicides, nitrides, phosphides, oxides, fluorides, chlorides, bromides, and iodides, or for example, from the group of high-temperature stable organic polymers and high-temperature stable silicones. In particular, a thin metal layer, between 500 Å and 5 μm thick, may be useful to protect the substrate by blocking the entry of contaminants at said second side during the fabrication, operation, and/or storage of the electrochemical apparatus. Furthermore, a metal layer, for example, nickel or titanium, may be useful because it can be deposited relatively fast and inexpensive compared to its ceramic counterparts, for example, TiC.
The blocking action of the second layer may, for example, include a chemical reaction of the second layer with the contaminants, which is known in the literature as chemical gettering, corrosion inhibition, or sacrificial layer provision, and is not limited to metal layers, but could also be accomplished with, for example, sub-oxides or sub-nitrides (insufficiently oxidized or nitrided film materials that can easily be fabricated by sputter depositions, for example) or, for example, nitrides or carbides that may convert into oxides or carbonates when reacting with the oxygen, moisture, or carbon dioxide contaminants present in the ambient environment during the fabrication, operation, and/or storage of the electrochemical apparatus.
One may fine-tune the second layer on the second side of the substrate by selecting materials that protect either mainly without a chemical reaction or mainly via chemical reaction. A further fine-tuning may then occur, for example, by selecting one of the latter materials but with a higher or a lesser reactivity under certain ambient environment conditions. For example, Al4C3 converts into Al2O3 at much lower temperatures and oxygen partial pressures than SiC to SiO2. Likewise, nitrides with a very small enthalpy of formation, such as CO2N, convert into the respective oxides at much lower temperatures and oxygen partial pressures than their counterparts that formed under a large negative enthalpy of formation, such as Si3N4 and ZrN.
Ultimately, it is up to the manufacturer of the electrochemical apparatus to decide on its optimum parameters relative to added costs for the fabrication of the second layer on the second side of the substrate, which is mainly a function of the materials selection and the fabricated thickness of the second layer, versus added protection of the substrate and the first electrochemically active cell against specific ambient environment conditions that exist for specific periods of time, which again is mainly a function of the materials selection and the fabricated thickness of said second layer.
Thin-film batteries may be manufactured in a batch fabrication process using sequential physical and/or chemical vapor deposition steps using shadow masks to build up the individual battery component layers. Electrochemically active cells may be fabricated with any of several structures. The features may include:
Depending on the electrical properties of the barrier layer, a cathode current collector may be fabricated prior to the deposition of the positive cathode. That is, if the barrier layer based on its sublayers is insulating in the area where the positive cathode is to be fabricated, then a cathode current collector may be deposited in order to create the necessary electrical access to the positive cathode from the positive terminal. If, however, the barrier layer based on its sublayers is electrically conductive in the area where the positive cathode is to be deposited, then an additional inert metal layer (“conduction enhancer”) may optionally be deposited between the barrier layer and the positive cathode in order to enhance the current collecting properties of the barrier layer.
The positive cathode, the cathode current collector, and the conduction enhancer of the barrier layer may be deposited by selecting any of the many deposition methods including sputtering (RF-magnetron, DC and DC pulse magnetron, AC magnetron, diode RF or DC or AC), electron beam evaporation, thermal (resistive) evaporation, plasma enhanced chemical vapor deposition, ion beam assisted deposition, cathodic arc deposition, electrochemical deposition, spray pyrolysis, etc.
After the deposition of the positive cathode a post-deposition anneal may follow in order to improve the physical, chemical, and electrochemical properties of the positive cathode. The most common post-deposition anneal occurs at 700° C. in air for about 30 minutes to 2 hours which completes the crystallization of positive cathode materials, LiCoO2, LiMn2O4, LiMnO2, LiNiO2, and derivatives thereof.
The composition of a given derivate and the parameters of the applied post-deposition anneal may inform the selection of the barrier layer material. For example, for pure LiCoO2 and a 700° C. anneal in air for 2 hours a 3000 Å gold cathode current collector that may be attached by a 300 Å cobalt adhesion layer to an electrically insulating barrier layer including two barrier sublayers, 5000 Å Al2O3 and 6000 Å CO3O4, on 50 μm of stainless steel 430 foil is one optional combination. The X-ray diffraction (XRD) pattern of this setup after the 700° C. anneal is shown in
Also after fabricating a pure LiCoO2 positive cathode over 3000 Å Au/300 Å Co cathode current collector attached to a barrier layer composed of two barrier sublayers, 5000 Å Si3N4 and 5000 Å SiO2, onto 300 μm thick undoped silicon substrate followed by an anneal at 700° C. in air for 2 hours, a well crystalline LiCoO2 positive cathode (ahex=2.8151(4) Å; chex=14.066(7) Å; sample grain size for the (101) plane of 1100 Å) may be obtained with virtually theoretical lattice parameters (e.g., ICDD 77-1370: ahex=2.815(1) Å; chex=14.05(1) Å). Having attained a well crystalline, stoichiometric LiCoO2 positive cathode film with layered structure and theoretical crystallographic lattice parameters provides, for example, that the crystalline LiCoO2 positive cathode film may not react with its surrounding materials, including the silicon substrate, as shown, for example, in
3.1.2 The Negative Anode Located between the Barrier Layer and the Positive Cathode, which may Provide Performance Approximating Deposition and Potential Post-Deposition Anneal of the Negative Anode Prior to the Deposition of the Positive Cathode: “Inverted Configuration”.
One example of an “inverted configuration” of an embodiment of the present invention is schematically shown in
The negative anode, the anode current collector, and the conduction enhancer of the barrier layer may be deposited by selecting any of the many deposition methods including sputtering (RF-magnetron, DC and DC pulse magnetron, AC magnetron, diode RF or DC or AC), electron beam evaporation, thermal (resistive) evaporation, plasma enhanced chemical vapor deposition, ion beam assisted deposition, cathodic arc deposition, electrochemical deposition, spray pyrolysis, etc.
The negative anode may be selected from the group of metal lithium, lithium-ion anodes, and so-called lithium-free anodes (see, e.g., U.S. Pat. No. 6,168,884, incorporated herein by reference in its entirety). After the deposition of the negative anode, a post-deposition anneal may follow in order to improve the physical, chemical, and electrochemical properties of the negative anode. Preferably, such an anneal may be applied to lithium-ion anodes, if at all, for example, to Li4Ti5O12, but, for example, not to metallic lithium, and not preferably to a group of lithium-free anodes.
The actual composition of the negative anode and the parameters of the applied post-deposition anneal may inform the selection of the barrier layer material. For example, for a metallic lithium negative anode, a barrier sublayer of 5000 Å of Si3N4 on silicon substrate that separates said silicon substrate from said metallic lithium negative anode, may provide the necessary barrier layer properties where the chemical inertness between the barrier layer and the metallic lithium may be accomplished through the positive enthalpy of reaction for the reaction path 12Li+Si3N4=4Li3N+3Si.
In an exemplary inverted configuration, the positive cathode may be deposited onto the electrolyte. Therefore, the temperatures permitted in a potential post-deposition anneal of the positive cathode may be limited, because for example, a chemical reaction between the electrolyte and the positive cathode is preferably avoided, as well as a reaction between the negative anode and the electrolyte.
3.2 Anode Configuration
Exemplary embodiments of “inverted configuration” have already been described above.
When fabricating an embodiment containing a negative anode entirely on top of the electrolyte, there may, for example, be no direct chemical interaction between the negative anode and the barrier layer.
When fabricating an embodiment of a negative anode partially on top of the electrolyte, the “normal configuration” (see 3.1.1) is preferable. The overhanging area of the negative anode over the electrolyte layer edge may be prevented from touching the barrier layer for the case where there is an anode current collector present (see
If the negative anode and/or its anode current collector make contact to the barrier layer, then two cases may need to be assessed: whether the negative anode and/or its anode current collector make contact to: 1) an insulating barrier sublayer, or 2) an electrically conductive barrier sublayer. In the first instance, it may be sufficient that this barrier sublayer be chemically inert to the negative anode and/or its anode current collector, such as Si3N4 when using a metallic lithium anode. For the second instance, in addition to the conductive barrier sublayer being in contact be chemically inert to the negative anode and/or its anode current collector, a more sophisticated barrier sublayer approach may, for example, be used for conductive substrates, for example, metallic ones and doped and undoped silicon (see examples in
The use of, for example, a 1 μm thick ZrN barrier sublayer is relatively simple and effective for the embodiment where a metallic lithium negative anode makes contact to this ZrN barrier sublayer, which in turn should not be shared with the positive part of the battery, but instead the positive part of the battery may be located over an insulating barrier sublayer such as Si3N4. One advantage of this latter example embodiment is that the ZrN barrier sublayer also may serve as the anode current collector for the negative metallic lithium anode (see
An anode current collector may comprise an inert metal, an inert alloy, or an inert nitride and thus may not be prone to reacting with the barrier layer or the negative anode. The anode current collector should preferably not make electrical contact to a conductive barrier sublayer to which also the positive cathode and/or the cathode current collector has electrical contact. Otherwise, the battery may be in a short-circuited state.
3.3 Substrate in Electrical Contact with the Electrochemically Active Cell
In an example embodiment where there is no reaction between the substrate and the positive cathode or the negative anode, the substrate with those electrodes may be brought into direct electrical contact or into indirect electrical contact via a current collector. However, for conductive substrates, such as metallic substrates, doped or undoped silicon wafers or metallized polymeric substrates, only one of those electrodes may, for example, be allowed to be in electrical contact with the substrate, because otherwise the electrochemically active cell may be shorted out or a strong current leakage may be introduced. This exemplary approach has the advantage of conveniently using the conductive substrate as one of, for example, two terminals of an electrochemical apparatus (see
3.4 Double Sided Electrochemical Apparatus
The present invention may include embodiments wherein an electrochemical apparatus has at least one electrochemically active cell on each side of the substrate. The fabrication, for example, of embodiments may include wherein each electrochemically active cell is deposited by a given electrochemically active cell component layer, such as the positive cathode, on both sides of the substrate using equipment that, for example, is capable of depositing both sides of the substrate at the same time prior to proceeding to the fabrication of the next battery component layer, which may also be deposited on both sides of the substrate at the same time.
The potential sequential fabrication process of the battery component layers may, for example, be done in the same manner as for a single sided electrochemical apparatus. As a result of this exemplary approach of layer completion on both sides of the substrates prior to depositing the next layer on both sides of the substrate, a potential post-deposition anneal might not be applied to a layer on the other side of the substrate that should not be subjected to such a post-deposition anneal.
Another exemplary approach may be to partially complete the fabrication of the first electrochemically active cell on the first side of the substrate before proceeding to the partial completion of the fabrication of the second electrochemically active cell on the second side of the substrate or any further electrochemically active cell on either the first or second side of the substrate. This approach may, for example, be employed when the available deposition equipment does not allow double sided depositions at the same time. For example, a deposit onto the first side of the substrate comprising a cathode current collector and then a positive cathode layer may be accomplished before depositing a cathode current collector and a positive cathode layer onto the second side of the substrate. After these steps, a post-deposition anneal may be applied to the partially completed electrochemically active cells on this substrate at the same time prior to continuing the fabrication of the electrochemically active cell on the first side of the substrate using the fabrication sequence electrolyte-anode current collector-anode. Subsequently, the same fabrication sequence may be applied to the second side of the substrate before both sides are encapsulated with heat sensitive polymeric laminates on both sides of the substrates at the same time or thin-film encapsulations that may be applied at the same time or sequentially.
Depending on the actual conditions of a potential post-deposition anneal of the positive cathode and/or negative anode, a third approach may be possible where the fabrication of the first electrochemically active cell on the first side of the substrate may completed prior to starting the fabrication of the second electrochemically active cell on the second side of the substrate.
3.5 Protective Encapsulation or Protective Encasing Design
For the purpose of the present invention, we define “protective encasing” as a protective enclosure such as, for example, a pouch or hermetically sealed metal can that contains the electrochemical apparatus, and in certain embodiments may fully enclose and/or entirely contain the apparatus. We define “protective encapsulation” as, for example, a protection that “caps” the electrochemical apparatus or one or more given individual electrochemically active cells of the electrochemical apparatus. The cap may, for example, be attached to the substrate area available next to the electrochemically active cell or any suitable substrate area of the electrochemical apparatus.
Before the electrochemical apparatus of the present invention may be operated in the ambient environment, it is, for example, preferred that it be protected against any reactive chemicals that may be present in a given ambient environment and which may detrimentally react or degrade the electrochemical apparatus. For example, if the ambient environment is air, the electrochemical apparatus of the present invention may preferably be protected against moisture, among other reactive chemicals such as O2 or CO2 (see for example, U.S. Pat. No. 6,916,679 incorporated herein in its entirety). One may protect the electrochemical apparatus of the present invention against those external, chemical factors, for example, inside a hermetically sealed metal can with electrical feed-throughs, such as, for example, laser welded stainless steel cans or vacuum-tight metal or glass tubes or vessels. However, the dimensions of such kinds of protective encasings may add too much inert volume and mass to an electrochemical apparatus whose components, except for the energy carrying positive cathode, can be minimized relative to their thicknesses. This strategy of minimization is particularly useful for the thickness of the inert components of the electrochemical apparatus, such as the substrate and any protective encasings, or protective encapsulations as well, whose mere presence is always reducing the densities of power, energy, and capacity of any electrochemically active cell, and thus the densities of power, energy, and capacity of the electrochemical device.
For the reasons described above, the protective encapsulation or protective encasing should preferably be as thin as possible while still being able to protect the electrochemical apparatus against a variety of chemicals present in the ambient environment in which the electrochemical apparatus is operated. Protection against those chemicals includes implicitly all of the pertaining temperatures of and exposure times to said chemicals, which the electrochemical apparatus encounters during its lifetime. However, it is the sole discretion of the manufacturer of the electrochemical apparatus to establish the optimum parameters of the electrochemical apparatus relative to manufacturing costs and performance. In this regard, an electrochemical apparatus, which may be operated only for a few days after its fabrication, for example, may receive a potentially cheaper and less sophisticated protective encapsulation or protective encasing than an electrochemical apparatus that, for example, may be designed to be operated for years.
Both protective encapsulation and protective encasing should allow external access to the terminals of the electrochemical apparatus. This external access may be accomplished by, for example, adopting one of the following three main engineering designs. First, the substrate and/or the protective encapsulation can serve as terminals to which direct external contact can be made (see, for example,
For improved lifetime, which represents a useful performance parameter of the electrochemical apparatus of the present invention, one may ensure, in particular for the case in which said opening of said third design is located near the electrolyte area, that the electrolyte receives added protection by, for example, a moisture protection layer, as schematically shown in
3.6 Current Collector and Terminals
Less electrically conducting electrode materials, such as a LiCoO2 positive cathode or a Li4Ti5O12 negative anode, may need a well conducting, inert backside contact (current collector), for example Au or Ni, in order to keep the electrical resistance of that electrode small, as well as minimize the ionic diffusion pathway inside the electrode, which is accomplished when the z-parameter (thickness) of the electronic and ionic pathway is kept to a minimum. This principle is implemented in most batteries where the electrodes are preferably built flat or thin (z-parameter), that is, have a length dimension (x-parameter) and width dimension (y-parameter) that is maximized compared to the thickness (z-parameter). Some electrodes are good electrical conductors, both electronically and ionically, and would not need a current collector for the aforementioned reasons. However, they may be chemically so reactive, such as a negative metallic Li anode, that they may preferably be separated from other battery parts, such as the negative terminal, by an appropriate inert “bridge”, such as Ni in the case of a negative Li metallic anode. This “bridge” may make contact to the reactive, well conducting electrode only in one corner or at one edge, in contrast to the full-area backside contact in the case of a poorly conducting electrode. The bridge serves as an inert medium between the reactive electrode and its terminal, and provides current collecting properties, and may thus be called “current collector” as well.
A terminal of the electrochemical apparatus of the present invention may, in one embodiment, be an extended current collector, and may thus made of the same material that makes contact to the electrode. However, the current collector used in thin-film batteries may be very thin and mechanically dense so that externally making contact to them, mechanically (e.g., clipping), soldering, or spot welding, for example, may not form a preferable permanent electrical contact. One may prefer to improve the contact properties of the current collector by adding, for example, thick and/or porous, well-conducting materials to the end of the current collector, which is the area called a “terminal”, to which a mechanical, soldered, or spot welded external electrical contact, for example, may be accomplished. In this regard, screen-printed silver and silver alloys, about 5-15 μm thick and fairly porous, have been successfully employed as a terminal that is printed in a manner so that the cathode or anode current collector may make good electrical contact to it while the screen-printed material does not chemically contaminate the electrochemically active cell, or cells, at any point during their fabrication, operation, or storage.
Example embodiments and implementations of the invention are described with reference to the drawings.
a illustrates an example embodiment of a barrier layer 310 containing a first barrier sublayer 311 and a second barrier sublayer 312, which may, for example, be electrically conductive for an embodiment wherein the electrical separation between the positive part and the negative part of the electrochemically active cell is accomplished through fabrication of the negative part entirely on top of the electrolyte 350. The positive part may, for example, constitute the second barrier sublayer 312, the cathode current collector 320, the positive terminal 330, and the positive cathode 340. When the first barrier layer 311 provided is electrically conductive, the positive part may additionally constitute the first barrier layer 311. For embodiments where the substrate 300 is electrically conductive, for example metallic, in conjunction with an electrically conductive first barrier layer 311, then this substrate may also become a part of the positive part. The negative part may constitute the negative anode 360, the anode current collector 370, and the negative terminal 380. In this particular example, the electrochemically active cell may be protected by an encapsulation 390 with an opening 391 to access the negative terminal 380.
b illustrates an example embodiment of a barrier layer 310 containing a first barrier sublayer 311 and a second barrier sublayer 312, which may for example be electrically conductive, for an embodiment where the electrical separation between the positive part and the negative part of the electrochemically active cell may, for example, be accomplished through fabrication of the negative part entirely on top of the electrolyte 350, while the cathode current collector 320, the positive terminal 330, and the positive cathode 340 may, for example, have electrical contact to the metallic substrate 300 via the second barrier sublayer 312. In this configuration, the metallic substrate 300 may serve as the positive terminal. The positive part may constitute a metallic substrate 300, a second barrier sublayer 312, a cathode current collector 320, a positive terminal 330, and a positive cathode 340. For an embodiment wherein the first barrier layer 311 is electrically conductive, the positive part may additionally include a first barrier layer 311. The negative part may include a negative anode 360, an anode current collector 370, and a negative terminal 380. In this particular example, an electrochemically active cell may be protected by an encapsulation 390 with an opening 391 to access the negative terminal 380.
c illustrates an example embodiment of a barrier layer 310 containing a first barrier sublayer 311 and a second barrier sublayer 312, which may, for example, be electrically conductive, for the case in which the electrical separation between the positive part and the negative part of the electrochemically active cell is accomplished through fabrication of the positive part entirely on top of the electrolyte 350 while the anode current collector 370, the negative terminal 380, and the negative anode may, for example, have electrical contact to the metallic substrate 300 via the second barrier layer 312. In this configuration, the substrate 300 may, for example, serve as the positive terminal as well. The positive part may constitute the cathode current collector 320, the positive terminal 330, and the positive cathode 340. The negative part may constitute metallic substrate 300, the second barrier sublayer 312, the negative anode 360, the anode current collector 370, and the negative terminal 380. In the case where the first barrier layer 311 is electrically conductive as well, the negative part may additionally constitute this first barrier layer 311. In this particular example, the electrochemically active cell may be protected by an encapsulation 390 with an opening 391 to access the positive terminal 330.
a illustrates an example embodiment of a barrier layer 410 containing electrically conductive barrier sublayers for the case in which the electrical separation between the positive and negative part of the electrochemically active cell may not be done via fabrication of the negative part entirely on top of the electrolyte 450. Together with the electrolyte 450 the second barrier layer 412, which is electrically insulating, may, for example, separate the positive from the negative part of the electrochemically active cell. The positive part may constitute a cathode current collector 420, a positive terminal 430, and a positive cathode 440. If the third barrier sublayer 413 is electrically conductive, then it may, for example, also become a member of the positive part. The first barrier sublayer 411 may be either electrically insulating or conductive. In the latter case, it may become a member of the negative part itself, for example, while making the substrate 400 a member of the negative part as well. Additionally, the negative part may constitute the negative anode 460, the anode current collector 470, and the negative terminal 480. In this configuration the metallic substrate also may serve as the negative terminal. Finally, the electrochemically active cell may be protected by an encapsulation 490.
b illustrates an embodiment of another example of a barrier layer 410 containing electrically conductive barrier sublayers for the case in which the electrical separation between the positive and negative part of the electrochemically active cell is not done via fabrication of the negative part entirely on top of the electrolyte 450. Together with the electrolyte 450, the second barrier layer 412, which is electrically insulating, may, for example, separate the positive from the negative part of the electrochemically active cell. The positive part may constitute a cathode current collector 420, a positive terminal 430, and a positive cathode 440. If the third barrier sublayer 413 is electrically conductive, then it may also become a member of the positive part. The first barrier sublayer 411 may be either electrically insulating or conductive. In the latter case, it may become a member of the negative part while making the substrate 400 a member of the negative part as well. Additionally, the negative part may constitute the negative anode 460, the anode current collector 470, and the negative terminal 480. In this configuration, the metallic substrate may serve as the negative terminal as well. Finally, the electrochemically active cell may be protected by an encapsulation 490.
c illustrates an embodiment of another example of a barrier layer 410 containing electrically conductive barrier sublayers for the case in which the electrical separation between the positive and negative part of the electrochemically active cell is not done via fabrication of the negative part entirely on top of the electrolyte 450. The negative anode 460 may, for example, have direct contact with the third barrier sublayer 413, which therefore is preferred to be chemically inert to negative anode 460. In this example, the third barrier sublayer 413 may, for example, be electrically insulating so that, together with the electrolyte 450, it may provide the electrical separation between the positive and the negative part of the electrochemically active cell. The positive part may constitute the cathode current collector 420, the positive terminal 430, and the positive cathode 440. If the second barrier sublayer 412 is electrically conductive, then it also may become a member of the positive part while also making the metallic substrate 400 a member of the positive part. The first barrier sublayer 411 may either be electrically insulating or conductive. In the latter case, it may also become a member of the positive part, but only if the second barrier layer 412 is as well. The negative part may constitute the negative anode 460, the anode current collector 470, and the negative terminal 480. In this configuration, the metallic substrate may serve as the negative terminal. Finally, the electrochemically active cell may be protected by an encapsulation 490.
a illustrates an embodiment of an anode configuration in which the negative anode 760 is not in direct contact with the barrier layer 710, and thus with any of its barrier sublayers 711, 712. While the first barrier sublayer 711 may either be electrically insulating or conductive, the second barrier sublayer 712 should be electrically insulating in order to avoid electrical short-circuiting of the electrochemical active cell and thus the electrochemical apparatus. In such a configuration where the negative anode 760 does not contact the barrier layer, it does not determine the selection of the chemical composition of the barrier sublayers 711, 712. The positive part of the electrochemically cell may, for example, include cathode current collector 720, the positive terminal 730, and the positive cathode 740 that are separated by the electrolyte 750 from the negative part, which may constitute the negative anode 760, the anode current collector 770, and the negative terminal 780. Finally, the electrochemically active cell may be protected by an encapsulation 790.
b illustrates a schematic of an anode configuration in which the negative anode 760 is in direct contact with the barrier layer 710, and thus with its barrier sublayer 712. While the first barrier sublayer 711 may either be electrically insulating or conductive, the second barrier sublayer 712 is preferably electrically insulating in order to avoid electrical short-circuiting of the electrochemical active cell and thus the electrochemical apparatus. In such a configuration, where the negative anode 760 has contact with the barrier layer, it may determine at least the selection of the chemical composition of that barrier sublayer 712 with which it is in contact. The positive part of the electrochemically cell may, for example, constitute the cathode current collector 720, the positive terminal 730, and the positive cathode 740 that are separated by the electrolyte 750 from the negative part, which may constitute the negative anode 760, the anode current collector 770, and the negative terminal 780. Finally, the electrochemically active cell may be protected by an encapsulation 790.
Although the invention has been particularly shown and described with reference to the various embodiments provided above, it will be understood by those skilled in the art that various changes in form and detail may be made to these various embodiments without departing from the spirit and scope of the invention.
The present application is a divisional, and claims the benefit under 35 U.S.C. §120, of U.S. patent application Ser. No. 11/209,536, filed Aug. 23, 2005, entitled “Electrochemical apparatus with barrier layer protected substrate,” now U.S. Pat. No. 8,021,778, issued Sep. 20, 2011, which is a continuation, and claims the benefit under 35 U.S.C. §120, of U.S. patent application Ser. No. 11/374,282, converted from U.S. provisional application Ser. No. 60/690,697, and filed on Jun. 15, 2005, entitled “Electrochemical apparatus with barrier layer protected substrate,” which is a continuation-in-part, and claims the benefit under 35 U.S.C. §120, of U.S. patent application Ser. No. 10/215,190, filed Aug. 9, 2002, entitled “Methods of and device for encapsulation and termination of electronic devices,” now U.S. Pat. No. 6,916,679, issued Jul. 12, 2005, which are incorporated herein by reference.
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| Number | Date | Country | |
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| 20090307896 A1 | Dec 2009 | US |
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| Parent | 11374282 | Jun 2005 | US |
| Child | 11209536 | US |
| Number | Date | Country | |
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| Parent | 10215190 | Aug 2002 | US |
| Child | 11374282 | US |
