KR20080033161A - Electrochemical apparatus with barrier layer protected substrate - Google Patents

Abstract

The present invention relates to apparatus, compositions and methods of fabricating high performance thin-film batteries on metallic substrates, polymeric substrates, or doped or undoped silicon substrates by fabricating an appropriate barrier layer composed, for example, of barrier sublayers between the substrate and the battery part of the present invention thereby separating these two parts chemically during the entire battery fabrication process as well as during any operation and storage of the electrochemical apparatus during its entire lifetime. In a preferred embodiment of the present invention thin-film batteries fabricated onto a thin, flexible stainless steel foil substrate using an appropriate barrier layer that is composed of barrier sublayers have uncompromised electrochemical performance compared to thin-film batteries fabricated onto ceramic substrates when using a 700°C post-deposition anneal process for a LiCoO2 positive cathode.

Description

ELECTROCHEMICAL APPARATUS WITH BARRIER LAYER PROTECTED SUBSTRATE}

Related Applications

This application is part of U.S. Provisional Patent Application Serial No. 60 / 690,697, filed June 15, 2005, filed partly, and in part of 35U.SC§120 of that application. Claims, relating to US application Ser. No. 11 / 209,536, filed August 23, 2005, which claims the benefit of 35U.SC§120 of that application, which documents are expressly incorporated herein by reference. do.

The field of the invention improves the capacity density, the energy density and the power density, and preferably is a lithium-based solid state with flexible form factor and crystalline LiCoO ₂ , LiNiO ₂ , LiMn ₂ O ₄ cathode and inducing material A device, structure and manufacture of thin film secondary and primary batteries.

Hereinafter, the needs and progress of related technologies in the field of thin film batteries will be described.

Thin film cells can be fabricated by sequential vacuum deposition of layered cell components onto the substrate, for example, in 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 the deposition process step (see, eg, US Pat. No. 6,916,679 to Wang et al., 143 J. Electrochem. Soc. 3203-12 (1996) or US Pat. No. 5,561,004). Optionally, the two terminals of the thin film cell do not simply include extensions of the positive and negative current collectors, but terminal contacts in electrical contact with each current collector can additionally be deposited. The positive cathode material may be insufficiently crystalline in the deposited state and may exhibit insufficient electrochemical properties in this regard (see, eg, Wang et al., Supra). Because of this, the positive cathode is crystallized during cell fabrication, which can be achieved by a high temperature (“anneal”) process after deposition (eg, Wang et al., Or New Trends in Electrochemical Technology : Energy Storage systems for Electronics (T. Osaka & M. Datta eds ., Gordon and See "Thin-Film Lithium Batteries" by Bates et al . , Breach 2000 ). The annealing process applied immediately after deposition of the positive cathode limits the selection of materials for the substrate and the positive cathode current collector, thereby limiting the capacity density, energy density, and power density of the thin film cell per volume and weight. For example, the influence of the substrate on these three amounts is described in detail below.

The volume and weight density of the intrinsic capacity, energy and power of the lithium-based solid state thin film secondary (chargeable) and primary (non-chargeable) cells (ie, without substrate and encapsulation) depends on the capacity of the positive cathode material. , Volume and weight density of energy and power. In the case of the secondary battery, the crystalline LiCoO ₂ has capacity, the bulk (not the film) in terms of energy, power and cycle capability and one example of a selected positive cathode material on either side of the thin film cell, a crystalline LiMn ₂ O _4, This is followed by crystalline LiMnO ₂ , and derivatives of crystalline LiNiO ₂ . These main parent positive cathode materials are Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru, Rh, La, Hf, Ta, W and Doping with other transition metals (which are derivatives), such as Ru, and major group elements selected from Groups 1, 2, 13, 14, 15, 16, and 17 has been found to improve LiCoO ₂ , LiMn for the overall improvement. ₂ O _4, it was found that very small changes to the characteristics of LiMnO _2, and LiNiO _2.

According to US Pat. No. 6,280,875, pure titanium oxide on a Ti substrate is not inert enough to prevent harmful reactions from occurring between the Ti substrate and the cell components. This approach is very limited because the choice of substrate material is limited to materials capable of forming pure surface oxides during the annealing step of the positive cathode. Apart from the present invention, metallic substrates comprising flexible foils that do not form pure surface oxides have not been successfully employed as thin film battery substrates. For example, direct deposition of a high temperature cathode material on a metallic substrate comprising a flexible foil other than Zr, followed by annealing at high temperature, such as 700 ° C. in air for 1 hour, to produce a solid state thin film secondary battery, This results in the substrate material reacting detrimentally to the extent that the positive cathode becomes useless. Pure Ti and Zr substrates are also relatively expensive.

Conventional thin film cells do not disclose the use of an effective barrier layer between the substrate and the cell, thus providing potential negative observations. There is a need for the invention, for example, as a creative barrier layer with sublayering properties to overcome certain problems of conventional thin film cells.

Summary of the Invention

As will be described in detail below as examples, various aspects and embodiments of the present invention address certain disadvantages of the prior art and emerging needs in the related industry.

The number of portable and on-board devices continues to increase rapidly, while the available physical dimensions may decrease. Batteries driving these devices must meet the needs of the device, such as potential size reduction while delivering the same power. The thinner the battery is, the more fields there are applicable. One possible power device is a thin film solid state cell. Footprint is a limiting factor, but if the capacity requirement is still "high", it becomes important to pack and stack as many battery cells as possible within the available space (footprint x height).

Batteries with the highest capacity, voltage, current, power, and chargeable cycle life can, for example, utilize LiCoO ₂ , LiMn ₂ O ₄ , LiMnO ₂ , LiNiO ₂ , and derivatives of today's most powerful positive cathode materials. .

When vacuum deposited into thin films, these materials may preferably include post-deposition annealing at high temperatures to improve crystallinity directly related to the development of the full range of electrochemical properties. In the case of an electrochemical device employing such a thin film cell, in order to be thin, the inert and electrochemically inactive part of the electrochemical device must be thinned. One approach may be to build the cell on a thin metal foil substrate instead of a thick bulk ceramic substrate. Metal foils are more flexible, thinner, and less expensive than ceramic substrates of the same footprint. In addition, they are readily available in very large areas, which leads to substantial cost reduction in manufacturing.

However, like other positive cathode materials, LiCoO ₂ is a strong oxidant and highly mobile and thus has reactive lithium ions. At the high annealing temperatures needed to crystallize the deposited LiCoO ₂ film, it reacts strongly with most compounds and most metals and alloys, with the exception of a limited number of inert ceramics. In other cases, undesired species can diffuse into LiCoO ₂ and contaminate the positive cathode during high annealing temperatures, thus detrimentally altering its electrochemical properties. If the annealing temperature is kept low enough to prevent reaction or unwanted diffusion, the positive cathode may not fully crystallize, and the capacity, energy, current and power capacity, and lifetime (number of cycles) for rechargeable cells This can be damaged.

High-power positive cathode materials can exhibit complete desired electrochemical properties in their crystalline state. Since these materials can be used, for example, in thin film form in the present invention, they are sputter deposition (RF, pulsed DC or AC), electron-beam evaporation, chemical vapor deposition, plasma enhanced chemical vapor deposition, spray pyrolysis, ion-assisted The deposition may be conventionally by one of the usual vapor deposition methods, such as beam evaporation, electron-beam direct vapor deposition, cathode arc deposition, and the like. These meteorological methods may not produce a deposited positive cathode film that exhibits electrochemical properties comparable to the positive cathode made from each well-crystallized powder used in bulk cells such as cell phone and camcorder type batteries. Thus, the poor electrochemical properties of such positive cathodes deposited by the thin film method can be attributed to the lack of the necessary crystallinity in the deposited state.

However, the crystallinity can be improved by post-deposition annealing at high temperatures, typically at 200 ° C to 900 ° C, preferably at 500 ° C to 850 ° C, more preferably at 650 ° C to 800 ° C. The atmosphere used for this annealing is typically air, O ₂ , N ₂ , Ar, He, H ₂ , H ₂ O, CO ₂ , vacuum (P <1 Torr), or a combination thereof. In order to achieve sufficient crystallization and thus to achieve improved electrochemical properties, the annealing time should preferably be extended if, for example, the annealing temperature is lowered below about 650 ° C. The crystallization rate is exponentially activated by the temperature, and thus can be significantly reduced at lower annealing temperatures. If the annealing temperature is too low, the energy applied from that annealing temperature may not be sufficient at all to exceed the thermal activation energy needed to cause the crystallization process to occur. For example, 900 ° C. anneal in air for 15 minutes may show the same crystallinity as in a magnetron-sputtered LiCoO ₂ membrane, about 1 hour anneal in air at 700 ° C., 12 hours anneal in air at 600 ° C. After annealing at 400 ° C. in air for 24 hours, the electrochemical quality of the magnetron-sputter deposited LiCoO ₂ cathode film remains poor and may not improve even after 72 hours at that temperature. Thus, the LiCoO ₂ cathode film produced via vapor phase can be annealed after deposition at 700 ° C. in air for about 30 minutes to 2 hours. However, such a relatively high annealing temperature can cause chemical miscibility problems, so such an annealing step is potentially undesirable in the manufacturing process of thin film cells, which can increase cost and reduce manufacturing yield. Can be.

Post-deposition annealing conditions greatly limit the choice of substrate material. The substrate must not only withstand the high annealing temperature (T> 500 ° C.), but also preferably be chemically inert to all cell membrane materials that are in contact with the substrate for the anneal atmosphere cell drive and applied storage conditions. Similarly, the substrate should preferably not be a source of impurities that can diffuse into the cell membrane material, either during manufacture or during subsequent drive and storage of the electrochemical device. Such impurities may harm any cell membrane material and may impair, seriously affect, or even destroy battery performance and lifespan. For example, the particular choice of substrate may be limited to chemically inert high temperature ceramics such as Al ₂ O ₃ , MgO, NaCl, SiC and quartz glass. Both metals, Zr and Ti, for example, have shown limited success as metal substrates. The electrochemical device of the present invention does not require that the substrate be Zr or Ti.

125㎛두께이고, 취성을 갖고, 비가요적(강성적)이며, 주어진 풋프린트 당 비교적 고가인 경향이 있다. 또한, 그것들의 얇은 면적 사이즈는 제한될 수 있다. 세라믹 기판이 얇을수록, 세라믹이 파손되지 않고 안전하게 취급될 수 있는 최대 면적은 더 작아진다. 예컨대, 1/4인치 두께의 12인치 × 12인치 플레이트 Al₂O₃는 상업적으로 쉽게 입수할 수 있다. 하지만, 10mil

250㎛ 두께의 박형화되고 폴리싱된 Al₂O₃ 세라믹 기판은 타당한 수율로 제조될 수 있는 면적을 대략 4인치 × 4인치 기판으로 감소시킨다. 박형의(< 20mil 또는 < 500㎛) 4인치 × 8인치 폴리싱된 세라믹 기판은 그것을 박막 전지의 대규모 제조를 위한 허용가능한 가격의 일반적인 재고로서가 아니라 소비자 주문으로 입수가능하다.Although the aforementioned ceramics have demonstrated their ability to withstand high temperatures without chemical reactions during thin film cell fabrication, their use in cost effective manufacture of thin film cells can present significant drawbacks. Ceramic is at least 5mil

It is 125 μm thick, brittle, inflexible (rigid), and tends to be relatively expensive per given footprint. In addition, their thin area size may be limited. The thinner the ceramic substrate, the smaller the maximum area that can be safely handled without breaking the ceramic. For example, a 1/4 inch thick 12 inch by 12 inch plate Al ₂ O ₃ is readily available commercially. But 10mil

A thin and polished Al ₂ O ₃ ceramic substrate of 250 μm thickness reduces the area that can be produced with reasonable yield to approximately 4 inch by 4 inch substrates. Thin (<20 mil or <500 μm) 4 inch by 8 inch polished ceramic substrates are available on consumer order, not as an acceptable inventory of acceptable prices for large-scale manufacture of thin film cells.

Due to their brittleness at about 100 μm or less, it may not be possible to use ceramics as substrate materials for thin film battery materials (see US Pat. No. 6,632,563, which describes mica substrates having a thickness of 100 μm or less). Despite the technology). One of the properties of mica is that it is very brittle, even at thicknesses above 100 μm. However, the use of a ceramic substrate thicker than 100 μm envisions that the electrochemically inert weight and volume of the substrate is also greater than 90% of the weight and volume of the entire cell, which may be undesirable.

For all of the above reasons, non-ceramic foils can be used as thin film battery substrates. For example, silicon and doped silicon can take intermediate positions beneath non-ceramic substrates, including metal and polymer substrates.

12-125㎛ 두께와, 수 미터의 폭과, 수 미터 길이의 롤로서 입수가능하다. 긴 롤로부터의 기판은 현재 실시되고 있는 통상적인 배치 모드 제조 프로세스보다 매우 낮은 비용에서 오픈 롤식(roll-to-roll) 제조의 가능성을 제시한다. 두껍고 강성인 기판상에서 제조된 박막 전지에 비하여, 전지 성능을 손상시키지 않으면서, 박막 전지를 얇고 더 가요성인 기판상에서 제조하는 것은 박막 전지 기술에 대한 특정 적용을 가능하게 하는 역할을 한다.For example, non-ceramic foils can provide advantages as substrates for thin film cells if the substrate material can tolerate contact with processing conditions including temperature, such as certain potential reactive cell layers. Compared to ceramic substrates of a given footprint, non-ceramic foil substrates are thinner, more flexible, cheaper, more readily available in large sizes, and reduce the electrochemically inert weight and volume of the entire cell. In doing so, the overall thickness of the cell or electrochemical device can be reduced, which will increase the capacity density, energy density, and power density of the cell. For example, the non-ceramic foil is for example 0.5-5 mil

Available as 12-125 μm thick, several meters wide and several meters long rolls. Substrates from long rolls offer the possibility of open roll-to-roll manufacturing at much lower costs than conventional batch mode manufacturing processes currently in place. Compared to thin film cells fabricated on thick and rigid substrates, making thin film cells on thinner and more flexible substrates without compromising cell performance serves to enable specific applications for thin film cell technology.

50㎛=0.005cm 두께의 호일 기판상에 동일한 풋프린트 및 동일한 전지 커패시티로 박막 전지를 제조하는 것은 그 체적 내에 최대 20개 전지의 적층을 더 허용할 것이다. 전지의 실제 수는 예컨대, 기판과 선택적인 보호 인캡슐레이션 또는 인케이싱을 포함하는 각 전지 셀의 두께에 의해서 결정된다. 두꺼운 세라믹 기판 대신에 얇은 비-세라믹 호일 기판을 사용하는 것은 커패시티 밀도, 에너지 밀도 및 파워 밀도에서의 많은 증가를 야기할 수 있다.By significantly thinning the substrate, reducing the electrochemically inert weight and volume of the cell can increase the cell's capacity density, energy density, and power density per unit weight and volume. For example, a given application may assign a volume of 2 cm x 2 cm x 0.1 cm to a cell. At present there is no conventional button cell or jelly roll (spiral wound or footnote) battery that can physically fit into such volume. In contrast, even thin film solid-state cells are manufactured from 0.05 cm ceramic substrates, since the entire cell, including selective protective encapsulation and encasing (see regulations below), is much thinner than 0.1 cm. It can fit into such a volume. 2mil

Fabricating thin film cells with the same footprint and the same cell capacity on a 50 μm = 0.005 cm thick foil substrate will further allow stacking of up to 20 cells in that volume. The actual number of batteries is determined by the thickness of each battery cell, including, for example, the substrate and optional protective encapsulation or encasing. The use of thin non-ceramic foil substrates instead of thick ceramic substrates can result in many increases in capacity density, energy density and power density.

For example, thin film cells can be made by sequentially stacking individual cell component layers on top of each other. As mentioned above, optimal positive cathodes include, but are not limited to, LiCoO ₂ , LiMn ₂ O ₄ , LiMnO ₂ , LiNiO ₂ , and derivatives thereof. The electrochemical device of the present invention does not require a Li _x V ₂ O _y cathode, where O <x ≤ 100 and 0 <y ≤ 5. The positive cathode may comprise post-deposition annealing at 500 ° C. or higher to fully crystallize and achieve their full electrochemical properties. Certain known solid state lithium electrolytes are in contact with the high temperature positive cathode at such high temperatures. The positive cathode is deposited and annealed before depositing the electrolyte layer because it can react destructively in the case.

Positive cathode materials can generally be regarded as poor semiconductors in at least some range of charge states during cell drive. To obtain maximum power from the cell and to external circuitry, a positive cathode layer can be deposited on a metallic back contact, cathode current collector (CCC) layer. This CCC must also perform a hot cathode anneal and at the same time not react with the positive cathode. Thus, for example, precious metals such as gold or alloys thereof, or equivalents thereof can be used.

The fact highlighted above suggests that for the purpose of improving the performance of the cell, the positive cathode material can be deposited as the second layer of the cell immediately after deposition of the CCC. Thus, post-deposition annealing of the positive cathode layer can achieve its crystallization prior to subsequent manufacturing steps and electrolyte deposition. Due to the proximity of the substrate and the hot cathode material, which can only be separated from each other by a relatively thin CCC (0.1-1 μm), when using a high temperature stable metal foil such as stainless steel instead of a ceramic substrate, Very harmful interdiffusion and strong reactions were observed. This interdiffusion may not be blocked by metallic CCC alone, for example for three main reasons. First, the CCC film is relatively thin (0.1-1 mu m), showing only a thin quasi-diffusion barrier. Second, the CCC shows a crystalline grain structure. The grain boundaries can be conventional locations for ion and electron diffusion and conduction, so the CCC should be viewed as inherently transmissive for ions and electrons from both the adjacent positive cathode layer and the adjacent metallic foil substrate. Thus, during the cathode annealing step, the foil substrate material and the cathode film material may be interdiffused. Third, metallic CCCs are alloyed with metal foil substrates to affect their current collection characteristics.

The thickness of the CCC is determined, for example, by cost, weight, volume and adhesion, all of which would be technically infeasible when producing CCCs thicker than about 2 μm, especially when using expensive precious metals such as gold. Can be. Potentially, CCC films that are significantly thicker than about 5 μm may avoid interdiffusion, for example, depending on the temperature of the annealing step and the associated residence time. However, the use of such thick CCCs may include, for example, increased material costs and potentially unreliable attachments.

The replacement of ceramic substrates with metal foil substrates creates numerous opportunities to enable new technologies using thin film cells, in addition to reducing manufacturing costs for thin film cells manufactured from ceramic substrates. In contrast to ceramic plates, metal foils are readily commercially available in thicknesses less than 75 μm, and some materials are available as thin as 4 μm. These foils are much more flexible than their ceramic counterparts, contribute less to the structural and inert weight to the cell, and most importantly substantially reduce the overall thickness of the finished thin film cell device. It should be emphasized that the reduction of the overall thickness of the cell and the increase in flexibility are particularly important for most thin film cell applications. Thinner thin-film cell devices can accommodate new and physically small applications. What could not be done with button-cell batteries is now possible with thin-film batteries (ie smart cards, etc.). The added flexibility of the foil substrate makes it possible, for example, to better match the new non-planar shape.

Also, thin metal foils can generally be less expensive per footprint area than ceramics, and can be of larger size, such as rolls. The availability of flexible, large-area substrates has the potential for the development of open-roll manufacturing methods, thereby further reducing manufacturing costs.

For example, new applications may be made possible by thin film cells that are intact or provide improved performance over conventional thin film cells fabricated on ceramic substrates. In this regard, the present invention may include depositing an interdiffusion barrier layer on a metal foil substrate, wherein the barrier layer is impurity as well as in the range between high and low post-deposition annealing temperatures, such as between 100 ° C. and the melting point of the substrate. The cell (ie, electrochemically active cell) portion is chemically separated from the substrate portion of the electrochemical device during the driving and storage state of the electrochemical device which is not a source of. An embodiment of this aspect of the invention is shown for example in FIG. 1.

The barrier layer, for example, prevents diffusion of any contaminants from the substrate into the cell, as well as diffusion of block ions that diffuse out of the cell into the substrate during, for example, battery manufacture and cell drive and storage conditions. Such a barrier layer may, for example, not exhibit grain structure at any time. That is, the barrier layer may be in an amorphous or glassy state in the deposited state, and may remain in such a state during the battery driving and storage state as well as during the entire annealing and cell manufacturing process. The absence of grain structures in the barrier layer can avoid harmful grain boundary diffusion or conduction of ions and electrons. As mentioned above, the grain boundary is a path through which impurities and contaminants move. If these specific conditions are met, a flexible, thinner, less flexible, and thicker thin film cell fabricated on a metal substrate is, for example, chemically inert and fabricated on a thick, heavy, rigid, expensive ceramic substrate. It can exhibit characteristics comparable to thin film cells.

Specific materials potentially suitable for the diffusion barrier layer include, for example, borides, carbides, diamonds, diamond-like carbons (DLCs), silicides, nitrides, phosphides, oxides, fluorides, chlorides, bromide, iodides, and It may be a material with weak ion conduction, such as any multinary compound thereof. Among these compounds, electrically insulating materials can further prevent possible reactions between the substrate and the cell layer, such as the blocking of electrons if these chemical reactions include diffusion of ions and electrons. As may be one means of blocking these exemplary chemical reactions. However, for example, an electrically conductive material such as ZrN can be used as long as it does not conduct any substrate ions or cell layer material. In some cases, metals, alloys and / or semi-metals may serve as sufficient barrier layers depending on the annealing temperature applied during the cell fabrication process and the substrate material used. Although amorphous or glassy structures are generally used due to the absence of grain boundaries that increase but act as sites of unwanted ionic and electron conduction, the diffusion barrier layer is, for example, single phase or multiphase, crystalline, glassy, amorphous or any of its It can be mixed.

Since a particular material blocks the conduction of various ions, such a particular material in certain lithium non-containing thin film cells, such as cells whose electron-active ions are, for example, beryllium, sodium, magnesium, potassium, calcium, boron, and aluminum. Can also be used. The thickness of the diffusion barrier layer may be, for example, in the range of 0.01 μm to 1 mm.

Although the concepts and principles of the barrier layer and / or sub-barrier layer for the thin film cell of the present invention were originally developed for metal substrates, for example, the related thin film cell applications are also commercially of interest for polymer substrates, doping and The same barrier layer material may be deposited on the non-doped silicon substrate. The post-deposition annealing temperature can be lower than, for example, the melting point of the silicon or polymer substrate used, regardless of the barrier layer applied to avoid melting of the substrate, for example.

Embodiments of the present invention relate to methods of manufacturing, for example, flexible high-capacity solid state thin film cells on thin foil substrates, such as metal substrates. For the purposes of the present invention, an electrochemical device is defined as a device comprising at least one electrochemically active cell such as a thin film cell, a suitable substrate such as a metal substrate, and a suitable diffusion barrier layer, the barrier layer being electrochemically It may consist of a plurality of barrier sublayers between the active cell and the substrate (see FIG. 1). In addition, the electrochemical device may comprise protective encapsulation or protective encapsulation, described in detail below.

It is believed that the success of the characteristic embodiments of the present invention is the utilization of appropriate chemically inert diffusion barrier layers and sublayers between these two parts, which can effectively separate between the substrate and the thin film cell of the electrochemical device. The diffusion barrier layer can withstand the high annealing temperatures that can be applied to the thin film cell during manufacture of the thin film cell portion on the substrate, is inert to both the substrate and the thin film cell portion, and is at least a source of impurities for the thin film cell portion. It is preferable that the thin film battery part is chemically separated from the substrate under the driving and storage state of the electrochemical device after the completion of manufacturing. In addition, the barrier layer may, for example, not only diffuse any contaminants that attempt to enter the thin film cell portion, but also block Li ions that attempt to diffuse out of the thin film cell portion to the substrate during cell manufacture and during all cell drive and storage conditions. It is desirable to prevent diffusion. As an added benefit, the barrier layer can also protect the substrate during processing from any thin film cell components already present in the manufacturing stage of the incomplete electrochemical device from the atmosphere applied during post-deposition annealing.

Fabrication of a diffusion barrier of a plurality of barrier sublayers allows for fine composition of the physical (mechanical (especially pinhole-free, flexible and adherent), electrical, magnetic, acoustical, thermal and optical) and chemical properties of the diffusion barrier layer. And Ti ₈₄ B ₁₆ which is a two-phase ("composite") of Si ₃ N ₄ or, for example, thermodynamically nearly equal amounts of TiB ₂ and beta-B ( binary , incorporated herein by reference). Alloy Phase Diagrams , 2 ^nd TiO ₂ -Ba _0.5 as described in Ed. (TB Massalski, H. Okamoto, PR Subramanian, and L. Kacprzak eds., ASM International 1990)) or US Pat. No. 6,444,336, which is incorporated herein by reference. Improves the performance and reliability of electrochemical devices compared to devices fabricated with diffusion barrier layers that may include only one single layer of a given material, such as an Sr _0.5 TiO ₃ composite material. In its simplest form, the diffusion barrier layer of the present invention comprises a thin (~ 1000 microns) barrier sublayer with additional adhesion improving properties such as Ti and one thicker (1 μm) barrier sublayer such as Si ₃ N ₄ . It may include.

The barrier sublayer material of the diffusion barrier layer of the present invention may include, but is not limited to, amorphous Si ₃ N ₄ , SiC, ZrN, and TiC, among others. These are exemplary compounds that can effectively act as barriers due to their ion barrier properties, amorphous structure, and chemical inertness to the substrate of the electrochemical device as well as to the cell part. The salient feature of these barrier layer chemistries is that they retain their amorphous state in the deposited state and during the preferred LiCoO ₂ crystallization deposition-annealing process, for example up to substantially high temperatures of 700 ° C. and at these temperatures for a long period of time, for example 2 hours. Their inherent ability to maintain their diffusion blocking properties. As a result, thin film cells having such barrier layers and fabricated on metal foils have the added advantage of maintaining good electrochemical properties, and being thinner and less expensive, for thin film cells of equivalent construction made on ceramic substrates. .

Embodiments of the invention relate to, for example, forming an appropriate barrier layer on a substrate in conjunction with subsequent thin film cell fabrication, wherein the barrier layer is used to fabricate the substrate during battery operation as well as during subsequent battery drive and storage conditions. It can be chemically separated from the battery compartment. Polymer substrates and doped and undoped silicon substrates may be used in addition to the metal substrate.

It is an object of embodiments of the present invention to provide an electrochemical device having, for example, a metal substrate, a polymer substrate, or a doped or undoped silicon substrate and having only one side of the substrate (electrochemically active cell).

Another object of an embodiment of the invention is, for example, an electrochemical device having a metal substrate, a polymer substrate, or a doped or undoped silicon substrate, and having two cells (two electrochemically active cells), one on each side of the substrate. To provide.

Another object of an embodiment of the present invention is to provide a method for producing an electrochemical device having, for example, a metal substrate, a polymer substrate, or a doped or undoped silicon substrate, and having a battery (electrochemically active cell) on only one side of the substrate. will be.

Another object of an embodiment of the invention is, for example, an electrochemical device having a metal substrate, a polymer substrate, or a doped or undoped silicon substrate, and having two cells (two electrochemically active cells), one on each side of the substrate. It is to provide a method for producing.

1 shows an exemplary schematic diagram of an embodiment for chemically separating a substrate from an electrochemically active cell portion of an electrochemical device through a barrier layer comprising a plurality of barrier sublayers.

2 shows a schematic diagram of an exemplary use of one embodiment of a barrier layer that provides electrical separation between the positive and negative portions of an electrochemically active cell and includes barrier sublayers of different area dimensions.

3A illustrates an embodiment of a barrier layer comprising an electrically conductive barrier sublayer for the case where electrical separation between the positive and negative portions of an electrochemically active cell is achieved through forming a negative portion throughout the top of the electrolyte. Shows a schematic of the enemy use.

3B illustrates an embodiment of a barrier layer including an electrically conductive barrier sublayer on a metal substrate for the case where electrical separation between the positive and negative portions of the cell is achieved through forming a negative portion throughout the top of the electrolyte. A schematic of another example use is shown.

3C illustrates an embodiment of a barrier layer including an electrically conductive barrier sublayer on a metal substrate for the case where electrical separation between the positive and negative portions of the cell is achieved through forming a positive portion throughout the top of the electrolyte. A schematic diagram of example use is shown.

4A illustrates an embodiment of a barrier layer comprising an electrically conductive barrier sublayer for the case where electrical separation between the positive and negative portions of the electrochemically active cell is not done through the formation of a negative portion throughout the top of the electrolyte. A schematic diagram of example use is shown.

4B illustrates an embodiment of a barrier layer including an electrically conductive barrier sublayer for the case where electrical separation between the positive and negative portions of the electrochemically active cell is not done through the formation of a negative portion throughout the top of the electrolyte. A schematic of another example use is shown.

4C shows an electrically conductive barrier for the case where the negative separation of the negative anode is in direct contact with the barrier sublayer without electrical separation between the positive and negative portions of the electrochemically active cell being made through the formation of a negative portion throughout the top of the electrolyte. A schematic diagram of an example use of one embodiment of a barrier layer that includes a sublayer is shown.

FIG. 5 shows a 3000 Å Au cathode current collector phase on a 300 부착 Co adhesion layer attached to an electrically insulating barrier layer consisting of two barrier sublayers of 5000 Å Al ₂ O ₃ and 6000 Å Co ₃ O ₄ on a 50 μm thick stainless steel foil type 430 substrate. A graph of the X-ray diffraction (XRD) pattern of one embodiment of a 1.6 μm thick LiCoO ₂ positive cathode film formed on the substrate is shown.

FIG. 6 shows a 1.6 μm thick LiCoO ₂ positive cathode film formed on a 3000 mA Au cathode current collector on a 300 mA Co adhesion layer on a barrier layer consisting of two sublayers of 5000 mA Si ₃ N ₄ and 5000 mA SiO ₂ on a 300 μm thick silicon substrate. A graph of the X-ray diffraction (XRD) pattern of the example is shown.

FIG. 7A shows a schematic diagram of one embodiment of an anode configuration of “typical configuration” in which the negative anode does not directly contact the barrier layer.

7B shows a schematic diagram of one embodiment of an anode configuration of “typical configuration” in which the negative anode is in direct contact with at least one of the barrier sublayers.

8 shows a schematic diagram of one embodiment of an "conventional configuration" anode configuration in which a negative anode is in direct contact with an electrically conductive ZrN barrier sublayer that also acts as an anode current collector.

FIG. 9 shows a schematic diagram of one embodiment of a cell configuration where the negative anode is in direct contact with the substrate when the substrate is electrochemically inactive with respect to the negative anode. In this embodiment, when the substrate is sufficiently electrically conductive, such as in the case of stainless steel, for example, the substrate can act as a negative anode current collector and negative terminal.

FIG. 10 shows a schematic diagram of one embodiment of the use of a moisture protection layer to protect the moisture-sensitive electrolyte layer from moisture present in the surrounding environment, with protective encapsulation formed with openings to provide connection to negative terminals; FIG. Illustrated.

It is to be understood that the present invention is not limited to the specific methodology, protocols, and the like described herein, but may be modified. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the invention, which is defined only by the claims.

As used in the claims and herein, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise.

All patents and other publications identified are hereby incorporated by reference in their entirety for the purpose of describing and disclosing, for example, the methodologies, apparatus and configurations described within such publications that may be used in connection with the present invention. These publications are provided only for disclosures prior to the filing date of the present invention. In this regard, the inventors should not be construed as prioritizing such disclosure by prior invention or as permission not entitled for any other purpose.

Unless defined otherwise, all technical terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although any known methods, devices, and materials may be used in the practice and testing of the present invention, certain exemplary preferred methods, devices, and materials are described herein in this regard.

Thin film cells can be produced, for example, in batch mode by depositing individual cell component layers sequentially. Once the substrate material is selected, the material can be prepared by cleaning and, if desired, by other pretreatment. Barrier layers consisting of barrier sublayers, which can be a total of 0.5-5 μm thick, are important for the successful manufacture of thin film cells on metal as well as metal and polymer foils. The barrier layer, together with the cathode current collector, must be able to withstand the annealing temperature for the positive cathode film, remain chemically inert and should not be a source of impurities.

Additionally, the barrier layer must not only diffuse all ions and atoms from the positive cathode and cathode current collector into the substrate during cell fabrication and during all cell drive and storage states, but also enters the positive cathode from the substrate. The spread of any contaminants should be prevented. The barrier layer can be deposited on a clean substrate and typically coats the substrate with a uniform and defect free film. The following battery layers can be deposited sequentially in a batch using a shadow mask to separate the boundaries of each layer of the thin film battery. The barrier layer breaks the grain boundary diffusion effect, thereby reacting between sequentially deposited positive cathodes such as LiCoO ₂ with a lower cathode current collector and substrates such as gold cathode current collectors and flexible stainless steel foil substrates. Can be designed and manufactured to eliminate. Hereinafter, an exemplary scheme of an embodiment in which a barrier layer including a barrier sublayer is deposited on a substrate on which a thin film battery is formed is proposed.

1. Board Selection and Preparation

First, the substrate material can be selected. Thin film cells can be fabricated on a variety of metal foils and sheets with various surface finishes. Thin foils of stainless steel can be used as the substrate. However, other materials, such as Ti and Ti alloys, Al and Al alloys, Cu and Cu alloys, and Ni and Ni alloys, including but not limited to, more expensive and thicker or lower melting point materials may also be used. In addition, the desired physical properties, surface roughness, homogeneity, and purity of the foils, such as those types of steel alloys, are left to the user to determine the optimum manufacturing parameters for the particular device. The electrochemical device of the present invention does not require the substrate to be Al coated with a metal or semi-metal comprising V, Mn, Mg, Fe, Ge, Cr, Ni, Zn and Co. In addition, the electrochemical device of the present invention does not require that the substrate be pure polyimide.

For example, once a stainless steel foil material is selected, it is generally cleaned to remove oil, particulates, and other surface contaminants that, if not removed, may interfere with the chemical or mechanical adhesion of the barrier layer to the substrate. Any cleaning procedure can be used in this regard, such as any suitable wet chemical cleaning or plasma cleaning process that provides a sufficiently clean surface. Optionally, the cleaned foil substrate can be further pretreated if desired. For example, to relieve the intrinsic stress of the metal foil, an annealing step at high temperature (eg 500 ° C.) may be employed prior to depositing the barrier layer, as long as the annealing temperature is kept below the melting point of the metal foil.

Although substantially independent of any foil material and its thickness, some annealing methods can further reduce or accommodate the thermal and mechanical stresses of the membrane base. For example, pre-annealing of the cleaned foil can be performed as described above to adjust the uncoated metal foil. In addition, other annealing steps may include, for example, any combination of post-deposition barrier layer anneal, post-deposition cathode current collector layer anneal, or post-deposition layer anneal prior to cathode crystallization anneal. Additional plasma treatment may be followed before or after such a step (eg DM Mattox, Handbook). of Physical Vapor Deposition ( PVD ) Processing , Society of Vacuum See Coaters , Albuquerque , New Mexico 660ff and 692ff (Noyes Publications 1998). Similarly, silicon and polymer substrates may be prepared.

2. Barrier layer  accumulation

The deposition of the barrier layer on the substrate may be performed in conjunction with thin film cell fabrication, such as chemically separating the substrate from the cell portion, as well as during cell fabrication, eg, during subsequent cell drive and storage conditions.

In general, chemical reactions between potential reactants are such that when their ions or their electrons are confined to each of the spaces of the reactants or are blocked at the interface of the reactants, preferably there is no interdiffusion of such species between the potential reactants. Can be prevented. In addition to the simple diffusion barrier properties, the material chosen for the barrier layer and the barrier sublayers constituting it must be capable of withstanding the annealing temperature for the positive cathode film with (a) the cathode current collector, and (b) It must be taken into account that it remains chemically inert and (c) is not a source of impurities.

For example, an electrically conductive material, such as ZrN, having appropriate diffusion barrier properties for ions can be deposited to chemically separate the substrate from the cell portion within the electrochemical device. In this case, the conductive barrier sublayer can also act as a current collector. ZrN may also be used as cathode current collector and / or anode current collector because it is stable in contact with negative anode material, in particular metallic lithium.

Although it is suitable in principle to configure the barrier layer as one single layer of a specific material, such as Si ₃ N ₄ , which is electrically insulating and blocks metal ions, each barrier layer composed of more than one suitable sublayer, It has been found that the sublayer of achieves higher barrier yields and thus higher reliability in cell performance over a given thin film cell life, for the purpose of providing different specific properties to the barrier layer and for fine tuning the barrier layer properties. For this reason, the present invention consists of more than one single layer, and preferably provides for the manufacture and provision of a barrier layer that chemically separates the substrate from the battery portion of the device while enabling reliable manufacture of the electrochemical device. Focus.

2.1 insulation Barrier Sublayer  Containing Barrier layer  Produce

The barrier layer can be deposited directly on the substrate. A barrier layer consisting of a barrier sublayer in which at least one barrier sublayer is amorphous or glassy avoids or minimizes the intergranular diffusion of ions and electrons, thereby avoiding unwanted paper during cell manufacture and subsequent drive and storage states of the cell. It can be designed and manufactured to reduce diffusion into or from the cell layer. It is desirable to prevent or minimize chemical reactions between cell components and the substrate.

For example, it may be sufficient to simply use an electrically insulating material that is inert to the substrate, current collector, and / or positive cathode, but each barrier sublayer may contain, for example, ions from the LiCoO ₂ cathode layer (lithium ions, cobalt ions). , And oxygen ions), atoms and ions from current collectors (gold, platinum, nickel, copper, etc.), and ions and atoms (iron, chromium, nickel, other heavy metals, and selected stainless steel types) from stainless steel substrates Element) and may be selected from the group of materials capable of blocking the diffusion of elements). The selection of the barrier layer, which consists of sublayers capable of blocking ions and electrons, obtains the substrate portion and the battery portion of the electrochemical device, which can be chemically separated during the manufacture of the electrochemical device and during subsequent driving and storage conditions. Can be considered a preferred approach.

Diamonds, pseudo-diamond carbons, high temperature stable organic polymers, and high temperature stable silicones, as well as groups of binary borides, carbides, silicides, nitrides, phosphides, oxides, fluorides, chlorides, bromides, and iodides In addition to the insulating properties, general ion blocking properties can be provided. Thus, these materials can be used as barrier sublayer materials. In addition to the preferred use of binary compounds of these materials, the barrier sublayer may be formed from, for example, materials such as oxy-nitrides, carbide-borides, carbon-oxidation-nitrides, silicide-carbon-nitrides, and oxide-fluorides. But may not be limited to any multi-component compound consisting of, but not limited to. The electrochemical device of the present invention does not require the barrier layer to be pure oxide.

The binary and multiple barrier sublayer materials listed above include sputtering (RF-magnetron, AC magnetron, DC and DC pulse magnetron, diode RF or DC or AC), electron beam evaporation, thermal (resistance) evaporation, plasma enhanced chemical vapor deposition, ion beam assist One or more of a variety of suitable thin film deposition methods can be selected and deposited, including deposition, cathode arc deposition, electrochemical deposition, spray pyrolysis, and the like. Si ₃ N ₄ barrier sublayers can be prepared utilizing, for example, pure silicon targets that are preferably deposited in RF magnetron sputter systems using an Ar—N ₂ reactive plasma environment. SiC and TiC barrier sublayer films are generally inert while their nitrogen doped derivatives, SiC: N and TiC: N, are deposited from SiC and TiC targets, respectively, in a reactive Ar-N ₂ plasma environment using RF magnetron sputter equipment. RF magnetron sputtered from targets of the same respective composition in an Ar plasma environment.

Optimized oxide-nitride, carbide-boride, carbide-nitride, silicide-carbide-nitride, oxide-oxide form, such as a fluoride is _{N 2, O 2, N 2} O, BF 3, C 2 F 6, B 2 By providing a sputter gas mixture, which may include H ₆ , CH ₄ , SiH ₄ , or the like, alone or in addition to an inert carrier gas such as argon, and / or providing elements from a sputter target. . For example, a thin film deposition of Ti ₃ SiC ₂ : N, which is a titanium silicide-carbon-nitride (or titanium silicon carbide nitride), deposits a mixed material layer having a TiC / SiC ratio of 3: 1 in the same substrate region at any given time. Using a single sputter target constructed of alternating areas of TiC and SiC at a total area ratio of 3: 1, or two separate sputter targets consisting of one TiC target and another SiC target. Can be achieved by RF magnetron sputtering in an Ar-N ₂ plasma atmosphere (dual target sputter deposition). The substrate coated with the barrier layer may or may not be post-deposited prior to continuing with cell fabrication.

The barrier sublayer material is Si ₃ N ₄ , SiN _x O _y (3x + 2y = 4), or an oxide-gradient Si ₃ N that can reach the stoichiometry at the surface of most SiO ₂ , or both surfaces if desired. ₄ is an example. In addition, SiC or TiC with or without nitrogen doping may be used as the barrier sublayer material.

Some specific derivatives of these materials may be most undesirable as ion blockers when used in barrier layers without any additional suitable barrier sublayers, which are non-stoichiometric ZrO ₂ , non-stoichiometric YSZ (yttrium). Stabilized zirconia), and non-stoichiometric LiI (lithium iodide), because they exhibit poor insulating properties while allowing the diffusion of certain ions during the manufacturing process or during battery operation and storage. In contrast to their stoichiometric counterparts, non-stoichiometry is the main reason why these materials are electrically conductive while allowing oxygen and lithium ion diffusion respectively.

Barrier sublayers are included to fine-tune certain barrier properties such as, for example, improved adhesion to substrate and / or cell portions, mechanical flexibility, stability to adjacent layers, pinhole-free, electrical resistance, and chemical inertness. A suitable barrier layer can be provided. For example, the barrier layers in the upper stainless steel 430. The substrate may be constructed as a barrier sub-layer stack (stack) of the following sequence: - 500Å SiO ₂ / 2000Å (oxide bonding for improved adhesion to the stainless steel substrate) Si ₃ N ₄ (electrically insulating, for example, diffusion barrier material for lithium ions, cobalt ions, oxygen ions, iron ions, chromium ions and gold ions) / 1000 Å SiC: N (lithium ions, cobalt ions, oxygen ions, iron ions, Strong diffusion barrier layer for chromium ions and gold atoms) / 2000Å Si ₃ N ₄ (electrically insulating, for example, diffusion barrier material for lithium ions, cobalt ions, oxygen ions, iron ions, chromium ions and gold ions) / 300 kV cobalt current collector adhesion layer and 500 kV SiO ₂ (adhesion promoter to current collector layer) onto which 3000 kV gold current collector can be deposited.

In some cases the insulating barrier sublayer may be in contact with the positive cathode and / or cathode current collector, as well as with the negative anode and / or anode current collector. In either case, the barrier sublayer is preferably chemically inert, for example with respect to all the materials it is in contact with. This feature is, for example, pure Al ₂ when in contact with a metallic lithium negative anode that can react detrimentally with Li ₂ O, LiAlO ₂ and Li-Al alloys, or Li ₂ O, Li ₂ SiO ₃ and Li-Si alloys. The use of O ₃ or SiO ₂ barrier layers can be limited.

2.2 at least one electrical conductivity Barrier With sub-layer  Done Barrier layer  Produce

For example, the conductive barrier sublayer may be equally effective, for example, if it satisfies the following desirable attributes: 1) preventing ion diffusion into / from the battery layer, and 2) during the manufacturing process, and No reaction with the substrate or cell layer during all subsequent cell drive and storage conditions. The barrier layer may, for example, also comprise an electrically insulating barrier sublayer. Such electrically insulating and electrically conductive sublayers may not all have the same shape and area size, for example. Thus, a barrier layer consisting of such a mixed stack of barrier sublayers may be electrically conductive, for example, in some areas in contact with the substrate portion or the battery portion, while exhibiting electrical insulating properties in other areas of contact with the substrate portion or the battery portion. have.

Materials for the electrically conductive barrier sublayers are, for example, groups consisting of conductive binary borides, carbides, silicides, nitrides, phosphides and oxides, as well as oxidized-nitrides, carbide-borides, carbide-oxidized-nitrides, silicide-carbonized- Nitrides, and oxidized-fluorides may be selected from the group consisting of any conductive polyvalent compounds thereof, including, but not limited to. In addition, hot-stable polymers and hot-stable silicones that are specifically treated to be electrically conductive can be used. A list of material choices for the electrically insulating barrier sublayer is presented in item 2.1 above and is included here. The barrier sub-layer, for _{example, 5000Å ZrN / 4000Å Si 3 N} 4 / 3000Å WC / 1000Å MoSi 2 of the barrier may be formed of a completely different composition as the barrier layer, which may be prepared as a sub-stack, each barrier sub-layer is For example, they may have different area dimensions.

As a result, for example, the Si ₃ N ₄ barrier sublayer may extend over the entire footprint region of the metal substrate, for example, the ZrN barrier sublayer may cover only the cathode current collector lower substrate region, and the WC and MoSi ₂ barrier The sublayer may further extend to the ZrN region, for example covering at least the entire region underneath the anode current collector. Due to their area size, the intervening Si ₃ N ₄ barrier sublayer provides for electrical separation of the electrically conductive ZrN barrier sublayer from, for example, the electrically conductive WC / MoSi ₂ barrier sublayer and thus the positive and negative portions of the cell. May provide electrical separation between (see FIG. 2).

In this embodiment, an electrically conductive barrier sublayer such as ZrN, TiN, WC, MoSi ₂ , TiB ₂ or NiP is used for sputter deposition (RF-magnetron, DC and DC pulse magnetron, AC magnetron, diode RF or DC or AC), It can be deposited on a substrate by standard deposition methods including electron beam evaporation, thermal (resistance) evaporation, plasma enhanced chemical vapor deposition, ion beam assisted deposition, cathode arc deposition, electrochemical deposition, spray pyrolysis and the like. For example, ZrN barrier sublayers can be prepared from ZrN sputter targets that perform DC magnetron sputter deposition in an inert Ar atmosphere or from metal Zr targets that also use DC magnetron sputter deposition in a reactive Ar-N ₂ atmosphere.

In addition, if the post-deposition annealing temperature required to crystallize the positive cathode is appropriate, such as 200 ° C.-500 ° C., certain metals (eg Au, Pt, Ir, Os, Ag, Pd), semi-metals (eg graphite Carbon, Si) and alloys (eg, based on, but not limited to, Au, Pt, Ir, Os, Ag, Pd, C and Si) may be preferably selected as electrically conductive barrier sublayers. The electrically conductive barrier sublayer may or may not be further heat treated prior to continuing the cell manufacturing process.

If properly fabricated in terms of electrical connectivity from the positive cell terminals, the conductive barrier sublayer may have the additional advantage of eliminating a separate cathode current collector, otherwise, for example, It should be chosen to coat with a more conductive and inert thin layer, such as gold, to optimize the electrical properties of the conductive barrier sublayer. The access of the conductive barrier sublayer, whether or not additionally coated with such a more conductive layer, simultaneously provides a conductive barrier sublayer in which the anode current collector and the negative anode are in electrical contact with the positive cathode and / or its cathode current collector. It can include separating from. This separation can be achieved, for example, as follows:

1) can be achieved by extending the electrolyte to an area such that the negative anode and its anode current collector are located entirely on top of the electrically insulating electrolyte, in which case this is a local barrier sub for the negative anode and its anode current collector. Can act effectively as a layer (see FIGS. 3A and 3B). If a particular manufacturing parameter of the positive cathode does not cause a reaction with an already existing electrolyte layer, the positive cathode and its cathode current collector can be similarly prepared over the entire top of the electrolyte, with the negative anode located at the bottom of the electrolyte (See FIG. 3C).

2) If the negative anode and / or anode current collector is not entirely located on top of the electrolyte, it may be in contact with the barrier layer and thus in contact with at least one of the barrier sublayers and / or the metal substrate. In this case, at least one of the sublayers must be insulating, while one or more of the barrier sublayers can be electrically conductive (see FIGS. 4A and 4B). In either case, all barrier sublayers must be chemically inert with respect to all materials in contact. This may preferably prohibit the use of the Pt ₂ Si barrier sublayer, for example when in contact with the negative metallic lithium anode, which would otherwise be Li _x Si (0 <x <= 4.4) and Li _y Pt (0 <y This is because a reaction with <= 2) may occur (see FIG. 4C).

2.3 Barrier layer  And substrate

One reason for installing the barrier layer is, for example, during the fabrication of the cell part, which may involve a process temperature up to the melting point of the substrate, and during all subsequent driving and storage states of the electrochemical device, for example, the electrical To provide chemical separation between the substrate portion and the battery portion of the chemical device. The same principles as described above can be applied to at least three substrate types of the present invention that can include metal substrates, polymer substrates, and doped or undoped silicon substrates.

Direct deposition of electrically insulating or conductive barrier sublayers can be achieved in a straightforward manner on the three substrate types as described above. Of course, the inherent physical and chemical limitations of each substrate type must be observed, and the deposition parameters for each barrier sublayer must be adjusted accordingly. For example, sputter deposition may be performed under high deposition rates, and the resulting deposition temperature at the substrate surface may exceed the melting point of the polymer substrate. Therefore, the deposition parameter should preferably be limited to comply with 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 first ignores any post-deposition annealing, so that the stress of the barrier sublayer during the deposition does not crack it prior to the deposition of any subsequent barrier sublayer and / or cell layer. It may be related to adjusting to fit. More specific examples may be given without limiting the scope of the present invention to the basic principles for the fabrication of barrier layers over substrates, including the possible use of all three substrate types and barrier sublayers.

3. Battery Manufacturing

Once the substrate with the barrier layer in the present invention has been fabricated, subsequent manufacturing steps of the electrochemical device may be followed by a second electrochemically active cell on the second side of the substrate to achieve the "duplex" electrochemical device described further below. It depends on whether or not to prepare. The electrochemical device of the present invention does not require that the first electrochemically active cell be a solar cell.

However, in the case of a "cross-section" electrochemical device in which only the first electrochemically active cell is fabricated on the first side of the substrate, the second layer may be formed of the substrate prior to the fabrication of the component layer of the first electrochemically active cell. It is selectively deposited on the second side. This second layer may be made for the purpose of protecting the substrate from the surrounding environment against chemical and mechanical factors during the manufacture, operation and storage of the electrochemical device. Furthermore, through the implementation of the second layer, the first electrochemically active cell enters and diffuses through the substrate on the second unprotected side, thereby potentially manufacturing, driving, and / or electrochemical devices. Or protected from chemical contaminants from the surrounding environment that can reach and react detrimentally with the first electrochemically active cell during storage. This protection of the first electrochemically active cell is in addition to the protection provided by the substrate itself and a barrier layer between the substrate and the first electrochemically active cell, in particular the barrier layer of which is below the first electrochemically active cell. If it may not cover the entire area, it may be present. Protection of both the substrate and the first electrochemically active cell will extend the life of the electrochemical device.

The second layer is for example from the group consisting of metals, semi-metals, alloys, borides, carbides, diamonds, pseudo diamond carbons, silicides, nitrides, phosphides, oxides, fluorides, chlorides, bromide, iodides, or for example boron Includes a chemical compound selected from the group of any polyvalent compound consisting of a cargo, carbide, silicide, nitride, phosphide, oxide, fluoride, chloride, bromide, and iodide, or for example, a group of high temperature stable organic polymers and high temperature stable silicon It can be made of a material. In particular, a thin metal layer between 500 microns and 5 microns thick may be useful to protect the substrate by blocking the ingress of contaminants on the second side during fabrication, driving, and / or storage of the electrochemical device. In addition, metal layers, such as nickel or titanium, can be useful because they can be deposited relatively quickly and inexpensive compared to ceramic counterparts such as TiC.

The blocking action of the second layer includes, for example, chemical reaction of the second layer with contaminants known in the literature, such as chemical gettering, corrosion protection, or sacrificial layer installation, and is not limited to metal layers, for example, Sub-oxides or sub-nitrides (e.g., insufficiently oxidized or nitrided membrane materials that can be readily prepared by sputter deposition) or, for example, present in the environment during the manufacture, operation, and / or storage of electrochemical devices. It can also be achieved by nitrides or carbides that can be converted into oxides or carbonates when reacting with oxygen, moisture, or carbon dioxide contaminants.

The second layer on the second side of the substrate can be fine tuned by selecting a material that primarily protects without a chemical reaction or a material that primarily protects through a chemical reaction. Further fine tuning can occur, for example, by selecting one of the latter materials having higher or lower reactivity under certain ambient environmental conditions. For example, Al ₄ C ₃ converts to Al ₂ O ₃ at much lower oxygen partial pressures and much lower temperatures than SiC to SiO ₂ . Similarly, nitrides with very small formation enthalpy such as Co ₂ N convert to respective oxides at much lower temperatures and oxygen partial pressures than their counterparts formed under large negative formation enthalpy such as Si ₃ N ₄ and ZrN.

Ultimately, it is up to the manufacturer of the electrochemical device to determine the optimal parameters with respect to the added cost for producing the second layer on the second side of the substrate, which is dependent on the material selection and the thickness of the second layer. It is a function of the additional protection of the substrate and the first electrochemically active cell with respect to certain ambient environmental conditions present for a certain period of time, which in turn is primarily a function of the material selection and the thickness produced of the second layer.

Thin film cells can be fabricated in a batch fabrication process that uses sequential physical and / or chemical vapor deposition steps that use shadow masks to build up individual cell component layers. Electrochemically active cells can be made in any of a variety of structures. Features may include:

(i) the positive cathode configuration to be used;

a. A positive cathode positioned between the barrier layer and the negative anode (anode deposition before anode deposition; "conventional configuration"), and a negative anode located between the barrier layer and the positive cathode (cathode deposition before cathode deposition; "opposite configuration")

b. Post-deposition annealing applied to the positive cathode

(ii) the anode configuration to be used;

a. Negative anode layer contacts or does not contact barrier layer

b. Anode current collector contacts or does not touch barrier layer

(iii) type of barrier layer to be used;

a. Electrically Insulating Sublayers to Electrically Conductive Sublayers

b. Area dimension of a given sublayer compared to other sublayers in a given barrier layer

c. Ordered combination of insulating and conductive sublayers within the barrier layer

(iv) the substrate is or is not in electrical contact with the electrochemically active cell (either its positive or negative portion)

(v) electrochemically active cells are prepared on one side of the substrate (cross-sectional electrochemical device) or on both sides of the substrate (double-sided electrochemical device)

(vi) the protection encapsulation or protection encapsulation design to be used.

a. Encapsulation vs. Encasing

b. No opening (s) to connect terminals to opening (s) in encapsulation or encasing

c. With or without moisture protection layer in the opening area

(vii) current collectors and terminals

3.1 Cathode  Configuration

3.1.1 Negative Anode  Positive before deposition Cathode  Sedimentation and Potential Post-Deposition At annealing Equivalent  Can, Barrier layer Negative Anode  Positive cathode located in between: "Typical configuration"

Depending on the electrical properties of the barrier layer, a current collector can be produced prior to deposition of the positive cathode. That is, if the barrier layer based on the sublayer is insulating in the area where the positive cathode is to be fabricated, the cathode current collector can be deposited to create the necessary electrical connection from the positive terminal to the positive cathode. However, if the barrier layer based on the sublayer is electrically conductive in the region where the positive cathode is to be deposited, then an additional inactive metal layer ("conduction enhancer") may be used to determine the current collecting property of the barrier layer. It may be selectively deposited between the barrier layer and the positive cathode to strengthen.

Positive cathodes, cathode current collectors, and conduction enhancers in the barrier layer can be sputtered (RF-magnetron, DC and DC pulse magnetron, AC magnetron, diode RF or DC or AC), electron beam evaporation, thermal (resistance) evaporation, plasma enhanced chemical Any one of several deposition methods can be selected and deposited, including vapor deposition, ion beam assisted deposition, cathode arc deposition, electrochemical deposition, spray pyrolysis, and the like.

After deposition of the positive cathode, post-deposition annealing may be followed to improve the physical, chemical, and electrochemical properties of the positive cathode. Most conventional post-deposition annealing takes place for about 30 minutes to 2 hours at 700 ° C. in air, completing the crystallization of the positive cathode materials LiCoO ₂ , LiMn ₂ O ₄ , LiMnO ₂ , LiNiO ₂ , and derivatives thereof.

The composition of a given derivative and the parameters of post-deposition anneal applied can provide information on the selection of the barrier layer material. For example, in the case of annealing for 2 hours at pure LiCoO ₂ and air at 700 ° C., an electrically insulating barrier layer comprising two barrier sublayers on a 50 μm stainless steel 430 foil, 5000Å Al ₂ O ₃ and 6000Å Co ₃ O ₄ . One optional combination may be a 3000 mA gold cathode current collector, which may be attached by a 300 mA cobalt adhesion layer. The X-ray diffraction (XRD) pattern of such a setup after 700 ° C. annealing is shown in FIG. 5. LiCoO ₂ positive cathodes have a lattice constant parameter (a _hex = 2.8146 (4) Å; c _hex = 14.0732 (8) Å) for (101) grains, and the theoretical value (e.g. ICDD 77-1370: a _hex = 2.815 ( 1) Å; c _hex = 14.05 (1) Å), showing a crystallite size of about 560 Å. This fact indicates that the crystalline LiCoO ₂ positive cathode film may not react with any material around it, including the substrate, while achieving the good crystallographic parameters needed to show optimal electrochemical behavior in the electrochemically active cell.

On a 300 μm thick undoped silicon substrate, a pure LiCoO ₂ positive cathode was prepared on a 3000 mA Au / 300 mA Co cathode current collector attached to a barrier layer consisting of two barrier sublayers, 5000 mA Si ₃ N ₄ and 5000 mA SiO ₂ , After annealing at 700 ° C. for 2 hours in air, a good crystalline LiCoO ₂ with nearly theoretical lattice parameters (eg ICDD 77-1370: a _hex = 2.815 (1) Å; c _hex = 14.05 (1) Å) A positive cathode (a _hex = 2.8151 (4) '; c _hex = 14.066 (7)'; sample grain size 1100 ms in the (101) plane) can be obtained. Acquisition of a good crystalline stoichiometric LiCoO ₂ positive cathode film having a layered structure and theoretical crystallographic lattice parameters can be achieved, for example, in which the crystalline LiCoO ₂ positive cathode film is reacted with a peripheral material comprising, for example, a silicon substrate as shown in FIG. Provide something you can't do. With the LiCoO ₂ positive cathode film in the above example produced on a stainless steel 430 foil substrate, the theoretical crystallographic lattice parameters (a _hex = 2.8151 (4) '; c _hex = 14.066 (7)') were obtained on the Si substrate. It may be suggested that the LiCoO ₂ positive cathode film may exhibit certain desirable electrochemical behavior.

3.1.2 Positive Cathode  Before deposition Negative Anode  Sedimentation and Potential Post-Deposition With annealing  Can provide near-performance Barrier layer  Positive Cathode  Located in between Negative Anode : "Reverse configuration"

An “opposite configuration” of one embodiment of the present invention is schematically illustrated in FIG. 3C for the case where the substrate may be a metal substrate. Depending on the electrical properties of the barrier layer, the anode current collector can be fabricated prior to the deposition of the negative anode. That is, based on that sublayer, if the barrier layer is insulating in the region where the negative anode will be fabricated, an anode current collector can be deposited to create the necessary electrical connection from the negative terminal to the negative anode. However, if the barrier layer based on the sublayer is electrically conductive in the region where the negative anode will be deposited, then an additional inert metal layer ("conductivity enhancer") is added between the barrier layer and the negative anode to enhance the current collection characteristics of the barrier layer. Can be deposited.

Negative anodes, anode current collectors, and conduction enhancers in the barrier layer are sputtered (RF-magnetron, DC and DC pulse magnetron, AC magnetron, diode RF or DC or AC), electron beam evaporation, thermal (resistance) evaporation, plasma enhancement Any one of several deposition methods can be selected and deposited, including chemical vapor deposition, ion beam assisted deposition, cathode arc deposition, electrochemical deposition, spray pyrolysis, and the like.

The negative anode can be selected from the group consisting of metal lithium, lithium-ion anode, and so-called lithium-free anode (see, eg, US Pat. No. 6,168,884, which is incorporated herein by reference in its entirety). After deposition of the negative anode, post-deposition anneal may be followed to improve the physical, chemical, and electrochemical properties of the negative anode. Preferably, such annealing can be applied to a lithium-ion anode, such as Li ₄ Ti ₅ O ₁₂ , but not for example to metallic lithium and is not preferred for the group of lithium-free anodes.

The actual composition of the negative anode and the parameters of the post-deposition annealing can provide selection information of the barrier layer material. For example, for a metal lithium negative anode, a 5000 μs Si ₃ N ₄ barrier sublayer on the silicon substrate that separates the silicon substrate from the metal lithium negative anode has a 12Li + Si ₃ N ₄ = 4Li chemical inertness between the barrier layer and the metal lithium. It can provide the necessary barrier layer properties that can be achieved through positive reaction enthalpy in the reaction path of ₃ N + ₃ Si.

In an exemplary reverse configuration, the positive cathode can be deposited on the electrolyte. Thus, for example, because the chemical reaction between the electrolyte and the positive cathode as well as the reaction between the negative anode and the electrolyte is preferably avoided, the temperature allowed in the potential post-deposition annealing of the positive cathode can be limited.

3.2 Anode  Configuration

Exemplary embodiments of "opposite configurations" have already been described above.

In the manufacture of embodiments that include a negative anode entirely on top of the electrolyte, there may be no direct chemical interaction, for example, between the negative anode and the barrier layer.

When preparing an embodiment of a negative anode partly on top of an electrolyte, a "normal configuration" (see item 3.1.1) is preferred. The overlapping region of the negative anode on the electrolyte layer edge can be prevented from contacting the barrier layer for the presence of an anode current collector (see FIG. 7A). In the absence of a properly configured anode current collector, the region overlapping the negative anode may contact the barrier layer (see FIG. 7B). In either case, the negative anode is preferably chemically inert, for example with respect to the barrier layer and its barrier sublayers in which the negative anode is in integrated contact, which, due to the limited thickness and grain boundary morphology, causes the anode current collector to have a negative anode and barrier layer. This may not provide adequate chemical separation between. In such a case, the choice of negative anode material determines the choice of barrier sublayer material. In this regard, a negative anode is lithium metal and the anode when the anode is in contact with the Co ₃ O ₄ barrier sub-layer, and Co ₃ O ₄ barrier sub-layer can not be used. Otherwise, metallic lithium can reactively degrade the Co ₃ O ₄ barrier sublayer with Li ₂ O, CoO, and a solid solution of Li (Co) and Co (Li).

If the negative anode and / or its anode current collector contacts the barrier layer, whether the negative anode and / or its anode current collector contacts 1) the insulating barrier sublayer, or 2) the electrically conductive barrier sublayer. Two cases on whether or not need to be evaluated. As a first example, when using a metal lithium anode, this barrier sublayer may be sufficiently inert to negative anodes such as Si ₃ N ₄ and / or its anode current collectors. As a second example, in addition to that the conductive barrier sublayer being in contact is chemically inactive with respect to the negative anode and / or its anode current collector, for example, more sophisticated barrier sublayer accesses are for example metal substrates, and doping and It can be used for conductive substrates such as undoped silicon substrates (see FIGS. 4A-4C). To insulate the polymer substrate and the second example, it is sufficient to use a non-continuous conductive barrier sublayer so that the positive and negative portions of the cell are not shorted through the electrically conductive barrier sublayer.

For example, a 1 μm thick ZrN barrier sublayer has a metal lithium negative anode in contact with this ZrN barrier sublayer and should not be shared with the positive portion of the cell, instead the positive portion of the cell is an insulating barrier sub such as Si ₃ N _4. For embodiments that can be located on a layer, it is relatively simple and effective. One advantage of this latter exemplary embodiment is that the ZrN barrier sublayer can also act as an anode current collector for negative metal lithium anodes (see FIG. 8).

The anode current collector may comprise an inert metal, an inert alloy, or an inert nitride, so it may not be easy to react with the barrier layer or negative anode. The anode current collector is preferably not in electrical contact with the conductive barrier sublayer to which the positive cathode and / or cathode current collector is also in electrical contact. Otherwise, the battery may be shorted.

3.3 Substrate in electrical contact with an electrochemically active cell

In an exemplary embodiment where there is no reaction between the substrate and the positive cathode or negative anode, the substrate with these electrodes may be in direct electrical contact or indirectly through a current collector. However, in the case of conductive substrates such as metal substrates, doped or undoped silicon wafers, or metallized polymer substrates, for example, only one of these electrodes is allowed for electrical contact with the substrate, otherwise the electrochemically active cell is shorted. Or strong current leakage may be introduced. This exemplary approach has the advantage of conveniently using a conductive substrate, for example as one of two terminals of an electrochemical device (see FIG. 9).

3.4 double-sided electrochemical devices

The invention may include embodiments in which the electrochemical device has at least one electrochemically active cell on each side of the substrate. For example, fabrication of an embodiment may be performed on each side of the substrate using equipment that can be deposited on both sides of the substrate at the same time, for example, prior to proceeding to fabrication of the next cell component layer that may be deposited on both sides of the substrate at the same time. Electrochemically active cells are deposited by a given layer of electrochemically active cell components, such as a positive cathode.

Potential sequential fabrication processes of the cell component layer can be done, for example, in the same manner as in cross-sectional electrochemical devices. As a result of this exemplary approach of layer completion on both sides of the substrate prior to depositing the next layer on both sides of the substrate, the potential post-deposition annealing is on the other side of the substrate where such post-deposition annealing should not be applied. It may not be applied to the layer.

Another exemplary approach is to obtain a second electrochemically active cell on the second side of the substrate or a first completion of the substrate prior to the partial completion of any further electrochemically active cell manufacture on the first or second side of the substrate. May be present to partially complete the first electrochemically active cell on the side. This approach can be employed, for example, if the available deposition equipment does not allow for double sided deposition at the same time. For example, deposition on the first side of the substrate including the cathode current collector and subsequent positive cathode layer may be achieved prior to deposition of the cathode current collector and the positive cathode layer on the second side of the substrate. After this step, the post-deposition annealing is applied simultaneously to the partially completed electrochemically active cell on this substrate before continuing with the manufacture of the electrochemically active cell on the first side of the substrate using the manufacturing sequence of the electrolyte-anode current collector-anode. Can be. The same manufacturing sequence can then be applied to the second side of the substrate before both sides of the substrate are simultaneously encapsulated with a thermally sensitive polymer stack on both sides of the substrate, or prior to thin film encapsulation that can be applied simultaneously or sequentially. have.

Depending on the actual conditions of potential post-deposition annealing of the positive cathode and / or negative anode, the preparation of the first electrochemically active cell on the first side of the substrate starts the preparation of the second electrochemically active cell on the second side of the substrate. A third approach is possible which can be completed previously.

3.5 Protection Encapsulation and Protection Encasing  design

For the purposes of the present invention, “protective encasing” is defined as a protective enclosure such as, for example, a pouch or hermetically sealed metal that may contain an electrochemical device therein, In certain embodiments, the device may be completely enclosed and / or encompassed entirely. “Protective encapsulation” is defined as a shield, eg, a cap that covers an electrochemical device or one or more given individual electrochemically active cells of an electrochemical device. The cap may be attached to any suitable substrate region of the electrochemical device or substrate region available for the next electrochemically active cell, for example.

Before the electrochemical device of the present invention is run in an ambient environment, it is for example to protect the electrochemical device from any reactive chemicals that may be present within a given ambient atmosphere and that may react detrimentally or degrade the electrochemical device. desirable. For example, if the ambient environment is air, the electrochemical device of the present invention may preferably be protected from moisture, among other reactive chemicals such as O ₂ or CO ₂ (see US Patent No., which is hereby incorporated by reference in its entirety). 6,916,679). Electrochemical devices of the invention, such as laser welded stainless steel cans or vacuum metal or glass tightly sealed metal interiors with electrical supply passageways, such as containers, can be protected from these external chemical factors. However, the dimensions of such types of protective encasing can add excessive inert volume and weight to electrochemical devices whose components, except for energy carrying positive cathodes, can be minimized for their thickness. This minimization strategy, because of its simple presence, always reduces the power, energy and capacity density of the electrochemically active cell, and thus the substrate and any protective encasing, which always reduces the power, energy and capacity density of the electrochemical device. Or particularly useful for the thickness of inactive components of electrochemical devices such as protective encapsulation.

For the reasons mentioned above, the protective encapsulation or protective casing should preferably be as thin as possible while protecting the electrochemical device from various chemicals present in the surrounding environment in which the electrochemical device is driven. Protection from these chemicals implicitly includes all, including the time and temperature of exposure to the chemical that the electrochemical device may face during its lifetime. However, it is the sole judgment of the electrochemical device manufacturer to establish optimal parameters for the electrochemical device in terms of manufacturing cost and performance. In this regard, electrochemical devices that can only be driven for a few days after their manufacture are, for example, potentially cheaper and less precise protection encapsulation or protection encapsulation than, for example, electrochemical devices that can be designed to run for years. This may apply.

Both protective encapsulation and protective encapsulation must allow external connection to the terminals of the electrochemical device. This external connection can be achieved, for example, by adopting one of the following three major engineering designs. First, the substrate and / or protective encapsulation can function as a terminal through which direct external contact can be made (see, for example, the substrate 300 acting as a positive terminal in FIG. 3B). Secondly, the terminal may extend further out of the protective encapsulation that is under the hermetically sealed edge of the protective encapsulation and is in contact (see, eg, layers 430 and 480 of FIG. 4A). Similarly, the terminals may reach through the hermetically sealed outlet or the opening of the protective encasing and may extend further out of the protective encasing where contact may be made (see eg, tetragonal Li-ion bulk cell technology). Third, an opening may be provided in the protective encapsulation or the protective encapsulation allowing direct external connection to the internal terminal of the electrochemical device, but the sensitive portion, eg, the moisture sensitive electrolyte, may be connected to the terminal from the surrounding environment such as moisture-containing air. Or by the thickness of its adjacent current collector.

For improved service life, which represents a useful performance parameter of the inventive electrochemical device, in particular when the opening of the third design is located near the electrolyte region, the electrolyte is for example in a moisture protective layer as schematically shown in FIG. It can be guaranteed to receive additional protection.

3.6 Current Collector  And terminals

Less electrically conductive electrode materials, such as LiCoO ₂ positive cathodes or Li ₄ Ti ₅ O ₁₂ negative anodes, are ion diffusion paths inside the electrode that can be achieved if the z-parameters (thickness) of the electron and ion paths are kept to a minimum. In addition to minimizing the electrical resistance of the electrode, it may be necessary to have a good conductive inactive backside contact (current collector) such as, for example, Au or Ni. This principle is most often when the electrodes are preferably flat or thin (z-parameters), i.e., with maximized length dimensions (x-parameters) and width dimensions (y-parameters) relative to thickness (z-parameters). It is implemented in the battery of. Some electrodes are electronically and ionically good electrical conductors and will not require a current collector for the reasons mentioned above. However, such electrodes are chemically very reactive, such as negative metal Li anodes, so that they are separated from other cell parts, such as negative terminals, by a suitable inert "bridge" such as Ni in the case of negative Li metal anodes. can do. Such "bridges" can only contact one responsive conductive electrode at one corner or one edge, as opposed to full-area backside contacts in the case of poor conductive electrodes. The bridge acts as an inert medium between the reactive electrode and its terminals and provides current collector characteristics, and thus may also be referred to as a "current collector".

In one embodiment, the terminal of the electrochemical device of the present invention may be an extended current collector and thus be made of the same material in contact with the electrode. However, current collectors used in thin film cells can be very thin and mechanically dense, such that external contact, mechanical (eg, clipping), soldering or spot welding does not form the desired permanent electrical contact. You may not. For example, a thick and / or porous good conductive material may be added to the end of the current collector in addition to the end of the current collector, which is a region called " terminal " in which mechanical, soldered, or spot welded external electrical contacts can be achieved. It may be desirable to improve contact properties. In this regard, screen-printed, highly porous silver and silver alloys of about 5-15 μm thickness may be used to produce the screen-printed material at any point during the manufacture, operation, or storage of an electrochemically active cell. Or it has been successfully adopted as a printed terminal in such a way that the cathode or anode current collector can make good electrical contact with it without chemically contaminating the cells.

Embodiments and embodiments of the present invention will be described with reference to the drawings.

1 illustrates one embodiment of an electrochemical device. The substrate portion 100 may be chemically separated from the battery portion 120 via, for example, a barrier layer 110 composed of barrier sublayers 111-114. Battery component layers 121-125 are installed. Positive battery terminal 126 and negative battery terminal 127 are further provided.

2 shows an exemplary barrier layer 210 comprised of an exemplary barrier sublayer 1000 ns MoSi ₂ 211, 3000 ns WC 212, 4000 ns Si ₃ N ₄ 213, and 5000 ns ZrN 214. An example is shown. As shown, the area dimensions of these sublayers, for example, still achieve desirable electrical separation between the positive portions 214, 220, 230, and 240 and the negative portions 260, 270, and 280 of the electrochemically active cell, for example, It can be very different from each other. The cathode current collector, the positive terminal, and the positive cathode are represented by items 220, 230, and 240, respectively. The positive portion of the electrochemically active cell may comprise at least a positive cathode, a cathode current collector and a positive terminal. The cathode current collector can act alone as a positive terminal. The negative anode, anode current collector and negative terminal are represented by 260, 270 and 280, respectively. The electrochemically active cell may comprise at least a negative anode, an anode current collector and a negative terminal. The extended anode collector also includes (1) a negative terminal; (2) an anode; And (3) act as anode current collector, anode and negative terminal. Electrolyte 250 may, for example, electrochemically separate the positive portion from the negative portion of the electrochemically active cell. In this particular case, the electrochemically active cell may be protected, for example, by encapsulation 290 having an opening 291 for connecting to negative terminal 280. Such encapsulated electrochemically active cells can be fabricated on a substrate 200 that together form an electrochemical device.

FIG. 3A illustrates a first barrier in which an electrical separation between the positive and negative portions of an electrochemically active cell can be achieved by making a negative portion throughout the electrolyte 350 top, eg, electrically conductive. An example embodiment of a barrier layer 310 is shown that includes a sublayer 311 and a second barrier sublayer 312. The positive portion may constitute, for example, the second barrier sublayer 312, the cathode current collector 320, the positive terminal 330, and the positive cathode 340. When the provided first barrier layer 311 is electrically conductive, the positive portion may additionally constitute the first barrier layer 311. With respect to the electrically conductive first barrier layer 311, when the substrate 300 is electrically conductive, for example in a metallic embodiment, such a substrate may be part of the positive portion. The negative portion 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 having an opening 391 for connecting to the negative terminal 380.

3B shows that electrical separation between the positive and negative portions of the electrochemically active cell can be achieved by fabricating negative portions over the entirety of the electrolyte 350, the cathode current collector 320, the positive terminal 330 and the positive portions. In one embodiment where the cathode 340 is electrically connected to the metal substrate 300 via, for example, the second barrier sublayer 312, the first barrier sublayer 311 and the first, which may be electrically conductive, for example An exemplary embodiment of a barrier layer 310 including two barrier sublayers 312 is shown. In this configuration, the metal substrate 300 can act as a positive terminal. The positive portion may constitute the metal substrate 300, the second barrier sublayer 312, the cathode current collector 320, the positive terminal 330, and the positive cathode 340. In embodiments where the first barrier layer 311 is electrically conductive, the positive portion may additionally include the first barrier layer 311. The negative portion may include negative anode 360, anode current collector 370, and negative terminal 380. In this particular example, the electrochemically active cell may be protected by an encapsulation 390 having an opening 391 for connecting to the negative terminal 380.

3C shows that electrical separation between the positive and negative portions of the electrochemically active cell can be achieved by fabricating the positive portion over the entirety of the electrolyte 350, with the anode current collector 370, negative terminal 380 and negative In one embodiment where the anode is electrically connected to the metal substrate 300, for example, via the second barrier layer 312, the first barrier sublayer 311 and the second barrier sublayer, which may be electrically conductive, for example. An example embodiment of a barrier layer 310 including 312 is shown. In such a configuration, the substrate 300 may also serve as a positive terminal, for example. The positive portion may constitute the cathode current collector 320, the positive terminal 330, and the positive cathode 340. The negative portion may constitute the metal substrate 300, the second barrier sublayer 312, the negative anode 360, the anode current collector 370, and the negative terminal 380. If the first barrier layer 311 is also electrically conductive, the negative portion may additionally constitute such a first barrier layer 311. In this particular example, the electrochemically active cell can be protected by an encapsulation 390 having an opening 391 for connecting to the positive terminal 330.

4A includes an electrically conductive barrier sublayer for the case where electrical separation between the positive and negative portions of the electrochemically active cell may not be done through the manufacture of the negative portion throughout the top of the electrolyte 450. An exemplary embodiment of the barrier layer 410 is shown. In conjunction with the electrolyte 450, an electrically insulating second barrier layer 412 may separate the positive portion from, for example, the negative portion of the electrochemically active cell. The positive portion may constitute the cathode current collector 420, the positive terminal 430, and the positive cathode 440. If the third barrier sublayer 413 is electrically conductive it may be, for example, a member of the positive portion. The first barrier sublayer 411 can be electrically insulating or conductive. In the latter case, it may be one member of the negative portion itself, making the substrate 400 one member of the negative portion. Additionally, the negative portion may constitute negative anode 460, anode current collector 470, and negative terminal 480. In this configuration the metal substrate can also serve as a negative terminal. Finally, the electrochemically active cell can be protected by encapsulation 490.

4B includes an electrically conductive barrier sublayer for the case where electrical separation between the positive and negative portions of the electrochemically active cell may not be done through the manufacture of the negative portion throughout the top of the electrolyte 450. Another exemplary embodiment of a barrier layer 410 is shown. In conjunction with the electrolyte 450, an electrically insulating second barrier layer 412 may separate the positive portion from, for example, the negative portion of the electrochemically active cell. The positive portion may constitute the cathode current collector 420, the positive terminal 430, and the positive cathode 440. If the third barrier sublayer 413 is electrically conductive it may be, for example, a member of the positive portion. The first barrier sublayer 411 can be electrically insulating or conductive. In the latter case, it may be one member of the negative portion, making the substrate 400 one member of the negative portion. Additionally, the negative portion may constitute negative anode 460, anode current collector 470, and negative terminal 480. In this configuration the metal substrate can also act as a negative terminal. Finally, the electrochemically active cell can be protected by encapsulation 490.

4C includes an electrically conductive barrier sublayer for the case where electrical separation between the positive and negative portions of the electrochemically active cell may not be done through the manufacture of the negative portion throughout the top of the electrolyte 450. Another exemplary embodiment of a barrier layer 410 is shown. Negative anode 460 may, for example, be in direct contact with third barrier sublayer 413, and therefore, is preferably chemically inert with respect to negative anode 460. In this example, the third barrier sublayer 413 can be electrically insulating, for example, to provide electrical separation between the positive and negative portions of the electrochemically active cell with the electrolyte 450. The positive portion 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, it may be one member of the positive portion, making the metal substrate 400 one member of the positive portion. The first barrier sublayer 411 may be electrically insulating or conductive. In the latter case it may be a member of the positive part, but that is only the case for the second barrier layer 412. The negative portion may constitute the negative anode 460, the anode current collector 470, and the negative terminal 480. In this configuration, the metal substrate can act as a negative terminal. Finally, the electrochemically active cell can be protected by encapsulation 490.

FIG. 5 shows 1.6 fabricated on a 3000 Å gold cathode current collector on a 300 Å cobalt adhesion layer on a barrier layer comprised of 5000 Å Al ₂ O ₃ and 6000 Å Co ₃ O ₄ , two barrier sublayers on a 50 μm thick stainless steel foil type 430 substrate. A graph of the X-ray diffraction (XRD) pattern of the μm thick LiCoO ₂ positive cathode film is shown. The LiCoO ₂ positive cathode is annealed after deposition for 2 hours at 700 ° C. in air, which affects the underlying substrate, barrier layer and its barrier sublayer, cathode current collector adhesion layer and cathode current collector in a similar thermal manner. The lattice parameter (a _hex = 2.8146 (4) '; c _hex = 14.0732 (8)') of the crystalline LiCoO ₂ positive cathode film is the theoretical value (e.g. ICDD 77-1370: a _hex = 2.815 (1) '; c _hex = 14.05 (1) '), which corresponds to a crystalline LiCoO ₂ positive cathode (degree of crystallinity for the (101) plane as estimated by the Schercher's equation: 560Å) with any of its surrounding materials, including the substrate. Indicates no reaction. "Au" represents a gold cathode current collector. "Au + S" represents the overlap peak of the gold cathode current collector and the stainless steel 430 substrate foil.

FIG. 6 shows a 1.6 μm thick LiCoO ₂ fabricated on a 3000 μg gold cathode current collector on a 300 μm cobalt adhesion layer on a barrier layer consisting of 5000 μm Si ₃ N ₄ and 5000 μm SiO ₂ on a 300 μm thick undoped silicon substrate. The graph of the X-ray diffraction (XRD) pattern of the positive cathode film is shown. The LiCoO ₂ positive cathode is annealed after deposition for 2 hours at 700 ° C. in air, which affects the underlying substrate, barrier layer and its barrier sublayer, cathode current collector adhesion layer and cathode current collector in a similar thermal manner. The lattice parameters (a _hex = 2.8151 (4) '; c _hex = 14.066 (6)') of the crystalline LiCoO ₂ positive cathode film were given the theoretical values given in the literature (eg ICDD 77-1370: a _hex = 2.815 (1) '); c _hex = 14.05 (1) '), which means that the crystalline LiCoO ₂ positive cathode (crystallinity for the (101) plane as estimated by the Schercher equation: 1100 Å) film contains the silicon substrate and any surroundings thereof. It does not react with the material. "Au" represents a gold cathode current collector. The peak of the single crystal silicon substrate is estimated by the theta-2 theta structure of the diffractometer.

FIG. 7A illustrates one embodiment of an anode configuration where the negative anode 760 is not in direct contact with the barrier layer 710 and thus not in direct contact with any of the barrier sublayers 711, 712. The first barrier sublayer 711 may be electrically insulating or electrically conductive, and the second barrier sublayer 712 may be electrically insulating to avoid electrical shorts in the electrochemically active cell and thus to avoid electrical shorts in the electrochemical device. Should be. In such a configuration where the negative anode 760 does not contact the barrier layer, it does not determine the choice of chemical composition of the barrier sublayers 711, 712. For example, the positive portion of the electrochemically active cell is cathode current collector 720 separated by electrolyte 750 from the negative portion, which may constitute negative anode 760, anode current collector 770, and negative terminal 780. , Positive terminal 730 and positive cathode 740. Finally, the electrochemically active cell can be protected by encapsulation 790.

FIG. 7B shows a schematic diagram of an anode configuration where the negative anode 760 is in direct contact with the barrier layer 710 and thus in direct contact with its barrier sublayer 712. The first barrier sublayer 711 may be electrically insulating or electrically conductive, and the second barrier sublayer 712 may be electrically insulating to avoid electrical shorts in the electrochemically active cell and thus to avoid electrical shorts in the electrochemical device. Is preferably. In such a configuration where the negative anode 760 is in contact with the barrier layer, at least the selection of the chemical composition of the barrier sublayer 712 that it is in contact with may be determined. For example, the positive portion of the electrochemically active cell is cathode current collector 720 separated by electrolyte 750 from the negative portion, which may constitute negative anode 760, anode current collector 770, and negative terminal 780. The positive terminal 730 and the positive cathode 740 may be configured. Finally, the electrochemically active cell can be protected by encapsulation 790.

FIG. 8 is an embodiment of an anode configuration in which the electrically conductive ZrN barrier sublayer 811 and the negative anode 860 are in direct contact with the first barrier sublayer of the illustrated electrochemical device, for example, which may act as an anode current collector. Shows. This anode current collector and barrier sublayer 811 may also be chemically inert to reactive negative anode 860, such as metallic lithium, for example when selected for negative anode 860. Due to the specific structure of the barrier sublayer 811 selected for the embodiment of the electrochemical device shown in this figure, the second barrier sublayer 812 is preferably electrically insulating, such as Si ₃ N ₄ . The positive portion of the electrochemical cell may include, for example, an electrolyte 850 from the negative portion, which may constitute the metal substrate 800, the ZrN barrier sublayer and anode current collector 811, negative anode 860, and negative terminal 870. Cathode current collector 820, positive terminal 830, and positive cathode 840. Finally, the electrochemically active cell can be protected by encapsulation 880.

9 illustrates one embodiment of a particular cell configuration in which the negative anode 960 may be in direct contact with the substrate 900 when the substrate is chemically inert, eg, with respect to the negative anode 960. In such a case, for example, if the substrate is sufficiently electrically conductive as in the case of stainless steel, the substrate can act as a negative anode current collector and negative terminal. The positive portion of the electrochemically active cell can include, for example, a cathode current collector 920, a positive terminal 930, a positive cathode 940, and, if electrically conductive, a second barrier sublayer 912. However, the first barrier layer 911 is preferably electrically insulating to avoid shorting of the electrochemical device to the negative portion, which may include, for example, the metal substrate 900 and the negative anode 960.

10 illustrates a moisture protection layer 1092, for example, against moisture present in the surrounding environment in an embodiment in which a protective encapsulation 1090 having an opening 1091 is provided that provides a connection to a negative terminal 1080. An embodiment of a particular cell configuration is shown to protect the moisture-sensitive electrolyte layer 1050. Negative terminal 1080 and anode current collector 1070 may not be thick enough, for example, and / or not moisture barrier to protect underlying electrolyte layer 1050 over a long period of time. The schematic configuration is a modified improvement of the electrochemical device shown in FIG. 3A. Substrate 1000 may be electrically insulative or conductive, as may barrier sublayers 1011 and 1012 that may constitute barrier layer 1010. Additional components of the electrochemical device shown in FIG. 10 are the cathode current collector 1020, the positive terminal 1030, the positive cathode 1040, and the negative anode 1060.

While the invention has been particularly shown and described with reference to the various embodiments described above, those skilled in the art will understand that various changes in form and details may be made within the spirit and scope of the invention.

Claims (117)

(a) a substrate selected from the group consisting of a metallic material, a polymeric material, or a doped or undoped silicon material on a first side, (b) a first electrochemically active cell on the first side having a negative part and a positive part, wherein the parts further comprise one or more terminals. Active cell, (c) a first barrier layer on said first side that chemically separates said first electrochemically active cell from said substrate, (d) the first barrier layer further comprises a plurality of sublayers. The method of claim 1, And a plurality of electrochemically active cells provided on said first side of said substrate. The method of claim 1, The first barrier layer, A material that is chemically inert with respect to the first electrochemically active cell and the substrate, Characterized in that it is adapted to block diffusion against the first electrochemically active cell and the substrate during the manufacture of the first electrochemically active cell on the substrate and during the driving and storage state of the electrochemical device. Electrochemical device. The method of claim 1, The sublayer is selected from the group of electrically conductive materials, electrically insulating materials or electrically semi-conductive materials, a) the positive portion of the first electrochemically active cell is not in electrical contact with the negative portion of the first electrochemically active cell, b) said positive portion of said first electrochemically active cell comprises at least a positive cathode, a cathode current collector and a positive terminal, c) said negative portion of said first electrochemically active cell comprises at least a negative anode, an anode current collector and a negative terminal. The method of claim 4, wherein And said cathode current collector comprises said positive terminal. The method of claim 4, wherein And said anode current collector comprises said negative terminal. The method of claim 4, wherein And said anode current collector comprises said anode. The method of claim 4, wherein And said anode current collector comprises said anode current collector, said anode and said negative terminal. The method of claim 1, The sublayers each having the same shape and area size. The method of claim 1, At least one of said sublayers has a shape and area size different from the others of said plurality of sublayers. The method of claim 1, And the first barrier layer only partially covers the substrate such that at least the positive portion of the first electrochemically active cell is chemically separated from the substrate. The method of claim 1, And the first barrier layer only partially covers the substrate such that at least the negative portion of the first electrochemically active cell is chemically separated from the substrate. The method of claim 1, And wherein the first barrier layer has a thickness in the range of 0.01 μm to 1 mm. The method of claim 1, And wherein the first barrier layer has a thickness in the range of 0.1 μm to 100 μm. The method of claim 1, And the first barrier layer has a thickness in the range of 0.5 μm to 5 μm. The method of claim 1, And the substrate has a thickness in the range of 0.1 μm to 1 cm. The method of claim 1, And the substrate has a thickness in the range of 1 μm to 1 mm. The method of claim 1, And the substrate has a thickness in the range of 10 μm to 100 μm. The method of claim 1, The sub layer, a) a group of metals, semi-metals, alloys, borides, carbides, diamonds, pseudodiamond carbons (DLC), silicides, nitrides, phosphides, oxides, fluorides, chlorides, bromide, iodides, b) a group of any polyvalent compound consisting of borides, carbides, silicides, nitrides, phosphides, oxides, fluorides, chlorides, bromides, and iodides, or c) a group of high temperature stable organic polymers and high temperature stable silicones An electrochemical device comprising a chemical compound selected from. The method of claim 1, At least one of said sublayers comprises a single phase crystalline, nano-crystalline, amorphous or glassy material, or a polyphase mixture, or a composite thereof. The method of claim 1, At least one of said sublayers comprises a single phase amorphous or glassy material. The method of claim 1, Wherein said first electrochemically active cell comprises a cell selected from the group of lithium metal anode cells, lithium-ion anode cells, and lithium free anode cells. The method of claim 22, The first electrochemically active cell comprises a positive thin film cathode deposited by vapor deposition; And the thickness of the positive thin film cathode is less than 200 μm. The method of claim 22, The first electrochemically active cell comprises a positive thin film cathode deposited by a non-vacuum deposition method, And the thickness of the positive thin film cathode is less than 200 μm. The method of claim 23, And wherein the positive thin film cathode comprises single crystallites having a size of at least 100 Hz. The method of claim 24, And the positive thin film cathode comprises a single crystal having a size of at least 100 Hz. The method of claim 1, And wherein said first electrochemically active cell comprises a thin film solid electrolyte having a thickness of less than 100 micrometers. The method of claim 1, The first electrochemically active cell comprises a thin film negative anode selected from the group consisting of lithium metal, lithium-ion anode, or a metal that does not form a mutual metal compound with lithium, And the thickness of the thin film negative anode is less than 200 μm. The method of claim 1, The electrochemically active cell further comprises protective encapsulation, The protective encapsulation is adapted to protect the first electrochemically active cell against at least mechanical and chemical factors from the environment. The method of claim 1, Further includes protection encasing, The protective encasing is adapted to protect the electrochemical device against at least mechanical and chemical factors from the environment. The method of claim 29, The encapsulation has at least one opening adapted to allow direct electrical contact to at least one terminal of the first electrochemically active cell. The method of claim 30, The protective casing has at least one opening adapted to allow direct contact with at least one terminal of the first electrochemical device. The method of claim 31, wherein The electrochemically active cell further comprises an electrolyte, And said at least one terminal is separated from said electrolyte by a moisture protective layer. The method of claim 32, The electrochemically active cell further comprises an electrolyte, And said at least one terminal is separated from said electrolyte by a moisture protective layer. The method of claim 33, wherein The moisture protective layer, A material having moisture barrier properties, a) a group of metals, semi-metals, alloys, borides, carbides, diamonds, pseudodiamond carbons (DLC), silicides, nitrides, phosphides, oxides, fluorides, chlorides, bromide, iodides, b) a group of any polyvalent compound consisting of borides, carbides, silicides, nitrides, phosphides, oxides, fluorides, chlorides, bromides, and iodides, or c) a group of high temperature stable organic polymers and high temperature stable silicones Electrochemical device, characterized in that selected from. The method of claim 33, wherein And the moisture protection layer comprises a single phase crystalline, nano-crystalline, amorphous or glassy material, or a multiphase mixture, or a composite thereof. The method of claim 34, wherein The moisture protective layer, A material having moisture barrier properties, a) a group of metals, semi-metals, alloys, borides, carbides, diamonds, pseudodiamond carbons (DLC), silicides, nitrides, phosphides, oxides, fluorides, chlorides, bromide, iodides, b) a group of any polyvalent compound consisting of borides, carbides, silicides, nitrides, phosphides, oxides, fluorides, chlorides, bromides, and iodides, or c) a group of high temperature stable organic polymers and high temperature stable silicones Electrochemical device, characterized in that selected from. The method of claim 34, wherein And the moisture protection layer comprises a single phase crystalline, nano-crystalline, amorphous or glassy material, or a multiphase mixture, or a composite thereof. The method of claim 1, And a second layer located on the second side of the substrate. The method of claim 39, The second layer, a) a group of metals, semi-metals, alloys, borides, carbides, diamonds, pseudodiamond carbons (DLC), silicides, nitrides, phosphides, oxides, fluorides, chlorides, bromide, iodides, b) a group of any polyvalent compound consisting of borides, carbides, silicides, nitrides, phosphides, oxides, fluorides, chlorides, bromides, and iodides, or c) a group of high temperature stable organic polymers and high temperature stable silicones An electrochemical device comprising a chemical compound selected from. a) a metal substrate, a polymer substrate, or a doped or undoped silicon substrate having a first side and a second side, b) a first electrochemically active cell on the first side further comprising a positive portion and a negative portion, wherein the portions further comprise one or more terminals; c) a first barrier layer on said first side that chemically separates said first electrochemically active cell from said metal substrate, polymer substrate, or doped or undoped silicon substrate; d) a second electrochemically active cell on the second side further comprising a positive portion and a negative portion, wherein the portions further comprise one or more terminals; e) a second barrier layer on said second side separating said second electrochemically active cell from said substrate, f) the first barrier layer comprises a plurality of sublayers, g) the second barrier layer comprises a plurality of sublayers. 42. The method of claim 41 wherein And a plurality of electrochemically active cells provided on said first side of said substrate. 42. The method of claim 41 wherein And a plurality of electrochemically active cells provided on said second side of said substrate. 42. The method of claim 41 wherein The barrier layer on both sides of the substrate, Is adapted to chemically separate the electrochemically active cell from the substrate, (a) said first barrier layer comprising said first electrochemically active cell on said first side of said substrate and a material that is chemically inert to said substrate; (b) further comprising the second barrier layer comprising the second electrochemically active cell on the second side of the substrate and a material that is chemically inert to the substrate, (c) the first barrier layer further has diffusion barrier properties for chemical elements in the first electrochemically active cell on the first side of the substrate, and (d) said second barrier layer further has diffusion barrier properties for chemical elements in said second electrochemically active cell on said second side of said substrate. 42. The method of claim 41 wherein a) the sublayer is selected from the group of electrically conductive materials, electrically insulating materials, or electrically semi-conductive materials, b) the positive portion of the electrochemically active cell is not in electrical contact with the negative portion of the electrochemically active cell on both sides of the substrate, c) said positive portion of said electrochemically active cell comprises at least a positive cathode, a cathode current collector and a positive terminal, d) said negative portion of said electrochemically active cell comprises at least a negative anode, an anode current collector and a negative terminal. The method of claim 45, And said cathode current collector comprises said positive terminal. The method of claim 45, And said anode current collector comprises said negative terminal. The method of claim 45, And said anode current collector comprises said anode. The method of claim 45, And said anode current collector comprises said anode current collector, said anode and said negative terminal. 42. The method of claim 41 wherein The sublayers each having the same shape and area size. 42. The method of claim 41 wherein At least one of said sublayers has a shape and area size different from the others of said plurality of sublayers. 42. The method of claim 41 wherein At least one of the barrier layers only partially covers the substrate, At least the positive portion of the electrochemically active cell is chemically separated from the substrate. 42. The method of claim 41 wherein At least one of the barrier layers only partially covers the substrate, At least the negative portion of the electrochemically active cell is chemically separated from the substrate. 42. The method of claim 41 wherein And the barrier layer on both sides of the substrate has a thickness in the range of 0.01 μm to 1 mm. 42. The method of claim 41 wherein And the barrier layer on both sides of the substrate has a thickness in the range of 0.1 μm to 100 μm. 42. The method of claim 41 wherein And the barrier layer on both sides of the substrate has a thickness in the range of 0.5 μm to 5 μm. 42. The method of claim 41 wherein And the substrate has a thickness in the range of 0.1 μm to 1 cm. 42. The method of claim 41 wherein And the substrate has a thickness in the range of 1 μm to 1 mm. 42. The method of claim 41 wherein And the substrate has a thickness in the range of 10 μm to 100 μm. 42. The method of claim 41 wherein At least one of the sub-layers, a) a group of metals, semi-metals, alloys, borides, carbides, diamonds, pseudodiamond carbons (DLC), silicides, nitrides, phosphides, oxides, fluorides, chlorides, bromide, iodides, b) a group of any polyvalent compound consisting of borides, carbides, silicides, nitrides, phosphides, oxides, fluorides, chlorides, bromides, and iodides, or c) a group of high temperature stable organic polymers and high temperature stable silicones An electrochemical device comprising a chemical compound selected from. 42. The method of claim 41 wherein At least one of said sublayers comprises a single phase crystalline, nano-crystalline, amorphous or glassy material, or any polyphase mixture, or a composite thereof. 42. The method of claim 41 wherein At least one of said sublayers comprises a single phase amorphous or glassy material. 42. The method of claim 41 wherein The electrochemically active cell on both sides of the substrate comprises a cell selected from the group of lithium metal anode cells, lithium-ion anode cells, and lithium free anode cells. 42. The method of claim 41 wherein The electrochemically active cell comprises a positive thin film cathode deposited by vapor deposition or non-vacuum deposition, And wherein the positive thin film cathode has a thickness of less than 200 μm. The method of claim 64, wherein And the positive thin film cathode comprises a single crystal having a size of at least 100 Hz. 42. The method of claim 41 wherein The electrochemically active cell further comprises a thin film solid electrolyte having a thickness of less than 100 μm. 42. The method of claim 41 wherein The electrochemically active cell comprises a thin film negative anode selected from the group consisting of lithium metal, lithium-ion anode, or a metal that does not form a mutual metal compound with lithium, And the thin film negative anode has a thickness of less than 200 μm. 42. The method of claim 41 wherein Each of said electrochemically active cells of said electrochemical device comprises protective encapsulation or protective encasing, The protective encapsulation or protective encapsulation is adapted to protect the electrochemically active cell or electrochemical device against at least mechanical and chemical factors in the surrounding environment. The method of claim 68, wherein Wherein said encapsulation or said casing has at least one opening adapted to allow direct electrical contact to at least one terminal of said each electrochemically active cell. The method of claim 69, The electrochemically active cell further comprises an electrolyte, The terminal is externally connectable by an opening in the encapsulation and is separated from the electrolyte by a moisture protection layer. The method of claim 70, The moisture protection layer comprises a material having moisture barrier properties, a) a group of metals, semi-metals, alloys, borides, carbides, diamonds, pseudodiamond carbons (DLC), silicides, nitrides, phosphides, oxides, fluorides, chlorides, bromide, iodides, b) a group of any polyvalent compound consisting of borides, carbides, silicides, nitrides, phosphides, oxides, fluorides, chlorides, bromides, and iodides, or c) a group of high temperature stable organic polymers and high temperature stable silicones Electrochemical device, characterized in that selected from. The method of claim 70, And the moisture protection layer comprises a single phase crystalline, nano-crystalline, amorphous or glassy material, or any polyphase mixture, or a composite thereof. As a manufacturing method of an electrochemical device, (a) providing a metal substrate, a polymer substrate, or a silicon substrate having a first side, (b) depositing a first barrier layer on the first side; (c) manufacturing a first electrochemically active cell comprising a negative portion and a positive portion, wherein the portions comprise one or more terminals, the cell on the first side on top of the first barrier layer; And wherein the barrier layer chemically separates the first electrochemically active cell from the substrate; (d) manufacturing the first barrier layer into a plurality of chemically different sublayers. The method of claim 73, wherein Providing a plurality of electrochemically active cells on the first side of the substrate. The method of claim 73, wherein (a) selecting the sublayer from a group of an electrically conductive material, an electrically insulating material, or an electrically semi-conductive material, (b) preventing the positive portion of the first electrochemically active cell from making electrical contact with the negative portion of the first electrochemically active cell; (c) providing a positive cathode, a cathode current collector and a positive terminal on the positive portion of the first electrochemically active cell; (d) providing a negative anode, an anode current collector and a negative terminal on the negative portion of the first electrochemically active cell. 76. The method of claim 75 wherein And providing said cathode current collector as said positive terminal. 76. The method of claim 75 wherein Providing the anode current collector as the negative terminal. 76. The method of claim 75 wherein Providing the anode current collector as the anode. 76. The method of claim 75 wherein Providing the anode current collector as the anode current collector, the anode, and the negative terminal. The method of claim 73, wherein Providing said sublayer as each sublayer having the same shape and area size. The method of claim 73, wherein Providing at least one of said sublayers having a shape and an area size different from others of said plurality of sublayers. The method of claim 73, wherein Only partially covering the substrate by the first barrier layer such that at least the positive portion of the first electrochemically active cell is chemically separated from the substrate. Way. The method of claim 73, wherein Providing the first barrier layer only partially covering the substrate such that at least the negative portion of the first electrochemically active cell is chemically separated from the substrate. Manufacturing method. The method of claim 73, wherein a) a group of metals, semi-metals, alloys, borides, carbides, diamonds, pseudo diamond carbons (DLC), silicides, nitrides, phosphides, oxides, fluorides, chlorides, bromide, iodides, b) a group of any polyvalent compound consisting of boride, carbide, silicide, nitride, phosphide, oxide, fluoride, chloride, bromide, and iodide, or a group of high temperature stable organic polymers and high temperature stable silicon The method of manufacturing an electrochemical device, further comprising the step of preparing the sub-layer with a chemical compound selected from. The method of claim 73, wherein Producing said sublayer as a single phase crystalline, nano-crystalline, amorphous or glassy material, or any polyphase mixture, or a composite thereof. The method of claim 73, wherein Manufacturing the sublayer from a single phase amorphous or glassy material. The method of claim 73, wherein The first electrochemical by an in-situ or ex-situ temperature process between 100 ° C. and the melting point of the substrate such that the positive cathode comprises crystallites having a size of at least 100 Hz. And manufacturing said positive cathode on an active cell. The method of claim 73, wherein Providing protection encapsulation or protection encapsulation to protect the first electrochemically active cell or the electrochemical device, respectively, against at least mechanical and chemical factors from the environment. Method of manufacturing a chemical device. 89. The method of claim 88 wherein Producing said encapsulation or said casing with at least one opening allowing direct electrical contact to said at least one terminal of said first electrochemically active cell. Method of preparation. 92. The method of claim 89, Providing an electrolyte in one of said electrochemically active cells, and separating said electrolyte from said at least one terminal by a moisture protective layer. 92. The method of claim 90, Manufacturing the moisture protective layer from a material having moisture barrier properties; a) a group of metals, semi-metals, alloys, borides, carbides, diamonds, pseudo diamond carbons (DLC), silicides, nitrides, phosphides, oxides, fluorides, chlorides, bromide, iodides, b) a group of any polyvalent compound consisting of boride, carbide, silicide, nitride, phosphide, oxide, fluoride, chloride, bromide, and iodide, c) a group of high temperature stable organic polymers and high temperature stable silicones Selecting from the chemical compound for the protective layer from the method of manufacturing an electrochemical device. 92. The method of claim 90, Manufacturing the moisture protective layer from a material comprising a single phase crystalline, nano-crystalline, amorphous or glassy material, or any polyphase mixture, or a composite thereof. The method of claim 73, wherein Depositing a second layer on the second side of the substrate for chemical protection of the substrate and the first electrochemically active cell on the first side of the substrate from the surrounding environment prior to fabrication of the first electrochemically active cell To do that, Chemically protecting the first electrochemically active cell by blocking diffusion of contaminants from the surrounding environment. 94. The method of claim 93, a) a group of metals, semi-metals, alloys, borides, carbides, diamonds, pseudo diamond carbons (DLC), silicides, nitrides, phosphides, oxides, fluorides, chlorides, bromide, iodides, b) a group of any polyvalent compound consisting of boride, carbide, silicide, nitride, phosphide, oxide, fluoride, chloride, bromide, and iodide, c) a group of high temperature stable organic polymers and high temperature stable silicones And manufacturing said second layer with a chemical compound selected from. 94. The method of claim 93, Thermally relaxing the first barrier layer and the second barrier layer by an in-situ or x-situ temperature process between 100 ° C. and the melting point of the substrate, The ex-situ temperature process further comprises applying the temperature process after deposition of the first barrier layer and the second barrier layer. As a manufacturing method of an electrochemical device, (a) providing a metal substrate, a polymer substrate, or a doped or undoped silicon substrate having a first side and a second side, (b) depositing a first barrier layer on the first side; (c) depositing a second barrier layer on the second side; (d) fabricating a first electrochemically active cell on the first side on top of the first barrier layer, the first barrier layer chemically transferring the first electrochemically active cell from the substrate. Preparing a first electrochemically active cell, which is to separate, (e) fabricating a second electrochemically active cell on the second side on top of the second barrier layer, the second barrier layer chemically transferring the second electrochemically active cell from the substrate. Preparing a second electrochemically active cell, which is to separate; (f) constructing the first barrier layer into a plurality of chemically different sublayers, (g) constructing the second barrier layer into a plurality of chemically different sublayers. 97. The method of claim 96, Providing a plurality of said electrochemically active cells on said first side of said substrate. 97. The method of claim 96, Providing a plurality of said electrochemically active cells on said second side of said substrate. 97. The method of claim 96, (a) selecting the sublayer from a group of an electrically conductive material, an electrically insulating material, or an electrically semi-conductive material, (b) avoiding electrical contact between the positive portion of the electrochemically active cell on both sides of the substrate and the negative portion of the electrochemically active cell; (c) providing a positive cathode, a cathode current collector and a positive terminal on the positive portion of the electrochemically active cell; (d) providing a negative anode, an anode current collector and a negative terminal on the negative portion of the electrochemically active cell. The method of claim 99, wherein And providing said cathode current collector as said positive terminal. The method of claim 99, wherein Providing the anode current collector as the negative terminal. The method of claim 99, wherein Providing the anode current collector as the anode. The method of claim 99, wherein Providing the anode current collector as the anode current collector, the anode, and the negative terminal. 97. The method of claim 96, And providing said sublayers having the same shape and area size. 97. The method of claim 96, Providing at least one of said sublayers having a shape and an area size different from others of said plurality of sublayers. 97. The method of claim 96, Only partially covering the substrate by at least one of the barrier layers, At least the positive portion of the electrochemically active cell is chemically separated from the substrate. 97. The method of claim 96, Only partially covering the substrate by at least one of the barrier layers, At least the negative portion of the electrochemically active cell is chemically separated from the substrate. 97. The method of claim 96, a) a group of metals, semi-metals, alloys, borides, carbides, diamonds, pseudo diamond carbons (DLC), silicides, nitrides, phosphides, oxides, fluorides, chlorides, bromide, iodides, b) a group of any polyvalent compound consisting of boride, carbide, silicide, nitride, phosphide, oxide, fluoride, chloride, bromide, and iodide, c) a group of high temperature stable organic polymers and high temperature stable silicones Manufacturing said sublayers on both sides of said substrate with a chemical compound selected from. 97. The method of claim 96, Producing said sublayer as a single phase crystalline, nano-crystalline, amorphous or glassy material, or any polyphase mixture, or a composite thereof. 97. The method of claim 96, Manufacturing the sublayer from a single phase amorphous or glassy material. 97. The method of claim 96, Thermally relaxing the first barrier layer and the second barrier layer by an in-situ or x-situ temperature process between 100 ° C. and the melting point of the substrate, And the ex-situ temperature process is applied after deposition of the first barrier layer and the second barrier layer. 97. The method of claim 96,  Preparing the positive cathode of the electrochemical cell by an in-situ or x-situ temperature process between 100 ° C. and the melting point of the substrate to provide a positive cathode comprising crystallites having a size of at least 100 Hz. Method for producing an electrochemical device comprising a. 97. The method of claim 96, Producing a protective encapsulation or protective encapsulation in each of the electrochemically active cells or electrochemical devices, thereby protecting each of the electrochemically active cells or the electrochemical devices against at least mechanical and chemical factors from the surrounding environment. The method of manufacturing an electrochemical device, further comprising the step. 115. The method of claim 113, Manufacturing the encapsulation or the casing with at least one opening allowing direct electrical contact to at least one of the terminals of each of the electrochemically active cells per encapsulation or the casing. The manufacturing method of the electrochemical device characterized by the above-mentioned. 116. The method of claim 114, wherein Providing an electrolyte in said electrochemically active cell, and separating said electrolyte from said terminal by a moisture protective layer. 116. The method of claim 115, a) a group of metals, semi-metals, alloys, borides, carbides, diamonds, pseudo diamond carbons (DLC), silicides, nitrides, phosphides, oxides, fluorides, chlorides, bromide, iodides, b) a group of any polyvalent compound consisting of boride, carbide, silicide, nitride, phosphide, oxide, fluoride, chloride, bromide, and iodide, c) a group of high temperature stable organic polymers and high temperature stable silicones And manufacturing said protective layer from a material having a chemical compound selected from said material having moisture barrier properties. 116. The method of claim 115, Manufacturing the moisture protective layer from a material comprising a single phase crystalline, nano-crystalline, amorphous or glassy material, or any polyphase mixture, or a composite thereof.

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