KR101497992B1 - Electrochemical apparatus with barrier layer protected substrate - Google Patents

Abstract

The present invention relates to a process for preparing an appropriate barrier layer consisting, for example, of a barrier sub-layer between the substrate portion and the cell portion of the present invention, for the entire lifetime of the electrochemical device, as well as any drive and storage of the electrochemical device, To a device, a composition and a method for producing a high performance thin film battery on a metal substrate, a polymer substrate, or a doped or undoped silicon substrate by chemically separating these two portions. In a preferred embodiment of the invention, the barrier of the thin film battery manufacturing thin flexible using a suitable barrier layer consisting of a sub-layer on a property of stainless steel foil substrate 700 ℃ deposition for LiCoO ₂ positive cathode-When using a post annealing process Has an undamaged electrochemical performance as compared to a thin film battery fabricated on a ceramic substrate.

An electrochemical device, a thin film battery, an electrochemically active cell, a barrier layer, a barrier sublayer

Description

ELECTROCHEMICAL APPARATUS WITH BARRIER LAYER PROTECTED SUBSTRATE FIELD OF THE INVENTION [0001]

Related application

This application is a continuation-in-part of U.S. Provisional Patent Application Serial No. 60 / 690,697, filed June 15, 2005, which is a continuation-in-part of US Application Serial Number Filed on August 23, 2005, and claims the benefit of 35 USC § 120 of that application, the disclosures of which are hereby expressly incorporated herein by reference do.

Field of the present invention capacity density, the energy density and the power density is improved, preferably a flexible form factor and a crystalline _{LiCoO 2, LiNiO 2, LiMn 2} O 4 lithium-based solid state having a cathode (cathode) and the inducing material The present invention relates to a device, construction and manufacture of thin film secondary and primary batteries.

The requirements and progress of the related art in the field of thin film batteries will be described below.

A thin film battery can be fabricated by sequentially depositing layered battery components on a corresponding substrate, for example, in the following order: a positive cathode current collector, a positive cathode, a negative anode current collector, an electrolyte ( Separator), a negative anode, and encapsulation. A deposition process may be used instead of the deposition process step (see, for example, U.S. Patent No. 6,916,679 (Wang et al.), 143 J. Electrochem. Soc. 3203-12 (1996) or U.S. Patent No. 5,561,004). Optionally, the two terminals of the thin film battery do not simply include extensions of the positive and negative current collectors, but terminal contacts that are in electrical contact with each current collector may be additionally deposited. The positive cathode material may be insufficiently crystalline in the deposited state and may exhibit insufficient electrochemical properties in connection with this fact (see, e. G., Wang et al., Supra). Therefore, the cathode is the positive et is crystallized during battery manufacturing, which can be achieved by high-temperature ( "annealing") process after deposition (e.g., Wang, or New Trends in Electrochemical Technology : Energy Storage Systems for Electronics (T. Osaka & M. Datta eds ., Gordon and Bates et al., "Thin-Film Lithium Batteries & quot ; , Breach 2000 ). The annealing process applied immediately after deposition of the positive cathode limits the choice of materials for the substrate and the positive cathode current collector to limit the capacity density, energy density, and power density of the thin film battery per volume and weight. For example, the influence of the substrate on these three quantities will be described in detail below.

The volume and weight density of the capacity, energy and power inherent in the lithium-based solid state thin film secondary (rechargeable) and primary (non-rechargeable) cells (ie, without substrate and encapsulation) , The volume and weight density of energy and power. In the case of a secondary cell, crystalline LiCoO ₂ is an example of a positive cathode material selection for both bulk (not thin film) and thin film cells in terms of capacity, energy, power and circulating capability, and crystalline LiMn ₂ O ₄ , Crystalline LiMnO ₂ , and derivatives of crystalline LiNiO ₂ . These main parent cathode materials are represented by Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru, Rh, La, Hf, Doping with other transition metals (which are derivatives) such as Ru and major group elements selected from Group 1, Group 2, Group 13, Group 14, Group 15, Group 16, and Group 17 is believed to be LiCoO ₂ , LiMn ₂ O ₄ , LiMnO ₂ , and LiNiO ₂ to a very small extent.

According to U. S. Patent No. 6,280, 875, pure titanium oxide on a Ti substrate is not sufficiently inert to prevent deleterious reactions between the Ti substrate and the battery components from occurring. This approach is very limited since the choice of substrate material is limited to a material that can form a pure surface oxide during the annealing step of the positive cathode. Apart from the present invention, a metallic substrate comprising a flexible foil that does not form a pure surface oxide has not been successfully employed as a thin film cell substrate. For example, directly depositing a high temperature cathode material on a metallic substrate comprising a flexible foil other than Zr, and then annealing at a high temperature such as 700 캜 in air for one hour to produce a solid state thin film secondary cell, Substrate material results in detrimental reaction to such an 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 a potential negative observation. For example, there is a need for the present invention, such as a novel barrier layer having sublayering properties to overcome the specific problems of conventional thin film batteries.

Summary of the Invention

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS As will be described in detail below by way of example, the various aspects and embodiments of the present invention refer to particular drawbacks of the prior art and the emerging need in the industry.

While the number of portable and on-board devices continues to increase rapidly, the available physical dimensions may decrease. Batteries driving these devices must meet the needs of the device, e. G., Delivering the same power, with potential size reduction. The thinner the battery, the more applications can be applied. One possible power device is a thin film solid state battery. It is important to pack and stack as many battery cells as possible within the available space (footprint x height) if the footprint is a limiting factor but the capacity demand is still "high ".

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

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

However, like other positive cathode materials, LiCoO ₂ is a strong oxidant and very mobile and thus has reactive lithium ions. At high annealing temperatures required to crystallize the deposited LiCoO ₂ film, it reacts strongly with most metals and alloys as well as with a variety of compounds, with the exception of a limited number of inert ceramics. In other cases, unwanted paper from the substrate during high annealing temperatures may diffuse into the LiCoO ₂ and contaminate the positive cathode, thereby detrimentally altering its electrochemical properties. If the annealing temperature is kept low enough to prevent reactive or undesired diffusion, the positive cathode may not be completely crystallized, and the capacity, energy, current and power capacity, and lifetime (number of cycles) Can be damaged.

The high-power positive cathode material can exhibit the complete desired electrochemical properties in its crystalline state. As these materials can be used in the form of thin films, for example, in the present invention, they can be used in a wide range of applications including, but not limited to, sputter deposition (RF, pulsed DC or AC), electron-beam evaporation, chemical vapor deposition, plasma enhanced chemical vapor deposition, For example, by conventional vapor phase thin film deposition methods such as electron beam evaporation, beam evaporation, electron-beam direct vapor deposition, cathode arc deposition, and the like. These vaporization processes may not produce a deposited positive cathode film exhibiting electrochemical properties comparable to positive cathodes fabricated from respective well-crystallized powders used in bulk batteries such as mobile phones and camcorder type cells. Thus, the lack of electrochemical properties of such positive cathodes deposited by thin-film processes can be attributed to the lack of required crystallinity in the deposited state.

However, the crystallinity can be improved by high-temperature annealing, usually at 200 ° C to 900 ° C, preferably at 500 ° C to 850 ° C, more preferably at 650 ° C to 800 ° C. The atmosphere used in this anneal is typically air, O ₂ , N ₂ , Ar, He, H ₂ , H ₂ O, CO ₂ , vacuum (P <1 torr), or a combination thereof. To achieve sufficient crystallization and thus achieve improved electrochemical properties, preferably the annealing time should be extended, for example, if the annealing temperature is lowered to below about 650 ° C. The crystallization rate is exponentially activated by the temperature, and can be significantly reduced at lower annealing temperatures. If the annealing temperature is too low, the applied energy from the annealing temperature may not be sufficient at all to exceed the thermal activation energy needed to cause the crystallization process to occur. For example, a 900 ° C anneal in air for 15 minutes can show the same crystallinity as in a magnetron-sputtered LiCoO ₂ film at 700 ° C for about 1 hour anneal, 600 ° C for 12 hours in air. 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 by the vapor phase method can be annealed after 700 ° C deposition in air for about 30 minutes to 2 hours. However, such relatively high annealing temperatures can cause chemical miscibility problems, and thus such annealing steps are not only potentially undesirable in thin film battery manufacturing processes, but also increase costs and reduce manufacturing yields .

Post-deposition annealing conditions greatly limit the choice of substrate material. The substrate must not only withstand the high annealing temperature (T > 500 [deg.] C), but also preferably chemically inert with respect to all cell membrane materials in contact with the substrate for annealed atmospheric 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 during the operation and storage of the electrochemical device, either during or after manufacture. Such impurities can be detrimental to any cell membrane material and may impair, seriously affect, or even destroy cell performance and lifetime. For example, the particular selection of substrates may be limited to chemically inert high temperature ceramics such as Al ₂ O ₃ , MgO, NaCl, SiC and quartz glass. The two metals, Zr and Ti, have shown limited success as, for example, 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 above-described ceramics have demonstrated their ability to withstand high temperatures without chemical reactions during thin-film cell fabrication, using them for cost-effective fabrication of thin-film batteries can have significant drawbacks. The ceramic is at least 5 mil

125 탆 thick, brittle, irreversible (rigid) and tends to be relatively expensive per given footprint. Also, their thin area size can be limited. The thinner the ceramic substrate, the smaller the maximum area that the ceramic can be handled safely without breaking. For example, a 12 inch by 12 inch plate Al ₂ O ₃ of 1/4 inch thickness is commercially available. However,

A thinned 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 inches by 4 inches substrate. A thin (<20 mil or <500 micron) 4 inch 8 inch polished ceramic substrate is available as a consumer order, not as a general inventory at an acceptable price for large scale fabrication of thin film cells.

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

For all of the reasons described above, non-ceramic foil can be used as a thin film cell substrate. Silicon and doped silicon can take intermediate positions, for example, below the non-ceramic substrate, 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, a non-ceramic foil can provide advantages as a substrate for a thin film battery if the substrate material can withstand processing conditions including temperature, for example, contact of a particular potential reactive cell layer. Compared to a ceramic substrate of a given footprint, the non-ceramic foil substrate is thinner, more flexible, less expensive, readily available in larger sizes, and reduces the electrochemically inactive weight and volume of the entire cell , The overall thickness of the battery or electrochemical device can be reduced, which will increase the battery's capacity density, energy density, and power density. For example, the non-ceramic foil may be, for example, 0.5-5 mil

Available as rolls of 12-125 micrometers thick, several meters wide, and several meters long. Substrates from long rolls offer the possibility of roll-to-roll manufacture at a much lower cost than conventional batch mode manufacturing processes currently in operation. Compared to thin film cells fabricated on thick and rigid substrates, the fabrication of thin film cells on thin and more flexible substrates, without compromising battery performance, allows 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 inactive weight and volume of the cell can increase the battery's capacity density, energy density, and power density per unit weight and volume. For example, a given application can allocate a volume of 2 cm x 2 cm x 0.1 cm to the cell. There are currently no conventional button cells or jelly rolls (spirally wound or prismatic) cells that can physically match such volumes. In contrast, even though the thin film solid state cell is fabricated with a 0.05 cm ceramic substrate, the entire cell, including the optional protective encapsulation and encasing (see below), is much thinner than 0.1 cm Such volume can be met. 2 mil

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

For example, thin film cells can be fabricated by sequentially layering individual battery component layers on top of each other. As described above, the optimal positive cathode includes, but is 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, 0 <y ≦ 5). The positive cathodes may also include post-deposition annealing at temperatures above 500 DEG C to fully crystallize and achieve their full electrochemical properties. Certain known solid state lithium electrolytes are capable of contacting the hot positive cathode at such high temperatures The positive cathode is deposited and annealed prior to depositing the electrolyte layer.

The positive cathode material can generally be regarded as a poor semiconductor in at least some range of charge states during battery operation. To obtain maximum power from the cell and into the external circuit, the positive cathode layer may be deposited in a metallic back contact, a cathode current collector (CCC) layer. The CCC should also perform a hot cathode anneal and at the same time not react with the positive cathode. For this reason, for example, noble metals such as gold or its alloys or their equivalents can be used.

It is emphasized that the positive cathode material can be deposited as the second layer of the battery immediately after the deposition of the CCC, in order to improve the performance of the battery. Thus, post-deposition annealing of the positive cathode layer can achieve its crystallization prior to subsequent fabrication steps and electrolyte deposition. Due to the proximity of the substrate and the hot cathode material that can be separated from each other only by a relatively thin CCC (0.1 - 1 mu m), when using a high temperature stable metal foil such as stainless steel instead of using a ceramic substrate, Very harmful interdiffusion and strong reaction were observed. This interdiffusion may not be blocked by the metallic CCC itself, for example, due to three main reasons. First, the CCC membrane is relatively thin (0.1 - 1 μm) and only shows a thin quasi-diffusion barrier. Second, CCC represents a crystalline grain structure. The grain boundaries can be conventional locations for ion and electron diffusion and conduction so that the CCC should be viewed as inherently transmissive to ions and electrons from both the adjacent positive cathode layer and the adjacent metallic foil substrate. Thus, during the cathode anneal step, the foil substrate material and the cathode film material can diffuse each other. Third, the metallic CCC becomes an alloy with the metal foil substrate and affects its current collecting characteristics.

The thickness of the CCC is determined, for example, by cost, weight, volume and adhesion, all of which would be technically impractical if the CCC is made thicker than about 2 microns, especially if expensive precious metals such as gold are used . Potentially, a CCC film that is significantly thicker than about 5 占 퐉 may avoid interdiffusion depending on, for example, the temperature of the annealing step and the associated residence time. However, the use of such a thick CCC may include, for example, increased material costs and potentially unreliable attachment.

The replacement of a ceramic substrate with a metal foil substrate creates numerous opportunities to enable new technologies using thin film batteries in addition to reducing manufacturing costs for thin film cells fabricated on ceramic substrates. In contrast to ceramic plates, metal foils are readily commercially available in thicknesses of less than 75 microns, and some materials are available as thin as 4 microns. These foils are much more flexible than their ceramic counterparts, contribute less to the structural and inactive weight for the cell, and most importantly substantially reduce the overall thickness of the finished thin film battery device. It should be emphasized that the overall thickness reduction of the cell and the increase in flexibility are particularly important in most thin film battery applications. The thinner the thin film battery device, the more new and physically smaller the application can be. What could not be done with a button-cell battery now becomes 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.

In addition, thin metal foils can generally be less costly per footprint area than ceramics, and can be larger in size, such as rolls. Due to the availability of flexible, oversized substrates, the potential for development of open-roll manufacturing methods exists, thereby further reducing manufacturing costs.

For example, new applications can be made possible by thin film cells that are not damaged or provide improved performance compared to conventional thin film cells fabricated on ceramic substrates. In this regard, the present invention can include depositing an interdiffusion barrier layer on a metal foil substrate, wherein the barrier layer is deposited not only in a range between high and low deposition-post anneal temperatures, such as between 100 DEG C and the melting point of the substrate, (I.e., the electrochemically active cell) portion from the substrate portion of the electrochemical device during the driving and storage states of the electrochemical device that is not the source of the electrochemical device. An embodiment of this aspect of the invention is shown, for example, in FIG.

The barrier layer prevents, for example, diffusion of any contaminants entering the cell from the substrate, as well as diffusion of block ions diffusing from the cell to the substrate during battery manufacturing and cell driving and storage conditions. Such a barrier layer, for example, may not exhibit a grain structure at any time. That is, the barrier layer may be in an amorphous or vitreous state in the deposited state, and may remain in such state during battery operating and storage conditions as well as in the overall annealing and battery manufacturing process. Members of the grain structure in the barrier layer can avoid deleterious grain boundary diffusion or conduction of ions and electrons. As described above, the grain boundaries are paths through which impurities and contaminants migrate. When these specific conditions are met, the thin, less flexible, thicker, thinner and thinner cells that are produced on the metal substrate are more flexible and thicker, for example, chemically inert and thicker, heavier, stronger, Which is comparable to a thin film battery.

Specific materials potentially suitable for the diffusion barrier layer include, for example, borides, carbides, diamonds, diamond-like carbon (DLC), silicides, nitrides, phosphides, oxides, fluorides, chlorides, bromides, iodides, and It may be a material whose ion conduction is weak, such as its arbitrary multinary compound. Among these compounds, an electrically insulating material may further prevent the possible reaction between the substrate and the cell layer to occur, for example, when these chemical reactions involve the diffusion of ions and electrons, Since it may be one means of blocking these exemplary chemical reactions. However, for example, an electrically conductive material such as ZrN may be used, as long as it does not conduct any substrate ions or cell layer materials. In some cases, the metal, alloy and / or semi-metal may act as a sufficient barrier layer depending on the annealing temperature applied during the cell manufacturing process and the substrate material used. Although an amorphous or glassy structure is commonly used due to the absence of a grain boundary that acts as an increased but undesirable ion and electron conduction position, the diffusion barrier layer may be formed, for example, as a single or multiple phase, crystalline, glassy, amorphous, Can be mixed.

Because certain materials block the conduction of various ions, certain lithium non-containing thin film cells, such as beryllium, sodium, magnesium, potassium, calcium, boron, and aluminum, May also be used. The thickness of the diffusion barrier layer may be in the range of, for example, 0.01 탆 to 1 mm.

Although the concepts and principles of the barrier layer and / or sub-barrier layer for the thin film battery of the present invention were originally developed for metal substrates, for example, the application of the associated thin film battery also includes a polymer substrate of commercial interest, The same barrier layer material may be deposited on the non-doped silicon substrate. The post-deposition anneal temperature may be, for example, lower than the melting point of the silicon or polymer substrate used, for example, regardless of the barrier layer applied to avoid melting of the substrate.

An embodiment of the present invention is directed to a method of manufacturing, for example, a flexible high-capacity solid state thin film battery on a thin foil substrate, such as a metal substrate. For purposes of the present invention, an electrochemical device is defined as an apparatus comprising at least one electrochemically active cell, such as a thin film cell, with a suitable substrate, such as a metal substrate, and a suitable diffusion barrier layer, And a plurality of barrier sub-layers between the active cell and the substrate (see FIG. 1). The electrochemical device may also include a protective encapsulation or protective encasing as described in detail below.

The success of the characteristic embodiments of the present invention is believed to be in the utilization of a suitable chemically inactive diffusion barrier layer and sub-layer between these two parts, which can effectively separate the substrate and the thin film battery of the electrochemical device. The diffusion barrier layer is capable of withstanding a high annealing temperature that can be applied to the thin film battery during fabrication of the thin film cell portion on the substrate and is inert with respect to both the substrate and the thin film cell portion, And it is preferable that the thin film battery portion is chemically separated and held from the substrate under the driving and storage conditions of the electrochemical device after the completion of the production. In addition, the barrier layer can be used to prevent diffusion of any contaminants that attempt to enter the thin film cell portion from the substrate, as well as the diffusion of block Li ions that will diffuse from the thin film cell portion to the substrate 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 of the thin film battery components already present in the fabrication step of the incomplete electrochemical device from the applied atmosphere during post-deposition annealing.

The fabrication of diffusion barriers of a plurality of barrier sublayers allows the 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 to, and therefore included by reference in the Si ₃ N ₄ or, for example, two-phase ( "complex") of Ti ₈₄ B ₁₆ (here of the thermodynamic approximately the same amount of TiB ₂ and the beta -B, Binary Alloy Phase Diagrams, 2 ^nd Or TiO ₂ -Ba 0 _.5 as described in U.S. Patent No. 6,444,336 (incorporated herein by reference), which is incorporated herein by reference in its entirety. It improves performance and reliability of an electrochemical device compared to Sr _0.5 TiO ₃ composite material and a manufacturing apparatus having a diffusion barrier layer which may comprise one single layer of a given material such. In its simplest form, the diffusion barrier layer of the present invention comprises a thin (~ 1000A) barrier sublayer with additional adhesion improving properties such as Ti and a thicker (1 mu m) barrier sublayer such as Si ₃ N ₄ .

The barrier sublayer material of the diffusion barrier layer of the present invention may include, among other things, amorphous Si ₃ N ₄ , SiC, ZrN and TiC, but is not limited thereto. These are exemplary compounds that can act effectively as a barrier due to their ion blocking properties, amorphous structure, and chemical inertness to the substrate as well as the substrate of the electrochemical device. They then annealed, for example up to a substantially high temperature of 700 ℃ during the process, and at this temperature, for example, for a long period of time of 2 hours remarkable features of the these barrier layers chemistry, maintain their amorphous in the deposited state, the preferred LiCoO ₂ crystallization deposited Lt; RTI ID = 0.0 &gt; blocking &lt; / RTI &gt; As a result, a thin film battery having such a barrier layer and fabricated on a metal foil has the added advantage that it maintains good electrochemical characteristics for thin film cells of equivalent configuration made on a ceramic substrate, is flexible, thinner, and inexpensive .

Embodiments of the present invention relate, for example, to forming a suitable barrier layer on a substrate in conjunction with subsequent thin film cell fabrication, wherein the barrier layer protects the substrate during battery manufacturing and subsequent storage as well as during battery fabrication. And can be chemically separated from the cell portion. Polymer substrates and doped and undoped silicon substrates may be used in addition to metal substrates.

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

Another object of an embodiment of the present invention is to provide 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 .

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

Another object of an embodiment of the present invention is to provide 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 And a method for producing the same.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 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 sub-layers.

Figure 2 shows a schematic diagram of an exemplary use of an embodiment of a barrier layer that provides electrical isolation between the positive and negative portions of an electrochemically active cell and includes barrier sub-layers of different area dimensions.

Figure 3a shows an example of an embodiment of a barrier layer comprising an electrically conductive barrier sub-layer for the case where electrical separation between the positive and negative portions of the electrochemically active cell is achieved through forming a negative portion over the top of the electrolyte Fig.

FIG. 3B is a cross-sectional view of one embodiment of a barrier layer comprising an electrically conductive barrier sub-layer on a metal substrate, wherein electrical separation between the positive and negative portions of the cell is achieved by forming a negative portion over the top of the electrolyte. &Lt; / RTI &gt; FIG.

FIG. 3c is a cross-sectional view of an embodiment of a barrier layer comprising an electrically conductive barrier sub-layer on a metal substrate, wherein electrical separation between the positive and negative portions of the cell is achieved by forming a positive portion over the top of the electrolyte. 1 shows a schematic diagram of an exemplary use.

FIG. 4A is a graphical representation of one embodiment of a barrier layer comprising an electrically conductive barrier sub-layer for the case where electrical separation between the positive and negative portions of the electrochemically active cell is not made through formation of a negative portion over the top of the electrolyte. 1 shows a schematic diagram of an exemplary use.

FIG. 4B is a cross-sectional view of an embodiment of a barrier layer comprising an electrically conductive barrier sub-layer for the case where electrical separation between the positive and negative portions of the electrochemically active cell is not made through formation of a negative portion over the top of the electrolyte. &Lt; / RTI &gt; FIG.

Figure 4c shows that the electrical separation between the positive and negative portions of the electrochemically active cell is not effected through the formation of the negative portion over the entire top of the electrolyte, Lt; RTI ID = 0.0 &gt; a &lt; / RTI &gt; barrier layer comprising a sub-layer.

Figure 5 shows a 3000 Å Au cathode current collector on a 300 Å Co adherent 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 Ray diffraction (XRD) pattern of an embodiment of a 1.6 탆 thick LiCoO ₂ positive cathode film formed on a substrate.

Figure 6 shows a cross-sectional view of a 1.6 탆 thick LiCoO ₂ positive cathode film formed on a 3000 Å Au cathode current collector on a 300 Å Co adhering layer on a barrier layer consisting of two sub-layers of 5000 Å Si ₃ N ₄ and 5000 Å SiO ₂ on a 300 μm thick silicon substrate Fig. 5 shows a graph of an X-ray diffraction (XRD) pattern of the example.

Figure 7a shows a schematic diagram of one embodiment of a "conventional configuration" anode configuration in which the negative anode is not in direct contact with the barrier layer.

Figure 7B shows a schematic diagram of one embodiment of a "conventional configuration" anode configuration in which the negative anode is in direct contact with at least one of the barrier sub-layers.

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

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

Figure 10 is a schematic view of one embodiment of the use of a moisture-protective layer to protect the moisture-sensitive electrolyte layer from moisture present in the surrounding environment, with an opening for providing a connection to the negative terminal and a protective encapsulation being formed Respectively.

It is to be understood that the invention is not limited to the particular methodology, protocols, etc. described herein. 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 solely by the claims.

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

All identified patents and other publications are incorporated herein by reference in their entirety for the purpose of describing and describing the methodologies, apparatus and configurations described in such publications that may be used in conjunction with the present invention. These publications are provided only for disclosure prior to the filing date of the present invention. In this connection, the inventor should not regard it as a permission to precede such disclosure by a previous invention or to be unqualified for any other purpose.

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

The thin film battery can be manufactured in a batch mode, for example, by sequentially depositing the individual battery component layers. Once the substrate material is selected, the material may be prepared by cleaning and, if desired, by other pretreatment. A barrier layer comprised of a barrier sub-layer, which may be a total of 0.5-5 占 퐉 thickness, is an important issue for the successful manufacture of silicon as well as thin-film cells on metal and polymer foils. The barrier layer should be able to withstand the annealing temperature for the positive cathode film with the cathode current collector, remain chemically inert, and should not be a source of impurities.

Additionally, the barrier layer must prevent diffusion of all ions and atoms from the positive cathode and cathode current collectors to the substrate during cell fabrication and during all cell driving and storage conditions, The diffusion of any contaminants must be prevented. The barrier layer can be deposited on a clean substrate, typically coating the substrate with a uniform, defect-free film. The following battery layers can be sequentially deposited in a batch manner using a shadow mask so as to divide the boundaries of each layer of the thin film battery. The barrier layer is formed by intercepting the intergranular diffusion effect and thereby causing a reaction between a sequentially deposited positive cathode, such as LiCoO _2, with a cathode current collector underneath, and a substrate such as a gold cathode current collector and a flexible stainless steel foil substrate And the like. Hereinafter, an exemplary method of depositing a barrier layer including a barrier sub-layer 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 batteries can be fabricated on a variety of metal foils and sheets with various surface finishes. A thin foil of stainless steel can be used as the substrate. However, other and more expensive and thicker materials, including, for example, Ti and Ti alloys, Al and Al alloys, Cu and Cu alloys, and Ni and Ni alloys, but are not limited thereto, or low melting point materials may also be used. In addition, the desired physical properties, surface roughness, homogeneity, and purity of the foil, such as steel alloys of that type, are left to the user to determine the optimal manufacturing parameters for the particular device. The electrochemical device of the present invention does not require that the substrate be Al coated with a metal or semi-metal containing V, Mn, Mg, Fe, Ge, Cr, Ni, Further, 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 typically cleaned to remove oils, particulates, and other surface contaminants that would otherwise interfere with chemical or mechanical adhesion of the barrier layer to the substrate if not removed. Any suitable wet chemical cleaning or plasma cleaning process that provides a sufficiently clean surface, such as a sufficiently clean surface, may be used in this regard. Optionally, the cleaned foil substrate can be further pre-treated if desired. For example, in order to alleviate the inherent stress of the metal foil, an annealing step at a high temperature (e.g., 500 캜) may be employed prior to depositing the barrier layer, as long as the annealing temperature is maintained 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 stresses and mechanical stresses of the membrane bases. For example, pre-annealing of the cleaned foil may be performed as described above to control the uncoated metal foil. Other annealing steps may also include any combination of post-deposition barrier layer anneal, post-deposition cathode current collector layer anneal, or post-deposition anneal prior to cathode crystallization anneal, for example. Additional plasma treatments may be followed before or after such steps (see, e.g., DM Mattox, Handbook of Physical Vapor Deposition ( PVD ) Processing , Society of Vacuum Coaters , Albuquerque , New Mexico 660ff and 692ff (Noyes Publications 1998)). Similarly, silicon and polymer substrates may be prepared.

2. Barrier layer  accumulation

Deposition of the barrier layer on the substrate can be performed not only during cell preparation, but also in conjunction with thin film cell fabrication, e.g., chemically separating the substrate from the cell portion during subsequent cell drive and storage conditions.

In general, the chemical reaction between the potential reactants is such that their ions or their electrons are either bound to each of the spaces of the reactants, or are blocked at the interface of the reactants, preferably without 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 sublayer constituting it must be such that the barrier layer can withstand (a) the annealing temperature for the positive cathode film with the cathode current collector, (b) (C) it should not be a source of impurities.

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

It is in principle suitable, for example, to construct the barrier layer as a single layer of a particular material, such as Si ₃ N ₄ , which is electrically insulating and blocks metal ions, but the barrier layer consisting of more than one suitable sub- Has been found to achieve higher manufacturing yields for the purpose of providing barrier layers with different specific properties and fine tuning the barrier layer properties and thus achieving high reliability in cell performance over a given film cell lifetime. For this reason, the present invention relates to the fabrication and provision of a barrier layer that is composed of more than one single layer and preferably chemically separates the substrate from the cell portion of the device, while enabling reliable fabrication of the electrochemical device. Focus on.

2.1 Insulation Barrier Sublayer  Included Barrier layer  Produce

The barrier layer may be deposited directly on the substrate. A barrier layer comprised of a barrier sub-layer wherein at least one barrier sub-layer is amorphous or glassy is capable of avoiding or minimizing intergranular diffusion of ions and electrons, thereby preventing undesired paper during and during the fabrication of the cell And may be designed and manufactured to reduce diffusion into or diffusion from the cell layer. It is desirable to prevent or minimize the chemical reaction between the battery component and the substrate.

For example, simple substrates, current collector, and / or positive for the cathode may be sufficient to use an inert, electrically insulating material, but the ions from the standing in each barrier beucheung is, for example, LiCoO ₂ cathode layer (lithium ion, cobalt ion (Iron, chromium, nickel, other heavy metals, and selected main groups of selected stainless steel types) from the current collector and atoms and ions (gold, platinum, nickel, copper, etc.) Element) that is capable of blocking the diffusion of the element. The choice of a barrier layer consisting of a sublayer capable of blocking ions and electrons is achieved during the manufacture of the battery chemistry device and after obtaining the substrate portion and the battery portion of the electrochemical device which can be chemically separated during the subsequent drive and storage states Can be regarded as a desirable approach in relation to doing so.

Like diamond carbons, high temperature stable organic polymers, and high temperature stabilized silicon as well as groups of boron carbide, bicarbonate, carbide, silicide, nitride, phosphide, oxide, fluoride, chloride, bromide and iodide, In addition to the insulating properties, general ion barrier properties can be provided. Thus, these materials can be used as barrier sub-layer materials. In addition to the preferably use of binary materials of these materials, the barrier sub-layer may be made of a material such as, for example, an oxide-nitride, a carbonized-boride, a carbonized-oxidized-nitride, But are not limited to, a &lt; / RTI &gt; The electrochemical device of the present invention does not require that the barrier layer be a pure oxide.

The binary and polyvalent barrier sub-layer materials listed above can be fabricated by 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, Deposition may be performed by depositing one or more of various suitable thin film deposition methods including deposition, cathodic arc deposition, electrochemical deposition, spray pyrolysis, and the like. The Si ₃ N ₄ barrier sublayer may be fabricated utilizing a pure silicon target that is preferably deposited in an RF magnetron sputter system, for example, using an Ar-N ₂ reactive plasma environment. SiC and TiC barrier sub-layer film their nitrogen doped derivatives SiC: N and TiC: N while the respectively deposited from SiC and TiC targets in reactive Ar-N ₂ plasma environment using the RF magnetron sputtering apparatus, generally inert RF magnetron sputtering is performed from targets of the same angular composition in an Ar plasma environment.

The formation of optimized oxidation-nitrides, carbonized-borides, carbonized-oxidized-nitrides, silicified-carbonized-nitrides, oxidized-fluorides and the like can be achieved by using N ₂ , O ₂ , N ₂ O, BF ₃ , C ₂ F ₆ , B ₂ H ₆ , CH ₄ , SiH _4, etc., alone or in addition to providing an element from a sputter target, in addition to an inert carrier gas such as argon . For example, thin film deposition of Ti ₃ SiC ₂ : N, a titanium silicide-carbonitride (or titanium silicon carbide nitride), deposits a layer of mixed material having a TiC / SiC ratio of 3: 1 in the same substrate region at any given time A single sputter target constructed with alternating areas of TiC and SiC at a total area ratio of 3: 1, or two individual sputter targets consisting of one TiC target and another SiC target , And 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 be post-deposited or not before continuing to manufacture the cell.

The barrier sub-layer material may be selected from the group consisting of Si ₃ N ₄ , SiN _x O _y (3x + 2y = 4), or an oxide-gradient Si ₃ N that can reach the stoichiometry on the surface of most SiO ₂ , _4, for example. In addition, SiC or TiC with or without nitrogen doping can be used as the barrier sub-layer material.

Some specific derivatives of these materials may be most undesirable as ionic blocking agents when used in a barrier layer without any additional suitable barrier sub-layer, which may be non-stoichiometric ZrO ₂ , non-stoichiometric YSZ Stabilized zirconia), and non-stoichiometric LiI (lithium iodide), while allowing them to diffuse certain ions during the manufacturing process or during battery operating and storage conditions. In contrast to their stoichiometric counterparts, the non-stoichiometry is the main reason why these materials are electrically conductive while allowing oxygen and lithium ion diffusion respectively.

For example, to fine tune certain barrier properties such as improved adhesion to the substrate and / or cell portions, mechanical flexibility, stability to adjacent layers, pinhole-free, electrical resistance, and chemical inertness, A suitable barrier layer may 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 (and electrically insulating, for example, lithium ions, cobalt ions, oxygen ions, iron ions, the diffusion of the chromium ion and gold ion barrier material) / 1000Å SiC: N (lithium ions, cobalt ions, oxygen ions, iron ions, (Diffusion barrier material for lithium ions, cobalt ions, oxygen ions, iron ions, chromium ions and gold ions) / 2000 Å Si ₃ N ₄ (electrically insulating, A 300 Å cobalt current collector attachment layer and a 500 Å SiO ₂ (adhesion promoter to the current collector layer) on which a 3000 Å gold current collector can be deposited.

In some cases, the insulating barrier sublayer may contact the negative anode and / or the anode current collector as well as contact the positive cathode and / or the cathode current collector. In any event, it is preferred that the barrier sublayer be chemically inert, for example, for all materials it is in contact with. This feature, for example, Li ₂ O, LiAlO _2, and Li-Al alloy, or Li ₂ O, Li ₂ SiO _3, and when in contact with the metallic lithium negative anode which can deleteriously react with the Li-Si alloy, pure Al ₂ O ₃ or SiO ₂ barrier layer.

2.2 At least one electrical conductivity Barrier Into the sublayer  Made Barrier layer  Produce

For example, the conductive barrier sublayer may be equally effective if, for example, the following desirable properties are met: 1) to prevent diffusion of ions to / from the cell layer, and 2) And is unresponsive to the substrate or cell layer during all subsequent cell driving and storage conditions. The barrier layer may also comprise, for example, an electrically insulating barrier sublayer. Such electrically insulating and electrically conductive sub-layers may not all have the same shape and area size, for example. Thus, a barrier layer made of such a mixed stack of barrier sub-layers may exhibit electrical insulation properties, for example, in the substrate portion or in some areas in contact with the cell portion, while in other regions of contact with the substrate portion or cell portion have.

The material for the electrically conductive barrier sub-layer may be selected from the group consisting of, for example, a group consisting of a conductive binary compound, a carbide, a silicide, a nitride, a phosphide and an oxide, as well as a group of oxides such as oxides, nitrides, carbides, borides, Oxides, nitrides, and oxide-fluorides of any of the conductive multiples thereof. In addition, high temperature-stable polymers and high temperature-stable silicon that are specially treated to be electrically conductive may be used. A material selection list for the electrically insulating barrier sublayer is presented in item 2.1 above and is incorporated herein. 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, have different area dimensions.

As a result, for example, the Si ₃ N ₄ barrier sublayer may extend, for example, over the entire footprint region of the metal substrate, the ZrN barrier sublayer may cover only the cathode current collector lower substrate region, and the WC and MoSi ₂ barrier The sub-layer may extend further into the ZrN region, for example, covering at least the entire region below the anode current collector. Due to its region size, the interposed Si ₃ N ₄ barrier sub-layer provides electrical isolation of the electrically conductive ZrN barrier sub-layer from, for example, the electrically-conductive WC / MoSi ₂ barrier sub-layer and thus allows the positive and negative portions (See FIG. 2).

In this embodiment, ZrN, TiN, WC, MoSi _2, TiB ₂ or electrically conductive barrier sub-layer is sputter deposited (RF- magnetron, pulsed DC, and DC magnetron, AC magnetron, RF diode or DC or AC), such as NiP, 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, For example, ZrN barrier sub-layer may be made from a Zr metal target using a DC magnetron sputter deposited also in an inert Ar atmosphere within the ZrN from the sputter target to perform DC magnetron sputter deposition or reactive Ar-N ₂ atmosphere.

In addition, when the post-deposition anneal temperature necessary for crystallizing the positive cathode is suitable, such as 200 ° C. to 500 ° C., a specific metal (eg, Au, Pt, Ir, Os, Ag, Pd) Carbon, Si), and alloys (e.g., Au, Pt, Ir, Os, Ag, Pd, C, and Si based) can be preferably selected as electrically conductive barrier sublayers. The electrically conductive barrier sub-layer may or may not be further heat treated before continuing the battery manufacturing process.

The conductive barrier sublayer may have the additional advantage of eliminating a separate cathode current collector, if properly manufactured in terms of electrical connectivity from the positive cell terminal, if not, for example, the conductive barrier sublayer It should be chosen to optimize the electrical properties of the conductive barrier sublayer by coating it with a more conductive and inert thin layer, e.g., gold. The approach of the conductive barrier sub-layer, whether or not additionally coated with such a more conductive layer, is such that the anode current collector and the negative anode are simultaneously electrically connected to the conductive barrier sub-layer in which the positive cathode and / As shown in FIG. This separation can be accomplished, for example, as follows:

1) It can be achieved by extending the electrolyte to a region where the negative anode and its anode current collector are located precisely above the electrically insulative electrolyte, which in this case is the local anode for the negative anode and its anode current collector Layer (see Figs. 3A and 3B). If a particular production parameter of the positive cathode does not cause a reaction with an already existing electrolyte layer, the positive cathode and its cathode current collector may be similarly fabricated on the entire upper portion of the electrolyte, and the negative anode may be located at the bottom of the electrolyte (See Fig. 3C).

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

2.3 Barrier layer  And a substrate

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

Direct deposition of an electrically insulating or conductive barrier sublayer 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 adhered to, so that the deposition parameters for each barrier sub-layer must be adjusted. For example, sputter deposition may be performed under a high deposition rate, and the resulting deposition temperature at the substrate surface may exceed the melting point of the polymer substrate. Thus, the deposition parameters should preferably be limited to adhere to the melting point of the substrate. In another example, a very thin Si substrate of only 10 mu m may be used. In such a case, this is done first by ignoring any post-deposition anneal, so that the stress of the barrier sub-layer during deposition does not cause cracking of it prior to deposition of any subsequent barrier sub-layer and / &Lt; / RTI &gt; A more specific example can be given without limiting the scope of the present invention to the possible use of all three substrate types and the basic principles for the fabrication of a barrier layer over a substrate including a barrier sublayer.

3. Battery Manufacturing

Once the substrate with the barrier layer in accordance with the present invention has been fabricated, subsequent fabrication steps of the electrochemical device may include forming a second electrochemically active cell on the second side of the substrate to achieve a " &Lt; / RTI &gt; 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 "single-faced" electrochemical device in which only a first electrochemically active cell is fabricated on the first side of the substrate, the second layer is formed prior to the fabrication of the constituent layers of the first electrochemically active cell And is selectively deposited on the second side. This second layer may be fabricated for the purpose of protecting the substrate from the environment for chemical and mechanical factors during the fabrication, operation, and storage of the electrochemical device. In addition, through the implementation of the second layer, the first electrochemically active cell can flow into and diffuse through the substrate on the second, unprotected side, thereby potentially producing, driving, and / Or may be protected from chemical contaminants from the surrounding environment that may reach the first electrochemically active cell during storage and react harmful thereto. This protection of the first electrochemically active cell is in addition to the protection provided by the substrate itself and the barrier layer between the substrate and the first electrochemically active cell, And may not cover the entire area. The protection of both the substrate and the first electrochemically active cell extends the life of the electrochemical device.

The second layer may be formed from the group consisting of, for example, a metal, a semi-metal, an alloy, a boride, a carbide, a diamond, a diamond like carbon, a silicide, a nitride, a phosphide, an oxide, a fluoride, a chloride, a bromide, A chemical compound selected from the group of any multi-component compound consisting of a carbohydrate, a carbide, a silicide, a nitride, a phosphide, an oxide, a fluoride, a chloride, a bromide, and an iodide or a group of high temperature stable organic polymers and high temperature stable silicon , &Lt; / RTI &gt; In particular, a thin metal layer of between 500 Å and 5 urn thickness may be useful for protecting the substrate by blocking the entry of contaminants on the second side during the fabrication, operation, 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 cheaper than ceramic counterparts such as TiC.

The blocking action of the second layer includes, for example, the chemical reaction of the second layer with known contaminants in literature such as chemical gettering, corrosion inhibition, or sacrificial layer deposition, and is not limited to metal layers, (E. G., An insufficiently oxidized or nitrided film material that can be easily prepared by sputter deposition) or a material that is present in the environment during the fabrication, operation, and / or storage of an electrochemical device Can also be achieved by nitrides or carbides that can be converted to oxides or carbonates when reacting with oxygen, moisture, or carbon dioxide contaminants.

It is possible to fine-tune the second layer on the second side of the substrate by selecting a material that primarily protects without 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 with higher or lower reactivity under certain ambient environmental conditions. For example, Al ₄ C ₃ converts to Al ₂ O ₃ at a much lower oxygen partial pressure than SiC to SiO ₂ . Similarly, the nitride having a very small formation enthalpy as Co ₂ N is converted to the respective oxides at much lower temperatures and oxygen partial pressures than the corresponding water formed under large negative enthalpy of formation as Si ₃ N ₄ and ZrN.

Ultimately, it is up to the manufacturer of the electrochemical device to determine the optimal parameters in relation to the added cost to produce the second layer on the second side of the substrate, Is a function of the additional protection of the substrate and the first electrochemically active cell against the specific ambient conditions present for a certain period of time, which is again primarily a function of the material selection and the thickness produced of the second layer.

Thin film cells may be fabricated in a batch manufacturing process that utilizes sequential physical and / or chemical vapor deposition steps that use shadow masks to build individual battery component layers. The electrochemically active cell may be fabricated in any of a variety of structures. Features may include:

(i) a positive cathode configuration to be used

a. (Cathode deposition prior to anode deposition; "conventional configuration") positioned between the barrier layer and the negative anode, and a negative anode (anode deposition before cathode deposition;

b. Post-deposition anneal applied to the positive cathode

(ii) the anode configuration to be used

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

b. The anode current collector does not contact or contact the barrier layer

(iii) the type of barrier layer to be used

a. Electrically insulating sublayer to electrically conductive sublayer

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

c. The order combination of the insulating sublayer and the conductive sublayer in the barrier layer

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

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

(vi) Protective encapsulation or protective encasing design to be used

a. Encapsulation versus inching

b. There is no opening (s) for connection to opening (s) to terminal (s) in encapsulation or encasing

c. The use or nonuse of the moisture protection layer in the opening area

(vii) Current collector and terminal

3.1 Cathode  Configuration

3.1.1 Negative Anode  Positive before deposition Cathode  Sedimentation and potential sedimentation - after To anneal Equivalent  Can, Barrier layer Negative Anode  Positive cathode located between: "conventional configuration"

Depending on the electrical properties of the barrier layer, a current collector can be fabricated before the deposition of the positive cathode. That is, if the barrier layer based on that sublayer is insulating in the region where the positive cathode is to be fabricated, a cathode current collector may be deposited to create the necessary electrical connection for the positive cathode from the positive terminal. However, if the barrier layer based on that sub-layer is electrically conductive in the region where the positive cathode is to be deposited, then an additional inactive metal layer ("conduction enhancer") will reduce the current collecting property of the barrier layer And may be selectively deposited between the barrier layer and the positive cathode to enhance it.

The conduction enhancer of the positive cathode, the cathode current collector, and the barrier layer may be selected from the group consisting of sputtering (RF-magnetron, DC and DC pulse magnetron, AC magnetron, diode RF or DC or AC), electron beam evaporation, Deposition can be performed by any one of various deposition methods including vapor deposition, ion beam assisted deposition, cathode arc deposition, electrochemical deposition, spray pyrolysis, and the like.

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

The composition of a given derivative and the applied post-anneal parameters can provide selection information for the barrier layer material. For example, in the case of pure LiCoO ₂ and air annealing at 700 ° C for 2 hours, an electrically insulating barrier layer containing 5000 Å Al ₂ O ₃ and 6000 Å Co ₃ O ₄ , two barrier sublayers on a 50 μm stainless steel 430 foil Lt; RTI ID = 0.0 &gt; 300 A &lt; / RTI &gt; gold cathode current collectors that can be attached by a 300 A cobalt deposition layer. An X-ray diffraction (XRD) pattern of such a setting after 700 ° C anneal is shown in FIG. LiCoO ₂ positive cathode for grain 101, the lattice constant parameter _{(a hex = 2.8146 (4)} Å; c hex = 14.0732 (8) Å) the theoretical value _{(e.g., ICDD 77-1370: a hex = 2.815} ( 1) Å; c _hex = 14.05 (1) Å), and showed a crystallite size of about 560 Å. This fact indicates that the crystalline LiCoO ₂ positive cathode film may not react with any material in its surroundings, including the substrate, while achieving the good crystallographic parameters needed to demonstrate the optimal electrochemical behavior in the electrochemically active cell.

A pure LiCoO ₂ positive cathode was fabricated on a 300 탆 thick undoped silicon substrate on a 3000 Å Au / 300 Å Co cathode current collector attached to a barrier layer consisting of two barrier sublayers of 5000 Å Si ₃ N ₄ and 5000 Å SiO ₂ , After annealing in air at 700 ° C for 2 hours, a good crystalline LiCoO ₂ with almost theoretical lattice parameters (e.g., ICDD 77-1370: a _hex = 2.815 (1) A; c _hex = 14.05 A sample cathode grain size of 1100 Å on the (101) plane can be obtained with a positive cathode (a _hex = 2.8151 (4) Å; c _hex = 14.066 (7) Å). Acquisition of a good crystalline stoichiometric LiCoO ₂ positive cathode film having a layered structure and a theoretical crystallographic lattice parameter can be achieved, for example, by allowing the crystalline LiCoO ₂ positive cathode film to react with, for example, a surrounding material comprising a silicon substrate, Provide what you can not do. The theoretical crystallographic lattice parameter (a _hex = 2.8151 (4) A; c _hex = 14.066 (7) A) was obtained on the Si substrate by the LiCoO ₂ positive cathode film in the above- It can be suggested that the LiCoO ₂ positive cathode film may exhibit certain desirable electrochemical behavior.

3.1.2 Positive Cathode  Sedimentation Negative Anode  After sedimentation and potential sedimentation Anne and  Can provide close performance, Barrier layer  Positive Cathode  Located between Negative Anode : "Reverse configuration"

An "opposite configuration" of an embodiment of the present invention is schematically illustrated in Figure 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 may be fabricated prior to deposition of the negative anode. That is, if the barrier layer is insulating in the region where the negative anode is to be fabricated, based on that sublayer, the anode current collector may be deposited to create the necessary electrical connection to the negative anode from the negative terminal. However, if the barrier layer based on that sublayer is electrically conductive in the region where the negative anode is to be deposited, an additional inactive metal layer ("conduction enhancer") may be provided between the barrier layer and the negative anode . &Lt; / RTI &gt;

Conduction enhancers for negative anodes, anode current collectors, and barrier layers include sputtering (RF-magnetron, DC and DC pulse magnetron, AC magnetron, diode RF or DC or AC), electron beam evaporation, Including any one of a variety of deposition methods including chemical vapor deposition, ion beam assisted deposition, cathode arc deposition, electrochemical deposition, spray pyrolysis, and the like.

Negative anodes may be selected from the group consisting of metal lithium, lithium-ion anodes, and so-called lithium-free anodes (see, for example, U.S. Patent No. 6,168,884, which is hereby incorporated by reference in its entirety). Following 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 an anneal can be applied to a lithium-ion anode, such as Li ₄ Ti ₅ O ₁₂ , but is not, for example, applied to metal lithium, and is not preferred for a group of lithium-free anodes.

The actual composition of the negative anode and the parameters of the applied deposition-after anneal can provide selection information of the barrier layer material. For example, the 5000 Å Si ₃ N ₄ barrier sub-layer on the silicon substrate that separates the silicon substrate from the metal lithium negative anode with respect to the metal lithium negative anode may have a chemical inertness between the barrier layer and the metal lithium of 12Li + Si ₃ N ₄ = 4Li _{3 &lt; /} RTI &gt; N &lt; RTI ID = 0.0 &gt; 3Si &lt; / RTI &gt; can be achieved through positive reaction and exfoliation.

In an exemplary contrary configuration, the positive cathode may be deposited on the electrolyte. Thus, the temperature allowed in the potential deposition-post anneal of the positive cathode may be limited, for example, because it is desirable that the reaction between the electrolyte and the positive cathode, as well as the reaction between the negative electrode and the electrolyte, be avoided.

3.2 Anode  Configuration

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

For example, there may be no direct chemical interaction between the negative anode and the barrier layer in the manufacture of an embodiment that includes a negative anode as a whole on top of the electrolyte.

When manufacturing an embodiment of a partially negative anode at the top of the electrolyte, a "conventional configuration" (see section 3.1.1) is preferred. The overlap region of the negative anode on the electrolyte layer edge can be prevented from contacting the barrier layer in the presence of the anode current collector (see FIG. 7A). In the absence of an appropriately configured anode current collector, the region overlying the negative anode can contact the barrier layer (see FIG. 7B). In any case, the negative anode is preferably chemically inert with respect to the barrier layer and its barrier sub-layer, for example, where the negative anode is in contact with the integrated anode, because of the limited thickness and the intergranular morphology, Because it may not provide adequate chemical separation between the two. In such a case, the selection of the negative anode material determines the choice of the barrier sub-layer 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, the metallic lithium may reactively degrade the Co ₃ O ₄ barrier sublayer with Li ₂ O, CoO, and solid solutions of Li (Co) and Co (Li).

If the negative anode and / or its anode current collector is in contact with the barrier layer, it is preferred that the negative anode and / or its anode current collector contact 1) the insulating barrier sublayer or 2) contact the electrically conductive barrier sublayer Both cases need to be evaluated. As a first example, if a metal lithium anode is used, this barrier sub-layer may be sufficiently inert to the negative anode such as Si ₃ N ₄ and / or its anode current collector. As a second example, in addition to the contacting conductive barrier sub-layer being chemically inert with respect to the negative anode and / or its anode current collector, for example, a more sophisticated barrier sub-layer approach may be used, Can be used for a conductive substrate such as an undoped silicon substrate (see Figs. 4A to 4C). To insulate the polymer substrate and the second example, it is sufficient to use a non-continuous conductive barrier sub-layer so that the positive and negative portions of the cell are not shorted through the electrically conductive barrier sub-layer.

For example, the thickness 1㎛ ZrN barrier sub-layer is metallic lithium negative anode is in contact with the ZrN barrier sub-layer, and not to be shared with the positive portion of the battery and, instead of the positive portion of the battery sub-insulating barrier, such as Si ₃ N ₄ in For embodiments that may be located on a layer, it is relatively simple and effective. One advantage of this latter exemplary embodiment is that the ZrN barrier sub-layer can also act as an anode current collector for the negative metal lithium anode (see FIG. 8).

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

3.3 Substrate in electrical contact with the electrochemically active cell

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

3.4 Double-sided electrochemical device

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

The potential sequential manufacturing process of the battery component layer can be done in the same way as for example in a cross-sectional electrochemical device. As a result of this exemplary approach of layer completion on both sides of the substrate prior to depositing the next layer on either side of the substrate, potential post-deposition anneal is performed on the other side of the substrate where such post- It may not be applied to the layer.

Another exemplary approach is to use a first electrochemically active cell on the second side of the substrate or a second electrochemically active cell on the second side of the substrate prior to partial completion of any additional electrochemically active cell fabrication on the first side or second side of the substrate. To partially complete the first electrochemically active cell on the first 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 a first side of a substrate comprising a cathode current collector and subsequent positive cathode layer can be achieved prior to deposition of a cathode current collector and a positive cathode layer on a second side of the substrate. After this step, the post-deposition anneal is applied simultaneously to the partially completed electrochemically active cell on the substrate before continuing to manufacture the electrochemically active cell on the first side of the substrate using the manufacturing sequence of the electrolyte-anode current collector-anode It is possible. The same manufacturing sequence can then be applied to the second side of the substrate before the thin film encapsulation, where both sides of the substrate are simultaneously encapsulated with the thermally sensitive polymer laminate on either side of the substrate, or simultaneously or sequentially, have.

According to the actual conditions of the potential deposition and post-anneal of the positive cathode and / or the negative anode, the fabrication of the first electrochemically active cell on the first side of the substrate results in the production of the second electrochemically active cell on the second side of the substrate A third approach that can be completed before is possible.

3.5 Protection Encapsulation and Protection Inquiring  design

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

It is contemplated that the electrochemical device of the present invention may be, for example, in a given ambient atmosphere before it is driven in a surrounding environment, and that the electrochemical device be protected from any reactive chemicals that may react detrimental or degrade the electrochemical device desirable. For example, if the ambient environment is air, the electrochemical device of the present invention can be preferably protected from moisture among other reactive chemicals such as O ₂ or CO ₂ (see US Pat. 6,916,679). The electrochemical devices of the present invention, such as laser welded stainless steel cans or vacuum metal or glass tubes or vessels, can protect the hermetically sealed metal interior with electrical supply passages from these external chemical agents. However, the dimensions of such types of protection encasing can add excessive inactivity volume and weight to electrochemical devices whose components, excluding the energy carrying positive cathode, can be minimized relative to their thickness. This minimization strategy is based on the fact that the presence of the substrate and any protective encasing, which always reduces the power, energy and capacity density of the electrochemically active cell due to its simple presence and thus reduces the power, energy and capacity density of the electrochemical device at all times, Or protective encapsulation of the electrochemical device.

For the reasons stated above, the protective encapsulation or protective encasing should preferably be as thin as possible while being capable of protecting the electrochemical device from various chemicals present in the ambient environment in which the electrochemical device is driven. Protection from these chemicals implicitly includes all that includes the exposure time and temperature to the chemical that the electrochemical device can encounter during its lifetime. However, it is the sole judgment of the manufacturer of the electrochemical device to establish the optimal parameters of the battery chemical apparatus in terms of manufacturing cost and performance. In this regard, an electrochemical device that can only be driven for a few days after its manufacture is, for example, a potentially cheaper and less precise protective encapsulation or protection encasing May be applied.

Both protective encapsulation and protective encasing should 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 (e.g., see FIG. 3B where the substrate 300 acts as a positive terminal). Second, the terminals may extend further to the exterior of the protective encapsulation that contacts the lower, airtightly sealed edge of the protective encapsulation (see, for example, layers 430 and 480 in FIG. 4A). Similarly, the terminals may extend through the openings of the hermetically sealed outlets or protective encasing, and may extend further to the outside of the protective encasing, where contact may be made (see, for example, the orthotropic Li-ion bulk battery technology). Third, the opening allowing the direct external connection to the electrochemical device internal terminal may be provided in the protective encapsulation or protective encasing, but the sensitive part, for example, the moisture sensitive electrolyte, Or by the thickness of its adjacent current collector.

For an improved lifetime representing useful performance parameters of the electrochemical device of the present invention, particularly when the opening of the third design is located near the electrolyte region, the electrolyte may be exposed to a moisture protective layer, for example, as schematically shown in FIG. 10 It can be ensured that it is subjected to additional protection.

3.6 Current Collector  And terminal

LiCoO ₂ positive cathode or Li ₄ Ti ₅ O ₁₂ negative when less electrically conductive electrode material as the anode is the z- parameters (thickness) of the electron and ion paths are kept to a minimum ion diffusion inside the electrode which can be achieved path It may require an inactive backside contact (current collector) of good conductivity, such as, for example, Au or Ni, in order to minimize the electrical resistance of the electrode. This principle is based on the fact that most of the electrodes have a maximum length dimension (x-parameter) and a width dimension (y-parameter) compared to the case where the electrode is preferably flat or thin (z-parameter) Lt; / RTI &gt; Some electrodes are electronically and ionically good electrical conductors and will not require current collectors for the reasons stated above. However, such electrodes are chemically very reactive, such as negative metal Li anodes, so that they are preferably separated from other cell portions, such as negative terminals, by suitable inert "bridges " such as Ni in the case of negative Li metal anodes can do. This "bridge" can only touch one conductive edge or one edge with a conductive electrode with good reactivity, as opposed to full-area backside contact in the case of a poor conductive electrode. The bridge acts as an inert medium between the reactive electrode and its terminals, provides current collector characteristics, and may thus be referred to as a "current collector. &Quot;

In one embodiment, the terminals of the electrochemical device of the present invention can be extended current collectors, and thus can be made of the same material in contact with the electrodes. However, the current collectors used in thin film batteries can be very thin and mechanically dense, so that external contact, mechanical (e.g., clipping), brazing or spot welding do not form the desired permanent electrical contact . For example, a conductive material that is thick and / or porous may be added to the end of the current collector, which is, for example, a region referred to as a "terminal" where mechanical, soldered, or spot welded external electrical contacts may be achieved, It may be desirable to improve the contact properties. In this regard, screen-printed silver and silver alloys, which are fairly porous, about 5-15 microns thick, are preferred because the screen-printed material is capable of forming a thin layer of the electrochemically active cell at any point during the manufacture, Or as printed terminals in a manner that allows the cathode or anode current collector to make good electrical contact therewith without chemically contaminating the cells.

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

Figure 1 shows an embodiment of an electrochemical device. The substrate portion 100 may be chemically isolated from the cell portion 120 through a barrier layer 110 comprised, for example, of barrier sublayers 111-114. The battery component layers 121 to 125 are provided. A positive battery terminal 126 and a negative battery terminal 127 are additionally provided.

2 is an exemplary illustration of a barrier layer 210 comprised of an exemplary barrier sublayer 1000 Å MoSi ₂ 211, 3000 Å WC 212, 4000 Å Si ₃ N ₄ 213 and 5000 Å ZrN 214. Fig. As shown, the area dimensions of these sub-layers can be varied to achieve the desired electrical separation between the positive portions 214, 220, 230 and 240 of the electrochemically active cell and the negative portions 260, 270 and 280, They can be very different from each other. The cathode current collector, the positive terminal, and the positive cathode are shown as 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. Negative anodes, anode current collectors and negative terminals are denoted 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) an anode current collector, an anode, and a 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 an encapsulation 290 having an opening 291 for connection to the negative terminal 280. These encapsulated electrochemically active cells may be fabricated on a substrate 200 that together form an electrochemical device.

Figure 3a illustrates that in one embodiment where electrical separation between the positive and negative portions of the electrochemically active cell may be achieved by fabricating a negative portion over the electrolyte 350, Illustrates an exemplary embodiment of a barrier layer 310 comprising a sublayer 311 and a second barrier sublayer 312. The positive portion may constitute, for example, a second barrier sublayer 312, a cathode current collector 320, a positive terminal 330 and a positive cathode 340. When the installed 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 the case of a metallic embodiment, such a substrate may be part of the positive portion. The negative portion can constitute a negative anode 360, an anode current collector 370, and a negative terminal 380. [ In this particular example, the electrochemically active cell may be protected by an encapsulation 390 having an opening 391 for connection to the negative terminal 380.

Figure 3b shows that electrical separation between the positive and negative portions of the electrochemically active cell can be achieved by fabricating a negative portion over the entire top of the electrolyte 350 and the cathode current collector 320, In one embodiment, where the cathode 340 is electrically connected to the metal substrate 300 through, for example, the second barrier sublayer 312, the first barrier sublayer 311, which may be electrically conductive, 2 barrier sublayer 312. The barrier layer 310 includes a first barrier sublayer 312 and a second barrier sublayer 312, In this configuration, the metal substrate 300 can act as a positive terminal. The positive portion may constitute a metal substrate 300, a second barrier sublayer 312, a cathode current collector 320, a positive terminal 330 and a positive cathode 340. In embodiments where the first barrier layer 311 is electrically conducting, the positive portion may additionally comprise a first barrier layer 311. [ The negative portion may include a negative anode 360, an anode current collector 370, and a negative terminal 380. In this particular example, the electrochemically active cell may be protected by an encapsulation 390 having an opening 391 for connection to the negative terminal 380.

FIG. 3C shows that electrical separation between the positive and negative portions of the electrochemically active cell can be achieved by manufacturing a positive portion over the entire top of the electrolyte 350, and the anode current collector 370, the negative terminal 380, In one embodiment, when the anode is electrically connected to the metal substrate 300 through the second barrier layer 312, for example, the first barrier sublayer 311 and the second barrier sublayer 311, which may be electrically conductive, Lt; RTI ID = 0.0 &gt; 310 &lt; / RTI &gt; In this configuration, the substrate 300 may also function as, for example, a positive terminal. The positive portion can constitute the cathode current collector 320, the positive terminal 330 and the positive cathode 340. The negative portion can constitute the metal substrate 300, the second barrier sublayer 312, the negative anode 360, the anode current collector 370 and the negative terminal 380. When the first barrier layer 311 is also electrically conductive, the negative portion can additionally constitute this first barrier layer 311. In this particular example, the electrochemically active cell may be protected by an encapsulation 390 having an opening 391 for connection to the positive terminal 330.

4A shows a schematic cross-sectional view of an electrochemical cell including an electrically conductive barrier sub-layer, where the electrical separation between the positive and negative portions of the electrochemically active cell may not be made through the fabrication of the negative portion over the top of the electrolyte 450 Barrier layer &lt; RTI ID = 0.0 &gt; 410 &lt; / RTI &gt; Along with the electrolyte 450, the electrically insulating second barrier layer 412 can separate the positive portion, for example, from the negative portion of the electrochemically active cell. The positive portion can constitute the cathode current collector 420, the positive terminal 430 and the positive cathode 440. If the third barrier sub-layer 413 is electrically conductive, it may, for example, be a member of the positive portion. The first barrier sublayer 411 may be electrically insulating or conductive. In the latter case, it may make the substrate 400 a member of the negative portion, while being a member of the negative portion itself. In addition, the negative portion can constitute the negative anode 460, the anode current collector 470, and the negative terminal 480. In this configuration, the metal substrate may also function as a negative terminal. Finally, the electrochemically active cell may be protected by encapsulation 490.

FIG. 4B shows the case where the electrical separation between the positive and negative portions of the electrochemically active cell may not be made through the fabrication of the negative portion over the top of the electrolyte 450, Lt; RTI ID = 0.0 &gt; 410 &lt; / RTI &gt; Along with the electrolyte 450, the electrically insulating second barrier layer 412 can separate the positive portion, for example, from the negative portion of the electrochemically active cell. The positive portion can constitute the cathode current collector 420, the positive terminal 430 and the positive cathode 440. If the third barrier sub-layer 413 is electrically conductive, it may, for example, be a member of the positive portion. The first barrier sublayer 411 may be electrically insulating or conductive. In the latter case, it may make the substrate 400 a member of the negative portion, while being a member of the negative portion. In addition, the negative portion can constitute the negative anode 460, the anode current collector 470, and the negative terminal 480. In this configuration, the metal substrate may also act as a negative terminal. Finally, the electrochemically active cell may be protected by encapsulation 490.

FIG. 4C shows the case where the electrical separation between the positive and negative portions of the electrochemically active cell may not be made through the fabrication of the negative portion over the top of the electrolyte 450, Lt; RTI ID = 0.0 &gt; 410 &lt; / RTI &gt; Negative anode 460 may, for example, be in direct contact with third barrier sub-layer 413, and thus is preferably chemically inert with respect to negative anode 460. In this example, the third barrier sub-layer 413 may be electrically insulating, for example, to provide electrical separation between the positive and negative portions of the electrochemically active cell along with the electrolyte 450. The positive portion can constitute the cathode current collector 420, the positive terminal 430 and the positive cathode 440. When the second barrier sublayer 412 is electrically conductive, it may be a member of the positive portion, and the metal substrate 400 may be a 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 portion, but the second barrier layer 412 is also such a case. The negative portion can 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 may be protected by the encapsulation 490.

Figure 5 shows a cross-sectional view of a 600 Å gold cathode current collector on a 300 Å cobalt adherent layer on a 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. Ray diffraction (XRD) pattern of a 탆 thick LiCoO ₂ positive cathode film. LiCoO ₂ positive cathode is deposited for two hours at 700 ℃ the air-and annealing after, which affects the substrate, a barrier layer and that of the barrier sub-layer, the cathode current collector, adhesion layer, and a cathode current collector to a similar thermal method. A crystalline LiCoO ₂ positive cathode film lattice parameter _{(a hex = 2.8146 (4)} Å; c hex = 14.0732 (8) Å) the theoretical value _{(e.g., ICDD 77-1370: a hex = 2.815} (1) Å; c hex = 14.05 (1) Å) with and closely matched, which crystalline LiCoO ₂ positive cathode crystallinity of the surface ((101, as estimated by the Scherer equation): 560Å) film that of any of the peripheral, including a substrate material and Indicating that they do not react. "Au" represents a gold cathode current collector. "Au + S" represents the superposition peak of the gold cathode current collector and the stainless steel 430 substrate foil.

Figure 6 shows a cross-sectional view of a 300 Å gold cobalt deposition layer on a barrier layer consisting of two barrier sublayers, 5000 Å Si ₃ N ₄ and 5000 Å SiO ₂ , on a 300 μm thick undoped silicon substrate, and a 1.6 μm thick LiCoO ₂ FIG. 7 shows a graph of an X-ray diffraction (XRD) pattern of a positive cathode film. FIG. LiCoO ₂ positive cathode is deposited for two hours at 700 ℃ the air-and annealing after, which affects the substrate, a barrier layer and that of the barrier sub-layer, the cathode current collector, adhesion layer, and a cathode current collector to a similar thermal method. The lattice parameter (a _hex = 2.8151 (4) A; c _hex = 14.066 (6) A) of the crystalline LiCoO ₂ positive cathode film is compared with the theoretical value given in the literature (for example ICDD 77-1370: a _hex = 2.815 (1) A; _{c hex = 14.05 (1) Å} ) and matching, which crystalline LiCoO ₂ positive cathode decision on the face ((101, as estimated by the Scherer equation) also: 1100Å) film is its arbitrary periphery of the, including the silicon substrate Indicating that they are not reacting 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 diffraction system.

7A shows an embodiment of an anode configuration in which the negative anode 760 does not directly contact the barrier layer 710 and thus does not come in direct contact with any of its barrier sub-layers 711, 712. The first barrier sublayer 711 may be electrically insulative or electrically conductive and the second barrier sublayer 712 may be electrically insulative to avoid electrical shorting of the electrochemically active cell and thus avoid electrical shorting of the electrochemical device It should be. In such a configuration that the negative anode 760 does not contact the barrier layer, it does not determine the choice of chemical composition of the barrier sub-layers 711, 712. For example, the positive portion of the electrochemically active cell includes a cathode current collector 720 that is separated by an electrolyte 750 from a negative portion that can constitute a negative anode 760, an anode current collector 770 and a negative terminal 780, A positive terminal 730, and a positive cathode 740. [ Finally, the electrochemically active cell can be protected by encapsulation 790.

7B shows a schematic view of the anode configuration in which 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 insulative or electrically conductive and the second barrier sublayer 712 may be electrically insulative to avoid electrical shorting of the electrochemically active cell and thus avoid electrical shorting of the electrochemical device . In such a configuration in which the negative anode 760 contacts the barrier layer, at least the selection of the chemical composition of that barrier sublayer 712 it contacts can be determined. For example, the positive portion of the electrochemically active cell includes a cathode current collector 720 that is separated by an electrolyte 750 from a negative portion that can constitute a negative anode 760, an anode current collector 770 and a negative terminal 780, The positive terminal 730, and the positive cathode 740, as shown in FIG. Finally, the electrochemically active cell can be protected by encapsulation 790.

8 is an embodiment of an anode configuration in which the first barrier sub-layer of the illustrated electrochemical device is in direct contact with the electrically conductive ZrN barrier sub-layer 811, which may serve as an anode current collector, for example, / RTI &gt; The anode current collector and barrier sublayer 811 may also be chemically inert to a reactive negative anode 860, such as metal lithium, if selected, for example, for the negative anode 860. Due to the particular structure of the barrier sub-layer 811 selected for the embodiment of the electrochemical device shown in this figure, the second barrier sub-layer 812 is preferably electrically insulative, such as Si ₃ N ₄ . The positive portion of the electrochemical cell may include an electrolyte 850 from a negative portion that can comprise, for example, a metal substrate 800, a ZrN barrier sublayer and an anode current collector 811, a negative anode 860, and a negative terminal 870. [ A cathode terminal 830, and a cathode 840 separated by a cathode current collector 820, Finally, the electrochemically active cell may be protected by encapsulation 880.

9 illustrates one embodiment of a particular battery configuration in which the negative anode 960 can be in direct contact with the substrate 900 when the substrate is chemically inert with respect to the negative electrode 960, for example. In such a case, for example, if the substrate is sufficiently electrically conductive as in the case of stainless steel, the substrate may serve as a negative anode current collector and a negative terminal. The positive portion of the electrochemically active cell may 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 insulative 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 that the moisture encapsulation 1090 is provided with a moisture protection layer 1092 against moisture present in the environment in an embodiment where a protective encapsulation 1090 having an opening 1091 providing a connection to the negative terminal 1080 is made, Sensitive electrolyte layer 1050 to protect the moisture-sensitive electrolyte layer 1050. [ Negative terminal 1080 and anode current collector 1070 may not be moisture resistant, for example, to be thick enough and / or 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 insulating or conductive, and so may barrier sublayers 1011 and 1012 that may constitute barrier layer 1010. [ 10 are a cathode current collector 1020, a positive terminal 1030, a positive cathode 1040 and a negative anode 1060.

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

Claims (117)

In an electrochemical device, (a) a substrate having a first side and being selected from the group consisting of a metallic material, a polymeric material, or a doped or undoped silicon material, (b) a first electrochemically active cell on the first side having a negative part and a positive part, the parts further comprising one or more terminals, An 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, wherein the first barrier layer is in electrical contact between the first electrochemically active cell and the substrate, . The method according to claim 1, And a plurality of electrochemically active cells provided on the first side of the substrate. The method according to claim 1, Wherein the first barrier layer comprises: A first electrochemically active cell and a material chemically inert with respect to the substrate, Wherein the first electrochemically active cell is configured to diverge against the first electrochemically active cell and the substrate during manufacture of the first electrochemically active cell on the substrate and during operation and storage of the electrochemical device. Electrochemical device. The method according to claim 1, The sub-layer is selected from the group of electrically conductive materials, electrically insulating materials or electrically semi- 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, and c) said negative portion of said first electrochemically active cell comprises at least a negative anode, an anode current collector and a negative terminal. Claim 5 has been abandoned due to the setting registration fee. 5. The method of claim 4, And the cathode current collector comprises the positive terminal. Claim 6 has been abandoned due to the setting registration fee. 5. The method of claim 4, Wherein the anode current collector comprises the negative terminal or the anode. Claim 7 has been abandoned due to the setting registration fee. 5. The method of claim 4, Wherein the anode current collector comprises the anode current collector, the anode and the negative terminal. The method according to claim 1, The sub-layers each having the same shape and area size, or the sub-layers each have a shape and an area size different from the others of the plurality of sub-layers. Claim 9 has been abandoned due to the setting registration fee. The method according to claim 1, Wherein the first barrier layer only partially covers the substrate such that at least the positive portion or at least the negative portion of the first electrochemically active cell is chemically separated from the substrate. The method according to claim 1, Wherein the first barrier layer has a thickness in the range of 0.01 [mu] m to 10 &lt; ³ &gt; [mu] m. The method according to claim 1, Wherein the first barrier layer has a thickness in the range of 0.1 占 퐉 to 100 占 퐉. The method according to claim 1, Wherein the first barrier layer has a thickness in the range of 0.5 [mu] m to 5 [mu] m. The method according to claim 1, Wherein the substrate has a thickness in the range of 0.1 占 퐉 to 10 ⁴占 퐉. The method according to claim 1, Wherein the substrate has a thickness in the range of 1 [mu] m to 10 &lt; ³ &gt; [mu] m. The method according to claim 1, Wherein the substrate has a thickness in the range of 10 [mu] m to 100 [mu] m. The method according to claim 1, The sub- a) a group of metals, semi-metals, alloys, borides, carbides, diamonds, quasi-diamond carbon (DLC), silicides, nitrides, phosphides, oxides, fluorides, chlorides, bromides, iodides, b) a group of any multi-component compounds consisting of borides, carbides, silicides, nitrides, phosphides, oxides, fluorides, chlorides, bromides and iodides, or c) Groups of high temperature stable organic polymers and high temperature stabilized silicon &Lt; / RTI &gt; wherein the chemical compound is selected from the group consisting of: The method according to claim 1, Wherein at least one of the sublayers comprises a single phase crystalline, nano-crystalline, amorphous or glassy material, or a poly phase mixture, or a composite thereof. Claim 18 has been abandoned due to the setting registration fee. The method according to claim 1, Wherein at least one of the sublayers comprises a single-phase amorphous or glassy material. The method according to claim 1, Wherein the first electrochemically active cell comprises a cell selected from the group of a lithium metal anode cell, a lithium-ion anode cell, and a lithium-free anode cell. 20. The method of claim 19, Wherein the first electrochemically active cell comprises a positive thin film cathode deposited by a vapor deposition method or a non-vacuum deposition method, Wherein the thickness of the positive thin film cathode is less than 200 占 퐉. 21. The method of claim 20, Wherein the positive thin film cathode comprises a single crystallite having a size of at least 100 angstroms. Claim 22 is abandoned in setting registration fee. The method according to claim 1, Wherein the first electrochemically active cell comprises a thin film solid electrolyte having a thickness of less than 100 mu m. The method according to claim 1, Wherein the first electrochemically active cell comprises a thin film negative anode selected from the group consisting of a lithium metal, a lithium-ion anode, or a metal that does not form a mutual metal compound with lithium, Wherein the thickness of the thin film negative anode is less than 200 占 퐉. The method according to claim 1, Wherein the first electrochemically active cell further comprises a protective encapsulation, Wherein the protective encapsulation is configured to protect the first electrochemically active cell against at least mechanical and chemical factors from the environment. The method according to claim 1, Further comprising protective encasing, Wherein the protective encasing is configured to protect the electrochemical device against at least mechanical and chemical factors from the surrounding environment. 25. The method of claim 24, Wherein the encapsulation has at least one opening configured to allow direct electrical contact to at least one terminal of the first electrochemically active cell. Claim 27 is abandoned due to the setting registration fee. 26. The method of claim 25, Wherein the protective encasing has at least one opening configured to permit direct contact with at least one terminal of the first electrochemical device. Claim 28 has been abandoned due to the set registration fee. 28. The method of claim 26 or 27, Wherein the electrochemically active cell further comprises an electrolyte, Wherein the at least one terminal is separated from the electrolyte by a moisture protection layer. 29. The method of claim 28, The moisture- Comprising a material having moisture barrier properties, a) a group of metals, semi-metals, alloys, borides, carbides, diamonds, quasi-diamond carbon (DLC), silicides, nitrides, phosphides, oxides, fluorides, chlorides, bromides, iodides, b) a group of any multi-component compounds consisting of borides, carbides, silicides, nitrides, phosphides, oxides, fluorides, chlorides, bromides and iodides, or c) Groups of high temperature stable organic polymers and high temperature stabilized silicon &Lt; / RTI &gt; 29. The method of claim 28, Wherein the moisture protection layer comprises a single-phase crystalline, nano-crystalline, amorphous or glassy material, or a polyphase mixture, or a composite thereof. The method according to claim 1, Wherein the electrochemical device further comprises a second layer located on a second side of the substrate. Claim 32 is abandoned due to the set registration fee. 32. The method of claim 31, Wherein the second layer comprises: a) a group of metals, semi-metals, alloys, borides, carbides, diamonds, quasi-diamond carbon (DLC), silicides, nitrides, phosphides, oxides, fluorides, chlorides, bromides, iodides, b) a group of any multi-component compounds consisting of borides, carbides, silicides, nitrides, phosphides, oxides, fluorides, chlorides, bromides and iodides, or c) Groups of high temperature stable organic polymers and high temperature stabilized silicon &Lt; / RTI &gt; wherein the chemical compound is selected from the group consisting of: The method according to claim 1, a) the substrate further comprising a second side, b) a second electrochemically active cell on said second side further comprising a positive portion and a negative portion, said portions further comprising one or more terminals; c) a second barrier layer on the second side separating the second electrochemically active cell from the substrate, d) the first barrier layer comprises a plurality of sublayers, e) the second barrier layer comprises a plurality of sub-layers. Claim 34 is abandoned in setting registration fee. 34. The method of claim 33, And a plurality of electrochemically active cells provided on the first side or the second side of the substrate. 34. The method of claim 33, (a) the first barrier layer comprising the first electrochemically active cell on the first side of the substrate and a material chemically inert to the substrate; and (b) the second barrier layer comprising the second electrochemically active cell on the second side of the substrate and a material chemically inert with respect to the substrate, (c) said first barrier layer further has a diffusion barrier characteristic for chemical elements in said first electrochemically active cell on said first side of said substrate, (d) said second barrier layer further has a diffusion barrier characteristic for chemical elements in said second electrochemically active cell on said second side of said substrate. Claim 36 is abandoned in setting registration fee. 34. The method of claim 33, Each of said electrochemically active cells of said electrochemical device comprising a protective encapsulation or protective encasing, Wherein the protective encapsulation or protective encasing is configured to protect the electrochemically active cell or electrochemical device against at least mechanical and chemical factors in the environment. Claim 37 is abandoned in setting registration fee. 37. The method of claim 36, Wherein the encapsulation or ingression has at least one opening configured to allow direct electrical contact to at least one terminal of the respective electrochemically active cell. Claim 38 is abandoned in setting registration fee. 39. The method of claim 37, Wherein the electrochemically active cell further comprises an electrolyte, Wherein the terminal is connectable from the outside by an opening in the encapsulation and is separated from the electrolyte by a moisture protection layer. delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete

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