TWI406443B - Hybrid thin-film battery - Google Patents

Description

Mixed thin film battery

The present invention relates to electrochemical devices and methods of making the same. More specifically, there are methods for synthesis, dissociation, and fabrication of solid-state, thin-film, secondary, and primary electrochemical devices, including batteries.

A thick positive cathode is suitable for producing a high energy thin film battery. A thick positive cathode substantially increases the mass of active cathode per unit area. However, there is a problem in the method of producing a cathode described above by using a conventional vacuum vapor phase process.

Cathodes produced by conventional vacuum gas phase methods have a number of limitations. For example, as shown in Fig. 1, vacuum vapor deposited materials are usually grown in a cylindrical manner. This figure outlines three micro-cylindrical cross-sections of the positive cathode layer of an electrochemical device grown by vacuum vapor deposition. When the process is lengthened into a cylinder, the bottom of the cylinder is continuously fixed on the surface of the substrate; and as the height of the cylinder increases, the cross-sectional area of the bottom remains virtually unchanged. As the height of the cylinder increases, the aspect ratio (cylinder height/cylindrical width) also increases, and since the cathode film contains these cylinders, the entire device is mechanically unstable, usually at an aspect ratio of about 15. Therefore, there are many limitations to the height (i.e., thickness) of the cylinder grown by the vacuum deposition process. The thickness of the cathode and the energy system of the electrochemical device per unit area produced by vacuum vapor deposition are directly related to the height limit. Furthermore, the vacuum vapor phase process takes a considerable amount of time to grow into a thick cathode and is therefore quite expensive. For example, since a vacuum deposition method requires a long deposition time to grow a lithium cobalt oxide (LiCoO ₂ ) positive cathode of about 3 μm thick, it is very expensive.

Therefore, there is a need for a fast and inexpensive manufacturing process for producing electrochemical devices having thick and reliable cathodes. In addition, in order to achieve the above requirements, any known non-vapor deposition technique and process can be used, for example, slurry coating, Meyer rod coating, direct and reverse roller coating ( Direct and reverse roll coating), doctor coating, spin coating, electrophoretic deposition, sol-gel deposition, spray coating, wet Dip coating, ink-jetting, and other means.

The thicker cathode system is deposited to increase the energy per unit area of the electrochemical device, but it increases the overall thickness of the device. Since it is not desirable to increase the overall thickness of a milli, micro or nano device, other ways must be found to eliminate the thickness increase described above. A commonly used method is to minimize the thickness and volume of non-energy providing parts in an electrochemical device.

One of the methods is to reduce the non-energy supply components in the electrochemical device. The encapsulation and substrate are parts that are inherent and large in the assembly.

For example, reducing the package thickness from 100 microns (typically the typical thickness of a laminate encapulation) to 1 to 10 microns thick for a true film package allows the electrochemical device manufacturer to thickness the cathode carrying the energy Increase by at least 100 microns without increasing the overall thickness of the device. The above method substantially enhances the energy, capacitance, and power volume of the electrochemical device. Since the physical performance described above needs to be present in a minimum volume, possibly a millimeter, micron or nano electrochemical device, it is important to reduce the non-energy supply components in the electrochemical device.

Another method is to fabricate the electrochemical device on as thin a substrate as possible, so that it can be sold as a stand-alone device. Unlike non-independent devices, manufacturers of the above-described stand-alone devices can utilize the free surface (wafer surface, printed circuit board surface, etc.) present in the electronic device and directly integrate, assemble or deposit the electrochemical device. On the non-fixed surface. This surface can also be used as a substrate for electrochemical devices. The electrochemical devices described above can be assembled into a substrate having a thickness of zero because the electrochemical device does not use other substrate thicknesses to the finished electronic device. More often, however, when a stand-alone device has not yet provided suitable chemical, physical, or institutional protection or functionality to support an electrochemical device, its substrate thickness has reached a critical value. Since most vacuum deposited cathode materials require a high temperature process to fully develop their physical properties, but they cause film stress and affect the substrate, the mechanical properties of the vacuum vapor deposited cathode material can affect the substrate due to mechanical deformation.

The result of the vacuum vapor deposition film combined with the high temperature process results in bending, curling or deformation of the substrate or even the entire electrochemical device. If this happens, it will be difficult to complete the fabrication of the electrochemical device, except that the deformed electrochemical device is not suitable for device integration. In contrast, non-vapor deposited cathode materials retain most or all of their physical properties during the deposition process, so no additional high temperature processes are required. Thus, the non-vapor deposited cathode material and other components of the electrochemical device create less stress on the substrate, so that a thinner substrate can be used without the risk of substantial deformation.

Accordingly, there is a need for packages that exhibit relatively high temperature characteristics.

Therefore, there is a need for an electrochemical device (i) whose cathode system can maintain thickness and reliability in a fast and inexpensive manufacturing process; (ii) its substrate thickness is as thin as possible while not being subjected to electrochemical device parts. (iii) its package is as thin as possible while still providing adequate protection for the device; and/or (iv) its package is composed of high temperature materials and provides thermal resistance to the entire electrochemical device Thermal resilience.

Various aspects and embodiments of the invention as set forth and enumerated below set forth the disadvantages of the prior art and the emerging needs of the related art.

In one aspect of the invention, an electrochemical device comprises: a positive cathode having a thickness greater than about 0.5 micrometers (μm) and less than about 200 microns, a thin electrolyte having a thickness less than about 10 microns, and a thickness less than about 30 microns. The anode. The device can also include a substrate, a current collector, a terminal, a moisture protection layer, and an encapsulation. In embodiments of the invention, the thickness of the cathode can be greater than about 5 microns and less than about 100 microns. The thickness of the cathode can also be greater than about 30 microns and less than about 80 microns.

In another aspect of the invention, an electrochemical device includes a non-vapor deposited cathode, an anode, and an electrolyte having a thickness of less than 10 microns. In embodiments of the invention, the thickness of the cathode can be greater than about 0.5 microns and less than about 200 microns, and the thickness of the anode can be less than about 30 microns.

The cathode according to an embodiment of the invention may be non-vapor deposited. One of the following methods can be used to deposit the cathode: slurry coating, Meyerrod coating, direct and reverse roll coating, doctor blade Coating), spin coating, electrophoretic deposition, or ink-jetting.

The cathode may comprise lithium cobalt oxide (LiCoO ₂ ), lithium manganese oxide (LiMn ₂ O ₄ ), lithium manganese oxide (LiMnO ₂ ), lithium nickel oxide (LiNiO ₂ ), lithium iron phosphate (LiFePO ₄ ) , lithium vanadium oxide (LiVO ₂ ), and mixtures or chemical derivatives thereof. Alternatively, these cathode materials may be doped with an element selected from Groups 1 to 17 of the periodic table.

In an embodiment, the electrolyte may comprise lithium phosphorus oxynitride (LiPON). The electrolyte may comprise a thin film electrolyte. The electrolyte can be deposited using a vacuum vapor phase growth mode or a non-gas phase mode.

The anode may comprise lithium, a lithium alloy or a metal which may form a solid solution or a lithium-containing compound, or a so-called lithium ion compound suitable for use in a lithium-containing battery, such as lithium titanium oxide (Li ₄ Ti ₅ O _{1 2} ), used as a negative anode material.

In another aspect of the invention, the electrochemical device can also be encapsulated by a sealing process selected from the vacuum vapor grown film disclosed in U.S. Patent No. 6,916,679 issued to Snyder et al. In the group of encapsulation, pressure-heat lamination (here incorporated by reference in its entirety for reference), metal foil attachment and metal canning.

The apparatus further includes a cathode current collector and a non-essential anode current collector located at the top or bottom of the thin film electrolyte layer. The electrolyte immediately adjacent the bottom of the optional anode current collector may be protected by a moisture barrier, such as zinc dioxide (ZrO ₂ ), which may have an optional anode current collector if the package has openings. Direct contact with the atmosphere.

According to one aspect of an embodiment of the present invention, a non-gas phase assembly method can be used to form a positive cathode, and all or a portion of the cathode and electrochemical device battery components are assembled by vacuum gas phase. The exemplary embodiment in combination with the above various modes is regarded as a hybrid manufacturing method, and the device manufactured by the method is, for example, a "hybrid thin-film battery".

In one aspect of an embodiment of the invention, the fabrication of the positive cathode system in a non-gas phase does not require high temperature, and the high temperature step limits the development of stress within the stack of parts of the electrochemical device. Further, a thinner substrate can be used. Although thinner substrates tend to deform at a certain stress intensity, the use of thin substrates allows for a relatively thin energy electrochemical device with a certain energy, capacitance and power performance. In other words, the use of a thinner substrate can increase the amount of energy, capacitance, and power of the electrochemical device.

In another aspect, the cathode can be grown in a vacuum vapor phase, or in a non-gaseous manner, and then embossed or otherwise formed into the cathode in a manner that increases its The same coating covers the surface area in the footprint, but with an increased maximum thickness and a reduced minimum thickness. This structure or configuration can reduce the average distance of any volume element inside the cathode from the adjacent solid film electrolyte layer, unlike electrochemical devices having a gel or liquid electrolyte that typically do not penetrate the cathode body. Therefore, minimizing the average distance between any volume element in the cathode to the solid film electrolyte can reduce the ion diffusion length during operation of the electrochemical device, thereby improving the power capability.

In another aspect of an embodiment of the present invention, an electronic conducting material, such as carbon, is mixed into a cathode structure having an embossing or other surface increase to reduce electron diffusion length in the cathode body, thereby improving The power capability of an electrochemical device.

In another aspect of an embodiment of the invention, the electrochemical device comprises a thin film encapsulation comprising or consisting of an inorganic material that exhibits relatively good high temperature properties.

In another aspect of an embodiment of the invention, a thin film encapsulation is used to minimize the effect of package thickness on the overall thickness of the electrochemical device.

In another aspect, a thin package, such as a thin film package, can overcompensate or at least partially or partially compensate for an increase in cathode thickness relative to the overall thickness of the electrochemical device. In addition, the use of a thinner package can directly increase the amount of energy, capacitance, and power of the electrochemical device, as compared to a pressure-heat laminate.

In another aspect of the embodiments of the present invention, the thin film encapsulation comprises a plurality of inorganic layers, the inorganic layer exhibiting high temperature stability of the body, which is an increase in temperature stability and restoring force of the entire electrochemical device to some kind The nature of the degree.

1 is a cross-sectional view of a conventional cathode layer 120 on a metal current collector 101 above a substrate 100. In an electrochemical device formed by a vacuum vapor deposition process, the cathode can be grown in the form of a cylinder 120 and has an inter-columnar void space 111. As also shown in Fig. 1, in the next layer in which the thin film electrochemical device is fabricated, the electrolyte 110 has a conventional bridging structure and is located above the cylindrical inner cavity space 111.

Figure 2 shows a hybrid thin film electrochemical device having a cathode 210 deposited without a vacuum vapor phase process. In this embodiment, the cathode 210 is deposited directly on the substrate 200. If there is a metal conduction, for example, the substrate 200 in the embodiment can also function as a cathode current collector. In other modes, a metal conduction current collector (not shown) may be disposed between the substrate 200 and the cathode 210. The cathode 210 may include, for example, lithium cobalt oxide (LiCoO ₂ ), lithium manganese oxide (LiMn ₂ O ₄ ), lithium manganese oxide (LiMnO ₂ ), lithium nickel oxide (LiNiO ₂ ), lithium iron phosphate ( LiFePO ₄ ), lithium vanadium oxide (LiVO ₂ ), and mixtures or chemical derivatives thereof. As shown in the embodiment, the cathode 210 can have a thickness between about 0.5 microns and about 200 microns. In a preferred embodiment, for example, cathode 210 can have a thickness between about 5 microns and about 100 microns. In a more preferred embodiment, for example, the thickness of the cathode 210 can be between about 30 microns and about 80 microns.

As shown in FIG. 2, an electrolyte layer 220 may be deposited on the upper surface of the cathode layer 210. The electrolyte layer may, for example, comprise a lithium phosphorus oxynitride (LiPON) or other solid state thin film electrolyte, such as the lithium aluminum iron compound (LiAlF ₄ ) described in U.S. Patent 4,367,267, or U.S. Patent 5,217,826, issued to Yamamura et al. the silicon doped with lithium sulfide (Li ₄ SiS ₄₎ of lithium phosphate (Li ₃ PO _4). The above patents are incorporated herein by reference. The thickness of the electrolyte layer 220 is, for example, less than about 10 microns.

Cathode 210 is thicker when compared to electrolyte 220, substrate 200, and anode 230 formed over electrolyte 220. In other embodiments, the cathode 210 is also relatively thicker when compared to the anode current collector 240 and the thin film package 250.

Electrolyte 220 can be deposited on cathode 210 in a variety of ways. These methods may include, for example, a vacuum vapor phase growth method or a non-gas phase method. The vacuum gas phase process may comprise, for example, reactive or non-reactive RF magnetron sputtering, reactive or non-reactive DC diode supttering, reactive or non-reactive Thermal (resistance) evaporation, reactive or non-reactive electron beam evaporation, ion-beam assisted deposition, plasma enhanced chemical vapor deposition, etc. the way. Non-gas phase processes can include, for example, spin coating, ink jet, thermal spray deposition, or dip coating. Rotary coatings are described in U.S. Patent No. 4,795,543 issued to Stetter et al., U.S. Patent No. 4,948,490 issued to Venkataset, or U.S. Patent No. 6,005,705 issued to Schmidt. The ink jet process is disclosed in U.S. Patent No. 5,865,860 issued to Delnick. The thermal spray deposition process is disclosed in U.S. Patent Publication No. 2004/0106046 to Inda. Wet coatings are disclosed in U.S. Patent No. 5,443,602 issued toKejha and U.S. Patent No. 6,134,773. Each of the above patents and patent publications is incorporated herein by reference.

As shown in Fig. 2, the lower layer on top of the electrolyte is a thin negative anode layer 230. The thin anode 230 may comprise, for example, lithium, a lithium alloy, a metal that can form a lithium-containing solid solution or compound, or a lithium ion compound that can be used as a negative anode material in a lithium-containing battery (eg, lithium titanium oxide (eg, lithium titanium oxide ( Li ₄ Ti ₅ O _{1 2} )). For example, the thin anode layer 230 can have a thickness of less than about 30 microns. The thin anode can be in contact with the anode current collector 240, which can electrically pass through an opening 260 located in the package 250. In an embodiment, the anode current collector has a thickness of less than about 2 microns. The thin film package 250 is electrically conductive in certain areas and thus acts as an anode current collector in some embodiments. In the above embodiments, an additional anode current collector 240 may not be required. The thickness of the thin film package 250 can be less than about 250 microns.

The cathode 210 of FIG. 2 can be deposited on the substrate 200 in a variety of ways. In a particular embodiment, a non-vapor deposition process is used to deposit the cathode material 210. The non-vapor deposition method does not need to be performed in a vacuum environment. Some non-vapor deposition methods are known. These methods include: slurry coating, Meyer bar coating, direct and reverse roller coating, blade coating, spin coating, electrophoretic deposition, sol deposition, spray coating, wet coating, inkjet, etc. the way. Other non-vapor deposition methods or other methods that do not require deposition in a vacuum may also be used without departing from the spirit, scope and embodiments of the invention. These non-gas phase, non-vacuum deposition methods produce a single phase cathode or composite cathode. The composite cathode can be deposited in nanometer, micrometer or millimeter size and can be composed of organic and/or inorganic materials, and can also be polymerized, for example, 'poly(vinyl pyrrolidone), sulfur sulfide (sulfur) Nitrile (SN) _x ), nano-tubed carbon or acetylene black.

All of the deposition steps noted herein may be followed by a drying step having a temperature of less than about 150 degrees, and/or a low temperature drying and adhesion improving step having a temperature between about 150 and 400 degrees, and / or a high temperature annealing step with a temperature of from about 400 degrees to about 1000 degrees. These steps aid in drying, adhesion enhancement, formation of a current film phase, and/or crystallization. A pure cathode deposition material may be used or mixed with a binder material containing (or not including) a carbon, metal or alloy type conductivity enhancer. When the cathode material is in a mixed form, the cathode material is a composite cathode material.

The method of coating a slurry for use in the manufacture of a battery is disclosed in the U.S. Patent No. 6,110,062 issued to Hikaru, or to U.S. Patent No. 4,125, 686 issued toK. The slurry coating directs deposition of a composite electrode composed of an electrochemically active material, which is a powder particle type in which a polymeric binder is bonded together, and some forms a conductive reinforcement such as carbon black or the like. Type. The slurry also contains a solvent that needs to be evaporated and/or pyrolyzed after film deposition.

According to an exemplary embodiment, the composite cathode may be deposited from a slurry comprising or consisting of crystalline lithium cobalt oxide powder, polyimide binder, and graphite conductive reinforcement. This slurry is then applied to an aluminum foil substrate and dried in air at a temperature below 150 degrees for a period of less than two days. Subsequently, in this embodiment, the cathode can be coated with, for example, a LiPON thin film electrolyte having a thickness of about 2 microns, a lithium negative anode of about 3 microns thick, and a Cu anode current collector of about 0.3 microns thick. Finally, a heat and pressure induced metal polymer laminate of about 100 microns thick can be applied to an electrochemical device such that the electrochemical performance of the device can be tested in air, wherein the metal polymer laminate is used to seal the Electrochemical device.

In another embodiment, dry slurry coating may require additional drying, lamination, forming, and/or crystallization steps in an environment at temperatures up to about 1000 degrees to complete the structure of the cathode or composite cathode. This method can produce a thick cathode quickly and easily without using a vacuum gas phase method. Furthermore, the resulting cathode does not have mechanical instability when generated by a vacuum vapor deposition method.

By means of mechanism displacement or removal, including embossing, stamping, abrading, scraping, forming, etc., the cathode 210 in Figure 2 is more variable. As shown in Figure 14. This layer change can be made on a wet or completely dry cathode. The change in cathode surface enhances the transfer efficiency of ions between the cathode body and the thin film electrolyte (e.g., composed of a LiPON layer (not shown), and thus improves the power performance of the electrochemical device.

Another improvement is that when the cathode 210 comprises or consists at least of an electrochemically active cathode material (eg, LiCoO ₂ ) and a carbon-containing conductive reinforcement, it can achieve power capabilities, and the carbon-containing conductive reinforcement is used The electron diffusion length in the composite cathode body is reduced.

Figure 3 shows a scanning electron micrograph of a LiPON coated composite cathode. The dimension calibration bar on the far left of the left figure represents a length of about 9 microns, while the illustration on the right side represents a length of about 3 microns.

The electrochemical cycle performance of an electrochemical device according to an exemplary embodiment of the present invention is shown in FIG.

In accordance with an embodiment of the present invention, the composite cathode can be deposited by coating with a variety of suspensions or solutions, such as the lithium cobalt oxide powder disclosed in U.S. Patent No. 6,907,352 issued to Principe. This is included in the case by reference. Alternatively, a polymeric binder such as polyamine, and/or a conductive reinforcement such as graphite may be blended. Coating on a substrate (eg, an aluminum foil substrate) can be dried in air at a temperature below about 150 degrees for two days. Subsequently, in this embodiment, the cathode can be coated with a LiPON thin film electrolyte of about 2 microns thick, a lithium negative anode of about 3 microns thick, and a copper anode current collector of about 0.3 microns thick. Finally, approximately 100 micron thick heat and pressure sensitive metal polymer laminates are applied to the electrochemical device such that the electrochemical performance of the device can be tested in air, wherein the metal polymer laminate can be used to seal the electrification Learning device.

In another embodiment, a dry Meyer rod coating may require additional drying, lamination, forming, and/or crystallization steps in an environment at temperatures up to about 1000 degrees to complete the cathode or composite cathode. structure. This method can produce thick cathodes quickly and easily without using a vacuum gas phase method. Furthermore, the resulting cathode does not have mechanical instability when generated by a vacuum vapor deposition method.

In accordance with an embodiment of the present invention, the composite cathode may utilize a lithium cobalt oxide powder as disclosed in U.S. Patent No. 3,535, 295 issued to Davis, which is incorporated herein by reference. ) deposited directly or in reverse roller coating. Alternatively, a polymeric binder, such as polyamidamine, and/or an electron conduction enhancer, such as graphite, may be mixed. Coating on a substrate (e.g., an aluminum foil substrate) can be dried in air at a temperature below about 150 degrees for less than two days. Subsequently, in this embodiment, a cathode can be coated using, for example, a LiPON thin film electrolyte of about 2 microns thick, a lithium negative anode of about 3 microns thick, and a copper anode current collector of about 0.3 microns thick. Finally, a heat and pressure induced metal polymer laminate of approximately 100 microns thickness can be applied to an electrochemical device such that the electrochemical performance of the device can be tested in air where the metal polymer layer is used. To seal the electrochemical device.

In another embodiment, dry direct or reverse roller coating may require additional drying, lamination, forming, and/or crystallization steps at temperatures up to about 1000 degrees to complete the structure of the cathode or composite cathode. This method can produce thick cathodes quickly and easily without using a vacuum gas phase method. Furthermore, the fabricated cathode does not have mechanical instability when formed by a vacuum vapor deposition method.

In accordance with an embodiment of the present invention, the squeegee technique disclosed in U.S. Patent No. 947,518, the disclosure of which is incorporated herein by reference. The deposition method is similar to the way cream is applied. Thus, for example, a doctor blade separates a cathode material (composed of an electrochemically active material) into a precursor or final form, and mixes with a solvent, a binder, and a conductive reinforcement material, and then coats a certain thickness of the cathode material paste. On the substrate. Depending on the composition of the cathode material paste, other drying, laminating, forming, and/or crystallization steps up to about 1000 degrees may be additionally employed to form the final cathode or composite cathode. This method can produce thick cathodes quickly and easily without using a vacuum gas phase method. Furthermore, the fabricated cathode does not have mechanical instability when formed by a vacuum vapor deposition method.

Rotary coating technology using various standard spin coaters supplied by well-known manufacturers is used in the film coating industry, for example, disclosed in Japanese Patent No. 1320728 to Hitachi, This is included in the case by reference. The cathode powder is suspended or dispersed in a low boiling (high volatility) solvent such as water, low molecular weight alcohol, low molecular weight ethers, low molecular weight ketones, low molecular weight esters, low molecular weight carbon by spin coating techniques Hydrogen compounds, etc. This suspension is then dropped onto a rapidly rotating substrate (typically 1000 to 3000 rpm), and due to the high centrifugal force exerted on the droplets, the suspension can be quickly dispersed into a film onto the substrate. Due to the aggressively low mass or volume per unit surface, the film of volatile solvent will quickly evaporate away from the solute or suspension or dispersion material that condenses on the substrate. The spin coating process can be repeated multiple times to increase the thickness of a given film. In order to accelerate the evaporation of the solvent and the solute or the suspension of the dispersed material, the rotating substrate can be heated. Alternatively, the spin coated suspension may additionally comprise a binder or binder precursor material and a conductive reinforcement material. All of the above materials are not easily vaporized during the spin coating process, whether in the atmosphere or at elevated temperatures and/or vacuum. Depending on the composition of the cathode material paste, other drying, lamination, forming, and/or crystallization steps at temperatures up to about 1000 degrees can be used to form the final cathode or composite cathode.

According to an embodiment of the present invention may be utilized electrophoretic deposition means such as Kanamura et al. In Journal Electrochem Solid State Letters (3 Electrochem.Solid State Letters 259-62 (2000 )) or a Lusk in British Patent 1,298,746 discussed herein to grow into Non-gas phase lithium cobalt oxide cathode films are incorporated herein by reference. For example, micron-sized, fully crystalline lithium cobalt oxide particles can be suspended in a solution of acetone, isopropanol, and/or iodine, and electrophoretically deposited fully crystalline lithium cobalt approximately 9 microns thick. The oxide film is on a stainless steel substrate without any columnar structure. This process can be carried out within about 30 minutes at room temperature and less than about 120 VDC.

Figure 5 is a scanning electron micrograph of a positive cathode film deposited by electrophoresis. The iodine impurity concentration shown in the figure is lower than the critical value (less than 1 wt%) detectable by the energy dispersive x-ray spectroscopic method. Also using electrophoretic deposition to make a composite having a relatively thin lithium cobalt oxide cathode electrochemical cell, e.g., containing about 200 ml of acetone, about 23 mg of iodine (I _2), about 38 mg and about 53 mg of carbon black polytetramethylene A solution of about 1 gram of fully crystalline lithium cobalt oxide fine particle powder is suspended in a solution of fluoroethylene (PTEF). In the above embodiment, a driving voltage of 50 VDC can be applied for about 30 seconds in electrophoretic deposition. Next, the deposited lithium cobalt oxide composite film can be annealed in air at a temperature of about 377 degrees for about 4 hours to improve the adhesion to the conductive substrate. Next, a lithium-phosphorus oxynitride electrolyte of about 2 μm thick was deposited by RF magnetron sputtering on a lithium cobalt oxide composite cathode, followed by electron beam evaporation to form a copper anode current collector film of about 0.3 μm thick, and finally Thermal (resistance) vacuum deposition of a metal lithium anode of approximately 3 microns thickness is used to complete the electrochemical device. The current discharge voltage representation of the above electrochemical device is shown in Fig. 6, and the electrochemical cycle stability is shown in Fig. 7. Depending on the composition of the electrophoretic suspension, other drying, lamination, shaping and/or crystallization steps up to about 1000 degrees can be used to form the final cathode or composite cathode.

According to an exemplary embodiment of the present invention, a sol method may be utilized to deposit a thick cathode. In this embodiment, for example, a precursor material of an oxide cathode film material to be deposited, such as an aqueous solution or an alcohol colloidal solution of lithium or cobalt ions neutralized by an anion counter ion or a chelate, is provided. These anionic counterions or chelates may comprise, for example, nitrates, glycolates, hydroxides, citrates, carboxylates, oxalates ( An oxalate, an alcoholate or an acetylacetonate, the above ingredients may be wet coated or sprayed onto a substrate and then dried at elevated temperatures for a period of time, for example, within two days. In addition, the finished film is placed in a high temperature pyrolysis process to convert the anionic counterion or chelate to a pure oxide. This method is presented in the Ph.D. paper by Bernd J. Neudecker, Stuttgart, Germany, 1994, and in the journal paper by J. Electrochem. Soc , published by Plichta et al. (139 J Electrotron. Soc . 1509-13 (1992)), and U.S. Patent 5,604,057 issued to Nazri. Alternatively, the sol may additionally comprise a binder or a binder precursor material and a conductive reinforcement material. All of the above additives are not easily evaporated during the drying process, whether in the atmosphere or at elevated temperatures. Depending on the composition of the sol, other drying, laminating, forming and/or crystallization steps up to about 1000 degrees can be used to form the final cathode or composite cathode.

In an embodiment of the invention, an inkjet method can be utilized to deposit a thick cathode. The inkjet method of the oxide film is described in Japanese Patent No. 2005011656 to Watanabe Kyoichi et al., U.S. Patent No. 6,713,389 to Speakman, and U.S. Patent No. 6,780,208 to Hopkins, incorporated herein by reference. The entire content of the case. In an embodiment of the invention, the fully crystalline lithium cobalt oxide powder can be ground until it has an average particle size of about 0.55 microns, which is then dispersed in about 0.05 vol% iso-octanol, about 5 vol%. Isopropanol, about 10 vol% ethylene glycol monobutyl ether, and about 10 vol% ethylene glycol in a solution. This solution can be ultrasonically shaken for about 1 hour to form a suitable inkjet solution. The lithium cobalt oxide film can be deposited through an inkjet head and a wet ceramic (for example, an alumina plate of about 250 micrometers thick) and a stainless steel substrate well (for example, a sheet of about 50 micrometers). After printing, the deposited lithium cobalt oxide film can be dried at a temperature of about 200 degrees for about two hours to remove excess solvent and improve the fit of the lithium cobalt oxide film to the substrate. After the ten nozzles pass through the same substrate region, a dry lithium cobalt oxide film of about 15 microns thickness can be formed. Fig. 8 is a view showing a scanning electron micrograph of the above lithium cobalt oxide film. Alternatively, the inkjet solution or suspension may comprise a binder, a binder precursor material, and/or a conductive reinforcement material. All of the above additives are not easily evaporated during the drying process, whether in the atmosphere or at elevated temperatures. Depending on the composition of the inkjet solution or suspension, other drying, bonding, forming and/or crystallization steps up to about 1000 degrees can be used to form the final cathode or composite cathode.

According to an exemplary embodiment, a cathode fabricated using non-vapor deposition may be coated with an inert, metallic conductive layer (eg, gold) in its completed or unfinished state. Subsequently, when the inert metal conductive coating is successively absorbed into the pores, pores and cracks of the cathode, the completed or unfinished cathode and the inert metal conductive coating may be heated together for drying, lamination, forming, and/or Crystallization, thereby improving the conductivity of the cathode.

The anodes of the above exemplary embodiments can be deposited by various methods. For example, the anode material may be deposited using a vacuum vapor phase growth method or a non-vapor phase growth method such as inkjet or wet coating.

Embodiments of the invention include a vacuum vapor phase growth process to deposit a negative anode material. Typical vacuum gas phase growth methods for negative anodes include, but are not limited to, reactive or non-reactive RF magnetron sputtering, reactive or non-reactive DC diode sputtering, reactive or non-reactive heat (resistance) Evaporation, reactive or non-reactive electron beam evaporation, ion beam assisted plating, plasma enhanced chemical vapor deposition, and the like. The negative anode can be, for example, metallic lithium, a lithium alloy, or a metal that can form a solid solution or a lithium-containing compound.

Other embodiments for depositing a negative anode can include a non-gaseous growth process. For example, a non-vapor phase growth method, for example, an inkjet method in which metal lithium powder is mixed to deposit a negative anode. The above method is described in U.S. Patent Publication No. 2005/0239917, filed by Nelson et al. Also, we can immerse the sample in the molten lithium metal in a protected atmosphere and cool and solidify the film formed on the sample. Similarly, by diluting the sample in the molten tin metal in the atmosphere or transferring the molten or hot tin metal onto the surface of the rod, and then covering the tin metal on the sample, we can make a lithium ion anode, for example, Metal lithium.

A wet coating technique with a sol can be similarly operated to deposit a negative anode material, which is described in Russian Patent No. 2,241,281, issued to Patrick, et al., which is incorporated herein by reference. For example, a lithium ion anode based on tin oxide (SnO ₂ ), which is a suitable anion component of an alkoxide, can be used, as described in U.S. Patent No. 6,235,260, to Toki Motoyuki, here. The content of the case is included by reference.

Figure 9 is a diagram showing a hybrid thin film electrochemical device fabricated without a substrate according to an exemplary embodiment of the present invention. This device is similar to that shown in Figure 2 but does not have a substrate. Instead of terminating the space with a thin metal layer 300, the thin metal layer acts as a current collector and an electrical terminal. In addition to the metal layer 300, the device in FIG. 9 includes at least one cathode 310, an electrolyte 320, and an anode 330.

The above-described embodiments can be sealed by a package 350 selected from a vacuum-glow-growth film package, a pressure-heat laminate of a protective polymeric composite (described in U.S. Patent No. 6,916,679 issued to Snyder). a pressure-heat-sensing adhesive surface coated foil pressure-heat laminate, and a group of canning.

An anode current collector 340, such as zirconium (Zr), may be disposed between the electrolyte 320, the anode 330, and the package 350. Further, a moisture barrier layer may be placed between the anode current collector 340 and the lower moisture sensing electrolyte 320 to protect the latter. Materials with moisture barrier properties may be selected: (1) selected from the group consisting of metals, semi-metals, alloys, borides, carbides, diamonds, diamond-like carbon, and bismuth. a group of silicides, nitrides, phosphides, oxides, fluorides, chlorides, bromides, iodides; (2) selected from any carbides, tellurides, nitrides a group of compounds synthesized from phosphides, oxides, fluorides, chlorides, bromides and iodides; (3) selected from the group consisting of high temperature stable organic polymers and high temperature stable polysiloxanes. group. The moisture barrier layer may comprise zirconium dioxide (ZrO ₂ ) or zirconium nitride (ZrN), and may be part of an anode current collector 340 having an oxide or nitride composition Gradient, thus achieving a stoichiometric amount of zirconium dioxide or zirconium nitride at the electrolyte interface.

Figure 10 shows an electrochemical device embodiment with a multilayer film encapsulation material. The multilayer film package 400 can be comprised of a plurality of materic getter layers 410 of alternating amorphous germanium or vitreous oxide or nitride layers 420. The strong metal absorbing layer 410 can be used to protect the device from moisture and oxygen due to its superior water and oxygen absorption capacity. The strong metal absorbing layer may be composed of zirconium, hafnium (Y), titanium (Ti), chromium (Cr), aluminum (Al) or an alloy of the above metals. The vitreous or amorphous germanium layer 420 can be a metal oxide or metal nitride or metal used in the absorber layer, for example, zirconium dioxide, zirconium nitride, hafnium oxide (Y ₂ O ₃ ), tantalum nitride (YN). Titanium dioxide (TiO ₂ ), titanium nitride (TiN), chromium oxide (Cr ₂ O ₃ ), chromium nitride (CrN), aluminum oxide (Al ₂ O ₃ ), aluminum nitride (AlN) or Any of the above multi-element compounds. A densely packed glassy or amorphous layer of material that is substantially free of grain boundaries is effective to block any moisture or oxygen from diffusing through the oxide or nitride. Therefore, the multilayer film package effectively protects the underlying, air sensitive metal anode.

In another embodiment, for example, the multilayer film package is comprised of an inorganic high temperature stable or recovery material. The use of the above described package can increase the high temperature stability of the electrochemical device as compared to the use of a polymer component in a package, such as the pressure-heat laminate package described in U.S. Patent No. 6,916,679 to Snyder.

Another example embodiment of an inorganic high temperature stabilization or recovery material can comprise a multilayer film package having an alternating layer of vacuum vapor deposition. For example, the thin film encapsulation may comprise or consist of 30 layers of layers having a thickness of 1000 angstroms, which may be zirconium dioxide/zirconium/zirconia/zirconium... (ZrO ₂ /Zr/ZrO ₂ /Zr/... ) or zirconium nitride / zirconium / zirconium nitride / zirconium ... (ZrN / Zr / ZrN / Zr / ...) alternate, it is understood that different thicknesses, cycles and materials can be used. For example, alternating layers can be deposited in a vacuum reaction chamber at a substrate temperature of less than about 100 degrees. The 30-layer film package described above can be only about 3 microns thick and has a high temperature stability of up to about 300 degrees.

The thin film package directly increases the energy, capacitance and power per unit volume of the electrochemical device (volume energy, volumetric capacitance, and volumetric power), while the electrochemical device using the pressure-thermal laminate package is about 3 microns longer than the current film. The package is typically at least one order of magnitude thick. For example, in an electrochemical device with a total thickness of 150 microns (for example, an actual 10 micron thick electrochemical cell, a 35 micron thick substrate, and a 100 micron thick autoclave package) can be packaged to a thickness of The 3 micron film is replaced, at which point the total thickness of the electrochemical device is only 48 microns, and the volume of energy, capacitance and power is increased by a factor of three.

Figure 11 shows an electrochemical device in accordance with an embodiment of the present invention. In addition to the conductive substrate 500, the positive cathode 510, the electrolyte membrane 520, the negative anode 530, the anode current collector 540, and the electrically insulating layer 550, this embodiment also includes an encapsulation layer 570. The package can be as multi-layered as shown in Figure 10. A second LiPON layer 560 can be placed between the encapsulation layer 570 and the anode 530. Encapsulation layer 570 can be fabricated on anode 530, which contains metallic lithium. The softness of the anode material 530 can cause the encapsulation layer 570 to rupture due to the weakened bottom of the soft anode 530 and/or the stress imbalance at the interface between the anode 530 and the package 570. Once ruptured, the package 570 can expose the susceptible anode 530 to the atmosphere and destroy the anode. When glass LiPON (or a derivative thereof) is used to condition layer 560 to seal the anode, it can mechanically stabilize the soft anode surface, in Figure 11, compared to electrolyte 520, substrate 500 (and cathodes in some embodiments) When the relative thickness of the current collector, the anode 530, the anode current collector 540, the electrically insulating layer 550, the LiPON layer 560, and the thin film package 570 are adjusted, the thickness of the cathode 510 may be thick.

The lower LiPON electrolyte layer 520 and the upper LiPON conditioning layer 560 also mechanically and chemically limit the anode while protecting the intermediate anode layer 530. In this configuration, the metal anode 530, such as metallic lithium, is melted when heated above its melting point of about 181 degrees. Due to its space limitations, the chemical protection and inertness of LiPON will exceed the melting point of lithium, so the metallic lithium anode 530 remains in a fixed position and remains intact as a negative anode material for the electrochemical device. This engineering design also enables the above electrochemical device to be used in a solder reflow process or a flip chip process.

Many materials can be used as anodes, such as copper-lithium alloys or solid solutions, such as lithium copper alloy (Li _x Cu), lithium chromium alloy (Li _x Zr), lithium vanadium alloy (Li _x V), lithium tungsten alloy (Li _x W), lithium niobium alloy (Li _x Be), lithium niobium copper alloy (Li _x Be _y Cu), and the like. Those skilled in the art will appreciate that the above and other materials can be used as anodes. These lithium alloys or solid solutions provide strong mechanical properties compared to soft metallic lithium, thus allowing direct deposition of the multilayer thin film package 570 without the need to be placed between the soft negative metal anode 530 and the multilayer thin film package 570. LiPON conditioning layer 560. In such a case, the LiPON conditioning layer 560 is redundant.

In the embodiment shown in Fig. 11, the electrochemical device can be fabricated on an aluminum substrate having a size of 25.4 mm x 25.4 mm and a thickness of 25 μm, which is coated with lithium cobalt oxide of 80 μm x 3.3 cm 2 . Composite positive cathode, the positive cathode consists of 62% volume concentration of lithium cobalt oxide powder and volume balanced polymeric binder and conductive carbon black powder (510), 1.5 micron thin film solid LiPON electrolyte (520), 10 micron thick negative Metal lithium anode (530), 0.5 micron thick nickel anode current collector (540), 0.5 micron thick zinc oxide electrically insulating layer (550), 0.5 micron thick LiPON conditioning layer (560) and 3 micron thick multilayer film The encapsulation layer consists of 15 layers of zirconium/1000 angstrom zirconia double stack (570) having a thickness of 1000 angstroms. In this example, the electrochemical device is 120 microns at its thickest profile and provides 10 milliamps per hour (mAh) at voltages ranging from 4.2 to 3.0 volts and an average voltage of 4.0 volts (V). Continuous capacitance, which produces 520 volumetric energy density (Wh/liter) for a complete electrochemical device. When a 25 micron thick aluminum substrate was used in place of a 25 micron substrate, the volumetric energy density of the device increased from 520 to 590 watt hours per liter (Wh/litter).

In another embodiment, a barrier layer can be included. The barrier layer can be deposited on a substrate, such as a foil substrate, wherein the barrier layer chemically separates the battery portion (ie, the electrochemically active battery) from the substrate portion of the electrochemical device. The barrier layer prevents any contaminants from entering the cell from the substrate during cell fabrication and battery handling and storage, as well as preventing ions from escaping into the cell and diffusing into the substrate. Some materials that can be used as barrier layers can contain non-good ion-conducting materials such as borides, carbides, diamonds, diamond-like carbons, tellurides, nitrides, phosphides, oxides, fluorides, chlorides, bromine. a compound, an iodide, and a compound of any of the above composition. Among the above compounds, the electrically insulating material can further avoid possible reactions between the substrate and the battery layer. For example, if a chemical reaction involving the diffusion of ions and electrons occurs, the insulating barrier layer blocks electrons, thus avoiding any chemical reaction. However, the barrier layer may also comprise a conductive material as long as the material does not contact ions of any substrate or battery layer material. For example, zirconium nitride is an effective conductive layer that avoids ion conduction. In some examples, depending on the annealing temperature applied to the cell fabrication process and the substrate material, the metal, alloy, and/or semi-metal may also serve as a barrier layer. The diffusion barrier layer may be single or multi-phase, crystalline, vitreous, amorphous germanium or any mixture of the above, but since the vitreous and amorphous germanium structures lack grain boundaries, they are preferred structures in some applications, wherein The boundary will be considered as an increased (but not required) position for ion and electron conduction.

The thin film encapsulation layers as shown in Figures 10 and 11 can be located above the device. Therefore, the flexible package allows the device to be stretched and contracted. The above-described glass-metal multilayer package exhibits appropriate elastic properties, which can be changed by changing the sputtering deposition parameters, and thus the density of the glass and/or metal. Another method of altering the mechanical properties of the film package composition and the film package can include varying the chemical dose of one or more components of the film package. For example, zirconium nitride (ZrN) can be changed to zirconium nitride (Zr ₂ N), which is equivalent to changing the specific composition of the nitride layer. In addition, the stacked metal can be changed. For example, in addition to the stack of zirconium/zirconium nitride/zirconium/zirconium nitride, a multilayer film package composed of zirconium/aluminum nitride/chromium/titanium nitride can be fabricated.

The thick positive cathode in the above embodiment is not only inexpensive but also reliable. The thick cathode can also be composed of a thin electrolyte, a thin anode and a thin package to maximize the bulk density of the capacitance, energy and power of the electrochemical device.

Figure 12 shows another embodiment of the invention showing the different configurations of the electrochemical device of Figure 12 and the converted thin film battery configuration. When the negative anode 610 is directly deposited on the substrate 600, the anode is selected from the same material as described in FIG. 2 and fabricated in the same manner, so that the substrate (eg, copper foil) is electrically conductive and chemical to the anode 610. Inert. In this particular configuration, the substrate can also be used as the anode current collector and negative terminal of the battery. If the substrate 600 is electrically insulated, another anode current collector, such as copper or nickel, can be placed between the substrate 600 and the negative anode 610 (not shown). The electrical path to the anode current collector can be accomplished by extending the anode current collector over the edge of the package 650 or providing an opening in the substrate 600. The opening in the substrate can be filled with a conductive material, such as copper glue, in such a manner that the material can be in electrical contact with the anode current collector. The same materials and methods as the electrolyte described in FIG. 2 are also used, and the electrolyte 620 is disposed above the anode 610. The same material and method of the positive cathode as described in FIG. 2 is also used, and the positive cathode 630 is disposed above the electrolyte 620. In order to electrically route the positive cathode 630, a cathode current collector 640, such as aluminum or gold, is located on top of the positive cathode 630. If the package 650 is used on an electrochemical device, an opening 660 can be provided on the package 650 to allow electrical path to the positive cathode 630.

Similarly, an electrochemical device having a converted thin film battery configuration can be fabricated using the elements, materials, and methods described in FIG. The electrochemical device is shown in Figure 13. First, the negative anode 710 is directly on the chemically inert substrate 700. To avoid shorting of the electrochemical device, an electrically insulating layer 750 can be fabricated that can partially cover the electrolyte 720 and can entirely cover the anode 710. After depositing the electrolyte 720, a positive cathode 730 is deposited and then a cathode current collector 740 is deposited. In order to utilize the thin film encapsulation 770 on the existing layer during fabrication of the electrochemical device, the mechanism and chemical conditioning layer 760 can be located in the cell portion of the electrochemical device, which is defined as the cathode. Those skilled in the art will appreciate that the present invention encompasses other conversion configurations that are accomplished via the combination of the non-converted batteries described above.

In other embodiments, the barrier layer can be located between the substrate and the battery portion of the electrochemical device, as claimed in the August 23, 2005 application entitled "Electrochemical Apparatus with a barrier protective substrate" Barrier Layer Protected Substrate) is described in U.S. Patent Application Serial No. 11/209,536, the disclosure of which is incorporated herein by reference. Depending on the material and configuration of the barrier layer, one or more additional current collectors can be fabricated on the barrier layer to improve electrical contact between the positive and negative anodes.

The above embodiments are for illustrative purposes only. Those skilled in the art can extend other embodiments that are still within the scope of the invention in the above-described embodiments. Accordingly, the invention is defined by the scope of the appended claims. The invention is to cover all modifications and variations of the scope of the appended claims. In addition, the specific description and the theory of the present invention are not intended to limit the scope of the disclosure or the scope of the patent application.

100. . . Substrate

101. . . Current collector

120. . . Cathode layer

110. . . Electrolyte

200. . . Substrate

210. . . cathode

220. . . Electrolyte layer

230. . . anode

240. . . Anode current collector

250. . . Package

260. . . Opening

300. . . Metal layer

310. . . cathode

320. . . Electrolyte

330. . . anode

350. . . Package

340. . . Anode current collector

400. . . Multilayer film package

410. . . Metal absorbing layer

500. . . Conductive substrate

510. . . cathode

520. . . Electrolyte membrane

530. . . anode

540. . . Anode current collector

550. . . Insulation

570. . . Encapsulation layer

560. . . Adjustment layer

600. . . Substrate

610. . . anode

620. . . Electrolyte

630. . . cathode

640. . . Cathode current collector

650. . . Package

660. . . Opening

700. . . Substrate

710. . . anode

720. . . Electrolyte

730. . . cathode

740. . . Cathode current collector

760. . . Adjustment layer

770. . . Thin film package

The drawings and descriptions of the invention are used to explain the invention. The drawings are as follows: Figure 1 shows a cathode having a cylinder grown according to the prior art; Figure 2 illustrates a hybrid thin film electrochemical device according to an exemplary embodiment of the present invention; and Figure 3 illustrates a composite lithium cobalt oxide (Fig. 3) LiCoO ₂ ) Scanning electron micrograph (SEM) of a cathode according to an exemplary embodiment of the invention, the cathode is deposited by slurry coating and coated with a lithium phosphorus oxynitride (LiPON) thin film electrolyte; An electrochemical cycle reaction of an electrochemical device using a composite LiCoO ₂ cathode and a LiPON thin film of FIG. 3 according to an exemplary embodiment of the present invention is shown; and FIG. 5 illustrates an electrophoretic deposition according to an embodiment of the present invention. Scanning electron micrograph of a 9 micron thick, fully crystalline LiCoO ₂ positive cathode film; Figure 6 shows the current discharge voltage performance of a thin film electrochemical device, the LiCoO ₂ positive cathode system of the electrochemical device The electrophoretic deposition of the embodiment of the invention is made; FIG. 7 is a diagram showing the relationship between the reversible discharge capacity of the thin film electrochemical device and the cycle number of the thin film electrochemical device. The LiCoO ₂ positive cathode system is fabricated by electrophoretic deposition of the embodiment of the present invention; and FIG. 8 is a scanning diagram of a 15 μm thick, fully crystallized LiCoO ₂ positive cathode film fabricated by inkjet according to an embodiment of the present invention. Electron micrograph; Fig. 9 is a view showing a hybrid thin film electrochemical device according to an exemplary embodiment of the present invention; Fig. 10 is a view showing a multilayer film for sealing an electrochemical device according to an exemplary embodiment of the present invention; An electrochemical device as shown in FIG. 2, comprising a regulating LiPON film and a multilayer thin film encapsulation layer; and FIG. 12 is a view showing an inverted thin-film battery configuration according to an exemplary embodiment of the present invention; The figure illustrates an embodiment of a converted thin film battery; and Figure 14 illustrates an embodiment of a cathode layer having surface embossing.

200. . . Substrate

210. . . cathode

220. . . Electrolyte layer

230. . . anode

240. . . Anode current collector

250. . . Package

260. . . Opening

Claims (171)

An electrochemical device comprising: a non-vapor deposited positive cathode having a thickness greater than about 4 microns and less than about 200 microns; a vapor deposited electrolyte having a thickness of less than about 10 microns; and a negative anode having a thickness less than about 30 microns. An electrochemical device comprising: a positive cathode having a thickness greater than about 0.5 microns and less than about 200 microns; a vapor deposited electrolyte having a thickness of less than about 10 microns; and a negative anode having a thickness less than about 30 microns; and wherein The positive cathode system is fabricated in a non-vapor phase deposition process. The electrochemical device according to claim 2, further comprising a substrate. The electrochemical device of claim 3, wherein the cathode is adjacent to the substrate. The electrochemical device of claim 1, further comprising a substrate, wherein the cathode is adjacent to the substrate. The electrochemical device of claim 3, further comprising the substrate having a thickness of up to about 50 microns. The electrochemical device of claim 3, further comprising the substrate having a thickness of up to about 10 microns. The electrochemical device of claim 3, wherein the substrate is selected from the group consisting of aluminum and aluminum alloy. The electrochemical device of claim 3, wherein the substrate comprises a current collector. The electrochemical device of claim 3, further comprising a barrier layer on the substrate. The electrochemical device of claim 10, wherein the barrier layer is used to prevent migration of electrons between the substrate and the anode or the cathode. The electrochemical device of claim 10, wherein the barrier layer is used to prevent migration of ions between the substrate and the anode or the cathode. The electrochemical device according to claim 2, further comprising a current collector. The electrochemical device of claim 2, wherein the cathode has a thickness greater than about 5 microns and less than about 100 microns. The electrochemical device of claim 2, wherein the cathode has a thickness greater than about 30 microns and less than about 80 microns. The electrochemical device of claim 2, wherein the vapor deposited electrolyte is a thin film electrolyte having a thickness of less than about 10 microns. The electrochemical device of claim 2, wherein the cathode is deposited by slurry coating of a cathode powder material, a binder, and a conductive reinforcement material. The electrochemical device of claim 2, wherein the cathode is deposited using a Meyer rod coating technique. An electrochemical device according to claim 2, wherein the cathode It was deposited using a direct roll coating technique. The electrochemical device of claim 2, wherein the cathode is deposited using a reverse roll coating technique. The electrochemical device of claim 2, wherein the cathode is deposited using a doctor blade technique. The electrochemical device of claim 2, wherein the cathode is deposited by spin coating. The electrochemical device of claim 2, wherein the cathode is deposited by electrophoretic deposition. The electrochemical device of claim 2, wherein the cathode is deposited by an ink-jetting process. The electrochemical device of claim 2, wherein the cathode system substantially absorbs one of the group consisting of an inert metal, an inert alloy, and a carbonaceous material. The electrochemical device of claim 2, wherein the cathode comprises lithium cobalt oxide (LiCoO ₂ ) or a derivative thereof. The electrochemical device according to claim 26, wherein the lithium cobalt oxide (LiCoO ₂ ) or a derivative thereof is doped with a group selected from the group consisting of elements of Groups 1 to 17 of the periodic table. The element in the middle. The electrochemical device according to claim 2, wherein the cathode comprises a material selected from the group consisting of lithium cobalt oxide (LiCoO ₂ ), lithium manganese oxide (LiMn ₂ O ₄ ), lithium manganese oxide (LiMnO ₂ ), lithium One of a group consisting of nickel oxide (LiNiO ₂ ), lithium iron phosphate (LiFePO ₄ ), lithium vanadium oxide (LiVO ₂ ), and any mixture thereof. The electrochemical device of claim 2, wherein the cathode system is formed in a structure having a plurality of vertical structures. The electrochemical device of claim 29, wherein the plurality of vertical structures are formed mechanically. The electrochemical device of claim 29, wherein the vertical structures have a height that is less than a maximum thickness of one of the cathode materials. The electrochemical device of claim 29, wherein the plurality of vertical structures are configured to reduce an average distance between any volume element within the cathode and a closest volume element of the electrolyte layer, the electrolyte layer The cathode is opposite. The electrochemical device of claim 2, wherein the cathode is a composite cathode further comprising at least a carbonaceous material. The electrochemical device of claim 33, wherein the composite cathode has a shape comprising one of a plurality of vertical structures. The electrochemical device of claim 34, wherein the plurality of vertical structures are configured to reduce a distance between any volume element within the cathode and a closest volume element of the electrolyte layer, the electrolyte layer The cathode is opposite. The electrochemical device of claim 2, wherein the electrolyte comprises lithium phosphorus oxynitride (LiPON). The electrochemical device of claim 2, wherein the anode is selected from the group consisting of lithium, a lithium alloy, a metal that forms a solid solution or a chemical compound with lithium, and any lithium ion compound that can serve as a negative anode. The electrochemical device of claim 2, wherein the vapor deposited electrolyte is deposited by a vacuum vapor deposition method. The electrochemical device according to claim 2, further comprising a package formed by a packaging process selected from the group consisting of a vacuum vapor-growth film package, a pressure-heat laminate of a protective polymer composite, The pressure-sensitive induction is applied to the pressure-heated laminate of the surface-coated metal foil, and the metal sheathing method. The electrochemical device according to claim 2, further comprising a package grown in a vacuum vapor phase process. The electrochemical device of claim 40, wherein the package consists of a multilayer stack of inorganic compounds and metals. The electrochemical device of claim 40, wherein the package is thinner than about 10 microns. The electrochemical device of claim 40, wherein the package is separated from the negative anode by a built-in conditioning layer. An electrochemical device according to claim 43, wherein the adjustment The layer layer contains lithium phosphorus oxynitride (LiPON). The electrochemical device of claim 43, wherein the conditioning layer is composed of lithium phosphorus oxynitride (LiPON). The electrochemical device according to claim 2, further comprising an anode current collector. The electrochemical device of claim 46, wherein a moisture barrier layer is between the anode current collector and the electrolyte. The electrochemical device according to claim 47, wherein the moisture barrier layer comprises a material having a moisture barrier property selected from the group consisting of a metal, a semi-metal, an alloy, and a boride. (borides), carbides, diamonds, diamond-like carbons, silicides, nitrides, phosphides, oxides, fluorides, chlorides, bromides, and iodine Compound. The electrochemical device of claim 47, wherein the moisture barrier layer comprises a material having a moisture barrier property selected from the group consisting of a boride, a carbide, a telluride, a nitride, and a phosphide. Any of oxides, fluorides, chlorides, bromides, and iodides Multi-component compounds. The electrochemical device according to claim 47, wherein the moisture barrier layer comprises a material having a moisture barrier property selected from the group consisting of a high temperature stable organic polymer and a high temperature stable polyoxyalkylene (silicone). ). An electrochemical device comprising: a non-vapor deposited cathode; an anode; and a vapor deposited electrolyte having a thickness of less than about 10 microns. The electrochemical device of claim 51, wherein the cathode has a thickness greater than about 0.5 microns and less than about 200 microns. The electrochemical device of claim 51, wherein the cathode has a thickness greater than about 10 microns and less than about 100 microns. The electrochemical device of claim 51, wherein the cathode has a thickness greater than about 30 microns and less than about 80 microns. An electrochemical device according to claim 51, wherein the anode The thickness of the pole is less than about 30 microns. The electrochemical device according to claim 51, further comprising a substrate. The electrochemical device of claim 56, wherein the substrate has a thickness of up to about 50 microns. The electrochemical device of claim 56, wherein the substrate has a thickness of up to about 10 microns. The electrochemical device of claim 56, wherein the substrate is selected from the group consisting of aluminum and aluminum alloy. The electrochemical device of claim 51, wherein the vapor deposited electrolyte is one of a thin film electrolyte having a thickness of less than about 10 microns. The electrochemical device of claim 51, wherein the cathode is deposited by slurry coating of a cathode powder material, a binder, a carbonaceous material, and a carbon-based electrical reinforcement. An electrochemical device according to claim 51, wherein the yin The poles were deposited using a Meyer rod coating technique. The electrochemical device of claim 51, wherein the cathode is deposited using a direct roll coating technique. The electrochemical device of claim 51, wherein the cathode is deposited using a reverse roll coating technique. The electrochemical device of claim 51, wherein the cathode is deposited using a doctor blade technique. The electrochemical device of claim 51, wherein the cathode is deposited by spin coating. The electrochemical device of claim 51, wherein the cathode is deposited by electrophoretic deposition. The electrochemical device of claim 51, wherein the cathode is deposited by an ink-ietting process. The electrochemical device of claim 51, wherein the cathode system substantially absorbs one material selected from the group consisting of inert metals, inert alloys, and carbonaceous materials. The electrochemical device of claim 51, wherein the cathode comprises lithium cobalt oxide (LiCoO ₂ ). The electrochemical device according to claim 51, wherein the cathode comprises a substance selected from the group consisting of lithium cobalt oxide (LiCoO ₂ ), lithium manganese oxide (LiMn ₂ O ₄ ), lithium manganese oxide (LiMnO ₂ ), lithium A group consisting of nickel oxide (LiNiO ₂ ), lithium iron phosphate (LiFePO ₄ ), lithium vanadium oxide (LiVO ₂ ), and any mixture thereof. The electrochemical device of claim 51, wherein the cathode is mechanically formed in a structure having a plurality of smaller vertical structures. The electrochemical device of claim 72, wherein the plurality of smaller vertical structures reduce an average distance between any volume element in the cathode and a nearest volume element of the electrolyte layer, the electrolyte layer The cathode is opposite. An electrochemical device according to claim 51, wherein the yin The pole is a composite cathode which further comprises at least a carbonaceous material. The electrochemical device of claim 74, wherein the composite cathode comprises a plurality of vertical structures. The electrochemical device of claim 75, wherein the plurality of vertical structures reduces an average distance between any volume element in the cathode and a nearest volume element of the electrolyte layer, the electrolyte layer being opposite the cathode . The electrochemical device of claim 51, wherein the electrolyte comprises lithium phosphorus oxynitride (LiPON). The electrochemical device according to claim 51, wherein the anode is selected from the group consisting of lithium, a lithium alloy, a metal which can form a solid solution or a chemical compound with lithium, and any lithium ion compound which can be regarded as a negative anode. Group of. The electrochemical device of claim 51, wherein the vapor deposited electrolyte is deposited by a vacuum vapor deposition method. An electrochemical device according to claim 51, wherein the electricity The chemical device is packaged in a packaging process selected from the group consisting of a vacuum vapor-growth film package, a pressure-heat laminate of a protective polymer composite, and a pressure-heat laminate of a foil coated with a heat-sensitive induction surface. And metal sheathing. The electrochemical device of claim 51, wherein the electrochemical device is packaged in a package that is grown using a vacuum vapor phase process. The electrochemical device of claim 81, wherein the package consists of a multilayer stack of inorganic compounds and metals. The electrochemical device of claim 81, wherein the package is thinner than about 10 microns. The electrochemical device of claim 81, wherein the package is separated from the negative anode by a built-in conditioning layer. The electrochemical device of claim 84, wherein the conditioning layer comprises lithium phosphorus oxynitride (LiPON). An electrochemical device according to claim 84, wherein the adjustment The layer is composed of lithium phosphorus oxynitride (LiPON). The electrochemical device according to claim 51, further comprising a cathode current collector. The electrochemical device according to claim 51, further comprising an anode current collector. The electrochemical device of claim 88, wherein the anode current collector is at least partially covered by a moisture barrier layer. The electrochemical device of claim 89, wherein the moisture barrier layer comprises zirconium oxide (ZrO ₂ ). A method of fabricating an electrochemical device comprising: depositing a positive cathode having a thickness greater than about 0.5 microns and less than about 200 microns; depositing an electrolyte having a thickness of less than about 10 microns by a vapor deposition process; depositing a negative anode, The thickness is less than about 30 microns; and the positive cathode is deposited in a non-vapor deposition process. The method of claim 91, wherein the cathode system sinks Accumulated on a substrate. The method of claim 92, further comprising depositing the cathode onto the substrate, the substrate having a thickness of equal to or less than about 50 microns. The method of claim 92, further comprising depositing the cathode onto the substrate, the substrate having a thickness equal to or less than about 10 microns. The method of claim 92, further comprising depositing the cathode on the substrate, and the substrate is selected from the group consisting of aluminum and aluminum alloy. The method of claim 92, wherein the substrate comprises a current collector. The method of claim 91, further comprising depositing a barrier layer. The method of claim 91, wherein the cathode has a thickness greater than about 5 microns and less than about 100 microns. The method of claim 91, wherein the cathode has a thickness greater than about 30 microns and less than about 80 microns. The method of claim 91, wherein the electrolyte is one of a thin film electrolyte having a thickness of less than about 10 microns. The method of claim 91, wherein the step of depositing a cathode comprises slurry coating of a cathode powder material, a binder, and a conductive reinforcement material. The method of claim 91, wherein the step of depositing a cathode comprises a Meyer bar coating technique. The method of claim 91, wherein the step of depositing a cathode comprises a direct roller coating technique. The method of claim 91, wherein the step of depositing a cathode comprises an inverse roller coating technique. The method of claim 91, wherein the step of depositing a cathode comprises a doctor blade application technique. The method of claim 91, wherein the step of depositing a cathode comprises spin coating. The method of claim 91, wherein the step of depositing a cathode comprises electrophoretic deposition. The method of claim 91, wherein the step of depositing a cathode comprises ink jetting. The method of claim 91, wherein the step of depositing a cathode comprises (1) coating a material selected from the group consisting of an inert metal and an alloy, coating when the cathode is completed or not completed. The cathode; and (2) applying a sufficient amount of heat to cause the cathode to substantially absorb the material. The method of claim 91, wherein the cathode comprises lithium cobalt oxide (LiCoO ₂ ) and a doped derivative thereof, wherein the doping element is selected from elements of Groups 1 to 17 of the periodic table. The elements in the group that is composed. The method of claim 91, wherein the cathode comprises an oxide selected from the group consisting of lithium cobalt oxide (LiCoO ₂ ), lithium manganese oxide (LiMn ₂ O ₄ ), lithium manganese oxide (LiMnO ₂ ), and lithium nickel. One of a group consisting of LiNiO ₂ , lithium iron phosphate (LiFePO ₄ ), lithium vanadium oxide (LiVO ₂ ), and any mixture thereof. The method of claim 91, wherein the cathode is mechanically formed in a structure having a plurality of vertical structures. The method of claim 112, wherein the plurality of vertical structures reduces an average distance between any volume element within the cathode and a nearest volume element of the electrolyte layer, the electrolyte layer being opposite the cathode. The method of claim 112, wherein one of the plurality of vertical structures is less than a maximum thickness of the cathode. The method of claim 91, wherein the cathode system is formed as a composite cathode further comprising at least a carbonaceous material. The method of claim 115, wherein the composite cathode system is fabricated in a structure having a plurality of vertical structures. The method of claim 116, wherein the plurality of vertical structures reduces an average distance between any volume element within the cathode and a nearest volume element of the electrolyte layer, the electrolyte layer being opposite the cathode. The method of claim 91, wherein the electrolyte comprises lithium phosphorus oxynitride (LiPON). The method of claim 91, wherein the anode comprises a group selected from the group consisting of lithium, a lithium alloy, a metal which can form a solid solution or a chemical compound with lithium, and any lithium ion compound which can be regarded as a negative anode. One of the materials in the group. The method of claim 91, wherein the vapor deposition process is a vacuum vapor deposition process. The method of claim 91, further comprising encapsulating the electrochemical device by a packaging process selected from the group consisting of a vacuum vapor-growth film package, a pressure-heat laminate of a protective polymer composite, and a heat treatment. The pressure-heat laminate of the metal foil coated on the surface is inductively bonded, as well as the metal sheathing method. The method of claim 91, wherein the electrochemical device is packaged in a package by a vacuum vapor phase process. The method of claim 122, further comprising depositing the package as a multilayer stack of an inorganic compound and a metal. The method of claim 122, further comprising depositing the package thinner than about 10 microns. The method of claim 122, further comprising separating the package from the negative anode with a built-in conditioning layer. The method of claim 125, further comprising depositing the conditioning layer as lithium phosphorus oxynitride (LiPON). The method of claim 91, further comprising depositing a cathode current collector. The method of claim 91, further comprising depositing an anode current collector. The method of claim 128, further comprising depositing a moisture barrier layer between the anode current collector and the electrolyte. The method of claim 129, wherein the moisture barrier layer comprises a material having a moisture barrier property selected from the group consisting of a metal, a semi-metal, an alloy, and a boride (borides). ), carbides, diamonds, diamond-like carbons, silicides, nitrides, phosphides, A group of oxides, fluorides, chlorides, bromides, and iodides. The method of claim 129, wherein the moisture barrier layer comprises a material having a moisture barrier property selected from the group consisting of a boride, a carbide, a telluride, a nitride, a phosphide, and an oxidation. A group consisting of any of a variety of compounds consisting of fluoride, chloride, bromide, and iodide. The method of claim 129, wherein the moisture barrier layer comprises a material having a moisture barrier property selected from the group consisting of a high temperature stable organic polymer and a high temperature stable polysiloxane. Group of. A method of fabricating an electrochemical device comprising: depositing a cathode using a non-vapor deposition process; depositing an electrolyte having a thickness of less than about 10 microns by a vapor deposition process; and depositing an anode. The method of claim 133, wherein the cathode has a thickness greater than about 0.5 microns and less than about 200 microns. The method of claim 133, wherein the cathode has a thickness greater than about 10 microns and less than about 100 microns. The method of claim 133, wherein the cathode has a thickness greater than about 30 microns and less than about 80 microns. The method of claim 133, wherein the anode has a thickness of less than about 30 microns. The method of claim 133, further comprising providing a substrate. The method of claim 138, further comprising the substrate having a thickness of up to about 50 microns. The method of claim 138, further comprising the substrate having a thickness of up to about 10 microns. The method of claim 138, wherein the substrate is selected from the group consisting of aluminum and aluminum alloy. The method of claim 133, wherein the electrolysis A thin film electrolyte having a thickness of less than about 10 microns. The method of claim 133, wherein the non-vapor deposition process comprises coating the cathode powder material, the binder, and the conductive reinforcement material with a slurry. The method of claim 133, wherein the non-vapor deposition process comprises a Meyer bar coating technique. The method of claim 133, wherein the non-vapor deposition process comprises a direct roller coating technique. The method of claim 133, wherein the non-vapor deposition process comprises a reverse roller coating technique. The method of claim 133, wherein the non-vapor deposition process comprises a doctor blade application technique. The method of claim 133, wherein the non-vapor deposition process comprises spin coating. The method of claim 133, wherein the non-vapor deposition process comprises electrophoretic deposition. The method of claim 133, wherein the non-vapor deposition process comprises inkjet. The method of claim 133, wherein the step of depositing a cathode comprises (1) coating the material in a group selected from the group consisting of an inert metal and an alloy, when the cathode is completed or not completed. The cathode; (2) applying a sufficient amount of heat to cause the cathode to substantially absorb the material. The method of claim 133, wherein the cathode comprises lithium cobalt oxide (LiCoO ₂ ). The electrochemical device according to claim 133, wherein the cathode comprises a material selected from the group consisting of lithium cobalt oxide (LiCoO ₂ ), lithium manganese oxide (LiMn ₂ O ₄ ), lithium manganese oxide (LiMnO ₂ ), lithium One of a group consisting of nickel oxide (LiNiO ₂ ), lithium iron phosphate (LiFePO ₄ ), lithium vanadium oxide (LiVO ₂ ), and any mixture thereof. The method of claim 133, further comprising mechanically forming the cathode in a structure having a plurality of smaller vertical structures. The method of claim 154, wherein the plurality of smaller vertical structures reduce an average distance between any volume element in the cathode and a nearest volume element of the electrolyte layer, the electrolyte layer being opposite the cathode . The method of claim 133, wherein the cathode system is formed as a composite cathode, which further comprises at least a carbonaceous material. The method of claim 156, wherein the composite cathode system is fabricated in a structure having a plurality of smaller vertical structures. The method of claim 157, wherein the plurality of vertical structures reduces an average distance between any volume element within the cathode and a nearest volume element of the electrolyte layer, the electrolyte layer being opposite the cathode. The method of claim 133, wherein the electrolyte comprises lithium phosphorus oxynitride (LiPON). The method of claim 133, wherein the anode is selected from the group consisting of lithium, a lithium alloy, a metal which can form a solid solution or a chemical compound with lithium, and any lithium ion compound which can be regarded as a negative anode. group. The method of claim 133, wherein the vapor deposition process is a vacuum vapor deposition process. The method of claim 133, further comprising encapsulating the electrochemical device by a packaging process selected from the group consisting of a vacuum vapor grown film package, a pressure-heat laminate of a protective polymer composite, and a heat treatment. A group of pressure-heat laminates and metal sheathing methods for inductively conforming surface-coated foils. The method of claim 133, further comprising encapsulating the electrochemical device in a package by a vacuum vapor phase process. The method of claim 163, further comprising fabricating the package by a multilayer stack of an inorganic compound and a metal. The method of claim 163, wherein the package is deposited to be thinner than 10 microns. The method of claim 163, further comprising separating the package from the negative anode by a built-in conditioning layer. The method of claim 166, wherein the adjustment The layer is composed of lithium phosphorus oxynitride (LiPON). The method of claim 133, further comprising depositing a cathode current collector. The method of claim 133, further comprising depositing an anode current collector on the top end of the thin electrolyte layer. The method of claim 169, further comprising depositing a moisture barrier layer between the thin electrolyte layer and the anode current collector. The method of claim 170, wherein the moisture barrier layer comprises zirconia (ZrO ₂ ).