Patent Grant
9077000
Embodiments of the present invention relate to thin film batteries, such as solid state lithium batteries, and their fabrication and packaging.
Thin film batteries are used in applications that require a small battery with a high energy density such as, for example, portable electronics, medical devices and space systems. A solid state battery is a thin film battery composed of solid materials and which is generally absent liquid electrolytes. A thin film, sold state battery comprises a support having one or more battery cells, each battery cell comprising a set of battery component films which cooperate to store electrical charge and generate a voltage. The battery component films include an electrolyte sandwiched between electrodes, and can include metal-containing films composed of elemental metal, metal oxide or other metal-containing compounds. For example, elemental metal films can be used as current collectors to receive or provide electrons, such as for example, cathode and anode current collectors. The cathode or electrolyte can be metal oxide or metal-containing compounds. Thin film batteries have thicknesses smaller than the thickness of conventional batteries with battery component films thicknesses of less than 1000 microns, or even less than 100 microns. The battery component films are often formed by processes such as physical and chemical vapor deposition (PVD or CVD), oxidation, nitridation, and electroplating processes. These batteries can either be used individually or stacked together to provide more power or energy.
In thin film battery fabrication processes, the battery component films can be exposed to heat during processing or heat treated to anneal, re-crystallize, or reduce lattice defects. For example, elemental metal films are heat treated to reduce lattice defects and provide better conductivity. Metal oxide films are sometimes heated in air to anneal and/or obtain better crystalline properties. As an example, a cathode comprising a metal oxide electrode, such as a lithium cobalt oxide, provides better electrical properties when annealed in oxygen-containing environment at temperatures ranging from 300 to 700° C. It is believed that the electrical characteristics of the annealed cathode are related to its oxygen content and crystallographic structure, and when annealed, the cathode can allow the battery capacity to reach as high as its theoretical value for a given thickness and area. Still further, the lithium oxide film can be deposited to form a thicker cathode by depositing an amorphous or microcrystalline film, or a stack of sequentially deposited thin films, and thereafter, crystallizing the amorphous film or stack of films by heating. Increasing the thickness of a lithium oxide cathode film increases the energy density of the battery by as the thicker cathode provides greater charge retention and faster charging and discharging, as for example, taught in commonly assigned U.S. Pat. No. 7,186,479, entitled “THIN FILM BATTERY AND METHOD OF MANUFACTURE” to Krasnov et al., which is incorporated by reference herein in its entirety.
However, such heating and heat treatment processes often occur after deposition of underlying battery component films, and as such, can result in thermal degradation or oxidation of underlying layers. For example, heat treatment of an overlying cathode of metal oxide can cause oxidation of any underlying metal layers. As an example, good electrical conductors such as aluminum and copper, partially oxidize when annealed in environments having low partial pressures of oxygen. Further, aluminum oxide, when formed, is a dielectric having a high electrical resistivity of 1×1014 square-cm, which renders even a thin layer of aluminum oxide undesirable for a battery cell. Similarly copper is also prone to oxidation at elevated temperatures and in oxygen containing environments.
Nonreactive noble metals, such as platinum or gold, have also been used in battery cells to prevent or reduce such thermal or oxidation degradation. For example, lithium batteries often use a cathode current collector composed of platinum underlying a metal oxide cathode which is heated in an oxygen-containing environment to anneal and/or crystallize the cathode material, as for example, described in commonly assigned U.S. Pat. No. 7,862,927, entitled “THIN FILM BATTERY AND MANUFACTURING METHOD” to Krasnov et al., which is incorporated by reference herein and in its entirety. Platinum avoids oxidation and remains in its electrically conductive elemental metal form without oxidizing even after being heated in an oxidizing environment.
However, cathode current collectors composed of noble materials, such as platinum or gold, can be costly and substantially increase the price of the battery. Still further, platinum can exhibit poor adhesion to certain battery supports. Also, the difference in thermal expansion coefficients between platinum and a battery support material can result in delamination of the deposited platinum film when heated. Thus an adhesive layer is often deposited on the battery support prior to deposition of the platinum layer to increase adhesion and reduce peeling-off. However, the additional deposition step required for forming the adhesion layer adds to fabrication costs and complexity.
For reasons including these and other deficiencies, and despite the development of various battery structures, and deposition and heat treatment processes for solid-state, thin film batteries, further improvements in such batteries and fabrication steps are continuously being sought.
A lithium battery comprises a battery support and a cathode current collector directly on and in contact with the battery support. The cathode current collector is composed of molybdenum and comprises a thickness of at least about 0.01 microns. A cathode is on the cathode current collector, an electrolyte on the cathode, and at least one of an anode or anode current collector on the electrolyte.
A lithium battery comprises a battery support and a cathode current collector directly on and in contact with the battery support. The cathode current collector is composed of nickel and comprises a thickness of at least about 0.01 microns. A cathode is on the cathode current collector, an electrolyte on the cathode, and at least one of an anode or anode current collector on the electrolyte.
A lithium battery comprises a battery support and a cathode current collector directly on and in contact with the battery support. The cathode current collector is composed of chromium and comprises a thickness of at least about 0.01 microns. A cathode is on the cathode current collector, an electrolyte on the cathode, and at least one of an anode or anode current collector on the electrolyte.
A lithium battery comprises a battery support and a cathode current collector directly on and in contact with the battery support. The cathode current collector is composed of tantalum and comprises a thickness of at least about 0.01 microns. A cathode is on the cathode current collector, an electrolyte on the cathode, and at least one of an anode or anode current collector on the electrolyte.
A lithium battery comprises a battery support and a cathode current collector directly on and in contact with the battery support. The cathode current collector is composed of titanium and comprises a thickness of at least about 0.01 microns. A cathode is on the cathode current collector, an electrolyte on the cathode, and at least one of an anode or anode current collector on the electrolyte.
A lithium battery comprises a battery support and a cathode current collector directly on and in contact with the battery support. The cathode current collector is composed of tungsten and comprises a thickness of at least about 0.01 microns. A cathode is on the cathode current collector, an electrolyte on the cathode, and at least one of an anode or anode current collector on the electrolyte.
A lithium battery manufacturing method comprises providing a support and forming a cathode current collector directly on the battery support and without an intervening adhesion layer. The cathode current collector is composed of molybdenum in a thickness of at least about 0.01 microns. A cathode is formed on the cathode current collector, an electrolyte on the cathode, and an anode on the electrolyte.
A battery fabrication method comprises forming on a support, at least a portion of a battery cell comprising a plurality of battery component films that include an underlying film with an overlying metal-containing film. A beam incident area on the metal-containing film is locally heated by directing onto the metal-containing film, an energy beam maintained at a fluence of at least about 800 J/cm2, wherein the metal-containing film is heated to a temperature that is at least 100° C. higher than the temperature attained by the underlying film.
In another version, the battery fabrication method comprises forming on a support, at least a portion of a battery cell comprising an elemental electrode and a metal oxide electrode. An energy beam is directed onto the metal oxide electrode, the energy beam being maintained at a sufficiently low power level to heat a beam incident area on the metal oxide electrode to a temperature of at least 400° C.
In still another version, the battery fabrication method comprises forming on a support, an elemental metal electrode and an overlying metal oxide electrode. An energy beam is selected such that the energy beam has at least one of the following characteristics: (i) a linear attenuation coefficient in the metal oxide electrode of at least about 5×10−4; and (ii) a reflection coefficient from the elemental metal electrode that is at least about 5%. The energy beam is directed onto the metal oxide electrode to heat treat the metal oxide electrode.
These features, aspects, and advantages of the present invention will become better understood with regard to the following description, appended claims, and accompanying drawings, which illustrate examples of the invention. However, it is to be understood that each of the features shown in the drawings can be used in the invention in general, not merely in the context of the particular drawings, and the invention includes any combination of these features, where:
Exemplary embodiments of a rechargeable, thin film, solid-state battery 20 having a protective casing 21 enclosing one or more solid-state battery cells 22 are shown in
Referring to
In the version shown in
In the version shown in
An exemplary embodiment of a method of fabricating a thin film battery 20 comprising a battery cell 22 on a support 24 will be illustrated with reference to
Referring to
After a clean top surface 26 is obtained, one or more battery component films 30, which can be metal-containing films or non-metallic films, are deposited on the surface 26 of the support 24 to form at least a portion of a battery cell 22 of a battery 20. An exemplary version of a completed battery 20 having one battery cell 22 is shown for example in
The type or number of battery component films 30, sequence of deposition of these films on the support 24, heat treatment of particular films 30 and not others, and number and location of the battery cells 22, can be changed as would be apparent to those of ordinary skill in the art. It should also be noted that before or after fabrication of any of the battery component layers 30, the battery cell 22, battery component layers 30, or support 24, can be shaped to form shaped features by removing portions of any of the battery component layers 30 or support 24. The shaping processes can be performed, for example, after deposition of the cathode 42 and electrolyte 44, to shape one or both of these films, such as by etching away the edge portions 77 or forming holes for the terminals 25a,b. Suitable shaping processes include pulsed laser, etching, another such processes, and these processes can be used to form the shapes of the battery component layers 30 shown in any of
Referring to
The first metal-containing film 32, in this version, is an elemental metal electrode 36 to collect electrons during battery charging and discharging processes. The elemental metal electrode 36 can be composed of a metal in its elemental form, such as for example, aluminum, platinum, silver or gold. The elemental metal electrode 36 can also comprise the same metal as the adhesion layer 34 which is deposited in a thickness that is sufficiently high to provide the desired electrical conductivity. A suitable thickness for the elemental metal electrode 36 is at least about 0.01 microns, or even from about 0.05 microns to about 2 microns.
An elemental metal electrode 36 that serves as a cathode current collector 38 collects electrons during charge and discharge process, and as such is selected to have an electrical conductivity of at least about 1×106 S/M. In addition, the cathode current collector 38 should be resistance to oxidation at elevated process temperatures; otherwise, a native oxide film formed on its surface during heat treatment can affect electrical conductance and reduce battery performance. More specifically, the internal resistance of the solid-state battery 20 increases due to the resultant thin surface oxide layer after annealing in oxygen-containing environments.
In one version, a cathode current collector 38 composed of platinum was used to provide both good oxidation resistance and electrical conductivity, and does not react with oxygen or water moisture at room temperatures. The platinum was deposited by DC magnetron sputtering of a sputtering target composed of platinum; a sputtering gas comprising argon at a gas pressure of from about 1 mTorr to about 50 mTorr, for example about 5 mTorr; a DC plasma formed from electrodes maintained at a power level of from about 10 to about 400 W, for example about 40 W; and a deposition time of from about 1 to about 20 minutes. An elemental metal electrode 36 of platinum can have a thickness of about 0.2 microns.
In another version, the elemental metal electrode 36 is composed of a non-conventional metal which was selected to serve as a cathode current collector 38. These materials all had a melting point that exceeds 1000° C. which provides enhanced resistance to oxidation when the cathode current collector 38 is heated in an oxygen-gas containing environment. The materials also were selected to have a high electronegativity under the Pauling scale of at least about 1.5, or even at least about 1.9, or even at least about 2, which all demonstrate good oxidation resistance. The materials were also selected to provide good adhesion to many support materials and lower thermal expansion than the noble metals. Any of these materials can be deposited by sputtering in sputtering chamber as shown in
In one example, a cathode current collector 38 composed of molybdenum (Mo) is deposited directly on a battery support 24. Molybdenum has found to provide good electrical conductivity, high oxidation resistance, and was also capable of adhering directly to a battery support 24 of mica without an intervening adhesion layer. The molybdenum layer was deposited using deposition conditions which included a deposition gas comprising argon at a flow rate of from about 1 sccm to about 30 sccm, a gas pressure of from about 1 mTorr to about 10 mTorr, a support temperature of from about 25° C. to about 150° C., and a DC plasma power level of from about 0.01 kW to about 1 kW. Good adhesion to the underlying mica support 24 was evidenced by visually observation, observing the film in an optical and scanning electron microscope, and applying an adhesion tape test. The molybdenum had a relatively low electrical resistivity of 53 nΩM to provide better conduction of the electrons. Molybdenum also has a high electronegativity using the Pauling scale of 2.19 which provides good oxidation resistance. In fact the deposited molybdenum layer was found not to exhibit bulk oxidation until heated to temperatures above 790° C. The deposited molybdenum layer was also found not to visibly react with oxygen or water vapor at room temperatures.
In yet another version, in which an adhesion layer 34 may not be needed, a cathode current collector 38 composed of nickel (Ni) is deposited on the support 24. The nickel layer can be deposited using deposition conditions such as, for example, a deposition gas comprising argon at a flow rate of from about 1 sccm to about 30 sccm, gas pressure of from about 1 mTorr to about 10 mTorr, a support temperature of from about 25° C. to about 150° C., and a DC plasma power level of from about 0.01 kW to about 1 kW. Good adhesion to the mica support can be evidenced by the adhesion tape test. Nickel also has good electrical properties including an electrical resistivity of 69 nΩM. The low resistivity provided better conduction of the electrons. Nickel also has a high electronegativity using the Pauling scale of 1.91 which provides good oxidation resistance and nickel does not exhibit bulk oxidation at room temperature. The deposited nickel layer was found not to visibly react with oxygen or water vapor at room temperature.
In still another version, the cathode current collector 38 is composed of tungsten (W). The tungsten layer can be deposited using deposition conditions such as a deposition gas comprising argon at a flow rate of from about 1 sccm to about 30 sccm, a gas pressure of from about 1 mTorr to about 10 mTorr, a support temperature of from about 25° C. to about 150° C., and a DC plasma power level of from about 0.01 kW to about 1 kW. Good adhesion to a mica support can be evidenced by an adhesion tape test. Tungsten also has good electrical properties including an electrical resistivity of 53 nΩM. The low resistivity provided better conduction of the electrons. Tungsten also has a high electronegativity using the Pauling scale of 2.36, which provides good oxidation resistance, and absence of bulk oxidation until heated to temperatures above 700° C. Tungsten also has a high melting point at 3695 K. A deposited tungsten layer was found not to visibly react with oxygen or water vapor at room temperature
In still another version, in which the adhesion layer 34 may not be needed, the cathode current collector 38 is composed of tantalum (Ta). The tantalum layer can be deposited using a PVD process in which a sputtering target of tantalum is sputtered using a sputtering gas comprising argon at a flow rate of from about 50 to about 250 sccm, a gas pressure of from about 3 mTorr to about 10 mTorr, a substrate temperature of less than 100° C., and a DC voltage plasma having a power level of from about 1 to about 10 KW. In addition, tantalum also had other good electrical properties including an electrical resistivity of which provided better 131 nΩM. Tantalum also has a high electronegativity using the Pauling scale of 1.5 which provides good oxidation resistance. Tantalum also has a high melting point at 3290 K.
In another version, in which the adhesion layer 34 may not be needed, the cathode current collector 38 is composed of titanium (Ti). The titanium layer can be deposited using a PVD process in which a sputtering target of titanium is sputtered using a sputtering gas comprising argon at a flow rate of from about 50 to about 250 sccm, a gas pressure of from about 3 mTorr to about 10 mTorr, a substrate temperature of less than 100° C., and a DC voltage plasma having a power level of from about 1 to about 10 KW. In addition, titanium also had other good electrical properties including an electrical resistivity of 420 nΩM, and a high electronegativity using the Pauling scale of 1.54 which provides good oxidation resistance.
In another version, in which the adhesion layer 34 may not be not needed, the cathode current collector 38 is composed of chromium (Cr). The chromium layer can be deposited using a PVD process in which a sputtering target of chromium is sputtered using a sputtering gas comprising argon at a flow rate of from about 50 to about 250 sccm, a gas pressure of from about 3 mTorr to about 10 mTorr, a substrate temperature of less than 100° C., and a DC voltage plasma having a power level of from about 1 to about 10 KW. Chromium also has other good electrical properties including an electrical resistivity of 125 nΩM and a high electronegativity using the Pauling scale of 1.66 which provides good oxidation resistance.
After deposition of the first metal-containing film 32, such the cathode current collector 38, a second metal-containing film 46, such as a metal oxide electrode 40, is formed to obtain a partially fabricated structure of a battery cell 22 as shown in
Suitable sputtering conditions for depositing the second metal-containing film 46 that is a metal oxide electrode 40, comprise selecting a sputtering target composed of the metal of the metal oxide to be deposited and mounting the target in a sputtering chamber such as the chamber shown in
In another method, a metal oxide electrode 40 is deposited by selecting a sputtering target composed of the desired metal oxide material to be deposited and mounting the target in the sputtering chamber; introducing a sputtering gas, such as for example argon, into a sputtering chamber at a flow rate of from about 50 to about 300 sccm; maintaining a sputtering gas pressure of from about 1 mTorr to about 10 Torr; and forming a plasma from the sputtering gas by charging electrodes in the sputtering chamber with an alternating current (AC) or radio-frequency (RF) plasma sputtering at a power level of from about 10 W to about 5 KW for from about 1 to 10 minutes. For example, a metal oxide electrode 40 composed of lithium cobalt oxide can be formed by alternating current (AC) or radio-frequency (RF) plasma sputtering at a frequency of from about 40 k Hz of a target comprising lithium and cobalt in a reactive gas environment, for example oxygen gas, introduced into the chamber at a flow rate of from about 10 to about 100 sccm and maintained a pressure of from about 1 mTorr to about 15 m Torr, or by other conventional methods.
In yet another version, a high efficiency cathode 42 is formed directly on the cathode current collector 38 without any intervening layers. A high efficiency cathode 42 Is one that is capable of reaching the theoretical value of the battery capacity for given thickness and area of the cathode 42. For example, the theoretical value of the battery capacity is about 1.2 mAh for a cathode 42 comprising lithium cobalt oxide in an area of about 2.9 cm2 and a thickness of about 6 micrometers. However, conventional cathodes 42 having the same dimensions and which are deposited without annealing typically only reach a battery capacity of 0.5 mAh at 0.1 mA discharge current. In contrast, a similarly sized, high efficiency cathode 42 fabricated according to the processes described herein can reach higher battery capacity of 1 mAh at 0.1 mA discharge current.
The higher efficiency cathode 42 can be obtained by conducting an annealing process after deposition of the cathode 42 to heat treat the deposited cathode material. The annealing process can be conducted directly in the sputtering chamber 100 or in a separate annealing chamber (not shown) having a heater to heat the battery support 24, cathode current collector 38 and overlying cathode 42. The annealed cathode efficiency is related to the annealing temperature with higher annealing temperatures generating better internal cathode microstructures, which in turn, provides a cathode with a higher efficiency. However, the higher annealing temperatures can also cause higher residual stress in the annealed battery cell 22 which can damage the battery cells 22 or partially oxidize the underlying cathode current collector 38.
In one version, after deposition of the cathode 42, an annealing step can be performed at temperatures of from about 300° C. to about 600° C., or even from about 300° C. to about 400° C. A thick cathode 42 having a thickness of at least about 10 microns can be deposited using the above-described sputtering conditions in a sputtering process conducted for at least about 300 minutes. Conversely, a thin cathode 42 having a thickness of less than about 5 microns can be deposited using the above-described sputtering conditions in a sputtering process conducted for less about 60 minutes.
It was also discovered that, during annealing, an oxygen-containing environment can provide a higher efficiency cathode as the oxygen content in the crystallographic structure of the cathode is related to higher battery charge capacity. For example, a high efficiency cathode 42 formed by annealing a cathode 42 overlying a cathode current collector 38 composed of platinum, at higher temperatures in oxygen containing environments. However, when the cathode 42 is annealed in oxygen-containing environment and the cathode current collector 38 underlying the cathode 42 is made of a metal other than platinum, a thin interfacial oxide layer forms at the annealing conditions even though bulk oxidation does not occur at these temperatures. The thin oxide layer, which is formed at the interface of the cathode 42 and the cathode current collector 38, undesirably increases the internal resistance of the battery cell 42. As result, the charge capacity of the battery cell 22 decreases as the thin interfacial oxide layer interferes with the migration of battery-charge-holding metal species through the oxide layer.
For the foregoing reasons, when the cathode current collector 38 is made from one of the selected materials as described above namely, molybdenum, nickel, tungsten, titanium, chromium, and tungsten—it was found that annealing the overlying cathode 42 in a non-oxygen-containing environment (which was substantially absent oxygen-containing species such as oxygen) substantially improved battery performance. In one version, the annealing process is performed in an inert gas environment, such as argon, helium or neon. In this version, the partially built battery cell 22 having a cathode current collector 38 composed of molybdenum, nickel, etc., is placed in a sputtering or annealing chamber and heated while inert gas is flowed into the chamber. For example, the volumetric flow rate of the selected inert gases can be from about 10 to about 10,000 sccm.
The annealing temperature set in the sputtering or annealing chamber depends upon the cathode current collector material being used. For example, when the cathode current collector 38 is made from molybdenum or tungsten, the cathode annealing step can be carried out at temperatures lower than 400° C., or even from about 300 to about 400° C., and in an inert gas environment comprising argon, to inhibit the formation of surface oxide which deteriorates the conductivity of a battery cell 22. As another example, when the cathode current collector 38 is made from nickel or titanium, the cathode annealing step can be carried out at temperatures lower than 400° C., or even from about 300 to about 350° C., and in an inert gas environment comprising argon, to inhibit the formation of surface oxide which deteriorates the conductivity of a battery cell 22.
In yet another version, the efficiency of the cathode 42 is further increased by depositing the cathode 42 using a sputtering plasma which is generated by applying a high power level current to a magnetron cathode 72 in a sputtering chamber 100 (as shown in
After deposition of one or more battery component films 30, an overlying battery component film 30 is heat treated by annealing in a tube oven or locally heat treated by directing an energy beam 80 onto a beam incident area 84 on a top surface 58 of the battery component film 30, as illustrated in
The energy beam 80 locally heats a beam incident area 84 on the overlying second metal-containing film 46 (or cathode 42) without excessively heating the underlying first metal-containing film 32 (or cathode current collector 38). The fluence of the energy beam 80 is the radiation flux integrated over time, and is a measure of the energy delivered per unit area in units of J/m2. For example, for an energy beam 80 of electromagnetic radiation, such as a pulsed laser beam, which has a pulse peak power, pulse duration, and a beam incident area 84 comprising a focal spot area, the fluence can be calculated as follows:
Fluence(J/m2)=laser pulse energy(J)/focal spot area;
where the laser pulse energy (J)=peak power (W)/pulse duration (s).
For example, a suitable fluence for an energy beam 80 to heat the cathode 42 to a temperature which is at least 100° C. higher than the temperature attained by the cathode current collector 38 is at least about 10 J/cm2, or even at least about 200 J/cm2, or even from about 50 to about 100 J/cm2. These levels of fluence were found to heat the cathode 42 to a temperature of at least 400° C., or even a temperature of from about 400 to about 700° C., while the peak temperature simultaneously attained by the cathode current collector 38 during the local heating process is maintained at less than 300° C. In one version, the underlying first metal-containing film 32 is heated to temperatures of less than 300° C. to avoid excessive heating of the underlying film to heat treat the metal oxide electrode 40 substantially without thermally degrading or oxidizing the underlying elemental metal electrode 36. The fluence of the energy beam 80 is selected by setting a power level and scanning speed of the energy beam 80, as described below.
In one version, the energy beam 80 is selected to have heating properties that selectively heat the upper or overlying battery component film 30 without excessively heating the underlying battery component film 30. For example, the energy beam 80 can be selected to have a linear attenuation coefficient in the overlying battery component film 30, which can be a metal-containing film such as the metal oxide electrode 40, of at least about 5×10−4. The measured intensity I of an energy beam 80 transmitted through a battery component film 30 having a thickness x is related to the incident intensity I0 according to the inverse exponential power law that is usually referred to as Beer-Lambert law I=I0e−αx where x denotes the path length of the energy beam 80 through the film thickness. The linear attenuation coefficient, α, describes the extent to which the intensity of the energy beam 80 is reduced as it passes through the thickness of the overlying battery component film 30, or in this case, the second metal-containing film 46. By selecting an energy beam 80 which has the desired linear attenuation coefficient in an overlying battery component film 30, the amount of energy transferred to the underlying battery component film 30, such as the first metal-containing film 32, is reduced to less than about 10% or even less than about 5%. This prevents heat build up in the underlying film, and consequently, allows the underlying film to remain at lower temperatures.
In still another version, the energy beam 80 is selected to have a Half Value Layer (also half-value thickness) in the overlying battery component film 30 of at least about 1 microns. The Half Value Layer is the thickness of the battery component film 30, or in this case the second metal-containing film 46, which reduces the intensity of radiation entering the material by half. By selecting an energy beam 80 which has a particular Half Value Layer in the overlying battery component film 30, the amount of energy transferred to the underlying battery component film 30, which is also the first metal-containing film 32, is reduced to less than 50% or even less than 10%. This further prevents heat build up in the underlying film, and consequently, allows the underlying film to remain at lower temperatures while the overlying film is being heated.
In yet another version, the energy beam 80 comprises an electromagnetic beam, and is selected to have a reflection coefficient from the underlying film of at least about 5×10−4. The reflection coefficient is the ratio of the amplitude of the reflected wave from the underlying battery component film 30 to the amplitude of the incident wave that reaches the interface at the underlying battery component film 30 after traveling through the overlying battery component film 30. For example, when the underlying battery component film is the first metal-containing film 32 and the overlying battery component film 30 is the second metal-containing film 46, then the reflection coefficient is the ratio of the amplitude of the reflected wave from the underlying metal-containing film to the amplitude of the incident wave that reaches the interface of the first and second metal-containing films 32, 46. The larger the reflection coefficient, the less radiation incident on the underlying film is absorbed by the underlying film to increase its temperature. Thus, it is desirable for the underlying film to have a high reflection coefficient to reduce the temperature of this film during heat treatment, and consequently, reduce thermal degradation of the film.
The energy beam 80 also has a beam width 82 selected in size to cover and heat a beam incident area 84 on the battery component film 30, which can be the second metal-containing film 46 or metal oxide electrode 40, without excessively heating adjacent regions 86 or adjacent battery component films. In one example, the energy beam 80 has a beam width 82 that is sized less than about 2000 microns, for example, from about 100 to about 1000 microns. In contrast to conventional heat treatment techniques in which the entire partially fabricated battery cell 22 is heated up in an oven, the localized heat treatment of a battery component film 30 with an energy beam 80 having a controlled beam width size and power level allows heating of a single overlying battery component film 30 without excessively heating adjacent regions 86 or underlying battery component films 30.
The localized heat treatment process can have diverse applications depending on the nature of the battery component film 30. For example, it is believed that the heat treatment process using the localized energy of the energy beam 80 anneals a battery component film 30 to reduce stresses, reduce the number of lattice defects, and/or even alter the crystallographic properties of the film. For example, a suitable heat treatment can induce changes in both crystal size and crystallographic preferred orientation in metal-containing films. As an example, when a metal-containing film comprising a metal oxide electrode 40 is heat treated, the heat treatment increases the electrical conductivity of the metal-containing oxide film by altering its crystallographic properties to improve the electrical properties of the electrode 40. It is particularly desirable to heat treat a metal oxide electrode 40 that serves as a cathode 42, when the cathode 42 is a thick layer deposited in a sequence of deposition process steps to build up the thickness of the cathode 42. The thicker cathode 42 has a thickness of at least about 4 microns, and serves to provide better cathode efficiency.
Still further, when a selected energy beam 80 such as a CO2 laser beam is scanned across a cathode 42 at room temperature, the metal oxide material of the metal oxide electrode 40 has a higher absorbance rate of the CO2 laser beam than the underlying elemental metal material of the elemental metal electrode 38. While the metal oxide cathode absorbs more than 90% of the incident energy of the CO2 laser beam to heat up this layer, the underlying elemental metal layer nearly totally reflects the CO2 laser beam without substantially changing temperature. The localized temperature increase in the overlying metal oxide layer transfers some heat to the underlying elemental oxide layer, but the underlying metal layer is isolated from the ambient environment by the overlying metal oxide layer and thus protected from oxidation for small temperature rises, and the pulse of transferred heat is localized and short, further limiting heat build-up. The localized heating of the overlying metal oxide layer 40 thus does not substantially increase the temperature of the underlying layer nor cause oxidation of the underlying metal.
As another example, the heat treatment process using localized energy of the energy beam 80 can also be used to heat treat a metal-containing film such as an elemental metal electrode 36, for example the cathode current collector 38 or anode current collector 50. Similarly, the anode current collector 50 can also be heat treated after deposition of this film. For example, a cathode or anode current collector 38, 50 comprising platinum can be heat treated to improve its crystalline properties. As one example, the energy beam 80 can be maintained at a sufficiently low power level to heat the beam incident area 84 on the elemental metal electrode 36 to a temperature of at least about 200° C., or even a temperature of at least about 400° C. Other battery component films 30 can also be heat treated using the energy beam 80, as would be apparent to those of ordinary skill in the art, and heat treatment of these films are included in the scope of the present application.
In the localized heat treatment process, an energy beam source 88 generates an energy beam 80 that is raster scanned across an entire top surface 58 of the battery component film 30 in a pattern that matches the shape and profile of the battery component film 30. In the example shown, the energy beam 80 is shown as being scanned across a battery component film 30 comprising a metal-containing film that is a metal oxide electrode 40, such as a cathode 42. However, the energy beam 80 can be scanned or otherwise moved across any of the battery component films 30 described herein, especially metal-containing films which can improve in electrical properties with heat treatment, or other battery component films 30 as would be apparent to those of ordinary skill in the art, using the same apparatus and methods of operation.
During scanning, the energy beam 80 can be manually operated or controlled by a controller 90 which controls the power applied to the energy beam source 88 and the motion of a movable stage 92 capable of moving the battery 20 during localized heating by the energy beam 80. The movable stage 92 can be a table that can be moved in the x and y directions by a stage motor 94 controlled by the controller 90. The movable stage 92 and controller 90 can include interpolative program code to enable movement of the table in the x-y plane using velocity or even acceleration vectors. In one embodiment, the movable stage 92 can be set to provide different vectorial velocities, for example from about 0.1 to about 400 mm/s, or even from 2 mm/sec to about 10 mm/sec. In another embodiment, the vectorial acceleration of the stage can be set with levels ranging from about 0.5 to about 50 mm/sec2, for example, at 0.8, 4, 20, and 40 mm/sec2. In one version, the movable stage 92 is capable of being positioned to an accuracy of greater than about 12 microns. A low power laser (not shown) can also be used to indicate the position of the energy beam 80 on the battery 20, such as for example, a He—Ne laser. The heating and scanning process can be carried out by either moving the energy beam or sample stage. The energy beam localized heating process can be conducted in a chamber, such as a dry box or even a clean room or dry room.
In still another process version, while a battery component film 30 such as a metal-containing film, for example a metal oxide electrode 40, is locally heated by the energy beam 80, a gaseous environment is maintained about the battery component film 30 to promote heat treatment. For example, an oxygen-containing gas can be maintained about a metal-containing film, such as a metal oxide electrode 40, for example the cathode 42, during heat treatment of this film. The oxygen-containing gas assists in reducing any lattice or other defects present in the as-deposited metal oxide electrode 40 or cathode 42. For example, the oxygen-containing gas can result in the film having a post heat treatment stochiometric composition that is closer to ideal by causing oxygen diffusion into the metal oxide electrode 40. Still further, the oxygen-containing gas can also increase the oxygen content in the annealed crystallographic structure of the metal oxide electrode 40 which improves the electrical characteristics of the electrode. However optimal annealing temperatures of from about 400 to about 750° C. can cause a thin oxide layer to form on metals other than noble metals at the annealing conditions, and bulk oxidation at higher temperatures. Thus annealing the metal oxide electrode 40 can increase the internal resistance of the battery cell 22 due to formation of a thin oxide layer in the oxygen-containing ambient atmosphere. The localized heating using the energy beam 80 avoids or entirely eliminates oxidation of the underlying layer.
A suitable oxygen-containing gas comprises oxygen, air, or other oxygen-containing gases. In one version, a suitable flow rate of the oxygen-containing gas, such as air or oxygen is introduced into a chamber, while the energy beam 80 is directed onto the battery component film 30, such as the metal-containing film which is a metal oxide electrode 40. For example, an oxygen-containing gas comprising oxygen can be introduced into the chamber (not shown) at a suitable flow rate. In still another version, a gas nozzle 93 is used to blow a gas stream 95 of an oxygen-containing gas onto the localized heating area 84 of the metal oxide electrode 40 during heat treatment, as for example, shown in
In one version, the energy beam 80 comprises a laser beam 101 generated by an energy beam source 88 that is a laser beam source 103. The laser beam source 103 is selected to generate the laser beam 101 at a sufficiently high power level to heat up the battery component film 30 when incident thereon without damaging underlying films 30. A suitable laser beam source 103 can generate a laser beam 101 having a wavelength in the ultra-violet (UV), visible, infrared (IR) or partial IR ranges, such as a range of from about 0.2 to about 50 microns. The laser beam source 103 can provide a laser beam 101 that is continuous or pulsed. In the continuous beam version, the laser beam source 103 generates a continuous laser output having a steady state equilibrium. An exemplary laser beam source 103 comprises a carbon dioxide laser. An exemplary embodiment of a carbon dioxide laser provides a laser beam 101 having a wavelength of from about from about 1 to about 100 microns, or even from about 10 microns to about 11 microns. A suitable carbon dioxide laser comprises a CB0805-30 available from Han's laser, Newberg, Oreg. 97132, USA. A continuous laser beam can also be generated by an ultraviolet laser providing a laser beam 101 having a wavelength of from about 100 to about 400 nm. An exemplary ultraviolet laser comprises a Hawk-II available from Quantronix, East Setauket, N.Y.
The laser beam source 103 can also generate a laser beam 101 that is a pulsed beam. In this version, the laser beam source 103 generates a laser beam 101 comprising pulsed laser bursts which have an output energy having a series of energy spikes that may be partially overlapping or entirely separated in time. For example, in one embodiment, a laser beam source 103 is programmed to provide laser beam bursts of ultraviolet light at a power level of from about 0.2 to about 1 watts, and with a duration of from about 40 to about 160 nanoseconds. These pulsed bursts can be provided at a pulse rate of from about 5 to about 200 Hz. The pulsed laser bursts can be moved across the battery support with a vectorial velocity of from about 0.1 to about 10 mm/s.
In another example, an energy beam comprising femtosecond pulsed laser beam 101 was set to provide an irradiance level of from about 10 to about 200 J/cm2, and pulsed laser bursts having a pulse duration of from about 10 to about 1000 femtoseconds, for example, about 150 femtosecond. Based on this pulse duration, the fluence level of the femtosecond pulsed laser beam 101 was calculated to be from about 10 to about 200 J/cm2. The pulse can be set to be from about 100 microjoules to about 2000 millijoules, in one example, about 500 microjoules. The pulse repetition rate should also be set to provide good cutting, and in one example, the pulse repetition rate was set to be from about 50 to about 1000 Hz, for example, about 125 Hz.
During localized heat treatment with the energy beam, a gas nozzle 93 can also be used to blow a gas stream 95 of a blowing gas onto the localized beam incident area 84 on the cathode 42 to remove any debris or vapors from the localized heating area. The gas nozzle 93 obtains the blowing gas from a gas source 96 and the gas flow rate can be controlled by a mass or volumetric gas flow controller. The blowing gas can be an inert gas such as argon or helium, nitrogen, or a mixture of such gases, and the pressure of the gas can be, for example, at least 2 Kg/cm3. In one version, the blowing gas comprises argon to maintain an inert gas environment around the cathode 42 being heat treated. In another version, the blowing gas comprises an oxygen-containing gas such as oxygen or air, to maintain an oxygen-containing environment around the metal oxide electrode 40 being heat treated.
A schematic diagram of an embodiment of an energy beam source 88 comprising a laser beam source 103 capable of locally heating a battery component film 30 of a battery cell 22 is illustrated with reference to
An exemplary version of the laser beam source 103 is a carbon dioxide laser operated at a power level of about 30 watts in a continuous laser beam mode (not pulse). The laser beam 101 is directed onto the battery component film 30 of a battery cell 22 on a support 24 which is placed on a movable stage 92 comprising a table that can be moved in the x and y directions by a stage motor 94 that is a synchronous or step motor. The stage motor 94 can operate in a grill or cellular system to provide a scanning speed of from about 0.1 to about 300 mm/sec across the support 24 and with a repeat accuracy of about ±0.03 mm. The controller 90 operating the motor 94 of the movable stage 92, can be for example, a WIN2000 industrial computer with program code to enable movement of the stage 92 in the x-y plane using velocity or even acceleration vectors. The apparatus has a 6 inch diameter vent and uses an air cooler for cooling. The apparatus operates with a power requirement of about 1.5 KW.
The continuous laser beam 101 generated by the laser beam source 103 is passed through a laser optical system 120 which comprises a neutral density filter 122, one or more focusing lenses 124, and a shutter 128. The neutral density filter 122 reduces the intensity of all wavelengths or colors equally. The focusing lens 124 can have a focal length of from about 1 cm to about 20 cm, such as for example, 10 cm. In the continuous laser beam mode, the shutter 128 is either not present or, if present, the shutter 128 kept open to allow the laser beam 101 to pass through the open shutter without interruption. In the pulse laser beam mode, the shutter 128 is operated to rapidly open or close. By opening and closing rapidly, the shutter 128 can generate a laser beam 101 having laser pulses with pulse durations in nanoseconds or femtoseconds. The shutter 128 can be a mechanical shutter, mode locking shutter, or electro-optical shutter.
In another version, the energy beam 80 comprises an ultrasonic energy beam 130 generated by an energy beam source 88 that is an ultrasonic beam source 132, as shown in
In yet another version, the energy beam 80 comprises a thermal energy beam 140 generated by an energy beam source 88 that is a thermal energy beam source 142, as shown in
After heat treatment of the metal oxide electrode 40, an electrolyte 44 is deposited over the metal oxide electrode 40. For lithium batteries, the electrolyte 44 can be, for example, an amorphous lithium phosphorus oxynitride film, also known as a LiPON film. In one embodiment, the deposited LiPON material has the stochiometric form LixPOyNz in an x:y:z ratio of about 2.9:3.3:0.46. In one version, the electrolyte 44 has a thickness of from about 0.1 microns to about 5 microns. This thickness is suitably large to provide sufficiently high ionic conductivity and suitably small to reduce ionic pathways to minimize electrical resistance and reduce stress. The electrolyte 44 can be formed by RF sputtering of target material comprising lithium and phosphorous in a reactive gas environment, for example oxygen gas. A suitable sputtering process uses a sputtering target composed of Li3PO4, a sputtering gas comprising nitrogen at a flow rate of from about 50 sccm to about 500 sccm, a pressure of from about 1 mTorr to about 20 mTorr, and a plasma formed by applying a RF current to the magnetron 72 at a power level of from about 0.5 KW to about 5 KW. An electrolyte 44 having a thickness of at least about 2 to 3 microns can be deposited using the above-described sputtering conditions in a sputtering process conducted for at least about 60 to 100 minutes.
Another metal-containing film 32 comprising an elemental metal electrode 36 is then formed on the electrolyte 44, to serve as an anode current collector 50. The second elemental metal electrode 36 can be made from the same material as the first elemental metal electrode 36, as already described. A suitable thickness of a second elemental metal electrode 36 is from about 0.1 microns to about 20 microns. In one version, the second elemental metal electrode 36 is made from lithium which is sufficiently conductive to serve as the anode current collector 50, and in this version, the anode 48 and anode current collector 50 are made of the same material. In another version, the anode current collector 50 is made from the same material as the cathode current collector 38 to provide a conducting surface from which electrons can be dissipated or collected from the anode 48. For example, the anode current collector 50 can be made from a non-reactive metal such as silver, gold, platinum, in a thickness of from about 0.05 microns to about 5 microns. In still another example, an anode composed of copper can be deposited by sputtering processes using a sputtering target composed of copper provided in the sputtering chamber 100; using a sputtering gas comprising argon maintained at a pressure of from about 1 mTorr to about 20 mTorr; a plasma power level of from about 200 W to about 2 KW; and a deposition time of from about 5 to about 60 minutes. The anode current collector 50 has a thickness of from about 0.05 microns to about 5 microns. The non-reactive metal can be deposited by conventional sputtering or PVD methods or by electroplating. The elemental metal electrode 36 comprising an anode current collector 50 can also be heat treated after deposition, using the energy beam 80, as described herein.
The anode 48 is formed on, or even abutting and directly over, the electrolyte 44 to receive electrons released by lithium ions that migrate through the electrolyte 44. The anode 48 can be a lithium-containing material which can be elemental lithium or a lithium compound, or a conducting metal such as copper. In one version, anode 48 is made from elemental lithium which is sufficiently conductive to serve as the anode current collector 50 allowing both the anode 48 and anode current collector 50 to be made of elemental lithium. The anode 48 can also be composed of the same material as the cathode 42, as previously described. A suitable thickness of the anode 48 is from about 0.1 microns to about 20 microns. The anode 48 can also be permeable as for example described in U.S. Pat. No. 6,713,987, entitled “RECHARGEABLE BATTERY HAVING PERMEABLE ANODE CURRENT COLLECTOR”, filed on Feb. 28, 2002, which is incorporated herein by reference in its entirety. The anode 48 can extend to cover the entire area of the cathode 42 or terminate short of the cathode area to provide reduced electrical shorting at the anode edges.
After fabrication of one or more battery cells 22 on a support 24, a protective casing 21 is fabricated to protect the battery cells 22 from degradation in the external environment. In one version, the protective casing 21 comprises a sealant 52 which is applied to extend across at least one, a plurality of, or even substantially the entire length of (or all of) the open peripheral side surfaces 54 along a perimeter 56 of battery 20, as shown in
Thereafter, a cap 60 which forms another portion of the protective casing 21, is positioned on top of, or spaced apart from, the polymer 52 to cover the battery cell 22, and laminated to the battery cell 22. In one version, the cap 60 is a rigid plate of a ceramic material, a metal foil, or a metal coated plastic film, or a plurality of ceramic and polymer films which are conformal to the shape of the battery. Suitable ceramic tools include aluminum oxide or diamond-like carbon (DLC), and a suitable composition of the polymer comprises polymer, epoxy, or even a thermoset or thermoplastic polymer. The cap 60 can also be made from the same material as the support 24. The cap 60 can have a thickness of less than 50 microns, for example, from about 7 to about 40 microns. After placement, a pressure is applied to press the cap 60 and the support 24 together to squeeze the polymer 52 therebetween. A suitable pressure may be 3 psi, or even from about 3 to about 60 psi, for example, about 10 psi. The laminating process can be conducted in air or in a non-reactive gas environment, such as argon or nitrogen. A vacuum can also be pulled on the partially fabricated battery 20 using a vacuum pump to remove trapped air and form a better laminate of the cap 60, polymer 52 and underlying support 24. A suitable vacuum comprises a pressure of from about 10 mTorr to about 10 Torr. While the pressure is being applied, the battery cell 22 can also be heated to cure or to soften the polymer 52, a suitable curing or softening temperature being at least 40° C., or even from about 50 to about 110° C. After curing of polymer 52, the edge portions of the polymer 52 overlying the sections of the cathode current collector 38 and anode current collector 50 that extend beyond the peripheral edge of the battery 20 are peeled off to expose underlying material that serves as the first and second terminals 25a,b, respectively.
After fabrication, one or more batteries 20 each comprising a single battery cell 22 or multiple battery cells 22 are cut out of the support 24. A suitable cutting process can include laser cutting using the previously described laser apparatus set to a higher power level, or by mechanical cutting. Prior to cutting, protective shadow masks (not shown) comprising a plate or polymer can also be used to protect portions of the battery films 30 from subsequent cutting processes. Laser cutting can also be performed using a pulsed laser process, such as a femtosecond laser comprising a diode—pumped solid-state laser with a lasing medium comprising a rod of titanium doped sapphire. In another exemplary embodiment, the pulsed laser source is be an ultraviolet laser such as an excimer or ‘excited dimer’ laser, which is a chemical laser that uses a combination of an inert gas, such as argon, krypton, or xenon; and a reactive gas such as fluorine or chlorine. Several exemplary laser source and cutting methods are described in U.S. Pat. No. 7,862,627 to Li et al. and co-pending U.S. Patent Publication No. US 2009-0208671 A1 to Nieh et al., both of which are incorporated by reference herein and in their entireties.
The battery component layers 30 that form some of the battery component films 30 of each battery cell 22, including the cathode current collector 38, cathode 42, electrolyte 44, anode 48, and anode current collector 50, can be sputter deposited onto a battery support 24 by sputtering one or more sputtering targets 62 mounted in a sputtering chamber 100 of a sputtering apparatus 97, as shown in
A sputtering target 62 comprising a backing support 70 supporting a lithium-containing sputtering member 64 is fastened in the sputtering chamber 100 opposing and facing a support carrier 105. The sputtering target 62 is positioned abutting a magnetron 72, which generates a magnetic field about the surface of the sputtering target 62 to provide a more uniform and continuous bombardment of the target 62 with sputtering plasma ions during the sputtering process. The magnetron 72 contains one or more magnets 74, and can be internally mounted inside the chamber 100 or externally mounted. A target power source 121 comprising one or more power supplies provides an AC voltage at a voltage level of from about 200V and about 1200V, or even from about 250V to about 450V. The voltage can be provided at a power level of from about 1 kW and about 20 kW, or even from about 3 KW to about 10 KW. The voltage can also be provided at a mid-frequency level of from about 10 to about 100 kHz, or even at a frequency of from about 20 kHz to about 80 kHz.
The sputtering target 62 comprises a lithium-containing sputtering member 64 to deposit a lithium-containing film 31 such as the anode 48 onto a battery support 24 positioned on a support carrier 105. The sputtering member 64 can be rectangular, circular or cylindrical in shape, depending on the shape or configuration of the chamber 100 or battery support 24. For example, the lithium-containing sputtering member 64 can be composed of a lithium compound, such as lithium, lithium oxide, lithium cobalt oxide, or other lithium compounds. The lithium-containing material is selected to obtain the desired composition of a lithium-containing film 31. For example, a cathode 42 of a battery cell 22 can deposited using a lithium-containing sputtering member 64 composed of lithium cobalt oxide having the stochiometric formula LiCoO2. As another example, an electrolyte 44 of a battery cell 22 can deposited using a lithium-containing sputtering member 64 composed of lithium, lithium oxide or lithium phosphate. As still another example, an anode 48 of a battery cell 22 can be deposited using a lithium-containing sputtering member 64 composed of lithium.
A support carrier 105 is transported into the sputtering chamber 100 and positioned facing the sputtering target 62 inside the chamber 100. The support carrier 105 is capable of holding one or more supports 24 so that at least one surface 26 of a single or plurality of supports 24, or both surfaces 26, 27 of one or more supports 24, are exposed to the sputtering zone 115. For example, the support carrier 105 can be a rotating carousel or mechanical conveyor. The support carrier 105 is typically fabricated from plates of a metal such as copper or stainless steel.
In a sputtering process, the sputtering chamber 100 is controlled by a controller 119 that comprises program code to operate and control the various components of the chamber 100 to deposit battery component films 30 on a plurality of battery supports 24 in the chamber 100. The controller 119 comprises, for example, a general purpose computer or control electronic box, which has program code to control the gas supply 123, gas distributor 126, exhaust 130 and throttle valve 134, target power source 121 to apply a power to the sputtering target 62 or magnetron 72, and other chamber components. For example, the chamber 100 can be evacuated to a preset pressure by the gas exhaust 133 to a pressure of less than about 10×10−5 Torr, prior to introduction of any cleaning or sputtering gas. Thereafter, controlled amounts of cleaning or sputtering gas are introduced into the chamber 100 via the gas distributor 126. For example, a cleaning plasma of an inert gas such as argon can also be used to clean residues from the sputtering target 62 and inner surfaces of the chamber 100.
The following examples illustrate annealing effect of heat treating a battery component film 30 such as a second metal-containing film 46 composed of a metal oxide electrode 40 that serves as the cathode 42, and which is deposited over a first metal-containing film 32 composed of an elemental metal electrode 36 that serves as the cathode current collector 38. The examples described herein are illustrative embodiments of the batteries and fabrication methods claimed herein but should not be used to limit the scope of the claims.
In these examples, the battery cell 22 is a solid state lithium battery cell on a support 24 of mica with an electrolyte 44 composed of lithium phosphorus oxynitride, a cathode 42 of lithium cobalt oxide, an anode 48 of lithium, an anode current collector 50 of platinum, and a cathode current collector 38 of either platinum or molybdenum. The battery cells 22 included an adhesion layer 34 of LixCoO2 when the cathode current collector was composed of platinum. The cathode 42 was deposited with a high deposition power applied during the sputtering process using deposition process conditions which included a sputtering gas comprising argon and oxygen in a flow rate of from about 100 sccm to about 500 sccm, a gas pressure of from about 5 mTorr to about 15 mTorr, and a plasma formed by applying to the sputtering target magnetron 72 and chamber walls or the support, a current at a power level of from about 0.5 KW to about 10 KW. After deposition of the cathode 42, some of the battery cells 22 are treated in different annealing processes while other battery cells 22 were not annealed. The annealing process conditions are described below.
Example 1 compares the performance of solid-state lithium batteries 20 which were heat treated in a tube oven or with localized energy from an energy beam 80 that is a CO2 laser beam, with other batteries which were not heat treated (designated “as-deposited”). The batteries 20 each contained a single battery cell 22 with the same internal battery component films 30, structure, and film thicknesses. The battery cells 22 each had a cathode 42 composed of lithium cobalt oxide and a cathode current collector 38 composed of platinum. The energy capacity of the heat treated and control batteries were measured by discharging the selected battery at a current of 1 mA from a voltage of 4.2 V to a voltage of 3.6 V.
Table I shows comparative test results demonstrating that the energy capacity of a number of batteries 20 having a cathode 42 of lithium cobalt oxide overlying a cathode current collector 38 of platinum, which were heat treated, was significantly higher than the energy capacity of not heat treated batteries. In these examples, the cathode 42 of the battery cells 22 had a thickness of approximately 4.2 microns. The number EFF represents the efficiency of the cathode 42 which is calculated by dividing the measured battery capacity by a theoretical maximum capacity value. It is seen that the EFF values significantly changed from non-heat-treated, as-deposited, EFF values of 30% to EFF values for heat treated batteries of 51% to 61%, a 20% increase in EFF values. Battery capacity increased from a range of from 254 to 284 for the non-heat-treated batteries to a range of from 438 to 522.
The results of the measured battery capacity values were also consistent with x-ray diffraction data which indicated that after localized heat treatment with the CO2 laser energy beam there were significant changes in the crystalline structure of the cathode 42.
In these examples, solid state lithium batteries 20 that each contained a single battery cell 22 containing a cathode current collector 38 composed of either platinum or molybdenum, underlying a cathode 42 composed of LiCoO2 were tested. In fabrication, after a cathode 42 was deposited over a cathode current collector 38, the cathode 42 was subjected to heat treatment or non-heat treatment including annealed, annealed in air or argon, or annealed using a laser. Thereafter, remaining battery component films 31 were formed on the battery cell 22, and the resultant battery sealed with the protective casing 21. The completely fabricated battery was then charged and tested to determine the battery capacity measured at a discharge current of 1 mA and internal resistance, and from these values the cathode efficiency was calculated as explained above.
Samples 2B to 2F were all batteries 20 which contained a battery cell 22 having a cathode current collector 38 composed of molybdenum, and a cathode composed of lithium cobalt oxide. The electrical properties of the samples 2B batteries (marked ASD1-5) were measured without heat treatment of the cathode 42 and in an as-deposited state. These battery cells 22 had an as-deposited high efficiency cathode 42 composed of lithium cobalt oxide deposited using a high deposition power plasma in an inert argon and environment and) a current collector 38 of molybdenum. It is seen that the internal resistance of the batteries 20 varied across a wide range of from about 250 to about 450 ohm, as did the battery capacities which range from 50 to about 280 microamp-hour. As result, the cathode efficiency of these batteries ranged from about 55% to about 70%. These results demonstrated that batteries containing a cathode current collector 38 composed of molybdenum but which did not have a heat-treated cathode 42, provided a wide range of electrical properties with occasionally abnormally low battery capacities.
Samples 2C were batteries 20 containing cathodes 42 which were heat treated at a relatively low temperature of 350° C. in air in an oven for 10 hours prior to fabrication of the completed battery. These samples represented the baseline performance of a battery cell 22 having a high efficiency cathode 42 deposited using a high deposition power plasma in an inert argon and environment and at low annealing temperatures of less than 400° C. The oxygen content in the air caused a thin oxide film to form at the interface of the cathode 42 and the current collector 38 of molybdenum. The deterioration in battery performance is seen in air annealed battery cells 22 as they had a battery capacity of from about to about 1 microAmp-hour, a RIN of about thousands of ohms, and a cathode efficiency of about zero. The battery capacity of these battery cells could not be measured due to the extremely high RIN which was attributed to the oxidation on the surface of cathode current collector 38 composed of molybdenum. This represented a hundred fold decrease in battery capacity, demonstrating that annealing in an oxygen-containing environment of significant deterioration of battery performance. As a result, the cathode efficiency of these batteries 20 even though they contained a cathode current collector 38 of molybdenum was near zero.
Samples 2D were batteries containing cathodes 42 which were heat treated at a temperature of 375° C. in an argon gas environment for 11 hours prior to fabrication of the completed battery cell. The argon flow rate was set at a low flow rate by adjusting a pressure gauge on a compressed tank of argon to 5 psi to provide an estimated flow rate of less than 0.5 liter/min. It is seen that all the electrical properties of these batteries improved compared to the heat treatment in air of Samples 2C, but still varied across wide levels with some measured battery capacities of close to zero. The measured battery capacity, RIN, and cathode efficiencies where scattered across a wide range due to partial oxidation of the surface of the molybdenum cathode current collector 38. It is believed that the flow rate of argon allowed some oxygen to permeate into the tube oven causing oxidation of some of the battery cells but not all of them, giving rise to scattered results.
Samples 2E were batteries 20 containing a cathode current collector 38 of molybdenum and a cathode 42 which was heat treated at a temperature of 400° C. in higher argon flow rates for 11 hours. The higher argon flow was obtained by setting the pressure gauge at 10 psi to provide an estimated flow rate of at least about 10 liters/min. The higher argon flow rates were found to protect better protection from oxidation by ambient oxygen to provide battery performance values that were stable and consistent. The higher temperature/high flow argon annealed battery cells 22 provided a battery capacity of from about to about 500 microAmps-hour and a RIN of about 160 ohms. It was seen that all the electrical properties significantly improved and gave cathode efficiencies of 65% and even higher to above 75%. This represented a 3 fold increase in battery capacity over the un-annealed battery cells 22, demonstrating that annealing in an oxygen-containing environment of significant deterioration of battery performance.
Samples 2F were batteries 20 containing a cathode current collector 38 of molybdenum and a cathode 42 which was heat treated using a localized heat treatment with a CO2 laser. The battery cells 221 were annealed by exposing the top surface of the cathode 42 to a carbon dioxide laser beam to locally anneal the cathode 42 in the beam exposed region by generating temperatures of about 400° C. across a beam width of the laser incident on to the cathodes 42. The laser beam was operated at a power level of from 6.7 to 6.8 Watts and raster scanned across the top cathode surface at a linear velocity of 3.5 mm/sec. The laser annealed battery cells 22 provided a battery capacity of from about 550 microAmp-hour at a 1 mA discharge current, a RIN of about 140 ohms, and a cathode efficiency of 79%. Further, the cathode efficiency for high power deposited batteries annealed in a high argon flow was as high as 76% and providing a small variation in range of less than 5%. The battery capacities of these batteries 20 were also the highest having values between 500 and 600 microAmp-hour.
These results demonstrate that the battery 20 comprising a battery cell 22 with a cathode current collector 38 consisting of molybdenum, and an overlying cathode 42 of lithium cobalt oxide, when heat-treated in non-oxidizing environment with for example high argon flow rates are using localized heating with a laser beam, provided the highest cathode efficiencies and a battery capacities.
While illustrative embodiments of the thin film battery 20 are described in the present application, it should be understood that other embodiments are also possible. For example, the locally heating method can be performed by other directed energy sources, such as ultrasonic beam, micro blowtorch, and rapid thermal annealing, as would be apparent to those of ordinary skill in the art. Further, the exemplary methods of fabricating the batteries described herein are provided only to illustrate the present invention, and other methods may be used to fabricate a battery 20 as would be apparent to those of ordinary skill in the art. Furthermore, the materials of the battery components films 30 are also exemplary and may comprise other materials. Also, the battery 20 may have a plurality of battery cells 22 arranged in a convoluted or non-symmetrical shape depending on the application. Thus the scope of the claims should not be limited by the exemplary methods of manufacture, materials and structures provided herein.
The present application is a continuation-in-part of U.S. patent application Ser. No. 13/434,775, filed on Mar. 29, 2012, entitled “LOCALIZED HEAT TREATMENT OF BATTERY COMPONENT FILMS” to Liang, which is incorporated by reference herein and in its entirety.
| Number | Name | Date | Kind |
|---|---|---|---|
| 3375135 | Moulton et al. | Mar 1968 | A |
| 3414685 | Geib et al. | Dec 1968 | A |
| 3530007 | Golubovic | Sep 1970 | A |
| 3844841 | Baker | Oct 1974 | A |
| 3969142 | Greatbatch et al. | Jul 1976 | A |
| 3993508 | Erlichman | Nov 1976 | A |
| 4031449 | Trombly | Jun 1977 | A |
| 4119769 | Schneider et al. | Oct 1978 | A |
| 4233371 | Dorrestijn | Nov 1980 | A |
| 4279726 | Baird et al. | Jul 1981 | A |
| 4309494 | Stockel | Jan 1982 | A |
| 4421835 | Manassen et al. | Dec 1983 | A |
| 4459328 | Mizuhara | Jul 1984 | A |
| 4543441 | Kumada et al. | Sep 1985 | A |
| 4565753 | Goebel et al. | Jan 1986 | A |
| 4597844 | Hiraki et al. | Jul 1986 | A |
| 4619865 | Keem et al. | Oct 1986 | A |
| 4663183 | Ovshinsky et al. | May 1987 | A |
| 4698256 | Giglia et al. | Oct 1987 | A |
| 4714660 | Gates, Jr. | Dec 1987 | A |
| 4725345 | Sakamoto et al. | Feb 1988 | A |
| 4777090 | Ovshinsky et al. | Oct 1988 | A |
| 4871433 | Wagner et al. | Oct 1989 | A |
| 4873115 | Matsumura et al. | Oct 1989 | A |
| 4877677 | Hirochi et al. | Oct 1989 | A |
| 4882212 | SingDeo et al. | Nov 1989 | A |
| 4904542 | Mroczkowski | Feb 1990 | A |
| 4996079 | Itoh | Feb 1991 | A |
| 5019467 | Fujiwara | May 1991 | A |
| 5171413 | Arntz et al. | Dec 1992 | A |
| 5197889 | Rizzo et al. | Mar 1993 | A |
| 5240794 | Thackeray et al. | Aug 1993 | A |
| 5249554 | Tamor et al. | Oct 1993 | A |
| 5250891 | Glasgow | Oct 1993 | A |
| 5253300 | Knapp | Oct 1993 | A |
| 5254415 | Williams et al. | Oct 1993 | A |
| 5262028 | Manley | Nov 1993 | A |
| 5330853 | Hofmann et al. | Jul 1994 | A |
| 5338625 | Bates et al. | Aug 1994 | A |
| 5368939 | Kawamura et al. | Nov 1994 | A |
| 5445906 | Hobson et al. | Aug 1995 | A |
| 5478456 | Humpal et al. | Dec 1995 | A |
| 5490911 | Makowiecki et al. | Feb 1996 | A |
| 5498490 | Brodd | Mar 1996 | A |
| 5503912 | Setoyama et al. | Apr 1996 | A |
| 5506858 | Takenaka et al. | Apr 1996 | A |
| 5511587 | Miya et al. | Apr 1996 | A |
| 5512147 | Bates et al. | Apr 1996 | A |
| 5512387 | Ovshinsky | Apr 1996 | A |
| 5516340 | Takeuchi et al. | May 1996 | A |
| 5547767 | Paidassi et al. | Aug 1996 | A |
| 5552242 | Ovshinsky et al. | Sep 1996 | A |
| 5554456 | Ovshinsky et al. | Sep 1996 | A |
| 5561004 | Bates et al. | Oct 1996 | A |
| 5597660 | Bates et al. | Jan 1997 | A |
| 5607789 | Treger et al. | Mar 1997 | A |
| 5612152 | Bates et al. | Mar 1997 | A |
| 5629560 | Katsui et al. | May 1997 | A |
| 5650243 | Ferment et al. | Jul 1997 | A |
| 5656364 | Rickerby et al. | Aug 1997 | A |
| 5663183 | Frost et al. | Sep 1997 | A |
| 5670252 | Makowiecki et al. | Sep 1997 | A |
| 5670272 | Cheu et al. | Sep 1997 | A |
| 5681666 | Treger et al. | Oct 1997 | A |
| 5700551 | Kukino et al. | Dec 1997 | A |
| 5705293 | Hobson | Jan 1998 | A |
| 5705297 | Warren | Jan 1998 | A |
| 5708297 | Clayton | Jan 1998 | A |
| 5725909 | Shaw et al. | Mar 1998 | A |
| 5786582 | Roustaei et al. | Jul 1998 | A |
| 5814195 | Lehan et al. | Sep 1998 | A |
| 5818199 | Beard | Oct 1998 | A |
| 5824374 | Bradley, Jr. et al. | Oct 1998 | A |
| 5871865 | Barker et al. | Feb 1999 | A |
| 5894656 | Menon et al. | Apr 1999 | A |
| 5932368 | Batawi et al. | Aug 1999 | A |
| 5961672 | Skotheim et al. | Oct 1999 | A |
| 5981102 | Grigg et al. | Nov 1999 | A |
| 5985485 | Ovshinsky et al. | Nov 1999 | A |
| 6017654 | Kumta et al. | Jan 2000 | A |
| 6022640 | Takada et al. | Feb 2000 | A |
| 6039850 | Schulz | Mar 2000 | A |
| 6040680 | Toya et al. | Mar 2000 | A |
| 6046575 | Demuro | Apr 2000 | A |
| 6051114 | Yao et al. | Apr 2000 | A |
| 6118248 | Gartstein et al. | Sep 2000 | A |
| 6146715 | Kim et al. | Nov 2000 | A |
| 6148503 | Delnick et al. | Nov 2000 | A |
| 6168884 | Neudecker et al. | Jan 2001 | B1 |
| 6197450 | Nathan et al. | Mar 2001 | B1 |
| 6217623 | Reichert et al. | Apr 2001 | B1 |
| 6218049 | Bates et al. | Apr 2001 | B1 |
| 6220765 | Tatoh | Apr 2001 | B1 |
| 6227204 | Baumann et al. | May 2001 | B1 |
| 6238847 | Axtell, III et al. | May 2001 | B1 |
| 6242129 | Johnson | Jun 2001 | B1 |
| 6264709 | Yoon et al. | Jul 2001 | B1 |
| 6280875 | Kwak et al. | Aug 2001 | B1 |
| 6287711 | Nieh et al. | Sep 2001 | B1 |
| 6340880 | Higashijima et al. | Jan 2002 | B1 |
| 6365010 | Hollars | Apr 2002 | B1 |
| 6379835 | Kucherovsky et al. | Apr 2002 | B1 |
| 6387039 | Moses | May 2002 | B1 |
| 6387563 | Bates | May 2002 | B1 |
| 6398824 | Johnson | Jun 2002 | B1 |
| 6402796 | Johnson | Jun 2002 | B1 |
| 6411780 | Maruyama | Jun 2002 | B1 |
| 6413645 | Graff et al. | Jul 2002 | B1 |
| 6461757 | Sasayama et al. | Oct 2002 | B1 |
| 6472295 | Morris et al. | Oct 2002 | B1 |
| 6517968 | Johnson | Feb 2003 | B2 |
| 6558836 | Whitacre et al. | May 2003 | B1 |
| 6632563 | Krasnov et al. | Oct 2003 | B1 |
| 6636017 | Zink et al. | Oct 2003 | B2 |
| 6645658 | Morozumi | Nov 2003 | B2 |
| 6658124 | Meadows | Dec 2003 | B1 |
| 6661197 | Zink et al. | Dec 2003 | B2 |
| 6696199 | Yoshida et al. | Feb 2004 | B2 |
| 6700766 | Sato | Mar 2004 | B2 |
| 6713987 | Krasnov et al. | Mar 2004 | B2 |
| 6780544 | Noh | Aug 2004 | B2 |
| 6805998 | Jenson et al. | Oct 2004 | B2 |
| 6863699 | Krasnov et al. | Mar 2005 | B1 |
| 6866901 | Burrows et al. | Mar 2005 | B2 |
| 6916679 | Snyder et al. | Jul 2005 | B2 |
| 6921464 | Krasnov et al. | Jul 2005 | B2 |
| 6940988 | Shennib et al. | Sep 2005 | B1 |
| 6982132 | Goldner et al. | Jan 2006 | B1 |
| 7037621 | Kikuchi et al. | May 2006 | B2 |
| 7056620 | Krasnov et al. | Jun 2006 | B2 |
| 7122908 | Jiang et al. | Oct 2006 | B2 |
| 7131189 | Jenson | Nov 2006 | B2 |
| 7157187 | Jenson | Jan 2007 | B2 |
| 7186479 | Krasnov et al. | Mar 2007 | B2 |
| 7194801 | Jenson et al. | Mar 2007 | B2 |
| 7194901 | Silverbrook et al. | Mar 2007 | B2 |
| 7204862 | Zhang | Apr 2007 | B1 |
| 7276878 | Phillips et al. | Oct 2007 | B2 |
| 7286479 | Bragg | Oct 2007 | B2 |
| 7308316 | Schommer | Dec 2007 | B2 |
| 7359590 | Hsu | Apr 2008 | B2 |
| 7397118 | Tominaga | Jul 2008 | B2 |
| 7494742 | Tarnowski et al. | Feb 2009 | B2 |
| 7501202 | Enomoto et al. | Mar 2009 | B2 |
| 7510582 | Krasnov et al. | Mar 2009 | B2 |
| 7524577 | Bates | Apr 2009 | B2 |
| 7701176 | Chen | Apr 2010 | B2 |
| 7846579 | Krasnov et al. | Dec 2010 | B2 |
| 7862627 | Li et al. | Jan 2011 | B2 |
| 7862927 | Krasnov et al. | Jan 2011 | B2 |
| 7959769 | Zhang et al. | Jun 2011 | B2 |
| 8030898 | Okuto | Oct 2011 | B2 |
| 8168322 | Krasnov et al. | May 2012 | B2 |
| 8502494 | Nieh et al. | Aug 2013 | B2 |
| 8628645 | Wang et al. | Jan 2014 | B2 |
| 8679674 | Liang et al. | Mar 2014 | B2 |
| 8728176 | Li et al. | May 2014 | B2 |
| 8753724 | Nieh et al. | Jun 2014 | B2 |
| 8864954 | Liang et al. | Oct 2014 | B2 |
| 8865340 | Liang et al. | Oct 2014 | B2 |
| 8870974 | Nieh et al. | Oct 2014 | B2 |
| 20010007335 | Tuttle et al. | Jul 2001 | A1 |
| 20010041294 | Chu et al. | Nov 2001 | A1 |
| 20010052645 | Op'T Eynde et al. | Dec 2001 | A1 |
| 20020001746 | Jaenson et al. | Jan 2002 | A1 |
| 20020004167 | Jenson et al. | Jan 2002 | A1 |
| 20020028384 | Krasnov et al. | Mar 2002 | A1 |
| 20020041930 | Erdemir et al. | Apr 2002 | A1 |
| 20020071989 | Verma et al. | Jun 2002 | A1 |
| 20020100989 | Jiang et al. | Aug 2002 | A1 |
| 20020102400 | Gorokhovsky et al. | Aug 2002 | A1 |
| 20020110733 | Johnson | Aug 2002 | A1 |
| 20020150823 | Breitkopf et al. | Oct 2002 | A1 |
| 20030121142 | Kikuchi et al. | Jul 2003 | A1 |
| 20030143460 | Yoshida et al. | Jul 2003 | A1 |
| 20030152829 | Zhang et al. | Aug 2003 | A1 |
| 20030160589 | Krasnov et al. | Aug 2003 | A1 |
| 20040018424 | Zhang et al. | Jan 2004 | A1 |
| 20040064937 | Krasnov et al. | Apr 2004 | A1 |
| 20040086762 | Maeda et al. | May 2004 | A1 |
| 20040175609 | Yageta et al. | Sep 2004 | A1 |
| 20050079418 | Kelley et al. | Apr 2005 | A1 |
| 20050112461 | Amine et al. | May 2005 | A1 |
| 20050130032 | Krasnov et al. | Jun 2005 | A1 |
| 20050147877 | Tarnowski et al. | Jul 2005 | A1 |
| 20050156573 | Lin | Jul 2005 | A1 |
| 20050275370 | Kim | Dec 2005 | A1 |
| 20060027937 | Benson et al. | Feb 2006 | A1 |
| 20060040169 | Liu et al. | Feb 2006 | A1 |
| 20060040170 | Liu et al. | Feb 2006 | A1 |
| 20060060956 | Tanikella | Mar 2006 | A1 |
| 20060068258 | Kinoshita | Mar 2006 | A1 |
| 20060115706 | Maeda et al. | Jun 2006 | A1 |
| 20060134522 | Zhang et al. | Jun 2006 | A1 |
| 20060152196 | Matsumoto et al. | Jul 2006 | A1 |
| 20060216589 | Krasnov et al. | Sep 2006 | A1 |
| 20060226812 | Patino et al. | Oct 2006 | A1 |
| 20060267546 | Shen et al. | Nov 2006 | A1 |
| 20060278617 | Anantharaman et al. | Dec 2006 | A1 |
| 20070000688 | Mobley | Jan 2007 | A1 |
| 20070037054 | Kikuchi et al. | Feb 2007 | A1 |
| 20070047750 | Sauer et al. | Mar 2007 | A1 |
| 20070047796 | Anantharaman et al. | Mar 2007 | A1 |
| 20070104343 | Bengtsson et al. | May 2007 | A1 |
| 20070104344 | Goldberg | May 2007 | A1 |
| 20070125638 | Zhang et al. | Jun 2007 | A1 |
| 20070141460 | You et al. | Jun 2007 | A1 |
| 20070166612 | Krasnov et al. | Jul 2007 | A1 |
| 20070172739 | Visco et al. | Jul 2007 | A1 |
| 20070200258 | Mahler et al. | Aug 2007 | A1 |
| 20070297108 | Collins et al. | Dec 2007 | A1 |
| 20080003492 | Bates | Jan 2008 | A1 |
| 20080087986 | Tanikella | Apr 2008 | A1 |
| 20080191342 | Otremba | Aug 2008 | A1 |
| 20080213664 | Krasnov et al. | Sep 2008 | A1 |
| 20080217162 | Delrue et al. | Sep 2008 | A1 |
| 20080253098 | Liu | Oct 2008 | A1 |
| 20080263855 | Li et al. | Oct 2008 | A1 |
| 20080290363 | Lin et al. | Nov 2008 | A1 |
| 20080303056 | Ward et al. | Dec 2008 | A1 |
| 20080308935 | Kim et al. | Dec 2008 | A1 |
| 20090010462 | Ekchian et al. | Jan 2009 | A1 |
| 20090029500 | Wan | Jan 2009 | A1 |
| 20090039498 | Bayerer | Feb 2009 | A1 |
| 20090057136 | Wang et al. | Mar 2009 | A1 |
| 20090114429 | Sri-Jayantha et al. | May 2009 | A1 |
| 20090115051 | Leung et al. | May 2009 | A1 |
| 20090136839 | Kraznov et al. | May 2009 | A1 |
| 20090159433 | Neudecker et al. | Jun 2009 | A1 |
| 20090208671 | Nieh et al. | Aug 2009 | A1 |
| 20090214899 | Shakespeare et al. | Aug 2009 | A1 |
| 20100028767 | Inose et al. | Feb 2010 | A1 |
| 20100247987 | Holung et al. | Sep 2010 | A1 |
| 20100264017 | Nam et al. | Oct 2010 | A1 |
| 20100291431 | Shih et al. | Nov 2010 | A1 |
| 20110050159 | Nieh et al. | Mar 2011 | A1 |
| 20110076550 | Liang et al. | Mar 2011 | A1 |
| 20110076567 | Bouillon | Mar 2011 | A1 |
| 20110094094 | Li et al. | Apr 2011 | A1 |
| 20110270477 | Ueki | Nov 2011 | A1 |
| 20120003520 | Lee et al. | Jan 2012 | A1 |
| 20120034502 | Nieh et al. | Feb 2012 | A1 |
| 20120080940 | Larsen | Apr 2012 | A1 |
| 20120251867 | Krasnov et al. | Oct 2012 | A1 |
| 20120268057 | Wu | Oct 2012 | A1 |
| 20130098532 | Liang et al. | Apr 2013 | A1 |
| 20130164607 | Shih | Jun 2013 | A1 |
| 20130260230 | Liang et al. | Oct 2013 | A1 |
| 20140087227 | Shih | Mar 2014 | A1 |
| 20140106203 | Shih | Apr 2014 | A1 |
| 20140106216 | Liang | Apr 2014 | A1 |
| 20140166471 | Wang et al. | Jun 2014 | A1 |
| Number | Date | Country |
|---|---|---|
| 1661354 | Aug 2005 | CN |
| 0 829 913 | Mar 1998 | EP |
| 0933827 | Aug 1999 | EP |
| 1 353 429 | Oct 2003 | EP |
| 1 458 037 | Sep 2004 | EP |
| 1 415 355 | Jan 2009 | EP |
| 2 403 652 | Apr 1979 | FR |
| 2251119 | Jun 1992 | GB |
| 59-032023 | Feb 1984 | JP |
| 59-226472 | Dec 1984 | JP |
| 60-072168 | Apr 1985 | JP |
| 61195563 | Aug 1986 | JP |
| 04-295015 | Oct 1992 | JP |
| 09-259929 | Oct 1997 | JP |
| H09-293516 | Nov 1997 | JP |
| 2001-044073 | Feb 2001 | JP |
| 2002-165358 | Jun 2002 | JP |
| 2002-313289 | Oct 2002 | JP |
| 2003-249199 | Sep 2003 | JP |
| 2009-123516 | Jun 2009 | JP |
| WO-9514311 | May 1995 | WO |
| WO-9808672 | Mar 1998 | WO |
| WO-9923714 | May 1999 | WO |
| WO-9952589 | Oct 1999 | WO |
| WO-0060689 | Oct 2000 | WO |
| WO-0173873 | Oct 2001 | WO |
| WO-02061828 | Aug 2002 | WO |
| WO-02021627 | Jan 2003 | WO |
| WO-02042516 | Jan 2003 | WO |
| WO-03061049 | Jul 2003 | WO |
| WO-03073531 | Dec 2003 | WO |
| WO-03005477 | Dec 2004 | WO |
| WO-2004111659 | Dec 2004 | WO |
| WO-2006042357 | Apr 2006 | WO |
| WO-2006105188 | Oct 2006 | WO |
| WO-2006105050 | Mar 2007 | WO |
| WO-2007042394 | Apr 2007 | WO |
| WO-2008004851 | Jan 2008 | WO |
| WO-2008101254 | Aug 2008 | WO |
| WO2008101254 | Aug 2008 | WO |
| WO-2008108999 | Nov 2008 | WO |
| WO-2008134053 | Nov 2008 | WO |
| WO-2009052683 | Apr 2009 | WO |
| WO-2009073150 | Jun 2009 | WO |
| WO 2011-066518 | Jun 2011 | WO |
| WO 2011-066518 | Jun 2011 | WO |
| Entry |
|---|
| Antaya et al. “Preparation and Characterization of LiCoO2 Thin Films by Laser Ablation Deposition”, J. Electrochem. Soc., vol. 140, No. 3, Mar. 1993, pp. 575-578. |
| Fragnaud et al. “Characterization of sprayed and sputter deposited LiCoO2 thin films for rechargeable microbatteries”, J. Power Sources, 63 (1996), pp. 187-191. |
| Birke et al. “Materials for lithium thin-film batteries for application in silicon technology”, Solid State Ionics, 93 (1997), pp. 1-15. |
| Benqlilou-Moudden et al. “Amorphous Lithium Cobalt and Nickel Oxides Thin Films Preparation and Characterization by RBS and PIGE”, Thin Solid Films 333 (1998), pp. 16-19. |
| Yang et al., “Effect of annealing temperature on structure and electrochemical properties of LiCoO2 cathode thin films”, Rare Metals, vol. 25, Dec. 2006, pp. 189-192. |
| PCT International Search Report in Application No. PCT/US2008/013213 (WO 2009/073150 A1), mailed Jun. 18, 2009. |
| Mattox, Donald M., Handbook of Physical Vapor Deposition (PVD) Processing, Film Formation, Adhesion, Surface Preparation and Contamination Control, 1998, pp. 127-135 and 343-364, Noyes Publications, Westwood, New Jersey, USA. |
| Non-Final Office Action dated Sep. 17, 2010 in U.S. Appl. No. 11/849,959, filed Sep. 4, 2007. |
| Final Office Action dated Feb. 15, 2010 in U.S. Appl. No. 11/849,959, filed Sep. 4, 2007. |
| Non-Final Office Action dated Aug. 13, 2012 in U.S. Appl. No. 11/849,959, filed Sep. 4, 2007. |
| Roh et al., “Effects of deposition condition on the ionic conductivity . . . ” Scripta Materialia, Dec. 17, 1999, pp. 43-49, vol. 42. No. 1, New York, NY. |
| Bolster et al., “Investigation of lithium intercalation metal oxides for thermalbatteries” Proceedings of the 34th Int'l Power Source Symposium, Jun. 25-28, 1990, pp. 136-140. |
| Liang et al., U.S. Appl. No. 13/278,082, filed Oct. 20, 2011, for Thin Film Battery Packaging Formed by Localized Heating. |
| Nieh et al., U.S. Appl. No. 13/627,977, filed Sep. 26, 2012, for Plasma Deposition on a Partially Formed Battery Through a Mesh Screen. |
| Shih et al., U.S. Appl. No. 13/626,842, filed Sep. 25, 2012, for Solid State Battery Having Mismatched Cells. |
| Liang, Jiuh-Ming, U.S. Appl. No. 13/434,775, filed Mar. 29, 2012, for Localized Heat Treatment of Battery Component Films. |
| Shih et al., U.S. Appl. No. 13/333,969, filed Dec. 21, 2011, for Laminated Lithium Battery. |
| Shih et al., U.S. Appl. No. 13/652,416, filed Oct. 15, 2012, for Lithium Battery Having Low Leakage Anode. |
| PCT International Search Report in Application No. PCT/US2011/046674 dated Feb. 17, 2012. |
| Bates et al., “Preferred orientation of polycrystalline LiCoO2 films” J. of the Electrochemical Society (2000), pp. 59-70, Issue No. 147 (1). |
| Wagner et al., “Fabrication and Testing of thermoelectric thin film devices” 15th Int'l Conf. on Thermoelectrics, Mar. 26-29, 1996, pp. 269-273. |
| Neudecker et al., “Lithium-Free Thin-Film Battery . . . ” Journal of the Electrochemical Society (2000), pp. 517-523, Issue No. 147 (2). |
| Park et al., “Characterization of tin oxide/LiMn2O4 thin-film cell,” Journal of Power Sources, Jun. 2000, pp. 250-254, vol. 88, No. 2, Elsevier Science S.A. |
| PCT International Preliminary Report on Patentability, Application No. PCT/US2008/013213 (WO09/073150), Mailed Jun. 10, 2010. |
| PCT International Search Report in Application No. PCT/US2012/063100, mailed Feb. 28, 2013. |
| U.S. Appl. No. 12/894,571, Final Office Action Jul. 18, 2011. |
| U.S. Appl. No. 12/894,571, BPAI Decision Dec. 18, 2013. |
| U.S. Appl. No. 12/894,571, Notice of Allowance Jan. 6, 2014. |
| U.S. Appl. No. 11/796,487, Notice of Allowance, Sep. 10, 2010. |
| U.S. Appl. No. 12/032,997, Corrected Notice of Allowance, Sep. 2, 2014. |
| U.S. Appl. No. 12/032,997, Final Office Action May 27, 2009. |
| U.S. Appl. No. 12/032,997, Final Office Action Jul. 15, 2010. |
| U.S. Appl. No. 12/032,997, Final Office Action Nov. 13, 2010. |
| U.S. Appl. No. 12/032,997, Office Action Jan. 15, 2013. |
| U.S. Appl. No. 12/032,997, Office Action Dec. 23, 2009. |
| U.S. Appl. No. 12/032,997, Office Action Nov. 11, 2008. |
| U.S. Appl. No. 12/894,571, Office Action Mar. 2, 2011. |
| PCT/US2008/005462, Int'l Report on Patentability Jul. 28, 2008. |
| PCT/US2013/034487, Int'l Report on Patentability Jul. 10, 2013. |
| PCT Search Report, PCT/US2013/034487, dated Jul. 10, 2013. |
| U.S. Appl. No. 13/278,082, Final Rejection, mailed on Feb. 13, 2014. |
| U.S. Appl. No. 13/278,082, Non-Final Rejection, mailed on Jul. 24, 2013. |
| Number | Date | Country | |
|---|---|---|---|
| 20140106216 A1 | Apr 2014 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 13434775 | Mar 2012 | US |
| Child | 13830550 | US |
