Patent Grant
8148455
The present invention relates to hybrid organic-inorganic nanocomposites that are useful as an active component of a lithium battery cathode and to methods for manufacturing the nanocomposites.
Lithium batteries are energy storage and production devices capable of being charged and discharged. Such batteries are widely used as autonomous power sources for various portable electronic devices (e.g., cellular phones, cameras, audio players, laptop computers, and the like). The development of batteries that are lightweight and have higher charge/discharge capacity is an important issue for autonomous energetics.
A typical lithium battery includes a cathode, an electrolyte and an anode. The charge/discharge characteristics of cathode materials are important factors in determining the capacity for energy storage. Crystalline oxides based on cobalt, manganese, nickel and vanadium are the most studied materials for the cathode materials in lithium batteries. Commercialized LiCoO2 has high redox potential along with long term stability. However, such materials tend to be costly and toxic while also having a low charge/discharge capacity. LiMn2O4 has been considered as an alternative to conventional LiCoO2 because of its sufficiently high redox potential and associated low cost. However, this material also suffers from a low charge/discharge capacity and long term stability at cycling. Although LiNiO2 is another potential cathode material because of its theoretically better discharge capacity than LiCoO2, this material presents significant difficulty with respect to its preparation. For the case of V2O5, there is a disadvantage with respect to the stability of the material at charge/discharge cycling. Therefore, there is an urgent demand in creation of a new electrode material to overcome the shortcomings of the known crystalline transition metal oxides.
Recent trends in the field of portable electrical devices have focused on reducing power consumption, which requires creation of a current source with a relatively low working voltage and a high energy density. To meet this end, a battery with high charge/discharge capacity is required.
Improved discharge capacity for electrochemical lithium insertion has been observed for the two-component hybrid host-guest nanocomposites based on vanadium oxide (V2O5) and conducting polymers (CPs): nanocomposites of V2O5 with intercalated polyaniline (PAn), which were disclosed by Nazar et al. [E. Leroux, G. Goward, W. P. Power and L. F. Nazar, “Electrochemical Li Insertion into Conductive Polymer/V2O5 Nanocomposites”, Journal of Materials Chemistry, 1995, vol. 5, p. 1985], Gómez-Romero et al. [M. Lira-Cantú and P. Gómez-Romero, “The Organic-Inorganic Polyaniline/V2O5System. Application as a High-Capacity Hybrid Cathode for Rechargeable Lithium Batteries”, Journal of the Electrochemical Society, 1999, vol. 146, p. 2029], Buttry et al. [F. Huguenin, R. M. Torresi and D. A. Buttry, Journal of the Electrochemical Society, 2002, vol. 149, p.A546]; nanocomposites of V2O5 with intercalated polypyrrole (PPy) and polythiophene (PTh), which were disclosed by Nazar et al. [G. Goward, E. Leroux, and L. F. Nazar, “Poly(pyrrole) and Poly(thiophene)/Vanadium Oxide nanocomposites: Positive Electrodes for Lithium Batteries”, Electrochimica Acta, 1998, vol. 43, p. 1307]; nanocomposites of V2O5 with intercalated poly(3,4-ethylene dioxythiophene), which were disclosed by Murugan et al. [A. V. Murugan, B. B. Kale, C.-W. Kwon, G. Campet and K. Vijayamohanan, “Synthesis and characterization of a new organo-inorganic poly(3,4-ethylene dioxythiophene) PEDOT/V2O5 nanocomposite by intercalation”, Journal of Materials Chemistry, 2001, vol. 11, p. 2470]. Also, improved discharge capacity for electrochemical lithium insertion and charge/discharge cycling ability, as compared with two-component nanocomposites, are observed for V2O5-based three-component hybrid host-guest nanocomposites: poly(2,5-dimercapto-1,3,4-thiadiazole)-PAn-V2O5 nanocomposites, disclosed by Park et al. [U.S. Pat. No. 6,582,850]; PAn-polyethylene oxide (PEO)-V2O5, disclosed by Pokhodenko et al. [UA Pat. No. 16318].
Accordingly, there is a need for improved methodology for forming cathode materials for lithium battery applications.
The present invention solves one or more problems of the prior art by providing in one embodiment a hybrid host-guest nanocomposite that is useful as a cathode in high discharge capacity lithium batteries. The nanocomposite of this embodiment includes V2O5 and conductive polymer or combinations of conductive polymers.
In another embodiment, a method for forming a hybrid two-component host-guest nanocomposite comprising a conducting conjugated polymer and vanadium oxide is provided. The method of this embodiment comprises combining a V2O5 xerogel and a monomer of one or more of conducting conjugated polymers to form a reaction mixture. The reaction mixture is then mechanically agitated to form the hybrid nanocomposite. This latter step is a mechanochemical treatment step. Advantageously, the mechanochemical treatment step is solvent-free.
In still another embodiment of the present invention, a method for forming a hybrid three-component host-guest nanocomposite comprising a conducting conjugated polymer, an ion conducting polymer, and vanadium oxide is provided. The method of this embodiment comprises combining a V2O5 xerogel and an ion conductive polymer to form a first reaction mixture. The first reaction mixture is then mechanically agitated to form a first hybrid nanocomposite. The first hybrid nanocomposite and a monomer of one or more of conductive polymers are then combined to form a second reaction mixture. The second reaction mixture is then mechanically agitated to form the hybrid three-component nanocomposite.
The two-component and three-component host-guest nanocomposites are advantageously prepared by effective and environmentally friendly methods. Moreover, these host-guest nanocomposites possess improved charge/discharge performance in comparison with the known prior art analogues. Accordingly, these nanocomposites can be used for creation of high discharge capacity-required lithium batteries.
Exemplary embodiments of the present invention will become more fully understood from the detailed description and the accompanying drawings, wherein:
Reference will now be made in detail to presently preferred compositions, embodiments and methods of the present invention, which constitute the best modes of practicing the invention presently known to the inventor. The figures are not necessarily to scale. However, it is to be understood that the disclosed embodiments are merely exemplary of the invention that may be embodied in various and alternative forms. Therefore, specific details disclosed herein are not to be interpreted as limiting, but merely as a representative basis for any aspect of the invention and/or as a representative basis for teaching one skilled in the art to variously employ the present invention.
Except in the examples, or where otherwise expressly indicated, all numerical quantities in this description indicating amounts of material or conditions of reaction and/or use are to be understood as modified by the word “about” in describing the broadest scope of the invention.
It is also to be understood that this invention is not limited to the specific embodiments and methods described below, as specific components and/or conditions may, of course, vary. Furthermore, the terminology used herein is used only for the purpose of describing particular embodiments of the present invention and is not intended to be limiting in any way.
It must also be noted that, as used in the specification and the appended claims, the singular form “a,” “an,” and “the” comprise plural referents unless the context clearly indicates otherwise. For example, reference to a component in the singular is intended to comprise a plurality of component.
With reference to
In an embodiment of the present invention, a hybrid organic-inorganic nanocomposites that is useful as a battery cathode material is provided. The nanocomposite of this embodiment includes V2O5 and a conductive polymer. In one variation, the nanocomposite is a two-component hybrid organic-inorganic nanocomposite. In another variation, the nanocomposite is a three-component hybrid organic-inorganic nanocomposite. The composites of the present embodiments consist of alternating layers with thicknesses in the angstrom to nanometer range.
In a refinement of the present embodiment, the conductive polymer is an electrically conducting conjugated polymer (“CCP”). Examples of suitable conducting conjugated polymers include, but are not limited to, polyaniline (“PAn”), polypyrrole (“PPy”), polythiophene (“PTh”), and combinations thereof, and derivatives thereof. Examples of suitable derivatives of these polymers include, but are not limited to, acid salts when the polymers include a basic group (e.g., acid chlorides of amines) and compounds formed by replacing a hydrogen atom with a halogen, an alkyl group (e.g., C1-C10 alkyl), an hydroxyl, an ester group, an alkoxy group, an aryl group, etc., and combinations thereof. In another refinement, the nanocomposite includes an ion conducting polymer. A non-limiting example of an ion conducting polymer is polyethylene oxide (“PEO”) and derivatives thereof. Examples of suitable derivatives of the PEO include, but are not limited to, acid salts when the polymers include a basic group (e.g., acid chlorides of amines) and compounds formed by replacing a hydrogen atom with a halogen, an alkyl group (e.g., C1-C10 alkyl), an hydroxyl, an ester group, an alkoxy group, an aryl group, etc., and combinations thereof. In still another refinement, the nanocomposite includes a conducting conjugated polymer and an ion conducting polymer.
In another embodiment of the present invention, a method of forming the nanocomposite set forth above is provided. The method of this embodiment includes a step of forming a reaction mixture comprising a vanadium oxide (e.g., V2O5) xerogel and a monomer of one or more of the polymers set forth above (i.e., CCP and/or PEO). The term “xerogel” as used herein refers to a solid formed by the removal of solvent or water of a gel. The reaction mixture is subsequently subjected to a mechanochemical treatment in which the reaction mixture is mechanically agitated. In a refinement, a predetermined amount of milling media is added to the reaction mixture prior to mechanochemical treatment.
In an embodiment in which a two component nanocomposite is formed, a V2O5 xerogel and a monomer of one or more of conducting conjugated polymers are combined to form a reaction mixture. Examples of useful monomers include, but are not limited to, aniline, pyrrole, thiophene, and derivatives thereof, and combinations thereof. Examples of suitable derivatives of the monomers include, but are not limited to, acid salts when the monomers include a basic group (e.g., acid chlorides of amines) and compounds formed by replacing a hydrogen atom with a halogen, an alkyl group (e.g., C1-C10 alkyl), an hydroxyl, an ester group, an alkoxy group, an aryl group, etc., and combinations thereof. The reaction mixture is then mechanically agitated in the mechanochemical treatment step to form the hybrid nanocomposite. In a refinement, the mechanochemical treatment step is solvent-free. In one variation, the V2O5 xerogel is present in an amount from about 83 to about 97 weight percent of the total weight of the total weight of the reaction mixture. In another variation, one or more of conducting conjugated polymers are present in an amount from about 3 to about 17 weight percent of the total weight of the total weight of the reaction mixture.
In an embodiment in which a three-component nanocomposite is formed, a V2O5 xerogel and an ion conductive polymer are combined to form a first reaction mixture. In one variation, the V2O5 xerogel is present in an amount from about 94 to about 98 weight percent of the total weight of the total weight of the first reaction mixture. In another variation, the ion conducting polymer is present in an amount from about 2 to about 6 weight percent of the total weight of the total weight of the reaction mixture. The first reaction mixture is then mechanically agitated in a mechanochemical treatment step to form a first hybrid nanocomposite. The first hybrid nanocomposite and a monomer of one or more of conductive polymers are then combined to form a second reaction mixture. The second reaction mixture is then mechanically agitated in a second mechanochemical treatment step to form the hybrid three-component nanocomposite. In a variation of this embodiment, the first hybrid nanocomposite is present in an about from about 86 to about 97 weight percent of the total weight second reaction mixture. In another variation, the one or more of conducting conjugated polymers are present in an amount from about 3 to about 14 weight percent of the total weight of the total weight of the second reaction mixture. In another variation of this embodiment one or more of the following conditions are present, the ion conducting polymer is present in an amount from about 2 to 6 percent of the total weight of the hybrid nanocomposite, the vanadium oxide is present in an amount from about 80 to 95 percent of the total weight of the hybrid nanocomposite, and the conducting conjugated polymer is present in an amount from about 3 to 14 percent of the total weight of the hybrid nanocomposite.
The V2O5 xerogel has a layered structure that is prepared by evaporation of an aqueous V2O5-containing sol. A number of techniques for preparing the V2O5-containing sol are known in the prior art. For example, the V2O5-containing sol may be prepared by reaction of crystalline V2O5 with hydrogen peroxide, or by interaction of melted V2O5 with water. Specifically, crystalline V2O5 is dissolved in aqueous hydrogen peroxide solution and then aged in air (typically about 2 week) at an elevated temperature (100° C. is suitable). The solvent is subsequently evaporated. The aged solution is then dried at an elevated temperature (e.g., about 120° C.) until a distance between V2O5 layers in the xerogel is from about 1.14 to about 1.19 nm. In a refinement, the distance between V2O5 layers in the xerogel is from about 1.15 to about 1.16 nm.
The reaction mixture, preferably with milling media therein, is subjected to mechanochemical treatment to promote intercalative polymerization in the case of the monomer of the corresponding CCP or intercalation of PEO macromolecules inside interlayer space of V2O5 xerogel. In a variation, the mechanochemical treatment is carried out under ambient conditions. In a refinement, the mechanochemical treatment is carried out at a temperature between 15° C. and 40° C. During mechanochemical treatment, a hybrid nanocomposite, organic macromolecules of which are located inside interlayer space of V2O5 xerogel, is formed.
The term “mechanochemical treatment” as used herein means a process in which mechanical energy is used to activate, initiate or promote a chemical reaction, a crystal structure transformation or a phase change in a material or a mixture of materials. Examples of mechanochemical treatment process include, but are not limited to, “mechanochemical synthesis”, “mechanochemical activation”, “reactive milling”, and related processes. In one variation, mechanochemical treatment includes a step in which a reaction mixture is agitated in the presence of a milling media to transfer mechanical energy to the reaction mixture. The reaction mixture can be contained in a closed vessel or chamber. The term “agitating” or “agitation” as used herein shall include applying at least one, or any combination of two or more of the fundamental kinematic motions including translation (e.g., side-to-side shaking), rotation (e.g., spinning or rotating) and inversion (e.g., end-over-end tumbling) to the reaction mixture. In a useful variation, all three motions are applied to the reaction mixture. It should be appreciated that such agitation can be accomplished with or without external stirring of the reaction mixture and milling media.
In a variation of the mechanochemical treatment step, a mixture of reactant powders or a mixture of reactant powder and liquid organic compound is combined in suitable proportions with milling media in a vessel or chamber that is mechanically agitated (i.e., with or without stirring) for a predetermined period of time at a predetermined intensity of agitation. In another variation of the mechanochemical treatment step, the reaction mixture is mechanically agitated (i.e., with or without stirring) for a predetermined period of time at a predetermined intensity of agitation under nominally ambient conditions in the absence of added liquids or organic solvents.
In still another variation of the method of forming the nanocomposites, a predetermined amount of milling media, preferably chemically-inert, rigid milling media, is added to a dry reaction mixture comprising xerogel V2O5 and organic component, which is a monomer of the corresponding CCP, or PEO herein, prior to mechanochemical treatment. Typically, the weight ratio of reaction mixture to milling media can range from about 1:3 to 1:40. The reaction mixture is subjected to mechanochemical treatment, for example, in a milling apparatus whereby the reaction mixture is agitated in the presence of milling media at ambient temperature (i.e., without the need for external heating). The term “chemically-inert” milling media as used herein means that the milling medium does not react chemically with any of the components of the reaction mixture. The rigid milling media advantageously comprises various materials such as natural minerals, ceramics, glass, metal or high-strength polymeric compositions, in a particulate form. Preferred ceramic materials, for example, can be selected from a wide array of ceramics desirably having sufficient hardness and friability to enable them to avoid being chipped or crushed during milling and also having sufficiently high density. Suitable densities for milling media are from about 3 to 15 g/cm3. Examples of ceramic materials include, but are not limited to, agate, aluminum oxide, zirconium oxide, zirconia-silica, yttria-stabilized zirconium oxide, magnesia-stabilized zirconium oxide, silicon nitride, silicon carbide, cobalt-stabilized tungsten carbide and the like, and combinations thereof. In a refinement, the glass milling media are spherical (e.g., beads), have a narrow size distribution, and are durable. Suitable metal milling media are typically spherical and generally have good hardness (i.e., Rockwell hardness RHC 60-70), extreme roundness, high wear resistance, and narrow size distribution. Metal milling media include, for example, balls fabricated from type 52100 chrome steel, type 316 or 440C stainless steel or type 1065 high carbon steel.
In a variation of the present embodiment, the mechanochemical treatment is accomplished by a milling apparatus that applies compressive forces and shear stress to the particles of the reaction mixture over a prolonged time. A suitable apparatus for accomplishment of the mechanochemical treatment of the present invention is a planetary ball mill, for example Pulverizette 6 available commercially from Fritsch.
Although the embodiments of the present invention are not limited to any particular theory of operation, it is believed that during the mechanochemical treatment of the reaction mixture, the impact of the milling media with particles of xerogel V2O5 and monomers of the corresponding CCP can result in the oxidation and polymerization of the organic molecules. It is further theorized that because of the layered structure of the xerogel particles, CCP can be advantageously inserted into the interlayer galleries (i.e., spaces) of the inorganic particles because of ion-exchange of protons in the matrix of the xerogel V2O5 by organic cations and the shear stress induced by mechanochemical treatment. It is also appreciated that polymerization and intercalation can take place simultaneously.
It is also theorized that the mechanochemical activation of interaction between particles of xerogel V2O5 and PEO can result in the insertion of the polymer chains into the interlayer galleries of V2O5 because of their affinity to protons in the matrix of the xerogel V2O5 and the shear stress induced by mechanochemical treatment. Moreover, it is also believed that in conditions of mechanochemical treatment of the prepared composite PEO-V2O5 particles and monomer of the corresponding CCP of the present invention can result in the oxidation and polymerization of the organic molecules. It is also believed that CCP can be advantageously inserted into the interlayer galleries of the inorganic particles because of ion-exchange of protons in the matrix of the xerogel V2O5 by organic cations and the shear stress induced by mechanochemical treatment because of the layered structure of the xerogel particles. It is not excluded by the applicants that polymerization and intercalation can take place simultaneously.
Mechanochemical treatment of the mixture of the xerogel V2O5 or the composite PEO-V2O5 and monomer of the corresponding CCP for an inadequate period of time (e.g., less than about 60 minutes) can result in non-homogeneity of the reaction mixture, incomplete polymerization and/or intercalation of the organic component and exhibits poor discharge performance. Prolonged mechanochemical treatment (e.g., >24 hours) is also undesirable since the hybrid nanocomposite becomes highly amorphous and also exhibits poor discharge performance. Therefore, in a refinement of the present embodiment, the mechanochemical treatment of the mixture is between 1 hour and 24 hours in duration.
The following examples illustrate the various embodiments of the present invention. Those skilled in the art will recognize many variations that are within the spirit of the present invention and scope of the claims.
A V2O5 xerogel is prepared by dissolving 15 g of crystalline V2O5 in 1.5 L of 10% hydrogen peroxide solution, which is aged for two weeks in air. Powder form of V2O5 is obtained by evaporation of the solution at the temperature of 100° C. and is dried at the temperature of 120° C., while the interlayer distance between the galleries of V2O5 becomes 1.14-1.19 nm, preferably 1.15-1.16 nm.
A two-component hybrid host-guest nanocomposite based on PAn and V2O5 is prepared by combining 3 g of xerogel V2O5 of Example 1 and 0.186 g of anilinium chloride preliminarily recrystallized in water with thirty 1 cm diameter spherical agate milling media in an 80 mL grinding jar. The weight ratio of reactants to milling media is about 1:14. The mixture is mechanochemically treated using a planetary ball mill Pulverizette 6 at an agitation speed of 300 rpm for a period of 8 hours. The product is separated from milling media by dry sieving and purified by 20-fold extraction with acetonitrile in a Soxlet apparatus. The nanocomposite PAn0.11V2O5 is finally obtained.
A two-component hybrid host-guest nanocomposite based on PPy and V2O5 is prepared by combining 3 g of xerogel V2O5 of Example 1 and 0.098 mL of pyrrole preliminarily distilled in an atmosphere of argon with thirty 1 cm diameter spherical agate milling media in an 80 mL grinding jar. The weight ratio of reactants to milling media is about 1:14. The mixture is mechanochemically treated using a planetary ball mill Pulverizette 6 at an agitation speed of 300 rpm for a period of 8 hours. The product—PPy0.1V2O5 nanocomposite—is separated from milling media by dry sieving.
A two-component hybrid host-guest nanocomposite based on PTh and V2O5 is prepared by combining 3 g of xerogel V2O5 of Example 1 and 0.118 g of bithiophene preliminarily recrystallized in ethanol with thirty 1 cm diameter spherical agate milling media in an 80 mL grinding jar. The weight ratio of reactants to milling media is about 1:14. The mixture is mechanochemically treated using a planetary ball mill Pulverizette 6 at an agitation speed of 300 rpm for a period of 8 hours. The product—PTh0.1V2O5 nanocomposite—is separated from milling media by dry sieving.
A two-component hybrid host-guest nanocomposite based on PEO and V2O5 is prepared by combining 6 g of xerogel V2O5 of Example 1 and 0.316 g of PEO (molecular weight 6·105, Aldrich) with thirty 1 cm diameter spherical agate milling media in an 80 mL grinding jar. The weight ratio of reactants to milling media is about 1:7. The mixture is mechanochemically treated using a planetary ball mill Pulverizette 6 at an agitation speed of 300 rpm for a period of 8 hours. The product—PEO0.25V2O5 nanocomposite—is separated from milling media by dry sieving.
A three-component hybrid host-guest nanocomposite based on PAn, PEO and V2O5 is prepared by combining 3 g of PEO0.25V2O5 nanocomposite of Example 5 and 0.302 g of anilinium chloride preliminarily recrystallized in water with thirty 1 cm diameter spherical agate milling media in an 80 mL grinding jar. The weight ratio of reactants to milling media is about 1:13. The mixture is mechanochemically treated using a planetary ball mill Pulverizette 6 at an agitation speed of 300 rpm for a period of 8 hours. The product is separated from milling media by dry sieving and purified by 20-fold extraction with acetonitrile in a Soxlet apparatus. The nanocomposite PAn0.12PEO0.22V2O5 is finally obtained.
A three-component hybrid host-guest nanocomposite based on PPy, PEO and V2O5 is prepared by combining 3 g of PEO0.25V2O5 nanocomposite of Example 5 and 0.102 mL of pyrrole preliminarily distilled in an atmosphere of argon with thirty 1 cm diameter spherical agate milling media in an 80 mL grinding jar. The weight ratio of reactants to milling media is about 1:14. The mixture is mechanochemically treated using a planetary ball mill Pulverizette 6 at an agitation speed of 300 rpm for a period of 8 hours. The product—PPy0.1PEO0.25V2O5 nanocomposite—is separated from milling media by dry sieving.
A three-component hybrid host-guest nanocomposite based on PAn, PEO and V2O5 is prepared by combining 3 g of PEO0.25V2O5 nanocomposite of Example 5 and 0.127 g of bithiophene preliminarily recrystallized in ethanol with thirty 1 cm diameter spherical agate milling media in an 80 mL grinding jar. The weight ratio of reactants to milling media is about 1:14. The mixture is mechanochemically treated using a planetary ball mill Pulverizette 6 at an agitation speed of 300 rpm for a period of 8 hours. The product—PTh0.1PEO0.25V2O5 nanocomposite—is separated from milling media by dry sieving.
FTIR Measurements
Three bands lower than 1000 cm−1 in spectrum (a) correspond to the typical vibrations of bonds between V and O. The bands about 1115, 1244, 1301, 1472 and 1558 cm−1 in spectrum (b) are characteristic of PAn. The bands about 794, 932, 1053, 1213, 1296, 1480 and 1563 cm−1 in spectrum (c) are characteristic of PPy. The bands about 690, 786, 1034, 1115, 1205 and 1334 cm−1 in spectrum (d) are characteristic of PTh. The bands about 1456, 1343, 1280, 1099 cm−1 in spectrum (e) are characteristic of PEO. The spectrum (f) clearly shows PAn and PEO co-existed inside the V2O5 layers. Spectrum (g) clearly shows PPy and PEO co-existed inside the V2O5 layers. Spectrum (h) clearly shows PTh and PEO co-existed inside the V2O5 layers.
X-Ray Diffraction (XRD) Measurements
Discharge Characteristics of as-Prepared Samples
A Swagelok™-type cell is assembled in the dry glove box for electrochemical measurements. The mixture of the synthesized hybrid organic-inorganic material, carbon black and the poly[(vinylidene fluoride)-co-hexafluoropropylene] (75:15:10 wt. %) is used as a cathode, Li foil as a negative electrode and 1M solution of LiClO4 in ethylene carbonate/dimethyl carbonate (50:50 vol. %) as an electrolyte.
Comparison of Cycling Ability
Variation of discharge capacity with respect to the number of cycles for the as-prepared materials is depicted in
The two-component nanocomposites based on PPy and V2O5 possess the greatest capacity. The three-component nanocomposites have somewhat lower capacity, nevertheless they are more stable at prolonged cycling. The presence of the macromolecules of PEO, which have ion conducting properties, inside nanoparticles of the inorganic component promotes the process of electrochemical intercalation of lithium ions and improves the stability at charge-discharge cycling.
While embodiments of the invention have been illustrated and described, it is not intended that these embodiments illustrate and describe all possible forms of the invention. Rather, the words used in the specification are words of description rather than limitation, and it is understood that various changes may be made without departing from the spirit and scope of the invention.
| Number | Name | Date | Kind |
|---|---|---|---|
| 5368957 | Kozmik et al. | Nov 1994 | A |
| 6582850 | Park et al. | Jun 2003 | B2 |
| 7819962 | Gu | Oct 2010 | B2 |
| 7899552 | Atanasoska et al. | Mar 2011 | B2 |
| 20090272949 | Buttry | Nov 2009 | A1 |
| Number | Date | Country |
|---|---|---|
| 16318 | Aug 2006 | UA |
| Number | Date | Country | |
|---|---|---|---|
| 20110121225 A1 | May 2011 | US |
