Elastomeric Gasket Contacting The Inner Surface Of The Casing Lid Of A Pulse Dischargeable Lithium Electrochemical Cell
20240021934 ยท 2024-01-18
Inventors
Cpc classification
H01M50/188
ELECTRICITY
International classification
H01M50/188
ELECTRICITY
Abstract
A pulse dischargeable electrochemical cell, preferably of a Li/SVO couple, is described. To help prevent lithium clusters from bridging to the terminal pin extending below the casing lid and connected to the cathode current collector tab, an elastomeric gasket directly contacts the inner surface of the lid. The elastomeric gasket is preferably a unitary member comprising an O-ring gasket portion that contacts the sealing glass of the glass-to-metal seal (GTMS), and a sheet-shaped gasket portion connected to the O-ring gasket portion and that contacts the inner surface of the lid. The GTMS does not have a ferrule. Instead, the sealing glass seals directly to the lid and to the terminal pin. The elastomeric gasket resides between the lid and an insulator compartment, which is described in co-assigned U.S. Pat. No. 10,629,862 to Roy et al.
Claims
1. An electrochemical cell, comprising: a) a casing comprising: i) a container having a sidewall extending from a closed bottom wall to an open end; and ii) a lid closing the open end of the container, wherein the lid has inner and outer lid surfaces extending to a peripheral edge, and wherein the lid has a terminal pin opening and an electrolyte fill port; and b) a terminal pin extending through the terminal pin opening; c) a glass-to-metal seal (GTMS) comprises a sealing glass that electrically isolates the terminal pin from the lid so that the terminal pin is in a non-conductive relation with the casing; d) an elastomeric gasket directly contacting the inner surface of the lid; e) an electrode assembly housed inside the casing, the electrode assembly comprising: i) an anode comprising an anode active material supported on an anode current collector, wherein the anode current collector comprises at least one anode lead conductively connected to the casing; ii) a cathode comprising a cathode active material supported on a cathode current collector, wherein the cathode current collector comprises at least one cathode tab extending outwardly beyond a perimeter edge of the cathode current collector, the perimeter edge from which the at least one cathode tab extends being spaced closer to the lid than a remainder of the cathode current collector; and iii) at least one separator positioned between the anode and the cathode to prevent direct physical contact between them; and f) an electrolyte provided in the casing to activate the electrode assembly.
2. The electrochemical cell of claim 1, wherein the elastomeric gasket comprises an O-ring gasket portion that contacts the sealing glass of the GTMS and a sheet-shaped gasket portion that is connected to the O-ring gasket portion and contacts the inner surface of the lid.
3. The electrochemical cell of claim 2, wherein the O-ring gasket portion and the sheet-shaped gasket portion are connected together as a unitary elastomeric gasket.
4. The electrochemical cell of claim 2, wherein the sealing glass of the GTMS has an inner meniscus that is recessed distally from the inner surface of the lid with the O-ring gasket portion of the elastomeric gasket contacting the inner meniscus.
5. The electrochemical cell of claim 2, wherein the peripheral edge of the lid comprises spaced apart upper and lower edge portions that meet with right and left end edge portions, and wherein the sheet-shaped gasket portion of the elastomeric gasket extends to the upper and lower lid edge portions but is spaced from the right and left end edge portions of the lid, wherein the sheet-shaped gasket portion of the elastomeric gasket spaced from the right and left end edge portions of the lid provides uncovered portions of the inner lid surface that extend from an outer edge of the elastomeric gasket to an inner surface of the container sidewall, and wherein the uncovered portions of the inner lid surface are where lithium clusters can contact the lid without bridging to the at least one cathode current tab connected to the terminal pin.
6. The electrochemical cell of claim 1, wherein the lid does not have a ferrule so that the sealing glass of the GTMS seals directly to the lid and directly to the terminal pin in the lid opening, and wherein the elastomeric gasket comprises an O-ring gasket portion that contacts the sealing glass of the GTMS and a sheet-shaped gasket portion that is connected to the O-ring gasket portion and contacts the inner surface of the lid.
7. The electrochemical cell of claim 1, having an insulator compartment comprising: a) a first insulator member having a first surrounding sidewall extending from a first major face wall to a first outer edge, the first major face wall being disposed adjacent to the insulator gasket contacting the inner surface of the lid with the first surrounding sidewall extending away from the lid toward the upper edge of the electrode assembly, wherein the terminal pin extends through a first opening in the first major face wall; and b) a second insulator member having a second surrounding sidewall extending from a second major face wall to a second outer edge, the second major face wall being disposed adjacent to the perimeter edge of the cathode current collector with the second surrounding sidewall extending away from the perimeter edge toward the lid, wherein the cathode tab extends through a second opening in the second major face wall, c) wherein the first and second insulator members are mated to each other with one of the first and second outer edges of the first and second surrounding sidewalls facing the other of the first and second major face walls so that at least a portion of the second surrounding sidewall is in an overlapping, direct contact relationship with at least a portion of the first surrounding sidewall to thereby form the insulator compartment residing between the perimeter edge and the lid, and d) wherein the terminal pin is connected to the cathode tab in the insulator compartment, and e) wherein the elastomeric gasket has a distal gasket surface spaced from a proximal gasket surface, and wherein the distal gasket surface directly contacts the inner surface of the lid, and the first major face wall of the first insulator member of the insulator compartment directly contacts the proximal gasket surface.
8. The electrochemical cell of claim 7, wherein the electrode assembly further comprises at least two cathode plates, each cathode plate having a cathode tab conductively connected to the terminal pin inside the insulator compartment, and wherein at least a portion of the anode resides between the at least two cathode plates.
9. The electrochemical cell of claim 8, wherein the anode has a serpentine shape with one of the at least two cathode plates interleaved between a fold of the serpentine anode, and wherein each of the at least two cathode plates has a cathode tab housed inside the insulator compartment where the cathode tabs are conductively connected to a cathode bridge, and wherein the cathode bridge is conductively connected to the terminal pin in the insulator compartment.
10. The electrochemical cell of claim 8, wherein the second opening in the second major face wall of the second insulator member is configured to receive the cathode tabs comprising the at least two cathodes connected to the cathode bridge.
11. The electrochemical cell of claim 7, wherein the first and second insulator members of the insulator compartment are composed of a material that is impervious to lithium-ion flow therethrough and which is selected from the group of polyethylene, polyethylenechlorotrifluoroethylene, polypropylene, ETFE, and PTFE, and combinations thereof.
12. The electrochemical cell of claim 1, wherein the cathode active material is selected from the group of silver vanadium oxide, CF.sub.x, SVO/current collector/CF.sub.x, copper silver vanadium oxide, V.sub.2O.sub.5, MnO.sub.2, LiCoO.sub.2, LiNiO.sub.2, LiMn.sub.2O.sub.4, TiS.sub.2, Cu.sub.2S, FeS, FeS.sub.2, Ag.sub.2O, Ag.sub.2O.sub.2, CuF.sub.2, Ag.sub.2CrO.sub.4, copper oxide, and copper vanadium oxide, and mixtures thereof.
13. An electrochemical cell, comprising: a) a casing comprising: i) a container having a sidewall extending from a closed bottom wall to an open end; and ii) a lid closing the open end of the container, wherein the lid has inner and outer lid surfaces extending to a peripheral edge, and wherein the lid has a terminal pin opening and an electrolyte fill port; and b) a terminal pin extending through the terminal pin opening with a sealing glass electrically isolating the terminal pin from the lid so that the terminal pin is in a non-conductive relation with the casing; c) an elastomeric gasket directly contacting the inner surface of the lid; d) an electrode assembly housed inside the casing, the electrode assembly comprising: i) an anode comprising lithium supported on an anode current collector, wherein the anode current collector comprises at least one anode lead conductively connected to the casing; ii) a cathode comprising a cathode current collector comprising opposed major surfaces, wherein silver vanadium oxide and CF.sub.x are contacted to the opposed major surfaces of the cathode current collector, and wherein the cathode current collector comprises a cathode tab extending outwardly beyond a perimeter edge of the cathode current collector; and iii) at least one separator positioned between the anode and the cathode to prevent direct physical contact between them; and e) an electrolyte provided in the casing to activate the electrode assembly.
14. The electrochemical cell of claim 13, wherein the elastomeric gasket comprises an O-ring gasket portion that contacts the sealing glass of the GTMS and a sheet-shaped gasket portion that is connected to the O-ring gasket portion and contacts the inner surface of the lid.
15. The electrochemical cell of claim 14, wherein the O-ring gasket portion and the sheet-shaped gasket portion are connected together as a unitary elastomeric gasket.
16. The electrochemical cell of claim 14, wherein the sealing glass of the GTMS has an inner meniscus that is recessed distally from the inner surface of the lid with the O-ring gasket portion of the elastomeric gasket contacting the inner meniscus.
17. The electrochemical cell of claim 14, wherein the peripheral edge of the lid comprises spaced apart upper and lower edge portions that meet with right and left end edge portions, and wherein the sheet-shaped gasket portion of the elastomeric gasket extends to the upper and lower lid edge portions but is spaced from the right and left end edge portions of the lid, wherein the sheet-shaped gasket portion of the elastomeric gasket spaced from the right and left end edge portions of the lid provides uncovered portions of the inner lid surface that extend from an outer edge of the elastomeric gasket to an inner surface of the container sidewall, and wherein the uncovered portions of the inner lid surface are where lithium clusters can contact the lid without bridging to the at least one cathode current tab connected to the terminal pin.
18. The electrochemical cell of claim 13, having an insulator compartment comprising: a) a first insulator member having a first surrounding sidewall extending from a first major face wall to a first outer edge, the first major face wall being disposed adjacent to the insulator gasket contacting the inner surface of the lid with the first surrounding sidewall extending away from the lid toward the upper edge of the electrode assembly, wherein the terminal pin extends through a first opening in the first major face wall; and b) a second insulator member having a second surrounding sidewall extending from a second major face wall to a second outer edge, the second major face wall being disposed adjacent to the perimeter edge of the cathode current collector with the second surrounding sidewall extending away from the perimeter edge toward the lid, wherein the cathode tab extends through a second opening in the second major face wall, c) wherein the first and second insulator members are mated to each other with one of the first and second outer edges of the first and second surrounding sidewalls facing the other of the first and second major face walls so that at least a portion of the second surrounding sidewall is in an overlapping, direct contact relationship with at least a portion of the first surrounding sidewall to thereby form the insulator compartment residing between the perimeter edge and the lid, and d) wherein the terminal pin is connected to the cathode tab in the insulator compartment, and e) wherein the elastomeric gasket has a distal gasket surface spaced from a proximal gasket surface, and wherein the distal gasket surface directly contacts the inner surface of the lid, and the first major face wall of the first insulator member of the insulator compartment directly contacts the proximal gasket surface.
19. The electrochemical cell of claim 18, a) wherein the electrode assembly further comprises at least two cathode plates, each cathode plate having a cathode tab conductively connected to the terminal pin inside the insulator compartment, and wherein at least a portion of the anode resides between the at least two cathode plates, or b) wherein the anode has a serpentine shape with one of the at least two cathode plates interleaved between a fold of the serpentine anode, and wherein each of the at least two cathode plates has a cathode tab housed inside the insulator compartment where the cathode tabs are conductively connected to a cathode bridge, and wherein the cathode bridge is conductively connected to the terminal pin in the insulator compartment.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0036] Referring now to the drawings,
[0037] As shown in
[0038] The exemplary electrochemical cell 10 shown in
[0039] Alternatively, a case-positive cell design may be constructed by reversing the electrical connections. In other words, terminal pin 38 is connected to the anode 32 via the anode tab 36A extending from the anode current collector 36 and the cathode 34 is electrically connected to the container and lid 14, 16 via the cathode tab 40A extending from the cathode current collector 40.
[0040] With respect to the orientation of the lid 16 shown in
[0041] As further shown in
[0042] Once the electrode assembly 28 is appropriately positioned inside the container 14, the lid 16 is fitted over the open end thereof. In a preferred embodiment, the perimeter edge of the lid 16 is positioned within an interior perimeter of the surrounding walls 18, 20, 22 and 24 forming the open-ended container 14. Alternatively, the lid 16 may be positioned with its inner surface 16B contacting an upper edge of the surrounding walls 18, 20, 22 and 24. In any event, the lid 16 is preferably welded to the open end of the container 14, preferably by a laser weld (not shown), to close the container and thereby provide the casing 12. Alternatively, other joining methods such as resistance welding, arc welding, magnetic pulse welding, or soldering may be used to join the lid 16 to the open-ended container 14. It will be apparent to those skilled in the art that conventional welding parameters may be used in joining the two parts 14, 16 together.
[0043]
[0044] The lid 16 also has a second opening 60 extending through its thickness. This opening 60 serves as an electrolyte fill port for filling the casing 12 with an electrolyte (not shown) after the electrode assembly 28 is housed in the container 14 and the open end of the container is closed by the lid 16. In its fully assembled condition shown in
[0045] As shown in
[0046] In contrast, according to the present invention shown in
[0047] Turning now to
[0048] To further help prevent lithium clusters from bridging between the anode 32 and the positive polarity components for the cells 10 and 10A, an insulator compartment 70 (
[0049] The first clamshell-shaped insulator member 72 has a first surrounding sidewall 72A meeting a first major face wall 72B. The first major face wall 72B is contacted to the planar sheet-shaped portion 68B of the unitary elastomeric gasket 68 which, in turn, is contacted the inner surface 16B of the lid 16 with the first surrounding sidewall 72A extending towards the electrode assemblies 28, 28A including the cathode 34, 34A. The first major face wall 72B has a first opening (not shown) through which the terminal pin 38 extends.
[0050] The second clamshell-shaped insulator member 74 has a second surrounding sidewall 74A meeting a second major face wall 74B. The second major face wall 74B is disposed adjacent to the upper edge of the electrode assemblies 28, 28A with the second surrounding sidewall 74A extending towards the lid 16. The second major face wall 74B has a second opening or window 76 for receiving the at least one cathode tab 40A of the electrochemical cell 10 shown in
[0051] The insulator compartment 70 is composed of an electrically insulative material, which is also chemically inert with respect to the anode and cathode active materials. Likewise, such insulative material is both chemically inert and insoluble with respect to the electrolyte, which is described in greater detail herein. To that end, illustrative embodiments of suitable insulator materials that are substantially impervious to lithium-ion flow are selected from polyethylene, polyethylenechlorotrifluoroethylene, polypropylene, ETFE, and PTFE, and combinations thereof. Suitable insulator material also include thermoplastic fluoropolymer, such as, but not limited to HALAR or TEFZEL.
[0052] As previously discussed, lithium deposition is induced by high-rate intermittent pulse discharge of a lithium/silver vanadium oxide cell, which can form lithium clusters that bridge between the negative casing 12 and the positive connection to the cathode 30 including the cathode tab 40A extending from the current collector 40 connected to the terminal pin 38. This conductive bridge can then result in an internal loading mechanism that could prematurely discharge the cell.
[0053] Moreover, as previously described, if the first major face wall of the first clamshell-shaped insulator member described by the '862 patent to Roy et al. is not positioned tightly against the inner surface of the lid 16, there can be a very small gap that could be wide enough for a lithium cluster to form and contact the terminal pin 38. Moreover, since the lid 16 is made of a metal material, for example, titanium and the insulator compartment 70 is made from a polymeric material, it is not always possible to get a tight seal between the metal lid and polymeric insulator compartment.
[0054] To help prevent lithium clusters from bridging from the anode to the positive polarity cathode connections including the cathode tab 40A extending from the cathode current collector 40 and connected to the terminal pin 38 in the electrochemical cell 10 shown in
[0055] Further, since the sheet-shaped portion 68B of the elastomeric gasket 68 has a width that extends from the rounded border 42A of the upper side edge portion 42 to the rounded border 44A of the lower side edge portion 44 of the lid 16, and the insulator compartment 70 is fitted into the container contacting the opposed container sidewalls 18, 20, there is no portion of the inside of the container 14 in this area that is not covered. However, the elastomeric gasket 68 and the insulator compartment 70 only extend toward but are spaced from the end walls 22 and 24 of the container 14. Not only does this leave the electrolyte fill port 60 uncovered, which is required to fill the casing 12 with electrolyte, but even though the lid is of a negative polarity in a case-negative cell design, it provides areas on the inner surface 16B on the lid 16 to which lithium clusters can bridge. These uncovered areas are considered to be far enough away from the cathode terminal connections so as to not present a problem with undesirable lithium cluster bridging and subsequent premature discharge the cells 10, 10A.
[0056] It should be noted that the electrochemical cells 10, 10A of the present invention, as illustrated in
[0057] In that respect, a primary electrochemical cell that possesses sufficient energy density and discharge capacity for the rigorous requirements of implantable medical devices comprises a lithium anode or its alloys, for example, LiSi, LiAl, LiB and LiSiB. The form of the anode may vary, but preferably it is of a thin sheet or foil pressed or rolled on the metallic anode current collector 36.
[0058] The cathode of a primary cell is of an electrically conductive material, preferably a solid material. The solid cathode may comprise a metal element, a metal oxide, a mixed metal oxide, and a metal sulfide, and combinations thereof. A preferred cathode active material is selected from the group consisting of silver vanadium oxide, copper silver vanadium oxide, manganese dioxide, cobalt nickel, nickel oxide, copper oxide, copper sulfide, iron sulfide, iron disulfide, titanium disulfide, copper vanadium oxide, and mixtures thereof. By way of example, in a case-negative primary electrochemical cell, silver vanadium oxide, as described in U.S. Pat. Nos. 4,310,609 and 4,391,729 to Liang et al., both assigned to the assignee of the present invention and incorporated herein by reference, is a suitable cathode active material.
[0059] Before fabrication into a cathode for incorporation into the electrochemical cells 10, 10A, however, the cathode active material is mixed with a binder material such as a powdered fluoro-polymer, more preferably powdered polytetrafluoroethylene or powdered polyvinylidene fluoride (PVDF) present at about 1 to about 5 weight percent of the cathode mixture. Further, up to about 10 weight percent of a conductive diluent is preferably added to the cathode mixture to improve conductivity. Suitable materials for that purpose include acetylene black, carbon black and/or graphite or a metallic powder such as powdered nickel, aluminum, titanium, and stainless steel. The preferred cathode active mixture thus includes a powdered fluoro-polymer binder present at about 3 weight percent, a conductive diluent present at about 3 weight percent, and about 94 weight percent of the cathode active material.
[0060] The cathode 34 may be prepared by rolling, spreading, or pressing the cathode active mixture onto a suitable cathode current collector 40. Cathodes prepared as described above are preferably in the form of a strip wound with a corresponding strip of anode material in a structure similar to a jellyroll or a flat-folded electrode stack. The prismatic design shown in
[0061] In order to prevent internal short circuit conditions, the cathode 34 is separated from the anode 32 by the separator 30. The separator 30 is preferably made of a fabric woven from fluoropolymeric fibers including polyvinylidine fluoride, polyethylenetetrafluoroethylene, and polyethylenechlorotrifluoroethylene used either alone or laminated with at least one of a fluoropolymeric microporous film, non-woven glass, polypropylene, polyethylene, glass fiber materials, ceramics, polytetrafluoroethylene membrane commercially available under the designation ZITEX (Chemplast Inc.), polypropylene membrane commercially available under the designation CELGARD (Celanese Plastic Company, Inc.), and a membrane commercially available under the designation DEXIGLAS (C. H. Dexter, Div., Dexter Corp.).
[0062] A primary electrochemical cell includes a nonaqueous, ionically conductive electrolyte having an inorganic, ionically conductive salt dissolved in a nonaqueous solvent and, more preferably, a lithium salt dissolved in a mixture of a low viscosity solvent and a high permittivity solvent. The salt serves as the vehicle for migration of anode ions to intercalate or react with the cathode active material, and suitable salts include LiPF.sub.6, LiBF.sub.4, LiAsF.sub.6, LiSbF.sub.6, LiClO.sub.4, LiO.sub.2, LiAlCl.sub.4, LiGaCl.sub.4, LiC (SO.sub.2CF.sub.3).sub.3, LiN (SO.sub.2CF.sub.3).sub.2, LiSCN, LiO.sub.3SCF.sub.3, LiC.sub.6F.sub.5SO.sub.3, LiO.sub.2CCF.sub.3, LiSO.sub.6F, LiB(C.sub.6H.sub.5).sub.4, LiCF.sub.3SO.sub.3, and mixtures thereof.
[0063] Suitable low viscosity solvents include esters, linear and cyclic ethers and dialkyl carbonates such as tetrahydrofuran (THE), methyl acetate (MA), diglyme, triglyme, tetragylme, dimethyl carbonate (DMC), 1,2-dimethoxyethane (DME), 1,2-diethoxyethane (DEE), 1-ethoxy,2-methoxyethane (EME), ethyl methyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, diethyl carbonate, dipropyl carbonate, and mixtures thereof. High permittivity solvents include cyclic carbonates, cyclic esters, and cyclic amides such as propylene carbonate (PC), ethylene carbonate (EC), butylene carbonate, acetonitrile, dimethyl sulfoxide, dimethyl, formamide, dimethyl acetamide, -valerolactone, -butyrolactone (GBL), N-methyl-pyrrolidinone (NMP), and mixtures thereof. The preferred electrolyte for a lithium primary cell, for example, a lithium/silver vanadium oxide electrochemical cell is 0.8M to 1.5M LiAsF.sub.6 or LiPF.sub.6 dissolved in a 50:50 mixture, by volume, of PC as the preferred high permittivity solvent and DME as the preferred low viscosity solvent.
[0064] In secondary electrochemical systems, the anode 32 comprises a material capable of intercalating and de-intercalating lithium. A carbonaceous anode comprising any of the various forms of carbon (e.g., coke, graphite, acetylene black, carbon black, glassy carbon, etc.), which are capable of reversibly retaining the lithium species, is preferred. Graphite is particularly preferred due to its relatively high lithium-retention capacity. Regardless of the form of the carbon, however, fibers of the carbonaceous material are particularly advantageous because they have excellent mechanical properties that permit them to be fabricated into rigid electrodes capable of withstanding degradation during repeated charge/discharge cycling.
[0065] The cathode 34 of a secondary cell preferably comprises a lithiated material that is stable in air and readily handled. Examples of such air-stable lithiated cathode materials include oxides, sulfides, selenides, and tellurides of such metals as vanadium, titanium, chromium, copper, molybdenum, niobium, iron, nickel, cobalt, and manganese. More preferred oxides include LiNiO.sub.2, LiMn.sub.2O.sub.4, LiCoO.sub.2, LiCo.sub.0.92Sn.sub.0.08O.sub.2, LiCo.sub.1-xNixO.sub.2, LiFePO.sub.4, LiNi.sub.xMn.sub.yCo.sub.1-x-yO.sub.2, and LiNi.sub.xCo.sub.yAl.sub.1-x-yO.sub.2.
[0066] The lithiated active material is preferably mixed with a conductive additive selected from acetylene black, carbon black, graphite, and powdered metals of nickel, aluminum, titanium, and stainless steel. The cathode further comprises a fluoro-resin binder, preferably in a powder form, such as PTFE, PVDF, ETFE, polyamides and polyimides, and mixtures thereof.
[0067] The respective current collectors 36, 40 are selected from stainless steel, titanium, tantalum, platinum, gold, aluminum, cobalt nickel alloys, highly alloyed ferritic stainless steel containing molybdenum and chromium, and nickel-, chromium- and molybdenum-containing alloys.
[0068] Suitable secondary electrochemical systems are comprised of nonaqueous electrolytes of an inorganic salt dissolved in a nonaqueous solvent and more preferably a lithium salt dissolved in a quaternary mixture of organic carbonate solvents. Suitable organic carbonate solvents comprise dialkyl (non-cyclic) carbonates selected from dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), ethyl methyl carbonate (EMC), methyl propyl carbonate (MPC), and ethyl propyl carbonate (EPC), and mixtures thereof, and at least one cyclic carbonate selected from propylene carbonate (PC), ethylene carbonate (EC), butylene carbonate (BC), and vinylene carbonate (VC), and mixtures thereof. Organic carbonates are generally used in the electrolyte solvent system for such electrochemical cell chemistries because they exhibit high oxidative stability toward cathode materials and good kinetic stability toward anode materials.
[0069] The electrochemical cells 10, 10A, whether of a primary or a secondary chemistry, are thereafter filled with the electrolyte described hereinabove and hermetically sealed such as by close-welding a titanium plug 62 into the fill port 60, but not limited thereto.
[0070] It is appreciated that various modifications to the inventive concepts described herein may be apparent to those skilled in the art without departing from the spirit and scope of the present invention as defined by the hereinafter appended claims.