Abstract:
An aspect of the present invention is an electrical device, where the device includes a current collector and a porous active layer electrically connected to the current collector to form an electrode. The porous active layer includes MgB x  particles, where x≧1, mixed with a conductive additive and a binder additive to form empty interstitial spaces between the MgB x  particles, the conductive additive, and the binder additive. The MgB x  particles include a plurality of boron sheets of boron atoms covalently bound together, with a plurality of magnesium atoms reversibly intercalated between the boron sheets and ionically bound to the boron atoms.

Description:
CROSS-REFERENCE TO RELATED APPLICATIONS 
     This application claims priority to U.S. Provisional Application No. 61/978,317, filed Apr. 11, 2014, the contents of which are incorporated by reference in their entirety. 
    
    
     CONTRACTUAL ORIGIN 
     The United States Government has rights in this invention under Contract No. DE-AC36-08G028308 between the United States Department of Energy and the Alliance for Sustainable Energy, LLC, the Manager and Operator of the National Renewable Energy Laboratory. 
    
    
     BACKGROUND 
     Rechargeable lithium ion batteries have found considerable use in applications such as hearing aids, computing devices, phones, and cameras. For example, lithium has served as the anode material for metal-air batteries due to its high energy density. However, the energy densities and efficiencies of currently available rechargeable lithium ion battery designs remain below what is needed for these types of batteries to meet the needs of the light duty transportation sector. Thus, the advancement of electrical vehicles and large-scale energy storage devices requires further development of high-energy-density, cost-effective, long lasting, and abuse-tolerant batteries. In addition, alternatives to lithium batteries are desirable due to lithium&#39;s tendency in some conditions to react violently, and due to lithium&#39;s tendency to form dendrites, which can limit lithium battery performance and lifespan. 
     Magnesium-ion batteries provide an attractive alternative electrode material to lithium-ion batteries because magnesium is abundant and has a low toxicity. Magnesium-ion batteries also offer the benefit of two-electron reactions instead of the one-electron reactions provided by lithium-ion batteries. Thus, magnesium-ion batteries may provide the energy requirements needed to meet the needs of portable devices, electric vehicles, and energy storage applications. However, to date, magnesium-ion batteries have seen only limited success. This is at least partially due to the formation of electronic and ionic insulating films on the magnesium-metal anode surfaces, in magnesium-ion batteries utilizing either non-aqueous or aqueous electrolytes. These films reduce the ability of the magnesium metal to continuously obtain magnesium ions. The chemistry of magnesium metal in aprotic electrolytic solutions often results in the growth of these films, which limits the reversible deposition/dissolution reaction of Mg/Mg 2+ . Thus, there remains a need for safer and more functional rechargeable electrodes and batteries that provide better performance than the incumbent technologies, while maintaining economic viability. 
     SUMMARY OF THE INVENTION 
     An aspect of the present invention is an electrical device, where the device includes a current collector and a porous active layer electrically connected to the current collector to form an electrode. The porous active layer includes MgB x  particles, where x≧1, mixed with a conductive additive and a binder additive to form empty interstitial spaces between the MgB x  particles, the conductive additive, and the binder additive. The MgB x  particles include a plurality of boron sheets of boron atoms covalently bound together, with a plurality of magnesium atoms reversibly intercalated between the boron sheets and ionically bound to the boron atoms. 
     In some embodiments of the present invention, the electrical device may include a second electrode and a non-aqueous liquid electrolyte, where at least the active layer of the first electrode and the second electrode are immersed in the electrolyte. The first electrode may have a first state, where up to 75% of the magnesium atoms are reversibly intercalated between the boron sheets, and a second state, where a portion of the magnesium atoms are reversibly deintercalated from the active layer, resulting in the transfer of Mg 2+  ions into the electrolyte. 
     In some embodiments of the present invention, the electrical device may include a conductive additive that is acetylene black. In some embodiments of the present invention, the electrical device may include a binder additive that is polyvinylidene fluoride. In some embodiments of the present invention, the active layer may include a MgB 2  content ranging from about 50 wt % MgB 2  to about 80 wt % MgB 2 , a conductive additive content ranging from about 10 wt % of the conductive additive to about 30 wt % of the conductive additive, and where the remainder of active layer may be the binder additive. 
     In some embodiments of the present invention, a current collector may be constructed from copper, gold, aluminum, and/or silver. In some embodiments of the present invention, the electrolyte may be a solution of magnesium tetrahydroborate in dimethoxyethane. In some embodiments of the present invention, the second electrode may include magnesium metal, vanadium oxide, and/or lithium metal. 
     A further aspect of the present invention is a method for storing energy in a battery, where the method includes immersing a first electrode and a second electrode in a liquid, non-aqueous, Mg 2+  ion-containing, electrolyte solution, where the first electrode includes boron sheets of boron atoms covalently bound together, with a plurality of magnesium atoms reversibly intercalated between the boron sheets and ionically bound to the boron atoms. The method also includes applying a voltage across the first electrode and the second electrode, where the voltage causes the reversible deintercalation of a portion of the magnesium atoms from between the boron sheets, creates a flux of Mg 2+  ions from the first electrode into the electrolyte solution, and produces the reversible transfer of at least some of the Mg 2+  ions from at least one of the flux and/or from the electrolyte solution to the second electrode, such that the energy stored in the battery ranges from about 6 mAh/g to about 10 mAh/g. 
     In some embodiments of the present invention, a method for storing energy in a battery may include applying a load across the first electrode and the second electrode, such that the load produces the reversible removal of magnesium atoms from the second electrode, creates a flux of Mg 2+  ions from the second electrode into the electrolyte solution, and produces the reversible intercalation between the boron sheets of the first electrode of at least some of the Mg 2+  ions from at least one of the flux from the second electrode and/or the electrolyte solution. In some embodiments of the present invention, the second electrode may include magnesium metal and the reversible transfer of at least some of the Mg 2+  ions to the second electrode may be by electrochemical plating of Mg 2+  ions onto the magnesium metal. In some embodiments of the present invention, the second electrode may include vanadium oxide and the reversible transfer of at least some of the Mg 2+  ions to the second electrode may be by intercalation of Mg 2+  ions into the vanadium oxide. 
     A further aspect of the present invention is a rechargeable magnesium-based air battery that includes an anode layer formed of magnesium boride having the formula MgB x , where x≧1, and is deposited onto a first support structure, a porous cathode layer, where the layer includes positive active material that at least activates carbon for absorbing oxygen in air, and where oxygen gas is used as the positive active material and is deposited onto a second support structure. The rechargeable magnesium-based air battery also includes an electrolyte, where the electrolyte is a non-aqueous solution where the solution contains Grignard reagents such as RMgX. The anode layer and cathode layer are connected electrically and the electrolyte is in contact with the first and second support structures. 
     In some embodiments of the present invention, the first and second support structures of a rechargeable magnesium-based air battery may be positive and negative current collectors. In some embodiments of the present invention, the anode layer may be doped. In some embodiments of the present invention, the anode layer may be doped with at least one of a Group IV/Group 14 element and/or a Group V/Group 15 element. In some embodiments of the present invention, the Group IV/Group 14 element may include at least one of carbon, silicon, germanium, tin, lead, flerovium, and/or combinations thereof. In some embodiments of the present invention, the Group V/Group 15 element may include at least one of nitrogen, phosphorous, arsenic, antimony, bismuth, and/or combinations thereof. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         FIG. 1  illustrates an active material for an electrode, including reversibly intercalated/deintercalated magnesium atoms/ions between boron sheets, according to exemplary embodiments of the present invention. 
         FIG. 2  illustrates an active material for an electrode, including reversibly intercalated/deintercalated magnesium atoms/ions between sheets of vanadium oxide, according to exemplary embodiments of the present invention. 
         FIG. 3  illustrates an electrical device, according to exemplary embodiments of the present invention. 
         FIG. 4  illustrates a coin battery, according to exemplary embodiments of the present invention. 
         FIGS. 5 a  and 5 b    illustrate experimental results of the reversible capacity for a battery including a MgB 2  first electrode, a magnesium metal second electrode, and a Mg-ion electrolyte, according to exemplary embodiments of the present invention. 
         FIG. 6  illustrates a rechargeable, magnesium-boride-based air battery, according to exemplary embodiments of the present invention. 
         FIG. 7  illustrates a method  200  to manufacture a rechargeable magnesium-boride-based air battery, according to exemplary embodiments of the present invention. 
     
    
    
     REFERENCE NUMERALS 
     
       
         
               
               
             
           
               
                   
               
             
             
               
                 100 
                 first electrode active material (first state) 
               
               
                 110 
                 first electrode active material (second state) 
               
               
                 120 
                 boron atom 
               
               
                 130 
                 intercalated magnesium atom 
               
               
                 140 
                 deintercalated magnesium ion 
               
               
                 150 
                 vacancy 
               
               
                 200 
                 second electrode active material (first state) 
               
               
                 210 
                 second electrode active material (second state) 
               
               
                 220 
                 vanadium atom 
               
               
                 230 
                 oxygen atom 
               
               
                 240 
                 intercalated magnesium atom 
               
               
                 250 
                 vacancy 
               
               
                 300 
                 electrical device 
               
               
                 305 
                 first electrode 
               
               
                 310 
                 electrode active material 
               
               
                 320 
                 binder additive 
               
               
                 330 
                 conductive additive 
               
               
                 340 
                 interstitial space 
               
               
                 350 
                 electrolyte 
               
               
                 360 
                 current collector 
               
               
                 400 
                 coin battery 
               
               
                 410 
                 first case 
               
               
                 420 
                 second case 
               
               
                 430 
                 spring 
               
               
                 440 
                 first electrode 
               
               
                 450 
                 separator 
               
               
                 460 
                 second electrode 
               
               
                 600 
                 magnesium-boride-based air battery 
               
               
                 602 
                 anode current collector 
               
               
                 604 
                 anode 
               
               
                 610 
                 cathode 
               
               
                 620 
                 breathable layer 
               
               
                 630 
                 diffusion layer 
               
               
                 640 
                 carbon conductive material 
               
               
                 650 
                 catalyst layer 
               
               
                 660 
                 cathode current collector 
               
               
                 670 
                 electrolyte 
               
               
                 700 
                 method of manufacture 
               
               
                 702 
                 fabricating a first support structure 
               
               
                 704 
                 depositing a magnesium boride based anode 
               
               
                 706 
                 forming a non-aqueous electrolyte 
               
               
                 708 
                 fabricating a porous cathode layer 
               
               
                 710 
                 depositing the electrolyte layer 
               
               
                   
               
             
          
         
       
     
     DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS 
       FIG. 1  illustrates two reversible states  100  and  110  for an electrode active material constructed of MgB x . A plurality of covalently bound boron atoms  120  forms layers of parallel crystalline sheets with spaces in between the sheets. A plurality of magnesium atoms  130  is positioned within the spaces and between the sheets of boron atoms. Magnesium atoms in this position are referred to as intercalated within the crystalline structure of the MgB x . X may be greater than or equal to one. In the case of magnesium diboride, MgB 2 , x is equal to two. 
     Applying a voltage, or alternatively, a load to a battery system that includes MgB x  as the active material for one of its two electrodes, may cause a portion of the intercalated magnesium atoms  130  to be removed from the MgB x  crystalline structure as Mg 2+  ions  140 , or deintercalate from the crystalline structure. The formation of the Mg 2+  ions  140  results in the release of 2 electrons (e − ), which are transferred to the second electrode through the external circuit. The Mg 2+  ions  140  may then enter the battery&#39;s electrolyte (not shown) to travel towards the second electrode (not shown) of the battery, to charge the battery. 
     This process is reversible because applying the opposite of what was just described, either a load or a voltage, can switch the battery from the second state  110  back to the first state  100 . For example, if deintercalation of Mg 2+  ions  140  was achieved by applying a voltage to the battery, the original state  100  may be renewed by applying a load to the battery. Alternatively, if deintercalation of Mg 2+  ions  140  was achieved by applying a load to the battery, the original state  100  may be renewed by applying a voltage to the battery. 
     The reversible intercalation/deintercalation process summarized in  FIG. 1  for a first electrode made from a MgB x  containing active material may be represented by the following reaction, where the left side of the reaction corresponds to the first state, and the right side of the reaction corresponds to the second state:
 
MgB x ←→Mg (1-y) B x +( y )Mg 2+ +(2 y ) e   −   Reaction 1
 
       FIG. 2  illustrates two exemplary reversible states  200  and  210  for a second electrode of a rechargeable battery that includes a first MgB x  electrode. In this example, reversible intercalation of Mg 2+  ions  140  may also be achieved at a second electrode constructed of vanadium oxide (e.g. V 2 O 5 ). In the first state  200 , the active material includes a plurality of covalently bound vanadium atoms  220  and oxygen atoms  230 , which form layers of parallel crystalline V 2 O 5  sheets with spaces in between the sheets. These spaces provide vacancies  250  for magnesium ions  140  to move into or intercalate. 
     Applying a voltage, or alternatively, a load to a battery system that includes V 2 O 5  as the active material for the second electrode, may cause a portion of the Mg 2+  ions  140  to move from the electrolyte solution (not shown) and intercalate between the sheets of V 2 O 5  to occupy the vacancies  250 . The electrons removed from the magnesium atoms at the first electrode may then counter-balance the intercalated Mg 2+  ions to form intercalated magnesium atoms  240 . 
     As with the MgB x  active material of the first electrode, a second electrode including V 2 O 5  active material may also be reversible between the two states  200  and  210 . Again, as with the first electrode, applying the opposite of what was just described, either a load or a voltage, may switch the battery from the second state  210  back to the first state  200 . For example, if intercalation of Mg 2+  ions was achieved by applying a voltage to the battery, the original state  200  may be renewed by applying a load to the battery. Alternatively, if intercalation of Mg 2+  ions was achieved by applying a load to the battery, the original state  200  may be renewed by applying a voltage to the battery. 
     The reversible intercalation/deintercalation process summarized in  FIG. 2  for a second electrode made from a V 2 O 5  containing active material may be represented by the following reaction:
 
V 2 O 5 +( y )Mg 2+ +(2 y ) e   − ←→Mg y V 2 O 5   Reaction 2
 
     In some examples of a MgB x  containing battery, the second electrode may be constructed using a metal active material such as magnesium metal or lithium metal. In these cases, Mg 2+  ions may not reversibly intercalate into the second electrode&#39;s active material. Instead, the reaction occurring in these examples may include the reversible electrochemical plating of magnesium metal onto the second electrode&#39;s active material. 
       FIG. 3  illustrates an exemplary electrical device  300  that utilizes the elements and features described above. In this example, a first electrode  305  may be constructed from a mixture of MgB 2  active material  310 , a conductive additive  330 , and a binder additive  320  to form a solid mixture with interstitial spaces between the MgB 2  active material  310 , the conductive additive  330 , and the binder additive  320 . The mixture of the MgB 2  active material  310 , the conductive additive  330 , and the binder additive  320  may be applied to a surface of a current collector  360  to form the first electrode  305 . The first electrode  305  may then be immersed in an electrolyte  350 . In some examples, the electrolyte  350  may be a non-aqueous liquid, which may flow into and fill the interstitial spaces  340 . 
     An electrode similar to the example illustrated in  FIG. 3  may be prepared from slurries ranging from about 50 wt % active material to about 99 wt % active material. For example a mixture of MgB 2  powder may be combined with a binder additive (e.g. polyvinylidene fluoride) and a conductive additive (e.g. carbon black) in a solvent (e.g. n-methyl pyrrolidone) to make a mixture. To insure a uniform distribution of the components is attained, the mixture may be agitated using an appropriate mixing device. Once a uniform distribution is attained, the mixture may be applied to the current collector (e.g. an Al and/or Cu foil) at a thickness ranging from about 10 μm to about 50 μm. After the mixture has been applied to the current collector, it may be dried and/or cured by heating the mixture and the current collector to a temperature ranging from about 50° C. to about 100° C., and maintaining the temperature for a period of time ranging from about 1 hour to about 10 hours, thus producing the electrode. A final circular shape may be attained by punching the foil containing the electrode mixture, using an appropriate punching mechanism. In some examples, the MgB 2  containing electrode may be punched into disks with diameters ranging from about 5/16 of an inch to about ½ an inch. 
     An electrode formed by such a method than may be utilized to fabricate a coin cell battery as illustrated in  FIG. 4 . For example, a coin cell battery  400  may be constructed by separating a first electrode  440  from a second electrode  460 , utilizing a separator  450 . The resultant “sandwich” of the first electrode  440 , the second electrode  460 , and the separator  450  may then be placed on a second case  420 , followed by the addition of electrolyte (not shown). The “sandwich” may then be secured between a first case  410  and the second case  420 , with sufficient force supplied by a spring  430 , to insure proper contact between all of the battery elements. In this exemplary case, the volume of electrolyte used may vary from about 0.1 ml of electrolyte to about 1 ml of electrolyte. 
       FIGS. 5 a  and 5 b    summarize experimental data obtained from an exemplary MgB 2  containing battery. In this example, the battery includes a cathode containing MgB 2  as the active material. The MgB 2  is mixed with acetylene black (e.g. conductive additive) and polyvinylidene fluoride (e.g. binder additive) at about 60 wt %, about 20 wt %, and about 20 wt %, respectively. This mixture is applied to a copper current collector and treated as described above to form the cathode. In this example, magnesium metal is used as the anode. Both electrodes are placed in an electrolyte solution of magnesium tetrahydroborate dissolved in dimethoxyethane.  FIGS. 5 a  and 5 b    summarize the cyclical behavior of this exemplary battery for a total of 50 charge-discharge cycles. 
     Magnesium-boride-based layered materials may replace magnesium metal in Mg-ion/air batteries. Magnesium boride as the anode material may also enable the use of non-aqueous electrolytes to achieve greater energy densities than current Li-ion technology. This disclosure describes, among other things, a magnesium boride electrode material for magnesium-based battery devices that are rechargeable, such as magnesium-boride-air batteries. 
     Magnesium-boride-air batteries usually comprise three parts: a magnesium-containing anode, an air cathode and an electrolyte. The reactions involved in an exemplary embodiment are as follows:
 
Anode: MgB x ←→Mg (1-y) B x +( y )Mg 2+ +(2 y ) e   −   Reaction 3
 
Cathode: O 2 +4 e   − →2O 2−  or  Reaction 4
 
O 2 +2 e   − →2O −  or  Reaction 5
 
O 2   +e   − →(O 2 ) −   Reaction 6
 
       FIG. 6  illustrates an example of a magnesium-boride-based air battery  600 . The battery  600  may include two current collectors, an anode current collector  602  and a cathode current collector  660 . The anode current collector  602  may serve as a point of contact for an anode  604 . The anode current collector  602  may include carbon, nickel, copper, and/or any other metal or non-metal material suitable for use as a durable, electrically conductive support structure. Further, the anode current collector  602  may be in contact with the anode  604 . The anode  604  is a source for Mg-ions. In this example, the anode  604  is constructed from magnesium boride. However, the anode  604  may be constructed from any magnesium boride containing material suitable for supplying magnesium ions. The anode  604  may be doped with carbon and/or carbon-derived materials such as graphite, graphene or any combination or variation thereof. Suitable dopants may include at least one Group IV/Group 14 elements, such as carbon, silicon, germanium, tin, lead, flerovium, Group V/Group 15 elements such as nitrogen, phosphorous, arsenic, antimony, bismuth, or any combination thereof. The anode current collector  602  and the anode  604  may be a single layer, or the same layer. Although not shown, one or more circuits may connect the anode  604  and the cathode  610  electrically. 
     Cathode  610  may include a metal foam/mesh as the current collector  660 , constructed from various types of conductive materials, for example, carbon nanofiber, carbon nanotubes, and/or nanostructured catalysts. The pore size, pore distribution, surface area, and electrochemical activity of the cathode layer  610  may be varied by selection of appropriate types and mixing ratios of the materials desired. An exemplary cathode may be include several layers: a waterproof breathable layer  620 , a gas diffusion layer  630 , and/or a catalyst layer  650  bound to a current collector  660  of a mesh/porous layer. As shown in  FIG. 6 , an exemplary cathode  610  may include several layers: a waterproof breathable layer  620  and a gas diffusion layer  630 , which may also include carbon conductive materials  640 , and a catalyst layer  650 . The waterproof breathable layer  620  may be constructed of a water-repellant porous substance. The gas diffusion layer  630  may have a high porosity and a high electronic conductivity, and may be constructed from acetylene black containing hydrophobic materials such as PTFE. The catalyst layer  650  may be primarily composed of active catalysts for the oxygen reduction reaction. In some case, noble metals such as Pt and Ag may be used in the catalyst layer  650  of the cathode  610 . In other examples, N-doped carbonaceous, metal oxides, and/or metal oxide-carbonaceous mixtures may be used as catalysts in the catalyst layer  650  of the cathode  610 . The battery  600  may also include a cathode current collector  660 . The cathode current collector may serve as a point of contact for the cathode  610 . The cathode current collector may be constructed of carbon, nickel, aluminum, and/or any other metal or non-metal material suitable for use as a lightweight, electrically conductive support structure. Further, the cathode current collector  660  and the cathode  610  may be a single layer of material. 
     The electrolyte  670  may be a non-aqueous electrolyte with a low vapor pressure. The electrolyte  670  may also have sufficient Mg-ion conductivity and oxygen solubility and preferably undergoes minimal or no side reactions with the anode and cathode materials. As described herein, the electrolyte may include a non-aqueous solution containing Grignard reagents such as RMgX, where R is an alkyl or aryl. For example, R may be a methyl group, an ethyl group, and/or a propyl group. In addition, R may be a phenyl group, a methyl substituted phenyl (tolyl) group and/or a dimethyl substituted phenyl group. 
       FIG. 7  illustrates an exemplary method  700  to manufacture a rechargeable magnesium-boride based air battery. The method  700  includes fabricating  702  a first support structure, depositing  704  a magnesium boride based anode onto the support structure, forming  706  a non-aqueous electrolyte, having Grignard reagents according to the formula RMgX, where the non-aqueous electrolyte may be deposited onto the anode. The method  700  continues with fabricating  708  a porous cathode layer for the cathode to absorb oxygen, and depositing  710  the electrolyte layer onto the cathode layer and/or a cathode current collector layer. The method  700  may include an anode current collector. The anode current collector may serve as a point of contact for the anode. The anode current collector may be constructed using carbon, nickel, copper, and/or any other metal or non-metal material suitable for use as a durable, electrically conductive support structure. Further, the anode current collector may be in contact with the anode. The anode may be a source for metal-ions. The anode may be magnesium boride and/or any magnesium-based material suitable for supplying magnesium ions. The anode may be doped with carbon, carbon-derived materials such as graphite, graphene and/or any combination thereof. Suitable dopants may include Group IV/Group 14 elements, such as carbon, silicon, germanium, tin, lead, flerovium, Group V/Group 15 elements such as nitrogen, phosphorous, arsenic, antimony, bismuth, or any combination thereof. The anode current collector and the anode may be constructed as a single layer of material. 
     The cathode in method  700  may include various types of conductive material such as carbon nanofiber, carbon nanotubes, and/or nanostructured catalysts. The pore size, pore distribution, surface area, and electrochemical activity of the cathode layer may be varied by the selection of the appropriate types and/or mixing ratios of the materials desired. The cathode may have several layers: a waterproof breathable layer, a gas diffusion layer and/or a catalyst layer bound to a current collector made of a mesh/porous layer. The waterproof layer may be constructed from a water-repellant porous substance. The gas diffusion layer may have a high porosity and/or electronic conductivity, and may be constructed, for example, from acetylene black and/or hydrophobic materials such as PTFE. The catalyst layer may primarily contain active catalyst for the oxygen reduction reaction. Active catalyst in the air cathode may be noble metals such as Pt and Ag. Other active catalyst materials for an air cathode may include N-doped carbonaceous, metal oxides and/or metal oxide-carbonaceous mixtures. The method  700  may include a cathode current collector. The cathode current collector may serve as a point of contact for the cathode. The cathode current collector may include carbon, nickel, aluminum, and/or any other metal and/or any non-metal material suitable for use as a lightweight, electrically conductive support structure. 
     The electrolyte in method  700  may be a non-aqueous electrolyte with a low vapor pressure. The electrolyte may also provide sufficient ion conductivity and oxygen solubility and preferably undergoes minimal or no side reactions with the magnesium oxide radical. The electrolyte may include a non-aqueous solution containing Grignard reagents such as RMgX, wherein R may be an alkyl group or an aryl group. R may be a methyl group, an ethyl group, and/or a propyl group. R may be a phenyl group, a methyl substituted phenyl (tolyl) group, and/or a dimethyl substituted phenyl group. 
     It is noted that there are alternative ways of implementing the embodiments disclosed herein. While a number of exemplary aspects and embodiments have been discussed above, those of skill in the art will recognize certain modifications, permutations, additions and sub combinations thereof. Accordingly, the present embodiments are to be considered as illustrative and not restrictive. Furthermore, the claims are not to be limited to the details given herein, and are entitled their full scope and equivalents thereof.