LEAD-ACID BATTERY DESIGN HAVING VERSATILE FORM FACTOR
An electrochemical storage device comprises a plurality of layer electrodes each including a first charged sector and a second charged sector. The plurality of layer electrodes are assembled with respect to each other such that the first charged sector of a first plate of the plurality of layer electrodes is laid below the second charged sector of a second plate of the plurality of layer electrodes located immediately above the first plate. The charges of the first charged sectors of the first and second plates have a first sign and the charges of the second charged sectors of the first and second plates have a second sign that is opposite the first sign. The device also comprises a separator sector located, and enabling ionic charge exchange, between the first charged sector of the first plate and the second charged sector of the second plate.
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This application is a continuation in part of application Ser. No. 13/350,686, filed Jan. 13, 2012, entitled “Lead-acid battery design having versatile form factor”, which incorporated by reference the entire disclosure of the concurrently filed U.S. application Ser. No. 13/350,505 entitled, “Improved Substrate for Electrode of Electrochemical Cell.”TECHNICAL FIELD
Embodiments of the present disclosure relate generally to electrochemical cells. More particularly, embodiments of the present disclosure relate to a design of a lead-acid electrochemical cell.BACKGROUND
Lead-acid electrochemical cells have been commercially successful as power cells for over one hundred years. For example, lead-acid batteries are widely used for starting, lighting, and ignition (SLI) applications in the automotive industry.
As an alternative to lead-acid batteries, nickel-metal hydride (“Ni-MH”) and lithium-ion (“Li-ion”) batteries have been used for hybrid and electric vehicle applications. Despite their higher cost, Ni-MH and Li-ion electro-chemistries have been favored over lead-acid electrochemistry for hybrid and electric vehicle applications due to their higher specific energy and energy density compared to lead-acid batteries.
While lead-acid, Ni-MH, and Li-ion batteries have each experienced commercial success, conventionally, each of these three types of chemistries have been limited to certain applications.
Lead-acid battery technology is low-cost, reliable, and relatively safe. Certain applications, such as complete or partial electrification of vehicles and back-up power applications, require higher specific energy than traditional SLI lead-acid batteries deliver. As shown in Table 1, lead-acid batteries suffer from low specific energy due to the weight of the components. Thus, there remains a need for low-cost, reliable, and relatively safe electrochemical cells for various applications that require high specific energy, including certain automotive and back-up power applications.
Lead-acid batteries have many advantages. First, they are a low-cost technology capable of being manufactured in any part of the world. Accordingly, production of lead-acid batteries can be readily scaled-up. Lead-acid batteries are available in large quantities in a variety of sizes and designs. In addition, they deliver good high-rate performance and moderately good low- and high-temperature performance. Lead-acid batteries are electrically efficient, with a turnaround efficiency of 75 to 80%, provide good “float” service (where the charge is maintained near the full-charge level by trickle charging), and exhibit good charge retention. Further, although lead is toxic, lead-acid battery components are easily recycled. An extremely high percentage of lead-acid battery components (in excess of 95%) are typically recycled.
Lead-acid batteries suffer from certain disadvantages as well. They offer relatively low cycle life, particularly in deep-discharge applications. Due to the weight of the lead components and other structural components needed to reinforce the plates, lead-acid batteries typically have limited energy density. If lead-acid batteries are stored for prolonged periods in a discharged condition, sulfation of the electrodes can occur, damaging the battery and impairing its performance. In addition, hydrogen can be evolved in some designs.
In contrast to lead-acid batteries, Ni-MH batteries use a metal hydride as the active negative material along with a conventional positive electrode such as nickel hydroxide. Ni-MH batteries feature relatively long cycle life, especially at a relatively low depth of discharge. The specific energy and energy density of Ni-MH batteries are higher than for lead-acid batteries. In addition, Ni-MH batteries are manufactured in small prismatic and cylindrical cells for a variety of applications and have been employed extensively in hybrid electric vehicles. Larger size Ni-MH cells have found limited use in electric vehicles.
The primary disadvantage of Ni-MH electrochemical cells is their high cost. Li-ion batteries share this disadvantage. In addition, improvements in energy density and specific energy of Li-ion designs have outpaced advances in Ni-MH designs in recent years. Thus, although nickel metal hydride batteries currently deliver substantially more power than designs of a decade ago, the progress of Li-ion batteries, in addition to their inherently higher operating voltage, has made them technically more competitive for many hybrid applications that would otherwise have employed Ni-MH batteries.
Li-ion batteries have captured a substantial share not only of the secondary consumer battery market but a major share of OEM hybrid battery, vehicle, and electric vehicle applications as well. Li-ion batteries provide high-energy density and high specific energy, as well as long cycle life. For example, Li-ion batteries can deliver greater than 1,000 cycles at 80% depth of discharge.
Li-ion batteries have certain advantages. They are available in a wide variety of shapes and sizes, and are much lighter than other secondary batteries that have a comparable energy capacity (both specific energy and energy density). In addition, they have higher open circuit voltage (typically ˜3.5 V vs. 2 V for lead-acid cells). In contrast to Ni—Cd and, to a lesser extent, Ni-MH batteries, Li-ion batteries suffer no “memory effect,” and have much lower rates of self discharge (approximately 5% per month) compared to Ni-MH batteries (up to 20% per month).
Li-ion batteries, however, have certain disadvantages as well. They are expensive. Rates of charge and discharge above 1 C at lower temperatures are challenging because lithium diffusion is slow and it does not allow for the ions to move fast enough. Further, Li-ion batteries use liquid electrolytes to allow for faster diffusion rates, which results in formation of dendritic deposits at the negative electrode, causing hard shorts and resulting in potentially dangerous conditions. Liquid electrolytes also form deposits (referred to as an SEI layer) at the electrolyte/electrode interface, that can inhibit electron transfer, indirectly causing the cell's rate capability and capacity to diminish over time. These problems can be exacerbated by high-charging levels and elevated temperatures. Li-ion cells may irreversibly lose capacity if operated in a float condition. Poor cooling and increased internal resistance cause temperatures to increase inside the cell, further degrading battery life. Most important, however, Li-ion batteries may suffer thermal runaway, if overheated, overcharged, or over-discharged. This can lead to cell rupture, exposing the active material to the atmosphere. In extreme cases, this can cause the battery to catch fire. Deep discharge may short-circuit the Li-ion cell, causing recharging to be unsafe.
To manage these risks, Li-ion batteries are typically manufactured with expensive and complex power and thermal management systems. In a typical Li-ion application for a hybrid vehicle, two-thirds of the volume of the battery module may be given over to collateral equipment for thermal management and power electronics and battery management, dramatically increasing the overall size and weight of the battery system, as well as its cost.
In addition to the differing advantages and disadvantages of lead-acid, Ni-MH and Li-ion batteries, the specific energy, energy density, specific power, and power density of these three electro-chemistries vary substantially. Typical values for systems used in HEV-type applications are provided in Table 1 below.
Although both Ni-MH and Li-ion battery chemistries have claimed a substantial role in hybrid and electrical vehicles, both chemistries are substantially more expensive than lead-acid batteries for vehicular propulsion assist. The present inventors believe that the embodiments of the present disclosure can substantially improve the capacity of lead-acid batteries to provide a viable, low-cost alternative to Ni-MH and Li-ion electro-chemistries in all types of hybrid and electrical vehicle applications.
In particular, certain applications have proved difficult for Ni-MH and Li-ion batteries, such as certain automotive and standby power applications. Standby power application requirements have gradually been raised. The standby batteries of today have to be truly maintenance free, have to be low-cost, have long cycle-life, have low self-discharge, be capable of operating at extreme temperatures, and, finally, should have high specific energy and high specific power. Emerging smart grid applications to improve energy efficiency require high power, long life, and lower cost for continued growth in the market place.
Automobile manufacturers have encountered substantial consumer resistance in launching fleets of electric vehicles and hybrid vehicles, due to the increased cost of these vehicles relative to conventional automobiles powered by an internal combustion engine (“ICE”). Environmental and energy independence concerns have exerted greater pressures on manufacturers to offer cost-effective alternatives to internal combustion engine-powered vehicles. Although hybrids and electric vehicles can meet that demand, they typically rely on subsidies to defray the higher cost of the energy storage systems.
Table 2 below compares the application of various battery electro-chemistries and the internal combustion engine (ICE) and their current roles in certain automotive applications. As used in Table 2, “SLI” means starting, lighting, ignition; “HEV” means hybrid electric vehicle; “PHEV” means plug-in hybrid electric vehicle; “EREV” means extended range electric vehicle; and “EV” means electric vehicle.
As shown in Table 2, there remains a need for specific applications in which partial electrification of the vehicle may provide environmental and energy efficiency advantages, without the same level of added costs associated with hybrid and electric vehicles using Ni-MH and Li-ion batteries. Even more specifically, there is a need for a low cost, energy efficient battery in the area of start/stop automotive applications.
Specific points in the duty cycle of an internal combustion engine entail far greater inefficiency than others. Internal combustion engines operate efficiently only over a relatively narrow range of crankshaft speeds. For example, when the vehicle is idling at a stop, fuel is being consumed with no useful work being done. Idle vehicle running time, stop/start events, power steering, air conditioning, or other power electronics component operation entail substantial inefficiencies in terms of fuel economy, as do rapid acceleration events. In addition, environmental pollution from a vehicle at these “start-stop” conditions is far worse than from a running vehicle that is moving. The partial electrification of the vehicle in relation to these more extreme operating conditions has been termed a “micro” or “mild” hybrid application, including start/stop electrification. Micro- and mild-hybrid technologies are unable to displace as much of the power delivered by the internal combustion engine as a full hybrid or electric vehicle. Nonetheless, they may be able to substantially increase fuel efficiency in a cost-effective manner without the substantial capital expenditure associated with full hybrid or full electric vehicle applications.
Conventional lead-acid batteries have not yet been able to fulfill this role. Conventional lead-acid batteries have been designed and optimized for the specific application of SLI operation. The needs of a mild hybrid application are different. A new process, design, and production process need to be developed and optimized for the mild hybrid application.
One need for a mild hybrid application is low-weight battery. Conventional lead-acid batteries are relatively heavy. This causes the battery to have a low specific energy due to the substantial weight of the lead components and other structural components that are necessary to provide rigidity to the plates. SLI lead-acid batteries typically have thinner plates, providing increased surface area needed to produce the power necessary to start the engine. But the grid thickness is limited to a minimum useful thickness because of the casting process and the mechanics of the grid hang. The minimum grid thickness is also determined on the positive electrode by corrosion processes. Positive plates are rarely less than 0.08″ (main outside framing wires) and 0.05″ on the face wires because of the difficulties of casting at production rates and, more importantly, concern over poor cycle-life issues. These parameters limit power. Lead-acid batteries designed for deeper discharge applications (such as motive power for forklifts) typically have heavier plates to enable them to withstand the deeper depth of discharge in these applications.
In addition, in typical lead-acid batteries, the active material is usually formed as a paste that is applied to the grid in order to form the plates as a composite material. Although the paste adheres well to itself, it does not adhere well to the grid materials because of paste shrinkage issues. This requires the use of grids that are more substantial and contain additional structural components to help support the active material, which, in turn, puts an extra weight burden on the cell.
Further, during the manufacture of conventional lead-acid batteries, the components are subjected to a number of mechanical stresses. Pasting active material onto the grid can stress the latticework of the grid. Expanded metal grids are lighter than cast grids, yet, the formation of the expanded grid itself introduces stress at each of the nodes of the expanded grid. These various structural materials, being subjected to substantial mechanical stresses during electrode pasting, handling, and cell operation, tend to corrode more readily in the acid-oxidizing environment of the battery after activation, especially when thin plates are used to increase power.
For example, cast and expanded metal grids have non-uniform stress during the life of the battery due to the molar volume change of converting the lead metal to PbO2. This volume change of the corrosion product puts huge stress on the grids in a non-uniform manner because of the irregular cross-sectional shapes of the grid wires in cast and expanded metals.
Another need for a mild hybrid application is that rechargeable batteries should be able to be charged and discharged with less than 0.001% energy loss at each cycle. This is a function of the internal resistance of the design and the overvoltage necessary to overcome it. The reaction should be energy-efficient and should involve minimal physical changes to the battery that might limit cycle life. Side chemical reactions that may deteriorate the cell components, cause loss of life, create gaseous byproducts, or loss of energy should be minimal or absent. In addition, a rechargeable battery should desirably have high specific energy, low resistance, and good performance over a wide range of temperatures and be able to mitigate the structural stresses caused by lattice expansion. When the design is optimized for minimum resistance, the charge and discharge efficiency will dramatically improve.
Lead-acid batteries have many of these characteristics. The charge-discharge process is essentially highly reversible. The lead-acid system has been extensively studied and the secondary chemical reactions have been identified. And their detrimental effects have been mitigated using catalyst materials or engineering approaches. Although its energy density and specific energy are relatively low, the lead-acid battery performs reliably over a wide range of temperatures, with good performance and good cycle life. A primary advantage of lead-acid batteries remains their low-cost.
A typical lead-acid electrochemical cell uses lead dioxide as an active material in the positive plate and metallic lead as the active material in the negative plate. These active materials are formed in situ. Typically, a charged positive electrode contains PbO2. The electrolyte is sulfuric acid solution, typically about 1.2 specific gravity or 37% acid by weight. The basic electrode process in the positive and negative electrodes in a typical cycle involves formation of PbO2/Pb via a dissolution-precipitation mechanism, causing non-uniform stresses within the positive electrode structure. The first stage in the discharge-charge mechanism is a double-sulfate formation reaction. Sulfuric acid in the electrolyte is consumed by discharge, producing water as the product. Unlike many other electrochemical systems, in lead-acid batteries the electrolyte is itself an active material and can be capacity-limiting.
In conventional lead-acid batteries, the major starting material is highly purified lead. Lead is used for the production of lead oxides for conversion first into paste and ultimately into the lead dioxide positive active material and sponge lead negative active material. Pure lead is generally too soft to be used as a grid material because of processing issues, except in very thick plates or spiral-wound batteries. Lead is typically hardened by the addition of alloying elements. Some of these alloying elements are grain refiners and corrosion inhibitors but others may be detrimental to grid production or battery performance generally. One of the mitigating factors in the corrosion of lead/lead grids is the high hydrogen over-potential for hydrogen evolution on lead. Since most corrosion reactions are accompanied by hydrogen evolution as the cathode reaction, reduced hydrogen evolution may inhibit anodic corrosion as well.
The purpose of the grid is to form the support structure for the active materials and to collect and carry the current generated during discharge from the active material to the cell terminals. Mechanical support can also be provided by non-metallic elements such as polymers, ceramics, and other components. But these components are not electrically conductive. Thus, they add weight without contributing to the specific energy of the cell.
Lead oxide is converted into a dough-like material that can be fixed to grids forming the plates. The process by which the paste is integrated into the grid is called pasting. Pasting can be a form of “ribbon” extrusion. The paste is pressed by hand trowel, or by machine, into the grid interstices. The amount of paste applied is regulated by the spacing of the hopper above the grid or the type of troweling. As plates are pasted, water is forced out of the paste.
The typical curing process for SLI lead-acid plates is different for the positive and negative plates. Typically water is driven off the plate in a flash dryer until the amount of water remaining in the plate is between about 8 to 20% by weight. The positive plate is hydro-set at low temperature (<55 C+/−5 C) and high humidity for 24 to 72 hours. The negative plate is hydro-set at about the same temperature and humidity for 5 to 12 hours. The negative plate may be dried to the lower end of the 8 to 20% range and the positive plate to the upper end of the range. More recently, manufacturers use curing ovens where temperature and humidity are more precisely controlled. In the conventional process steps, the “hydro-set process” causes shrinkage of the “paste” active material that, in turn, causes it to break away from the grid in a non-uniform manner. The grid metal that is exposed is corroded preferentially and, since it is not in contact locally with the active material, results in increased resistance as well as formation, and life issues.
A simple cell consists of one positive and one negative plate, with one separator positioned between them. Most practical lead-acid electrochemical cells contain between 3 and 30 plates with separators between them. Leaf separators are typically used, although envelope separators may be used as well. The separator electrically insulates each plate from its nearest counter-electrode but must be porous enough to allow acid transport in or out of the plates.
A variety of different processes are used to seal battery cases and covers together. Enclosed cells are necessary to minimize safety hazards associated with the acidic electrolyte, potentially explosive gases produced on overcharge, and electric shock. Most SLI batteries are sealed with fusion of the case and cover, although some deep-cycling batteries are heat sealed. A wide variety of glues, clamps, and fasteners are also well-known in the art.
Typically, formation is initiated after the battery has been completely assembled. Formation activates the active materials. Batteries are then tested, packaged, and shipped.
A number of trade-offs must be considered in optimizing lead-acid batteries for various standby power and transportation uses. High-power density requires that the initial resistance of the battery be minimal. High-power and energy densities also require the plates and separators be porous and, typically, that the paste density also be very low. High cycle life, in contrast, requires premium separators, high paste density, and the presence of binders, modest depth of discharge, good maintenance, and the presence of alloying elements and thick positive plates. Low-cost, in further contrast, requires both minimum fixed and variable costs, high-speed automated processing, and that no premium materials be used for the grid, paste, separator, or other cell and battery components.
A number of improvements have been made in the basic design of lead-acid electrochemical cells. Many of these have involved improvements in the characteristics of the substrate, the active material, as well as the bus bars or collector elements. For example, a variety of fibers or metals have been added to or embedded in the substrate material to help strengthen it. The active material has been strengthened with a variety of materials, including synthetic fibers and other additions. Particularly with respect to lead-acid batteries, these various approaches represent a trade-off between durability, capacity, and specific energy. The addition of various non-conductive strengthening elements helps strengthen the supporting grid but replaces conductive substrate and active material with non-conductive components.
In order to reduce the weight of the lead-acid electrochemical cells relative to their specific energy, various improvements have been disclosed. One approach has been to coat a light-weight, high-tensile strength fiber with sufficient lead to make a composite wire that could be used to support the grid of the electrode. Robertson, U.S. Pat. No. 275,859 discloses an apparatus for extrusion of lead onto a core material for use as a telegraph cable. Barnes, U.S. Pat. No. 3,808,040 discloses strengthening a conductive latticework to serve as a grid element by depositing strips of synthetic resin. Specifically, Barnes '040 patent discloses a lead-coated glass fiber. These approaches, however, have been unable to produce a material with sufficient properties of high-corrosion resistance and high-tensile strength to be able to fabricate a commercially viable lead-acid battery that can survive chemical attack from the electrolyte.
Blayner, et al., have disclosed further improvements in the composition of the substrate to reduce the weight of the electrodes and to increase the proportion of conductive material. Blayner, U.S. Pat. Nos. 5,010,637 and 4,658,623. Blayner discloses a method and apparatus for coating a fiber with an extruded, corrosion-resistant metal. Blayner discloses a variety of core materials that can include high-tensile strength fibrous material, such as an optical glass fiber, or highly-conductive metal wire. Similarly, Blayner discloses that the extruded, corrosion-resistant metal can be any of a number of metals such as lead, zinc, or nickel.
Blayner discloses that a corrosion-resistant metal is extruded through die. The core material is drawn through the die as the metal is extruded onto the core material. Continuous lengths of metal wire or fiber are coated with a uniform layer of extruded, corrosion-resistant metal. The wire is then used to weave a screen that acts as a substrate for the active material. There are no fusion points at the intersections of the woven wires. The electrode may be constructed using such a screen as a grid with the active material being applied onto the grid. Rechargeable lead-acid electrochemical cells are constructed using pairs of electrodes.
Blayner discloses further improvements regarding the grain structure of the metal coating on the core material. In particular, Blayner discloses that the extruded corrosion-resistant metal has a longitudinally-oriented grain structure and uniform grain size. U.S. Pat. Nos. 5,925,470 and 6,027,822.
Fang, et al., disclose in their paper, Effect of Gap Size on Coating Extrusion of Pb-GF Composite Wire by Theoretical Calculation and Experimental Investigation, J. Mater. Sci. Technol., Vol. 21, No. 5 (2005), optimizing the gap in extruding lead-coated glass fiber. Although Blayner does not disclose the relationship between gap size and extrusion of the lead coated composite wire, Fang characterizes gap size as a key parameter for the continuous coating extrusion process. Fang reports that a gap between 0.12 mm and 0.24 mm is necessary, with a gap of 0.18 mm being optimal. Fang further reports that continuous fiber composite wire can enhance load and improve energy utilization.
The present inventors have found that, despite improvements in lead-acid electrochemical cells for automotive applications, prior known lead-acid batteries have not been able to achieve the same performance as Li-ion or Ni-MH cells for similar applications. There remains a need, therefore, for further improvements in the design and composition of lead-acid electrochemical cells to meet the specialized needs of the automotive and standby power markets. Specifically, there remains a need for a reliable replacement for lithium-ion electrochemical cells in certain applications that do not entail the same safety concerns raised by Li-ion electrochemical cells. Similarly, there remains a need for a reliable replacement for Ni-MH and Li-ion electrochemical cells with the added benefits of low-cost and reliability of lead-acid electrochemical cells. In addition, there remains a need for substantial improvement in battery production capacity to meet the growing needs of the automotive and standby power segments.
The United States Department of Energy (USDOE) has issued Corporate Average Fuel Efficiency (CAFE) guidelines for automotive fleets. Previously, SUVs and light trucks were excluded from the CAFE averages for motor vehicles. More recently, however, integrated guidelines have emerged specifying fuel efficiency standards for passenger vehicles, light trucks, and SUVs. These guidelines require an average fuel efficiency of 31.4 miles per gallon by 2016. http://www.epa.gov/oms/climate/regulations/420r10009.pdf.
Anticipated improvements in internal combustion engine technology do not appear to be able to reach this goal. Similarly, the manufacturing capacity for pure hybrids and pure electric vehicles does not appear sufficient to be able to reach this goal. Thus, it is anticipated that some combination of micro-hybrids or mild hybrids, in which electrochemical cells provide some of the power for either stop/start or certain acceleration applications, will be necessary in order to meet the CAFE standards.
Lead-acid battery systems may provide a reliable replacement for Li-ion or Ni-MH batteries in these applications, without the substantial safety concerns associated with Li-ion electrochemistry and the increased cost associated with both Li-ion and Ni-MH batteries.
Further, the improved batteries of the present invention may be combined in hybrid systems with other types of electrochemical cells to provide electric power that is tailored to the unique automotive application. For example, a lead-acid battery of the present invention which features high-power can be combined with a Lithium-ion (“Li-ion”) or Nickel metal hydride (“Ni-MH”) electrochemical cell offering high energy, to provide a composite battery system tailored to the needs of the particular automotive standby or stationary power application, while reducing the relative sizes of each component.SUMMARY
An aspect of the present disclosure includes an electrochemical cell having an electrode assembly, wherein the electrode assembly may include a plurality of electrode plates. Each electrode plate may include a current collector having a first portion and a second portion, and wherein each first and second portion may have a first surface and a second surface opposing the first surface. The first and second surfaces of the first portion may include a positively charged active material, and the first and second surfaces of the second portion may include a negatively charged active material. The plurality of electrode plates may include at least three electrode plates, such that the electrochemical cell may be arranged with a first portion of one plate of the at least three electrode plates electrochemically connected to a second portion of a second plate of the at least three electrode plates, and a first portion of the second plate of the at least three electrode plates electrochemically may be connected to a second portion of a third plate of the at least three electrode plates.
In various embodiments, the electrochemical cell may include the following features, either alone or in combination: each electrode plate may include a plurality of electrode connectors connecting the first portion to the second portion; each electrode plate may include shunt current mitigating means; the current collector may include a uniform current density; a first separator may be attached to the first surface of the first portion and a second separator may be attached to the first surface of the second portion; a plurality of electrode assemblies may be stacked in series for building voltage; an insulator may be connected to the top electrode plate, and the insulator may include at least one slit therein with an electrode plate extending there through; the electrochemical cell may be a lead-acid electrochemical cell; the electrode assembly may be connected to tabs; at least two electrode assemblies may be stacked in parallel for building capacity; there may be at least one power bus assembly including at least one bolt for building capacity; at least two of the electrode plates may be electrochemically connected at a ninety degree angle relative to one another; and the electrochemical cell may include a cross-sectional shaped selected from one of circular, rectangular, square, L-shaped, or U-shaped.
In some embodiments, an electrochemical storage device comprises a plurality of layer electrodes, wherein each layer electrode includes a first charged sector and a second charged sector, wherein the second charged sector is charged oppositely compared to the first charged sector, and wherein the plurality of layer electrodes are assembled with respect to each other such that the first charged sector of a first plate of the plurality of layer electrodes is laid below the second charged sector of a second plate of the plurality of layer electrodes located immediately above the first plate, wherein the charges of the first charged sectors of the first and second plates have a first sign and the charges of the second charged sectors of the first and second plates have a second sign that is opposite the first sign; a separator sector located, and enabling ionic charge exchange between the first charged sector of the first plate and the second charged sector of the second plate.
In some embodiments, the second charged sector of the first plate is laid below the first charged sector of the second plate, the electrochemical device further comprising an insulator sector located, and preventing ionic or conductive charge exchange, between the second charged sector of the first plate and the first charged sector of the second plate. In some embodiments, each of the plurality of the layer electrodes in circular.
In some embodiments, each sector has a semi-circle shape sized to about half of the corresponding layer electrode. In some embodiments, each plate of the plurality of layer electrodes further comprises a frame which houses the first charged sector and the second charged sector of the corresponding plate. In some embodiments, the electrochemical storage device further comprises a first cap and a second cap for encasing the plurality of layer electrodes. In some embodiments, the electrochemical storage device further comprises a conductive substrate for providing a conductive connection between the first charge sector and the second charged sector.
In some embodiments, each of the plurality of the layer electrodes has a rectangular shape. In some embodiments, each sector has a half-rectangle shape sized to about half of the corresponding layer electrode.
In some embodiments, an electrochemical storage device comprises a first electrochemical cell and a second electrochemical cell disposed in a common casing and each comprising an anode and a cathode, wherein the anode of the first electrochemical cell is disposed opposite the cathode of the second electrochemical cell; a separator disposed between the anode of the first electrochemical cell and the cathode of the second electrochemical cell, wherein the anode of the first electrochemical cell and the cathode of the second electrochemical cell are electrically insulated and in communication through an ionically conductive medium adsorbed in the separator; a common current collector disposed on the anode of the first electrochemical cell and the cathode of the second electrochemical cell, wherein the first and second electrochemical cells are electrically connected and insulated from ionic conduction and wherein the ionic separation of said first and second electrochemical cells mitigates shunt currents.
In some embodiments, the device further comprises said current collector providing substantially uniform current collection granting uniform current density. In some embodiments, the device further comprises a hydrophobic coating disposed on the portion of the common current collector between said anode and said cathode. In some embodiments, the device further comprises a physical barrier to ionically insulate said first and second electrochemical cells. In some embodiments, the device further comprises one positive and one negative terminal connection. In some embodiments, the device further comprises an insulation frame for disposing anodes and cathodes of two or more electrochemical cells in substantially the same plane.
Additional objects and advantages of the disclosure will be set forth in part in the description which follows, and in part will be apparent from the description, or may be learned by practice of the disclosure. The objects and advantages of the disclosure will be realized and attained by means of the elements and combinations particularly pointed out in the appended claims.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as claimed.
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate one embodiments of the disclosure and together with the description, serve to explain the principles of the disclosure.
The following detailed description refers to the accompanying drawings. Wherever possible, the same reference numbers may be used in the drawings and the following description to refer to the same or similar parts. Also, similarly-named elements may perform similar functions and may be similarly designed. Numerous details are set forth to provide an understanding of the embodiments described herein. In some cases, the embodiments may be practiced without these details. In other instances, well-known techniques and/or components may not be described in detail to avoid obscuring described embodiments. While several exemplary embodiments and features are described herein, modifications, adaptations, and other implementations are possible, without departing from the spirit and scope of the invention. Accordingly, the following detailed description does not limit the invention. Instead, the proper scope of the invention is defined by the appended claims.
Embodiments of the present disclosure generally relate to a design of a lead-acid electrochemical cell. Lead-acid electrochemical cells typically are in the form of stacked plates with separators between the plates. Accordingly, embodiments of the present disclosure relate to improved stacking of electrode plates in a variety of form factors. The improved stacking and variety of form factors of the lead-acid electrochemical cell design may enable lead-acid electrochemical cells to be used as part of lead-acid batteries, which, in turn, may be used in automobiles to aid in increasing fuel efficiency.
More specifically, embodiments of the present disclosure may include improvements to the design of a lead-acid electrochemical cell which may include improvements to the orientation of electrode plates as well as improvements for mitigating shunt currents. The improvements may result in a lead-acid electrochemical cell that may have a higher voltage while maintaining a lower weight and size. Alternatively, it also enables production of cells having higher capacity at the same relative voltage.
Embodiments of the present disclosure may allow for the use of lead-acid batteries in micro and mild-hybrid applications of vehicles, either alone or in combination with Ni-MH or Li-ion batteries. Some embodiments use other electrochemical batteries having a specific energy above 50 Wh/kg and a specific power above 500 W/kg. It should be emphasized, however, that embodiments of the present disclosure are not limited to transportation and automotive applications. Embodiments of the present disclosure may be of use in any area known to those skilled in the art where use of lead-acid batteries is desired, such as stationary power uses and energy storage systems for back-up power situations. Further, the present inventors intend that the elements or components of the various embodiments disclosed herein may be used together with other elements or components of other embodiments.
In addition, as shown in
Each electrode assembly 12 in the lead-acid electrochemical cell may be separated by an insulator 14 (
As shown in
Thus, the substrate may include a grid-like structure formed of conductive material, with spaces there between for supporting active material. Accordingly, the substrate may include a sheet of material having aligned dimple-like spaces or a plurality of through-holes in linear patterns. Alternatively, the substrate may include a plurality of pieces of material, such as wires, woven together to form a mesh. In a further embodiment, the substrate may include an expanded sheet of material with holes there through. The substrate may include material that may result in an increased adhesion between the substrate and the active material, as well as increased surface conductivity and reduced corrosion of the electrode plate.
As shown in
The substrate may further be formed such that a relatively constant current density may be maintained throughout each electrode plate. For example, in the first embodiment of the electrode plate of
The active material may be placed onto each portion of the substrate such that a pseudo bi-polar electrode plate may be formed. The pseudo bi-polar design may be accomplished by disposing both positive and negative active materials in alternating fields on a common substrate. In one embodiment shown in
Each positive portion 16 and negative portion 20 of each electrode plate may further include a top surface and a bottom surface. As shown in
As previously disclosed, each electrode assembly 12 may include four electrode plates 24A-D as shown in
Upon placement of the fourth electrode plate 24D, insulator 14 may be placed on the electrode assembly. As previously discussed, and shown in
Alternatively, the electrode assembly may be formed such that the free portion of the fourth plate 24D is a positive portion and the free portion of the first plate 24A is a negative portion. In addition, the free portion of the fourth plate 24D of the top electrode assembly in the spiral configuration may be connected to a single portion plate in order to complete the circuit. In an alternative embodiment, the top plate 24D of the top electrode assembly may only be a single portion plate, thereby completing the circuit with the connection to the third plate 24D.
In some embodiments the electrode assembly is formed by solid-state plates, wherein the positive and the negative portion of the plates include thin-film active material produced through solid state deposition processes. Processes suitable to form active materials include but are not limited to physical vapor deposition, chemical vapor deposition, spray deposition, dip coating, spin coating, electroless deposition, electroplating and any combination of suitable processes to form thin-film coatings. Suitable forms of the film materials include materials formed in a high vacuum process, under an inert gas environment and in room atmosphere and pressures.
In some embodiments, the separator material is a thin film membrane that allows for ionic diffusion and transfer of hydrogen, oxygen and sulfate ions, e.g. H+, OH−, SO4− at rates that are comparable to liquid electrolyte diffusion. In some embodiments, the separator membrane is a polymeric membrane e.g. Nafion material.
In some embodiments the substrate material of the plates is a suitable thin film electrically conductive medium in a form of a foil or a solid film, In some embodiments, the thin film is a woven material selected from the group including metals, e.g. lead, conductive polymers, e.g. aniline based polymer, conductive ceramics, e.g. ebonex or conductive tin or titanium oxides. In various embodiments, the substrate material has a polished surface with a suitable attachment layer or a patterned surface to promote adhesion of the active material including holes, ridges, dimples interlocking features and stress mitigating features.
In various embodiments, the suitable electrolyte is fully solid or in the form of a gel or a liquid and dispersed with the positive and active materials in stoichiometric quantities or impregnated in the separator membrane or other parts of the electrode assembly acting as electrolyte reservoirs;
Alternatively, in some embodiments, the positive and negative electrode assembly constitutes a fuel cell relying on separation principles of a ionically conductive membrane. In some embodiments, a suitable fuel fluid is a gas, e.g. hydrogen or other suitable fuel.
The pseudo bi-polar design of each electrode plate may allow for the spiral configuration to build voltage in the lead-acid electrochemical cell to any desired value (e.g., 24V, 36V, 42V, or 48V) at a constant capacity, while maintaining a low weight of the lead-acid electrochemical cell. The low weight may be due to the sizes of the components of the electrode assembly, as well as the material-make up of each electrode plate. In addition, the stacking of the electrode plates at a ninety degree angle relative to one another may allow for thinner components. For example, in one embodiment, the electrode assembly 12 may include a diameter of about 8 inches and may be about 0.3 inches thick. More specifically, the positive portion 16 of the electrode may be about 0.082 inches thick; the negative portion 20 of the electrode may be about 0.06 inches thick; the separators 18 may be about 0.06 inches thick; and the pasting paper 22 may be about 0.004 inches thick.
Persons of ordinary skill in the art will understand that stacking of the electrode plates may be accomplished in any of a variety of ways. For example, the plates can be stacked so that the plates build, one upon the other, in a step-wise manner with each positive 16 and negative 20 portion and their accompanying connections 26, lying in the same plane, as shown in
The lead-acid electrochemical cell may further include means for mitigating shunt currents due to leakage of electrolyte fluid from the electrodes and separators onto the electrode connectors, which may cause the electrodes to self-discharge. In one embodiment, the electrode connectors 26 and inner portion of a container proximate the electrode plates may be treated with a hydrophobic coating, which may prevent excess electrolyte fluid from wetting the electrodes, or electrode connectors 26, or casing. In other alternative embodiments, the electrode connectors 26 may be blocked from leaking electrolyte fluid due to barriers formed on the edges of the positive and negative portions 16, 20 of each electrode plate. The barrier may be a coating or other material, including frame material or even excess active material that may frame each positive and negative portion and contain the electrolyte. Alternatively, in a further embodiment, the insulator may have a diameter that is larger than the diameter of both the electrode assembly the container in which the spiral configuration resides, such that the insulator may form a barrier with the container wall and soak up leaking electrolyte fluid.
As previously disclosed, the spiral configuration may connect electrode assemblies 12 in order to build voltage while maintaining a constant capacity of the lead-acid electrochemical cell. In a second, alternative embodiment, the electrode assemblies 12 may be stacked such that the voltage of the lead-acid electrochemical cell remains constant while building capacity. Accordingly, in this second embodiment, instead of the top plate 24D of one electrode assembly 12 being connected to the bottom plate 24a of another electrode assembly 12, the top and bottom plates of a single electrode assembly may be connected to complete the circuit. Each electrode assembly 12 may be connected to a tab 50, which may further be connected to a power bus assembly 500 for capacity building.
As shown in
Power bus 502 may include an elongate member having a length that is substantially the same as the height of the lead-acid electrochemical cell. Power bus 502 may further have slits disposed along its length, the slits being configured to receive connections from electrode plates, where the connections are solidified by compressing the power bus 502 in compression. Further, as shown in
In a third embodiment of the present disclosure, the electrode plates may be rectangular in shape. The rectangular plates may be similar in area to the semi-circular electrode plates and may used to form similar-sized electrode assemblies and modules. For example,
Similar to the electrode assembly 12 of
The lead-acid electrochemical cell 100 may further include a tab 50 connected to a positive end and a tab 50 connected to a negative end of the spiral configuration. Tabs 50 may be securely connected to the positive and negative ends via any means known to those skilled in the art. For example, tabs 50 may be connected via soldering or ultrasonic welding. Tabs 50 may each contain a through-hole 52, which may allow for passage of posts 148. In addition, openings 141, 143, 147 in each of the casing 140, slotted tray 142, and drip tray 146, respectively, may also allow for posts 148 to pass there through.
As shown in
A fourth embodiment may employ the square electrode assembly 112 geometry of the third embodiment to build capacity at a constant voltage, rather than building voltage as in the third embodiment. Similar to that disclosed in relation to the second embodiment, this fourth embodiment may include connecting the free portion of the top plate 124D with the free portion of the first plate 124A in order to complete the circuit and therefore form a 12V electrode assembly 112. The electrode assemblies may 112 then be stacked and connected to the power bus assembly 500 in order to build capacity while maintaining a constant 12V of the lead-acid electrochemical cell. The fourth embodiment of the lead-acid electrochemical cell may further include a module that may be similar to that of the third embodiment.
The electrode plates may further be used form electrode assemblies, and thereby lead-acid electrochemical cell configurations, having a variety of cross-sectional shapes, in addition to circular and square. This variety of cross-sectional shapes may allow for stacked or spiral configurations of the lead-acid electrochemical cell to be placed in a variety of locations (e.g., in a vehicle) with little or no modification of the design of the location (e.g., vehicle frame) to accommodate the lead-acid electrochemical cell system. In these further embodiments, for example, each electrode assembly may include more than four plates. In addition, formation of these electrode assemblies may include stacking of the electrode plates linearly relative to one another, as well as at a ninety degree angle relative to one another. For example, in one embodiment, rectangular plates may be used to form a spiral configuration with a rectangular cross-section. Accordingly, there may be more electrode plates along the length of each electrode assembly than along the width.
In one embodiment, electrode plates may be oriented such that resulting electrochemical cells may provide volumetric efficiency in three orthogonal directions. For instance, the orientation of the electrochemical cells may provide improved dimensions in an x-direction, a y-direction, and/or a z-direction, where the xyz axes are not oriented in any particular way relative to an electrochemical cell casing. Alternatively, the orientation of the electrochemical cells may provide improved dimensions in an x-direction, a y-direction, and/or a z-direction, where the xyz axes are oriented relative to an electrochemical cell casing. As described above and below, the electrochemical cells may be united through ionic connections and a common current collector in such as way as to build voltage or capacity in the direction of one of the orthogonal directions x, y, z.
A fifth embodiment of the present disclosure may include formation of electrode plates into an electrode assembly, where the electrode assembly may include an L-shaped cross-section. Each electrode assembly may include electrode plates with positive and negative portions connected by electrode connectors. In addition, each electrode plate may include pasting paper and separators. Further, each electrode assembly may be separated by an L-shaped insulator having at least one slit to enable spiral connection of the L-shaped electrode assemblies. In addition, each electrode plate may further include means for mitigating shunt currents (e.g., hydrophobic coating on electrode connectors, hydrophobic framing of the plates, or an oversized insulator for soaking up electrolyte fluid).
The L-shaped lead-acid electrochemical cell may further include an L-shaped module. Similar to the circular and square modules, the L-shaped module may include a casing, slotted tray, and drip tray for collecting leaking electrolyte fluid. There may further be a tab connected to positive and negative ends of the L-shaped spiral configuration, such that the tabs may be connected to shafts that form terminals of the L-shaped lead-acid electrochemical cell.
An alternative, sixth embodiment of the L-shaped electrode assemblies may further include a capacity building geometry, similar to the other capacity-building embodiments disclosed herein. The L-shaped electrode assemblies in the sixth embodiment may each be connected in parallel, with each assembly terminating in a tab, with each of the respective tabs connected to the power bus assembly 500. The capacity-building L-shaped electrochemical cell may be housed within a module that is similar to the L-shaped module for the spiral configuration.
A seventh embodiment of the present disclosure may an electrode assembly having a U-shaped cross-sectional shape. The seventh embodiment may build voltage at a constant capacity, as disclosed herein. Alternatively, an eighth embodiment may include a U-shaped electrode assembly disposed to build capacity.
As a further alternative, the electrochemical cell may be configured in an elongated rectangular shape.
In the ninth embodiment, as shown in
Various embodiments use novel shapes for the electrode plates and accordingly increase the charge capacity or efficiency of the battery.
In the embodiments of
When assembling the module shown in
Various embodiments use different combinations of layer electrodes and layer negative or positive terminals to result in various battery powers for the module. For example, in some embodiments such as the one shown in
These parts are assembled in the order and orientations shown in
In various embodiments, layer electrodes 1920E are assembled such that negative and positive half layers of abutting layer electrodes come in contact. In particular, when a second layer electrode 1920E is positioned over a first layer electrode to form a module 1900, such as that seen in
In various embodiments, the insulator half layer is an insulating layer that prevents the active half layers on its two sides from exchanging charges. In the above described exemplary set-up, for instance, the insulator half layer of the second layer electrode prevents positive half layer 1926 of the first layer electrode from exchanging charges with the negative half layer of the second layer electrode located above it. Similarly, insulator half layer 1925 prevents negative half layer 1924 from exchanging charges with the positive half layer of the third layer electrode located below it.
In various embodiments, the separator half layer is an ionically conductive layer that is in contact with one or two active half layers. In some embodiments, the separator half layer preserves some of the electrolyte in the active half layer to which it contacts. Further, in various embodiments, the separator half layer is in contact with two active half layers on its two sides, enables ionic charge exchanges between those half layers, thus forming a unit cell. In the above described exemplary set-up, for instance, thin separator half layer 1927t-1 is in contact with negative active material 1924 above it and preserves and exchanges ions with that negative half layer. Similarly, thin separator half layer 1927t-2 is in contact with a positive active material located below it. Thick separator half layer 1927T, on the other hand, enables ionic charge exchanges between positive half layer 1926 of the first layer electrode and the negative half layer of the third layer electrode below. Similarly, the thick separator half layer of the second layer electrode enables ionic charge exchanges between negative half layer 1924 and the positive half layer electrode of the second layer electrode. This combination of positive half layer, separator half layer, and negative half layer creates a unit cell inside module 1900. Thus in
In various embodiments, the wire substrate is a mesh created by a single-direction conductive wire, which enables conductive electron exchanges between the two active half layers that it connects. The wire substrate thus connects within the same layer electrode the positive half layer of one unit cell to the negative half layer of another unit cell. In the above-described exemplary set-up, for instance, in the first layer electrode shown in
In various embodiments, circular plate module 1900 includes a set of unit cells connected in series. In some embodiments, each unit cell the middle is formed between two abutting layer electrodes, in the manner detailed above. Further, two end unit cells are formed between a layer electrode and an abutting layer positive terminal or layer negative terminal For example, in the embodiment shown in
In some embodiments PVC is used to manufacture circular frame 1920F, insulator half layer 1925, cap 1910, and PVC half layers 1958 and 1958h. Moreover, lead is used to manufacture wire substrate 1020W, terminals 1956 and 1956L. Further, EPDM rubber of 70 A durometer is used in manufacturing o-rings 1921 and 1957, and gasket half layers 1952 and 1952h.
Parts 1924 and 1926 are respectively the negative and positive active materials. Thin and thick separators 1927t and 1927T are made of fiberglass mats of different thicknesses. In particular, in the embodiment shown in
In various embodiments, the layer electrodes are assembled into a circular plate module in a manner that provide a continuous charge path among the plates.
In various embodiments, layer electrodes 1920E or layers for positive and negative terminals are manufactured by assembling its various parts in some specific order. In the embodiment shown in
Different embodiments use different structures for the wired-frame assembly or for combining the wired-frame assembly with the remaining parts of a an layer electrode.
O-ring sealing 2258 provides a sealing mechanism to prevent leakage of the byproducts, such as acids, or gases generated by the battery. Moreover, in some embodiments, such leakage is also prevented in the center by cutting out along diameter section 2220Fd, a channel such as potting compound area 2257. After lead-wire substrate is strung on circular frame 2220F, an epoxy is poured into area 2257 to seal in the wire. In some embodiments, the epoxy can be wax or other suitable hydrophobic materials. The epoxy is used to prevent or reduce the leakage of the battery between half layers.
Various embodiments change the shape or geometry of the module covers to improve the characteristics of the battery.
In some embodiments, a battery module is made of plates that have non-circular shapes.
Rectangular active module 2520 fits inside rectangular nest module 2530. Rectangular active module 2520 includes a rectangular frame 2520F that houses a rectangular negative half layer 2524 and a rectangular positive half layer 2526. Rectangular nest module 2530, on the other hand, contains a rectangular isolator 2525 and a rectangular separator 2527.
In various embodiments, two different frames thus comprise one layer of the battery module, in a manner similar to that shown in
In some embodiments, a number of rectangular layers are assembled to form a rectangular module with a desired output voltage.
Various embodiments combine a larger number of rectangular frames to create rectangular modules with a larger output.
Some embodiments use a spiral configuration of unit cells. In some embodiments, the spiral configuration provides a multi-helix current path through the electrode stack.
In this manner, a set of partial modules 2810 form a group of unit cells connected in series. In particular, each unit cell includes the negative half sector of partial module 2810-i, the positive half sector of the partial module 2810-i+1 located above the negative half sector, and the separator between these two half sectors. Each unit cell, thus formed, is connected in series with the cells before or after it by the trans-electrode substrates 2816. For example, one unit cell forms between the negative half sector of partial module 2810-1 and the positive half sector of partial module 2810-2 located above it. This unit cell is connected serially to the unit cell before and after it respectively by the trans-electrode substrate 2816 in partial modules 2810-1 and 2810-2.
In some embodiments, the above-discussed design is used in solid-state batteries, lead acid batteries, fuel cell batteries, or some other types of electrochemical batteries. Other embodiments of the disclosure will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein. For example, various elements or components of the disclosed embodiments may be combined with other elements or components of other embodiments, as appropriate for the desired application. Thus, it is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the disclosure being indicated by the following claims.
1. An electrochemical storage device, comprising:
- a plurality of layer electrodes, wherein each layer electrode includes a first charged sector and a second charged sector, wherein the second charged sector is charged oppositely compared to the first charged sector, and wherein the plurality of layer electrodes are assembled with respect to each other such that the first charged sector of a first plate of the plurality of layer electrodes is laid below the second charged sector of a second plate of the plurality of layer electrodes located immediately above the first plate, wherein the charges of the first charged sectors of the first and second plates have a first sign and the charges of the second charged sectors of the first and second plates have a second sign that is opposite the first sign;
- a separator sector located, and enabling ionic charge exchange between the first charged sector of the first plate and the second charged sector of the second plate.
2. The electrochemical storage device of claim 1, wherein the second charged sector of the first plate is laid below the first charged sector of the second plate, the electrochemical device further comprising an insulator sector located, and preventing ionic or conductive charge exchange, between the second charged sector of the first plate and the first charged sector of the second plate.
3. The electrochemical storage device of claim 1, wherein each of the plurality of the layer electrodes in circular.
4. The electrochemical storage device of claim 2, wherein each sector has a semi-circle shape sized to about half of the corresponding layer electrode.
5. The electrochemical storage device of claim 1, wherein each plate of the plurality of layer electrodes further comprises a frame which houses the first charged sector and the second charged sector of the corresponding plate.
6. The electrochemical storage device of claim 1, further comprising a first cap and a second cap for encasing the plurality of layer electrodes.
7. The electrochemical storage device of claim 1, further comprising a conductive substrate for providing a conductive connection between the first charge sector and the second charged sector.
8. The electrochemical storage device of claim 1, wherein each of the plurality of the layer electrodes has a rectangular shape
9. The electrochemical storage device of claim 8, wherein each sector has a half-rectangle shape sized to about half of the corresponding layer electrode.
10. An electrochemical storage device, comprising:
- a first electrochemical cell and a second electrochemical cell disposed in a common casing and each comprising an anode and a cathode, wherein the anode of the first electrochemical cell is disposed opposite the cathode of the second electrochemical cell;
- a separator disposed between the anode of the first electrochemical cell and the cathode of the second electrochemical cell, wherein the anode of the first electrochemical cell and the cathode of the second electrochemical cell are electrically insulated and in communication through an ionically conductive medium adsorbed in the separator;
- a common current collector disposed on the anode of the first electrochemical cell and the cathode of the second electrochemical cell, wherein the first and second electrochemical cells are electrically connected and insulated from ionic conduction and wherein the ionic separation of said first and second electrochemical cells mitigates shunt currents.
11. The device of claim 10, further comprising said current collector providing substantially uniform current collection granting uniform current density.
12. The device of claim 10, further comprising a hydrophobic coating disposed on the portion of the common current collector between said anode and said cathode.
13. The device of claim 10, further comprising a physical barrier to ionically insulate said first and second electrochemical cells.
14. The device of claim 10, further comprising one positive and one negative terminal connection.
15. The device of claim 10, further comprising an insulation frame for disposing anodes and cathodes of two or more electrochemical cells in substantially the same plane.
Filed: Sep 25, 2012
Publication Date: Mar 10, 2016
Applicant: ENERGY POWER SYSTEMS LLC (Troy, MI)
Inventors: Subhash Dhar (Bloomfield Hills, MI), William Koetting (Davisburg, MI), Kwok Tom (Madison Heights, MI), Frank Martin (Rochester, MI), Jorge Espinel (Troy, MI), Michael Nielson (Royal Oak, MI)
Application Number: 13/626,426