Systems and methods for shunt current and mechanical loss mitigation in electrochemical systems
10074859 ยท 2018-09-11
Assignee
Inventors
Cpc classification
H01M8/20
ELECTRICITY
H01M8/04276
ELECTRICITY
Y02E60/50
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
H01M8/0273
ELECTRICITY
H01M8/188
ELECTRICITY
F16L37/1225
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
International classification
H01M8/04276
ELECTRICITY
F16L37/12
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
H01M8/18
ELECTRICITY
H01M8/20
ELECTRICITY
Abstract
Systems and methods for shunt current and mechanical loss mitigation in electrochemical systems include a conduit providing at least a portion of an electrically conductive pathway between the first and second electrochemical cells, wherein the conduit includes at least one shunt current suppression device configured as a loop, and/or a connector assembly for maintaining first and second connecting portions in adjacent positioning.
Claims
1. A redox flow battery system, comprising: (a) an anolyte storage tank for containing a liquid anolyte; (b) a catholyte storage tank for containing a liquid catholyte; (c) at least first and second stacks of electrochemical cells, each of the first and second stacks of electrochemical cells including a plurality of electrochemical cells; (d) a conduit external to the first and second stacks of electrochemical cells providing at least a portion of an electrically conductive fluid pathway between the first and second stacks of electrochemical cells, wherein the conduit includes only one inlet to or one outlet from the first stack of electrochemical cells and only one inlet to or one outlet from the second stack of electrochemical cells, a common manifold configured for liquid anolyte or liquid catholyte flow between the first and second stacks of electrochemical cells, and at least one shunt current suppression device configured as a loop extending between the only one inlet or outlet of at least one of the first and second stacks of electrochemical cells to the common manifold, wherein the loop crosses itself defining at least one full turn and wherein the looping pattern is in a substantially continuously sloped configuration to allow for downward fluid flow.
2. The system of claim 1, wherein the shunt current suppression device includes first and second connections.
3. The system of claim 2, wherein the shunt current suppression device is continuous tubing extending between the first and second connections.
4. The system of claim 2, wherein the shunt current suppression device does not include elbow fittings.
5. The system of claim 1, wherein the shunt current suppression device is made from a flexible material.
6. The system of claim 1, wherein the shunt current suppression device is made from a plastic material that is annealed during the forming process.
7. The system of claim 1, wherein the shunt current suppression device is made from a material selected from the group consisting of polyethylene, polypropylene (PP), polytetrafluoroethylene (PTFE), polyvinylchloride (PVC), and polyvinylidene fluoride (PVDF).
8. The system of claim 1, wherein each of the plurality of loops has a radius of curvature at any point along the length of the loop.
9. The system of claim 1, wherein each of the plurality of loops is configured in a substantially circular shape, substantially oval shape, substantially rectangular shape, substantially rectangular shape with rounded ends, or a substantially elliptical shape.
10. The system of claim 1, further comprising at least a third electrochemical cell.
11. The system of claim 1, wherein the conduit providing an electrically conductive fluid pathway between the first and second stacks of electrochemical cells includes a common manifold for one of catholyte inlets, catholyte outlets, anolyte inlets, and anolyte outlets.
12. The system of claim 1, further comprising a shunt current suppression device for each of catholyte inlets, catholyte outlets, anolyte inlets, and anolyte outlets.
13. The system of claim 1, further comprising a support assembly for supporting the conduit.
14. The system of claim 13, wherein the support assembly includes a support frame.
15. The system of claim 13, wherein the support assembly includes a cover configured to support the conduit.
16. A redox flow system, comprising: (a) an anolyte storage tank for containing a liquid anolyte; (b) a catholyte storage tank for containing a liquid catholyte; (c) at least first and second electrochemical cells; (d) a conduit providing at least a portion of an electrically conductive fluid pathway between the first and second electrochemical cells, wherein the conduit includes a common manifold between the first and second stacks of electrochemical cells and at least one shunt current suppression device configured as a loop extending from at least one of the first and second electrochemical cells to the common manifold, wherein the loop crosses itself defining at least one full turn; and (e) a support assembly for supporting the conduit, wherein the support assembly is configured to support flexible tubing in a substantially continuously sloped configuration to allow for downward fluid flow.
17. The system of claim 1, wherein the power saved by shunt current loss reduction is greater than the power used for increased mechanical loss imparted by the shunt current suppression device.
18. A redox flow battery system, comprising: (a) an anolyte storage tank for containing a liquid anolyte; (b) a catholyte storage tank for containing a liquid catholyte; (c) at least first and second electrochemical stacks, wherein the first and second electrochemical cells are stacks of multiple electrochemical cells; (d) a conduit providing at least a portion of an electrically conductive fluid pathway between the first and second electrochemical stacks, wherein the conduit includes a common manifold between the first and second electrochemical cells and at least one shunt current suppression device configured in a looping pattern extending from at least one of the first and second electrochemical cells to the common manifold, wherein at least one loop crosses itself and wherein the looping pattern is in a substantially continuously sloped configuration to allow for downward fluid flow.
19. A redox flow battery system, comprising: (a) an anolyte storage tank for containing a liquid anolyte; (b) a catholyte storage tank for containing a liquid catholyte; (c) at least first and second electrochemical cells, wherein the first and second electrochemical cells are stacks, wherein each stack includes a plurality of single electrochemical cells; (d) a conduit providing at least a portion of an electrically conductive fluid pathway between the first and second electrochemical cells, wherein the conduit includes a common manifold configured for liquid anolyte or liquid catholyte flow between the first and second electrochemical cells and first and second shunt current suppression devices connected to each of the first and second electrochemical stacks, each of the first and second shunt current suppression devices configured as a looping pattern extending between a single exit or entry connection to each of the first and second electrochemical stacks and the common manifold, wherein at least one loop crosses itself defining at least one full turn and wherein the looping pattern is in a substantially continuously sloped configuration to allow for downward fluid flow.
20. A redox flow battery system, comprising: (a) at least first and second stacks of electrochemical cells, each of the first and second stacks of electrochemical cells including a plurality of electrochemical cells including an electrolyte; and (b) an electrolyte conduit external to the first and second stacks of electrochemical cells providing at least a portion of an electrically conductive pathway between the first and second stacks of electrochemical cells, wherein the conduit includes only one inlet to or one outlet from the first stack of electrochemical cells and only one inlet to or one outlet from the second stack of electrochemical cells, and at least one shunt current suppression device in the electrolyte conduit configured as a loop, wherein the loop crosses itself defining at least one full turn and wherein the looping pattern is in a substantially continuously sloped configuration to allow for downward fluid flow.
Description
DESCRIPTION OF THE DRAWINGS
(1) The foregoing aspects and many of the attendant advantages of this disclosure will become more readily appreciated as the same become better understood by reference to the following detailed description, when taken in conjunction with the accompanying drawings, wherein:
(2)
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DETAILED DESCRIPTION
(10) Embodiments of the present disclosure are directed to shunt current suppression systems and assemblies for electrochemical systems and methods for achieving shunt current suppression while minimizing mechanical pumping losses within the system. Referring to
(11) In some embodiments of the present disclosure, the flow electrochemical energy systems are described in the context of a vanadium redox flow battery (VRFB), wherein a V.sup.3+/ V.sup.2+ sulfate solution serves as the negative electrolyte (anolyte) and a V.sup.5+/V.sup.4+ sulfate solution serves as the positive electrolyte (catholyte). It is to be understood, however, that other redox chemistries are contemplated and within the scope of the present disclosure, including, as non-limiting examples, V.sup.2+/V.sup.3+ vs. Br.sup./ClBr.sub.2, Br.sub.2/Br.sup. vs. S/S.sup.2, Br.sup./Br.sub.2 vs. Zn.sup.2+/Zn, Ce.sup.4+/Ce.sup.3+ vs. V.sup.2+/V.sup.3+, Fe.sup.3+/Fe.sup.2+ vs. Br.sub.2/Br.sup., Mn.sup.2+/Mn.sup.3+ vs. Br.sub.2/Br.sup., Fe.sup.3+/Fe.sup.2+ vs. Ti.sup.2+/Ti.sup.4+, etc.
(12) Although shown and described with reference to a redox flow battery system 20, it should be appreciated that the shunt current suppression devices described herein are not limited to those used in RFBs. The shunt current suppression devices can be used in any system having a plurality of electrochemical cells and that would benefit from shunt current suppression, such as fuel cells.
(13) Referring to the schematic in
(14) In a second (discharge) mode of operation, the redox flow battery system 20 is operated to transform chemical potential stored in the catholyte and anolyte into electrical energy that is then discharged on demand by power and control elements that supply an electrical load.
(15) Each electrochemical cell in the system 20 includes a positive electrode, a negative electrode, at least one catholyte channel, at least one anolyte channel, and an ion transfer membrane separating the catholyte channel and the anolyte channel. The ion transfer membrane separates the electrochemical cell into a positive side and a negative side. Selected ions (e.g., H+) are allowed to transport across the ion transfer membrane as part of the electrochemical charge and discharge process. The positive and negative electrodes are configured to cause electrons to flow along an axis normal to the ion transfer membrane during electrochemical cell charge and discharge (see, e.g., line 10 shown in
(16) To obtain high voltage/power systems, a plurality of single electrochemical cells may be assembled together in series to form a stack of electrochemical cells (referred to herein as a stack, a cell stack, or an electrochemical cell stack). Several cell stacks may then be further assembled together to form a battery system. A MW-level RFB system can be created and generally has a plurality of cell stacks, for example, with each cell stack having more than twenty electrochemical cells. As described for individual electrochemical cells, the stack is also arranged with positive and negative current collectors that cause electrons to flow through the cell stack along an axis normal to the ion transfer membranes and current collectors during electrochemical charge and discharge (see, e.g., line 10 shown in
(17) A shunt is a device that allows electric current to pass around another point in a circuit by creating a low resistance path. Shunt currents in a redox flow battery flow though ionically conductive fluid paths that pass around the desired cell stack electron flow path described above, thus reducing system efficiency. To reduce shunt currents, it is desirable to increase electrical resistance in selected fluid pathways where shunt currents may be present.
(18) In designing shunt current suppression devices in accordance with embodiments of the present disclosure, it is also desirable to minimize mechanical flow resistance in these same fluid pathways. For any fluid flow rate, mechanical resistance can be added to the system by, for example, reducing the diameter of the conduit, increasing the length of the conduit, changing the material and roughness of the conduit, adding any connecting weld, or adding fittings such as connectors or elbows in the conduit, etc. Added mechanical flow resistance in fluid pathways adds mechanical work that the system must perform to operate, for example, by requiring additional pumping power for electrolyte flow. Mechanical work added to the system by shunt current suppression devices may offset added system efficiency produced by mitigating shunt currents. Therefore, in some embodiments of the present disclosure, designs for mitigating shunt currents increase electrical resistance in fluid pathways while minimizing mechanical flow resistance.
(19) The performance of comparative designs considering combined shunt and pump losses imparted by the design are graphically illustrated for an exemplary system in
(20) In the illustrated embodiment of
(21) In the illustrated embodiment, the first cell 26 is arranged in a common housing 60 with cell 27 to form cell stack 36, and the second cell 28 is arranged in a common housing 60 with cell 29 to form cell stack 38. Cell stacks 36 and 38 are electrically connected in series and fluidly connected in parallel (as seen in the schematic of
(22) The system 20 may include more cells or cells stacks than those illustrated and described above. As a non-limiting example, the system 20 may include a third stack, for example including cells 34 and 35. In another non-limiting example, the system 20 may include more than three cell stacks. The stacks may be in fluid communication with each other in series or in parallel. Therefore, it should be appreciated that embodiments of the present disclosure include any number of stacks in a system and any number of cells in a stack, including a single cell stack.
(23) As non-limiting examples, the system 20 may include a single stack having up to 150 cells in the stack. As other non-limiting examples, the system 20 may include up to 75 stacks with 2 cells each, or 6 stacks with 25 cells each.
(24) The fluid pathways between cell stacks 36 and 38 will now be described with reference to
(25) In the illustrated embodiment of
(26) Referring to the simplified comparative drawings of
(27) As mentioned above, shunt currents can be reduced by increasing electrical resistance in the fluid pathways of the conductive electrolyte. For example, electrical resistance may be increased by increasing the length of the fluid pathway. Accordingly, embodiments of the present disclosure are directed to increasing the length of the fluid pathways by using elongated electrolyte conduits, for example, arranged in a looping pattern to add length in a compact space. As can be seen in
(28) In the illustrated embodiment, the shunt current suppression devices 32 are located along the fluid path adjacent the respective catholyte outlets 46 of the first and second cell stacks 36 and 38. However, it should be appreciated that the shunt current suppression devices 32 may be positioned anywhere along the fluid path to increase conduit length and reduce shunt currents. In the system 20 shown in
(29) Referring to the illustrated embodiment of
(30) The shape of the loop when viewed in a top view may form a closed shape and may be of one or many different shapes. In the illustrated embodiment of
(31) Also, in accordance with embodiments of the present disclosure, there may be multiple loops with no pattern to the looping. In that regard, each loop may be of a different shape. In one embodiment of the present disclosure, the loop may have a curved outer surface, with either a constant or variable radius of curvature. In another embodiment, the loop may have corners and elbows and no radius of curvature along the outer perimeter. It should be appreciated, however, that a design with elbows or corner fittings may increase the mechanical pumping losses of the fluid flow, as compared to a curved design.
(32) In addition to imparting electrical resistance in the conductive fluid pathways, the loop may also be designed to minimize increases to mechanical flow resistance in these same fluid pathways. As mentioned above, mechanical flow resistance is calculated based on many factors and can increase as the result of, for example, the diameter of the conduit, the length of the conduit, the material and roughness of the conduit, connecting welds, and any fittings such as connectors or elbows in the conduit. In some embodiments, the shunt current suppression devices are continuous conduits. In that regard, the shunt current suppression devices may be comprised of continuous tubing between connection ends. In some embodiments, the shunt current suppression devices may have minimal fittings, such as elbow fittings, along their fluid travel path to minimize additional mechanical resistance in the fluid flow path caused by such fittings. In some embodiments, the shunt current suppression devices may not be continuous, but may include welds or joiners that are designed to minimize mechanical resistance in the fluid flow path. In other embodiments, the shunt current suppression devices have fittings, for example, at junctions or connection ends, but such fittings may be designed for minimized mechanical resistance in a fluid flow path. A reduced number of fittings not only reduces mechanical flow resistance in the conduit, but also reduces potential leak points in the conduit.
(33) Each shunt current suppression device includes one or more selected tube cross sections, length, and loop configuration to impart the desired relationship between added electrical resistance for shunt current mitigation and associated mechanical losses. For example, the conduit diameter of the shunt current suppression device may be, as non-limiting examples, tubing of , , or diameter. As shown in the graphical representation of data in
(34) Shunt current suppression devices 32 are also designed for ease of assembly, and to reduce fatigue failure. In some embodiments of the present disclosure, the current suppression devices are made from a resilient and flexible material. Resilience and flexibility in the material may allow the looping shunt current suppression devices to provide a mechanical spring action that reduces mechanical fatigue cracking caused by thermal and fluidic cycling, as well as by stresses caused from transporting the system 20 from one location to another. Such flexibility and resilience may also allow ease of assembly in connecting the conduits to the cells stacks 36 and 38 shown in
(35) Non-limiting examples of suitable materials for the shunt current suppression devices may include, but are not limited to, cross-linked polyethylene (PEX), high density polyethylene (HDPE), polypropylene (PP), polytetrafluoroethylene (PTFE also known as TEFLON), polyvinylchloride (PVC), or polyvinylidene fluoride (PVDF also known as KYNAR), for example.
(36) In some embodiments, the shunt current suppression devices are formed from a flexible material into a shaped pattern, then annealed after being formed to help the material maintain its intended shape or to impart some rigidity to the material. In other embodiments, the shunt current suppression devices are made from rigid or semi-rigid materials.
(37) Regarding fatigue failure, even if a rigid or semi-rigid material, such as CPVC, is used for the looping shunt current suppression devices, the looping configuration can still contribute to reducing fatigue failure. In that regard, because there is very little lateral support in a looping system, a certain level of flexibility is imparted by the looping structure, even if constructed from a rigid or semi-rigid material. Moreover, a rigid shunt current suppression device with a radius of curvature and a single loop may also have reduced fatigue failure because of the absence of any joints or couplings and therefore, the absence of any strain on such joints or couplings.
(38) Regarding assembly, a certain amount of flexibility may be desirable, for example, to lower the dimensional tolerance requirement for assembly components. Also, flexibility may minimize the time required to assemble components.
(39) Referring to the illustrated embodiment of
(40) Referring to
(41) As can be seen in
(42) In addition to the support frame 80, the system 20 in the illustrated embodiment of
EXAMPLE
Mechanical and Electrical Resistance
(43) Data provided in
(44) One method of calculation for mechanical pumping losses and shunt current losses associated with the loops is described below. It should be appreciated that alternate testing and analytical methods may also be used to obtain such results.
Pumping Loss Calculations
(45) The friction factor is first calculated, followed by calculations for pressure drop. Friction factor calculation variables are defined as follows: D: Pipe Internal Diameter R: Radius of coil helix (measured from axis to pipe centerline) De: Dean number Re.sub.e: Transitional Reynolds number for a coil f.sub.e: Friction factor for a coil of smooth pipe f.sub.rough: Friction factor for rough pipe f.sub.smooth: Friction factor for smooth pipe
(46) For single-phase flow in a coil, a secondary flow pattern that changes fluid behavior is established in the pipe that stabilizes fluid flow, increasing the Reynolds number at which the flow enters the transition from laminar to turbulent flow. A Reynolds number correction is shown.
(47)
Here R is the radius of the coil helix, taken from the center of the pipe.
(48) Below this calculated Reynolds number the fluid flow is laminar, and above this calculated Reynolds number the fluid is in transition or turbulent flow. Using the corrected Reynolds number, a Darcy friction factor for flow in coils is estimated for the purpose of calculating the pressure drop:
(49) To determine the friction factor in the coil the Dean number (De) is required:
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(51) The friction factor for flow in a coil of smooth pipe can then be calculated as follows:
(52)
(53) For fully turbulent flow in smooth coils the correlation below may be used:
(54)
(55) This equation immediately above is applicable in the ranges:
(56)
(57) To account for the effect of roughness the following correction may be employed:
f.sub.c,rough=f.sub.c.f.sub.r
(58) Where f.sub.r represents the ratio of friction factors for smooth pipe and rough pipe for the inside diameter of the pipe making up the coil:
f.sub.r=f.sub.roughf.sub.smooth
(59) The following formula may be used to calculate pressure drop in the helical coil:
p=f.sub.c,rough(l/d.sub.h)(v.sup.2/2) Where: p=pressure drop f.sub.c,rough=Coil rough friction l=length of pipe in the coil d.sub.h=pipe inside diameter =electrolyte density v=flow velocity
(60) With a known pressure drop (p), electrolyte flow rate (Q), and pump efficiency, the mechanical pumping losses Wp, included in
Wp=(p)(Q) (pump efficiency)
Shunt Current Loss Reduction Calculations
(61) Shunt current magnitude calculations are based on Ohm's Law, I=V/R, where:
(62) I=shunt current
(63) V=voltage gradient that induces shunt current flow
(64) R=resistance to current flow in ionically conductive fluid pathways as determined by pipe diameter and length, and electrolyte conductivity. Shunt current losses Ws, included in
(65) Ws=power in kilowatts
(66) V=voltage gradient that induces shunt current flow
(67) I=shunt current
Combined Shunt and Pump Losses
(68) As illustrated in
(69) Using any combination of analytical and empirical methods, it can be seen that shunt current suppression devices can be designed to improve system performance while minimizing associated mechanical losses.
(70) Referring now to
(71) Referring to
(72) Referring to
(73) Referring to
(74) When the first and second connector portions 92 and 94 are mated (see
(75) Although shown as including first and second flanges 96 and 104, it should be appreciated that the connector assembly 90 may include other features that are capable of connection in adjacent positioning. For example, flanges may be replaced by grooves that would be capable of receiving a retaining mechanism to secure adjacent positioning.
(76) To minimize mechanical losses through the connector assembly 90, the fluid flow path 108 is configured to minimize joints, elbows, or constraint on the fluid. In that regard, the fluid flow path 108 is a substantially straight fluid path through the connector assembly 90.
(77) In addition, a coupling conduit 112 between the connector assembly 90 and the shunt current mitigation device 32 may be designed to further minimize mechanical losses. In the illustrated embodiment, the coupling conduit 112 between the connector assembly 90 and the shunt current mitigation device 32 is a length of tube designed and configured for ease of transition from the connector to the looping shunt current mitigation device without introducing elbows or opportunities for other flow restrictions of the fluid flow path 108.
(78) The various parts of the connector assembly 90 may be constructed from any suitable materials. For example, the first and second portions 92 and 94 may be constructed from materials described above with reference to the shunt current mitigation device. Likewise, the coupling conduit 112 may be constructed from plastic and may be welded to the connector assembly 90 and the shunt current mitigation device 32 using known welding techniques. Alternatively, the coupling conduit 112 may be integrally formed with either of the connector assembly 90 and the shunt current mitigation device 32.
(79) In accordance with some embodiments of the present disclosure, the first and second connector portions 92 and 94 of the connector assembly 90 are designed to be connectable by welding to any suitable pipe or connector, whether standard or custom, that is made from suitable materials for welding. Such connector assemblies may be used in redox flow battery systems or in any other systems for fluid flow.
(80) While illustrative embodiments have been illustrated and described, it will be appreciated that various changes can be made therein without departing from the spirit and scope of the disclosure.