Patent Application
20130011702
This invention generally relates to reduction-oxidation (redox) flow battery energy storage systems, and more particularly to redox flow battery energy storage systems comprising a plurality of independent purpose-configured stack assemblies.
The current electric grid in the U.S. suffers from a substantial limitation due to its lack of any storage capacity. All electricity produced by generation facilities must by consumed immediately. This need to exactly match supply with demand has created a complex network of electric generation facilities whose output can be increased or decreased to match demand at any given moment.
Many renewable energy technologies, while economically viable and environmentally beneficial, suffer from the disadvantage of periodic and unpredictable power generation. It is very difficult, if not impossible to control such intermittent generation technologies in order to match grid demand. Such technologies can arguably be used to provide a minimum “baseline” power to the grid, but this limits the expansion possibilities for such alternative generation technologies. To enable renewable energy technologies to expand, large scale energy storage systems are required in order to allow electricity generated by intermittent generation technologies to be reliably delivered to the grid to match demand.
Additionally, many conventional electric generation technologies, such as coal, gas-fired and nuclear power plants, as well as promising alternative energy generation technologies, such as fuel cells, function best when operated at constant power. Because power demanded by the electric grid fluctuates dramatically based on the variable needs of electricity consumers, such generation facilities are often operated in less-efficient modes. Thus, these conventional generation facilities can also benefit from energy storage systems that can store energy during off-peak hours and deliver peak power during times of peak demand.
Reduction/oxidation or “redox” flow batteries represent a promising large-scale energy storage technology. Redox flow batteries are electrochemical systems in which both the anode and cathode are dissolved in liquid electrolytes. With all four reactant states (i.e., charged and discharged states of cathode and anode), dissolved in a liquid, the storage capacity of such systems is a function of tank size.
In some embodiments, redox flow battery systems may be configured with four distinct tank spaces, while utilizing only two tank structures by using one or more dividers within the each tank. This provides for a flow battery system which may operate in a more efficient four-tank mode while keeping tank costs down relative to a system with four complete tanks.
In the various embodiments, tank separators are provided to avoid or mitigate a rate of mixing between liquids in two volume portions within a tank due to convection, either natural convection or convection forced by the pumping of electrolyte into or out of the tank. The tank separator can comprise a movable seal positioned by the liquids in the two volume portions. For vertically stacked volume portions, the tank separator can comprise a solid or immiscible liquid having a density that has a value between the respective densities of the two liquids in the two volume portions. The tank separator can comprise a porous matrix comprised of material that mitigates convective mixing and may also reduce the rate of diffusion of charged species by increasing a path length for diffusion.
In one aspect, a reduction-oxidation (redox) flow battery system may comprise a first electrolyte storage tank, a movable tank separator configured to divide a volume of the first electrolyte storage tank into a first volume portion and a second volume portion, a second electrolyte storage tank, and at least one redox flow battery stack assembly joined in fluid communication with the first electrolyte storage tank and the second electrolyte storage tank.
In another aspect, the present disclosure provides a method of reducing mixing of two electrolytes stored within one tank volume. A first electrolyte is placed in a first volume portion of a tank. A second electrolyte is placed in a second volume portion of the tank separated from the first volume by a tank separator that is movable. The first electrolyte and the second electrolyte are communicated with at least one redox flow battery stack to perform oxidation and reduction reactions, wherein the tank separator moves within the tank to accommodate a related change in quantity of the first and second electrolytes in the first and second volume portions respectively.
In an additional aspect, the present disclosure provides a method of reducing mixing of two electrolytes stored within one tank volume. A first electrolyte is placed in a first volume portion at a bottom portion of the tank. A second electrolyte is placed in a second volume portion at a top portion of the tank, wherein the first electrolyte is more dense than the second electrolyte, and wherein the tank separator comprises a porous matrix spanning an interface of the first and second electrolytes between the first and second volume portions.
The accompanying drawings, which are incorporated herein and constitute part of this specification, illustrate exemplary embodiments of the invention, and together with the general description given above and the detailed description given below, serve to explain the features of the invention.
The various embodiments will be described in detail with reference to the accompanying drawings. Wherever possible, the same reference numbers will be used throughout the drawings to refer to the same or like parts. References made to particular examples and implementations are for illustrative purposes, and are not intended to limit the scope of the invention or the claims.
As used herein, the terms “about” or “approximately” for any numerical values or ranges indicates a suitable temperature or dimensional tolerance that allows the part or collection of components to function for its intended purpose as described herein.
The term “engineered cascade flow battery” is used herein to refer generally to a cascade flow battery in which cells, stages and/or arrays within the battery are configured in terms of materials, design shapes and sizes, reactant flow, and/or other design variables based on an expected condition of reactants (e.g., the state of charge of electrolytes) so as to increase the battery's performance (e.g., energy storage efficiency, power generation efficiency, reduced electrolyte breakdown, reduced hydrogen generation, or other performance) over that achievable in a cascade flow battery in which all cells, stages and/or arrays along the reactant flow path are substantially the same as one another. References to “optimized” or “optimum” are merely intended to indicate design parameters which may be controlled or varied in an engineered cascade flow battery in order to improve performance and to distinguish the embodiments from designs in which there is no configuration based on expected local properties of reactants. Use of these terms is not intended to imply or require that the any cells, stages and/or arrays or components thereof are designed for the best possible or theoretical performance.
As used herein the phrase “state of charge” and its abbreviation “SOC” refer to the chemical species composition of at least one liquid electrolyte. In particular, state of charge and SOC refer to the proportion of reactants in the electrolyte that have been converted (e.g. oxidized or reduced) to a “charged” state from a “discharged” state. For example, in a redox flow battery based on an Fe/Cr redox couple, the state of charge of the catholyte (positive electrolyte) may be defined as the percent of total Fe which has been oxidized from the Fe2+ state to the Fe3+ state, and the state of charge of the anolyte (negative electrolyte) may be defined as the percent of total Cr which has been reduced from the Cr3+ state to the Cr2+ state. In some embodiments, the state of charge of the two electrolytes may be changed or measured independent of one another. Thus, the terms “state of charge” and “SOC” may refer to the chemical composition of only one or of both electrolytes in an all-liquid redox flow battery system. The skilled artisan will also recognize that the state of charge of one or both electrolytes can be changed by processes other than electrochemical processes (e.g., by adding quantities of one or more reactant species).
The embodiments provide an energy storage system based upon a reduction/oxidation (redox) flow battery system that is suitable for storing and delivering electric energy under a wide variety of conditions. Electric energy stored by the redox flow battery system can be produced from a wide variety of electric generation or conversion methods, including hydroelectric, natural gas, coal, gasoline, diesel or other liquid petroleum fuel, nuclear, wave power, tidal power, solar, thermal energy, wind, etc. The redox flow battery systems of the various embodiments are also capable of delivering stored energy to a wide variety of loads, including a distributed electrical grid, a data center, an irrigation pump, a cellular telephone station, another energy storage system, a vehicle, a vehicle charging system, a building, or any other electrical load.
Flow batteries are electrochemical energy storage systems in which electrochemical reactants are dissolved in liquid electrolytes (sometimes referred to herein collectively as “reactant” or “reactants”), which are pumped through reaction cells (referred to herein as “cells”) where energy is either added to or extracted from the battery. In applications where megawatts of electrical energy must be stored and discharged, a redox flow battery system can be expanded to the required energy storage capacity by increasing tank sizes and expanded to produce the required output power by adding electrochemical cells or cell blocks (i.e., groups of multiple cells which are sometimes referred to herein as “cell arrays”).
A system diagram of an embodiment of a redox flow battery energy storage system is illustrated in
Referring to
The conductive surfaces 22, 24 are coupled to conductors 42, 43 which complete a circuit through either an electrical power source 45 (for charging) or an electrical power load 46 (for discharge), which may be selected in single stack embodiments via an electrical switch 44. The cathode electrolyte (“catholyte) and anode electrolyte (“anolyte”) are stored in electrolyte tanks 26, 28, and are pumped by pumps 30, 32 to provide the input flows 34, 36 to the redox flow battery stack assembly 10, with battery output flows 38, 40 returning to the electrolyte tanks 26, 28. The redox flow battery stack assembly 10 may be designed for reduced cost by keeping the complexity and part count of the stack to a minimum. The redox flow battery stack assembly 10 may be further designed to minimize shunt current losses and maximizing reactant utilization.
The redox flow battery stack assembly 10 is configured to include an array of independent battery cells, assembly frames as illustrated in
Some types of flow battery electrolytes operate more efficiently (i.e., retaining and discharging electrical power with lower losses) when the fluids are heated to an optimum temperature. To take advantage of this characteristic, the redox flow battery cell layer assembly 48 may be configured with tubes 60, 62, 64, 66 or channels through which a heating fluid can be circulated. Circulating a heating fluid around and/or within the battery stack assembly can keep the electrolytes at a controlled temperature. By including heating fluid tubes 60, 62, 64, 66 before and after each battery cell, the operating temperature of each cell can be controlled individually so as to enable each cell to operate at a preferred or optimum temperature corresponding to the state of charge of electrolytes within the cell. The heating fluid tubes are optional because in an embodiment the electrolytes may be preheated within the tanks 26, 28, such as via a heat exchanger circulating a heating fluid so that the electrolytes enter the cell layers 48 at a sufficient temperature for charging or discharging operations. As described more fully below, the heating fluid may draw thermal energy from waste heat generated by either the source of the charging power 45 (e.g., from a generator cooling system) or the load 46 (e.g., from an equipment cooling system).
A conceptual build of a single cell of a cell section within the cell layer 48 of a flow battery stack is illustrated in
The anolyte and catholyte reactants are separated by a planar membrane separator 12 which is suspended between the two planar structural members 80, 82 by frame members 84, 86, 88, and 90. It should be noted that the frame members 84, 86, 88, 90 maybe in the form of two exterior frames as illustrated in
At the reactant inlet of each battery cell 50, manifold holes 92, 94 may be provided to direct the incoming electrolyte flows into the reaction area of the cell 50. In an embodiment, the manifolds may include flow directing structures to cause proper mixing of the electrolytes as they enter each reaction cell 50. Such flow directing structures may be configured to adjust or control the reactant flow in each cell 50 within the redox flow battery stack assembly 10 based upon the expected state of charge and other fluid properties within each cell.
The planar structural members 80, 82, as well as separator frame members 84, 86, 88, 90 may include passages through which heat exchanger fluid pipes 60, 62 can pass. Positioning optional heat exchanger fluid pipes 60 within the cell input manifolds 92, 94 enables heat from the thermal fluid within the pipes to raise the temperature of the reactant flows before the reactants enter the cell chamber. Similarly, positioning heat exchanger pipes 62 within the cell output manifolds 96, 98 enables the thermal fluid to extract heat from the electrolytes after the reactants leave a final cell 56, thereby conserving thermal energy and enabling the electrolytes to be returned to storage tanks at a cooler temperature. In a preferred embodiment the thermal fluid is heated to a temperature of about 40 to 65° C. for Fe/Cr reactants.
A redox flow battery stack assembly 10 may be formed by stacking layers 48 in series to form a battery stack. In this battery stack assembly the conductive surfaces 22, 24 provide the electrical connectivity between cells in each stack cell layer as described below with reference to
The planar structural members 80, 82 which form the bipolar frame may be electrically conductive throughout their area, or may be made in such a way that only the conductive surfaces 22, 24 immediately adjacent to the electrochemically active portion of the cell 50 are electrically conductive, as illustrated in
To form each cell layer 48 as illustrated in
In the redox flow battery system of the various embodiments the cells can be replaceable and recyclable. Since the materials of construction are primarily plastics (e.g., polypropylene or polyethylene), carbon fiber felts, and carbon fiber electrodes, the cells contain no heavy metals or toxins that could pose an environmental impact. Further, the reactants, such as Fe/Cr, are no more toxic or dangerous than battery acid. Thus, the redox flow battery system of the various embodiments are ideal for providing the energy storage capacity required for renewable energy systems in a distributed fashion close to the population and load centers.
As explained more fully below with reference to
A variety of reactants and catalysts may be used in the redox flow battery system. A preferred embodiment set of electrolyte reactants is based upon the iron and chromium reactions illustrated in
An undesirable non-faradic electron transfer reaction can occur between Fe3+ and Cr2+ if these ions come into proximity to one another. Therefore, to maintain a high level of coulombic efficiency, electrolyte cross-mixing within a Fe/Cr redox flow battery stack should be minimized. One way to minimize electrolyte cross-mixing is to use a highly selective membrane separator 12 such as Nafion®-117 ion-exchange membrane (DuPont, USA). A disadvantage of highly-selective membrane separators is that they have low ionic conductivity which results in lower voltage efficiency within the redox flow battery stack. Additionally, ion-exchange membranes are expensive, with a price in the neighborhood of $500/m2. Since the DC energy storage efficiency of a redox flow battery is the product of coulombic and voltage efficiencies, an optimization tradeoff exists.
A particular embodiment of the Fe/Cr system is what is known as the mixed reactant system where FeCl2 (Fe2+) is added to the anolyte and CrCl3 (Cr3+) is added to the catholyte, as described in U.S. Pat. No. 4,543,302, the entire contents of which are incorporated herein by reference. An advantage of the mixed reactant system is that the discharged anolyte and discharged catholyte are identical. Furthermore, when the total concentration of Fe in the anolyte is the same as the catholyte, and the total concentration of Cr in the catholyte is the same as the anolyte, the concentration gradients across the membrane separators 12 are eliminated. In this way the driving force for cross-mixing between anolyte and catholyte is reduced. When the driving force for cross-mixing is reduced less selective membrane separators may be used, thereby providing lower ionic resistance and lower system costs. Examples of less-selective membrane separators include microporous membrane separators manufactured by Celgard LLC, and membrane separators made by Daramic LLC, both of which cost in the neighborhood of $5 to 10/m2. By optimizing the cell characteristics for the reactant state of charge and completing the charge or discharge in one pass, the embodiments described herein provide suitably high efficiency in a redox flow battery stack comprised of materials that are approximately two orders of magnitude lower cost than in conventional redox flow battery designs.
In both the unmixed and mixed reactant embodiments, the reactants are dissolved in HCl, which is typically about 1-3 M concentration. The electrocatalyst, which may be a combination of Pb, Bi and Au or ZrC, is provided at the negative electrode to improve the rate of reaction of recharging when Cr3+ in the anolyte is reduced to Cr2+, thereby reducing or eliminating hydrogen evolution. Hydrogen evolution is undesirable as it unbalances the anolyte from the catholyte and is a competing reaction to Cr3+ reduction leading to a reduction in coulombic efficiency.
The cell, cell layer and redox flow battery stack designs described herein can be used with other reactant combinations that include reactants dissolved in an electrolyte. One example is a stack containing the vanadium reactants V(II)/V(III) or V2+/V3+ at the negative electrode (anolyte) and V(IV)/V(V) or V4+/V5+ at the positive electrode (catholyte). The anolyte and catholyte reactants in such a system are dissolved in sulfuric acid. This type of battery is often called the all-vanadium battery because both the anolyte and catholyte contain vanadium species. Other combinations of reactants in a flow battery that can utilize the embodiment cell and stack designs include Sn (anolyte)/Fe (catholyte), Mn (anolyte)/Fe (catholyte), V (anolyte)/Ce (catholyte), V (anolyte)/Br2 (catholyte), Fe (anolyte)/Br2 (catholyte), and S (anolyte)/Br2 (catholyte). In each of these example chemistries, the reactants are present as dissolved ionic species in the electrolytes, which permits the use of battery cell and stack designs in which electrolyte flow through a plurality of battery cells series along the flow path (i.e., cascade flow), with the cells and having different physical properties along the flow path (cell size, type of membrane or separator, type and amount of catalyst). A further example of a workable redox flow battery chemistry and system is provided in U.S. Pat. No. 6,475,661, the entire contents of which are incorporated herein by reference.
A number of cell chambers are formed in each bipolar frame in a redox flow battery stack array.
Due to the variation in reactant ion concentrations as the reactants flow through the various cells in each layer, the amounts of catalytic coating may be varied to match the state of charge condition in each of the respective cells. Additionally, the catalytic coating formations applied to the porous electrodes 18, 20 may be varied in formulation (e.g., varying amounts of zirconium or bismuth compounds) to better match the state of charge condition in each cell. For example, typically the cell with the lower reactant concentrations will require a higher catalyst loading on the porous electrodes to achieve optimum performance.
The various embodiments include a unique redox flow battery stack configuration that includes multiple independent cells within a flow path as illustrated in
As illustrated in design trend line 116, other design parameters—illustrated as Group B parameters—may be increased from one end of a cell layer 48 to the other to configure the battery design so that the values increase from reactant inlet to outlet from the cell layer in discharge mode and decrease from reactant inlet to outlet from the cell layer in charging mode. As illustrated in
For example, as described above, the discharge catalyst loading and discharge catalyst activity (both Group B design parameters) may be increased in each cell along the flow path of redox flow battery stack assembly 10 from inlet to outlet in the discharge mode and decreased in each cell along the flow path of redox flow battery stack assembly 10 from inlet to outlet in the charge mode to compensate for decreasing reactant concentrations, as indicated by the design trend line 116.
Similarly, the charge catalyst loading and charge catalyst activity (both Group A design parameters) may be decreased in each cell along the flow path of redox flow battery stack assembly 10 from inlet to outlet in the discharge mode and increased in each cell along the flow path of redox flow battery stack assembly 10 from inlet to outlet in the charge mode to compensate for decreasing reactant concentrations, as indicated by the design trend line 112. The specific catalyst loading and catalysts activity implemented within each cell along the flow path can be determined using the design trend line 116 with respect to discharging, trend line 112 with respect to charging, and the number of cells in the path.
Using the design trend lines 112, 116 illustrated in
Similarly, the various embodiments may control the temperature of reactants as they flow through the redox flow battery stack depending upon whether the stack is charging or discharging.
In a similar manner, the various embodiments improve electrochemical performance by configuring the redox flow battery stack assembly 10 so that the reactant mass transport rate varies from cell to cell along the flow path.
In a similar manner, embodiment redox flow battery cells may be configured with different membrane separator 12 materials along the reactant flow path.
Thus, in an embodiment redox flow battery stack assembly 10 may include cells at one end of the flow path having membrane separators 12 made from a material with high membrane selectivity at the cost of greater ohmic losses, while cells at the other end of the flow path will have membrane separators 12 made from a material with lower ohmic losses. This design approach works because the driving force for cross mixing is greatly diminished due to the low concentrations of spontaneously-reacting active species at the outlet end in the discharge mode and at the inlet end in the charge mode. In the case of an Fe/Cr redox flow battery (
As mentioned above, the particular design configuration of each cell within a particular redox flow battery stack assembly 10 may be determined by applying the design trend lines illustrated in
By varying the design configurations of independent cells along the reactant flow path through the redox flow battery cell layer 48 and stack assembly 10 the various embodiments are able to achieve significant charging/discharging performance improvements over conventional redox flow battery designs. This performance improvement is illustrated in
By forming the conducting regions (e.g., conductive surfaces 22, 24) only on the active areas of the bipolar frame as illustrated in
Instead of assembling cells within a unibody frame for each cell layer, each cell may be assembled within cell frames 52a-56c in an embodiment illustrated in
As mentioned above, one source of losses in a redox flow battery is due to mixing or leakage of reactants along the edges of the membrane separator 12. As illustrated in
As mentioned above, the performance of a redox flow battery stack assembly 10 can be enhanced by heating the reactants to optimum temperatures at various stages within the battery flow path. Various embodiments accomplish such heating by using waste heat or alternative energy heat sources, thereby enhancing electrical performance while reducing parasitic losses. The various embodiments have a number of useful applications in energy generation applications as well as industrial applications which use electrical power and generate waste heat (e.g., heat sinks from air-conditioning and equipment cooling systems). As discussed in the embodiments below, alternative energy sources such as wind turbines and solar panels require cooling to enhance performance and prevent mechanical breakdown. Larger energy storage systems using the Fe/Cr redox flow battery technology can be thermally integrated with wind turbine farms and photovoltaic solar farms as illustrated in
Integrating a wind turbine system with a redox flow battery system provides a renewable power generation system which can operate more efficiently and economically than a wind turbine farm that does not have energy storage capacity. Such a system can store power whenever the wind is blowing, and meet the power demands of the electrical power grid regardless of the current wind conditions. This enables a wind turbine/redox flow battery system to meet utility contractual obligations to provide consistent power to the electrical power grid, thereby avoiding economic penalties for failing to supply contracted power levels during times of little or no wind. Additionally, the system allows electrical power to be supplied to the power grid during periods of peak demand, enabling the system owner to sell electrical power at the most favorable rates regardless of when peak winds occur.
An embodiment energy generation and storage system combining a wind turbine farm 170 with a redox flow battery is illustrated in
Similar to the wind turbine/redox flow battery system described above with reference to
A solar energy conversion system, such as a photovoltaic (PV) array, concentrating photovoltaic (CPV) array, a solar thermal energy power plant, or a solar hot water system, can be thermally and electrically integrated with the redox flow battery system to provide a more economical and efficient renewable energy generation system 180, 190 as illustrated in
Thermally integrating a solar thermal energy collection system with a redox flow battery system can be accomplished in at least two configurations. In a first configuration illustrated in
In a third configuration illustrated in
Thermally integrating a solar collector or solar energy conversion system with a redox flow battery system can use either pump circulation as illustrated in
The thermosiphon solar heating system operates in closed loop configuration for both embodiments illustrated in
The table in
Thermal integration of a redox flow battery system with conventional power generation systems, such as nuclear and coal-fired power plants, can provide significant energy and economic efficiencies since such systems generate a large amount of low grade waste heat. As described above, thermally integrating the redox flow battery system with sources of waste heat improves the battery operating efficiency without the expense or parasitic losses of electrical or fossil fuel heaters. Electrically integrating a redox flow battery energy storage system with conventional power generation systems also provides significant economic advantages since the battery system can enable base-loaded power plants to accommodate grid support (ancillary services) or peak power demands without varying their output. As is well known, nuclear and coal-fired power plants operate most efficiently and economically when run at constant power levels. Peak power demands can be met by charging the redox flow battery energy storage system during periods of reduced demand (e.g., off-peak hours in the late evening) and then augmenting the electrical output of the power plant with electricity drawn from the battery system during periods of peak power demand. Such a combined power plant/energy storage system can be economically advantageous since electrical power can be generated in the most economical manner (i.e., at constant output 24 hours per day) but sold at times of peak demand when electricity prices are greatest. Further economic benefits can be obtained by adding a redox flow battery energy storage system to an established conventional power plant to meet growing demands for peak power without building additional power plants. The sizing flexibility of redox flow battery systems, in which energy storage capacity can be increased simply by increasing the size or number of reactant storage tanks, means the economic advantages of adding a flow battery storage system to a conventional power plant can be obtained without having to invest in a system sized for future demands.
Geothermal energy can also be used to heat the reactant storage tanks. This approach could provide a stable system with a large amount of thermal inertia. Low grade geothermal energy can be used to provide heat to the redox flow battery stack assembly 10 or to the reactant storage tanks. In this embodiment heat is obtained from geothermal energy deep within the Earth which can be conveyed by a thermal fluid around the reactant storage tanks and/or through a heat exchanger before and after the battery stack.
The redox flow battery storage system does not necessarily need to be placed in close proximity to the power generation system. For example, if there is a low cost source of waste heat from an industrial process or a solar array (PV or CPV) used to a building, it may be economically and efficiently advantageous to locate a redox flow battery within or near the building in which the process is accomplished or the solar array located. In this manner, the waste heat from the industrial process or on-site power or thermal energy generation can be used to enhance the battery efficiency, while the energy storage capacity of the battery is used to meet peak power demands or enable purchasing electrical power during off-peak hours when electricity rates are lower. Thus, if the industrial process uses large amounts of electricity, thermally and electrically integrating the process with a redox flow battery system can meet the process's demand for electrical power while electricity is purchased to charge the battery system during off-peak hours when electricity rates are lower. This type of implementation may reduce cooling costs for the industrial process over periods when the electricity rates are high, thus providing further cost savings.
All the previously mentioned low grade heat sources can also be applied to heating the reactant tanks instead of or in addition to heating the redox flow battery stack assembly 10. Heating the reactant tanks enables the system to respond very quickly to load changes without any thermal management problems because the reactant fluid is constantly maintained at the operating temperature ready to be utilized in the flow battery. Costs and complexities of heating and insulating the reactant storage tanks may be offset by the cost advantages of simplifying the redox flow battery stack design because this approach eliminates the need for heat exchanger elements within the battery stack assembly. Further, combining these alternative embodiments, such as heating storage tanks and providing heat exchangers within the stack may provide the optimum design approach for providing clean, low cost and reliable heat to the redox flow battery.
Four additional example system embodiments of the redox flow battery system for use in battery energy storage systems (BESS) are illustrated in
In a first example embodiment illustrated in
Electrical power is generated from the chemical energy stored in the electrolytes in a second (discharging) redox flow battery stack 212. Electrolyte from the storage tanks 214, 216 is directed to the second redox flow battery stack 212 via inlet flows 218, 220. Within the second redox flow battery stack 212, electricity is generated by converting Fe3+ ions to the Fe2+ state and Cr2+ ions to the Cr3+ state (see
Reactants flowing out of the second redox flow battery stack 212 (outflows 222, 224) may be pumped into the first redox flow battery stack 210 for recharging, thereby providing a single charging and discharging loop. Since the electricity provided to the DC load 206 is generated from electrolytes in the second redox flow battery stack 212, the output current is completely isolated from the electrical sources of charging power, enabling the output power to reliably follow the DC load without power spikes or power drops. This arrangement ensures power variations from the grid, on-site renewable energy generators, or on-site distributed generators do not disrupt power to the DC load 206. Conversely, the power fluctuations associated with a large and widely varying load, such as an electric vehicle charging station or industrial batch process (e.g., a mixer), remain isolated from the utility grid 202 and other energy sources. This is beneficial to utilities as it reduces stress on the grid and also is beneficial to charge station owners as it circumvents large power demand charges. The unique characteristics of the redox flow battery system also enables DC□DC conversion to be accomplished with high overall system efficiency by a suitable choice of the number of cells connected in series within each stack to achieve V1 in the charge stack and V2 in the discharge stack. Also, the facility owner can choose when to charge the system so as to select the lowest cost electricity in order to maximize gross profit margins.
As described above, electrical efficiencies of the first and second redox flow battery stacks 210, 212 can be enhanced by heating the reactants to an elevated temperature, such as about 40 to 65° C., using on-site waste heat from equipment or facility cooling systems or geothermal heating systems 236. As described above, a heating fluid from waste heat recovery systems, solar hot water system, or geothermal heating systems 236 may be provided to a heat exchanger within the redox flow battery stacks 210, 212 (as illustrated in flow 238) and/or to heat the reactant storage tanks 214, 216 (as illustrated in flow 240).
The embodiment illustrated in
A particularly attractive application for the Fe/Cr redox flow battery system 200 embodiment illustrated in
As described above with reference to
In a second example embodiment illustrated in
The vehicle charging station 250 embodiment illustrated in
Similar to the embodiment described above with reference to
Similar to the embodiments described above with reference to
In a fourth example embodiment illustrated in
In this embodiment, the chemical fuel, such as hydrogen or natural gas, may be provided from a fuel source 356 via a fuel pipe 354 to the fuel cell 352. For example, the fuel cell/redox flow battery system 350 may be located at or near a source of natural gas, such as in an oil field, so that natural gas extracted from the ground can be provided to the fuel cell. The fuel cell 352 converts the fuel into electricity and effluents (e.g., water and carbon dioxide). Electricity output from the fuel cell 352 is provided to the first redox flow battery stack 210 where the power is used to charge the electrolytes stored in the electrolyte storage tanks 214, 216. As described above, electrical energy stored in the electrolyte species is converted into electricity in the second redox flow battery stack 212. Electricity output 234 from the second redox flow battery stack 212 can be provided to an inverter 358 which converts the DC current generated by the battery into AC current compatible with the utility grid 202 or industrial facility 359. The inverter 358 may be a solid-state electrical DC-AC inverter or a motor-generator as are well-known in the art. In this embodiment, flow of the electrolyte through the second redox battery stack 212 can be controlled by adjusting the speed of the pumps 226, 228 so as to generate electricity to meet the demands of the grid 202. When demand from the utility grid 202 or industrial facility 359 exceeds the steady-state output of the fuel cell 252, stored energy in the electrolyte is used to meet the additional demand. When demand from the utility grid 202 is less than the steady-state output of the fuel cell 252, the excess energy is stored in the electrolyte. Thus, the system 350 can follow the peak demands of the utility grid 202 or industrial facility 359 without having to operate the fuel cell 352 in an inefficient or potentially damaging manner. In a similar but alternative manner, the system 350 can be used as an on-site distributed generator to follow the peak demands of a co-located industrial facility load 359. The base load demand of an industrial facility 359 can be satisfied by the utility grid 202 or an independent stand-alone fuel cell system 352.
Similar to the embodiments described above with reference to
In a further embodiment illustrated in
Since the goal of the embodiment illustrated in
Additionally, since the goal of the embodiment illustrated in
Operation of the gravity-driven redox flow battery system 400 is illustrated in
As illustrated in
As illustrated in
The advantage of eliminating pumps from the flow battery system in the embodiment illustrated in
The control valves 418, 420, 422, 424 are the only moving mechanical components apart from the rotation mechanism. The system can be operated flexibly by switching between charge and discharge mode at any time. For example, once the system has discharged through one cycle it may be advantageous to discharge a second time by rotating the system through 180° to flow reactants back into the proper tanks for discharging without applying power to the battery stack 410, and then rotating the system another 180° to restart the discharge process. Doing so will generate more electrical power stored in the reactants, although the power output will be lower than the first discharge cycle. Likewise the system can be charged through a number of cycles in a similar process. Also the system can switch from charge to discharge mode without the need to rotate the tanks if needed, although the efficiency of the system will be reduced.
The simplicity of design and operation of the embodiment described above with reference to FIGS. 14 and 15A-15C, as well as the safety of the Fe/Cr electrolyte reactants, makes the embodiment system ideal for small power storage applications. For example, this embodiment may be ideally suited for use in remote power applications, such as remote towns and villages beyond the reach of a utility grid that use solar photovoltaic arrays and/or wind turbine generators for electricity. Adding a redox flow battery system similar to this embodiment would allow remote towns and villages to be supplied with electrical power at night, for example. Similarly, one or two systems according to this embodiment may be used in remote electric vehicle charging stations using utility grid power or local renewable energy sources to charge the system when no cars need to be charged, and rotating the storage system to provide electrical power for recharging an electric vehicle when required.
It is also possible to size this embodiment system to fit inside standard sized shipping containers. Because these systems are fully sealed and self-contained they can be safely operated inside the shipping container, enabling the systems to be packaged for rapid deployment. For transportation purposes the electrolyte may be transported as a salt, e.g., a ferric chloride, which may be stored in the tanks. This can significantly reduce the weight of the system for transportation. Then once the system is in place, water can be added to reach the required concentrations for operation. In this manner, systems such as the embodiment described above with reference to
FIGS. 14 and 15A-15C show the battery stack 410 fully integrated with the tanks 404, 406, 414, 416, and fixed plumbing within the support structure 402. However, in another embodiment the tanks 404, 406, 414, 416 may be separated from the battery stack 410 so that the tanks may be rotated to achieve the desired gravity feed through the battery stack 410 which remains stationary. This alternative embodiment may be more flexible in terms of the ability to easily add more tank/storage capacity. This alternative embodiment will require flexible piping or include fluid couples that accommodate rotation without leaking.
As mentioned above, the various embodiments utilize independent cells with different configurations along the reactant flow path to increase overall electrical performance.
Further representative stack design parameters and performance characteristics for a three-cell configuration are listed in Table 1 below. All values are approximate.
The various system embodiments may employ a variety of electrolyte storage tank configurations as described below. In a simple embodiment, a single tank may be used to store each electrolyte as illustrated in
In a second approach, charged and discharged electrolytes can be stored separately in system embodiments illustrated in
In a further embodiment illustrated in
The tank separator 502, 506 inhibits mixing of the charged electrolyte 504, 514 that is fed to the redox flow battery stack assembly 10 with the discharged electrolyte 506, 516 which flows back into the electrolyte tanks 26, 28. This prevents dilution of the charged electrolytes and keeps the charged electrolyte concentrations at a constant level throughout the discharging cycle, thereby maintaining the battery cell potentials constant. If mixing were to occur the charged electrolyte concentrations in the electrolyte tanks 26, 28 would be reduced over time as more and more discharged electrolyte 506, 516 is returned to the tanks.
While
The tank separator embodiments include two forms of movable tank separator designs; a tank separator with flow passages which can be opened to enable electrolyte to flow through the separator, and a tank separator with no flow passages. Operation of these two embodiment configurations are illustrated below with reference to
In a first embodiment illustrated in
During a charge or discharge cycle, initial (either charged or discharged) electrolyte 504 is drawn from the tank 26 from below the tank separator 502 and passed through the redox flow battery stack assembly 10 while electrolyte exiting the battery 506 is pumped into the tank 26 on top of the tank separator 502. This is illustrated in
Since the tank separator 502 is buoyant, opening the louvers 503 (or other valve structures) enables the tank separator 502 to begin floating towards the top of the tank. This is illustrated in
When the tank separator 502 reaches the top of the electrolyte 506 as illustrated in
Closing or opening the valve structures of the tank separator 502 can be controlled via an external drive which may be coupled magnetically to the valve mechanism, such as louvers 503. In this manner no wires or other connections are required between an outside controller or power supply and the separator. In a redox flow battery system the electrolyte flows through a completely closed system to avoid contact with air. This makes it difficult to perform maintenance on the valve mechanisms inside the electrolyte tank 26 for long periods. Therefore, an external control mechanism using magnetism as a coupling mechanism, for example, may have advantages for controlling the tank separator 502 inside the electrolyte tank 26.
Alternatively, the valve mechanisms or louvers 503 may be controlled by mechanical mechanisms activated by the position of the tank separator 502 within the tank 26. For example, the valve mechanisms, such as louver 503 may be configured to shut when the structure surfaces, such as a buoyant lever that latches the louvers closed when it rises above the fluid surface, and may be configured to open upon a portion of the structure contacting the bottom of the tank, such as a latch release mechanism.
In an alternative embodiment the tank separator 602 may be vertically oriented and configured to traverse the length of a horizontally disposed electrolyte tank 600 as illustrated in
To begin discharging the battery, the direction of the electrolytes flowing through the redox flow battery stack assembly 10 are reversed as shown in
At any time the flow through the redox flow battery stack assembly 10 can be reversed in order to switch from charging to discharging, or discharging to charging. Thus, as illustrated in
In the embodiment illustrated in
In some embodiments, a movable plastic tank divider may be used with either vertically-oriented or horizontally-oriented tanks. In some embodiments, a movable divider may be configured to seal against an internal tank wall while allowing substantially free movement of the divider as one volume fills and the other empties. In some embodiments, such a divider may have an aspect ratio, defined here as the ratio of the divider's diameter (assuming a circular tank cross-section) to the thickness of the divider at a region of contact with the tank wall, of between about 3:1 and about 8:1. In some embodiments, the aspect ratio may be about 3:1, about 4:1, about 5:1, about 6:1, about 7:1 or about 8:1 for relatively small-diameter tanks. In some embodiments, a tank divider for a large-diameter tank (e.g., tanks with diameters on the order of about 25 feet or more) may have an aspect ratio of about 25:1 or more. In some cases, as the diameter of a tank increases, resistance to movement of the divider caused by interactions between a sealing surface of a divider and a tank wall (e.g., “racking” or uneven ratcheting movement of a divider within a tank) may decrease relative to other design factors. Thus, in some embodiments, as tank size increases, dividers may be provided with smaller edge-thickness relative to diameter. In some embodiments, a divider may comprise a varying profile such that a central portion comprises a relatively thin layer, while the edge region which contacts the tank wall is substantially thicker.
The seal between the tank separator 502, 602 and the electrolyte tank 26, 600 does not need to exceptionally leak proof because a small amount of leakage around the edges will have very little impact on the overall system efficiency if the tank volume is sufficiently large. Also some leakage, while undesirable, does not pose any threat to the flow battery system other than slightly reducing its overall efficiency.
Since the tank separator moves due to electrolyte being extracted from the tank when it is in one state-of-charge and re-injected when it is in the opposite state-of-charge, the position of the tank separator can function as a state-of-charge indicator. By incorporating a passive or active signaling device, such as a RFID chip or a large piece of metal, the position of the tank separator and hence the system state-of-charge, can be determined by a position sensitive reader of the signal from the RFID chip or induced magnetic field of the metal piece. Multiple RFID chips or metal pieces can be used to increase signal strength and/or provide redundancy.
The horizontal or vertical tank embodiments described in
As mentioned above, the electrolytes stored within the tanks 214, 218 in
Other design approaches may be used to keep charged and discharged electrolytes separate. In some embodiments, one or more flexible bladders may be provided within a tank and sealed such that the volume within a bladder is separated from a volume outside of a bladder. In some embodiments, a single bladder may be sealed to the tank and may be sized appropriately to accommodate the full volume of charged and discharged electrolytes. For example, discharged electrolyte may be pumped into the bladder while charged electrolyte occupies the volume within the tank outside of the bladder. In this example, the bladder prevents the discharged electrolyte from mixing with the charged electrolyte in the remainder of the tank. The use of an in-tank bladder is similar to the movable partition embodiment described above with reference to
In an alternative embodiment, two bladders may be provided within one tank such that each electrolyte is stored within a separate bladder volume. In some embodiments, one bladder may be placed inside of another, such that one volume occupies a space between an exterior of one bladder and an interior of the second bladder. Alternatively, both bladders may be placed within the tank separately. In some two-bladder embodiments, a space between a bladder exterior and a tank interior may contain a ballast fluid (such as oil or water) which may be used to measure pressure or level changes in the tank and/or to lubricate relative movement of the two bladders relative to one another and relative to the tank. Alternatively, a space between a tank and bladders therein may be entirely or substantially empty. In some two-bladder embodiments, the tank need not be entirely enclosed.
In some embodiments, such movable bladders may be provided with accordion folds or other features to facilitate expansion and collapse of the bladder as electrolytes are pumped into and out of the bladder. Such bladders may be used in either vertically-oriented or horizontally-oriented tanks.
In a second alternative approach, a series of tanks may be used for each electrolyte that in aggregate have a larger volume than the volume of electrolyte. The tanks for an electrolyte may be coupled to the redox flow battery stack assembly such that the discharged and charged electrolytes are distributed among the tanks during each half cycle of the battery system. This “N+1” configuration obviates the need for a movable partition or sealed part with the tradeoff of additional plumbing, valves, and control complexity. In some such embodiments, a single tank may be divided into two tanks by welding a solid fixed separator into a center of the tank. Alternatively, a flexible diaphragm may be fixed to a central portion of a tank to provide a small degree of flexibility in relative volumes.
Other alternative designs may leverage the fact that in some embodiments, the discharged state the two electrolytes in the Fe/Cr mixed reactant system may have identical chemical compositions. Thus, for a system that is designed to operate over a state-of-charge range that goes to full discharge (i.e., zero state-of-charge), a three tank system may be used where a first tank holds charged anolyte, a second tank holds charged catholyte, and a third, larger tank, holds the combined discharged electrolytes. In a further alternative embodiment, one tank may be sized to hold at minimum the volumes of both the anolyte and catholyte. In a further approach, the one tank may include two partitions inside which move from the middle of the tank to the two ends. In this alternative, charged anolyte may be pumped into/out of one end of the tank while charged catholyte may be pumped into/out of the other end of the tank, and discharged anolyte and catholyte may be pumped into/out of the middle of tank. As discharged electrolyte fills the inner section, its expanding volume pushes the partitions towards each end, compensating for the decreasing volume of the charged electrolytes. In a further alternative, bladders may be used instead of partitions to create the three separate volumes within a single tank.
In an alternative embodiment, a tank separator arrangement may be configured to take advantage of variations in density of charged electrolytes relative to discharged electrolytes.
In some embodiments, a tank separator such as that illustrated in FIGS. 17 and 18A-18F may be made of a relatively thin, substantially electrolyte-impermeable element which has a density selected such that the separator floats exactly at the junction of the higher-density electrolyte and the lower-density electrolyte within a single tank. Such a “neutral-density” tank separator may be configured to have a greater density than the less-dense electrolyte and a lesser density than the more-dense electrolyte.
For example, for an Fe/Cr flow battery, the density curves of
In some embodiments, it may be desirable to provide a flange, a flexible gasket, O-ring, lip seal, stack of split rings (like piston rings), or other structure around a periphery of a movable separator in order to seal the separator against an interior tank wall, thereby substantially preventing mixing of electrolytes around the periphery of the separator. In some embodiments, a double seal arrangement may be used to provide the combined function of substantially preventing mixing and preventing the movable separator from racking as the separator travels along the tank. In some embodiments, first and second seals may be displaced along the axis of separator movement. For example, if a separator is provided with a flange extending perpendicular to the surface of the separator, one seal may be located at one end of the flange and a second seal may be located at the other end of the flange, thereby providing some mechanical separation of the seals and establishing a moment to prevent racking of the separator.
In some embodiments, with the tanks of
The tank arrangement of
In some cases, charging electrolytes is an endothermic process. As a result, charged electrolytes may be colder and therefore more dense than charged electrolytes. Thus, in some embodiments, the density difference between two electrolytes may be further increased by heating a less-dense electrolyte or cooling a more-dense electrolyte.
In alternative embodiments, a layer of an electrolyte immiscible fluid may be used as a tank separator between a more-dense electrolyte and a less-dense electrolyte. In some embodiments, an electrolyte immiscible fluid used for a separator layer may be selected to have a density substantially in between the densities of the more-dense and less-dense electrolytes. In some embodiments, the fluid may be substantially immiscible to both electrolytes. For example, the fluid layer can comprise an oil for separating water-soluble electrolytes. For another example, the fluid layer can comprise a water-soluble fluid for separating oil-based electrolytes.
An electrolyte-separating fluid layer may be substantially thick so as to avoid being entirely disrupted by swirling or other motion of one or both electrolytes in the tank. In some embodiments, a fluid layer tank divider may have a similar thickness to a solid tank divider in a similarly sized tank. In other embodiments, a fluid layer tank divider may be substantially thicker than a solid divider in a similarly sized tank. For example in some embodiments, a fluid layer divider may have an aspect ratio, defined here as the ratio of the tank's internal diameter (assuming a circular tank cross-section) to the thickness of the divider fluid layer of as low as about 3:1 and up to about 100:1 or more for very large-diameter tanks. For example in some embodiments, a fluid layer with an aspect ratio of 20:1, 30:1, 50:1, 100:1 or greater may be used as a tank divider.
In some embodiments, an oil separator layer may use any fluid that is substantially immiscible with the electrolyte. In some embodiments of an aqueous, ionic electrolyte, the fluid may be a hydrocarbon oil. The density of the hydrocarbon oil may be varied by controlling the functional groups of the hydrocarbon structure. For example, in a paraffin based oil, hydrogen may be replaced by chlorine, bromine, or fluorine atoms to increase the density of the oil into the range where its density is between the densities of the electrolytes which are to be separated. Other functional groups and other basic molecular structures may be chosen in a similar way to establish immiscibility and control density. In other embodiments, density of an oil separator layer may be adjusted also by simply mixing oils of different densities which are miscible in each other, but are both immiscible in the liquids to be separated. For example, paraffin oil (density less than water) may be mixed with perfluorinated oil (density much greater than water) to produce any intermediate density.
In embodiments using an oil layer tank separator, tank inlets and outlets may include baffles or other flow directing structures configured to minimize disturbances of the oil layer caused by electrolytes flowing into or out of the tank sections at expected flow rates.
If the density of either electrolyte varies substantially from a designed value, an oil layer separator may float to the top of the less-dense electrolyte or may sink to the bottom of the more-dense electrolyte. Either event could be problematic if the oil were to be pumped out of the tank and into the flow battery system. Thus, in some embodiments, porous guard layers may be provided at top and bottom sections of the tank. Such porous guard layers may be made of a material selected to be highly permeable to electrolyte but substantially impermeable to oil. For example, a carbon or polymer felt material may be used. In an exemplary aspect, a suitable polymer felt material can be used rather than a carbon felt material to avoid a surface that could catalyze the reduction of protons in a parasitic side reaction. Such guard layers may be configured and positioned to trap any oil that reaches an upper or lower region of the tank to prevent the oil from being pumped out of the tank. Alternatively on in addition, a heel of electrolyte can be left in the tank to avoid pumping down to the oil layer. In some embodiments, a flow battery system may be configured to leave an excess volume of electrolyte in each tank section such that an oil layer separator remains a desired distance from tank inlets and outlets.
In another embodiment, a density-neutral tank separator may comprise a layer of relatively small hollow blocks, which may be designed to have a neutral density between the two electrolytes. In some embodiments, a separator made up of a plurality of individual blocks may further comprise a net, a bag, or top and/or bottom fabric layers configured to trap the blocks in a rough shape while still allowing some flexibility of movement. In some embodiments, blocks used for a separator layer may be spherical (such as ping-pong balls). In other embodiments, the blocks have any desired shape and need not be spherical. For example, in some embodiments, such blocks may have a cubic shape, a rectangular shape, a cylindrical shape, or a polyhedron shape. In some embodiments, a tank separator made up of individual blocks may have any desired thickness, such as a single layer of blocks, two layers of blocks, three layers of blocks or more layers. In some embodiments, each block may be filled with a liquid or gas selected to achieve the desired density. In some embodiments, blocks may be provided with a range of densities, such that a top layer of blocks may be less dense than a bottom layer of blocks. In this way, a separator made up of a plurality of blocks may be designed to have a range of densities.
In another embodiment, a tank separator may be formed from an inflatable balloon that may be inflated and/or deflated with a selected gas or liquid to variably control the density of the balloon. In some embodiments, the density of a balloon may be controlled in response to a measured value of state-of-charge of an electrolyte. In such embodiments, the density of one or both electrolytes may be assumed from or theoretical or empirically-determined relationship between an electrolyte's state-of-charge and its density. In other embodiments, the density of a balloon may be controlled in response to a measured value of density of a charged and/or discharged electrolyte.
In some embodiments, the density of a balloon may be controlled by increasing or decreasing a volume of a suitably selected liquid or gas. In alternative embodiments, the density of a balloon may be controlled by heating or cooling a liquid or gas within the balloon.
In alternative embodiments, a solid or flexible flat disc separator may be supported by one or more dynamically controlled balloons. In such embodiments, dynamically controlled balloons may be attached to a bottom or a top of a tank separator. In other embodiments, a solid or flexible flat disc separator may be configured to float on at least the more-dense electrolyte, and may be tethered to a tank bottom by an adjustable mechanism. In some embodiments, such an adjustable mechanism may include an inflatable balloon, a cable, a chain or other device.
In other embodiments, a tank divider of any suitable design may be attached to a float and a sinker, each having a density optimized to retain a divider at a neutral point in between. In some embodiments, one or more balloons may be attached to an upper portion of the separator and may be configured to float in the upper electrolyte (i.e. it may be statically or dynamically controlled to be less dense than the lower-density electrolyte), thereby pulling the separator upwards. One or more sinkers may be attached to a lower portion of the separator, and may be configured to sink in the lower (more dense) electrolyte. By optimizing the upward force of the balloon and the downward force of the sinker, a separator may be retained at a desired point in between.
In another embodiment, a tank divider may comprise a substantially solid divider configured to be driven along the axis of the tank in order to drive the motion of an electrolyte. A tank divider of this embodiment may resemble a piston configured to push and pull electrolytes through the system. In some embodiments, such a piston divider may be oriented horizontally in a vertical tank such that a first electrolyte volume is vertically above a second electrolyte volume. In such embodiments, the piston may be configured such that gravity provides a substantial degree of the pumping force needed to pump a bottom electrolyte out of the tank, through the stack and into the top portion of the tank. Such embodiments would generally require a seal between the top and bottom electrolyte volumes. Such a seal would need to be sufficient to prevent significant migration of electrolytes from a high-pressure side to a low pressure side.
In some embodiments, flow battery systems using a divided tank arrangement for storing liquid electrolytes may include an excess volume of electrolyte such that some quantity of electrolyte remains in both tank sections at all times. The size of such an excess volume may depend on the details of a chosen tank separator design, but may generally be sufficient to prevent a moving tank separator from reaching the extreme ends of a tank.
All tank arrangements in the embodiments described above (except for those illustrated in
Containerizing the electrolyte tanks described above may enable them to be more easily deployed than tanks that are constructed onsite or require custom foundations that must be built onsite. Also packaging the stacks, redox flow battery control system, and the power conditioning system inside standard shipping containers can create an entire system configuration that is easily shipped by rail and/or tractor trailer and deployed with relatively minimal onsite work. Thus, containerized redox flow battery systems can provide turn-key power energy storage systems that need only be connected to a utility grid or other source of electric power. A system design in which the containers housing the redox flow battery stacks, control system, and power conditioning system are placed above containers housing the electrolyte storage tanks yields an energy storage system that can be readily transported and set-up at the destination, and that facilitates control over electrolyte flows and full or partial draining of the stacks when the battery system is idle for short or extended periods of time.
In a further embodiment, the redox flow battery stack assembly may be configured so that the battery can perform charging and discharging operations with reactants flowing in a single direction. In one configuration, electrolyte tanks 26, 28 that allow mixing of charge and discharge electrolytes, such as shown in
Embodiments of redox flow battery cells, stack assemblies and systems described herein may be used with any electrochemical reactant combinations that include reactants dissolved in an electrolyte. One example is a stack assembly containing the vanadium reactants V(II)/V(III) or V 2+/V 3+ at the negative electrode (anolyte) and V(IV)/V(V) or V 4+/V 5+ at the positive electrode (catholyte). The anolyte and catholyte reactants in such a system are dissolved in sulfuric acid. This type of battery is often called the all-vanadium battery because both the anolyte and catholyte contain vanadium species. Other combinations of reactants in a flow battery that can utilize the features and advantages of the systems described herein include Sn (anolyte)/Fe (catholyte), Mn (anolyte)/Fe (catholyte), V (anolyte)/Ce (catholyte), V (anolyte)/Br 2 (catholyte), Fe (anolyte)/Br 2 (catholyte), and S (anolyte)/Br 2 (catholyte). In each of these example chemistries, the reactants are present as dissolved ionic species in the electrolytes, which permits the advantageous use of configured cascade flow battery cell and stack assembly designs in which cells have different physical, chemical or electrochemical properties along the cascade flow path (e.g. cell size, type of membrane or separator, type and amount of catalyst, etc.). A further example of a workable redox flow battery chemistry and system is provided in U.S. Pat. No. 6,475,661, the entire contents of which are incorporated herein by reference.
By virtue of the foregoing, the present disclosure provides a reduction-oxidation flow battery system comprising, a first electrolyte storage tank, a movable tank separator configured to divide a volume of the first electrolyte storage tank into a first volume portion and a second volume portion, and at least one reduction-oxidation flow battery stack assembly joined in fluid communication with the first electrolyte storage tank. In one embodiment, the reduction-oxidation flow battery system has a second electrolyte storage tank, and a second tank separator configured to divide a volume of the second electrolyte storage tank into two volume portions, wherein the at least one reduction-oxidation flow battery stack assembly is further joined in fluid communication with the second electrolyte storage tank. Alternatively, a second electrolyte storage tank is included but is not divided by a tank separator.
In another embodiment, the reduction-oxidation flow battery system of claim 1 has a movable tank separator that is configured to float at an interface between a more-dense electrolyte in the first volume portion and a less-dense electrolyte in the second volume portion. In an exemplary embodiment, the movable tank separator is configured to have a density between a density of the more-dense electrolyte and a density of the less-dense electrolyte. For instance, an embodiment of the movable tank separator is a plurality of blocks. Alternatively, another embodiment of the movable tank separator is a layer of fluid that is immiscible in the more-dense electrolyte and the less-dense electrolyte. Alternatively, an additional embodiment of the movable tank separator is an inflatable balloon, where the reduction-oxidation flow battery system includes a pump and a control system configured to control a density of the inflatable balloon by controlling the pump to fill or empty the inflatable balloon.
In an additional embodiment, the reduction-oxidation flow battery system has a movable tank separator that is a seal configured to movably engage a side wall of the first electrolyte storage tank. In an exemplary embodiment, the reduction-oxidation flow battery system has a ratio between a diameter of the movable tank separator and a thickness of a separator region closest to the side wall of the first electrolyte storage tank of at least about 5:1. Alternatively or in addition, the movable tank separator can have a circumferential ring of greater thickness than a central region of the tank separator.
In a further embodiment, the reduction-oxidation flow battery system of claim 1 can have a movable tank separator that is a flexible bladder. In one particular embodiment, the reduction-oxidation flow battery system can have a second flexible bladder within the first electrolyte storage tank, wherein the second flexible bladder defining a third volume portion. In addition, the first volume portion can contain a charged electrolyte, the third volume portion can contain a discharged electrolyte, and the second volume portion can contain a ballast fluid. Alternatively, in one embodiment the flexible bladder defines the first volume portion within the flexible bladder and the second volume portion between the flexible bladder and the first electrolyte storage tank. For instance, the first volume portion can contain a charged catholyte and the second volume portion can contain a discharged catholyte. Alternatively, the first volume portion can contain a charged anolyte and the second volume portion can contain a discharged anolyte.
In yet another embodiment, the movable tank separator is or includes mechanically operable louvers.
In one embodiment, the present disclosure provides a reduction-oxidation flow battery system that has a first electrolyte storage tank, a tank separator configured to divide a volume of the first electrolyte storage tank into a first volume portion and a second volume portion, wherein the tank separator comprises a porous matrix configured to prevent convective mixing or agitation at an interface between the first volume comprising a top tank segment and the second volume comprising a bottom tank segment, and at least one reduction-oxidation flow battery stack assembly joined in fluid communication with the first electrolyte storage tank.
In another embodiment, the present disclosure provides a method of reducing mixing of two electrolytes stored within one tank by placing a first electrolyte in a first volume portion of a tank, placing a second electrolyte in a second volume portion of the tank separated from the first volume portion by a tank separator that is movable, and communicating the first electrolyte and the second electrolyte with at least one reduction-oxidation flow battery stack to perform oxidation and reduction reactions, wherein the tank separator moves within the tank to accommodate a related change in quantity of the first and second electrolytes in the first and second volume portions respectively.
In one exemplary embodiment, the method can further provide placing the first electrolyte in the first volume portion at a bottom portion of the tank, and placing the second electrolyte in the second volume portion at a top portion of the tank, wherein the first electrolyte is more dense than the second electrolyte, wherein the tank separator is configured to freely move in the tank and to have a density that is less than the first electrolyte and greater than the second electrolyte. In a particular aspect, the first electrolyte is at a first state-of-charge, wherein the second electrolyte is at a second state-of-charge that is different than the first state-of-charge. The first electrolyte and the second electrolyte are a same member of a group consisting of an anolyte and a catholyte.
In an additional embodiment, the present disclosure provides a method of reducing mixing of two electrolytes stored within one tank by placing a first electrolyte in a first volume portion at a bottom portion of the tank, placing a second electrolyte in a second volume portion at a top portion of the tank, wherein the first electrolyte is more dense than the second electrolyte, and communicating the first electrolyte and the second electrolyte with at least one reduction-oxidation flow battery stack to perform oxidation and reduction reactions, wherein a tank separator comprising a porous matrix spans an interface of the first and second electrolytes between the first and second volume portions.
The foregoing description of the various embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications or alternate uses of these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein, and instead the claims should be accorded the widest scope consistent with the principles and novel features disclosed herein.
This application is a continuation-in-part of U.S. patent application Ser. No. 12/883,511 filed Sep. 16, 2010, which is a Divisional of U.S. patent application Ser. No. 12/498,103, filed on Jul. 6, 2009, now U.S. Pat. No. 7,820,321, which claimed the benefit of priority to U.S. Provisional Application No. 61/078,691 filed Jul. 7, 2008 and U.S. Provisional Application No. 61/093,017 filed Aug. 29, 2008. This application also claims the benefit of U.S. Provisional Patent Application 61/430,783, filed Jan. 7, 2011. The entire contents of each of the above patent applications are hereby incorporated by reference herein for all purposes.
Inventions conceived after the filing of the priority application (U.S. patent application Ser. No. 12/498,103, filed on Jul. 6, 2009) that are included in this continuation-in-part patent application were made with Government support under DE-0E0000225 “Recovery Act—Flow Battery Solution for Smart Grid Renewable Energy Applications” awarded by the US Department of Energy (DOE). The Government has certain rights in such inventions. However, the Government does not have rights in U.S. Pat. No. 7,820,321 which was conceived and filed without Government support, nor in the direct continuation and divisional applications thereof.
| Number | Date | Country | |
|---|---|---|---|
| 61430783 | Jan 2011 | US | |
| 61078691 | Jul 2008 | US | |
| 61093017 | Aug 2008 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 12498103 | Jul 2009 | US |
| Child | 12883511 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 12883511 | Sep 2010 | US |
| Child | 13345599 | US |
