Patent Grant
9293781
All patents, patent applications and publications cited herein are hereby incorporated by reference in their entirety in order to more fully describe the state of the art as known to those skilled therein as of the date of the invention described herein.
Redox flow batteries, also known as a flow cells or redox batteries or reversible fuel cells, are energy storage devices in which the positive and negative electrode reactants are soluble metal ions in liquid solution that are oxidized or reduced during the operation of the cell. Using two soluble redox couples, one at the positive electrode and one at the negative electrode, solid-state reactions are avoided. A redox flow cell typically has a power-generating assembly comprising at least an ionically transporting membrane separating the positive and negative electrode reactants (also called cathode slurry and anode slurry, respectively), and positive and negative current collectors (also called electrodes) which facilitate the transfer of electrons to the external circuit but do not participate in the redox reaction (i.e., the current collector materials themselves do not undergo Faradaic activity).
Differences in terminology for the components of a flow battery and those of conventional primary or secondary batteries are herein noted. The electrode-active solutions in a flow battery are typically referred to as electrolytes, and specifically as the cathode slurry and anode slurry, in contrast to the practice in lithium ion batteries where the electrolyte is solely the ion transport medium and does not undergo Faradaic activity. In a flow battery the non-electrochemically active components at which the redox reactions take place and electrons are transported to or from the external circuit are known as electrodes, whereas in a conventional primary or secondary battery they are known as current collectors.
While redox flow batteries have many attractive features, including the fact that they can be built to almost any value of total charge capacity by increasing the size of the cathode slurry and anode slurry reservoirs, one of their limitations is that their energy density, being in large part determined by the solubility of the metal ion redox couples in liquid solvents, is relatively low. The extent to which metal ion solubilities may be increased is limited.
In the field of aqueous electrolyte batteries, and specifically batteries that utilize zinc as an electroactive material, electrolytes that comprise a suspension of metal particles and in which the suspension is flowed past the membrane and current collector, have been described. See for example U.S. Pat. Nos. 4,126,733 and 5,368,952 and European Patent EP 0330290B1. The stated purpose of such electrodes is to prevent detrimental Zn metal dendrite formation, to prevent detrimental passivation of the electrodes, or to increase the amount of zincate that can be dissolved in the positive electrode as the cell discharges. However, the energy density of such aqueous batteries even when electrolytes with a suspension of particles are used remains relatively low. Such batteries cannot provide a high enough specific energy to permit practical operation of an electric vehicle, nor do they provide a substantial improvement in specific energy or energy density over conventional redox batteries for stationary energy storage, including for example applications in grid services or storage of intermittent renewable energy sources such as wind and solar power.
Swappable fuel tank for fueled vehicles using flow cells is described. The swappable fuel tank includes a cathode slurry and/or an anode slurry that can be used in a redox flow battery to generate power. As described in greater detail below, the anode and cathode slurries flow past an ion permeable membrane and electrodes connected to an external circuit and thereby engage in redox chemistry. The swappable fuel tanks and the flow battery cells (in combination referred to as a “stack”) are referred to, in combination, as the ‘power system.’ The fuel tank is configured to be easily removed from the power system and easily emptied and refilled. Thus, spent fuel can be replaced and/or the quality or properties can be varied from filling to filling to provide greater versatility or functionality to the power system.
In other embodiments, the power system is equipped with internal monitoring capability so that the state of the battery is known. Power system attributes that may be monitored can provide information of the state of charge of the anode and cathode slurries, i.e., whether the tank ‘full’ or ‘empty’. The monitoring system can also provide information regarding other properties of the system to generally provide information about the state of health of the power system and identify conditions that can be dangerous or require correction.
In another aspect, the power system can include an electrical energy storage device and power source that is simultaneously a conventional rechargeable battery and a flow cell in one integrated device. It is applicable to various battery chemistries, including aqueous batteries such as nickel metal hydride types, and nonaqueous batteries including lithium rechargeable batteries, sodium rechargeable batteries, or batteries based on other alkali or alkaline earth or non-alkaline working ions. Considering one embodiment based on lithium ion chemistry, the basic construction of such a cell has a separator, on one side of which is a lithium battery positive electrode or a negative electrode, or both, as in a conventional rechargeable lithium battery. That is, said electrodes comprise cathode or anode active material, and may comprise a coating of the active material on a metallic current collector, or may be a stand-alone electrode layer such as a densified or sintered layer comprising the active material, optionally with other constituents such as polymer binders or carbonaceous conductive additives or metallic additives or binders. These ion-storage electrodes will be referred to as the stationary electrodes. However, unlike a conventional lithium battery electrode, one or both of said stationary electrodes is permeable to a flow cell cathode slurry or anode slurry, so that during operation of the device, it is possible to charge or discharge only the active materials on the stationary electrode, only the flow cell cathode slurry or anode slurry, or both.
In one or more embodiments, the redox flow batteries have a multi-cell stack design including semi-solid or condensed liquid reactant in anode slurry or cathode slurry. In some embodiments, the redox flow batteries are connected to anode slurry and cathode slurry storage tanks through flow valves and pumps. In some embodiments, the direction of the flow of the anode slurry/cathode slurry can be reversed depending on the charge/discharge stages of the anode slurry/cathode slurry. In some specific embodiments, the storage tank include a bladder which stores the discharged semi-solid or condensed liquid reactant the discharged material can be transferred back into the device for charging. In some embodiments, the semi-solid or condensed liquid reactant is introduced into each cell compartment of the stacked cell through a manifold. In some embodiments, valves can be installed on the manifold. In some embodiments, the valve can be positioned just before the inlet of the cell compartment. In some embodiments, the valve can be positioned just after the outlet of the cell compartment. The valves can reduced the risk of short-circuit of the system.
In some embodiments, one or more injectors are connected to the manifold of the semi-solid multi-stack cell and pressurized regions (plenum) are formed within the manifold. The plenum can be used to deliver cathode slurry or anode slurry into a single cell compartment or a group of cell compartments.
In some embodiments, the semi-solid or condensed liquid redox flow multi-cell stack can be assembled by stacked plates. The manifolds of the redox flow multi-cell stack are formed by stacking plates together. In some specific embodiments, the inside surfaces of the manifold can be coated with non-electrically-conducting material to minimize shunt current across liquid.
In one aspect, a method of operating a portable device including a power system housed within the device is described, including:
In any preceding embodiment, the method further includes refueling the power system by replacing the dispensing vessel with a new dispensing vessel containing fresh flowable redox composition.
In any preceding embodiment, the method further includes replacing the receiving vessel with a new empty receiving vessel.
In any preceding embodiment, the portable device is a vehicle.
In any preceding embodiment, the portable device is a portable power generator.
In any preceding embodiment, the vehicle is a land, air, or water vehicle.
In any preceding embodiment, the redox composition comprises a flowable semi-solid or condensed liquid ion-storing redox composition capable of taking up and releasing the ions during operation of the cell.
In any preceding embodiment, the method further includes refueling the power system by replacing the dispensing vessel containing the redox composition with a new dispensing vessel containing a fresh flowable redox composition.
In any preceding embodiment, the fresh redox composition has at least one different characteristic from the redox composition.
In any preceding embodiment, the fresh redox composition and the redox composition has different power densities.
In any preceding embodiment, the fresh redox composition and the redox composition has different energy densities.
In any preceding embodiment, the fresh redox composition and the redox composition has different semi-solid particle sizes.
In any preceding embodiment, the fresh redox composition and the redox composition has different electroactive material concentrations.
In any preceding embodiment, the fresh redox composition has smaller semi-solid particle size and higher power density than the redox composition.
In any preceding embodiment, the fresh redox composition has higher electroactive material concentration and higher energy density than the redox composition.
In any preceding embodiment, the dispensing vessel and receiving vessel form a unitary body.
In any preceding embodiment, the plurality of flow cells form a stack of flow cells, and the dispensing and receiving vessels are reversibly connected with the flow cell stack.
In any preceding embodiment, the flow cells are connected in parallel.
In any preceding embodiment, the flow cells are connected in series.
In any preceding embodiment, the method further includes providing comprising a pump disposed between one or both of the dispensing and receiving vessels and the flow cell stack.
In any preceding embodiment, the pump is a reversible flow pump that is operable for flow in both directions.
In any preceding embodiment, the dispensing or receiving vessels comprise a flexible bladder.
In any preceding embodiment, the method further includes valves positioned at the entrance of each fuel cell to control the flow of redox composition into the respective flow cell and minimize shunt current between adjacent flow cells.
In any preceding embodiment, the method further includes providing a multiport injection system configured and arranged to control the amount of redox composition delivered to each electroactive zone of each flow cell.
In any preceding embodiment, the multiport injection system comprises a plurality of compartments, each compartment in flow communication with a subset of the flow cells in the flow cell stack and injectors for introducing redox composition into each compartment.
In any preceding embodiment, the pressure in the plurality of compartment is greater than the pressure in the electroactive zone pressure.
In any preceding embodiment, the method further includes comprising a cooling system for circulating a coolant in the flow cell stack.
In any preceding embodiment, the method further includes providing a monitoring meter connected to one or both of the dispensing and receiving vessels for monitoring the volume or content of the redox composition in one or both of the dispensing or receiving vessel.
In any preceding embodiment, the method further includes replenishing the dispensing vessel with fresh redox composition.
In any preceding embodiment, replenishing the dispensing vessel comprises introducing new redox composition into the dispensing vessel.
In any preceding embodiment, the method further includes removing the discharged redox composition from the receiving vessel.
In any preceding embodiment, removing the discharged redox composition from the receiving vessel comprises emptying the receiving vessel of discharged redox composition.
In any preceding embodiment, the dispensing and receiving vessel form a unitary body, the unitary body having a movable membrane between the receiving and dispensing compartments and the method further comprised replacing the unitary body with a new unitary body comprising a power storage vessel containing fresh flowable semi-solid or condensed liquid ion-storing redox compositions and an empty spent redox composition storage vessel.
In any preceding embodiment, the method further includes monitoring the levels of the flowable redox compositions in the dispensing or receiving vessels.
In any preceding embodiment, the method further includes
In any preceding embodiment, the method further includes advancing the recharged redox composition from the electroactive zone to the dispensing vessel for storage.
In any preceding embodiment, the flow of the spent redox composition is controlled by a reversible pump.
In any preceding embodiment, the particle size of the flowable semi-solid ion-storing redox composition being discharged is selected to provide a preselected power density.
In any preceding embodiment, the load in wt percent of the flowable semi-solid ion-storing redox composition being discharged is selected to provide a preselected energy capacity of the redox composition.
In any preceding embodiment, the method further includes monitoring the condition of the redox composition before during or after discharge.
In any preceding embodiment, the condition monitored comprises the temperature, flow rates, or the relative amounts of the cathode or anode redox compositions.
In any preceding embodiment, the method further includes modifying a property of the redox composition based on the results of the monitoring.
In any preceding embodiment, the method further includes increasing the flow rate of the redox composition along the electroactive zone to increase the power of the flow cell.
In any preceding embodiment, the method further includes reconditioning the flowable semi-solid or condensed liquid ion-storing redox composition.
In any preceding embodiment, the reconditioning comprises
In any preceding embodiment, at least one of the flow cells comprises:
In another aspect, a method of operating a stationary device comprising a power system housed within the device is described, comprising:
In any preceding embodiment, the method further includes further comprising refueling the power system by replacing the dispensing vessel with a new dispensing vessel containing fresh flowable redox composition.
In any preceding embodiment, the method further includes replacing the receiving vessel with a new empty receiving vessel.
In any preceding embodiment, the stationary device is a stationary power generator.
In any preceding embodiment, the redox composition comprises a flowable semi-solid or condensed liquid ion-storing redox composition capable of taking up and releasing the ions during operation of the cell.
In any preceding embodiment, the method further includes refueling the power system by replacing the dispensing vessel containing the redox composition with a new dispensing vessel containing a fresh flowable redox composition.
In any preceding embodiment, the fresh redox composition has at least one different characteristics from the redox composition.
In any preceding embodiment, the fresh redox composition and the redox composition has different power densities.
In any preceding embodiment, the fresh redox composition and the redox composition has different energy densities.
In any preceding embodiment, the plurality of flow cells form a stack of flow cells, and the dispensing and receiving vessels are reversibly connected with the flow cell stack.
In any preceding embodiment, the method further includes providing a monitoring meter connected to one or both of the dispensing and receiving vessels for monitoring the volume or content of the redox composition in one or both of the dispensing or receiving vessel.
In any preceding embodiment, the dispensing and receiving vessel form a unitary body, the unitary body having a movable membrane between the receiving and dispensing compartments and the method further comprises replacing the unitary body with a new unitary body comprising a power storage vessel containing fresh flowable semi-solid or condensed liquid ion-storing redox compositions and an empty spent redox composition storage vessel.
In any preceding embodiment, the method further includes
In yet another aspect, a vehicle comprising a power system housed within the vehicle is described, the power system comprising:
In any preceding embodiment, the power system is capable of being refueled by replacing the dispensing vessel containing the flowable redox composition with a new dispensing vessel containing fresh flowable redox composition.
In any preceding embodiment, the receiving vessel is capable of being replaced with a new empty receiving vessel.
In any preceding embodiment, the redox composition comprises a flowable semi-solid or condensed liquid ion-storing redox composition capable of taking up and releasing the ions during operation of the cell.
In any preceding embodiment, the power system is capable of being refueled by replacing the dispensing vessel containing the flowable redox composition with a new dispensing vessel containing fresh flowable redox composition.
In any preceding embodiment, the fresh redox composition has at least one different characteristic from the redox composition.
In any preceding embodiment, the fresh redox composition and the redox composition has different power densities.
In any preceding embodiment, the fresh redox composition and the redox composition has different energy densities.
In any preceding embodiment, the fresh redox composition and the redox composition has different semi-solid particle sizes.
In any preceding embodiment, the fresh redox composition and the redox composition has different electroactive material concentrations.
In any preceding embodiment, the dispensing vessel and receiving vessel form a unitary body.
In any preceding embodiment, the plurality of flow cells form a stack of flow cells, and the dispensing and receiving vessels are reversibly connected with the flow cell stack.
In any preceding embodiment, the power system further comprising a pump disposed between one or both of the dispensing and receiving vessels and the flow cell stack.
In any preceding embodiment, the pump is a reversible flow pump that is operable for flow in both directions.
In any preceding embodiment, the dispensing and receiving vessels comprise a flexible bladder.
In any preceding embodiment, the vehicle further includes valves positioned at the entrance of each fuel cell to control the flow of redox composition into the respective flow cell and minimize shunt current between adjacent fuel cells.
In any preceding embodiment, the vehicle further includes a multiport injection system configured and arranged to control the amount of redox composition delivered to each electroactive zone of each flow cell.
In any preceding embodiment, the vehicle further includes a monitoring meter connected to one or both of the dispensing and receiving vessels for monitoring the volume or content of the redox composition in one or both of the dispensing or receiving vessel.
In any preceding embodiment, the dispensing and receiving vessel form a unitary body, the unitary body having a movable membrane between the receiving and dispensing compartments and the method further comprises replacing the unitary body with a new unitary body comprising a power storage vessel containing fresh flowable semi-solid or condensed liquid ion-storing redox compositions and an empty spent redox composition storage vessel.
In yet another aspect, a power system comprising, comprising:
In any preceding embodiment, the positive electrode comprises a cathode slurry comprising the flowable semi-solid or condensed liquid ion-storing redox compositions and the negative electrode comprises an anode slurry comprising the flowable semi-solid or condensed liquid ion-storing redox compositions.
In any preceding embodiment, the power storage vessel and the spent redox composition storage vessel form a unitary body.
In any preceding embodiment, the plurality of flow cells form a stack of flow cells, wherein each flow cell comprises at least one electrode comprising a flowable semi-solid or condensed liquid ion-storing redox composition which is capable of taking up or releasing the ions during operation of the cell; and the dispensing and receiving vessels are reversibly connected with the flow cell stack.
In any preceding embodiment, the flow cells are connected in parallel.
In any preceding embodiment, the flow cells are connected in series.
In any preceding embodiment, the power system further includes a pump disposed between one or both of the dispensing and receiving vessels and the flow cell.
In any preceding embodiment, the pump is a reversible flow pump.
In any preceding embodiment, the dispensing and receiving vessels comprise a flexible bladder.
In any preceding embodiment, the power system further includes valves positioned at the entrance of each fuel cell to control the flow of redox composition into the respective flow cell and minimize shunt current between adjacent fuel cells.
In any preceding embodiment, the power system further includes a multiport injection system configured and arranged to control the amount of redox composition delivered to each electroactive zone of each flow cell.
In any preceding embodiment, the multiport injection system comprises injectors for introducing redox composition into a compartment supplying redox composition to a sub-portion of the total flow cells.
In any preceding embodiment, the multiport injection system provides a greater compartment pressure than electroactive zone pressure to minimize shunt current between each flow cell.
In any preceding embodiment, the power system further includes a cooling system for circulating a coolant in the flow cell.
In any preceding embodiment, the power system further includes comprising a level meter connected to the power storage vessel for monitoring the state of charge of the flowable semi-solid or condensed liquid ion-storing redox composition.
In yet another aspect, a method of operating a power system is described, comprising:
In any preceding embodiment, the method further includes replacing the receiving vessel with a new empty receiving vessel.
In any preceding embodiment, the fresh redox composition has at least one different characteristic from the redox composition.
In any preceding embodiment, the fresh redox composition and the redox composition has different power densities.
In any preceding embodiment, the fresh redox composition and the redox composition has different energy densities.
In any preceding embodiment, the fresh redox composition and the redox composition has different semi-solid particle sizes.
In any preceding embodiment, the fresh redox composition and the redox composition has different electroactive material concentrations.
In any preceding embodiment, the fresh redox composition has smaller semi-solid particle size and higher power density than the redox composition.
In any preceding embodiment, the fresh redox composition has higher electroactive material concentration and higher energy density than the redox composition.
In any preceding embodiment, the dispensing vessel and receiving vessel form a unitary body.
In any preceding embodiment, the plurality of flow cells form a stack of flow cells, and the dispensing and receiving vessels are reversibly connected with the flow cell stack.
In any preceding embodiment, the flow cells are connected in parallel.
In any preceding embodiment, the flow cells are connected in series.
In any preceding embodiment, the power system further comprises a pump disposed between one or both of the dispensing and receiving vessels and the flow cell stack.
In any preceding embodiment, the pump is a reversible flow pump that is operable for flow in both directions.
In any preceding embodiment, the dispensing or receiving vessels comprise a flexible bladder.
In any preceding embodiment, the method further includes providing valves positioned at the entrance of each fuel cell to control the flow of redox composition into the respective flow cell and minimize shunt current between adjacent flow cells.
In any preceding embodiment, the method further includes providing a multiport injection system configured and arranged to control the amount of redox composition delivered to each electroactive zone of each flow cell.
In any preceding embodiment, the multiport injection system comprises a plurality of compartments, each compartment in flow communication with a subset of the flow cells in the flow cell stack and injectors for introducing redox composition into each compartment.
In any preceding embodiment, the pressure in the plurality of compartment is greater than the pressure in the electroactive zone pressure.
In any preceding embodiment, the method further includes a cooling system tor circulating a coolant in the flow cell stack.
In any preceding embodiment, the method further includes providing a monitoring meter connected to one or both of the dispensing and receiving vessels for monitoring the volume or content of the redox composition in one or both of the dispensing or receiving vessel.
In any preceding embodiment, the method further includes replenishing the dispensing vessel with fresh redox composition.
In any preceding embodiment, replenishing the dispensing vessel comprises introducing new redox composition into the dispensing vessel.
In any preceding embodiment, the method further includes removing the discharged redox composition from the receiving vessel.
In any preceding embodiment, removing the discharged redox composition from the receiving vessel comprises emptying the receiving vessel of discharged redox composition.
In any preceding embodiment, the dispensing und receiving vessel form a unitary body, the unitary body having a movable membrane between the receiving and dispensing compartments and the method further comprises replacing the unitary body with a new unitary body comprising a power storage vessel containing fresh flowable semi-solid or condensed liquid ion-storing redox compositions and an empty spent redox composition storage vessel.
In any preceding embodiment, the method further includes monitoring the levels of the flowable redox compositions in the dispensing or receiving vessels.
In any preceding embodiment, the method further includes
In any preceding embodiment, the method further includes advancing the recharged redox composition from the electroactive zone to the dispensing vessel for storage.
In any preceding embodiment, the flow of the spent redox composition is controlled by a reversible pump.
In any preceding embodiment, the particle size of the flowable semi-solid ion-storing redox composition being discharged is selected to provide a preselected power density.
In any preceding embodiment, the load in wt percent of the flowable semi-solid ion-storing redox composition being discharged is selected to provide a preselected energy capacity of the redox composition.
In any preceding embodiment, the method further includes monitoring the condition of the redox composition before during or after discharge.
In any preceding embodiment, the condition monitored comprises the temperature, flow rates, or the relative amounts of the cathode or anode redox compositions.
In any preceding embodiment, the method further includes modifying a property of the redox composition based on the results of the monitoring.
In any preceding embodiment, the method further includes increasing the flow rate of the redox composition along the electroactive zone to increase the power of the flow cell.
In any preceding embodiment, the method further includes reconditioning the flowable semi-solid or condensed liquid ion-storing redox composition.
In any preceding embodiment, the reconditioning comprises
In any preceding embodiment, at least one of the flow cells comprises:
The subject matter is described with reference to the following figures, which are presented for the purpose of illustration only and are not intended to be limiting of the invention.
An automotive or other power system including a flow cell, in which the stack that provides power is readily isolated from the storage vessels holding the cathode slurry and anode slurry (alternatively called “fuel”) is described. A method of use is also provided, in which the “fuel” tanks are removable and are separately charged in a charging station, and the charged fuel, plus tanks, are placed back in the vehicle or other power system, allowing fast refueling. The technology also provides a charging system in which discharged fuel is charged. The charged fuel can be placed into storage tanks at the power source or returned to the vehicle. In some embodiments, the charged fuel in the storage tanks can be used at a later date. The charged fuel can be transported or stored for use in a different place or time.
A power system according to one or more embodiments includes a redox flow battery in which at least one of the positive electrode or anode slurries of the fuel is semi-solid or is a condensed liquid reactant, and in which at least one of the electrode-active materials is transported to and from an assembly at which the electrochemical reaction occurs, producing electrical energy. By “semi-solid” it is meant that the material is a mixture of liquid phase and solid phases, such a mixture also being known as a slurry, particle suspension, colloidal suspension, emulsion, or micelle. In some embodiments, the solid constituents of the semi-solid comprise at least one material that undergoes reaction or alloying or intercalation with the working ions of the battery to generate or store electrical energy. As a result, during the operation of the cell, the electroactive material of the redox couple can remain in the semi-solid in both of its oxidative states without going into solution. Therefore, the solubility of the electroactive material no longer limits its concentration in the electroactive zone, resulting in a large increase of the effective concentration of the electroactive materials in the flow cell. As a result, the energy density of the cell using semi-solid redox composition is greatly increased. The liquid supporting the electroactive component can be aqueous or non-aqueous. In some embodiments the redox flow buttery comprises a non-aqueous cell, including but not limited to an alkali ion rechargeable cell wherein the working ion is an alkali ion. Solvents typically used as electrolyte solvents may be used as the liquid in the semi-solid cathode or anode slurries. As used herein, condensed liquid or condensed ion-storing liquid refers to a liquid that is not merely a solvent as it is in the case of an aqueous flow cell catholyte or anolyte, but rather that the liquid is itself redox-active. The liquid form can also be diluted by or mixed with another, non-redox-active liquid that is a diluent or solvent, including mixing with such a diluents to form a lower-melting liquid phase, emulsion or micelles including the ion-storing liquid. Similarly, during the operation of the cell, the working ion of the redox couple can remain in the condensed liquid phase in both of its oxidative states without going into solution. Therefore, the solubility of the electroactive material no longer limits its concentration in the electroactive zone, resulting in a large increase of the effective concentration of the electroactive materials in the flow cell. As a result, the energy density of the cell using condensed liquid redox composition is greatly increased.
In some embodiments the redox flow battery is a lithium battery of primary or rechargeable type. In some embodiments at least one of the energy storing electrodes comprises a condensed liquid of a redox active material, including but not limited to lithium metal, gallium and indium alloys, molten transition metal chlorides, thionyl chloride, and the like. Further information on redox batteries may be found in co-pending provisional patent application No. 61/060,972, filed Jun. 12, 2008, entitled “High Energy Density Redox Flow Battery”, which is incorporated herein in its entirety by reference.
One distinction between a conventional flow battery anolyte and catholyte and the ion-storing solid or liquid phases as exemplified herein is the molar concentration or molarity of redox species in the storage compound. For example, conventional anolytes or catholytes that have redox species dissolved in aqueous solution may be limited in molarity to typically 2M to 8M concentration. Highly acidic solutions may be necessary to reach the higher end of this concentration range. By contrast, any flowable semi-solid or condensed liquid ion-storing redox composition as described herein may have, when taken in moles per liter or molarity, at least 10M concentration of redox species, preferably at least 12M, still preferably at least 15M, and still preferably at least 20M, because the solubility of the electroactive materials no longer limits it concentration in the flow cell. The electrochemically active material can be an ion storage material or any other compound or ion complex that is capable of undergoing Faradaic reaction in order to store energy. The electroactive material can also be a multiphase material including the above-described redox-active solid or liquid phase mixed with a non-redox-active phase, including solid-liquid suspensions, or liquid-liquid multiphase mixtures, including micelles or emulsions having a liquid ion-storage material intimately mixed with a supporting liquid phase. In the case of both semi-solid and condensed liquid storage compounds for the flowable ion-storing redox compositions, systems that utilize various working ions are contemplated, including aqueous systems in which H+ or OH− are the working ions, nonaqueous systems in which Li+, Na+, or other alkali ions are the working ions, even alkaline earth working ions such as Ca2+ and Mg2+, and Al3+. In each of these instances, a negative electrode storage material and a positive electrode storage material may be required, the negative electrode storing the working ion of interest at a lower absolute electrical potential than the positive electrode. The cell voltage can be determined approximately by the difference in ion-storage potentials of the two ion-storage electrode materials.
In some embodiments the “stack” or electricity generating portion of the battery is reversibly coupled to vessels or containers holding the cathode slurry and anode slurry. The power system is illustrated in
The conduit can be rigid or flexible and can be prepared from conventional materials capable of withstanding a range of temperature conditions and which are chemically stable in contact with the slurries. Exemplary materials include metals such as copper or brass or stainless steel, elastomers, polyolefins, and fluoropolymers such as Teflon™. The fittings may be any conventional fitting used to connect and disconnect tubing or piping, selected to provide a hermetic seal and to be chemically stable in contact with the slurries of the invention. Exemplary fittings include those commonly referred to as quick disconnect hose fittings or hydraulic quick disconnect couplers.
The energy stack can be arranged to provide a plurality of electrochemical cells that are electrically connected in parallel or in series to provide a power system having a desired set of properties. Battery packs get their desired operating voltage by connecting several cells in series. For example, electrochemical cells that are connected in series will result in a cell in which the overall voltage of the system is the sum of the individual cell voltages. If higher capacity and current handling is required, the cells are connected in parallel. Some packs have a combination of serial and parallel connections.
In operation, each of the energy stacks has a manifold to distribute the input cathode slurry and anode slurry to the individual cells as shown in
According to one or more embodiments, the flow cell stack is intergrated into an energy system.
The current collector (electrode) is electronically conductive and should be electrochemically inactive under the operation conditions of the cell. Typical current collectors for lithium redox flow cells include copper, aluminum, or titanium for the negative current collector and aluminum for the positive current collector, in the form of sheets or mesh, or any configuration for which the current collector may be distributed in the electrolyte and permit fluid flow. Selection of current collector materials is well-known to those skilled in the art. In some embodiments, aluminum is used as the current collector for positive electrode. In some embodiments, copper is used as the current collector for negative electrode.
The membrane can be any conventional membrane that is capable of ion transport. In one or more embodiments, the membrane is a liquid-impermeable membrane that permits the transport of ions therethrough, namely a solid or gel ionic conductor. In other embodiments the membrane is a porous polymer membrane infused with a liquid electrolyte that allows for the shuttling of ions between the anode and cathode electroactive materials, while preventing the transfer of electrons. In some embodiments, the membrane is a microporous membrane that prevents particles forming the positive and negative electrode flowable compositions from crossing the membrane. Exemplary membrane materials include polyethyleneoxide (PEO) polymer in which a lithium salt is complexed to provide lithium conductivity, or Nafion™ membranes which are proton conductors. For example, PEO based electrolytes can be used as the membrane, which is pinhole-free and a solid ionic conductor, optionally stabilized with other membranes such as glass fiber separators as supporting layers. PEO can also be used as a slurry stabilizer, dispersant, etc. in the positive or negative flowable redox compositions. PEO is stable in contact with typical alkyl carbonate-based electrolytes. This can be especially useful in phosphate-based cell chemistries with cell potential at the positive electrode that is less than about 3.6 V with respect to Li metal. The operating temperature of the redox cell can be elevated as necessary to improve the ionic conductivity of the membrane.
In some embodiments, a bipolar electrode includes a cathode and an anode separated by a coolant region for introducing a coolant through the bipolar electrode. Non-limiting examples of coolants include ethylene glycol and water.
The multi-cell stack device is connected to an anode slurry storage tank 1002 which stores the anode slurry. As shown in
A positive displacement pump causes a fluid to move by trapping a fixed amount of it then forcing (displacing) that trapped volume through the pump. Positive displacement pump 1004 or 1005 can minimize the loss of the fluid through the pump, and any positive displacement pump known in the art can be used. In addition, other means of fluid transport can be used. Flow meter 1006 or 1023 measures and controls the amount of anode slurry or cathode slurry that is pumped into the cell compartments. Any type of flow meter known in the art can be used. Non-limiting examples of flow meters include electric flow meters, turbine flow meters, mass flow meters and positive displacement flow meters. Check valves 1007 and 1024 are used to prevent the back flow of the fluids. Any check valves known in the art can be used. Non-limiting examples of flow valves 1011 and 1012 include any mechanical or electrical valves. Flow valves are further discussed in greater details in
As shown in
Similarly, cathode slurry storage tank 1104 further contains a bladder 1105. During operation (discharge of the device), the charged cathode slurry in storage tank 1104 is pumped, in the direction as indicated by arrow 1111, by using a reversible flow pump 1107. The cathode slurry passes flow meter 1120, flow valve 1121 and into the manifold 1113. The manifold 1113 delivers charged cathode slurry into cathode slurry cell compartments such as 1116. After use, the discharged cathode slurry can be removed through manifold 1114 and pumped through valve 1123 into bladder 1105 for storage. During charging of the device, the flow direction within the reversible flow pump 1107 is reversed and the discharged cathode slurry in bladder 1105 can be pumped, in the direction as indicated by arrow 1112, through valve 1123 and into manifold 1114, which delivers the discharged cathode slurry into the cathode slurry compartments such as 1116. A voltage is then applied to the device and the discharged cathode slurry can be recharged. The flow valves and flow meters are as described above.
The semi-solid or condensed liquid anode slurry or cathode slurry as described above are electrically conductive materials. Thus, during operation of the device, shunt current may occur to bypass one or more cell compartments and/or bipolar electrodes in the device. For example, the current can go through the cathode slurry or anode slurry in the manifold to bypass one or more cell compartments and/or bipolar electrodes in the device. When a bipolar stack comprising multiple individual cells is used, the occurrence of shunt current from cathode to cathode and anode to anode will decrease the stack voltage. In one or more embodiments, non-conductive valves can be introduced at the inlet or outlet position of the manifold to reduce or prevent the shunt current.
The valves described above are any mechanical or electrical operated valves. In some embodiments, the valve is a solenoid valve. Non-limiting examples of suitable non-conductive valves are illustrated in
In one or more embodiments, the inside of the manifold used to deliver cathode and anode slurries and, optionally, coolant, is coated with non-conductive materials to minimize shunt current across the fluids. In one or more embodiments, the manifold itself is made of an electrically insulating material such as a polymer or ceramic.
With reference to
In some embodiments, the fuel containers are adapted to both deliver the fresh fuel and accept the spent fuel, as shown in
In still yet another embodiment, a single tank 700 is used for the out flow and uptake of both anode slurry and cathode slurry. In
The particular type of tank used may depend on the intended use of the power system. For systems with adequate storage room in the engine, the four tank system described in
Another feature of the redox composition is the availability of various “grades” of “fuel” or slurry. For example, a premium grade of fuel may include a cathode slurry or anode slurry or both that provides higher power, or longer operational time and therefore driving range, or both, in the same volume of “fuel.” Compared to an internal combustion engine powered vehicle, where the differences in power between “regular” and “premium” gasoline are often not detectable or are very subtly different to the consumer, the differences in power and range provided by properly engineered slurries can be very dramatic—the power may be 10% or 20% or 50% or even 100% greater for one slurry than another, as may be the driving range, for the same size “gas tank.”
Thus, one use model of the invention is to provide, within the same volume or size of “fuel tank” or total system size including stacks, widely varying performance capabilities.
In yet another embodiment, the power of the fuel is modified and the consumer may select between regular, plus power and premium power batteries. In
Another use model is to provide to the consumer various tank sizes. Unlike a conventional vehicle in which the size of the fuel tank is determined at time of manufacturing, in the present invention the ability to readily exchange slurry tanks for refueling, one can provide tanks of different sizes for different needs. For example, a consumer may purchase a larger tank of fuel, and give up some storage space in a car, when taking a longer trip.
The ability to conveniently exchange the fuel tanks provides several options for recharging, as illustrated in
In other embodiments, for example, when traveling or short on time, the user can swap fuel tanks at a recharging station. The user returns spent fuels at a recharging station and receives fresh slurries. The charging station can replace the fuel tanks (like the model used for refilling propane tanks) or simply empty and refill the existing tanks. The ability to swap fuel tanks would provide flexibility in the type of fuel and fuel capacity available to the user, as discussed above. The user can change grade, power or tank capacity from refill to refill.
In conventional batteries the cathode/anode ratio is fixed at the time of manufacturing and cannot be changed if the operating conditions of the battery require it, such as if at high power one of the electrodes has slower kinetics and therefore more of that electrode would be advantageous. In a power system as described herein, the properties of the power system can be varied or altered as needed.
In one or more embodiments, the flow rates of the cathode and anode slurries can be different. For example, a lithium phosphate-bused cathode suspension used with a graphite anode suspension may be rate-limited by the lithium uptake capability of the anode because too fast a charge rate may result in Li plating at the anode. However, by flowing the anode slurry at a higher rate than the cathode slurry under such high power charge conditions, the plating can be avoided. Also, the voltage of the cell will remain higher because anode slurry will exit the stack at a higher state of charge.
In another embodiment, the flow rates of the cathode and anode slurries, or Cathode/Anode ratio in-situ, can be varied to accommodate any degradation of the electrode slurries that occurred during use. Rather than simply replacing or discarding the slurry, it may be used at a different flow rate to improve the performance of the cell, for example, keeping performance within specifications, even if lower than with new slurries. That is, the operating life of the cell can be improved and extended by increasing the flow rate of one or both slurries, or by changing the Cathode/Anode ratio up or down.
Another operational mode that is advantageous in the redox composition is that power can be improved when needed. In one or more embodiments, the cell voltage is maintained at a relatively higher level by increasing the flow rate of both slurries, so that each is operating at a high state of charge during periods of higher power demand. The energy available in the slurries may not be fully utilized during such operational periods, but the power can be improved. Of course, this can be accomplished by increasing the flow rate of just one electrode slurry as well to keep that slurry at higher rate.
In one or more embodiments, the stack includes monitoring devices that provide the power system or a power management system with information concerning the condition of the power system. This information may be used, in real time or prior to use, to select the optimal operating conditions of the power system. By way of example, the temperature, flow rates, and relative amounts of the cathode and anode slurries can be controlled.
Another use model is to evaluate, replenish, or recondition the fuel slurries at a service provider or manufacturer at one or more times in the life of the fuel slurries. In a conventional battery, the electrodes cannot be reconditioned during the battery's life. In the redox power system, each slurry can be reconditioned to restore or extend the battery life. When a power system is first brought into the service station, the fuel may first be tested at the service provider to evaluate its condition when it is returned for charging or service. Secondly, it can be reconditioned in several ways. For example, residual water may be sequestered from the suspension. Additional salt to improve ion conductivity may be added. Solvents or electrolyte additives may be added. Additional solid phases including active materials used for ion storage, or conductive additives, may be added. The solid phases may be separated from the liquid electrolyte, for example by filtering centrifugation, or the addition of coagulation aids to cause the solid phases to be less well suspended. The solids or solid-enriched suspension and the separated liquid electrolyte may be individually treated, or even replaced.
Of course, any combination of replenishing or reconditioning steps may be performed as well. Doing so can decrease the expense of the system over its useful life by selectively replacing or reconditioning specific failed components, improve lifetime or performance as new additives or components are discovered, or aid in the recycling of the materials.
Another use model is to replace the power “stack” of the flow battery separately from the fuel tanks or other components. Unlike a conventional battery, the ability to replace only certain components as they degrade, or as upgrades are desired, provides economic advantages to both the user and the service provider or manufacturer. Thus, in one or more embodiments, the energy stack is removed from the power system and is replaced or repaired.
In another aspect, the power system can include an electrical energy storage device and power source that is simultaneously a conventional rechargeable battery and a flow cell in one integrated device. It is applicable to various battery chemistries, including aqueous batteries such as nickel metal hydride types, and nonaqueous batteries including lithium rechargeable batteries, sodium rechargeable batteries, or batteries based on other alkali or alkaline earth or non-alkaline working ions. Considering one embodiment based on lithium ion chemistry, the basic construction of such a cell has a separator, on one side of which is a lithium battery positive electrode or a negative electrode, or both, as in a conventional rechargeable lithium battery. That is, the electrodes comprise cathode or anode active material, and may comprise a coating of the active material on a metallic current collector, or may be a stand-alone electrode layer such as a densified or sintered layer comprising the active material, optionally with other constituents such as polymer binders or carbonaceous conductive additives or metallic additives or binders. These ion-storage electrodes will be referred to as the stationary electrodes. However, unlike a conventional lithium battery electrode, one or both of the stationary electrodes is permeable to a flow cell cathode slurry or anode slurry, so that during operation of the device, it is possible to charge or discharge only the active materials on the stationary electrode, only the flow cell cathode slurry or anode slurry, or both.
One embodiment of the invention uses a cathode slurry or anode slurry that is a semi-solid fluid, or suspension, or slurry, as described in previous filings.
In one embodiment, one or both of the stationary electrodes are immediately adjacent to the separator layer, including being coated on the separator. As in a conventional battery, this permits relatively rapid charge and discharge of the battery using the working ions stored in the stationary electrodes. In addition, the ions stored in the cathode slurry and anode slurry are also available to the device and can be charged and discharged, although this may occur at a different kinetic rate than the stationary electrodes. Such a design allows the single device to provide a high power charge or discharge for a relatively shorter period of time, while also having the high energy provided by the flow cell aspects of the design. Thus the stationary electrodes are situated between the separator and the flow cell reactants, and optionally may also serve as the current collectors for one or more of the flow cell reactants. Another advantage of such a design is that the stationary electrodes can provide mechanical support to the separator layer or reduce abrasion or wear of the separator when the cathode slurry and anode slurry are in the form of a semi-solid fluid or suspension or slurry.
In another embodiment, one or more of the flow cell reactants flow in between the separator layer and the stationary electrodes.
In either case, as the stationary electrodes are charged or discharged, the flow cell cathode slurry or anode slurry can add or remove working ions from the stationary electrodes. For example, after a high power discharge pulse, the stationary negative electrode may be relatively depleted, and the stationary positive electrode relatively saturated, with the working ions. The flow cell cathode slurry and anode slurry can exchange ions with the stationary electrodes to bring the entire cell back towards a charged state, from which it is able to provide another high power discharge pulse. Thus this design can provide high pulse power capability, as is required for electric vehicles, while also providing the high storage energy characteristics of a flow cell.
Upon review of the description and embodiments of the present invention, those skilled in the art will understand that modifications and equivalent substitutions may be performed in carrying out the invention without departing from the essence of the invention. Thus, the invention is not meant to be limiting by the embodiments described explicitly above, and is limited only by the claims which follow.
This application is a continuation of U.S. patent application Ser. No. 14/306,610, filed Jun. 17, 2014, which is a continuation of U.S. patent application Ser. No. 12/755,379, filed Apr. 6, 2010, now U.S. Pat. No. 8,778,552, entitled “Fuel System Using Redox Flow Battery,” which claims priority to and the benefit of U.S. Provisional Application No. 61/235,859, filed on Aug. 21, 2009, entitled “Fuel System Using Redox Flow Battery,” and U.S. Provisional Application No. 61/166,958, filed on Apr. 6, 2009, entitled “Fuel System Using Redox Flow Battery,” the disclosures of which are hereby incorporated by reference in their entirety.
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| Number | Date | Country | |
|---|---|---|---|
| 20160013507 A1 | Jan 2016 | US |
| Number | Date | Country | |
|---|---|---|---|
| 61235859 | Aug 2009 | US | |
| 61166958 | Apr 2009 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 14306610 | Jun 2014 | US |
| Child | 14824664 | US | |
| Parent | 12755379 | Apr 2010 | US |
| Child | 14306610 | US |
