Patent Publication Number: US-2022223895-A1

Title: Rechargeable liquid fuel cell system and method

Description:
RELATED APPLICATIONS 
     Reference is made to and this application claims priority from and the benefit of U.S. Provisional Application Ser. No. 63/135,921, filed Jan. 11, 2021, entitled “RECHARGEABLE LIQUID FUEL CELL SYSTEM AND METHOD”, which application is incorporated herein in its entirety by reference. 
    
    
     BACKGROUND OF THE INVENTION 
     This disclosure relates generally to fuel cells and, more specifically, to a reversible fuel cell that utilizes a novel liquid fuel chemistry. 
     A rechargeable liquid fuel-cell (RLFC) system can provide an attractive means for transporting and storing energy for a variety of applications, such as electric vehicles (EVs) or grid-scale electrical-energy storage (EES). However, the liquids proposed for RLFCs to date have suffered from relatively poor performance, especially with liquids that have reasonably high energy densities (i.e., on par with conventional Lithium-ion batteries). These performance issues are due to, for example, slow reaction kinetics of the liquid species, challenges associated with the reversibility of the air electrode, and crossover of one or more of the species in the liquid to the air electrode that negatively impacts the air electrode. 
     BRIEF SUMMARY OF THE INVENTION 
     In accordance with one aspect of the disclosure, a reversible aqueous liquid fuel for a rechargeable fuel cell system includes a formate salt and a bicarbonate salt. The formate salt electrochemically converts to the bicarbonate salt upon discharge, and the bicarbonate salt electrochemically converts to the formate salt upon charge. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
       The features described herein can be better understood with reference to the drawings described below. The drawings are not necessarily to scale, emphasis instead generally being placed upon illustrating the principles of the invention. In the drawings, like numerals are used to indicate like parts throughout the various views. 
         FIG. 1  schematically illustrates a rechargeable fuel cell system according to one embodiment of the present invention; 
         FIG. 2  depicts a plot showing the calculated equilibrium concentrations of the three carbonate species in seawater; 
         FIG. 3  depicts a table showing the electrochemical potential E° for key reactions; 
         FIG. 4  depicts a plot showing expected energy densities of a rechargeable liquid at expected concentrations; 
         FIG. 5  depicts an schematic cross sectional exploded view of a generic fuel cell, according to one embodiment of the invention; 
         FIG. 6  depicts a description of material choices for the separator shown in  FIG. 5 ; 
         FIG. 7  depicts a description of design options for the separator shown in  FIG. 5 ; 
         FIG. 8  depicts drawings of design options for the separator shown in  FIG. 5 ; 
         FIG. 9  depicts a description and drawings of material options for the bipolar plate shown in  FIG. 5 ; 
         FIG. 10  depicts a description of design options for the bipolar plate shown in  FIG. 5 ; 
         FIG. 11  depicts drawings of design options for the bipolar plate shown in  FIG. 5 ; 
         FIG. 12  depicts a description of design options for the flow fields in the negative and positive electrodes shown in  FIG. 5 ; 
         FIG. 13  depicts a drawings of design options for the flow fields in the negative and positive electrodes shown in  FIG. 5 ; 
         FIG. 14  depicts a description of the impact of species crossover in the separator shown in  FIG. 5  with an acidic gas electrode; 
         FIG. 15  depicts drawings of the impact of species crossover in the separator shown in  FIG. 5  with an acidic gas electrode; 
         FIG. 16  depicts a description of the impact of species crossover in the separator shown in  FIG. 5  with an alkaline gas electrode; 
         FIGS. 17 and 18  depict a description and drawings of the removal of carbonates on the gas electrode shown in  FIG. 5  in an alkaline system; 
         FIG. 19  depicts a description of a method for removing accumulated foreign ions in the ionomer or in the ion-exchange membrane shown in  FIG. 5 ; 
         FIG. 20  depicts a description of a method for charging and discharging the liquid shown in  FIG. 5 ; 
         FIG. 21  depicts a description and drawings of a method for the storing reactants shown in  FIG. 5 ; 
         FIGS. 22 and 23  depict a description, drawings, and method of operation for a symmetrical cell according to another embodiment of the present invention; 
         FIG. 24  depicts a description of a method for recovering from inadvertent precipitation on the liquid electrode shown in  FIG. 5 ; 
         FIG. 25  depicts a description of a method for recovering from persistent precipitation outside the cells; and 
         FIGS. 26 and 27  depict a description, drawings, and method of operation for maximizing the energy density of the charge solution shown in  FIG. 5 . 
     
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     A rechargeable aqueous liquid with formate salts produces the corresponding bicarbonate salts on discharge. These bicarbonate salts may be subsequently charged to the original formate salts. This rechargeable-liquid chemistry is accomplished with a unique fuel cell system and operating strategies that enables the necessary conditions are maintained to ensure the desired reactions. It also includes a number of recovery strategies to mitigate the impact of decay mechanisms in order to maximize the lifetime of the liquid and the fuel-cell system. 
       FIG. 1  depicts a rechargeable liquid fuel cell system  10  according to one embodiment of the present invention. The system  10  includes a first electrode  12 , a second electrode  14 , and an electrolyte separator  16  arranged between the electrodes  12 ,  14 . The electrodes  12 ,  14  are connected to an electric circuit  18 . 
     The first electrode  12  includes an electrochemically-reversible aqueous liquid fuel  20  comprising a formate salt and a bicarbonate salt. The system  10  further includes at least one vessel  22  fluidly connected in a recirculation loop  24  with the first electrode  12 . The vessel  22  can hold the liquid fuel solution  20  for recirculation through the first electrode  12  during operation of the fuel cell system  10 . The recirculation loop  24  may also include one or more pumps  26  to facilitate the recirculation of the liquid solution  20  through the loop  24 , vessel  22 , and first electrode  12 . 
     The second electrode  14  may be a gas electrode, such as an oxygen-containing gas, including air. In one embodiment, the second electrode  14  is a reversible air electrode. 
     Further description of the first and second electrodes  14 ,  16  and the electrolyte separator  16  will be provided below. 
     As noted, the liquid fuel  20  includes an aqueous solution including formate salts and bicarbonate salts. Aqueous solutions with carbonate species consist of three species in equilibrium: dissolved CO 2(aq) , bicarbonate ions HCO 3   − , and carbonate ions CO 3   2− . The ratios of the three species strongly depend on pH. For example,  FIG. 2  depicts a plot showing the calculated equilibrium concentrations of the three carbonate species in seawater. According to the invention, it is desirable for the aqueous solution to have a high concentration of bicarbonate ions, a low concentration of carbonate ions, and minimize, to the extent possible, the concentration of dissolved carbon dioxide. Thus, in one embodiment, the pH range of the aqueous liquid fuel  20  is preferably between about 5 and 10, and most preferably between about 7 and 8. Under these conditions, the bicarbonates concentrations are at least 10 to 20 times higher than the carbonates or CO 2 . 
     Maintaining the pH of the bulk liquid  20  in a range between 5 and 10 may be important to achieving the desired electrochemical reactions. For example, if the fuel  20  becomes too acidic, the bicarbonates will become carbonic acid, which will then decompose to CO 2  and H 2 O according to the following exemplary reactions (which should be avoided): 
       NaHCO 3 +HCl→H 2 CO 3 +NaCl  (1)
 
       H 2 CO 3 →CO 2 +H 2 O  (2)
 
     During discharge of the fuel cell  10 , i.e., when generating electricity, the formate salts in the liquid electrolyte  20  are electrochemically converted to bicarbonate salts and electrical energy is generated. The desired reactions are dependent upon proper pH range, and straddle the neutral pH of 7; being slightly acidic or basic. Accordingly, the reactions at the positive and negative electrodes will be different depending on the pH being above or below 7. 
     On the negative electrode, i.e., anode, the desired reaction for the direct oxidation of formate ions to bicarbonate ions in a slightly basic liquid electrolyte solution  20  (pH˜7 to 10) is 
       HCOO −   (aq) +2OH −   (aq) →HCO 3   −   (aq) +H 2 O+2 e   − ,  (3.1)
 
     while in a slightly acidic liquid electrolyte solution  20  (pH˜5 to 7) the desired reaction for the direct oxidation is 
       HCOO −   (aq) +H 2 O  43  HCO 3   −   (aq) +2H + +2 e   − .  (3.2)
 
     On the positive electrode, i.e., cathode, the desired reaction for the oxygen-reduction reaction ORR for the slightly basic case is 
       ½O 2(gas) +H 2 O+2 e   − →2OH −   (aq) ,  (4.1)
 
     and the desired reaction for the ORR for the slightly acidic case the is 
       ½O 2(gas) +2H + (aq)+2 e   − →H 2 O.  (4.2)
 
     In the acidic case the oxygen is being reduced to water, and in the basic case oxygen is being reduced to hydroxyls (OH groups). The overall cell reaction for each case, slightly acidic or basic, is the same: 
       ½O 2 +2H + +2 e   − →H 2 O
 
       HCOO − +H 2 O→HCO 3   − +2H + +2 e   − 
 
       ½O 2 +HCOO − →HCO 3   −   (5)
 
       ½O 2 +H 2 O+2 e   − →2OH − 
 
       HCOO − +2OH − →HCO 3   − +H 2 +2 e   − 
 
       ½O 2 +HCOO − →HCO 3   −   (6)
 
     During charging of the fuel cell  10 , the bicarbonate salts in the liquid electrolyte  20  are electrochemically converted back to formate salts with electrical energy input. The desired reactions are also dependent upon proper pH range, and straddle the neutral pH of 7; being slightly acidic or basic. Accordingly, the reactions at the positive and negative electrodes will be different depending on the pH being above or below 7. 
     On the negative electrode, i.e., cathode, the desired reaction for the direct reduction of bicarbonate ions to formate ions in a slightly basic liquid electrolyte solution  20  (pH≈7 to 10) is 
       HCO 3   −   (aq) +H 2 O+2 e   − →HCOO −   (aq) +2OH −   (aq) ,  (7.1)
 
     while in a slightly acidic liquid electrolyte solution  20  (pH˜5 to 7) the desired reaction for the direct reduction is 
       HCO 3   −   (aq) +2H +   (aq) +2 e   − →HCOO −   (aq) +H 2 O.  (7.2)
 
     Of note, a significant side reaction that is not desirable, but may occur, is the protons combining with themselves to form hydrogen gas: 
       2H +   (aq) +2 e   − →H 2(gas)   (7.3)
 
     On the positive electrode. i.e., anode, protons are generated via reactions that depend upon the reactant and the local pH. In one embodiment, the air electrode  14  is reversible and a desired reaction is an oxygen evolution reaction (OER). For the slightly basic case, the OER reaction is 
       2OH −   (aq) →½O 2 +H 2 O+2 e   − ,  (8.1)
 
     and the desired reaction for the OER for the slightly acidic case is to split water into oxygen and protons: 
       H 2 O→½O 2 +2H +   (aq) +2 e   − .  (8.2)
 
     In another embodiment, hydrogen may be supplied to the air electrode  14  to rehydrogenate the liquid  20  with protons by oxidizing hydrogen instead of splitting water. For the slightly basic case, the hydrogen oxidation reaction (HOR) is: 
       H 2 + 2 OH −   (aq) →2H 2 O+2 e   − ,  (8.3)
 
     and for the slightly acidic case the HOR is: 
       H 2 →2H +   (aq) +2 e   − .  (8.4)
 
     The overall cell reaction for each OER case, slightly acidic or basic, is the reverse of the reactions shown in Eqs. (5) and (6). The overall cell reaction for each HOR case, slightly acidic or basic, is: 
       H 2 →2H + +2 − 
 
       HCO 3   − +2H + +2 e   − →HCOO − +H 2 O
 
       HCO 3   − +H 2 →HCOO − +H 2 O  (9)
 
       H 2 +2OH − →2H 2 O+2 e   − 
 
       HCO 3   − +H 2 O+2 e   − →HCOO − +2OH − 
 
       HCO 3   − +H 2 →HCOO − +H 2 O  (10)
 
     In either case, if some H 2 O is lost during discharge (e.g., exits in the air exhaust), it can potentially be made up during the recharging process. The generated water may be utilized in fuel cell water balance or it may be exhausted, for example. The exhausted water may be utilized to remove heat for fuel cell thermal balance. 
       FIG. 3  depicts a table showing the electrochemical potential E 0  for key reactions, derived from the Gibbs formation energy of the individual elements and calculated stoichiometry. The overall cell discharging reaction potential of 1.22 V is similar to a PEM fuel cell, and the overall cell charging reaction with hydrogen yields almost no charge potential (0.007 V). In other words, the energetics of putting hydrogen into the molecules is almost zero, demonstrating bicarbonates are an ideal hydrogen storage medium. 
     Regarding the composition of the rechargeable liquid  20 , a range of both salt compositions (e.g., choice of cations) and concentrations is possible. The energy density of the liquid  20  depends on the concentration, e.g., how many moles of the formate can be dissolved in water will dictate how much energy is in the liquid. For single-phase operation (i.e., all solids remain dissolved in the aqueous liquid), the desired concentration is about 1M to 5M. 
     Higher formate concentrations (about 5M to 20M) may be enabled by utilizing a 2-phase (solid/liquid) solution stored inside the vessel  22 , in which case the system is not limited by solubility. In this example, the liquid  20  is supersaturated in both formate and bicarbonate species. As the liquid  20  charges and discharges, one of the species is being depleted and the second species is added to. The species being added to will tend to precipitate because it has reached its saturation limit, and the other species that is being depleted, if it is in contact with that solid, will tend to dissolve some of that solid. Thus, the liquid can be replenished by having it in quasi-equilibrium with the solid salts in the vessel  22 , which generally are not circulated. 
       FIG. 4  illustrates expected energy densities of the rechargeable liquid  20  at expected concentrations. The y-value of 2.44 V (1.22 V×2 electrons per molecule) is plotted against x-value concentrations of 3 to 10 moles/liter, disclosing that energy densities of 250 Wh/kg to near 700 Wh/kg are possible. By way of comparison, the energy density of lithium-ion batteries is about 200 Wh/kg. Therefore, the disclosed fuel cell system may have application in vehicles, where the liquid fuel  20  can be recharged in minutes, while decoupled from the power grid. 
     The choice of the cation for the formate/bicarbonate salt can impact solubility, and depends on many factors, including: the solubility and pH of both salts, the impact on reaction kinetics, and the viscosity and ionic conductivity of the solution. In one example, the cations may be relatively large to mitigate membrane crossover. This may also enhance the solubility of the bicarbonates, as well as reaction kinetics. The cations may be selected from a group comprising metals and the like, alkaline metals, or transition metals. Examples include sodium (Na + ), potassium (K + ), lithium (Li + ), and cesium (Cs + ), but the cations are not so limited. The cations may also comprise complex compounds such as ammonium (NH 4   + ), tetrabutylammonium (TBA + ), or tetraethylammonium (TEA + ). Furthermore, a mix of cations may be used, which may be advantageous in achieving the desired properties such as solubility, pH, etc. 
     Turning to  FIG. 5 , shown is a typical fuel cell  11  which, in general, comprises the first (negative) electrode  12  and the second (positive) electrode  14  separated by an ionomer membrane  16 . The negative electrode  12  may include a negative catalyst layer  30   n  and the positive electrode  14  may include a positive catalyst layer  30   p  formed on respective sides of the generally planar membrane  16 . This assembly is typically referred to as a membrane electrode assembly (MEA)  32 . 
     Reactants (i.e., liquid  20  and air) are directed to the MEA  32  by a flow field plate  34  that typically includes reactant flow channels (indicated by dashed lines). Flow field plate  34  is shown as a bipolar plate, which includes reactant flow channels for both the fuel and oxidant. The reactants pass from the channels through a diffusion layer  36   n ,  36   p  abutting the flow field plate  34 . The negative electrode diffusion layer  36   n  may comprise a liquid diffusion layer (LDL), and the positive diffusion layer  36   p  may include a gas diffusion layer (GDL) and a microporous layer (MPL)  38   p  that is positioned between the GDL and the respective catalyst layer  30   p . Although not illustrated, the microporous layer  38   p  may also include a catalyst layer abutting the catalyst layer  30   p . 
     The catalyst layers  30   n ,  30   p  may include catalysts that promote the desired reactions. The catalysts may be supported on electrically-conductive supports, for example carbons or metal oxides. Furthermore, the catalysts may be more than one layer on either electrode to promote the desired charge and discharge reactions. The catalyst layers  30   n ,  30   p  may include an ionomer (i.e., a polymer with ionic groups) to enhance ionic conductivity in the layer, and may serve as a binder for the layer. Ionomer is desirable in the negative electrode since the liquid is a weak electrolyte with low ionic conductivity. Ionomer is needed in positive electrode since reactants are non-ionic. 
     The design and composition of the positive electrode  14  may be similar to cathodes used in fuel cells with polymer membranes, which include both proton-exchange membrane fuel cells (PEMFCs) and anion-exchange membranes (AEMFCs). The gas-diffusion layer (GDL)  36   p  may be hydrophobic (e.g., carbon paper or cloth with some PTFE added). This may be particularly desirable if the reactant is H 2  during charging. As noted, the GDL may consist of a micro-porous layer and macro-porous layer. The catalyst layer  30   p  may consist of two distinct layers with catalysts that promote the two desired reactions (charge and discharge). Alternatively, these multiple catalysts may be mixed in a single layer. 
     For a cell designed to operate under slightly acidic conditions with protons as the desired charge carriers, the catalysts may comprise Pt or other platinum-group metals (PGMs) or alloys. The ionomer will be a cation-exchange material, such as PFSA or other materials used in PEMFCs. 
     For a cell designed to operate under slightly alkaline conditions with hydroxyls as the desired charge carriers, the catalysts may comprise a wide variety of materials, such as those used on the cathodes of AEMFCs. For example, Ni 3 S 2  and Bi/C. The ionomer may be a anion-exchange material, such the material used for membranes in AEMFCs. It may be desirable to make the pH of this electrode moderate (e.g., between ˜7 to 10), which can be enabled by using ionomers comprised of weak basic anion (WBA) ion-exchange resins, that will keep water phase in this electrode near-neutral. 
     The design and composition of the diffusion layer  36   n  in the negative electrode  12  may be similar to those used in rechargeable flow batteries (RFBs). This layer is hydrophilic on the negative side (e.g., carbon paper or cloth that has been pre-oxidized). Unlike most RFB electrodes, there may also be a catalyst layer included to help promote the desired redox reaction on this electrode. The catalyst layer may comprise two distinct layers with catalysts that promote the two desired reactions (charge and discharge) or mixed catalysts in one layer. 
     For a cell designed to operate under slightly acidic conditions with protons as the desired charge carriers, the catalysts  30   n  may be supported on carbon and consist of Pd or alloys of Pd, other PGMs, or Bi (e.g., Bi/C). The ionomer will be a cation-exchange material; however, it may be desirable to make the pH of this electrode moderate (e.g., between ˜6 to 7), which can be enabled by using ionomers comprised of weak acid ion-exchange resins, that will keep this electrode near-neutral. 
     For a cell designed to operate under slightly alkaline conditions with hydroxyls as the desired charge carriers, the catalysts may be the same as those noted above, or of a broader range of materials enabled by this non-acidic conditions (i.e., not PGMs). The ionomer may be a anion-exchange material, such as the material used for membranes in AEMFCs. 
       FIG. 6  depicts a description of the material choices for the separator  16 , corresponding to Slide  42  of the above-named priority provisional application. 
       FIGS. 7 and 8  depict a description and drawings of design options for the separator  16 , corresponding to Slide  42  of the above-named priority provisional application. 
       FIG. 9  depicts a description and drawings of material options for the bipolar plate  34 , corresponding to Slide  37  of the above-named priority provisional application. 
       FIGS. 10 and 11  depict a description and drawings of design options for the bipolar plate  34 , corresponding to Slide  38  of the above-named priority provisional application. 
       FIGS. 12 and 13  depict a description and drawings of design options for the flow fields in the negative and positive electrodes  12 ,  14 , corresponding to Slide  39  of the above-named priority provisional application. 
       FIGS. 14 and 15  depict a description and drawings of the impact of species crossover in the separator  16  with an acidic gas electrode  14  of the disclosed fuel cell system  10 , corresponding to Slide  44  of the above-named priority provisional application. 
       FIG. 16  depicts a description of the impact of species crossover in the separator  16  with an alkaline gas electrode  14  of the disclosed fuel cell system  10 , corresponding to Slide  45  of the above-named priority provisional application. 
       FIGS. 17 and 18  depict a description and drawings of the removal of carbonates on the gas electrode  14  in an alkaline system  10 , corresponding to Slides  46  and  47  of the above-named priority provisional application. 
       FIG. 19  depicts a description of a method for removing accumulated foreign ions in the ionomer or in the ion-exchange membrane  16 , corresponding to Slide  48  of the above-named priority provisional application. 
       FIG. 20  depicts a description of a method for charging the liquid  20  using bicarbonate salt or bicarbonate and formate salt electrolyte solution and gaseous reductant, such as hydrogen, and discharging using formate salt or formate and bicarbonate salt electrolyte solution and gaseous oxidant, such as oxygen or air, corresponding to Slides  49  and  50  of the above-named priority provisional application. 
       FIG. 21  depicts a description and drawings of a method for storing reactants, corresponding to Slide  51  of the above-named priority provisional application. 
       FIGS. 22 and 23  depict a description, drawings, and method of operation for a symmetrical cell, corresponding to Slides  52  and  53  of the above-named priority provisional application. 
       FIG. 24  depicts a description of a method for recovering from inadvertent precipitation on the liquid electrode  12 , corresponding to Slide  54  of the above-named priority provisional application. 
       FIG. 25  depicts a description of a method for recovering from persistent precipitation outside the cells, corresponding to Slide  55  of the above-named priority provisional application. 
       FIGS. 26 and 27  depict a description, drawings, and method of operation for maximizing the energy density of the charge solution, corresponding to Slides  56  and  57  of the above-named priority provisional application. 
     While the present invention has been described with reference to a number of specific embodiments, it will be understood that the true spirit and scope of the invention should be determined only with respect to claims that can be supported by the present specification. Further, while in numerous cases herein wherein systems and apparatuses and methods are described as having a certain number of elements it will be understood that such systems, apparatuses and methods can be practiced with fewer than the mentioned certain number of elements. Also, while a number of particular embodiments have been described, it will be understood that features and aspects that have been described with reference to each particular embodiment can be used with each remaining particularly described embodiment.