Highly energy-efficient and environmentally friendly zinc / aqueous polysulfide rechargeable flow battery

Abstract

The present invention is 2+ The present invention relates to a zinc / aqueous polysulfide rechargeable flow battery (100) made of a first half-cell (110) including a first electrolyte (114) containing an ion source and a static electrode (112) or flowing electrode disposed within the first half-cell, the first half-cell being connected in a closed-loop configuration through a first pump (116) to a first external tank (115) containing the first electrolyte; a second half-cell (120) including a second electrolyte (124) having a polysulfide dissolved therein and a static electrode (122) or flowing electrode disposed within the second half-cell, the second half-cell being connected in a closed-loop configuration through a second pump (126) to a second external tank (125) containing the second electrolyte; a catalyst in the second half-cell in the form of particles on the surface of the static electrode or dispersed in the second electrolyte; and a separator (130) between the two half-cells. The rechargeable flow battery of the present invention avoids the use of toxic or environmentally harmful chemicals.

Description

[Technical Field]

[0001] The present invention relates to a zinc / aqueous polysulfide rechargeable flow battery that avoids the use of toxic or environmentally harmful chemicals. [Background technology]

[0002] In recent years, the need for energy has been constantly increasing, and new renewable clean energy sources are gradually being adopted to replace traditional fossil fuels. However, renewable energy sources are highly dependent on atmospheric conditions, so they need to be connected to reliable energy storage systems. One common form of energy storage system is represented by batteries, which can store energy in the form of chemical energy and release it in the form of electricity whenever needed.

[0003] For example, redox flow batteries (RFBs) represent a promising and versatile architecture capable of storing large amounts of energy and characterized by a long life cycle. RFB batteries are primarily composed of two half-cells, each containing an electrode (positive and negative, respectively) and an electrolyte, separated by a membrane (i.e., separator). Current collectors are generally in contact with an electrical circuit outside the RFB, and bipolar plates separate the current collectors from the electrodes. The electrolytes, called anolyte and catholyte, contain redox-active species dissolved in an aqueous or non-aqueous solvent and are pumped through the half-cells by an external pump in contact with the electrodes.

[0004] In contrast to conventional static battery architectures, this structure completely decouples the power output and energy density of the device because the active materials are stored in two external tanks outside the battery. In this way, the volume of the reservoirs determines the total energy density of the battery, ensuring the possibility of scaling up the system as needed. To achieve a useful volumetric energy density, the solubility of the active species must be considered and optimized.

[0005] On the other hand, since only the electrolyte inside the battery is involved in the redox reaction, the output power is determined by the active area of ​​the electrodes. The most common electrodes are carbon materials such as carbon felt because they have a high active surface area and are chemically inert to most solutions and pH levels.

[0006] Different types of RFBs have been studied since the 70s, the most common being the all-vanadium, Fe-Cr and Zn-Br systems. The capacity fade and toxicity of the last two systems, as well as the high cost of vanadium salts, have limited their commercialization worldwide, thus necessitating the need for improved RFB systems.

[0007] The paper "Polysulfide flow batteries enabled by percolating nanoscale conductor networks," FY Fan et al., Nano Lett. 2014, 14, 4, 2210-2218, describes RFBs based on lithium-polysulfide systems. The presence of lithium necessitates the use of organic polar aprotic solvents, and the paper exemplified the use of tetraethylene glycol dimethyl ether. The use of this type of solvent complicates the fabrication of these batteries and, especially, their disposal at the end of their life, further increasing their cost and making them unsuitable for widespread fabrication and use.

[0008] US Patent Application Publication No. 2020 / 0006796A1 describes aqueous polysulfide-based electrochemical cells with polysulfide-based electrolytes used as anolytes for the assembly of rechargeable flow batteries under alkaline conditions in combination with manganate, permanganate or iron-cyanide ion-based catholytes that utilize redox reactions of ions dissolved therein.

[0009] The paper "Rechargeable zinc-aqueous polysulfide battery with a mediator-ion solid electrolyte," M.M. Gross et al., ACS Appl. Mater. Interfaces 2018, 10, 13, 10612-10617, describes an aqueous-based zinc / polysulfide battery. The battery described in this paper is a static device, and therefore not of the RFB type, and has several limitations and drawbacks. First, on the positive electrode side (catholyte), low concentrations of polysulfide species and hydroxide ions in the electrolyte (0.1 M Na2S4, 0.1 M NaOH) result in electrochemical redox reactions (S4 2- →HS - ) has been involved in HS - The species aid in the generation of gaseous hydrogen sulfide, which severely impacts device reliability in terms of capacity and cycling, and thus total battery cycle life, thereby degrading battery performance and resulting in poor electrochemical reversibility; moreover, the generation of gaseous H2S may cause excessive pressure inside electrochemical flow batteries that are sealed to prevent liquid leakage, along with hazardous concerns of H2S representing a very high risk to human health. The second problem with the battery in this paper is that under the conditions disclosed, OH - The seed is Zn 2+ +4OH - →Zn(OH)4 2- It is related to the negative half-cell (anolyte) because it is consumed according to the reaction, and the solubility of the zincate species is OH - Since the pH of the electrolyte increases with the concentration of cations, a decrease in the electrolyte pH favors the formation of a passive layer on the electrode surface, causing a decrease in conductivity over time. These limitations hinder the transfer of the system described in this paper to RFB batteries. Finally, the solid ceramic separator reported by Gross et al. has an inherently low ionic conductivity (1 mScm). -1 ) and large thickness (500 μm), which prevents the battery from operating at high current and power densities, up to 2.5 mA cm -2 at 1mWcm -2It has a low peak output. Summary of the Invention [Problem to be solved by the invention]

[0010] It is an object of the present invention to provide a rechargeable flow battery that overcomes the shortcomings of the prior art. In particular, it is an object of the present invention to provide a rechargeable flow battery that can maintain high cycle counts with high energy efficiency by using, for the first time, a polysulfide-based solution as a catholyte in combination with a zinc-based anolyte under alkaline conditions, avoiding the use of toxic and potentially environmentally harmful chemicals such as cyanide species, in this case by utilizing metal deposition of zinc on one side of the battery, thus obtaining a hybrid metal-polysulfide rechargeable flow battery. Furthermore, it is a further object of the present invention to promote the polysulfide reaction using appropriately tailored catalytic materials. [Means for solving the problem]

[0011] The present invention relates to a rechargeable flow battery based on safe, low-cost, earth-abundant materials that can provide a power source with high energy efficiency.

[0012] In particular, the present invention provides Zn 2+ a first half-cell including a first electrolyte containing an ion source and a static or flowing electrode disposed within the first half-cell, the first half-cell connected in a closed loop configuration through a first pump to a first external tank containing the first electrolyte; a second half-cell including a second electrolyte having a polysulfide dissolved therein and a static or flowing electrode disposed within the second half-cell, the second half-cell connected in a closed loop configuration through a second pump to a second external tank containing the second electrolyte; In the second half-cell, a catalyst is present in the form of particles on the surface of the static electrode or dispersed in the second electrolyte; A separator between the two half-cells The present invention provides a zinc-polysulfide RFB comprising:

[0013] The two electrolytes are circulated to / from the corresponding half-cells using two pumps.

[0014] In the two half-cells, oxidation and reduction reactions occur due to charging and discharging of the cell. The electrodes in the two half-cells may be static, e.g., metal slurry electrodes or porous carbon electrodes, or, independently of each other, the electrodes in the two half-cells may be flowable, i.e., the first electrolyte may contain electrodes in the form of dispersed conductive particles onto which Zn can be deposited, and / or the second electrolyte may contain electrodes in the form of dispersed conductive particles on which polysulfide oxidation-reduction (redox) reactions can take place.

[0015] Furthermore, in the present invention, the electrodes contained in the second half-cell are modified with a catalyst necessary to promote and maintain the electrochemical reactions involving sulfur species during the charge and discharge phases of the cell. The term "catalyst" herein may refer to a single catalyst or a mixture of different catalytic materials, as explained below.

[0016] Some additives may be preferentially included in either or both electrolytes. In particular, the first electrolyte may include a hydrogen evolution inhibitor, a complexing agent, and / or a buffering agent. The second electrolyte may include a complexing agent and / or a buffering agent. In the case of dispersed electrodes, thickener additives may also be included in the electrolyte formulation.

[0017] The present invention will be explained in detail below with reference to the drawings. [Brief explanation of the drawings]

[0018] [Figure 1] 1 shows a schematic diagram of a flow battery according to the present invention in its most general embodiment. [Figure 2-7] FIG. 1 shows a schematic diagram of a possible first half-cell for the construction of a flow battery according to the present invention. [Figure 8-25] FIG. 1 shows a schematic diagram of a second possible half-cell for the construction of a flow battery according to the present invention. [Figure 26] FIG. 1 shows a schematic diagram of a flow battery according to the present invention, in which two half-cells are separated by a separator membrane in the form of multiple layers, one of the layers containing catalyst and electroactive particles. [Figure 27-28] 1 shows a graph of cyclic voltammetry for a Zn-based electrolyte using a slurry electrode of the present invention. [Figure 29] 1 shows a graph of cyclic voltammetry for a polysulfide-based electrolyte using a slurry electrode of the present invention. [Figure 30-31] 1 shows X-ray diffraction results for a catalyst for use in a second half-cell of the present invention. [Figure 32] 1 shows the effect of catalysts on a single charge and discharge cycle for a Zn-polysulfide RFB according to the present invention. [Figure 33] 1 shows the effect of catalysts on charge and discharge cycling for a Zn-polysulfide RFB according to the present invention. [Figure 34] 1 shows charge and discharge cycles for a Zn-polysulfide RFB according to the present invention. [Figure 35] 1 shows the coulombic efficiency versus cycle number for the Zn-polysulfide RFB of the present invention. [Figure 36-39] 1 shows charge and discharge cycles for different Zn-polysulfide RFBs according to the present invention. [Figure 40] 1 shows the volumetric capacity of the RFB of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0019] In the present invention, an aqueous RFB is obtained by combining an alkaline zinc electrolyte with an aqueous polysulfide electrolyte. The present invention not only addresses the previously described problems associated with toxicity and high cost of prior art RFB systems, but also makes it possible to achieve high efficiency and safety; indeed, zinc is one of the most abundant and cheapest elements, and sulfur, another very cheap element, exhibits high solubility in aqueous electrolytes in the presence of alkali metal ions, forming polysulfide chains with different lengths, thus increasing the energy density of the battery.

[0020] Unlike other types of chemical systems involving zinc salts, such as zinc-bromine or zinc-iron batteries, the chemistry of the RFB of the present invention allows it to operate under alkaline conditions, avoiding the problems associated with acidic environments.

[0021] Moreover, in comparison to the static batteries described in the Gross et al. article referenced above, the batteries of the present invention are rechargeable flow batteries, in which the electrolyte flows from an external tank into the electrochemical cell, thus decoupling the power output and energy density of the device and enabling the possibility of charging and discharging the battery at higher current densities for longer periods of time.

[0022] Unlike the system in the M.M. Gross et al. paper discussed above, the cathode compartment of the RFB of the present invention, i.e., S4 2- →S 2- The redox reaction occurring in does not allow for the production of HS, increasing energy density and extending the life of the battery, and avoiding the risks associated with the possible leakage of toxic gases from the battery. The RFB of the present invention also avoids the problems encountered with the anolyte half-cell and solid ceramic separator of M.M. Gross et al. As shown below, the system described in this invention operates at current densities up to 50 times higher than any available prior art device based on similar chemistry, and has greater stability through cycling and longer battery life.

[0023] In the following description and claims, the definition of "solvent" when referring to the liquid phase of the electrolyte (both anolyte and catholyte) means an aqueous mixture containing at least 40% by volume of water together with water or one or more compounds selected from C1-C4 alcohols, ethylene glycol, acetic acid, glycerin, or a combination of two or more thereof, preferably C1-C4 alcohols, ethylene glycol, or a combination thereof. In a preferred embodiment of the invention, the solvent comprises water and a polar protic solvent having a proportion of water greater than 70% by volume, preferably greater than 80% by volume, and even more preferably greater than 90% by volume.

[0024] In this specification and the accompanying drawings, like elements are identified by like reference numerals in all embodiments.

[0025] Finally, the preparation of the first and second electrolytes of the present invention will be described below in different embodiments. For clarity, the preparation of every electrolyte will be described as a series of steps (i), (ii), .... The first step (i) of every preparation involves providing a solvent and adding a first compound to form an ionically conductive solution, but as will be apparent to those skilled in the art, the order of the following steps (i.e., the order of addition of components to obtain the complete composition of each electrolyte) can be varied, and the following components can be added in any order:

[0026] Rechargeable flow batteries act as an energy source when operated in a discharge mode, and as an energy storage device when operated in a charge (recharge) mode.

[0027] In the RFB of the present invention, the two different half-cell reactions involved during the charge and discharge phases are: 1. Charging stage: [ka] 2. Discharge stage: [ka]

[0028] In other words, during the charging phase, zinc is electroplated onto the negative electrode, and S n 2- Ion is S m 2- (m>n), and during the discharge phase the reverse reaction occurs, i.e., zinc is oxidized to Zn 2+ is oxidized to S m 2- is reduced, returning the electrolyte to its initial state.

[0029] The electrolyte containing the zinc ions that react at the negative electrode is called the anolyte, and the electrolyte containing the polysulfide ions that react at the positive electrode is called the catholyte.

[0030] 1 schematically illustrates a zinc-polysulfide RFB 100 of the present invention in its most general embodiment. The RFB 100 is formed by coupling a first half-cell 110 to a second half-cell 120 via a membrane separator 130. The first half-cell comprises a vessel 111 in electrical contact with a current collector 113, within which resides a first electrolyte 114 and an electrode 112, which may be either a flow-through (3D) or planar (2D) configuration; the first electrolyte 114 is recycled to an external reservoir 115 using a pump 116, a valve system (not shown), and piping 117. Similarly, the second half-cell comprises a vessel 121 in electrical contact with a current collector 123, within which resides a second electrolyte 124 and an electrode 122, which may be either a flow-through (3D) or planar (2D) configuration; the second electrolyte 124 is recycled to an external reservoir 125 using a pump 126, a valve system (not shown), and piping 127. The second half-cell also contains the catalyst necessary to promote the redox reaction of the polysulfide chains, although the catalyst is not depicted in the general embodiment of Figure 1, which is intended to represent a general construction of an RFB of the present invention. Various possible methods for introducing the catalyst into the second half-cell are described in more detail below with reference to the description of various specific embodiments of the present invention.

[0031] A description of the operation of the RFB of the present invention in its most general configuration is reported below, divided into two distinct parts: the first part refers to the charging or recharging phase (i.e., the RFB acts as an energy storage device), and the second part refers to the discharging phase (i.e., the RFB acts as an energy source). This is to avoid ambiguity in the use of terms such as cathode / anode and similar terms.

[0032] Operation during the (re)charging phase Upon (re)charging, the cathodic reaction occurs in the first half-cell 110, i.e., Zn 2+ to metallic zinc. A first electrolyte 114 is stored in an external tank 115 and flows through the half-cell 110 by a pump 116 while the redox reaction occurs. Once the redox reaction has occurred, the first electrolyte is recycled to the storage tank 115 through an external pipe 117, while fresh / regenerated electrolyte can enter the electrolytic cell.

[0033] Similarly, the second half-cell 120 comprises a second electrolyte 124 and an electrode 122 in contact with a current collector (123), where the anodic reaction (oxidation of polysulfides) occurs at the surface of the electrode 122. The second electrolyte 124 is stored in an external tank 125 and flows through the half-cell 120 by a pump 126 while the redox reaction occurs. Once the redox reaction has occurred, the second electrolyte is recycled to the storage tank 125 through an external pipe 127, allowing fresh / regenerated electrolyte to enter the electrolytic cell.

[0034] Discharge Phase Operation During the discharge phase, the zinc-polysulfide RFB 100 of the present invention operates inversely to the (re)charge phase described above. The elements of the RFB are the same, but in this case, the first half-cell contains metallic zinc, Zn 2+ In the first half-cell, an oxidation reaction to HCl occurs, and in the second half-cell, a reduction reaction to polysulfides occurs.

[0035] As described above with reference to Figure 1, the complete RFB of the present invention is constructed by combining two different half-cells separated by a membrane separator. The specific construction of each half-cell, particularly the type of electrodes and catalyst placement used in the first and second half-cells, is primarily determined by the composition of the first and second electrolytes. The electrolyte, electrodes, catalyst, and membrane separator, as well as other optional elements of the present invention, are described separately below.

[0036] Zn-based alkaline electrolyte (first electrolyte) The first electrolyte, i.e., the anolyte, of the present invention is Zn 2+ ions and may be prepared by dissolving any suitable source of zinc ions in an aqueous supporting electrolyte containing one or more hydroxides.

[0037] In the first, simplest possible embodiment, the anolyte is prepared by dissolving a zinc compound, such as zinc oxide (ZnO), zinc hydroxide (Zn(OH)), zinc acetate (Zn(CHCOO)), zinc chloride (ZnCl), zinc carbonate (ZnCO), or a combination of two or more thereof, in a solvent. In a preferred embodiment, the electrolyte contains 0.001M to 1.5M, preferably 0.01M to 1M, and even more preferably 0.1M to 1M Zn. 2+ To obtain a zinc hydroxide solution having an ionic concentration, zinc acetate or zinc chloride is dissolved in a solvent containing one or more compounds selected from sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide, bismuth hydroxide, or a combination of two or more thereof. In a preferred embodiment, the total hydroxide concentration is 0.5 M to 20 M, preferably 1 M to 12 M, and even more preferably 1.5 M to 10 M.

[0038] As an example, in one embodiment, 0.3M to 1M Zn 2+ ZnO is dissolved in an aqueous solution containing NaOH at a concentration in the range of 5M to 10M in an amount such that an ion concentration is obtained.

[0039] A first half-cell using this anolyte of a first possible composition is represented schematically in FIG. 2 and corresponds to the first half-cell 110 already described with reference to FIG. 1 (in this figure and all figures described below depicting half-cells, the presence of a membrane separator is also shown), with this basic anolyte containing only solvent, zinc ions, and at least one hydroxide being the electrolyte 114.

[0040] In a second embodiment of the present invention, the anolyte comprises: (i) dissolving one or more compounds selected from sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide, bismuth hydroxide, or a combination of two or more thereof in a solvent, wherein in a preferred embodiment, the total hydroxide concentration is 0.5M to 20M, preferably 1M to 12M, and even more preferably 1.5M to 10M; (ii) dissolving any suitable zinc ion source, such as zinc oxide (ZnO), zinc hydroxide (Zn(OH)), zinc acetate (Zn(CHCOO)), zinc chloride (ZnCl), zinc carbonate (ZnCO), or a combination of two or more thereof, in the solution of step (i), in a preferred embodiment, the electrolyte has a concentration of 0.001M to 1.5M, preferably 0.01M to 1M, and even more preferably 0.1M to 1M Zn 2+ generating a zinc acetate or zinc chloride solution having an ionic concentration; and (iii) suspending conductive particles, preferably zinc-based and / or carbon-based particles selected from zinc particles, zinc oxide particles, zinc-coated particles, graphene, expanded graphite, reduced graphene oxide, activated carbon, carbon black, acetylene black, carbon nanotubes or a combination of two or more thereof, in the solution of step (ii), wherein these particles are introduced to form conductive percolation paths in the electrolyte, and in a preferred embodiment, the total concentration ranges from 0.01% to 20% by weight of the electrolyte, preferably from 0.1% to 10% by weight, even more preferably from 1% to 5% by weight. is obtained by

[0041] A first half-cell 310 using an anolyte having this second possible composition is represented schematically in Figure 3. The anolyte 314 in this embodiment is obtained by adding conductive particles 311 to the electrolyte 114, as shown in the inset of Figure 3. Inside the electrochemical cell, the anolyte is in contact with a planar electrode 112.

[0042] In a third possible embodiment of the present invention, the anolyte contains electroactive particles comprising zinc in a supporting electrolyte, the particles having an average size in the range of 10 nm to 1000 μm, preferably 20 nm to 500 μm, more preferably 20 nm to 200 μm, and even more preferably 20 nm to 10 μm. The electrolyte is (i) dissolving one or more compounds selected from sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide, bismuth hydroxide, or a combination of two or more thereof in a solvent, wherein in a preferred embodiment, the total hydroxide concentration is 0.5M to 20M, preferably 1M to 12M, and even more preferably 1.5M to 10M; (ii) dissolving a suitable zinc ion source, such as zinc oxide (ZnO), zinc hydroxide (Zn(OH)), zinc acetate (Zn(CHCOO)), zinc chloride (ZnCl), zinc carbonate (ZnCO), or a combination of two or more thereof, in the solution of step (i), in a preferred embodiment, the electrolyte has a concentration of 0.001M to 1.5M, preferably 0.01M to 1M, and even more preferably 0.1M to 1M Zn 2+ generating a zinc acetate or zinc chloride solution having an ionic concentration; and (iii) dissolving or suspending in the solution of step (ii) organic and / or inorganic electroactive particles containing zinc ions of different oxidation states capable of undergoing a redox reaction at the surface of the electrode, wherein the redox reaction can result in a change in the coordination number of the ions either within the crystal lattice of the electroactive particles or at the interface between the electroactive particles and the current collector, and the electroactive particles functioning as a source of Zn ions can be introduced in an amount ranging from 0.01% to 50% by weight, preferably from 1% to 30% by weight, and even more preferably from 5% to 20% by weight. It may also be prepared by

[0043] A first half-cell 410 using an anolyte according to this third possible composition is represented schematically in Figure 4. The anolyte 414 in this embodiment is obtained by adding electroactive particles 411 to the electrolyte 114, as shown in the inset of Figure 4. Inside the electrochemical cell, the anolyte is in contact with a planar electrode 112.

[0044] In yet another (fourth) embodiment of the present invention, the anolyte is obtained by dissolving or suspending electroactive particles, including zinc and carbon particles that form a percolated conductive network in / on which redox reactions can occur, in a supporting electrolyte. The average size of both particles in this dispersion ranges from 10 nm to 1000 μm, preferably from 20 nm to 500 μm, more preferably from 20 nm to 200 μm, and even more preferably from 20 nm to 10 μm. The electrolyte is (i) dissolving one or more compounds selected from sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide, bismuth hydroxide, or a combination of two or more thereof in a solvent, wherein in a preferred embodiment, the total hydroxide concentration is 0.5M to 20M, preferably 1M to 12M, and even more preferably 1.5M to 10M; (ii) dissolving any suitable zinc ion source, such as zinc oxide (ZnO), zinc hydroxide (Zn(OH)), zinc acetate (Zn(CHCOO)), zinc chloride (ZnCl), zinc carbonate (ZnCO), or a combination of two or more thereof, in the solution of step (i), in a preferred embodiment, the electrolyte has a concentration of 0.001M to 1.5M, preferably 0.01M to 1M, and even more preferably 0.1M to 1M Zn 2+ generating a zinc acetate or zinc chloride solution having an ionic concentration of zinc acetate or zinc chloride by dissolving the zinc acetate or zinc chloride solution; (iii) dissolving or suspending in the solution of step (ii) organic and / or inorganic electroactive particles containing zinc ions in different oxidation states capable of undergoing a redox reaction, the redox reaction resulting in a change in the coordination number of the ions either within the crystal lattice of the electroactive particles or at the interface between the electroactive particles and a current collector, the electroactive particles functioning as a source of Zn ions can be introduced in an amount ranging from 0.01% to 50% by weight, preferably from 1% to 30% by weight, and even more preferably from 5% to 20% by weight; and (iv) suspending conductive particles, preferably zinc-based and / or carbon-based particles selected from graphene, expanded graphite, reduced graphene oxide, activated carbon, carbon black, acetylene black, carbon nanotubes or a combination of two or more thereof, in the solution of step (iii), in a preferred embodiment at a total concentration ranging from 0.01% to 20% by weight, preferably from 0.1% to 10% by weight, even more preferably from 1% to 5% by weight. It may also be prepared by

[0045] A first half-cell 510 using an anolyte according to this fourth possible composition is represented schematically in Figure 5. The anolyte 514 of this embodiment is obtained by adding conductive particles 311, in this case only carbon-based particles, and zinc-based electroactive particles 411 to the electrolyte 114, as shown in the inset of Figure 5. Inside the electrochemical cell, the anolyte is in contact with a planar electrode 112.

[0046] In a fifth possible embodiment of the present invention, the anolyte contains electroactive particles comprising zinc in a supporting electrolyte, the particles having an average size in the range of 10 nm to 1000 μm, preferably 20 nm to 500 μm, more preferably 20 nm to 200 μm, and even more preferably 20 nm to 10 μm. The electrolyte is (i) dissolving one or more compounds selected from sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide, bismuth hydroxide, or a combination of two or more thereof in a solvent, wherein in a preferred embodiment, the total hydroxide concentration is 0.5M to 20M, preferably 1M to 12M, and even more preferably 1.5M to 10M; and (ii) dissolving or suspending in the solution of step (i) organic and / or inorganic electroactive particles containing zinc ions in different oxidation states that are capable of redox reaction at the surface of the electrode, wherein the redox reaction can result in a change in the coordination number of the ions either within the crystal lattice of the electroactive particles or at the interface between the electroactive particles and the current collector, and the electroactive particles that function as a source of Zn ions can be introduced in an amount ranging from 0.01% to 50% by weight, preferably from 1% to 30% by weight, and even more preferably from 5% to 20% by weight. It may also be prepared by

[0047] A first half-cell 610 using an anolyte according to this fifth possible composition is represented schematically in Figure 6. The liquid phase of this anolyte differs from the electrolyte 114 of the previous embodiment in that it contains a solvent and hydroxide, but does not contain dissolved zinc salt; therefore, this liquid phase functions as a supporting electrolyte and is designated by the reference numeral 134. The anolyte 614 of this embodiment is obtained by adding electroactive particles 411 to the supporting electrolyte 134, as shown in the inset of Figure 6. Inside the electrochemical cell, the anolyte is in contact with the planar electrode 112.

[0048] In yet another (sixth) embodiment of the present invention, the anolyte is obtained by dissolving or suspending electroactive particles, including zinc and carbon particles that form a percolated conductive network in / on which redox reactions can occur, in a supporting electrolyte. The average size of both particles in this dispersion ranges from 10 nm to 1000 μm, preferably from 20 nm to 500 μm, more preferably from 20 nm to 200 μm, and even more preferably from 20 nm to 10 μm. The electrolyte is (i) dissolving one or more compounds selected from sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide, bismuth hydroxide, or a combination of two or more thereof in a solvent, wherein in a preferred embodiment, the total hydroxide concentration is 0.5M to 20M, preferably 1M to 12M, and even more preferably 1.5M to 10M; (ii) dissolving or suspending in the solution of step (i) organic and / or inorganic electroactive particles containing zinc ions in different oxidation states capable of undergoing a redox reaction, the redox reaction resulting in a change in the coordination number of the ions either within the crystal lattice of the electroactive particles or at the interface between the electroactive particles and a current collector, the electroactive particles functioning as a source of Zn ions can be introduced in an amount ranging from 0.01% to 50% by weight, preferably from 1% to 30% by weight, and even more preferably from 5% to 20% by weight; and (iii) suspending conductive particles, preferably zinc-based and / or carbon-based particles selected from graphene, expanded graphite, reduced graphene oxide, activated carbon, carbon black, acetylene black, carbon nanotubes or a combination of two or more thereof, in the solution of step (ii), in a preferred embodiment at a total concentration ranging from 0.01% to 20% by weight, preferably from 0.1% to 10% by weight, even more preferably from 1% to 5% by weight. It may also be prepared by

[0049] A first half-cell 710 using an anolyte according to this sixth possible composition is represented schematically in Figure 7. The anolyte 714 of this embodiment is obtained by adding conductive particles 311, in this case only carbon-based particles, and zinc-based electroactive particles 411 to the supporting electrolyte 134, as shown in the inset of Figure 7. Inside the electrochemical cell, the anolyte is in contact with a planar electrode 112.

[0050] Any suitable metal element capable of co-depositing with zinc to form an alloy can be added to the anolyte of any one of the above embodiments. Metal elements, particularly in ionic form, are obtained from their respective salts, oxides, and hydroxides and are appropriately selected to (i) alter the zinc electrochemical potential and (ii) increase the overpotential for hydrogen evolution. These metal elements are selected from among Pb, Mn, Sn, Fe, Ni, Cu, Mg, Ti, Co, Al, Li, Zr, or a combination of two or more thereof. In a preferred embodiment, they are introduced at a concentration ranging from 0.001 M to 1 M, preferably from 0.01 M to 0.5 M, and even more preferably from 0.05 M to 0.3 M.

[0051] Additionally, any one of the above anolytes may further contain additives such as hydrogen evolution inhibitors, Zn complexing agents, leveling agents, brighteners, anti-corrosion compounds, and the like to stabilize the operation of the first half-cell and enhance cell performance, as described in more detail below.

[0052] A first possible additive for the first electrolyte is a hydrogen generation inhibitor. This component is added to increase the battery coulombic efficiency and reduce side reactions during the charging phase, and this additive may also be effective in preventing pH fluctuations in the electrolyte. The hydrogen generation inhibitor may be selected from silicates, Pb, Bi, Mn, W, Cd, As, Sb, Sn, In and their oxides, boric acid, or a combination thereof, in a total concentration ranging from 0.001 M to 5 M, preferably from 0.01 M to 2 M, and even more preferably from 0.05 M to 1 M.

[0053] The anolyte may further contain Rochelle salt at a concentration of 0.001 M to 10 M, preferably 0.1 M to 5 M, preferably 0.5 M to 2 M, which salt functions to complex the zinc ions and increases the conductivity of the electrolyte.

[0054] Another possible additive to the anolyte is a leveling agent, which reduces dendritic growth of the electrodeposited zinc, which can affect the long-term performance of the battery. Leveling agents include, for example, polyethylene glycol (PEG), polyethyleneimine (PEI), thiourea, quaternary ammonium salts, dextrin, cyclodextrin, sucrose, polytetrafluoroethylene (PTFE), sodium dodecyl sulfate (SDS), polyacrylic acid, glucose, and cellulose, or combinations thereof, at concentrations of 0.0001 ppm to 10,000 ppm, preferably 0.002 ppm to 5,000 ppm, and even more preferably 1 ppm to 1,000 ppm. In a preferred embodiment, the Zn-based electrolyte contains 0.01 ppm to 5,000 ppm, preferably 1 ppm to 2,000 ppm, and even more preferably 5 ppm to 1,000 ppm of PEI.

[0055] In another embodiment, plasticizer additives may be added to the electrolyte formulation, including polyols (polyethylene glycol (PEG), ethylene glycol, diethylene glycol (DEG), tetraethylene glycol (TEG), propylene glycol (PG), glycerin, mannitol, sorbitol, xylitol, etc.), monosaccharides (e.g., glucose, mannose, fructose, sucrose), fatty acids, urea, ethanolamine, triethanolamine, vegetable oils, lecithin, waxes, amino acids, surfactants, and oleic acid, in the range of 0.1% to 5% by weight, more preferably 0.3% to 3% by weight, and even more preferably 0.5% to 1% by weight.

[0056] In yet another embodiment, the present invention also relates to the addition of thickener additives necessary to ensure the best particle dispersion and suitable electrolyte viscosity in case of dispersed particles, the amount of these organic additives being comprised in the range of 0.0001% to 10% by weight of the electrolyte, preferably 0.1% to 5% by weight, and even more preferably 0.1% to 1% by weight.

[0057] In a preferred embodiment, the zinc-based electrolyte contains an organic additive selected from among xanthan gum, gum arabic, carboxymethyl cellulose, chitosan, agar, sodium alginate and polyethylene oxide in an amount comprised between 0.0001% and 10% by weight of the electrolyte, preferably between 0.1% and 5% by weight, and even more preferably between 0.1% and 1% by weight.

[0058] Aqueous polysulfide-based electrolyte (second electrolyte) The second electrolyte or catholyte of the present invention contains polysulfide ions and requires the presence of a catalyst for its operation. The coexistence of polysulfide ions and catalyst may be achieved according to very different embodiments, which are described in detail below. The selection of water or aqueous mixtures as the liquid phase of the electrolyte and their combination with other chemicals described below allows for the utilization of the electrochemical reaction of short polysulfide chains, which is promoted in combination with the developed electrocatalytic materials.

[0059] The first second electrolyte or catholyte of the present invention comprises: (i) dissolving one or more compounds selected from sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide, bismuth hydroxide, or a combination of two or more thereof in a solvent, wherein in a preferred embodiment, the total hydroxide concentration is 0.5M to 20M, preferably 1M to 12M, and even more preferably 1.5M to 10M; (ii) dissolving any suitable polysulfide source selected from lithium sulfide (LiS), sodium sulfide (NaS), potassium sulfide (KS) or a combination of two or more thereof in water or an aqueous solvent into the solution obtained in step (i), wherein in a preferred embodiment the total concentration of alkali sulfides is 0.5M to 8M, preferably 1M to 7M, and even more preferably 2M to 6M; and (iii) A2S n dissolving elemental sulfur S in the solution obtained in step (ii) to form chains, wherein n=2-6 and A may be selected from Li, Na, K and combinations thereof, wherein in a preferred embodiment the total concentration of elemental sulfur added is 0.5M-40M, preferably 1M-35M, even more preferably 2M-30M. It may also be prepared by

[0060] In one embodiment of the present invention, Na2S is dissolved at a concentration of 2M to 3M in an aqueous solution containing NaOH at a concentration in the range of 2M to 8M, together with elemental sulfur at a concentration of 3M to 12M.

[0061] To effectively use the catholyte of this first embodiment, the static electrode contained in the second half-cell is modified with the catalyst necessary to promote the catholyte electrochemical reaction. This is typically a catalytic metal M selected from the group of metals Mo, Zr, Ti, Ni, In, Pb, Zn, Fe, Co, Cu, Mn, Cd, Bi, Al, Ga, Cr, W, Nb, Au, Ag, Pt, Ru, Ir, Pd and their alloys, as well as compounds of one or more of these metals. These compounds are sometimes referred to below adopting the general nomenclature MX (or M-M'-X) to refer to all possible compositions of metal cations M, M' and indicating anions in a crystalline phase. Examples of possible catalytic compounds are metal oxides or mixed oxides (MO or M-M'-O), chalcogenide compounds containing sulfur anions and at least one metal cation (MX or M-M'-X = Co-S, Cu-S, Fe-S, Ni-S, Zn-S, Sn-S, Cu-Zn-S, Cu-Sn-S, etc.) or other chalcogenides such as selenides and tellurides (MX = M-Se, M-Te), nitrides (MN), oxynitrides (MON) and carbonitrides (MCN) or carbon-based non-noble metals (M / N / C). Catalysts are described in more detail below.

[0062] A second half-cell 620 using a catholyte according to this first possible composition is shown schematically in Figure 8. The catholyte 124 in this embodiment contains a solvent, at least one hydroxide, and polysulfide ions. In this half-cell embodiment, the catalyst is present in the form of particles 623 deposited on the surface of the electrode 622.

[0063] A second embodiment of the catholyte of the present invention is obtained by incorporating dispersed catalyst particles therein. (i) dissolving one or more compounds selected from sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide, bismuth hydroxide, or a combination of two or more thereof in a solvent, wherein in a preferred embodiment, the total hydroxide concentration is 0.5M to 20M, preferably 1M to 12M, and even more preferably 1.5M to 10M; (ii) S with a total concentration of 0.5M to 8M, preferably 1M to 7M, and even more preferably 2M to 6M n 2- For Aeon, A2S n dissolving a sulfide salt and elemental sulfur in the solution obtained in step (i) in a ratio greater than 1:1 (A2S2), preferably comprised between 1:3 and 1:4, to produce: (iii) suspending in the solution obtained in step (ii) catalyst particles containing MX compounds in different oxidation states capable of catalyzing polysulfide redox reactions at the surface of the static electrode, the catalyst particles being introduced in an amount ranging from 0.001% to 10% by weight, preferably from 0.01% to 5% by weight, and even more preferably from 0.1% to 1% by weight. It may also be prepared by

[0064] The average size of the dispersed catalyst particles is in the range of 10 nm to 1000 μm, preferably 20 nm to 500 μm, more preferably 20 nm to 200 μm, and even more preferably 20 nm to 10 μm.

[0065] These catalyst particles may be made of the same metals and metal alloys and compounds listed above as modifiers for electrode 622 .

[0066] A second half-cell 720 using a catholyte according to this second possible composition is represented diagrammatically in Figure 9. The catholyte 721 in this embodiment is obtained by adding catalyst particles 711 (represented by stars in the inset in the figure) to the electrolyte 124. In this case, the planar electrode 722 in contact with the catholyte 721 does not have catalyst particles attached to its surface.

[0067] A third possible embodiment of the catholyte of the present invention is obtained by introducing the dispersed catalyst particles and conductive particles, preferably carbon-based particles, described above, into a supporting electrolyte to form a percolated conductive network in / on which redox reactions can occur, with the average particle size of the dispersion ranging from 10 nm to 1000 μm, preferably from 20 nm to 500 μm, more preferably from 20 nm to 200 μm, and even more preferably from 20 nm to 10 μm.

[0068] This electrolyte is (i) dissolving one or more compounds selected from sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide, bismuth hydroxide, or a combination of two or more thereof in a solvent, wherein in a preferred embodiment, the total hydroxide concentration is 0.5M to 20M, preferably 1M to 12M, and even more preferably 1.5M to 10M; (ii) S with a total concentration of 0.5M to 8M, preferably 1M to 7M, and even more preferably 2M to 6M n 2- For Aeon, A2S n dissolving a sulfide salt and elemental sulfur in the solution obtained in step (i) in a ratio greater than 1:1 (A2S2), preferably comprised between 1:3 and 1:4, to produce: (iii) suspending catalyst particles containing MX compounds in different oxidation states capable of catalyzing polysulfide redox reactions in the solution obtained in step (ii), the catalyst particles being introduced in an amount ranging from 0.001% to 10% by weight, preferably from 0.01% to 5% by weight, and even more preferably from 0.1% to 1% by weight; and (iv) suspending conductive particles, preferably carbon-based particles selected from graphene, expanded graphite, reduced graphene oxide, activated carbon, carbon black, acetylene black, carbon nanotubes or a combination of two or more thereof, in the solution obtained in step (iii) to be introduced to form conductive percolation paths in the electrolyte, in a preferred embodiment at a total concentration ranging from 0.01% to 20% by weight, preferably from 0.1% to 10% by weight, even more preferably from 1% to 5% by weight. It may also be prepared by

[0069] A second half-cell 820 using a catholyte according to this third possible composition is shown schematically in Figure 10. The catholyte 821 in this embodiment is obtained by adding catalytic particles 711 and conductive particles 811 (both types of particles are shown in the inset in the figure) to the previously described electrolyte 124. Also in this case, the planar electrode 822 in contact with the catholyte 821 does not need catalytic particles attached to its surface.

[0070] In a fourth possible embodiment of the invention, the catholyte comprises several conductive particles modified by catalytic particles dispersed in the electrolyte, forming a percolated conductive network in / on which redox reactions can occur.

[0071] The average size of the conductive particles is in the range of 10 nm to 1000 μm, preferably 20 nm to 500 μm, more preferably 20 nm to 200 μm, and even more preferably 20 nm to 10 μm. (i) dissolving a supporting electrolyte containing one or more compounds selected from sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide, bismuth hydroxide, or a combination of two or more thereof in a solvent, wherein in a preferred embodiment, the total hydroxide concentration is 0.5 M to 20 M, preferably 1 M to 12 M, and even more preferably 1.5 M to 10 M; (ii) Sn at a total concentration of 0.5M to 8M, preferably 1M to 7M, and even more preferably 2M to 6M2- For Aeon, A2S n dissolving a sulfide salt and elemental sulfur in the solution obtained in step (i) in a ratio greater than 1:1 (A2S2), preferably comprised between 1:3 and 1:4, to produce: (iii) suspending, in the solution obtained in step (ii), conductive particles previously modified with catalyst particles and introduced to form conductive percolation paths in the electrolyte, preferably carbon-based particles selected from graphene, expanded graphite, reduced graphene oxide, activated carbon, carbon black, acetylene black, carbon nanotubes or a combination of two or more thereof, in a preferred embodiment at a total concentration ranging from 0.01% to 20% by weight, preferably from 0.1% to 10% by weight, even more preferably from 1% to 5% by weight. It may also be prepared by

[0072] A second half-cell 920 using a catholyte according to this fourth possible composition is represented schematically in Figure 11. The catholyte 921 of this embodiment is obtained by adding previously described particles 911 (inset), obtained by modifying basic conductive particles with catalytic particles, to the electrolyte 124. The electrode 922 does not have catalytic particles attached to its surface.

[0073] A fifth possible embodiment of the present invention is a catholyte comprising electroactive particles containing sulfide ions dispersed in a supporting electrolyte and reacting by a redox reaction thanks to the presence of a catalyst on the surface of a static electrode. The average size of the electroactive particles ranges from 10 nm to 1000 μm, preferably from 20 nm to 500 μm, more preferably from 20 nm to 200 μm, and even more preferably from 20 nm to 10 μm. This electrolyte is (i) dissolving one or more compounds selected from sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide, bismuth hydroxide, or a combination of two or more thereof in a solvent, wherein in a preferred embodiment, the total hydroxide concentration is 0.5M to 20M, preferably 1M to 12M, and even more preferably 1.5M to 10M; and (ii) dissolving or suspending in the solution obtained in step (i) organic and / or inorganic sulfide-based electroactive particles containing sulfide ions in different oxidation states capable of undergoing a redox reaction, which can cause a change in the coordination number of the ions either within the crystal lattice of the electroactive particles or at the interface between the electroactive particles and the current collector, the electroactive particles functioning as a source of polysulfide ions can be introduced in an amount ranging from 0.01% to 50% by weight, preferably from 1% to 30% by weight, and even more preferably from 5% to 20% by weight. It may also be prepared by

[0074] A second half-cell 1020 employing a catholyte according to this fifth possible composition is represented schematically in Figure 12. The liquid phase of this catholyte differs from the electrolyte 124 of the previous embodiment in that it contains solvent and hydroxide, but does not contain sulfide; therefore, this liquid phase functions as a supporting electrolyte, designated by the numeral 144. Catholyte 1021 in this embodiment consists of supporting electrolyte 144 to which electroactive particles 1011 containing sulfide ions have been added. In this embodiment of the invention, electrode 1022 may be a catalytically modified static electrode similar to electrode 622, or may be in the form of a slurry electrode.

[0075] In a sixth embodiment of the present invention, the catholyte contains sulfide ions dispersed in a supporting electrolyte and contains several electroactive particles that react via a redox reaction thanks to the presence of catalyst particles co-dispersed therein, the particles having an average size ranging from 10 nm to 1000 μm, preferably from 20 nm to 500 μm, more preferably from 20 nm to 200 μm, and even more preferably from 20 nm to 10 μm.

[0076] This electrolyte is (i) dissolving one or more compounds selected from sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide, bismuth hydroxide, or a combination of two or more thereof in a solvent, wherein in a preferred embodiment, the total hydroxide concentration is 0.5M to 20M, preferably 1M to 12M, and even more preferably 1.5M to 10M; (ii) dissolving or suspending in the solution obtained in step (i) organic and / or inorganic sulfide-based electroactive particles containing sulfide ions in different oxidation states capable of undergoing a redox reaction, which can cause a change in the coordination number of the ions either within the crystal lattice of the electroactive particles or at the interface between the electroactive particles and the current collector, the electroactive particles functioning as a source of polysulfide ions can be introduced in an amount ranging from 0.01% to 50% by weight, preferably from 1% to 30% by weight, and even more preferably from 5% to 20% by weight; (iii) suspending catalyst particles containing MX compounds in different oxidation states capable of catalyzing polysulfide redox reactions in the solution obtained in step (ii), the catalyst particles may be introduced in an amount ranging from 0.001% to 10% by weight, preferably from 0.01% to 5% by weight, and even more preferably from 0.1% to 1% by weight. It may also be prepared by

[0077] A second half-cell 1120 using a catholyte according to this sixth possible composition is represented schematically in Figure 13. The catholyte 1121 in this embodiment consists of a supporting electrolyte 144 to which electroactive particles 1011 containing sulfide ions and catalyst particles 711 have been added. Inside the electrochemical cell, the catholyte is in contact with a planar electrode 1122.

[0078] In a seventh embodiment of the catholyte of the present invention, it comprises (i) electroactive particles containing sulfide ions dispersed in a supporting electrolyte, (ii) catalyst particles necessary to promote the redox reaction of the catholyte, and (iii) a flowable electrode in the form of conductive particles, preferably carbon-based particles, that form a percolated conductive network in / on which the redox reaction can occur. The average size of all dispersed particles is in the range of 10 nm to 1000 μm, preferably 20 nm to 500 μm, more preferably 20 nm to 200 μm, and even more preferably 20 nm to 10 μm.

[0079] This electrolyte is (i) dissolving one or more compounds selected from sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide, bismuth hydroxide, or a combination of two or more thereof in a solvent, wherein in a preferred embodiment, the total hydroxide concentration is 0.5M to 20M, preferably 1M to 12M, and even more preferably 1.5M to 10M; (ii) dissolving or suspending in the solution obtained in step (i) organic and / or inorganic sulfide-based electroactive particles containing sulfide ions in different oxidation states capable of undergoing a redox reaction, which can cause a change in the coordination number of the ions either within the crystal lattice of the electroactive particles or at the interface between the electroactive particles and the current collector, the electroactive particles functioning as a source of polysulfide ions can be introduced in an amount ranging from 0.01% to 50% by weight, preferably from 1% to 30% by weight, and even more preferably from 5% to 20% by weight; (iii) suspending catalyst particles containing MX compounds in different oxidation states capable of catalyzing polysulfide redox reactions in the solution obtained in step (ii), the catalyst particles being introduced in an amount ranging from 0.001% to 10% by weight, preferably from 0.01% to 5% by weight, and even more preferably from 0.1% to 1% by weight; and (iv) suspending conductive particles, preferably carbon-based particles selected from graphene, expanded graphite, reduced graphene oxide, activated carbon, carbon black, acetylene black, carbon nanotubes or a combination of two or more thereof, in the solution obtained in step (iii) to be introduced to form conductive percolation paths in the electrolyte, in a preferred embodiment at a total concentration ranging from 0.01% to 20% by weight, preferably from 0.1% to 10% by weight, even more preferably from 1% to 5% by weight. It may also be prepared by

[0080] A second half-cell 1220 using a catholyte according to this seventh possible composition is represented schematically in Figure 14. The catholyte 1221 in this embodiment consists of supporting electrolyte 144 to which sulfide ion-containing electroactive particles 1011, catalyst particles 711, and conductive particles 811 have been added, which in this case form a slurry / flowable electrode in contact with a 2D electrode 1222.

[0081] In an eighth embodiment of the present invention, the catholyte comprises several electroactive particles containing sulfide ions modified by catalytic particles dispersed in a supporting electrolyte, and a static electrode with or without catalyst on which a redox reaction can occur. The average size of the modified electroactive particles ranges from 10 nm to 1000 μm, preferably from 20 nm to 500 μm, more preferably from 20 nm to 200 μm, and even more preferably from 20 nm to 10 μm. The electrolyte is (i) dissolving one or more compounds selected from sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide, bismuth hydroxide, or a combination of two or more thereof in a solvent, wherein in a preferred embodiment, the total hydroxide concentration is 0.5M to 20M, preferably 1M to 12M, and even more preferably 1.5M to 10M; and (ii) dissolving or suspending in the solution obtained in step (i) organic and / or inorganic sulfide-based electroactive particles containing sulfide ions in different oxidation states capable of undergoing a redox reaction, the redox reaction occurring at the interface between the electroactive particles and the electrode thanks to the presence of a catalyst on the surface of the electroactive particles themselves; these modified electroactive particles, functioning as both a source of polysulfide ions and a source of catalyst, can be introduced in an amount ranging from 0.01% to 50% by weight, preferably from 1% to 30% by weight, and even more preferably from 5% to 20% by weight. It may also be prepared by

[0082] This composition of catholyte 1321 and the resulting second half-cell is depicted in FIG. 15, in which inset 1311 denotes sulfide-based electroactive particles having catalyst particles on their surfaces suspended in supporting electrolyte 144.

[0083] According to a ninth possible embodiment of the present invention, the catholyte comprises several electroactive particles containing sulfide ions modified by catalytic particles dispersed in a supporting electrolyte, and a flowable electrode in the form of conductive particles, preferably carbon-based particles, forming a percolated conductive network in / on which redox reactions can occur. The average size of the modified electroactive particles ranges from 10 nm to 1000 μm, preferably from 20 nm to 500 μm, more preferably from 20 nm to 200 μm, and even more preferably from 20 nm to 10 μm. This electrolyte is (i) dissolving one or more compounds selected from sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide, bismuth hydroxide, or a combination of two or more thereof in a solvent, wherein in a preferred embodiment, the total hydroxide concentration is 0.5M to 20M, preferably 1M to 12M, and even more preferably 1.5M to 10M; (ii) dissolving or suspending in the solution obtained in step (i) organic and / or inorganic sulfide-based electroactive particles containing sulfide ions in different oxidation states capable of undergoing a redox reaction, the redox reaction occurring at the interface between the electroactive particles and the flowable electrode thanks to the presence of a catalyst on the surface of the electroactive particles themselves; these modified electroactive particles, functioning as both a source of polysulfide ions and a source of catalyst, can be introduced in an amount ranging from 0.01% to 50% by weight, preferably from 1% to 30% by weight, and even more preferably from 5% to 20% by weight; and (iii) suspending conductive particles, preferably carbon-based particles selected from graphene, expanded graphite, reduced graphene oxide, activated carbon, carbon black, acetylene black, carbon nanotubes or a combination of two or more thereof, in the solution obtained in step (ii) to be introduced to form conductive percolation paths in the electrolyte, in a preferred embodiment at a total concentration ranging from 0.01% to 20% by weight, preferably from 0.1% to 10% by weight, even more preferably from 1% to 5% by weight. It may also be prepared by

[0084] A second half-cell 1420 resulting from this ninth possible catholyte composition 1421 is represented schematically in Figure 16. In the inset, numeral 1311 denotes sulfide-based electroactive particles having catalytic particles on their surfaces, and numeral 811 denotes conductive particles. The particles are dispersed in a supporting electrolyte 144.

[0085] In a tenth possible embodiment of the present invention, the catholyte comprises several electroactive particles containing sulfide ions dispersed in a supporting electrolyte and a flowable electrode in the form of conductive particles, preferably carbon-based particles, modified with catalytic particles that form a percolated conductive network in / on which redox reactions can occur, the average size of said particles being in the range of 10 nm to 1000 μm, preferably 20 nm to 500 μm, more preferably 20 nm to 200 μm, and even more preferably 20 nm to 10 μm.

[0086] In this case, the catholyte is (i) dissolving one or more compounds selected from sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide, bismuth hydroxide, or a combination of two or more thereof in a solvent, wherein in a preferred embodiment, the total hydroxide concentration is 0.5M to 20M, preferably 1M to 12M, and even more preferably 1.5M to 10M; (ii) dissolving or suspending in the solution obtained in step (i) organic and / or inorganic sulfide-based electroactive particles containing sulfide ions in different oxidation states capable of undergoing a redox reaction, the redox reaction being induced by a change in the coordination number of the ions either within the crystal lattice of the electroactive particles or at the interface between the electroactive particles and a current collector, the electroactive particles functioning as a source of polysulfide ions can be introduced in an amount ranging from 0.01% to 50% by weight, preferably from 1% to 30% by weight, and even more preferably from 5% to 20% by weight; and (iii) suspending conductive particles, preferably carbon-based particles selected from graphene, expanded graphite, reduced graphene oxide, activated carbon, carbon black, acetylene black, carbon nanotubes or a combination of two or more thereof, modified by catalytic particles and introduced to form conductive percolation paths in the electrolyte and to provide catalyst for the electrochemical reaction, in the solution obtained in step (ii), in a preferred embodiment at a total concentration ranging from 0.01% to 20% by weight, preferably from 0.1% to 10% by weight, even more preferably from 1% to 5% by weight. It may also be prepared by

[0087] A second half-cell 1520 resulting from this tenth possible catholyte composition 1521 is represented schematically in Figure 17. In the inset, numeral 1011 denotes sulfide-based electroactive particles and numeral 911 denotes conductive particles having catalytic particles on their surfaces. The particles are dispersed in a supporting electrolyte 144, and within the electrochemical cell, the catholyte is in contact with a planar electrode 1522.

[0088] In an eleventh embodiment of the catholyte of the present invention, this comprises (i) electroactive particles containing sulfide ions dispersed in a supporting electrolyte, (ii) catalyst particles necessary to promote the redox reaction of the catholyte, and (iii) a flowable electrode in the form of conductive particles, preferably carbon-based particles, that form a percolated conductive network in / on which the redox reaction can occur. The average size of all dispersed particles is in the range of 10 nm to 1000 μm, preferably 20 nm to 500 μm, more preferably 20 nm to 200 μm, and even more preferably 20 nm to 10 μm.

[0089] This electrolyte is (i) dissolving one or more compounds selected from sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide, bismuth hydroxide, or a combination of two or more thereof in a solvent, wherein in a preferred embodiment, the total hydroxide concentration is 0.5M to 20M, preferably 1M to 12M, and even more preferably 1.5M to 10M; (ii) dissolving or suspending in the solution obtained in step (i) organic and / or inorganic sulfide-based electroactive particles containing sulfide ions in different oxidation states capable of undergoing a redox reaction, which can cause a change in the coordination number of the ions either within the crystal lattice of the electroactive particles or at the interface between the electroactive particles and the current collector, the electroactive particles functioning as a source of polysulfide ions can be introduced in an amount ranging from 0.01% to 50% by weight, preferably from 1% to 30% by weight, and even more preferably from 5% to 20% by weight; (iii) suspending conductive particles, preferably carbon-based particles selected from graphene, expanded graphite, reduced graphene oxide, activated carbon, carbon black, acetylene black, carbon nanotubes or a combination of two or more thereof, in the solution obtained in step (ii) to be introduced to form conductive percolation paths in the electrolyte, in a preferred embodiment at a total concentration ranging from 0.01% to 20% by weight, preferably from 0.1% to 10% by weight, even more preferably from 1% to 5% by weight. It may also be prepared by

[0090] A second half-cell 1620 using a catholyte according to this eleventh possible composition is represented schematically in Figure 18. The catholyte 1621 in this embodiment consists of sulfide ion-containing electroactive particles 1011 and supporting electrolyte 144 doped with conductive particles 811, which in this case form a slurry / flowable electrode in contact with a 2D catalytically modified static electrode 1622 similar to electrode 622, which includes catalyst particles 623 on its surface.

[0091] A twelfth possible embodiment of the present invention is a catholyte comprising electroactive particles containing sulfide ions dispersed in a supporting electrolyte and reacting by a redox reaction thanks to the presence of a catalyst on the surface of a static electrode. The average size of the electroactive particles ranges from 10 nm to 1000 μm, preferably from 20 nm to 500 μm, more preferably from 20 nm to 200 μm, and even more preferably from 20 nm to 10 μm. The electrolyte is (i) dissolving one or more compounds selected from sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide, bismuth hydroxide, or a combination of two or more thereof in a solvent, wherein in a preferred embodiment, the total hydroxide concentration is 0.5M to 20M, preferably 1M to 12M, and even more preferably 1.5M to 10M; and (ii) S with a total concentration of 0.5M to 8M, preferably 1M to 7M, and even more preferably 2M to 6M n 2- For Aeon, A2S ndissolving a sulfide salt and elemental sulfur in the solution obtained in step (i) in a ratio greater than 1:1 (A2S2), preferably comprised between 1:3 and 1:4, to produce: (iii) dissolving or suspending in the solution obtained in step (ii) organic and / or inorganic sulfide-based electroactive particles containing sulfide ions in different oxidation states capable of undergoing a redox reaction, which can cause a change in the coordination number of the ions either within the crystal lattice of the electroactive particles or at the interface between the electroactive particles and the current collector, the electroactive particles functioning as a source of polysulfide ions can be introduced in an amount ranging from 0.01 wt. % to 50 wt. %, preferably from 1 wt. % to 30 wt. %, and even more preferably from 5 wt. % to 20 wt. %. It may also be prepared by

[0092] A second half-cell 1720 using a catholyte according to this twelfth possible composition is represented schematically in Figure 19. Catholyte 1721 in this embodiment is obtained by adding electroactive particles 1011 containing sulfide ions to electrolyte 124. In this embodiment of the invention, electrode 1722 may be a catalytically modified static electrode similar to electrode 622.

[0093] In a thirteenth embodiment of the present invention, the catholyte contains sulfide ions dispersed in a supporting electrolyte and contains several electroactive particles that react via a redox reaction thanks to the presence of catalyst particles co-dispersed therein, the particles having an average size in the range of 10 nm to 1000 μm, preferably 20 nm to 500 μm, more preferably 20 nm to 200 μm, and even more preferably 20 nm to 10 μm.

[0094] This electrolyte is (i) dissolving one or more compounds selected from sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide, bismuth hydroxide, or a combination of two or more thereof in a solvent, wherein in a preferred embodiment, the total hydroxide concentration is 0.5M to 20M, preferably 1M to 12M, and even more preferably 1.5M to 10M; (ii) Sn at a total concentration of 0.5M to 8M, preferably 1M to 7M, and even more preferably 2M to 6M 2- For Aeon, A2S n dissolving a sulfide salt and elemental sulfur in the solution obtained in step (i) in a ratio greater than 1:1 (A2S2), preferably comprised between 1:3 and 1:4, to produce: (iii) dissolving or suspending in the solution obtained in step (i) organic and / or inorganic sulfide-based electroactive particles containing sulfide ions in different oxidation states capable of undergoing a redox reaction, which can cause a change in the coordination number of the ions either within the crystal lattice of the electroactive particles or at the interface between the electroactive particles and the current collector, the electroactive particles functioning as a source of polysulfide ions can be introduced in an amount ranging from 0.01% to 50% by weight, preferably from 1% to 30% by weight, and even more preferably from 5% to 20% by weight; and (iv) suspending catalyst particles containing MX compounds in different oxidation states capable of catalyzing polysulfide redox reactions in the solution obtained in step (iii), the catalyst particles may be introduced in an amount ranging from 0.001% to 10% by weight, preferably from 0.01% to 5% by weight, even more preferably from 0.1% to 1% by weight. It may also be prepared by

[0095] A second half-cell 1820 using a catholyte according to this thirteenth possible composition is represented schematically in Figure 20. The catholyte 1821 in this embodiment comprises an electrolyte 124 doped with electroactive particles 1011 containing sulfide ions and catalyst particles 711. Inside the electrochemical cell, the catholyte is in contact with a planar electrode 1822.

[0096] In a fourteenth embodiment of the catholyte of the present invention, this comprises (i) electroactive particles containing sulfide ions dispersed in a supporting electrolyte, (ii) catalyst particles necessary to promote the redox reaction of the catholyte, and (iii) a flowable electrode in the form of conductive particles, preferably carbon-based particles, that form a percolated conductive network in / on which the redox reaction can occur. The average size of all dispersed particles is in the range of 10 nm to 1000 μm, preferably 20 nm to 500 μm, more preferably 20 nm to 200 μm, and even more preferably 20 nm to 10 μm.

[0097] This electrolyte is (i) dissolving one or more compounds selected from sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide, bismuth hydroxide, or a combination of two or more thereof in a solvent, wherein in a preferred embodiment, the total hydroxide concentration is 0.5M to 20M, preferably 1M to 12M, and even more preferably 1.5M to 10M; (ii) S with a total concentration of 0.5M to 8M, preferably 1M to 7M, and even more preferably 2M to 6M n 2- For Aeon, A2S n dissolving a sulfide salt and elemental sulfur in the solution obtained in step (i) in a ratio greater than 1:1 (A2S2), preferably comprised between 1:3 and 1:4, to produce: (iii) dissolving or suspending in the solution obtained in step (ii) organic and / or inorganic sulfide-based electroactive particles containing sulfide ions in different oxidation states capable of undergoing a redox reaction, which can cause a change in the coordination number of the ions either within the crystal lattice of the electroactive particles or at the interface between the electroactive particles and the current collector, the electroactive particles functioning as a source of polysulfide ions can be introduced in an amount ranging from 0.01 wt. % to 50 wt. %, preferably from 1 wt. % to 30 wt. %, and even more preferably from 5 wt. % to 20 wt. %, (iv) suspending catalyst particles containing MX compounds in different oxidation states capable of catalyzing polysulfide redox reactions in the solution obtained in step (iii), the catalyst particles being introduced in an amount ranging from 0.001% to 10% by weight, preferably from 0.01% to 5% by weight, and even more preferably from 0.1% to 1% by weight; and (v) suspending conductive particles, preferably carbon-based particles selected from graphene, expanded graphite, reduced graphene oxide, activated carbon, carbon black, acetylene black, carbon nanotubes or a combination of two or more thereof, in the solution obtained in step (iv) to be introduced to form conductive percolation paths in the electrolyte, in a preferred embodiment at a total concentration ranging from 0.01% to 20% by weight, preferably from 0.1% to 10% by weight, even more preferably from 1% to 5% by weight. It may also be prepared by

[0098] A second half-cell 1920 using a catholyte according to this fourteenth possible composition is represented schematically in Figure 21. The catholyte 1921 in this embodiment consists of electrolyte 124 doped with sulfide ion-containing electroactive particles 1011, catalyst particles 711, and conductive particles 811, which in this case form a slurry / flowable electrode in contact with a 2D electrode 1922.

[0099] In another (fifteenth) embodiment of the present invention, the catholyte comprises several electroactive particles containing sulfide ions modified by catalytic particles dispersed in a supporting electrolyte and a catalytically or non-catalyzed static electrode on which a redox reaction can occur, the average size of the modified electroactive particles being in the range of 10 nm to 1000 μm, preferably 20 nm to 500 μm, more preferably 20 nm to 200 μm, and even more preferably 20 nm to 10 μm.

[0100] This electrolyte is (i) dissolving one or more compounds selected from sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide, bismuth hydroxide, or a combination of two or more thereof in a solvent, wherein in a preferred embodiment, the total hydroxide concentration is 0.5M to 20M, preferably 1M to 12M, and even more preferably 1.5M to 10M; and (ii) Sn at a total concentration of 0.5M to 8M, preferably 1M to 7M, and even more preferably 2M to 6M 2- For Aeon, A2S n dissolving a sulfide salt and elemental sulfur in the solution obtained in step (i) in a ratio greater than 1:1 (A2S2), preferably comprised between 1:3 and 1:4, to produce: (iii) dissolving or suspending in the solution obtained in step (ii) organic and / or inorganic sulfide-based electroactive particles containing sulfide ions in different oxidation states capable of redox reactions, which can occur at the interface between the electroactive particles and the electrode thanks to the presence of catalysts on the surface of the electroactive particles themselves; these modified electroactive particles, which function as both a source of polysulfide ions and a source of catalyst, can be introduced in an amount ranging from 0.01% to 50% by weight, preferably from 1% to 30% by weight, and even more preferably from 5% to 20% by weight. It may also be prepared by

[0101] This composition of catholyte 2021 and the resulting second half-cell 2020 is depicted in FIG. 22, in which inset 1311 denotes sulfide-based electroactive particles having catalyst particles on their surfaces suspended in electrolyte 124.

[0102] According to a sixteenth possible embodiment of the present invention, the catholyte comprises several electroactive particles containing sulfide ions modified by catalytic particles dispersed in a supporting electrolyte, and a flowable electrode in the form of conductive particles, preferably carbon-based particles, forming a percolated conductive network in / on which redox reactions can occur. The average size of the modified electroactive particles ranges from 10 nm to 1000 μm, preferably from 20 nm to 500 μm, more preferably from 20 nm to 200 μm, and even more preferably from 20 nm to 10 μm. This electrolyte is (i) dissolving one or more compounds selected from sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide, bismuth hydroxide, or a combination of two or more thereof in a solvent, wherein in a preferred embodiment, the total hydroxide concentration is 0.5M to 20M, preferably 1M to 12M, and even more preferably 1.5M to 10M; (ii) S with a total concentration of 0.5M to 8M, preferably 1M to 7M, and even more preferably 2M to 6M n 2- For Aeon, A2S n dissolving a sulfide salt and elemental sulfur in the solution obtained in step (i) in a ratio greater than 1:1 (A2S2), preferably comprised between 1:3 and 1:4, to produce: (iii) dissolving or suspending in the solution obtained in step (ii) organic and / or inorganic sulfide-based electroactive particles containing sulfide ions in different oxidation states capable of undergoing a redox reaction, the redox reaction occurring at the interface between the electroactive particles and the flowable electrode thanks to the presence of a catalyst on the surface of the electroactive particles themselves; these modified electroactive particles, functioning as both a source of polysulfide ions and a source of catalyst, can be introduced in an amount ranging from 0.01% to 50% by weight, preferably from 1% to 30% by weight, and even more preferably from 5% to 20% by weight; and (iv) suspending conductive particles, preferably carbon-based particles selected from graphene, expanded graphite, reduced graphene oxide, activated carbon, carbon black, acetylene black, carbon nanotubes or a combination of two or more thereof, in the solution obtained in step (iii) to be introduced to form conductive percolation paths in the electrolyte, in a preferred embodiment at a total concentration ranging from 0.01% to 20% by weight, preferably from 0.1% to 10% by weight, even more preferably from 1% to 5% by weight. It may also be prepared by

[0103] The second half-cell 2120 resulting from this sixteenth possible catholyte composition 2121 is represented schematically in Figure 23. In the inset, numeral 1311 denotes sulfide-based electroactive particles having catalytic particles on their surfaces, and numeral 811 denotes conductive particles. These particles are dispersed in electrolyte 124.

[0104] In a seventeenth possible embodiment of the present invention, the catholyte comprises several electroactive particles containing sulfide ions dispersed in a supporting electrolyte and a flowable electrode in the form of conductive particles, preferably carbon-based particles, modified with catalytic particles that form a percolated conductive network in / on which redox reactions can occur, the average size of said particles being in the range of 10 nm to 1000 μm, preferably 20 nm to 500 μm, more preferably 20 nm to 200 μm, and even more preferably 20 nm to 10 μm.

[0105] In this case, the catholyte is (i) dissolving one or more compounds selected from sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide, bismuth hydroxide, or a combination of two or more thereof in a solvent, wherein in a preferred embodiment, the total hydroxide concentration is 0.5M to 20M, preferably 1M to 12M, and even more preferably 1.5M to 10M; (ii) Sn at a total concentration of 0.5M to 8M, preferably 1M to 7M, and even more preferably 2M to 6M 2- For Aeon, A2S n dissolving a sulfide salt and elemental sulfur in the solution obtained in step (i) in a ratio greater than 1:1 (A2S2), preferably comprised between 1:3 and 1:4, to produce: (iii) dissolving or suspending in the solution obtained in step (i) organic and / or inorganic sulfide-based electroactive particles containing sulfide ions in different oxidation states capable of undergoing a redox reaction, the redox reaction being induced by a change in the coordination number of the ions either within the crystal lattice of the electroactive particles or at the interface between the electroactive particles and a current collector, the electroactive particles functioning as a source of polysulfide ions can be introduced in an amount ranging from 0.01 wt. % to 50 wt. %, preferably from 1 wt. % to 30 wt. %, and even more preferably from 5 wt. % to 20 wt. %, and (iv) suspending conductive particles, preferably carbon-based particles selected from graphene, expanded graphite, reduced graphene oxide, activated carbon, carbon black, acetylene black, carbon nanotubes or a combination of two or more thereof, modified by catalytic particles and introduced to form conductive percolation paths in the electrolyte and to provide catalyst for the electrochemical reactions, in the solution obtained in step (ii), in a preferred embodiment at a total concentration ranging from 0.01% to 20% by weight, preferably from 0.1% to 10% by weight, even more preferably from 1% to 5% by weight. It may also be prepared by

[0106] The second half-cell 2220 resulting from this eighteenth possible catholyte composition 2221 is represented schematically in Figure 24. In the inset, numeral 1011 denotes sulfide-based electroactive particles, and numeral 911 denotes conductive particles having catalytic particles on their surfaces. These particles are dispersed in an electrolyte 124, and inside the electrochemical cell, the catholyte is in contact with a planar electrode 2222.

[0107] In an eighteenth embodiment of the catholyte of the present invention, this comprises (i) electroactive particles containing sulfide ions dispersed in a supporting electrolyte, (ii) catalyst particles necessary to promote the redox reaction of the catholyte, and (iii) a flowable electrode in the form of conductive particles, preferably carbon-based particles, that form a percolated conductive network in / on which the redox reaction can occur. The average size of all dispersed particles is in the range of 10 nm to 1000 μm, preferably 20 nm to 500 μm, more preferably 20 nm to 200 μm, and even more preferably 20 nm to 10 μm.

[0108] This electrolyte is (i) dissolving one or more compounds selected from sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide, bismuth hydroxide, or a combination of two or more thereof in a solvent, wherein in a preferred embodiment, the total hydroxide concentration is 0.5M to 20M, preferably 1M to 12M, and even more preferably 1.5M to 10M; (ii) Sn at a total concentration of 0.5M to 8M, preferably 1M to 7M, and even more preferably 2M to 6M 2- For Aeon, A2S n dissolving a sulfide salt and elemental sulfur in the solution obtained in step (i) in a ratio greater than 1:1 (A2S2), preferably comprised between 1:3 and 1:4, to produce: (iii) dissolving or suspending in the solution obtained in step (ii) organic and / or inorganic sulfide-based electroactive particles containing sulfide ions in different oxidation states capable of undergoing a redox reaction, which can cause a change in the coordination number of the ions either within the crystal lattice of the electroactive particles or at the interface between the electroactive particles and the current collector, the electroactive particles functioning as a source of polysulfide ions can be introduced in an amount ranging from 0.01 wt. % to 50 wt. %, preferably from 1 wt. % to 30 wt. %, and even more preferably from 5 wt. % to 20 wt. %, (iv) suspending conductive particles, preferably carbon-based particles selected from graphene, expanded graphite, reduced graphene oxide, activated carbon, carbon black, acetylene black, carbon nanotubes or a combination of two or more thereof, in the solution obtained in step (iii) to be introduced to form conductive percolation paths in the electrolyte, in a preferred embodiment at a total concentration ranging from 0.01% to 20% by weight, preferably from 0.1% to 10% by weight, even more preferably from 1% to 5% by weight. It may also be prepared by

[0109] A second half-cell 2320 using a catholyte according to this 19th possible composition is represented schematically in Figure 25. The catholyte 2321 in this embodiment consists of electrolyte 124 doped with sulfide ion-containing electroactive particles 1011 and conductive particles 811, which in this case form a slurry / flowable electrode in contact with a 2D catalytically modified static electrode 2322 similar to electrode 622.

[0110] Any one of the above catholytes can be obtained using a sulfur-based solution, preferably chosen from among those resulting from purification processes for the treatment of sulfur dioxide or any other S-containing waste compounds and / or solutions.

[0111] Any one of the above catholytes may further contain a plasticizer and / or a thickener as additives to stabilize the operation of the second half-cell and enhance cell performance.

[0112] Plasticizer additives that can be added include polyols (polyethylene glycol (PEG), ethylene glycol, diethylene glycol (DEG), tetraethylene glycol (TEG), propylene glycol (PG), glycerin, mannitol, sorbitol, xylitol, etc.), monosaccharides (e.g., glucose, mannose, fructose, sucrose), fatty acids, urea, ethanolamine, triethanolamine, vegetable oils, lecithin, waxes, amino acids, surfactants, and oleic acid in the range of 0.1 wt % to 5 wt %, more preferably 0.3 wt % to 3 wt %, and even more preferably 0.5 wt % to 1 wt %.

[0113] The thickener additives ensure the best particle dispersion and suitable electrolyte viscosity in the case of dispersed particles and dispersed catalysts. The amount of these organic additives ranges from 0.0001% to 10% by weight of the electrolyte, preferably from 0.1% to 5% by weight, and even more preferably from 0.1% to 1% by weight. In a preferred embodiment, the catholyte contains an organic additive selected from xanthan gum, gum arabic, carboxymethylcellulose, chitosan, agar, sodium alginate, and polyethylene oxide.

[0114] electrode The electrodes used in the Zn-polysulfide RFB of the present invention can be selected from any type of electrode material.

[0115] The electrodes may be made of carbon-based or metallic materials (e.g., in the form of plates or foams or meshes), or may be in the form of dispersed electrodes, the former of which are referred to herein as static electrodes and may be flow-through 3D such as carbon felt or planar 2D such as graphite plates, the latter of which are referred to as flow-through electrodes.

[0116] The carbon-based static electrode may be, for example, a graphite sheet, carbon felt, or carbon-based fabric, or may be formed from carbon-based conductive particles dispersed in a polymer matrix. Carbon-based electrodes are suitable for both the first and second half-cells.

[0117] Preferably, the metal static electrode for use in the first half-cell may consist of a Zn metal plate, a Zn-coated metal plate, a Zn metal foam, a Zn-coated metal foam, or a mesh. In the second half-cell, the static electrode, either the metal electrode or the carbon-based electrode, is modified with a catalyst necessary to promote and maintain the redox reaction of the dissolved species, as described below. Preferably, in the second half-cell, the carbon-based electrode is a carbon felt-modified electrode. In another preferred embodiment of the present invention, the metal electrode used in the second half-cell is a modified metal foam.

[0118] The fluidized dispersed electrodes in the form of a percolated network of dispersed conductive particles may consist of organic or inorganic conductive particles, functionalized particles, or fluidized-bed electrodes in the form of particles. These electrodes may be dispersed in both electrolytes, and are particles in / on which redox reactions can occur. Examples of these dispersed electrodes include metal particles, expanded graphite, graphite, graphene, graphene oxide, reduced graphene oxide, activated carbon, transition metal oxide particles, carbon-based materials modified with metal oxide particles, carbon nanotubes, carbon black particles, acetylene black particles, metal-coated particles, or combinations of two or more thereof, with an average particle size ranging from 10 nm to 1000 μm, preferably from 20 nm to 500 μm, more preferably from 20 nm to 200 μm, and even more preferably from 20 nm to 10 μm. In a preferred embodiment, a flowable electrode in a Zn-based electrolyte may contain Zn particles, Zn oxide particles, Zn-coated particles, and / or carbon-based particles selected from graphene, expanded graphite, reduced graphene oxide, activated carbon, carbon black, acetylene black, carbon nanotubes, or a combination of two or more thereof, introduced to form a conductive percolation path within the electrolyte. In a preferred embodiment, the total concentration ranges from 0.01% to 20% by weight, preferably from 0.1% to 10% by weight, and even more preferably from 1% to 5% by weight.

[0119] In a preferred embodiment, the flowable electrode in the second half-cell may contain conductive particles, preferably carbon-based particles selected from graphene, expanded graphite, reduced graphene oxide, activated carbon, carbon black, acetylene black, carbon nanotubes, or a combination of two or more thereof, introduced to form a conductive percolation path in the electrolyte. In a preferred embodiment, the total concentration ranges from 0.01% to 20% by weight, preferably from 0.1% to 10% by weight, and even more preferably from 1% to 5% by weight.

[0120] The use of fluid dispersed electrodes provides a high surface area to minimize overpotential for zinc plating / dissolution and a higher cycle life (compared to plating on planar electrodes), and in the case of fluid dispersed electrodes in polysulfide half-cells, the addition of fluid dispersed electrodes can induce higher cell capacity and better behavior at high operating speeds.

[0121] Slurry / flowable electrodes are in the form of an ink of conductive particles in / on which redox reactions can occur. Materials useful for producing these slurry electrodes include metal particles, graphite, graphene, graphene oxide, transition metal oxide particles, carbon-based materials modified with metal oxide particles, carbon nanotubes, carbon black particles, acetylene black particles, metal-coated particles, reduced graphene oxide, activated carbon, or combinations of two or more thereof. The average particle size of the slurry ranges from 10 nm to 1000 μm, preferably 20 nm to 500 μm, more preferably 20 nm to 200 μm, and even more preferably 20 nm to 10 μm. A polymer powder can be introduced into the mixture, which acts as a binder for the other particles. In a preferred embodiment, the amount of conductive carbon particles in the slurry electrode is selected from 50% to 95% of the total electrode mass, 60% to 90% in another embodiment, and 70% to 80% in yet another embodiment. The amount of zinc-containing active particles can be selected from 1% to 50%, more preferably 5% to 30%, and even more preferably 10% to 20% of the total electrode mass. The amount of binder can be selected from 0.1% to 20%, more preferably 0.5% to 10%, and even more preferably 5% to 10% of the total electrode mass. The composition of the slurry can be adjusted to provide electrode conductivity for the two electrolytes.

[0122] In a preferred embodiment, the slurry electrode used in the first half-cell has Zn 2+A slurry of conductive particles capable of undergoing a Zn / Zn redox reaction is used to produce these slurry electrodes. Materials useful for producing these slurry electrodes include metal particles, Zn particles, Zn-coated particles, graphite, expanded graphite, graphene, graphene oxide, transition metal oxide particles, carbon-based materials modified with metal oxide particles, carbon nanotubes, carbon black particles, acetylene black particles, reduced graphene oxide, activated carbon, or a combination of two or more thereof, and the average particle size of the slurry is in the range of 10 nm to 1000 μm, preferably 20 nm to 500 μm, more preferably 20 nm to 200 μm, and even more preferably 20 nm to 10 μm.

[0123] In a preferred embodiment, the slurry electrode for use in the second half-cell is formed from a slurry of conductive particles on which a sulfide redox reaction can occur, and materials useful for producing this slurry electrode include, for example, metal powder, graphite, expanded graphite, graphene oxide, carbon nanotubes, transition metal oxide particles, carbon-based materials modified with metal oxide particles, reduced graphene oxide, activated carbon, acetylene black, or a combination of two or more thereof, and the average size of the particles in the slurry is in the range of 10 nm to 1000 μm, preferably 20 nm to 500 μm, more preferably 20 nm to 200 μm, and even more preferably 20 nm to 100 μm.

[0124] catalyst In the present invention, the electrodes contained in the second half-cell are modified with a catalytic material to promote and maintain the electrochemical reactions involving sulfur species during the charging and discharging phases of the cell. The catalytic material is generally a catalytic metal M selected from the group of metals, alloys and intermetallic compounds thereof, and compounds of one or more metals, in particular Mo, Zr, Ti, Ni, In, Pb, Zn, Fe, Co, Cu, Mn, Cd, Bi, Al, Ga, Cr, W, Nb, Au, Ag, Pt, Ru, Ir, Pd. Examples of alloys / intermetallic compounds useful for the purposes of the present invention are Co3Ni, Fe3Co, Fe9Co7, and Co3Cu.

[0125] These compounds are shown below, sometimes adopting the general nomenclature MX (or M-M'-X), which refers to all possible compositions of metal cations M, M' and the indicated anion in the crystalline phase. Examples of possible catalyst compounds are metal oxides or mixed oxides (MO or M-M'-O), chalcogenide compounds containing sulfur anions and at least one metal cation (MX or M-M'-X = Co-S, Cu-S, Fe-S, Ni-S, Zn-S, Sn-S, Cu-Zn-S, Cu-Sn-S, etc.) or other chalcogenides such as selenides and tellurides (MX = M-Se, M-Te), nitrides (MN), oxynitrides (MON), and carbonitrides (MCN) or carbon-based non-noble metals (M / N / C).

[0126] The catalyst may comprise a mixture of two or more materials belonging to the same or different subclasses, such as two different sulfides, a sulfide and an oxide, a sulfide and a selenide, an oxide and a selenide, and all combinations of chalcogenides. The invention also relates to mixtures of different crystalline phases for materials having the same (e.g., hexagonal or cubic Co) or different elemental compositions (e.g., CoS, CoS2, Co3S4, Co9S8); amorphous compounds are also contemplated. Preferred catalysts for use in the present invention are CoOOH, CO(OH)2, Co3O4, CoO, CoO2, Co3S4, Co9S8, CoS2, CoSe, CoSe2, Co3Se4, Co9Se8, NiSe, NiSe2, Ni3Se4, Ni9Se8, MoSe2, Bi2S3, WS2, WSe2, CuO, Cu3Se2, Co2CuS4, CoCuS4, CoNiOOH, CoFeOOH, NiCo2O4, Co5NiS8, Co2NiS4, Co2NiSe4, CoNiSe4 or mixtures thereof. In a more preferred embodiment, Co3S4, CoS2 or mixtures thereof are used.

[0127] In the present invention, catalysts may be deposited directly on the electrode surface by any suitable method known in the art, including chemical means (e.g., hydrothermal, chemical bath deposition, etc.), physical means (e.g., sputtering, evaporation, reactive annealing, etc.), and electrochemical means (e.g., electrodeposition, etc.), or a combination thereof. In one embodiment, sulfide compounds may be synthesized by direct co-electrodeposition of metal and sulfur, or by a two-step process: growth of a metal layer followed by reactive annealing in a sulfur-containing atmosphere. In another embodiment, deposition of a metal oxide is followed by a reactive process, either chemical or physical, to obtain the desired chalcogenide (e.g., sulfide, selenide, etc.). Additionally, the formation of nanostructures, such as nanowires and nanorods, may be achieved by direct growth on a carbon current collector electrode by hydrothermal annealing.

[0128] In another embodiment, the metal catalyst may be in the form of a slurry, obtained by chemical reaction, optionally in combination with ball milling, and the resulting catalyst powder may be dispersed in a binder and applied to the electrode. The average size of the catalyst particles in the slurry ranges from 10 nm to 1000 μm, preferably from 20 nm to 500 μm, more preferably from 20 nm to 200 μm, and even more preferably from 20 nm to 10 μm. A polymer powder may be incorporated into the mixture, which acts as a binder for the other particles. In a preferred embodiment, the amount of catalyst particles in the slurry is selected from 50% to 95% of the total electrode mass, from 60% to 90% in another embodiment, and from 70% to 80% in yet another embodiment. The amount of binder is selected from 0.1% to 20% of the total electrode mass, more preferably from 0.5% to 10%, and even more preferably from 5% to 10%. In yet another embodiment, the slurry also contains conductive particles selected from metal particles, graphite, graphene, graphene oxide, reduced graphene oxide, activated carbon, metal oxide particles, carbon-based materials modified with metal oxide particles, carbon nanotubes, carbon black particles, acetylene black carbon, metal-coated particles, or a combination of two or more thereof. The average size of the catalyst particles in the slurry is in the range of 10 nm to 1000 μm, preferably 20 nm to 500 μm, more preferably 20 nm to 200 μm, and even more preferably 20 nm to 10 μm.

[0129] In one embodiment of the present invention, the catalyst is dispersed in the form of particles in the polysulfide-based catholyte. The materials from which these particles are made are the same as those reported above for the embodiment in which the catalyst modifies the electrode. These particles can be obtained by any suitable method known in the art, such as chemical precipitation of metal particles, hydrothermal synthesis, reactive annealing, reactive ball milling, chemical conversion.

[0130] Membrane Separator The two half-cells are in contact via a membrane separator. The separator can be selected as desired for a particular purpose or application. In one embodiment, the separator is a porous separator that does not contain any active ion exchange material, and a Celgard® separator or similar can be used. In a further embodiment, solid state glass can also be used. In one embodiment, the Na + or Li + To ensure the cation exchange of ions, Na-ion or Li-ion glasses selected from the sulfide family are used. In another embodiment, the membrane is an ion-selective porous membrane. The separator can be selected from all suitable materials that function as ionic membranes depending on the purpose. In a first possible embodiment, the membrane is a cation membrane suitable for batteries in which the anolyte and catholyte have different pH values, in order to reduce electrolyte cross-mixing as much as possible. In some battery configurations, Nafion™ (a copolymer of perfluorosulfonic acid and polytetrafluoroethylene) membranes are used.

[0131] In another embodiment of the present invention, ionic (cationic or anionic, depending on the purpose) particles, together with conductive particles, preferably carbon-based particles, are dispersed in a solid / semi-solid polymer electrolyte selected from among perfluorosulfonic acid and polytetrafluoroethylene copolymers, polyvinyl alcohol (PVA), chitosan, polyacrylic acid (PAA), gelatin, etc., and then coated onto one of the previously introduced ionic membranes, thus obtaining a multilayer separator. The role of the ionic particles is to block the active ions of the two electrolytes and reduce the cross-mixing effect. In yet another embodiment of the present invention, a catalyst is coated onto the separator between two half-cells. In this embodiment, a catalyst is dispersed together with conductive particles, preferably carbon-based particles, in a polymer binder selected from among perfluorosulfonic acid and polytetrafluoroethylene copolymers, PVA, chitosan, PAA, gelatin, etc., and then coated onto one of the previously mentioned ionic membranes, thereby obtaining a multilayer separator, herein referred to as a catalyst-modified separator. In a further embodiment of the present invention, catalyst-modified carbon-based particles are coated onto the separator between two half-cells. In this embodiment, the carbon-modified particles are dispersed in a polymer binder selected from among copolymers of perfluorosulfonic acid and polytetrafluoroethylene, PVA, chitosan, PAA, gelatin, etc., and applied to one of the previously mentioned ionic membranes to obtain a multilayer separator, referred to herein as a catalyst-modified separator. An example application is shown in Figure 26, where a multilayer separator 160 consists of a first homogenous layer 161 bonded to a second layer 162 containing carbon-based particles modified with a catalyst (163) and non-catalytic particles (164). This type of separator can be applied to any RFB configuration described in this application. In a preferred embodiment, for all ion exchange materials and in all configurations (i.e., single layer or multilayer), the membrane is swollen in 1 M NaOH or 1 M KOH solution prior to application to ensure proper and efficient ion exchange between the anolyte and catholyte during the electrochemical reaction. The swelling time is selected depending on the type of membrane. Other membranes, including all known solid / semi-solid organic / inorganic hybrid electrolytes, are also contemplated.

[0132] An RFB can be obtained according to the present invention by combining any first half-cell with any second half-cell and using any of the above membrane separators.

[0133] Zn-polysulfide flow batteries of the present invention can generally have a cell potential of about 0.7 V to 1.4 V, depending on the amount of polysulfide and the catalyst used. Zn-polysulfide RFBs are generally environmentally friendly, non-toxic, and safer when compared to other flow batteries. Relative to commercially available RFBs, the electrochemical devices of the present invention can operate at higher pH values, extending battery life and significantly reducing maintenance costs.

[0134] Furthermore, the Zn-polysulfide flow battery of the present invention is significantly cheaper than known RFBs: the cost of the battery can be less than 200 USD / kWh for the battery components and less than 60 USD / kWh for the electrolyte and tank, while achieving energy efficiencies as high as 70-85%.

[0135] The RFB cells of the present invention may also be electrically connected in a so-called stack configuration, connected in series to obtain higher voltage values, or in parallel to obtain higher current output.

[0136] The present invention is further illustrated by the following examples. [Example]

[0137] Example 1 Preparation of zinc-based electrolytes for RFB half-cells. A solution was prepared by dissolving sodium hydroxide (NaOH) at 6 M and then zinc oxide (ZnO) at 0.1 M concentration in Millipore water at room temperature. Bismuth oxide (Bi2O3) was added to increase the conductivity of the final solution. The final formulation is shown in Table 1. The as-prepared solution can be used at 25°C to 70°C. [Table 1]

[0138] Example 2 Preparation of zinc-based electrolytes for RFB half-cells. Potassium hydroxide (KOH) was dissolved in Millipore water at room temperature along with zinc acetate (Zn(CHCOO)) at a concentration of 6 M and then 0.1 M to prepare a solution, and lithium hydroxide (LiOH) was added to increase the conductivity of the final solution. The final formulation is shown in Table 2. The as-prepared solution can be worked at 25°C - 70°C. [Table 2]

[0139] Example 3 Preparation of zinc-based electrolytes for RFB half-cells. Potassium hydroxide (KOH) was dissolved in Millipore water at room temperature along with zinc acetate (Zn(CHCOO)) at a concentration of 6 M and then 0.1 M to prepare a solution, to which 3 wt.% of carbon black particles with an average diameter ranging from 500 to 700 nm was added as a flowable electrode. The final formulation is shown in Table 3. The as-prepared solution can work at 25°C to 70°C. [Table 3]

[0140] Example 4 Preparation of zinc-based electrolytes for RFB half-cells. Solutions were prepared by dissolving sodium hydroxide (NaOH) and potassium hydroxide (KOH) at 7 M, followed by zinc acetate (Zn(CHCOO)) at a total concentration of 0.3 M, in Millipore water at room temperature. Lithium hydroxide (LiOH) was added to increase the conductivity of the final solution. The final formulation is shown in Table 4. The as-prepared solution can be worked at 25°C - 70°C. [Table 4]

[0141] Example 5 Preparation of zinc-based electrolytes using dispersed electrodes To increase the battery capacity, power output, and energy density, the dispersed electrodes were added to a 6 M KOH supporting electrolyte. The electrolyte formulation was slightly modified to properly disperse the functionalized particles that served as electrodes in the half-cell. For example, 1 wt. % xanthan gum was added as a thickener additive to increase the electrolyte viscosity. 2 wt. % zinc oxide particles and 15 wt. % zinc particles were added. The particle diameters ranged from 10 μm to 60 μm. The final formulation is shown in Table 5. [Table 5]

[0142] Example 6 Preparation of aqueous polysulfide-based electrolytes for RFB half-cells Solutions were prepared by dissolving NaOH at 4M and then 3M with elemental sulfur (S) in Millipore water at room temperature. Once the S was completely dissolved, 1M NaS was added to the solution to increase the S content in the solution. The final formulation is shown in Table 6. The as-prepared solution can be used at 25°C to 70°C. [Table 6]

[0143] Example 7 Preparation of aqueous polysulfide-based electrolytes for RFB half-cells Solutions were prepared by dissolving KOH at 3M and then 1M with elemental sulfur (S) in Millipore water at room temperature. Once the S was completely dissolved, 1M K2S was added to the solution to increase the S content in the solution. The final formulation is shown in Table 7. The as-prepared solution can be worked at 25°C-70°C. [Table 7]

[0144] Example 8 Preparation of polysulfide-based electrolytes using dispersed electrodes Solutions were prepared by dissolving NaOH and KOH in Millipore water at room temperature, along with elemental sulfur to a total concentration of 5M and then 2M. Once the sulfur was completely dissolved, 0.5M Na2S and 0.5M K2S were added to the solution to increase the sulfur content. 3% by weight of carbon black particles with an average diameter of 100-200 μm was added as a flowable electrode. The final formulation is shown in Table 8. The as-prepared solution can be used at 25°C-70°C. [Table 8]

[0145] Example 9 Preparation of polysulfide-based electrolytes using dispersed catalyst particles Solutions were prepared by dissolving NaOH and KOH in Millipore water at room temperature, along with elemental sulfur (S) to a total concentration of 5M and then 2M. Once the S was completely dissolved, 0.5M NaS and 0.5M KS were added to the solution to increase the S content in the solution. The final formulation is shown in Table 8. 1 wt% CoS was then added to the electrolyte as a dispersed catalyst. The as-prepared solution can be operated at 25°C to 70°C. [Table 9]

[0146] Example 10 Catalyst synthesis In this case, the catalyst deposition was obtained following a two-step procedure: (i) deposition of cobalt on a carbon felt electrode, followed by (ii) reactive annealing in a tubular furnace under a sulfur-containing atmosphere. Electrodeposition of the metallic Co layer was performed for 10 min at a current of 20 mA / cm. 2The experiment was carried out under acidic conditions, applying a current density of 1000 kJ / cm. The metal-coated samples were subjected to a sulfurization process in a tubular furnace at a temperature of 400 °C under a nitrogen flow of 3 L / min for 30 min. The samples were inserted directly into the preheated furnace and then cooled in air. Sulfur powder (20 mg) was placed with a cobalt-coated carbon felt electrode.

[0147] Example 11 Catalyst synthesis In this case, the catalyst deposition was obtained following a two-step procedure: (i) deposition of cobalt on a carbon felt electrode, followed by (ii) reactive annealing in a tubular furnace under a sulfur-containing atmosphere. Electrodeposition of the metallic Co layer was performed for 10 min at a current of 20 mA / cm. 2 The sulfurization process was carried out under acidic conditions while applying a current density of 1000 kJ / cm2. The metal-coated sample was subjected to a sulfurization process in a tubular furnace at a temperature of 400 °C under a nitrogen flow of 3 L / h for 60 minutes. The sample was inserted directly into the preheated furnace and then cooled in air. Sulfur powder (100 mg) was placed with a cobalt-coated carbon felt electrode.

[0148] Example 12 Electrochemical characterization of zinc-based electrolytes for RFB half-cells The electrochemical behavior of the solutions prepared according to Example 1 was characterized by cyclic voltammetry performed at 25°C in a classical three-electrode cell using a BioLogic VSP300 potentiostat / galvanostat with carbon felt as the working electrode, a MMO (mixed metal oxide) mesh electrode as the counter electrode, and Pt as the pseudo-reference electrode, and the results are shown in Figure 27.

[0149] Example 13 Electrochemical characterization of zinc-based electrolytes for RFB half-cells The electrochemical behavior of the solutions prepared according to Example 2 was characterized by cyclic voltammetry performed at 25° C. in a classical three-electrode cell with a BioLogic VSP300 potentiostat / galvanostat using carbon felt as the working electrode, a MMO (mixed metal oxide) mesh electrode as the counter electrode, and Pt as the pseudo-reference electrode, and the results are shown in FIG.

[0150] Example 14 Electrochemical characterization of aqueous polysulfide-based electrolytes for RFB half-cells The electrochemical behavior of the solution prepared according to Example 5 was characterized by cyclic voltammetry performed at 25°C in a classical three-electrode cell with a BioLogic VSP300 potentiostat / galvanostat using carbon felt as the working electrode modified with the catalyst prepared according to Example 11, a MMO (mixed metal oxide) mesh electrode as the counter electrode, and Pt as the pseudo-reference electrode. The results are shown in Figure 29.

[0151] Example 15 Catalyst characterization The catalyst prepared according to Example 10 was characterized by X-ray diffraction (XRD) technique, and the results are shown in Figure 30. The synthesis resulted in the formation of different sulfide phases, mainly CoS2 and Co3S4, along with unreacted Co.

[0152] Example 16 Catalyst characterization The catalyst prepared according to Example 11 was characterized by X-ray diffraction (XRD) technique, and the results are shown in Figure 31. The synthesis resulted in the formation of different sulfide phases, mainly Co3S4.

[0153] Example 17 Effect of catalysts on Zn-polysulfide RFB This example compares the performance results of an RFB made in accordance with the present invention with a comparative RFB without a catalyst and an RFB made in accordance with the prior art.

[0154] Using the electrolytes prepared in Examples 1 and 6, a Zn-polysulfide RFB was fabricated by combining a first half-cell according to FIG. 2 with a second half-cell according to FIG. 8 via a monolayer membrane separator 130. This first RFB did not contain a catalyst. This RFB was pumped at 10 mAcm using a BioLogic VMP-300 potentiostat / galvanostat with a pumping system. -2 The electrochemical test was carried out by applying a current density of 1000 kJ / cm. The nominal area of ​​the two electrodes was 25 cm. 2 This resulted in a total applied current of 250 mA during the charge phase and -250 mA during the discharge phase. The catalytic effect on cell performance is highlighted in a single charge / discharge cycle, and the graph obtained from this test is shown as the dotted line in Figure 32. Without the catalyst, a high cell voltage was recorded during the charge phase as an indication of the high overpotential required to sustain the oxidation process. Furthermore, the cell voltage quickly dropped to 0.3 V during the discharge phase, indicating the ability of the bare carbon felt to induce polysulfide redox reactions.

[0155] The same procedure was used to prepare a second RFB containing cobalt sulfide material obtained according to the procedure described in Gross et al. (page 10614), shown in Figures 32 and 33 as (Co-S). The performance of this RFB was tested over a single charge / discharge cycle as in the previous case, and the results of this test are represented by the dashed line in Figure 32. This RFB produced a faradaic efficiency (FE) of 92.2% and an energy efficiency (EE) of 71.6%.

[0156] Finally, an RFB was fabricated similarly to the two previous cases, with the difference that in this case (in accordance with the present invention) the catholyte half-cell used a cobalt sulfide catalyst obtained as described in Example 11. The adoption of the catalyst of the present invention improved the overall performance of the cell. The charge and discharge cycles of this RFB are reproduced in Figure 32 by the solid line and show values ​​of FE = 96.1% and EE = 79.4%, a 10.9% increase in energy efficiency over the RFB using the prior art catalyst. Furthermore, when the prior art (Gross et al.) catalyst was used, RFB performance was unstable over the long term throughout the cycle, adversely affecting RFB performance and cycle life. On the other hand, the novel implementation of the sulfide catalyst obtained as described in Example 11 of the present invention provided greater stability throughout the cycle. Figure 33 shows the charge and discharge cycles of an RFB fabricated using the prior art (Gross et al.) catalyst, represented as a dotted line, and an RFB fabricated using the catalyst of the present invention, represented as a solid line.

[0157] Example 18 Zn-polysulfide RFB with tailored electrolyte The electrolytes prepared in Examples 1 and 6 were used to fabricate a Zn-polysulfide RFB obtained by combining a first half-cell according to FIG. 2 with a second half-cell according to FIG. 8 via a monolayer membrane separator 130. The catalyst for the catholyte half-cell was obtained according to Example 11. In this RFB, a BioLogic VMP-300 potentiostat / galvanostat with a pumping system was used to pump 10 mAcm. -2 The electrochemical test was carried out by applying a current density of 1000 kJ / cm. The nominal area of ​​the two electrodes was 25 cm. 2 This resulted in a total applied current of 250 mA during the charge phase and -250 mA during the discharge phase. Figure 34 shows a classic graph of the charge and discharge cycles of this RFB. The relative cycle current efficiency is also reported in Figure 35.

[0158] Example 19 Zn-polysulfide RFB with tailored electrolyte The electrolytes prepared in Examples 1 and 7 were used to fabricate a Zn-polysulfide RFB having the same structure as the battery in Example 18. This RFB was supplied with 10 mAcm by a pumping system using a BioLogic VMP-300 potentiostat / galvanostat. -2 The electrochemical test was carried out by applying a current density of 1000 kJ / cm. The nominal area of ​​the two electrodes was 25 cm. 2 This resulted in a total applied current of 250 mA during the charge phase and -250 mA during the discharge phase. Figure 36 shows a classic graph of the charge and discharge cycle of this RFB.

[0159] Example 20 Zn-polysulfide RFB with tailored electrolyte Using the electrolytes prepared in Examples 4 and 6, a Zn-polysulfide RFB having the same structure as the battery in Example 18 was fabricated. This RFB was supplied with 10 mAcm by a pumping system using a BioLogic VMP-300 potentiostat / galvanostat. -2 The electrochemical test was carried out by applying a current density of 1000 kJ / cm. The nominal area of ​​the two electrodes was 25 cm. 2 This resulted in a total applied current of 250 mA during the charge phase and -250 mA during the discharge phase. Figure 37 shows a classic graph of the charge and discharge cycle of this RFB.

[0160] Example 21 Zn-polysulfide RFB with tailored electrolyte The electrolytes prepared in Examples 3 and 7 were used to fabricate a Zn-polysulfide RFB having the same structure as the battery in Example 18. This RFB was supplied with 10 mAcm by a pumping system using a BioLogic VMP-300 potentiostat / galvanostat. -2 The electrochemical test was carried out by applying a current density of 1000 kJ / cm. The nominal area of ​​the two electrodes was 25 cm. 2 This resulted in a total applied current of 250 mA during the charge phase and -250 mA during the discharge phase. Figure 38 shows a classic graph of the charge and discharge cycle of this RFB.

[0161] Example 22 Zn-polysulfide RFB with tailored electrolyte Using the electrolytes prepared in Examples 2 and 6, a Zn-polysulfide RFB was fabricated with a structure obtained by combining the first half-cell of FIG. 3 with the second half-cell of FIG. 8. The catalyst for the catholyte half-cell was obtained according to Example 11. This RFB was supplied with 10 mAcm by a pumping system using a BioLogic VMP-300 potentiostat / galvanostat. -2 The electrochemical test was carried out by applying a current density of 1000 kJ / cm. The nominal area of ​​the two electrodes was 25 cm. 2 This resulted in a total applied current of 250 mA during the charge phase and -250 mA during the discharge phase. Figure 39 shows a classic graph of the charge and discharge cycles of this RFB. The volumetric capacity of a battery using the same electrolyte is shown in Figure 40.

Claims

1. Zn ２＋ A first half-cell (110; 310; 410; 510; 610; 710) comprising a first electrolyte (114; 314; 414; 514; 614; 714) containing an ion source and a static electrode (112) or a flowing electrode disposed within the first half-cell, said first half-cell being connected in a closed-loop configuration through a first pump (116) to a first external tank (115) containing said first electrolyte, said first electrolyte being: a solvent selected from water and an aqueous mixture containing at least 40% by volume of water together with one or more compounds selected from C1-C4 alcohols, ethylene glycol, acetic acid, glycerin, or a combination of two or more thereof; one or more compounds selected from sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide, and bismuth hydroxide at a total concentration of 5 M to 20 M; a first half-cell further comprising: a second electrolyte (124; 721; 821; 921; 1021; 1121; 1221; 1321; 1421; 1521; 1621; 1721; 1821; 1921; 2021; 2121; 2221; 2321) having polysulfide dissolved therein and a static electrode (122; 622; 722; 822; 922; 1022; 1122; 1222; 1322; 1422; 1522; 1622; 1722; 1822; 1922; 2022) disposed within the second half-cell; 2122; 2222; 2322) or a second half-cell (120; 620; 720; 820; 920; 1020; 1120; 1220; 1320; 1420; 1520; 1620; 1720; 1820; 1920; 2020; 2120; 2220; 2320) comprising a flowable electrode, said second half-cell being connected in a closed loop configuration through a second pump (126) to a second external tank (125) containing said second electrolyte, said second electrolyte being a solvent selected from water and an aqueous mixture containing at least 40% by volume of water together with one or more compounds selected from C1-C4 alcohols, ethylene glycol, acetic acid, glycerin, or a combination of two or more thereof; one or more compounds selected from sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide and bismuth hydroxide in a total concentration of 0.01 M to 20 M; a polysulfide source selected from lithium sulfide, sodium sulfide, potassium sulfide, or a combination of two or more thereof; a second half-cell further comprising: In the second half-cell, a catalyst (623) in the form of particles (711; 911) on the surface of a static electrode (622) or dispersed in the second electrolyte; Separator (130; 160) between the two half-cells A zinc-polysulfide rechargeable flow battery (100) comprising:

2. The first electrolyte (114) is 0.001M to 1.5M Zn ２＋ 10. The zinc-polysulfide rechargeable flow battery of claim 1, comprising a zinc ion source selected from zinc oxide, zinc hydroxide, zinc acetate, zinc chloride, zinc carbonate, or combinations thereof, in an amount such that the zinc ion concentration is

3. The first electrolyte (314; 414; 514) is zinc-based and / or carbon-based conductive particles (311) selected from zinc particles, zinc oxide particles, zinc-coated particles, graphene, expanded graphite, reduced graphene oxide, activated carbon, carbon black, acetylene black, carbon nanotubes or combinations thereof in a total concentration of 0.01% to 20% by weight, and / or Organic and / or inorganic electroactive particles (411) containing zinc ions in different oxidation states in amounts ranging from 0.01% to 50% by weight.

3. The zinc-polysulfide rechargeable flow battery of claim 2, further comprising:

4. The first electrolyte (614, 714) comprises: organic and / or inorganic electroactive particles (411) containing zinc ions in different oxidation states in an amount ranging from 0.01% to 50% by weight as a zinc ion source; zinc-based and / or carbon-based conductive particles (311) selected from zinc particles, zinc oxide particles, zinc-coated particles, graphene, expanded graphite, reduced graphene oxide, activated carbon, carbon black, acetylene black, carbon nanotubes, or combinations thereof, in a total concentration of 0.01 wt. % to 20 wt. %; 10. The zinc-polysulfide rechargeable flow battery of claim 1, comprising:

5. The first electrolyte is a salt, oxide or hydroxide of one or more metals selected from Pb, Mn, Sn, Fe, Ni, Cu, Mg, Ti, Co, Al, Li, Zr in a concentration ranging from 0.001 M to 1 M, capable of changing the zinc electrochemical potential and increasing the overpotential for hydrogen evolution; a hydrogen generation inhibitor selected from silicates, boric acid, metals Pb, Bi, Mn, W, Cd, As, Sb, Sn and In, oxides of said metals or combinations thereof, in a total concentration ranging from 0.001 M to 5 M; Rochelle salt at a concentration of 0.001M to 10M, a leveling agent selected from polyethylene glycol, polyethyleneimine, thiourea, quaternary ammonium salts, dextrin, cyclodextrin, sucrose, polytetrafluoroethylene, sodium dodecyl sulfate, polyacrylic acid, glucose, cellulose, and combinations thereof, having a concentration of 0.0001 ppm to 10,000 ppm; a plasticizer additive selected from polyols, ethylene glycol, diethylene glycol, tetraethylene glycol, propylene glycol, glycerin, mannitol, sorbitol, xylitol, monosaccharides, fatty acids, urea, ethanolamine, triethanolamine, vegetable oils, lecithin, waxes, amino acids, surfactants, and oleic acid in the range of 0.1% to 5% by weight of the first electrolyte; a thickener additive in the range of 0.0001% to 10% by weight of the first electrolyte; and an organic additive selected from xanthan gum, gum arabic, carboxymethyl cellulose, chitosan, agar, sodium alginate, and polyethylene oxide in an amount of 0.0001% to 10% by weight of the first electrolyte; The zinc-polysulfide rechargeable flow battery of any one of claims 1 to 4, further comprising one or more of:

6. The second electrolyte (124) comprises: S from 0.01M to 20M ２－ the polysulfide source in an amount such that the total concentration of ions is A ２ S ４ a stoichiometric amount of elemental sulfur S to form a chain (wherein A is Li, Na, K or a combination thereof); 10. The zinc-polysulfide rechargeable flow battery of claim 1, comprising:

7. The second electrolyte (721; 821; 921; 1721; 1821; 1921; 2021; 2121; 2221; 2321) is Catalyst particles (711) in an amount of 0.001% to 10% by weight of said second electrolyte; Conductive particles (811) selected from graphene, expanded graphite, reduced graphene oxide, activated carbon, carbon black, acetylene black, carbon nanotubes, or a combination of two or more thereof, in a total concentration of 0.01% to 20% by weight of the second electrolyte; Conductive particles modified by catalyst particles (911), wherein the conductive particles are selected from graphene, expanded graphite, reduced graphene oxide, activated carbon, carbon black, acetylene black, carbon nanotubes, or a combination of two or more thereof, and the conductive particles modified by the catalyst particles are present in a concentration of 0.01% to 20% by weight of the second electrolyte; organic and / or inorganic sulfide-based electroactive particles (1011) containing sulfide ions in different oxidation states in an amount ranging from 0.01% to 50% by weight of said second electrolyte; and Organic and / or inorganic sulfide-based electroactive particles containing sulfide ions in an amount of 0.01% to 50% by weight of said second electrolyte and modified with catalytic particles (1311).

7. The zinc-polysulfide rechargeable flow battery of claim 6, further comprising at least one of:

8. 10. The zinc-polysulfide rechargeable flow battery of claim 1, wherein the second electrolyte (1021) comprises organic and / or inorganic sulfide-based electroactive particles (1011) containing sulfide ions that function as a source of polysulfide ions in an amount ranging from 0.01% to 50% by weight.

9. 10. The zinc-polysulfide rechargeable flow battery of claim 1, wherein the second electrolyte (1321) contains sulfide ions in an amount between 0.01% and 50% by weight of the second electrolyte and comprises organic and / or inorganic sulfide-based electroactive particles (1311) modified with catalytic particles.

10. The second electrolyte (1121; 1221; 1421; 1521; 1621) is Catalyst particles (711) in an amount of 0.001% to 10% by weight of said second electrolyte; Conductive particles (811) selected from graphene, expanded graphite, reduced graphene oxide, activated carbon, carbon black, acetylene black, carbon nanotubes, or a combination of two or more thereof, in a total concentration of 0.01% to 20% by weight of the second electrolyte; Conductive particles (911) modified by catalyst particles, wherein the conductive particles are selected from graphene, expanded graphite, reduced graphene oxide, activated carbon, carbon black, acetylene black, carbon nanotubes, or a combination of two or more thereof, and the conductive particles modified by catalyst particles are present in a concentration of 0.01% to 20% by weight of the second electrolyte.

10. The zinc-polysulfide rechargeable flow battery of claim 8 or 9, further comprising at least one of:

11. The catalyst, which is in the form of particles on the surface of the static electrode or dispersed in the second electrolyte, a metal selected from the group consisting of Mo, Zr, Ti, Ni, In, Pb, Zn, Fe, Co, Cu, Mn, Cd, Bi, Al, Ga, Cr, W, Nb, Au, Ag, Pt, Ru, Ir, Pd; an alloy of said metals; an intermetallic compound of said metal, and Chemical compounds of said metals The zinc-polysulfide rechargeable flow battery of any one of claims 1 to 10, wherein the zinc-polysulfide rechargeable flow battery is selected from the group consisting of:

12. The zinc-polysulfide rechargeable flow battery of claim 11, wherein said chemical compound of said metal is selected from oxides, mixed oxides, chalcogenides, mixed chalcogenides, nitrides, oxynitrides and carbonitrides of said metals and carbon-based compounds of non-noble metals.

13. The chemical compounds of the metals are CoOOH, Co(OH) ２ , Co ３ O ４ , CoO, CoO ２ , Co ３ S ４ , Co ９ S ８ , CoS ２ , CoSe, CoSe ２ , Co ３ Se ４ , Co ９ Se ８ , NiSe, NiSe ２ , Ni ３ Se ４ , Ni ９ Se ８ , MoSe ２ , Bi ２ S ３ , W.S. ２ , WSe ２ , CuO, Cu ３ Se ２ , Co ２ CuS ４ , CoCUS ４ , CoNiOOH, CoFeOOH, NiCo ２ O ４ , Co ５ NiS ８ , Co ２ NiS ４ , Co ２ NiSe ４ , CoNiSe ４ 13. The zinc-polysulfide rechargeable flow battery of claim 12, wherein the zinc-polysulfide rechargeable flow battery is selected from the group consisting of:

14. The second electrolyte is a plasticizer additive selected from polyols, ethylene glycol, diethylene glycol, tetraethylene glycol, propylene glycol, glycerin, mannitol, sorbitol, xylitol, monosaccharides, fatty acids, urea, ethanolamine, triethanolamine, vegetable oils, lecithin, waxes, amino acids, surfactants, and oleic acid in the range of 0.1% to 5% by weight of the second electrolyte; a thickener additive in the range of 0.0001% to 10% by weight of the first electrolyte; and an organic additive selected from xanthan gum, gum arabic, carboxymethyl cellulose, chitosan, agar, sodium alginate, and polyethylene oxide in an amount of 0.0001% to 10% by weight of the first electrolyte; The zinc-polysulfide rechargeable flow battery of any one of claims 1 to 13, further comprising one or more of:

15. The separator is a separator (130) of uniform composition selected from the group consisting of a porous separator containing no active ion exchange material, an ion-selective porous membrane, a solid-state ceramic separator or a glass-ceramic separator, a Na-ion sulfide-based glass, a Li-ion sulfide-based glass, or a membrane made of a copolymer of perfluorosulfonic acid and polytetrafluoroethylene; A multilayer separator (160) comprising a first homogeneous layer (161) bonded to at least a second layer (162), said second layer being made of one of polyvinyl alcohol (PVA), chitosan, polyacrylic acid (PAA), gelatin, and a copolymer of perfluorosulfonic acid and polytetrafluoroethylene, said second layer containing ionic particles and / or carbon-based conductive particles. The zinc-polysulfide rechargeable flow battery of any one of claims 1 to 14, wherein the zinc-polysulfide rechargeable flow battery is selected from the group consisting of:

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