阅读说明：本技术 用于氧化还原液流电池组的阴离子交换膜 (Anion exchange membranes for redox flow batteries ) 是由 G·Y·顾 萨瓦斯·哈德吉基里亚库 西蒙·保罗·杜克斯 迈克尔·J·肖 于 2018-12-13 设计创作，主要内容包括：公开了一种具有至少一个可再充电电池的液流电池组。该至少一个可再充电电池可以包括阳极电解液隔室、阴极电解液隔室和被定位在阳极电解液隔室和阴极电解液隔室之间的阴离子交换膜。阴离子交换膜可以具有小于100μm的厚度和关于可再充电电池的电解质中的阳离子物质的小于0.4ppm/h/cm<Sup>2</Sup>的稳态扩散率。还公开了一种促进液流电池组的使用的方法,该方法包括提供阴离子交换膜。还公开了一种促进电荷的储存的方法,该方法包括提供液流电池组。还公开了一种生产阴离子交换膜的方法。(A flow battery having at least one rechargeable battery is disclosed. The at least one rechargeable battery may include an anolyte compartment, a catholyte compartment, and an anion exchange membrane positioned between the anolyte compartment and the catholyte compartment. The anion exchange membrane may have a thickness of less than 100 μm and electrolysis with respect to a rechargeable batteryLess than 0.4ppm/h/cm of cationic species in the biomass 2 Steady state diffusivity of. Also disclosed is a method of facilitating use of a flow battery, the method comprising providing an anion exchange membrane. Also disclosed is a method of facilitating storage of an electrical charge, the method comprising providing a flow battery. A method of producing an anion exchange membrane is also disclosed.)

1. A flow battery comprising:

at least one rechargeable battery comprising

An anolyte compartment configured to hold a first electrolyte having a first cationic species;

a catholyte compartment configured to hold a second electrolyte having a second cationic species; and

an anion exchange membrane positioned between the anolyte compartment and the catholyte compartment configured to be ionically conductive between the first electrolyte and the second electrolyte, the anion exchange membraneThe membrane has a thickness of less than 100 μm and less than 0.4ppm/h/cm with respect to at least one of the first and second cationic species²Steady state diffusivity of.

2. The flow battery of claim 1, wherein at least one of the first cationic species and the second cationic species is a metal ion.

3. The flow battery of claim 2, wherein at least one of the first cationic species and the second cationic species is selected from the group consisting of zinc, copper, cerium, and vanadium.

4. The flow battery of claim 3, wherein the anion exchange membrane has a service life of at least about 12 weeks as determined when the internal potential drop is at least about 2.5V.

5. The flow battery of claim 1, wherein the anion exchange membrane has a thickness of less than about 55 μ ι η.

6. The flow battery of claim 5, wherein the anion exchange membrane has a thickness between about 15 μm and about 35 μm.

7. The flow battery of claim 6, wherein the anion exchange membrane has a thickness of about 25 μm.

8. The flow battery of claim 7, wherein the anion exchange membrane has less than 0.12ppm/h/cm relative to at least one of the first cationic species and the second cationic species²Steady state diffusivity of.

9. The flow battery of claim 1, wherein the anion exchange membrane has a ph of about 3.0 Ω -cm when measured on direct current after equilibration in 0.5M NaCl solution at 25 ℃²And about 10.0 omega-cm²The resistance in between.

10. The flow battery of claim 9, wherein the anion exchange membrane has a ph of about 5.0 Ω -cm when measured on direct current after equilibration in 0.5M NaCl solution at 25 ℃²And about 8.0 ohm-cm²The resistance in between.

11. The flow battery of claim 10, wherein the anion exchange membrane has a co-ion transport number for at least one non-redox species of at least about 0.95.

12. The flow battery of claim 1, configured to be compatible with High Voltage Direct Current (HVDC) transmission lines and provide a voltage between about 1000V and about 800 KV.

13. The flow battery of claim 1, configured to be compatible with a vehicle and provide a voltage between about 100V and about 500V.

14. A method of facilitating use of a flow battery, comprising:

providing at least one anion exchange membrane having a thickness of less than 100 μm and less than 0.4ppm/h/cm with respect to at least one of the first and second metal cation species²Steady state diffusivity of; and

instructions are provided to install each anion exchange membrane in a rechargeable cell of the flow battery between an anolyte compartment and a catholyte compartment.

15. The method of claim 14, wherein providing the anion exchange membrane comprises providing an anion exchange membrane having a thickness between about 15 μ ι η and about 35 μ ι η.

16. The method of claim 15, wherein providing the anion exchange membrane comprises providing a membrane having a pore sizeLess than 0.12ppm/h/cm of at least one of the first metal cation species and the second metal cation species²The first metal cation species and the second metal cation species are independently selected from the group consisting of zinc, copper, cerium, and vanadium.

17. The method of claim 16, further comprising providing instructions to charge the flow battery and continuously operate the flow battery.

18. A method of facilitating storage of a charge, comprising:

providing a flow battery comprising a plurality of rechargeable batteries, each rechargeable battery comprising:

an anolyte compartment configured to hold a first electrolyte having a first cationic species;

a catholyte compartment configured to hold a second electrolyte having a second cationic species; and

an anion exchange membrane positioned between the anolyte compartment and the catholyte compartment configured to be ionically conductive between the first electrolyte and the second electrolyte, the anion exchange membrane having a thickness of less than 100 μm and less than 0.4ppm/h/cm for at least one of the first cationic species and the second cationic species²Steady state diffusivity of; and

providing instructions to charge the flow battery.

19. The method of claim 18, further comprising providing instructions to charge the flow battery by electrically connecting the flow battery to a variable energy supply.

20. The method of claim 18, further comprising providing instructions to electrically connect the flow battery pack to a High Voltage Direct Current (HVDC) transmission line.

21. The method of claim 20, further comprising providing instructions to replace at least one of the first electrolyte and the second electrolyte after discharge of the flow battery.

22. A method of producing an anion exchange membrane comprising:

incorporating a cationic functional monomer having a crosslinking group into a polymerization product substantially free of a crosslinking agent; and

coating a microporous substrate having a thickness of less than about 100 μm with the polymerized product.

23. The method of claim 22, wherein the microporous substrate has a thickness of about 25 μ ι η.

24. The method of claim 25, wherein the microporous substrate comprises at least one of polypropylene, high molecular weight polyethylene, ultra high molecular weight polyethylene, polyvinyl chloride, polyvinylidene fluoride, polysulfone, and combinations thereof.

25. The method of claim 24, wherein the microporous substrate has a porosity of between about 25% and about 45% and an average pore size of between about 50nm and about 10 μ ι η.

26. The method of claim 25, wherein the microporous substrate comprises ultra-high molecular weight polyethylene having a porosity of about 35% and an average pore diameter of about 200 nm.

Technical Field

Aspects and embodiments disclosed herein relate generally to redox flow batteries (redox flow batteries), and more particularly, to anion exchange membranes for redox flow batteries.

SUMMARY

According to one aspect, a flow battery is provided. The flow battery pack may include at least one rechargeable cell. The at least one rechargeable battery may include an anolyte compartment (anolyte), a catholyte compartment (catholyte compartment), and a separator positioned between the anolyte compartment and the catholyte compartmentThe anion exchange membrane of (1). The anolyte compartment may be configured to contain a first electrolyte having a first cationic species (first cation species). The catholyte compartment may be configured to hold a second electrolyte having a second cationic species. The anion exchange membrane may be configured to be ionically conductive between the first electrolyte and the second electrolyte. The anion exchange membrane may have a thickness of less than 100 μm and less than 0.4ppm/h/cm with respect to at least one of the first cationic species and the second cationic species²Steady state diffusion rate (steady state diffusion).

In some embodiments, at least one of the first cationic species and the second cationic species is a metal ion. At least one of the first and second cationic species may be selected from zinc, copper, cerium, and vanadium.

The anion exchange membrane can have a service life of at least about 12 weeks, as determined when the internal potential drop is at least about 2.5V.

The anion exchange membrane can have a thickness of less than about 55 μm. In some embodiments, the anion exchange membrane can have a thickness between about 15 μm and about 35 μm. For example, the anion exchange membrane may have a thickness of about 25 μm.

In some embodiments, the anion exchange membrane can have less than 0.12ppm/h/cm with respect to at least one of the first cationic species and the second cationic species²Steady state diffusivity of.

The anion exchange membrane may have a concentration of about 3.0 Ω -cm when measured by direct current after equilibration in 0.5M NaCl solution at 25 ℃²And about 10.0 ohm-cm²The resistance in between. The anion exchange membrane may have a concentration of about 5.0 Ω -cm when measured by direct current after equilibration in 0.5M NaCl solution at 25 ℃²And about 8.0 ohm-cm²The resistance in between. In some embodiments, the anion exchange membrane can have a co-ion transport number (co-ion transport number) of at least about 0.95 for at least one non-redox species.

The flow battery pack may be configured to be compatible with High Voltage Direct Current (HVDC) transmission lines and provide a voltage between about 1000V and about 800 KV.

The flow battery pack can be configured to be compatible with a vehicle and provide a voltage between about 100V and about 500V.

According to another aspect, a method of facilitating use of a flow battery is provided. The method can include providing at least one anion exchange membrane and providing instructions to install each anion exchange membrane in a rechargeable battery of a flow battery. The anion exchange membrane may have a thickness of less than 100 μm and less than 0.4ppm/h/cm with respect to at least one of the first metal cation species and the second metal cation species²Steady state diffusivity of. Each anion exchange membrane may be mounted between the anolyte compartment and the catholyte compartment.

According to certain embodiments, providing an anion exchange membrane may comprise providing an anion exchange membrane having a thickness between about 15 μm and about 35 μm.

According to certain embodiments, providing an anion exchange membrane may comprise providing a membrane having less than 0.12ppm/h/cm with respect to at least one of the first metal cation species and the second metal cation species²The first metal cation species and the second metal cation species are independently selected from the group consisting of zinc, copper, cerium, and vanadium.

The method can also include providing instructions to charge the flow battery and continuously operate the flow battery.

According to another aspect, a method of facilitating storage of a charge is provided. The method can include providing a flow battery and providing instructions to charge the flow battery. The flow battery may include a plurality of rechargeable batteries. Each cell may include an anolyte compartment, a catholyte compartment, and an anion exchange membrane positioned between the anolyte compartment and the catholyte compartment. The anolyte compartment may be configured to contain a first electrolyte having a first cationic species. The catholyte compartment may be configured to hold a second electrolyte having a second cationic species. The anion exchange membrane can be configured to be at a first powerThe electrolyte and the second electrolyte are ionically conductive. The anion exchange membrane may have a thickness of less than 100 μm and less than 0.4ppm/h/cm with respect to at least one of the first cationic species and the second cationic species²Steady state diffusivity of.

The method can further include providing instructions to charge the flow battery by electrically connecting the flow battery to a variable energy supply (variable energy supply).

The method may further include providing instructions to electrically connect the flow battery pack to a High Voltage Direct Current (HVDC) transmission line.

In some embodiments, the method may further include providing instructions to replace at least one of the first electrolyte and the second electrolyte after discharge of the flow battery.

According to another aspect, a method of producing an anion exchange membrane is provided. The method may include integrating a cationic functional monomer having a crosslinking group into a polymerization product and coating a microporous substrate having a thickness of less than about 100 μm with the polymerization product. In some embodiments, the polymerization product may be substantially free of crosslinking agents.

According to certain embodiments, the microporous substrate may have a thickness of about 25 μm. The microporous substrate may include at least one of polypropylene, high molecular weight polyethylene, ultra high molecular weight polyethylene, polyvinyl chloride, polyvinylidene fluoride, polysulfone, and combinations thereof. The microporous substrate may have a porosity between about 25% and about 45% and an average pore size between about 50nm and about 10 μm. The microporous substrate may comprise ultra-high molecular weight polyethylene having a porosity of about 35% and an average pore diameter of about 200 nm.

The present disclosure contemplates all combinations of any one or more of the foregoing aspects and/or embodiments, as well as combinations with any one or more embodiments and any examples set forth in the detailed description.

Brief Description of Drawings

The drawings are not intended to be drawn to scale. In the drawings, each identical or nearly identical component that is illustrated in various figures is represented by a like numeral. For purposes of clarity, not every component may be labeled in every drawing. In the drawings:

fig. 1 is a schematic diagram of a rechargeable flow battery according to one embodiment;

fig. 2 is a schematic diagram of a flow battery according to one embodiment;

fig. 3 is a schematic diagram of a zinc-copper redox flow battery according to an embodiment;

FIG. 4 is a schematic diagram of a film production line according to one embodiment; and

figure 5 is a graph of copper diffusion over time for several sample ion exchange membranes.

Detailed Description

Flow batteries are a class of electrochemical cells. In a typical flow battery, chemical energy may be provided by two liquid electrolytes contained in respective chambers and separated by an ion exchange membrane. The flow of electrical current and the corresponding ion exchange can take place through an ion exchange membrane, while both liquid electrolytes are circulated through their chambers. Generally, the energy capacity (energy capacity) of a flow battery is a function of the volume of the liquid electrolyte, and the power is a function of the surface area of the electrodes.

The flow battery can be operated in two modes. In the first mode, similar to a fuel cell, used electrolyte may be extracted and new electrolyte added to the system. The spent electrolyte may be regenerated by a chemical process for further use. In the second mode, an electrical power source (electric power source) may be connected to the flow battery for regeneration of the electrolyte, similar to a rechargeable battery.

According to one aspect, a flow battery is provided. The flow battery may include at least one rechargeable battery. In some embodiments, the flow battery pack can include a plurality of rechargeable batteries, for example, within a housing. A rechargeable battery may generally include an anolyte compartment, a catholyte compartment, and an ion exchange membrane positioned between the anolyte compartment and the catholyte compartment. The additional electrolyte may be stored externally, for example, in a tank. The additional electrolyte may be pumped through the anolyte compartment or the catholyte compartment of the one or more rechargeable batteries. In some embodiments, the additional electrolyte may be transferred via a gravity feed system.

Fig. 1 is a schematic diagram of an exemplary rechargeable flow battery. The exemplary rechargeable flow battery 100 can include an anolyte compartment 120 and a catholyte compartment 122. The anolyte compartment 120 and the catholyte compartment 122 may be separated by the ion exchange membrane 110. The arrows show the direction of electrolyte flow through the flow battery 100. Flow battery 100 can also include electrodes 160, 162. In some embodiments, flow battery 100 may include a bipolar electrode positioned between adjacent anolyte compartment 120 and catholyte compartment 122.

Fig. 2 is a schematic diagram of an exemplary flow battery 150 that includes a rechargeable flow battery 100. Although only one rechargeable flow battery 100 is shown in fig. 2, it should be understood that multiple flow batteries 100 can typically be included in the flow battery pack 150. The anolyte compartment 120 and the catholyte compartment 122 of the flow battery 100 may be fluidly connected to an external anolyte tank 130 and catholyte tank 132, respectively. The flow battery 150 may include pumps 140, 142 to circulate the electrolyte. The flow battery pack 150 can be electrically connected to a charging source 152. As shown in fig. 2, the electrodes 160, 162 are electrically connected to the charging source 152.

Redox Flow Batteries (RFBs) operate by storing energy in two different electrolytes, which are typically aqueous in nature. The amount of energy stored may depend on the volume of both electrolytes. The RFB can be designed to store a specific amount of energy by selecting the electrolyte volume. Such techniques may be used to store energy from renewable sources operating intermittently. Another possible application for RFB is in electric vehicles. Their use may address one of the drawbacks of battery powered vehicles (battery-powered vehicles) -the time it takes to recharge batteries by allowing for rapid replacement of used electrolyte in lieu of recharging.

A typical recharge process may take several hours to fully charge the battery pack. With RFB, the electrolyte can be quickly changed off the vehicle. The discharged electrolyte may be removed and replaced with a fully charged electrolyte. Furthermore, because the electrolyte is typically in a liquid state, RFB vehicles can be "refueled" in the same amount of time as is required to refuel a conventional gasoline powered vehicle. Once the electrolyte is removed and replaced, the discharged electrolyte may be recharged or regenerated outside the vehicle and used again at a later time.

In any of the foregoing RFB applications, an ion exchange membrane may be required for the electrochemical cell. In certain RFB applications, an anion exchange membrane may be required. The anion exchange membranes described herein are well suited for RFB applications and are not limited to any particular type or application of RFB technology.

RFBs use oxidation-reduction reactions to charge and discharge batteries. During charge and discharge cycles of a flow battery, RFBs are typically operated in a single electrode compartment based on redox couples (reductant and oxidant) functioning as "rocking chairs". The ion exchange membrane may be positioned to separate the anolyte and the catholyte. The ion exchange membrane may be selected to prevent the release of energy through a chemical reaction between the oxidant and the reductant, ensuring that electrical energy is delivered to an external load. Exemplary RFBs use zinc and cerium. Examples of charge and discharge electrochemical reactions are shown below:

anodic reactionE⁰＝-0.763V

Cathode reactionE⁰＝1.44V

In this exemplary RFB, the total potential of the stack is 2.203 volts. Such RFB includes a material containing zinc ion (Zn)^{2 +}) And an anolyte ofContaining cerium ions (Ce)⁴⁺) The catholyte solution of (1).

Alternative examples of charge and discharge electrochemical reactions are shown below:

cathode reactionE⁰＝-0.763V

Anodic reactionE⁰＝0.340V

In this exemplary RFB, the total potential of the stack is 1.103 volts. Such RFB includes a material containing zinc ion (Zn)^{2 +}) And a catholyte solution containing copper ions (Cu)²⁺) The anolyte of (1). Fig. 3 is a schematic of a zinc-copper RFB under charging operating conditions. An exemplary RFB is charged by a DC charging source and includes a zinc catholyte external tank and a copper anolyte external tank. The tanks are fluidly connected to respective compartments positioned on opposite sides of the anion exchange membrane.

According to certain embodiments, one or more rechargeable batteries disclosed herein may include a first electrolyte and a second electrolyte. Each of the first electrolyte and the second electrolyte may include a cation. Cations generally refer to the redox species required for electrode reactions in a flow battery. Each electrolyte may contain a redox species as well as a non-redox species. Thus, the anolyte compartment may be configured to hold a first electrolyte having a first cationic species, while the catholyte compartment may be configured to hold a second electrolyte having a second cationic species. In some embodiments, at least one of the cationic species is a metal ion. For example, at least one of the cationic species may be selected from zinc, copper, cerium and vanadium.

The cationic species may be the same or different. In certain non-limiting exemplary embodiments, the rechargeable battery may include zinc-cerium, zinc-copper, zinc-zinc, or vanadium-vanadium. The same applies to the anolyte and catholyteIn the case of the cationic species of (3), the cationic species may have different ionic states. For example, a zinc flow battery can include Zn⁰Or Zn²⁺. The vanadium flow battery can include V²⁺、V³⁺、V⁴⁺And/or V⁵⁺. Other cations that may be used include bromine, nickel, iron, and cyanide (e.g., ferricyanide).

The exemplary zinc-cerium RFBs described above may generally include an anion membrane to allow transfer of anions from the anode compartment to the cathode compartment during discharge and from the cathode compartment to the anode compartment during charge. According to certain embodiments, the rechargeable battery disclosed herein may include an anion exchange membrane positioned between the anolyte compartment and the catholyte compartment. The anion exchange membrane may be configured to be ionically conductive between the electrolytes. In use, the anion exchange membrane may be ionically conductive between the electrolytes. In general, anion exchange membranes can be ionically conductive between ions that do not participate in electrode reactions.

Anion exchange membranes are generally capable of transporting anions under an electrical potential. Anion exchange membranes may have a fixed positive charge and a mobile anion (anion). The properties of the ion-exchange membrane can be controlled by the amount, type and distribution of the immobilized ionic groups in the membrane. For example, quaternary ammonium and tertiary amine functional groups can produce fixed positively charged groups in strong and weak base anion exchange membranes. Bipolar membranes may comprise a cation exchange membrane and an anion exchange membrane laminated or bonded together, sometimes with a thin neutral layer between them.

A Polymer Electrolyte Membrane (PEM) is an ion exchange membrane that functions both as an electrolyte and as a separator for the anolyte and catholyte. The anionic PEM may contain positively charged groups, such as sulfonic acid groups and/or amine groups, attached to or as part of the polymer from which the PEM is made. In use, protons or positive ions can generally move through the membrane by transferring from one fixed positive charge to another to penetrate the membrane.

When selecting a membrane, the parameters typically include sufficient chemical, thermal, electrochemical and mechanical stability. Sufficient mechanical stability and strength upon swelling and under mechanical stress may also be considered. Other parameters may include low resistance, low or preferably no migration of electrolyte species, and low cost. The development of ion exchange membranes may include balancing some or all of these properties to overcome competing effects. The ion exchange membrane may be selected to satisfy certain characteristics, including (1) low electrical resistance to reduce potential drop during operation and improve energy efficiency; (2) high co-ion transport numbers, e.g., high permeability to counterions but approximately impermeable to co-ions; (3) high chemical stability, including the ability to withstand any pH and oxidizing chemicals from 0 to 14; (4) high mechanical strength to withstand the stresses handled when being manufactured into modules or other processing devices (processing devices); and (5) good dimensional stability in operation, e.g., sufficient resistance to swelling or shrinkage when the fluid in contact changes concentration or temperature.

According to certain non-limiting embodiments, the anionic membrane for the RFB can be selected to have chemical stability with respect to the battery electrolyte for many cycles, to have high conductivity to minimize voltage drop during discharge cycles (including at high amperage operation), and to have excellent selectivity to prevent co-ion migration and maintain the RFB at high efficiency over its lifetime.

The inventors have recognized that for a given ion exchange membrane, a thinner membrane can generally provide lower electrical resistance and also allow more membrane area per unit volume of the device. However, thinner membranes are generally more susceptible to dimensional changes from environmental effects, such as changes in the ion concentration or operating temperature of the fluid in contact. In general, thinner films may be more difficult to develop and produce without defects because there may be a smaller margin of error during production than thicker films in which the thickness may cover the defects that occurred during formation.

By making the utensilThe polymerization of cationic functional monomers having crosslinking groups can produce thin anion exchange membranes with low electrical resistance, low diffusivity, high co-ion transport number, and good chemical stability. As described herein, a composite ion exchange membrane comprising a microporous membrane substrate saturated with a crosslinked polymer having charged ionic groups was developed. The anion exchange membranes disclosed herein can have a thickness of less than 100 μm, at about 5.0 Ω -cm when used²And about 8.0 ohm-cm²And provides less than 0.4ppm/h/cm with respect to at least one cationic species²Steady state diffusivity of. The properties of the ion exchange membranes described herein may generally allow the membranes to operate at low electrical resistance (high conductance to non-redox species) without sacrificing membrane integrity. While the present disclosure generally contemplates anion exchange membranes, it is understood that similar processes can be performed to produce cation exchange membranes. I.e. wherein the ionomer comprises the relevant functional groups.

International application publication No. WO/2011/025867, which is incorporated herein by reference in its entirety, describes a method of producing an ion exchange membrane comprising combining one or more monofunctional ionizable monomers (ionogenic monomers) with at least one multifunctional crosslinking monomer, and polymerizing the monomers in the pores of a porous substrate.

According to one aspect, there is provided a method of producing an ion exchange membrane as described herein. The present disclosure generally describes chemistries and materials for producing exemplary ion exchange membranes. To produce a crosslinked membrane, the micropores of the substrate may be saturated with the polymerization product comprising the crosslinking functional monomer, followed by polymerizing the monomer in the micropores.

The monomer may comprise a functional group and a crosslinking group. As used herein, the term crosslinking group may refer to a monomeric substituent or monomeric moiety having a polymerization reactive site, which may form a network polymer or a crosslinked polymer. The term ionic functional group may refer to a monomeric substituent or monomeric moiety having a covalently attached charged group. The charged groups may be positively or negatively charged. The monomers described herein may generally comprise at least one functional group and at least one crosslinking group. According to certain embodiments, the molecules described herein may comprise a hydrocarbyl structure.

The functional crosslinking monomer can provide stability to the membrane. The stability and relative tightness of the membrane generally depend on the degree of crosslinking with the same monomer. Stability also depends on the miscibility between the functional group and the crosslinking group. When the two groups are immiscible, a solvent may be added to produce the polymerization solution, typically due to the hydrophobicity and hydrophilicity of each of the crosslinking group and the ionic group. During thermal polymerization, volatile solvents may evaporate, which changes the distribution of the monomers in solution. Solvents may also change the reactivity of these two groups due to solvation effects. The result is generally the formation of block copolymers, rather than a uniform distribution of monomers.

If the functional monomer itself is not crosslinked, the functional group may risk detachment from the polymer network. When each functional group is crosslinked, hydrolysis of the ester group only reduces the degree of crosslinking, which may reduce the degradation rate of the film. Thus, as provided by the functional crosslinking monomers disclosed herein, the monomers can become fully crosslinked and the functional groups can be covalently attached to the polymer backbone of the membrane. Degradation of the membrane may be reduced, resulting in increased chemical stability and significantly extended lifetime in the electrolyte solution. Further, due to the crosslinking group, the polymerization product may be substantially free of a crosslinking agent.

In certain non-limiting embodiments, the method can include integrating a cationic functional monomer having a crosslinking group into the polymerization product and coating a microporous substrate having a thickness of less than about 100 μm with the polymerization product. The polymerization product may be substantially free of crosslinking agents. The polymerization product may include a solvent. The polymerization product may include a polymerization initiator.

The functional group may include a positively charged amine group, such as a quaternary ammonium group. The tertiary amine groups may be quaternized with a quaternizing chemical (quaternizing chemical). The quaternary ammonium functionality can be strongly basic and ionized to function in the pH range of 0 to 14, which allows for a wide operating range.

The crosslinking group can produce a film with a high crosslinking density without the addition of an external crosslinking agent. The crosslinking monomer may have at least one polymerization reaction site. In some embodiments, the crosslinking monomer may have more than one polymerization site. In some embodiments, the polymer is 100% crosslinked.

The cationic functional monomer may be copolymerized with at least one second functional monomer. The second functional monomer may be configured or selected to alter the ion exchange capacity without crosslinking. The second functional monomer may be selected from the group including, but not limited to: vinylbenzyltrimethylammonium chloride, ethyltrimethylammonium methacrylate chloride (trimethylammonium chloride), methacrylamidopropyltrimethylammonium chloride, (3-acrylamidopropyl) trimethylammonium chloride, 2-and 4-vinylpyridines, and one or more polymerization initiators.

In some embodiments, the non-functional second monomer may be selected from the group including, but not limited to, styrene, vinyltoluene, 4-methylstyrene, t-butylstyrene, α -methylstyrene, methacrylic anhydride, methacrylic acid, n-vinyl-2-pyrrolidone, vinyltrimethoxysilane, vinyltriethoxysilane, vinyl-tris- (2-methoxyethoxy) silane, vinylidene chloride, vinylidene fluoride, vinylmethyldimethoxysilane, 2, 2-trifluoroethylamine, vinylpyridine, allyl anhydride, methyl methacrylate, ethyl methacrylate, or ethyl methacrylate.

In some embodiments, and for certain contemplated uses, a cross-linking agent may be incorporated. Such cross-linking agents may be selected from, for example, propylene glycol dimethacrylate, isobutylene glycol dimethacrylate, octavinylOctavinyldimethylsilyl groupVinyl radicalMixture, octavinyl groupTrisilanol ethyl(TrisilabolethylTrisilanol isobutyl esterTrisilanol isooctylOctadosilaneOctahydro groupEpoxy cyclohexyl-Clathrate mixture, glycidyl-Clathrate mixture, methacryloyl groupCage mixtures (methacryl)cagemixture) or acrylCage mixtures (Acrylo)cage texture), all of which are distributed by Hybrid Plastics (Hattiesburg, Mississippi).

The method may include coating the microporous substrate with the polymeric product. The polymerization product may include one or more solvents. Solvents that may be incorporated include 1-propanol and dipropylene glycol (dipropylene glycol). In some embodiments, a hydroxyl-containing solvent, such as an alcohol (e.g., isopropanol, butanol, a glycol such as various glycols, or a polyol such as glycerol) may be incorporated. In addition, aprotic solvents such as N-methylpyrrolidone and dimethylacetamide may be incorporated. These solvents are exemplary and additional or alternative solvents will be apparent to those of ordinary skill in the art.

The polymerization product may include a radical initiator such as Benzoyl Peroxide (BPO), ammonium persulfate, 2' -Azobisisobutyronitrile (AIBN), 2' -azobis (2-methylpropionamidine) dihydrochloride, 2' -azobis [2- (2-imidazolin-2-yl) propane ] and dimethyl 2,2' -azobis (2-methylpropionate) dimethyl 2,2' -azobis.

The microporous substrate may be selected to have sufficient mechanical stability, porosity, and thickness. According to certain embodiments, the microporous substrate may have a thickness of less than 100 μm, a porosity of between about 25% and about 45%, and an average pore diameter of between about 50nm and about 10 μm. The microporous substrate may include at least one of polypropylene, high molecular weight polyethylene, ultra high molecular weight polyethylene, polyvinyl chloride, polyvinylidene fluoride, polysulfone, and combinations thereof. These exemplary materials may typically have high mechanical stability at a thickness of 15 μm or more.

In general, the thickness of the microporous substrate can be as small as possible while providing sufficient mechanical stability to the anion exchange membrane. The thickness of the microporous membrane can be measured regardless of the depth of the pores. In some embodiments, the microporous substrate may have a thickness of less than about 155 μm. The microporous substrate may have a thickness of less than about 100 μm. The microporous substrate may have a thickness of less than about 75 μm. The microporous substrate may have a thickness of less than about 55 μm. According to certain embodiments, the microporous substrate may have a thickness of about 25 μm. The microporous substrate may have a thickness of about 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, or 45 μm.

The porosity may be selected such that a sufficient coating on the substrate can be achieved while maintaining sufficient mechanical stability. Thus, the porosity may be selected based on the coating composition, the substrate material, and/or the substrate thickness. Porosity, expressed as a percentage, may refer to the volume of pores relative to the total volume of the substrate. In some embodiments, the microporous membrane may have a porosity of between about 25% and about 45%. The microporous membrane may have a porosity between 20% and 40%. The microporous membrane may have a porosity of about 20%, about 25%, about 30%, about 35%, about 40%, or about 45%. In other embodiments, the porosity may be greater than about 45%. For example, the porosity may be greater than about 69%, or greater than about 70%. In a non-limiting exemplary embodiment, the substrate material may be ultra-high molecular weight polyethylene, the thickness of the substrate may be between about 15 μm and about 35 μm, and the porosity may be selected to be about 35%.

The porosity may also be selected to correspond to a selected average pore size, and vice versa. The average pore size may also be selected based on the coating composition and/or the substrate material. For example, the average pore size may be selected to enable a substantially uniform coating on the substrate. The average pore size may additionally or alternatively be selected to have an effect on membrane performance. The pore size of the membrane can change the resistance, diffusivity, ion transport number and compactness of the membrane structure. While not wishing to be bound by any particular theory, it is believed that selected membrane parameters (pore size, degree of crosslinking, ionic functionality and thickness, among others) together enable membrane performance.

In some embodiments, the average pore size may be in a range between about 50nm and about 10 μm. The average size may be from about 100nm to about 1.0 μm. The average pore size may be from about 100nm to about 200 nm. The average pore size may be about 100nm, about 125nm, about 150nm, about 175nm, about 200nm, about 225nm, or about 250 nm.

The microporous substrate material may be selected to have sufficient mechanical stability at a desired thickness and porosity. In some embodiments, the microporous substrate may include at least one of polypropylene, high molecular weight polyethylene, ultra high molecular weight polyethylene, polyvinyl chloride, polyvinylidene fluoride, polysulfone, and combinations thereof. These exemplary materials may typically have high mechanical stability at a thickness of 15 μm or more. Furthermore, exemplary materials may have high mechanical stability at such thicknesses, and have a porosity of up to 70%.

The method may also include heating the coated microporous substrate or performing the coating step at an elevated temperature. For example, substrate pore filling or saturation may be performed at a temperature above 40 ℃ or about 40 ℃ to reduce air solubility. In some embodiments, the substrate may be coated under vacuum treatment by immersion in a polymerization solution followed by a heating step.

The method may include removing bubbles after coating the microporous substrate. In some embodiments, the substrate sample may be pre-soaked and treated to remove air bubbles, for example, by being placed on a polyester or similar sheet, covered with a cover sheet, and flattened (smoothened out) to remove air bubbles. The process may be performed on a single sheet or in an aggregate.

The polymerization can be carried out in a heating unit or on a heated surface. The coated substrate may be placed on a heated surface at a temperature and for a duration sufficient to initiate and complete polymerization. Sufficient time and temperature may generally depend on the composition of the polymerization product. Alternative methods for polymerization may be employed, for example, treatment with ultraviolet light or ionizing radiation (e.g., gamma radiation or electron beam radiation).

According to certain embodiments, the methods disclosed herein can significantly reduce production time, for example, by requiring only one coating step. Production time can be additionally reduced by not incorporating a crosslinking agent. A subsequent cross-linking step can be avoided. In addition, the anion exchange membranes produced can have a thickness as low as 25 μm or 15 μm while maintaining the desired mechanical strength and chemical stability when in use.

The film may be produced on a production line as shown in fig. 4. The exemplary production line 200 of fig. 4 includes a solution tank 210 for coating a film substrate. The exemplary production line 200 may move the coated substrate along a heating zone 220 on a mechanical motion element 230. The mechanical motion element may be a conveyor belt 230, optionally including a motor 232. The motor may be operated to control the speed along the heating zone 220 (as described in more detail in the embodiments). The heating zone 220 may include a plurality of heating blocks 221, 222, 223, 224. Here, the exemplary heating zone 220 includes four heating blocks, but the heating zone 220 may include more or fewer heating blocks. The number of heating blocks may affect the speed of operation of the mechanically moving element 230. The production line 200 may also include a roller 240 for removing bubbles. In an alternative embodiment, the heating zone 220 may be a photoinitiator rather than a thermal initiator. In some embodiments, the heating zone 220 may comprise an ultraviolet radiation zone.

Generally, the thickness of the ion exchange membrane may allow for lower internal resistance and/or greater power output. The thickness of the anion exchange membrane may depend on the thickness of the microporous substrate. Thus, the anion exchange membrane may have a thickness of less than about 155 μm. The anion exchange membrane can have a thickness of less than about 100 μm. The anion exchange membrane can have a thickness of less than about 75 μm. The anion exchange membrane can have a thickness of less than about 55 μm. The anion exchange membrane may have a thickness of about 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, or 45 μm.

In some embodiments, the anion exchange membrane can have a thickness between about 15 μm and about 100 μm. The anion exchange membrane can have a thickness between about 15 μm and about 75 μm. The anion exchange membrane can have a thickness between about 15 μm and about 50 μm. The anion exchange membrane can have a thickness between about 15 μm and about 35 μm. The anion exchange membrane can have a thickness between about 15 μm and about 25 μm.

The ion exchange membranes described herein can provide superior diffusivity when compared to conventional membranes of similar thickness. In general, diffusivity may refer to the number of ions passing through a unit area of an ion-exchange membrane in a given time. Thus, the membrane diffusivity can be driven by the difference in concentration of substances across the membrane. Steady state diffusivity may refer to diffusivity at which the flux of ions is substantially constant over time. As disclosed herein, steady state diffusivity values are measured with respect to at least one of the cationic species. In addition, the steady state diffusivity values can be determined by measuring 0.4M CuSO at 25 deg.C₄Membrane sample between solution and 0.5M NaCl solution, and Cu in the 0.5M NaCl solution compartment was monitored²⁺To be determined.

In some embodiments, the anion exchange membrane can have less than 0.4ppm/h/cm with respect to at least one of the cationic species disclosed herein²Steady state diffusivity of. In some embodiments, the anion exchange membrane can have less than 0.4ppm/h/cm for both cationic species²Steady state diffusivity of. The anion exchange membrane can have less than about 0.3ppm/h/cm²Less than about 0.2ppm/h/cm²Less than about 0.15ppm/h/cm²Less than about 0.12ppm/h/cm²Less than about 0.1ppm/h/cm²Less than about 0.08ppm/h/cm²Less than about 0.05ppm/h/cm²Or less than about 0.03ppm/h/cm²Steady state diffusivity of. Thus, when tested at 25 ℃ 0.4M CuSO₄Membrane between solution and 0.5M NaCl solution and monitoring Cu in the 0.5M NaCl solution compartment²⁺The diffusivity values described above are accurate.

The lower resistance of the membrane may reduce the electrical energy required for operation. The specific membrane resistance is usually reported in ohm-length (Ω cm). However, the resistance may not be evenly distributed along the film area. Area membrane resistance (area membrane resistance) in ohm-area (omega cm)²) And (6) measuring. The area membrane resistance can be measured by comparing the electrolyte resistance of a flow battery with an ion exchange membrane and a flow battery without an ion exchange membrane. For example, a cell having two electrodes of known area (typically platinum or black graphite may be used) in an electrolyte solution may be provided. One cell may have a sample of ion exchange membrane of known area between the electrodes. The electrodes are positioned so as not to contact the membrane. The membrane resistance can be estimated by subtracting the electrolyte resistance without the membrane from the electrolyte resistance with the membrane in place.

The resistance of an ion exchange membrane can also be measured by determining the voltage versus current curve in a cell having two well-stirred chambers separated by a membrane. Calomel electrodes may be positioned to measure the potential drop across the membrane. The slope of the potential drop may be plotted against a current curve, which may be obtained by varying the voltage and measuring the current.

Electrochemical impedance can also be used to measure the resistance of an ion exchange membrane. In this method, an alternating current may be applied across the membrane. Measurements at a single frequency generally give data relating to the electrochemical properties of the membrane. By using frequency and amplitude variations, detailed structural information can be obtained.

In some embodiments, the anion exchange membrane can have a ph of about 3.0 Ω -cm when measured with direct current after equilibration in 0.5M NaCl solution at 25 ℃²And about 10.0 ohm-cm²The resistance in between. The anion exchange membrane may have a concentration of about 5.0 Ω -cm when measured by direct current after equilibration in 0.5M NaCl solution at 25 ℃²And about 8.0 ohm-cm²The resistance in between. The anion exchange membrane may have a concentration of about 6.0 Ω -cm when measured by direct current after equilibration in 0.5M NaCl solution at 25 ℃²And about 7.0 ohm-cm²The resistance in between.The resistance may be chosen as low as possible and is determined by other parameters of the film (e.g. material, thickness, etc.). In some embodiments, an ion exchange membrane produced as described herein that is substantially free of a cross-linking agent can have a lower electrical resistance than an ion exchange membrane produced with a cross-linking agent. The anion exchange membrane may have a thickness of about 3.0 Ω -cm when measured by direct current after equilibration in 0.5M NaCl solution at 25 ℃²About 4.0. omega. -cm²About 5.0. omega. -cm²About 5.5. omega. -cm²About 6.0. omega. -cm²About 6.5. omega. -cm²About 7.0. omega. -cm²About 7.5. omega. -cm²About 8.0. omega. -cm²About 9.0. omega. -cm²Or about 10.0 ohm-cm²The resistance of (2).

The co-ion transport number may generally refer to the relative migration of counter ions relative to co-ions during use of the flow battery. An ideal cation exchange membrane may allow only positively charged ions to pass through the membrane, which gives a co-ion transport number of 1.0. When membranes separate monovalent salt solutions of different concentrations, the co-ion transport number of the membrane can be determined by measuring the potential across the membrane. The methods and calculations used herein are described in more detail in the examples section.

In some embodiments, the anion exchange membrane can have a co-ion transport number of at least about 0.95 for at least one non-redox species. The non-redox species may include any non-redox species of the electrolyte. The anion exchange membrane can have a co-ion transport number for all non-redox species of at least about 0.95. The anion exchange membrane may have a co-ion transport number of at least about 0.9, at least about 0.91, at least about 0.92, at least about 0.93, at least about 0.94, at least about 0.95, at least about 0.96, at least about 0.97, at least about 0.98, or at least about 0.99.

The flow battery can additionally include at least one electrode. The power of the flow battery can be a function of the surface area of the electrode. The one electrode may be a bipolar electrode positioned in fluid communication with the first electrolyte and the second electrolyte. The bipolar electrode may be positioned between the first electrolyte and the second electrolyte. The electrodes disclosed herein may be constructed of corrosion resistant conductive materials selected for sufficient electrical, chemical and mechanical stability in use. The bipolar electrode may comprise a conductive material or a layer of conductive material. In some embodiments, the bipolar electrode may include zinc.

A flow battery can include a first electrode and a second electrode, each electrode positioned in each half-cell. The first electrode may be positioned in a half cell comprising a first electrolyte, and the second electrode may be positioned in a half cell comprising a second electrolyte. The electrodes may comprise a conductive material or one or more layers of conductive material. In some embodiments, the electrode may comprise platinum or black graphite. The flow battery may include at least one separator configured to keep the ion exchange membrane and the electrode out of contact with each other.

The flow battery pack can include a plurality of flow batteries. In some embodiments, the flow battery may include an external electrolyte tank. The flow battery can be configured to feed electrolyte from the tank through the cell, the electrolyte contacting the ion exchange membrane and/or the electrodes. The flow battery may include one or more pumps configured to circulate electrolyte through the cells. The flow batteries can be fluidly connected to each other. In some embodiments, the flow batteries are not fluidly connected to each other.

According to another aspect, a method of facilitating use of a flow battery is provided. The method can include providing at least one ion exchange membrane as disclosed herein and providing instructions to install the ion exchange membrane in a rechargeable battery of a flow battery. The ion exchange membrane may be an anion exchange membrane. The ion exchange membrane may typically be mounted between the anolyte compartment and the catholyte compartment of the rechargeable battery. The method can also include providing instructions to charge the flow battery and continuously operate the flow battery.

In some embodiments, the flow battery may be operated for a lifetime of at least about 6 weeks until replacement or recharging of the electrolyte is required. The flow battery can be operated for a lifetime of at least about 12 weeks. In some embodiments, the ion exchange membrane may have a useful life of about 6 weeks, 8 weeks, 10 weeks, 12 weeks, 14 weeks, or 16 weeks. In certain embodiments, the ion exchange membrane may have a service life of up to about 20 weeks. The useful life of the membrane can be translated into the number of cycles the membrane can operate before electrolyte replacement is required. In some embodiments, the ion exchange membrane may be operated for more than 4000 cycles. For example, the ion exchange membrane may be operated for about 4500 cycles, about 5000 cycles, about 5500 cycles, about 6000 cycles, about 6500 cycles, or about 7000 cycles.

As disclosed herein, service life may refer to the life of a flow battery or ion exchange membrane in continuous use before the electrolyte needs to be replaced or recharged. In a non-limiting exemplary embodiment, when Cu²⁺Diffusion to Zn²⁺Compartment (or vice versa, Zn)²⁺Diffusion to Cu²⁺Compartment) of Cu²⁺Can react with Zn metal formed during discharge. The reaction may be carried out with Cu²⁺Conversion to Cu⁰This reduces conductivity or increases voltage at constant current. The voltage may be Cu diffused through the film²⁺A good indicator of the amount of (c). Thus, when the internal potential drop is high and the output is low, the useful life of the ion exchange membrane may reach a threshold value, indicating that the electrolyte may need to be replaced or recharged. In some embodiments, the useful life threshold of the ion exchange membrane may be reached when the internal potential drop is between about 2.0 volts and about 3.0 volts. The threshold lifetime of the ion exchange membrane may be reached when the internal potential drop is at least about 2.5 volts. The flow battery pack disclosed herein can include a sensor for determining an internal potential drop and optionally a user interface for indicating when the internal potential drop has reached a useful life threshold.

The useful life of the ion exchange membrane may depend on the use of the membrane. For example, the service life may vary with the choice of electrolyte or electrode material. The useful life of the ion exchange membrane may vary with the size of the rechargeable battery, the electrodes and/or the electrolyte compartment. In addition, the useful life of the ion exchange membrane may vary with the material selected. For example, the service life may vary with the coating material, the substrate material, and whether or not the substrate is coated with the crosslinking agent. Typically, the ion exchange membrane may have a useful life of between about 6 weeks and about 16 weeks. The method may further comprise providing instructions for determining the useful life of the ion exchange membrane, and optionally instructions for replacing the electrolyte after expiration. In some extreme cases, the method may include replacing the ion exchange membrane after expiration.

According to certain embodiments, the flow battery pack may be configured to be compatible with High Voltage Direct Current (HVDC) transmission lines. The flow battery pack may be operated to store electrical energy for use on the HVDC transmission line. Typically, such flow battery packs may be capable of providing between about 1000V and about 800 KV.

According to certain embodiments, the flow battery pack may be configured to be compatible with a vehicle. The flow battery can be operated to store electrical energy for use in a vehicle. Such flow battery packs may be configured to provide a voltage between about 100V and about 500V consistent with conventional vehicle batteries.

According to another aspect, a method of facilitating storage of a charge is provided. The method may include providing a flow battery as disclosed herein and providing instructions to charge the flow battery. The flow battery may be charged by connection to an energy supply. In certain embodiments, the flow battery may be charged by connecting to a variable energy supply. The variable energy supply may comprise any energy source that is not schedulable due to its fluctuating nature. Examples of variable energy sources include solar systems, wind systems, and hydraulic systems, such as wave power and tidal force. Other variable energy sources will be readily apparent to those skilled in the art. In general, variable energy sources may include those sources that require high energy storage to provide continuous operation. Thus, the method may further include providing instructions to charge the flow battery by electrically connecting the flow battery to an energy supply, such as a variable energy supply.

The method can also include providing instructions to electrically connect the flow battery to an energy transmission line or directly to a point of use (e.g., a consumer). The flow battery pack may be electrically connected to the HVDC transmission line. HVDC transmission lines can be used for long distance power transmission. HVDC transmission lines may also be electrically connected to regional power distribution systems, such as Alternating Current (AC) regional systems.

In some embodiments, the method may include providing instructions to recharge the flow battery pack after discharging. The flow battery can be discharged and recharged after use for the life of the ion exchange membrane. In other embodiments, the method may further include providing instructions to replace at least one of the first electrolyte and the second electrolyte after discharge of the flow battery. The electrolyte may be extracted as a used electrolyte and replaced with a new electrolyte for quick recharge. The used electrolyte may be regenerated for further use.

The function and advantages of these and other embodiments may be better understood from the following examples. These examples are intended to be illustrative in nature and are not to be construed as limiting the scope of the invention. In the following examples, ion exchange membranes of desired quality were produced by coating microporous substrates with the polymeric product.

Examples