Polymer electrolyte composites

Abstract

The present disclosure relates to a composite material comprising a reinforcing material and a cationic polyelectrolyte, for example, a porous reinforcing material impregnated with a cationic polyelectrolyte. The present disclosure further relates to a membrane electrode assembly comprising the composite of the present disclosure and an electrochemical device comprising the disclosed membrane electrode assembly.

Description

[Technical Field]

[0001] Related applications This application claims the benefits of U.S. Provisional Application No. 63 / 063,730, filed on 10 August 2020. All teachings of the said application are incorporated herein by reference.

[0002] government support This invention was made with government support under grant number 1746486, awarded by the National Science Fund (NSF). The government has certain rights in this invention. [Background technology]

[0003] Background of the Invention Polymer electrolytes currently used in fuel cells, electrolyzers, redox flow batteries, and water purification systems have low durability, mechanical strength, and conductivity. Current materials are not optimized for performance, durability, and cost, reducing the commercial viability of new technologies. Therefore, high-performance polymer electrolytes characterized by high ionic conductivity and durability under harsh chemical conditions and high temperatures are needed. [Overview of the project]

[0004] Summary of the Invention In a first embodiment, the present invention relates to a composite material comprising a reinforcing material and a polymer electrolyte in contact with the reinforcing material, wherein the polymer electrolyte has structural formula I, II, II, or IV: [ka] (In the formula: [ka] This indicates a point of connection to other repeating units; R 11 , R 21 , R 31 and R 41 Each of them is independently C1-4 is alkyl; R 12 、R 13 、R 22 、R 23 、R 32 、R 33 、R 42 and R 43 are each independently C 1-4 alkyl or C 5-7 cycloalkyl; Z 11 、Z 21 、Z 31 and Z 41 are each independently C -1-10 alkylene or *O-(C 1-10 alkylene), where * indicates the point of attachment to the polymer backbone; X - is halide, OH - 、HCO3 - 、CO3 2- 、CO2(R 10 ) - 、O(R 10 ) - 、NO3 - 、CN - 、PF6 - or BF4 - ; R 10 is C 1-4 alkyl) and includes a first repeating unit selected from the moieties represented by

[0005] In a second aspect, the present invention is a film comprising a film of any of the composite materials described herein with respect to the first aspect and its various aspects.

[0006] In a third aspect, the present invention is a membrane electrode assembly comprising a membrane as described herein with respect to the second aspect and its various aspects and an electrode.

[0007] In a fourth aspect, the present invention is an electrochemical device comprising any membrane electrode assembly and current collector described herein with respect to a third aspect and various aspects thereof. [Brief explanation of the drawing]

[0008] Brief explanation of the drawing [Figure 1] Figure 1 shows a comparison of the properties of an unsupported polymer electrolyte (T-17-80) and a composite material containing a polymer electrolyte and a porous support (MP-37-360). [Figure 2] Figure 2 shows the structural formula of the Tetrakis® polymer. [Figure 3] Figure 3 shows the reaction sequence for the synthesis of Tetrakis® polymer. [Figure 4] Figure 4 shows a bar chart illustrating the hydroxide conductivity at room temperature of different polymers containing phosphonium cations and proposed structural modifications of Tetrakis® monomers. [Figure 5] Figure 5 shows the chemical structure (top) of an exemplary cationic polymer synthesized from a dicationic monomer, and a plot (bottom) showing the temperature-dependent ionic conductivity of the polymer. [Figure 6] Figure 6 shows two synthetic strategies for developing monomers containing two phosphonium cations. [Figure 7] Figure 7 shows examples of cyclooctene monomers having hydrophobic functional groups. [Figure 8] Figure 8 shows the chemical structure of a crosslinked ammonium anion exchange membrane (AEM) containing a dicationic segment, and a plot illustrating the relationship between the hydroxide conductivity of the polymer and the ratio of cis-cyclooctene COE (CAS #931-87-3) to the cationic monomer (referred to as 1). [Figure 9] Figure 9 shows the chemical structure of 2-acetoxy-dicyclopentadiene, a crosslinking monomer that can stimulate thermal crosslinking. [Figure 10]Figure 10 shows plots illustrating the alkali stability of Tetrakis® polymers after exposure to different concentrations of KOH at different temperatures. [Figure 11] Figure 11 shows a schematic diagram of easy ion transfer in an AEM composite for an unstructured AEM. [Figure 12] Figure 12 shows a table listing the physical properties of the support materials: PE (polyethylene), PP (polypropylene), PTFE-MP (polytetrafluoroethylene membrane purchased from Millipore Sigma), and PTFE-HHPS (polytetrafluoroethylene membrane purchased from Sumitomo Electric under the trade name "HHPS"). [Figure 13] Figure 13 shows a notation scheme for Tetrakis® polymers and their corresponding composites. [Figure 14] Figure 14 shows a schematic representation of a method for preparing polymer electrolyte composites. [Figure 15] Figure 15 shows the EDS map of MP-37-360 stained with iodine. Boxes 1-3 are within the steel shim region, and boxes 4-6 are within the composite region. Inset: SEM of the composite held by the shim. [Figure 16] Figure 16 shows the elemental spectrum of iodine absorption at 3.93 keV using Gaussian fitting from a cross section of MP-37-360. Inset: SEM cross section of the region used for elemental mapping. The red box indicates the analyzed region. [Figure 17] Figure 17 shows a bar chart illustrating the ion accessibility of T-17-180, T-37-360, and MP-37-360. [Figure 18] Figure 18 shows bar charts (left) illustrating the carbonate conductivity of T-17-180 and MP-37-380, as well as the temperature-dependent conductivity profile of MP-37-360 between 20°C and 60°C (right). [Figure 19] Figure 19 shows a table summarizing the room-temperature ionic conductivity of T-17-180, T-37-360, and MP-37-360. [Figure 20] Figure 20 shows plots illustrating the temperature-dependent thickness of wet MP-37-360, T-17-180, and T-37-360. [Figure 21] Figure 21 shows plots illustrating the stress-strain curves for PTFE-MP supports, MP-37-360 (wet and dry) and T-37-360 (wet). [Figure 22] Figure 22 shows plots of thermogravimetric analysis (TGA) results for PTFE supports, T-37-360 and MP-37-360. [Figure 23] Figure 23 shows a plot illustrating the ion accessibility of MP-37-360 over 1000 hours. [Figure 24] Figure 24 shows examples of porous supports, their manufacturing methods, and their effects on the morphology of the supports. [Figure 25] Figure 25 shows examples of pore sizes in porous materials. [Figure 26] Figure 26 shows examples of different porosity properties of porous materials with the same pore size. [Figure 27] Figure 27 shows examples of composites with different void volumes. [Figure 28] Figure 28 shows the manufacturing process of a membrane electrode assembly (MEA): preparation of catalyst ink (A); preparation of electrodes using film applicator technology (B); and preparation of a catalyst coating film (CCM) using decal transfer (C). [Figure 29] Figure 29 shows the catalyst coating MP-37-360 after testing. [Figure 30] Figure 30 shows a flowchart of the MEA fabrication process. [Figure 31] Figure 31 shows the polarization plot of the MEA in electrolytic device mode. [Figure 32] Figure 32 shows a plot illustrating the durability of the MEA after 17 hours. [Figure 33] Figure 33 shows the polarization curves of the MEA due to 0.12% ionomer in CCM at 50°C (top) and 70°C (bottom). [Figure 34] Figure 34 shows the polarization curve of the MEA due to 0.12% ionomer in CCM at 70°C. [Figure 35] Figure 35 shows a table listing the CO3 2-conductivity of PTFE-MP and PP-based composites under different removal conditions. [Figure 36] Figure 36 shows the CO3 2-conductivity of composites fabricated using T-37-360 with different support materials. [Figure 37] Figure 37 shows SEM images of different porous supports. [Figure 38] Figure 38 shows the polarization curves for T-17-180. [Figure 39] Figure 39 shows plots of dynamic mechanical analysis (DMA) (left) and thermogravimetric analysis (TGA) (right) of support materials PE, PP, and PTFE-MP in a tensile test configuration. [Modes for carrying out the invention]

[0009] Detailed explanation Developing AEMs containing durable polymer backbones and cationic groups is necessary for the commercialization of fuel cells, electrolytic devices, redox flow batteries, water purifiers, and other electrochemical devices. Alkaline systems retain several advantages over acidic counterparts, particularly the ability to produce less expensive electrodes and bipolar plates, as well as devices with longer lifespans. Because oxygen reduction at higher pH is easier and lower overpotentials are required, alkaline electrochemical devices are an exciting alternative to proton exchange membrane (PEM) devices, allowing the use of metals other than platinum as electrocatalysts. Phosphonium-containing polymer electrolytes, such as the Tetrakis® polymer shown in Figure 2, are deeply needed enabling components for the widespread adoption of alkaline electrochemical devices.

[0010] A composite comprising a phosphonium-containing polymer electrolyte and a reinforcing material, such as MP-37-360 (Figure 13), is disclosed herein. The composite exhibits several advantages over a support-less AEM, as shown in Figure 1. The composite is advantageous because the mechanical and chemical durability of the reinforcing material can be optimized independently of the ionic conductivity of the polymer electrolyte. Therefore, the final composite may benefit from the synergistic effect of the customized properties of the reinforcing material and the finely tuned conductivity of the polymer electrolyte.

[0011] The composite exhibits high ionic conductivity, comparable to a similar support-free AEM (T-17-180, Figure 13), and has a significantly lower polymer electrolyte material content of <5 wt%. The low polymer load results in a dramatic reduction in the cost of materials for fabricating the composite compared to unsupported membranes. Furthermore, the composite exhibits significantly lower expansion (136% lower) in water at 80°C, accompanied by improved mechanical and thermal properties. The composite was chemically stable for 1000 hours at 80°C in 1M KOH. Additionally, a membrane electrode assembly (MEA) was successfully fabricated using the MP-37-360 composite and ionomer. The MEA was tested in a fuel cell configuration, achieving a maximum current density of 520 mA / cm² at 80°C.

[0012] Polymer electrolyte. In some embodiments, the polymer electrolyte consists of tetrakis(dialkylamino)phosphonium cations added to a non-aromatic hydrocarbon backbone, which is essentially modified polyethylene (Figure 2 shows an exemplary Tetrakis® polymer). Polymers containing tetrakis(dialkylamino)phosphonium cations were prepared by ring-opening metathesis polymerization (ROMP) of cis-cyclooctene and functionalized cyclooctene using a Grubbs second-generation catalyst, as shown in Figure 3. This powerful synthetic tool utilizes a functional group-tolerant catalyst that allows for direct polymerization of cationic monomers to a full conversion (≧98%) under mild conditions (22°C) and short reaction times (<24 hours).

[0013] Copolymerization with non-functionalized monomers allows for precise control of the cation content in the polymer product simply by changing the ratio of the two monomers. The polymer molecular weight can be easily adjusted by varying the amount of catalyst added, resulting in polymers with high average molecular weights. This approach contrasts with typical AEM synthesis, which uses step growth polymerization techniques involving long reaction times and aggressive conditions to achieve moderate transformations. Other common approaches include energy-intensive fluoropolymer synthesis using toxic reagents. Furthermore, the polymer backbone of the polymers disclosed herein does not contain functional groups that decompose under alkaline conditions, such as other AEMs. The resulting polymers are prepared using accurate and highly reproducible compositions optimized for ionic conductivity, chemical stability, processability, and mechanical properties.

[0014] The chemical structure of an AEM, including the polymer backbone and protruding functional groups, directly determines its electrochemical performance, mechanical properties, and chemical durability. High-performance AEMs that meet all the stringent requirements of competitive commercial products are achieved solely by modifying the polymer's chemical structure. Modification of standard phosphonium cations in Tetrakis® monomers containing methyl and cyclohexyl nitrogen substituents results in higher hydroxide conductivity at room temperature, as shown in Figure 4. The structures of the PDM3M and PMiP3M polymers are shown below: [ka]

[0015] Increasing the ion exchange capacity (IEC) is a proven method for enhancing the ionic conductivity of AEMs. Polymers with high charge density contain more sites for efficient ion mobility. However, polymers with high IEC can over-expand, leading to AEM failure. Higher IEC is often achieved by changing the ratio between cationic monomers and structural comonomers. However, the maximum IEC achievable by this method alone is typically limited (<1.5 meq / g). Preparing monomers with two cations (dications) or introducing two cations into a single repeating unit of the polymer is an effective strategy for raising the IEC beyond the typical limit, thus increasing ionic conductivity. An example is shown in Figure 5, where a high IEC (2.5–3.5 meq / g) resulted in very high hydroxide conductivity (120 mS / cm at 80°C). Tetrakis® monomers can similarly be modified to retain two cationic moieties in a single monomer. Two strategies for developing ROMP monomers containing two phosphonium cations are shown in Figure 6. Both examples are equally readily available, and there are no foreseeable challenges associated with their synthesis. The pathway toward the compound on the right involves the inclusion of additional ether functional groups in the monomer, which may offer advantages. The inclusion of hydrophilic features on or near the cationic group has been shown to better hydrate the cation, increasing conductivity and stability.

[0016] Phase separation in polymers containing immiscible component segments has been shown to improve the performance of AEMs. The excellent electrochemical properties of Nafion® are attributed to the micelle structure observed for fluoride chains capped with sulfonate ions. In AEMs, this is often achieved by preparing block copolymers by microphase separation to obtain distinct forms. Unfortunately, these methods are not compatible with all polymerization techniques and still need to be achieved for aliphatic hydrocarbon copolymers. Another method to promote phase separation between structural and functional segments in AEMs is to increase the hydrophobicity of the non-cationic moiety. This is possible by integrating long-chain hydrocarbons, aromatic groups, and fluoride moieties. Inducing phase separation in phosphonium AEMs can be achieved by polymerization of hydrophobic ROMP monomers, thereby improving conductivity. An example of a cyclooctene monomer with hydrophobic functional groups is shown in Figure 7.

[0017] The advantages of increasing the AEM charge density are diminished when the polymer affinity for water is too high. While some water incorporation is necessary for proper ion transport, excessive expansion has negative effects. This reduces the mechanical properties of unsupported AEMs, and 3D expansion reduces ionic conductivity by increasing the distance ions travel. Large changes in polymer dimensions during humidity circulation increase stress on the membrane, which is problematic, especially for fuel cell electrolytes. Furthermore, AEMs can become water-soluble at very high IEC values. Reinforced AEMs (composites) are less susceptible to mechanical problems, but water solubility remains a problem. Increasing the polymer molecular weight is readily achieved by the disclosed polymerization procedure, but further modifications are needed to inhibit water solubility at optimal IEC values. Crosslinking the polymer is a common method to completely prevent solubility. An example of a crosslinked ammonium-based AEM, including dicationic segments, is shown in Figure 8. High IEC and hydroxide conductivity were observed for these insoluble AEMs, which also possessed stronger mechanical properties. These AEMs were prepared using monomers that crosslinked the polymer during polymerization. While efficient, this method does not allow for the processing required to integrate the polymer into a mesoporous support. Functional groups that react with heat or UV energy must be integrated into the polymer during synthesis in order to crosslink after polymerization. Various functional groups are commonly used for heat or UV curing. An example of an established ROMP monomer that can stimulate thermal crosslinking, 2-acetoxy-dicyclopentadiene, is shown in Figure 9. Since Grubbs' ROMP catalyst is functional group-tolerant, several crosslinking monomers that remain stable under alkaline conditions can be investigated.

[0018] To demonstrate the exceptional chemical stability of phosphonium AEM, Tetrakis® polymers were treated under strongly alkaline conditions (15M KOH(aq) at 22°C or 1M KOH(aq) at 80°C). In-plane hydroxide conductivity (22°C) was measured over 1,000–3,000 hours of exposure. As shown in Figure 10, no significant change in conductivity was observed for these polymers, indicating that these films possess excellent chemical durability in operating devices.

[0019] To further compell the AEM, it is important to reduce the overall resistance by decreasing the thickness of the electrolyte layer and increasing ionic conductivity without sacrificing mechanical strength. Conventional methods for increasing conductivity include increasing the ion content or IEC in the polymer. This strategy is readily achieved by ROMP technology. However, higher ion content leads to higher water incorporation and excessive expansion of the polymer electrolyte, resulting in mechanical failure. Certain AEMs are flexible films that are not brittle at reduced thickness, but the expansion of such films in high-temperature water can make the film highly viscoelastic. Further aspects of the system that allow for higher IEC, mechanical strength, and reduced dimensional changes in the hydrated electrolyte simultaneously result in the desired AEM product.

[0020] In some embodiments, the desired thinner electrolytes include composite AEMs by filling a porous polymer support with phosphonium-containing AEM material. Polyethylene (PE), polypropylene (PP), and polytetrafluoroethylene (PTFE) structural supports were selected to investigate the effect of the support material on the resulting composites (Figure 12). In addition to enabling higher IEC, porous composites can provide less bent paths to facilitate the passage of anions through the electrolyte layer, further increasing performance without compromising mechanics or stability (Figure 11). Unsupported Tetrakis® membranes can be prepared up to a thickness of 30 μm, producing films that are easy to handle and manipulate. However, using supports allows for a wider range of thicknesses by shaping the membrane into a thin composite material.

[0021] AEM consists of an inherently stable polyethylene-like main chain and a phosphonium moiety. These features exhibit unprecedented chemical durability under the most intense conditions, making AEMs with these properties very strong candidates for high-performance products. However, polyethylene is known to be chemically resistant but viscoelastic (low stress resistance) and deforms at temperatures of about 100°C (low heat resistance). As described herein, the mechanical and thermal properties of the disclosed composites are considerably higher than those of unreinforced AEMs and mimic the properties of the support.

[0022] Two methods are provided for filling a support with phosphonium-containing AEM material: 1) immersion in a solution containing a pre-formed polymer, and 2) carrying out a polymerization reaction within the support. The mesh support is immersed in a solution of Tetrakis® polymer electrolyte solution to fill the pores of the composite. Due to the flexibility of the polymerization method (ROMP), the polymerization step can also be completed within the polymer mesh. Composites prepared via both methods were characterized to determine the simplest route for proof of concept. The fabricated composites were characterized by several ex-situ techniques to understand how well the AEM material penetrates the support and to understand the properties of the resulting composites. Imaging techniques, differential weight analysis, and IEC measurements provide information on how much polymer is inside the support material. Performance was evaluated by ionic conductivity, water uptake, mechanical testing, thermal analysis, and chemical stability. The optimized polymer electrolyte composites were fabricated into membrane electrode assemblies (MEAs) to evaluate their performance in fuel cell configurations. The in-situ performance of these initial prototypes is necessary to develop a clear plan for further optimization, including polymer support selection, AEM composition, and methods for fabricating composites. Each of these steps is critical to achieving AEM products that meet the demanding requirements for device performance and to break through the competitive market.

[0023] Porous support. This disclosure provides a method for injecting phosphonium AEM material into unoccupied spaces within various porous polymer structural supports. The structural hardness and mechanical strength of the support were successfully matched with the electrochemical properties of the polymer electrolyte. The resulting composites were thoroughly characterized for analysis of the level of polymer impregnation, water incorporation level, thermal properties, and electrochemical performance. Polymer materials from several international companies, such as polyethylene (PE), polypropylene (PP), and polytetrafluoroethylene (PTFE) supports, were obtained having the properties shown in Figure 12.

[0024] An optimal amount of void space remains in the dried AEM composite after fabrication. Essentially, the exposed porous support has a predetermined amount of pore volume. During fabrication, the AEM material is dissolved in a solvent compatible with the support, and then the mixture is applied to the support to fill the pores in the support material. When the solvent is removed, the dried composite has a new void volume. The reinforced AEM is hydrated before use in electrochemical devices, causing the polymer embedded in the support to expand and many of the void spaces to be filled once again. A certain amount of void space is required in the dried AEM to maintain a high density of cations for ion transport, but also includes a suitable amount of space for water. The exact amount of void space is specific to each type of polymer electrolyte and porous support combination (Figure 27).

[0025] BET can be used to analyze how void volume changes from the exposed support and the dried composite. Key variables for modulating the void space are solvent identity and polymer concentration in solution, as well as the method of introducing the solution into the support matrix. The selected solvent must be compatible with the support polymer and must solubilize the AEM to the desired level. Often, co-solvent mixtures are also investigated. The concentration must also be optimized, as excessively high concentrations may prevent the AEM from reaching the support, while too low concentrations will prevent sufficient AEM from penetrating the support. A rheometer may be used to characterize the viscosity of the polymer solution, and a Zetasizer may be used to analyze the homogeneity and dispersion of polymer particles. Measuring these solution properties, which affect the amount and distribution of AEM in the support, aids in composite optimization. Ionic conductivity with respect to void volume may be measured to establish the relationship between physical properties and electrochemical performance.

[0026] Porous polymer supports are typically designed for the filtration and separation of solids, liquids, and gases, or for sterilizing biological solutions, and are not optimized to be filled with other polymers to create high-performance components for electrochemical devices. Generally, optimizing the specifications of supports for these applications does not provide sufficient overlap in the categories of supports required for composites. Therefore, it is important to develop polymer supports that are specifically designed with composites as the end application in mind.

[0027] The first requirement for designing a support for a composite to order is determining what polymer material to use. PTFE, PE, and PP are polymers with chemical resistance. The best thermal properties are observed with PTFE, but it is a very expensive raw material, not recyclable, and processing methods for creating porous materials from PTFE are limited to expanding. PE and PP are both not significantly more expensive than PTFE, and they are both recyclable and can be processed using many different methods. Their thermal properties are considerably lower than PTFE, but this disadvantage can be addressed by crosslinking the polymer electrolyte within the support.

[0028] The next requirements for designing the ordered support are the selection of fibers and the method of fabricating the fibers into a mat or sheet of material. The method may be limited to a few polymers; for example, only PTFE can be spread into a sheet. PE and PP films can be prepared by various polymer fabrication methods. The type of fabrication has a significant effect on the morphology and alignment of the polymer strands (Figure 24). These characteristics affect the performance of the composite, as they can influence how the polymer electrolyte interacts with the support and how easily the polymer electrolyte fills the voids. Furthermore, the mechanical properties of the support vary based on the diameter of the fibers used and how the fibers are aligned relative to each other, affecting the durability of the composite. Both characteristics must be considered to obtain the best properties in the final material. The overall thickness of the support must also be designed. Previous results show that AEMs with lower thicknesses also have lower resistance (an AEM with a thickness of 57 μm had a resistance of 256 mΩ, while an AEM with a thickness of 74 μm had a resistance of 458 mΩ).

[0029] Further characteristics of a customizable porous support include pore size and porosity. Pore size simply indicates the average pore size within a given section of the support. Porosity indicates how much of the volume within a given region is free volume relative to what is absorbed by the support. Porosity is another way to characterize the free volume of an exposed support. Both of these characteristics affect how the polymer electrolyte fills the voids in the support and the resulting mechanical strength of the composite. Figures 25 and 26 illustrate how these qualities relate to each other.

[0030] The pore size and porosity of the support are measured by BET before and after filling with the polymer electrolyte to validate the fabrication method and support the development of optimized composites. Dynamic light scattering (DLS) by Zetasizer and rheological measurements is useful for characterizing the immersion coating solution and catalyst ink formulations.

[0031] Optimization of polymer compositions. All polymer compositions were synthesized using ring-opening metathesis polymerization (ROMP) of cis-cyclooctene and functionalized cis-cyclooctene with a Grubbs second-generation catalyst, as shown in Figure 3. The synthesis of Tetrakis® monomers and Tetrakis® polymers is described, for example, in Noonan, KJT; Hugar, KM; Kostalik, HA, IV; Lobkovsky, EB; Abruna, HD; Coates, GWJ Am. Chem. Soc. 2012, 134 (44), 18161-18164. In some embodiments, Tetrakis® AEM has a 17% cation content and a molecular weight of 180,000 g / mol, and is denoted as T-17-180. To increase conductivity, the percentage cation content in the polymer can be increased simply by increasing the percentage of functionalized cis-cyclooctene in polymerization. The polymer molecular weight increased with increasing cation content to reduce undesirable water solubility in AEM. The highest molecular weight investigated in the current optimization was 360,000 g / mol; however, higher molecular weights may be obtained by the polymerization method described herein. After synthesizing several polymers with high cation monomer content (50%–72%) that were soluble in water at 80°C, a polymer with a 37% cation content was selected for further testing. However, higher cation content is possible, particularly using higher molecular weight polymers. To establish the feasibility of AEM composites, to develop a protocol for composite preparation, and to characterize an initial prototype, a Tetrakis® polymer with 37% cation and a molecular weight of 360,000 g / mol was selected and designated T-37-360 (shown in Figure 13).

[0032] Preparation of composite materials. For each of the commercial supports investigated (Figure 12), a composite was prepared by the method described in Figure 14. The supports were washed in ethanol (A and B) to remove contaminants from the preparation. The supports were then immersed in a solution (4:1 ethanol:85 mM T-37-360 in toluene) overnight at room temperature to fill them with polymer (C). To remove organic solvents, the composites were air-dried on a polyethylene terephthalate (PET) backing. During drying, water was added to move the final AEM composite from the backing (D). To prepare for characterization, the composites were hydrated overnight in water at 80°C (E).

[0033] Several criteria in the disclosed method required optimization. The polymer immersion step (C) was optimized by varying the cosolvent mixture, polymer concentration, and support load (mmol polymer / support surface area). Other influential variables were the temperature of the immersion solution and the rate of stirring. The best results were obtained using a room-temperature solution without stirring. To optimize the drying step (D), the composites were spread on different backing materials, either glass or PET, and air-dried to remove the organic solvent. Significant differences in performance were observed based on how flat the composites were during the drying step. Flat composites without large wrinkles or folds yielded the best results; "wrinkled" composites had significantly lower conductivity. The best method for removing the composites from the backing material involved hydrating the composites in water at ≥60°C. Gentle mechanical peeling with tweezers to remove the composites from the backing significantly reduced the performance of the samples. PET backings were used because they were easier to handle than glass, and the composites typically moved easily from the PET. The temperature and time of hydration in water (step E) were also varied. Temperature (60°C vs. 80°C) did not appear to have an effect, but it was found that the length of time for maximum performance was ≥6 hours. The decisive variables for the AEM composites were the concentration of the polymer solution, the amount of composite in the solution, and the method of removing the composite from the backing material. The optimal amount of polymer in the immersion solution per composite surface area depends on the internal surface area of ​​each type of support and should therefore be optimized for each support. Composites were prepared using Millipore-Sigma porous PTFE filters and Tetrakis® polymer, T-37-360, using the method outlined above. These composites are referred to herein as MP-37-360.

[0034] Verification of polymer penetration into the support. To verify the penetration of T-37-360 into the support, cross-sectional scanning electron microscopy (SEM) images were obtained using elemental mapping (EDS). To increase elemental contrast, MP-37-360 samples were stained with iodide ions. Hydrated MP-37-360 composites were immersed in a) 1M KOH for 40 minutes, b) 1M KI for 120 minutes, changing to fresh 1M KI solution every 40 minutes, and then c) DI water for 60 minutes, changing to fresh water every 20 minutes. The iodide morphology of MP-37-360 was air-dried and analyzed by SEM (Figure 15). The samples were mounted on steel shims, sputtered with a thin layer of gold, and imaged at an accelerating voltage of 20 keV. Previous researchers have observed flat cross-sections indicating loss of porosity in composite SEM images. As indicated by the roughness at the center in Figures 15 (inset) and 16 (inset), some porosity remained in the MP-37-360. Iodine levels in the MP-37-360 sample were analyzed by elemental spectroscopy. With the sample mounted between steel shims, trace amounts of iodine in the steel can be seen along the top and bottom of the image (Figure 15, regions 1-3). This elemental map shows a relatively uniform distribution of iodine along the cross section (Figure 15, regions 4-6). Analysis of cross-sectional sections and spectra of the composite by EDS shows a strong absorption at 3.93 keV characteristic of iodine (Figure 16). The intensity of the absorption exceeds a signal-to-noise ratio (S / N) of 10x, indicating that this is a true signal.

[0035] Characterization of polymers and ion content in composites. After verifying that the polymer had penetrated the support, the amount of polymer in the MP-37-360 composite was analyzed. The mobility of ions in the composite depends on the polymer embedded in the support, and the support alone is non-conductive. To determine how much polymer had penetrated the MP-37-360, the support material was weighed before and after filling with T-37-360, and via this method the polymer content was found to be approximately 2 wt%. To analyze the accessibility of ions in the T-17-180 and T-36-360 polymers, back titrations were performed to determine the IEC. Briefly, the polymers were dried overnight under vacuum and weighed to determine their dry mass. The polymers were exchanged into the hydroxide form, rinsed with water, and immersed overnight in a precisely known amount of hydrochloric acid. The remaining HCl solution was then back titrated to determine the amount of hydroxide ions exchanged in the polymer. The ratio of hydroxide (mmol) to grams of dry polymer provides a measure of how accessible the polymer is to ions (IEC, Equation 1). T-17-180 had an IEC of 0.67 meq / g and T-37-360 had an IEC of 1.20 meq / g; this difference indicates, as expected, that the increased cation content results in an increase in cation accessibility. For the composite film, since the mass of the sample is the sum of the dry weights of the support + polymer, the IEC is not as straightforward. Therefore, this experiment describes the ion accessibility (IA, Equation 2) in the polymer composite within the support. The ion accessibility of the MP-37-360 composite was measured to be 0.10 meq / g (Figure 17). Increasing the amount of polymer in the composite increases the ion accessibility and results in higher conductivity.

Number

[0036] Evaluation of the ionic conductivity of the composite. The functional property of polymer electrolytes is ion transport. In fuel cells during operation, hydroxide anions move across the membrane from the cathode to the anode, and the use of polymer electrolytes is necessary in these types of devices. To analyze the ability of the MP-37-360 composite to transport anions, the ionic conductivity through the plane of MP-37-260 was measured. The selected orientation is most similar to the orientation used in membrane electrode assemblies and complete devices. It is important to note that ionic conductivity is orientation-dependent. For example, reinforced Nafion XL has conductivity in the plane >72 mS / cm and >50.5 mS / cm for geometry through the plane.

[0037] The conductivity through the plane of T-17-180 films, T-37-360 films, and MP-37-360 composites was analyzed (see Figures 18 and 19 and Equation 3). An AEM was clamped between two carbon-coated gas diffusion layers inside two graphite blocks containing a serpentine flow field. A small oscillating voltage (amplitude = 10 mV) was swept from 1 MHz to 100 Hz and applied to one facet of the film, and the current response was measured using a Gamry 1000E potentiostat in EIS mode. An inductance-compensated constant-phase element was used to fit the diffusion model and the resulting Nyquist plot, and the true resistance at high frequencies was used as the cell resistance. Conductivity (σ) was calculated using bulk resistance (R), film active region (L), and film thickness (A) (Equation 3).

number

[0038] The conductivity of both hydroxide and carbonate ions was measured; anions were exchanged using the previously described ion exchange procedure. Potassium carbonate and potassium hydroxide were used for both carbonate and hydroxide anion exchange, respectively. As expected, the hydroxide conductivity of the composite was significantly higher than that of the carbonate (Figure 19). Reinforced AEMs are known to have hydroxide conductivity ranging from 2 to 60 mS / cm depending on the polymer used. For the MP-37-360 composite, temperature-dependent conductivity was measured from 20°C to 60°C. Higher temperatures (>60°C) were not possible due to reaching the detection limits of the potentiostat and the limits of the heating equipment. Nevertheless, the measurements provided important insights into how the film may respond in the device.

[0039] Hydration analysis of composite materials. Two advantages of using composite membranes instead of polymer membranes are 1) reduced expansion due to water uptake and 2) enhanced mechanical properties. AEM hydration is important for the mobility of hydroxide ions through the membrane; however, excessive expansion can negatively affect the mechanical properties of the polymer film. Furthermore, large changes in AEM dimensions as the electrochemical system passes through temperature and humidity circulation can lead to cell failure. To understand the forces and their impact on physical / mechanical properties that the membrane experiences under operating conditions, expansion (i.e., changes in dimensions; where X = length; Y = width; Z = thickness) and water uptake (i.e., the mass of water absorbed) must be determined. Generally, this is determined by measuring the dimensions and weight of the polymer sample in dry halide form and evaluating the changes when converted to hydrated hydroxide form.

[0040] Water absorption was analyzed by heating the composites in water overnight at a constant temperature. The thickness was determined and compared with the dry measurements (Equation 4). T-17-180 showed significant expansion up to 80°C, and T-37-360 expanded considerably and collapsed above 30°C. However, the MP-37-360 composite did not change significantly over this temperature range (Figure 20). This verifies that supporting the phosphonium-containing polymer reduces harmful temperature-dependent film expansion.

number

[0041] Evaluation of the mechanical properties of composite materials. The mechanical properties of AEMs are significantly influenced by the type of polymer backbone (i.e., fluoropolymer, polyaromatic, polyolefin, polyaryletherketone, etc.), molecular weight, cation identity (i.e., ammonium, imidazolium, phosphonium, etc.), and cation content (IEC). AEMs that can be processed into thin films are desirable because they have lower ionic resistance than thick films. Reporting stress and elongation at rupture is a universal method for characterizing the intrinsic polymer mechanical properties. These measurements can be performed using a dynamic mechanical analyzer (DMA) or tensile tester. The mechanical properties of AEMs are highly dependent on hydration state and temperature, and these environmental conditions may be modified to observe relevant effects.

[0042] The mechanical properties of the composites were analyzed using DMA. Under a constant force mode on a TA Instruments DMA Q800, the polymers and composites were pulled at 1 N / min until they broke or the apparatus reached maximum displacement. The T-37-360 polymer was viscoelastic, and the PTFE-MP support was tougher (Figure 21). The MP-37-360 composite was tougher than the support, but showed no significant difference based on hydration level. The dry MP-37-360 composite had the same response as the wet one (room temperature hydration). This indicates that the structural stability of the MP-37-360 composite was not impaired by expansion due to hydration.

[0043] Evaluation of the thermal properties of composite materials. The thermal properties of the composites were also considered using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). DSC analysis showed a clear thermal transition at 116°C in both the T-37-360 polymer and the MP-37-360 composite. DSC traces for T-37-360 and MP-37-360 are shown in Figure 22. No thermal transition was observed in the PTFE support. TGA analysis showed no decomposition up to approximately 500°C for the PTFE support, but some transitions were observed for T-37-360 (Figure 22). In the MP-37-360 composite, a small transition was observed at approximately 150°C. A larger transition at approximately 260°C corresponds to significant decomposition in the polymer. Since the polymer completely decomposes by 470°C and the PTFE support decomposes at 490°C, the weight percentage of the polymer can be determined to be approximately 4.5%. To verify this, the composites were prepared and their weights were recorded before and after immersion. Using this method, the polymer content in the MP-37-360 composite is approximately 2%. The discrepancy in these figures may be due to the small amount of polymer mass in the support, with the mass difference / composite ranging from 2 to 3 mg.

[0044] Evaluation of the alkaline stability of composite materials. Alkali stability testing is used to evaluate the chemical stability of AEM under conditions associated with an operating alkaline electrolyzer or fuel cell, with standard conditions being 1M aqueous KOH at 80°C. At each point in time, stability can be verified using at least two analytical techniques: 1) ambient hydroxide conductivity to evaluate the functional cationic properties of the film and 2) FT-IR to monitor structural changes.

[0045] The long-term stability of the MP-37-360 composite was evaluated. This measurement method is important for potential devices where long-term film stability is critical. Previous work has established that Tetrakis® films are stable for 1000 hours under various harsh conditions (Figure 10). The MP-37-360 composite was tested in 1M KOH at 80°C for 1000 hours, and ion accessibility was analyzed at several time points. No change in ion accessibility was observed (Figure 23), indicating that the MP-37-360 composite is stable for 1000 hours.

[0046] MEA fabrication and fuel cell test results. After thoroughly characterizing the excitation properties of the MP-37-360 composite, their performance in a membrane electrode assembly (MEA) was analyzed. The MP-37-360 composite was subjected to a 1 cm³ test. 2A catalyst / ionomer coating was applied to the region to form a catalyst coating film (CCM). Catalyst ink solutions were prepared using water, n-propanol, Tetrakis® ionomer, and platinum black. The ratios of solvent, ionomer, and catalyst were all important for achieving good device performance. The CCM was sandwiched between two gas diffusion layers (GDL, AvCarb 280) at a controlled 90% compression level using a Teflon gasket and clamped between two graphite blocks with a serpentine flow field. These MEAs were symmetrical, with both the anode and cathode having the same amount and type of applied ink. Two different ink formulations were considered: one containing 0.12% ionomer (Test 1) and one containing 0.05% ionomer (Test 2). Carbon dioxide-free air and pure hydrogen are passed across the cathode and anode at a rate of 50-200 cm. 3 Each was flowed at a rate of 1 / min, and the gas flow, voltage, and current were controlled by a PEM Technologies test station. The voltage was systematically stepped from the open-circuit voltage (approximately 0.8V) to 0.1V to balance the cell between processes. The cell temperature was increased as desired using pad heaters mounted on the external metal casing of the MEA.

[0047] For Test 1, the cell was heated to 50°C, resulting in a 65 mA / cm² reading with first-order ohm behavior. 2 The voltage was stepped to obtain the polarization curve (voltage vs. current) showing the maximum current (Figure 33, top). The ionomer load in the CCM was 0.12%. No activation region (increased gradient change at high voltage) or mass transport region (increased gradient change at low voltage) was observed. This MEA was then subjected to a constant gas flow (50 cm³) on both electrodes for 17 hours at 50°C. 3A short-term endurance test was conducted with a current density of 0.05% mA / cm². During the first two hours, the current density decreased, which is most likely due to limited water access to the membrane (Figure 32). Since water is a reagent at the cathode in the AEM fuel cell, limited water reduces overall performance. After the endurance test, a similar polarization curve was obtained by increasing the temperature to 70°C and stepping up the voltage (Figure 30, bottom). The maximum current density was approximately 100 mA / cm². By increasing the temperature to 80°C, the cell was able to reach a maximum current density of 520 mA / cm²; however, the cell did not maintain the current density beyond a few minutes. A second MEA, labeled Test 2, had a CCM with a 0.05% ionomer load and was analyzed in a similar manner. The polarization curve at 70°C was 150 mA / cm². 2 This shows an increase in current density up to (Figure 34). This significant increase in current density indicates that the ink formulation is important for the function of the MEA.

[0048] A composite material having PE and PP supports. Commercially available supports of PE, PP, and PTFE were introduced into the composites, and the unexpectedly low ionic conductivity of the composites was prepared using PE and PP supports (Figure 36). It was initially proposed that polyolefin supports compatible with the Tetrakis® polymer backbone would be preferred over over-fluorinated supports such as Millipore Sigma's PTFE supports. However, this was not the case. Composites made using polyethylene, PE-37-360, and composites made using polypropylene, PP-37-360, exhibited approximately 90% lower carbonate conductivity. Evaluating PTFE supports from different suppliers, HHPS-37-360, revealed that these supports, while having the same chemical composition as MP-37-360, exhibited considerably lower conductivity. As summarized in Figure 12, these supports have very different properties (i.e., pore size, porosity, and thickness); however, no trend could be determined that would explain the relationship between support structure and composite performance. SEM analysis of the exposed support material revealed previously unknown factors—the macroscopic structure of the support (Figure 37).

[0049] Mechanical strength of PE, PP, and PTFE support materials using dynamic mechanical analysis in a tensile test configuration (Figure 39, left). The PE and PP supports were significantly stronger compared to the PTFE-MP support. The thermal properties of the bare supports show that PTFE-MP has higher thermal stability compared to PE and PP, but all support materials are sufficiently stable beyond the operating limits of the intended electrochemical device (Figure 39, right).

[0050] The data of the present disclosure suggest that the key to developing AEM composites with excellent performance is initiated with the development of porous polymer supports using an appropriate combination of chemical identity and macrostructure specifically designed for this application. Commercially available supports serve other purposes well; they are not optimized to meet the difficult goals for AEM materials. This data suggests that pore size, porosity, and how the polymer chains in the support material are processed have a significant impact.

[0051] As shown in Figure 36, the carbonate conductivity through the plane of MP-37-360 is similar to that of T-17-180, and for the composite, the mechanical strength is high and the swelling is reduced. Considering that only 4.5% of the composite is the active material (weight % measured by TGA), this conductivity is significantly high. Increasing the amount of polymer within the MP-37-360 composite naturally follows that it dramatically increases the conductivity and similarly does not reduce the mechanical improvement.

[0052] Electrode fabrication. A flowchart for the fabrication of catalyst coating films (CCMs) is shown in Figure 30. A stable catalyst ink dispersion is prepared in a suitable solvent. The electrode is fabricated as a homogeneous layer containing the dry catalyst and ionomer. Typical methods include painting or spray coating using a film applicator or draw bar. The membrane electrode assembly (MEA) (electrode + composite) is assembled with gaskets, sub-gaskets, and a gaseous dispersed phase (GDL), and then tested under relevant operating conditions. The MEA structure is typically custom-ordered around each specific polymer electrolyte, and this work must be developed in-house for rapid iteration through variables.

[0053] Catalyst ink is ideally a homogeneous dispersion of catalyst particles and ionomers in an organic solvent / water mixture. The ionomer solution (n-propanol, ethanol, or NMP) is further diluted and mixed with the catalyst and water. Factors to adjust to optimize the catalyst ink include 1) organic solvent, 2) ionomer load, 3) catalyst load, 4) water:solvent ratio, and 5) dispersion technique (i.e., heating and mixing method). Importantly, the catalyst ink dispersion should be chemically and physically stable for reproducible results. A catalyst ink for Tetrakis® polymer is shown in Figure 30(A). As shown in Figure 30(B), the catalyst ink is spread uniformly on a Teflon surface to prepare a decal. To prepare the CCM, fragments are cut for electrodes and transferred to a film in a method called decal transfer. An example is shown in Figure 30(C). Variables affecting electrode fabrication include temperature, pressure, and transfer time. The particle size distribution of catalyst and ionomer clumps in inks using different solvents is tested to help achieve formulations with desired viscosity and surface tension, which is important when using deposition techniques such as doctor blading with a film applicator. Figure 29 shows an image of the catalyst-coated MP-37-360 composite after testing.

[0054] Assembling the MEA involves selecting materials for the gasket and sub-gasket, which depend on the thickness of the composite. An appropriate gasket size should be used to control electrode compression. Using a sub-gasket equal in size to the CCM can improve membrane creep.

[0055] Fabricating non-platinum electrodes and creating MEAs using newly developed composites represents the most significant work for reducing both material and switching costs. Platinum accounts for a large portion of the cost of current commercial devices, limiting the applicability of these technologies. The ability to use other catalysts is one of the strongest incentives for moving towards alkaline electrochemical systems.

[0056] Non-platinum electrodes may be used to construct the MEA using the disclosed composites and alternative catalysts. For example, 5 cm using 1 M KOH at 60°C. 2 1 A / cm² at 1.9 V using NiFe2O4 anode and FeNiCo cathode catalysts in a cell 2 The performance of the following has been previously demonstrated: A current density of 1 A / cm² at 1.9 V can be achieved using a NiMo cathode for the hydrogen release reaction and an iridium black anode in 1 M KOH at 50°C. For alkaline fuel cells, a NiMo / KB catalyst (carbon-supported bimetallic nickel-molybdenum) can be used for the hydrogen oxidation reaction, achieving 120 mW / cm² at 0.5 V under H2 / O2 operating conditions. 2 It is possible to achieve a power density of this magnitude.

[0057] Measuring MEA performance. The in situ electrochemical performance of the MEA can be evaluated for alkaline fuel cells and electrolysis. Prior to AEMFC performance evaluation, the hydrogen crossover during MEA operation can be electrochemically evaluated for sufficiently humid H2 and air at ambient pressure and temperature. The open-circuit voltage can be evaluated under standard operating conditions (humid H2 and O2, and aqueous KOH, respectively) for AEMFC and AEME (alkaline exchange membrane fuel cell and alkaline exchange membrane electrolyzer), and then the IV curve can be recovered by sweeping the potential from the OCV down to 0.1V for the fuel cell and 2.1V for the electrolyzer. The maximum current density is recorded at key values ​​(0.65V for the fuel cell and 1.8 and 2.1V for the electrolyzer). Exemplary performance data for an unsupported AEM of T-17-80 is shown in Figure 31.

[0058] Further cationic polymer electrolytes In an alternative embodiment, the composite material of the present invention may use alkylammonium ionomers (polymer electrolytes) as described in U.S. Patent No. 9,493,397, which is incorporated herein by reference. Specifically, in one aspect, the present invention relates to structure I: [ka] The present invention provides an ionomer having a first unit derived from an ionic strained olefin ring monomer (ISOM unit) and a second unit derived from a strained olefin ring monomer without an ionic moiety (SOM unit). The ionomer is a random copolymer comprising ISOM units and SOM units or ISOM units and ISOM units. In one embodiment, the ionomer comprises a predetermined number of tetraalkylammonium moieties, the tetraalkylammonium moieties being in predetermined positions.

[0059] In one embodiment, adjacent ISOM and SOM units or ISOM and ISOM or SOM and SOM units are linked by a carbon-carbon single bond or a carbon-carbon double bond. An ISOM unit is a hydrocarbon repeating unit containing at least one alkyltetraalkylammonium moiety. When the carbon atom is at the β position relative to the ammonium nitrogen, the carbon atom does not have a hydrogen substituent. A SOM unit is a hydrocarbon repeating unit. The value of x can be from 0.05 to 1, encompassing all values ​​up to 0.01 and the entire range in between. The ionomer contains a predetermined number of ionic moieties, with at least one alkyltetraalkylammonium moiety in a predetermined position.

[0060] The ionomer according to claim 1, wherein the number-average molecular weight, Mn, is between 5,000 and 2,000,000, encompassing all integers and ranges within that range. The weight-average molecular weight, Mw, of the ionomer is between 5,000 and 2,000,000, encompassing all integers and ranges within that range. The Mn or Mw of the ionomer may be determined by a conventional method, such as gel permeation chromatography.

[0061] In one embodiment, the terminal groups of the ionomer are =CH2, =CHR (wherein R can be CH2W, where W is a halide, hydroxide, or acetate), =CHPh, -CH3, -CH2R (wherein R can be CH2W, where W is a halide, hydroxide, or acetate), and -CH2Ph.

[0062] The tetraalkylammonium cation in the ionomer of the present invention is any anion (A - ) may have. Examples of suitable anions include any halide, hydroxide, hexafluorophosphate, borate, carbonate, bicarbonate, and carboxylate.

[0063] In the following structure, R 1 , R 2 , R 3 and R 4 C1~C 20 It is the basis of C1~C20 The group has 1 to 20 carbon atoms, for example, all integers between them, and includes groups such as linear or branched alkyl groups (which can be substituted), cyclic alkyl groups (which can be saturated, unsaturated, or aromatic), and alkylcyclic alkyl groups (which can be saturated, unsaturated, or aromatic). C1~C 20 An example of the base is the following structure (where the wavy line indicates a point of connection): [ka] This is shown, where n is between 0 and 20. 1 , R 2 , R 3 Regarding C1~C 20 If the group has a β-carbon relative to the ammonium nitrogen, then C1~C relative to the ammonium nitrogen 20 The β-carbon of the group does not have a hydrogen substituent. The ionomer may or may not be crosslinked. In one embodiment, the ionomer is not crosslinked. Structure II is an example of an unsaturated, uncrosslinked ionomer: [ka] This is shown, where n is 1 to 20. An example of a saturated non-crosslinked ionomer is shown in Structure III: [ka] As shown, where n is between 1 and 20. For example, the x values ​​of the ionomer in this embodiment include 0.29 or 0.33. The ionomer may or may not be crosslinked. In one embodiment, the ionomer is not crosslinked.

[0064] In another embodiment, the ionomer is crosslinked. In one embodiment, at least one first ISOM or SOM unit is C1-C 20 Linked by polyatomic linking groups (PALs) containing the group C1~C 20 If the group has a carbon atom at the β position relative to the ammonium nitrogen atom, C1~C 20The β-carbon of the group does not have a hydrogen substituent relative to the second ISOM or SOM unit. The second ISOM or SOM unit may be in the same ionomer chain as the first ISOM or SOM unit, or the second ISOM or SOM unit may be in a different ionomer chain than the first ISOM or SOM unit. For example, crosslinking between SOM units results from the polymerization of monomers having multiple polymerizable alkene functional groups. Structure IV shows an example of an unsaturated SOM-crosslinked ionomer: [ka] As shown, here R 4 is C1~C 20 The base (R 1 , R 2 and R 3 (As described above). Ionomers are bridged by carbon-carbon double bonds between y units (SOM) in the same or different ionomer chains and a second y unit. The value of x is 0.05 to 1, including all values ​​up to 0.01 and the range in between, and x+y+z=1. For example, the value of x for the ionomer of structure IV includes 0.33 or 0.5. An example of a saturated SOM-bridged ionomer is structure V: [ka] As shown, here R 4 C1~C 20 The base (R 1 , R 2 and R 3 (As described above). The ionomer is bridged by a carbon-carbon single bond between the y unit (SOM) in the same or different ionomer chain and the second y unit. The value of x is 0.05 to 1, including all values ​​up to 0.01 and the range in between, and x+y+z=1. In these two examples, the SOM block is derived from dicyclopentadiene and has multiple polymerizable alkene functional groups. For example, the value of x for the ionomer of structure V includes 0.33 or 0.5.

[0065] In another embodiment, the ionomer is crosslinked, where the crosslinking is derived from a polyfunctional monomer having two ISOM moieties linked by a polyatomic linking group (PAL), for example, structure VI or VII: [ka] It has, and here each PAL independently, C1~C 20 The base (R 1 , R 2 and R 3 This includes (as described above). The value of y is from 0 to 20, including all integers and ranges within that range. Examples of unsaturated (structure VIII) and saturated (structure IX) ionomers derived from polyfunctional monomers having two ISOM moieties linked by polyatomic linking groups (PALs) are shown below: [ka] As shown below, for example, the values ​​of x for the ionomers of structures VIII and IX include 0.25, 0.29, 0.33, 0.40, and 0.50.

[0066] In another aspect, the present invention provides a compound comprising at least one alkyltetraalkylammonium group, which can be used as a monomer from which an ISOM unit may be derived. In one embodiment, the compound has the following structure: [ka] It holds.

[0067] In this embodiment, R 1 C4~C 20 These are cycloalkenyl groups, such as cyclooctene, norbornene, and cyclooctadiene. 2 , R 3 , R 4 , R 5 , R 6 and R 7 Each of them is independent, C1~C 20is a group. For each of these groups having a carbon at the β-position relative to the ammonium nitrogen, the β-carbon does not have a hydrogen substituent. In one embodiment, R 2 is a C4 - C 20 cycloalkenyl group, such as cyclooctene, norbornene, cyclooctadiene, etc., and the carbon at the β-position relative to the ammonium nitrogen does not have a hydrogen substituent. The value of n is from 0 to 20, including all integers and ranges therebetween. A - is any halide, hydroxide, hexafluorophosphate, any borate, any carbonate, any bicarbonate or any carboxylate.

[0068] In one embodiment, the monomer has the following structure:

Chemical formula

[0069] In one embodiment, the compound has the following structure:

Chemical formula

[0070] In one embodiment, the present invention provides a polyfunctional monomer (MFM) having at least two ISOM moieties. These two moieties are linked by a polyatomic linking group (PAL). The MFM has structure X: [ka] It may have PAL (R 7 PAL is a hydrocarbon group containing 1 to 20 carbon atoms, encompassing all integers and ranges between two ammonium groups. Examples of PAL groups include, for example, linear or branched alkyl groups (which may be substituted), cyclic alkyl groups (which may be saturated, unsaturated, or aromatic), and alkylcyclic alkyl groups (which may be saturated, unsaturated, or aromatic). In one embodiment, R 7 The structure is as follows (where the wavy lines indicate the points of connection): [ka] It holds.

[0071] In one embodiment, the MFM has the following structure: [ka] It holds.

[0072] In one embodiment, the present invention provides an ionomer synthesized by polymerization of the above-mentioned compounds. For example, a homopolymer of one of the above-mentioned compounds derived from an ISOM unit is produced. In another embodiment, the above-mentioned compounds and another monomer that does not have an ionic moiety such as an alkyltetraalkylammonium group, derived from an SOM unit, are polymerized. For example, a random copolymer of one of the above-mentioned compounds and another monomer that does not have an ionic moiety (e.g., substituted or unsubstituted cyclooctene, norbornene, or dicyclopentadiene).

[0073] The ionomer comprises an ISOM unit or an ISOM unit and a SOM unit. The ISOM unit is derived from monomers (ionic strained olefin monomers - ISOM monomers), such as the compounds of the present invention described above, which have both a strained ring structure and one or more alkene moieties that can be polymerized (e.g., by ring-opening metathesis polymerization) and at least one ionic moiety (e.g., a tetraalkylammonium group). The SOM unit is derived from monomers (strained olefin monomers - SOMs) which have a strained ring structure and an alkene moiety that can be polymerized (e.g., by ring-opening metathesis polymerization) but does not have an ionic moiety.

[0074] A strained ring structure means that the molecule is reactive to ring-opening metathesis polymerization due to the unfavorable high-energy spatial orientation of its atoms, for example, the bond angles between some ring atoms being optimal tetrahedrons (109.5°(sp) 3 (for the bond) and triangular plane (120°) (sp 2 An angular distortion occurs when the bond angle becomes sharper than the bond angle (relative to the bond).

[0075] An ionomer has ISOM units and SOM units or ISOM units and ISOM units, where adjacent units are linked by carbon-carbon single bonds or carbon-carbon double bonds. For example, an ionomer having ISOM units and SOM units or ISOM units and ISOM units linked by carbon-carbon double bonds can be subjected to reaction conditions such that the carbon-carbon double bonds are reduced to carbon-carbon single bonds. In one embodiment, for a non-crosslinked ionomer having ISOM units and SOM units or ISOM units and ISOM units linked by carbon-carbon double bonds, 100% of the carbon-carbon double bonds are reduced to carbon-carbon single bonds. In various embodiments, for an ionomer having ISOM units and SOM units or ISOM units and ISOM units linked by carbon-carbon double bonds, at least 50%, 75%, 90%, 95%, or 99% or higher than 99% or 100% of the carbon-carbon double bonds in the ionomer are reduced to carbon-carbon single bonds. While not intended to be bound by any particular theory, hydrogenation of carbon-carbon double bonds in ionomers is thought to increase the mechanical strength of films made from hydrogenated monomers.

[0076] Monomers derived from SOM units (SOM monomers) are hydrocarbons having at least one polymerizable alkene group. SOMs can have multiple alkene moieties that can form ionomers that are crosslinked as a result of polymerization of two alkene moieties derived from two different SOM units. An example of such an SOM is dicyclopentadiene.

[0077] In one embodiment, the ROMP synthesis of the ionomer of the present invention is performed using the following structure: [ka] This is performed using SOM monomers selected from those combinations. 10 These are independent of H and C1-C 20The base (as described herein) is selected. The value of h is between 1 and 10, including all integers in that range. The value of g is either 1 or 2. The values ​​of j and k are independently between 0 and 5, including all integers in that range.

[0078] In one embodiment, ROMP synthesis provides a crosslinked polymer. For example, ISOM monomers and monomers having multiple polymerizable alkene functional groups, such as DCPD, can be copolymerized to provide a crosslinked ionomer.

[0079] In one embodiment, ROMP synthesis provides the following structure for a crosslinked ionomer: [ka] Use SOM monomers having one of the combinations thereof. 10 These are independent of H and C1-C 20 Selected from the bases (as described herein). The value of m is 1 or 2. The values ​​of p and q are independently 1 or 2. The value of n is 1 to 20, including all integers in between. The values ​​of each s are independently 0 to 5.

[0080] In one aspect, the present invention provides a method for synthesizing ionomer materials. Ionomers can be synthesized by ring-opening metathesis polymerization (ROMP), which can be carried out using, for example, a transition metal (e.g., ruthenium-based) metathesis catalyst (e.g., a second-generation Grubbs-type catalyst). The ROMP polymerization process is known in the art. For example, the method includes the step of providing an ISOM monomer and optionally an SOM monomer and a catalyst (e.g., a ruthenium-based alkene metathesis catalyst). The monomer(s) and catalyst are combined, and optionally a suitable solvent is added. The reaction mixture is heated under conditions such that an ionomer is formed.

[0081] In one embodiment, ISOM monomers and SOM monomers are combined under conditions that allow a ring-opening metathesis polymerization reaction to occur in the presence of a catalyst (e.g., a second-generation Grubbs ROMP catalyst) to form ionomers having structures I to V. Since air-stable Grubbs-type catalysts are resistant to various functional groups, functionalized monomers are polymerized using an air-stable Grubbs-type catalyst. Since no post-polymerization modification is required, film synthesis is greatly simplified by using monomers that already have a tetraalkylammonium moiety.

[0082] In another embodiment, polyfunctional monomers (MFMs) or MFMs and SOM monomers are combined in the presence of a catalyst (e.g., a second-generation Grubbs ROMP catalyst) under conditions that allow a ring-opening metathesis polymerization reaction to occur, to form an ionomer having, for example, structure VI or VII.

[0083] It is desirable that the ionomer material has hydroxide anions. Therefore, in one embodiment, if the ionomer material does not have hydroxide anions, the ionomer material is subjected to ion exchange conditions such that non-hydroxide anions are exchanged for hydroxide anions, and the resulting ionomer material has hydroxide anions.

[0084] In one aspect, the ionomer material of the present invention can be used in devices such as fuel cells, hydrogen generators, and water purification devices. In one embodiment, the present invention provides a fuel cell that operates under alkaline conditions, comprising an alkali anion exchange membrane (AAEM) containing an ionomer of structure I.

[0085] In fuel cells, ion exchange membranes act as a conductive interface between the anode and cathode by transporting ions while remaining impermeable to gaseous and liquid fuels. It is desirable for ion exchange membranes to possess the following four properties:

[0086] Ionomer interface materials are typically derived from solvent-processable ionomers. Ideally, solvent-processable ionomers should be insoluble in water and methanol or aqueous methanol, but soluble in other low-boiling point solvents (removal of high-boiling point solvents is considered difficult and unsafe in the presence of finely dispersed catalysts), such as n-propanol or a mixture of aqueous n-propanol. To form electrodes, the soluble ionomer is combined with an electrode catalyst and "coated" onto either a gaseous dispersion layer (GDL) or the film itself. This combination of ionomer, electrode catalyst, and GDL forms the electrode. The ionomer should also possess high hydroxide conductivity.

[0087] It is desirable that the AAEM containing the ionomer material of the present invention has at least the following properties: (1) Low methanol solubility and complete methanol insolubility of the ionomer are desirable; (2) Hydroxide conductivity of 1 mS / cm to 300 mS / cm, including all integers and ranges in between. In various embodiments, AAEM has a hydroxide conductivity of at least 1, 5, 10, 25, 50, 100, 150, 200 or 300 mS / cm. Hydroxide conductivity is measured by methods known in the art; (3) Mechanical properties such that the ionomer-containing membrane of the present invention does not rupture or crack under fuel cell operating conditions. In one embodiment, the membrane does not fail (e.g., rupture or crack) under fuel cell operating conditions under tensile stresses of 1 to 500 MPa, including all integers and ranges therein, and strains of 5% to 1000%, including all integers and ranges therein; and (4) Under alkaline fuel cell conditions, there is little or no expansion / hydrogel formation. In one embodiment, the expansion is 0-20% of the original AAEM film thickness, including all integers and ranges in between. Expansion of the ion exchange membrane increases its resistance, thereby decreasing its conductivity and ultimately leading to a decrease in fuel cell performance. If the expansion results in hydrogel formation, the membrane becomes permeable to gas and ceases to function. Consequently, excessive membrane expansion that causes hydrogel formation should be avoided.

[0088] In one embodiment, the present invention provides an AAEM comprising the ionomer of the present invention. The AAEM exhibits the desired properties described above. The thickness of the AAEM comprising the ionomer material of the present invention can be 1 μm to 300 μm, including all values ​​up to 1 μm and the range in between.

[0089] In some embodiments, the present invention provides a water electrolysis cell comprising an alkaline anion exchange membrane (AAEM) containing the ionomer of the present invention. Using the water electrolysis cell, oxygen and hydrogen can be produced from water.

[0090] In an alternative embodiment, the composite material of the present invention may use an alkylammonium ionomer (polymer electrolyte) as described in U.S. Patent Application Publication No. 2019 / 0047963, which is incorporated herein by reference. Specifically,

[0091] In one aspect, the present invention relates to formula (I) or (II): [ka] We provide compounds of the formula in R 1 C2-C 16 Selected from hydrocarbyl, here C2-C 16 One carbon atom of hydrocarbyl can be optionally substituted with O; R 2 Each of these consists of 0 to 3 substituents R selected individually from C1-C3 alkyl groups. 6 A phenyl substituted with; R 3 C2-C 16 Selected from hydrocarbyl; R 4 and R 5 Each is C1-C 16 Selected from hydrocarbil, or together with R 4 and R 5 These, together with the carbon atoms to which they bond, form a ring selected from benzene, cyclooctene, and norbornene; X- is the counterion.

[0092] As shown above, the compound of formula (I) is an imidazole compound (where R is the same as in the formula). 1 (It does not exist), and the compound of formula (II) is a positively charged imidazolium cation.

[0093] R 1 C2-C 16 Hydrocarbyl (i.e., C2, C3, C4, C5, C6, C7, C8, C9, C 10 , C 11 , C 12 , C 13 , C 14 , C 15 or C 16 Selected from hydrocarbyl, here C2-C 16 One carbon atom (and any hydrogen atoms bonded to that carbon atom) of hydrocarbyl can optionally be substituted with oxygen (O).

[0094] In some embodiments, R 1 C2-C 16 It is selected from hydrocarbyl compounds (where the carbon atoms are not substituted with oxygen).

[0095] In some embodiments, R 1 is C2-C 16 Selected from hydrocarbyl (or any of its subgroups), where R is relative to the nitrogen at position 1 of the imidazole ring. 1 The single carbon atom not located at a bonding point is replaced by oxygen.

[0096] In some embodiments, R 1 is C2-C 12 Selected from hydrocarbyl, here C2-C 12 One of the carbon atoms in hydrocarbyl can be optionally substituted with oxygen.

[0097] In some embodiments, R 1 is C2-C 10 Selected from hydrocarbyl, here C2-C 10 One of the carbon atoms in hydrocarbyl can be optionally substituted with oxygen.

[0098] In some embodiments, R 1 The C2-C7 hydrocarbyl is selected from C2-C7 hydrocarbyls, where one carbon atom of the C2-C7 hydrocarbyl can be optionally substituted with oxygen.

[0099] In some embodiments, R 1 The C2-C4 hydrocarbyl is selected from C2-C4 hydrocarbyls, where one carbon atom of the C2-C4 hydrocarbyl can be optionally substituted with oxygen.

[0100] In some embodiments, R 1 The C2-C8 alkyl group is selected from C2-C8 alkyl groups, where one carbon atom of the C2-C8 alkyl group may be optionally substituted with oxygen.

[0101] In some embodiments, R 1 The C2-C6 alkyl group is selected from C2-C6 alkyl groups, where one carbon atom of the C2-C6 alkyl group may be optionally substituted with oxygen.

[0102] In some embodiments, R 1 The methyl group is selected from ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, and hexyl, where one carbon atom may be optionally substituted with oxygen.

[0103] In some embodiments, R 1 R is an alkylaralkyl group, where one carbon atom of the alkylaralkyl group can optionally be substituted with O. For example, in some embodiments, 1 H(CH2)p-(Ph)q-(CH2)r-*, where * indicates the bond point to the nitrogen at position 1 of the imidazole; p is 1-6; q is 0 or 1; r is 1-6, where R is 0. 1 The total number of carbon atoms in the compound is between 2 and 16, where one carbon atom may be optionally substituted with oxygen. As used herein, the abbreviation "Ph" refers to phenyl.

[0104] In some embodiments, R 1The compound is H(CH2)p-(Ph)q-(CH2)r-*, where * indicates the bond point to the nitrogen at position 1 of the imidazole; p is 1-6; q is 0 or 1; r is 1-6, where R is 1-6. 1 The total number of carbon atoms in the molecule is between 2 and 16, where one carbon atom in (CH2)p can be arbitrarily substituted with oxygen.

[0105] In some embodiments, R 1 teeth: [ka] Herein, * indicates the bond point to the nitrogen atom at position 1 of the imidazolium ring; m is 0 or 1; n is 1 to 8, however the sum of m + n does not exceed 8. These aspects (and R 1 Other embodiments (having other strained cycloolefin rings) have found specific uses in ring-opening metathesis polymerization (ROMP), which is one technique that can be used to integrate imidazolium cations into polymers as described below.

[0106] In some embodiments, R 1 It is benzyl.

[0107] In some embodiments, R 1 It is not benzyl.

[0108] R 2 This has 0 to 3 substituents R 6 It is replaced by (i.e., R 6 It is phenyl (substituted 0, 1, 2, or 3 times). Each R 6 If present, each is selected from C1-C3 alkyl groups.

[0109] The applicant is R 2We discovered that imidazolium cation compounds containing a phenyl group are more basicly stable than those containing an alkyl group. This observation contrasts with the trend observed by Lin et al., Chem. Mater., 25, 1858 (2013), where alkyl substituents improved stability compared to phenyl groups.

[0110] In some embodiments, R 2 It is an unsubstituted phenyl compound.

[0111] In some embodiments, R 2 R 6 It is substituted 1 to 3 times, and each R 6 These are individually selected from methyl, ethyl, n-propyl, and isopropyl.

[0112] In some embodiments, R 2 is equation (R 2a This is the part of: Here: the point of binding to the imidazole or imidazolium ring is indicated; R 6a , R 6b and R 6c Each is individually selected from hydrogen and C1-C3 alkyl groups.

[0113] In some embodiments, R 6a , R 6b and R 6c At least two of these are individually selected from methyl and isopropyl.

[0114] R 3 is C2-C 16 Hydrocarbyl (i.e., C2, C3, C4, C5, C6, C7, C8, C9, C 10 , C 11 , C 12 , C 13 , C 14 , C 15 or C 16 Selected from hydrocarbyl.

[0115] In some embodiments, R 3is C2-C 12 Selected from hydrocarbil.

[0116] In some embodiments, R 3 is C2-C 10 Selected from hydrocarbil.

[0117] In some embodiments, R 3 It is selected from C2-C7 hydrocarbils.

[0118] In some embodiments, R 3 It is selected from C2-C4 hydrocarbils.

[0119] In some embodiments, R 3 It is selected from C2-C8 alkyl groups.

[0120] In some embodiments, R 3 It is selected from C2-C6 alkyl groups.

[0121] In some embodiments, R 3 The compounds are selected from ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, and hexyl.

[0122] In some embodiments, R 3 It is benzyl.

[0123] In some embodiments, R 3 It is not benzyl.

[0124] R 4 and R 5 These are individually C1-C 16 Selected from hydrocarbil, or together with R 4 and R 5 These, together with the carbon atoms to which they bond, form a ring selected from benzene, cyclooctene, and norbornene.

[0125] In some embodiments, R 4 and R 5 Each is C1-C 12 Selected from hydrocarbil. In some embodiments, R 4 and R 5 Each is C1-C 10 Selected from hydrocarbil.

[0126] In some embodiments, R 4 and R 5 These are individually selected from C1-C7 hydrocarbils.

[0127] In some embodiments, R 4 and R 5 These are individually selected from C1-C4 hydrocarbyls.

[0128] In some embodiments, R 4 and R 5 Each is individually selected from C1-C8 alkyl groups.

[0129] In some embodiments, R 4 and R 5 Each is individually selected from C1-C6 alkyl groups.

[0130] In some embodiments, R 4 and R 5 These are individually selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, and hexyl.

[0131] In some embodiments, R 4 and R 5 Each is individually selected from phenyls substituted with C1-C6 alkyl groups and optionally C1-C3 alkyl groups.

[0132] X- is the counterion.

[0133] In some embodiments, X- is selected from hydroxides, halides, bicarbonates, carbonates, nitrates, cyanides, carboxylates, and alkoxides.

[0134] In certain embodiments, X- is a hydroxide.

[0135] In some embodiments, X- is fluoride (F - ), chloride (Cl - ), bromide (Br - ) and iodide (I - It is a halogen selected from ).

[0136] In some embodiments, R 1 ~R 6 The total number of carbon atoms inside is 10 or more.

[0137] In some embodiments, R 1 ~R 6 The total number of carbon atoms in it is 10 to 60, including any and all ranges and subranges within it (e.g., 10 to 50, 15 to 45, 18 to 45, etc.) (i.e., 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, or 60 carbon atoms).

[0138] In some embodiments, the present invention provides compounds of formula (I), where R 3 is C2-C 12 We offer a compound selected from hydrocarbyl or of formula (II), where R 1 and R 3 It is independently C2-C 12 Selected from hydrocarbil.

[0139] In some embodiments, the present invention provides compounds of formula (I), where R 3is selected from C2-C7 hydrocarbyl compounds or provides compounds of formula (II), where R 1 and R 3 These are independently selected from C2-C7 hydrocarbils.

[0140] In some embodiments, the present invention provides compounds of formula (I), where R 3 is selected from C2-C4 alkyl and benzyl compounds, or provides compounds of formula (II), where R 1 and R 3 These are independently selected from C2-C4 alkyl and benzyl.

[0141] In some embodiments, the present invention provides compounds, where R 4 and R 5 Each is individually selected from phenyl and C1-3 alkyl groups.

[0142] In some embodiments, the present invention provides compounds, where R 2 This is the part R shown above. 2a The compound is: This is the result of equation (I), where :R 3 is n-butyl; R 6a and R 6c is methyl, and R 6b is hydrogen; R 4 and R 5 These are individually selected from phenyl and methyl; or This is the result of equation (II), where :R 1 and R 3 Each of these is n-butyl; R 6a and R 6c is methyl, and R 6b is hydrogen; R 4 and R 5 These are individually selected from phenyl and methyl.

[0143] In some embodiments, the present invention provides compounds of formula (II), for example, formulas (IIA), (IIB), or (IIC): [ka] It is a monomer.

[0144] In some embodiments, the present invention provides compounds having improved alkali stability. As described above, imidazole compounds and / or imidazolium cations (and polymers containing such compounds) that are stable under basic conditions are of great importance for a variety of applications.

[0145] In some embodiments, the present invention provides an alkali-stable compound in which 75% to 100% of cations remain after 30 days at 80°C in 5M KOH / CD3OH, including any and all ranges and subranges (e.g., 80% to 100%, 85% to 100%, 90% to 100%, 95% to 100%, etc.). The stability is determined by preparing a solution of cations in basicized methanol-d3(KOH / CD3OH) and storing it at 80°C in a flame-sealed NMR tube. At uniform time intervals, the amount of cations remaining relative to the internal standard is measured in the solution. H Analysis is performed by NMR spectroscopy. The use of CD3OH causes a reduction in the cation signal (unrelated to decomposition) and excludes the hydrogen / deuterium exchange process that masks the signal of the novel product. A key aspect of the cation decomposition pathway is revealed by this novel protocol, which facilitates the design of new imidazolium compounds with substituents strategically replaced to prevent decomposition.

[0146] In some embodiments, the present invention provides alkali-stable compounds in which 80% or more (e.g., 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, or 99% or more) of cations remain in 5M KOH / CD3OH after 30 days at 80°C.

[0147] In some embodiments, the present invention relates to formula (I): [ka] We provide a compound of R 2 ~R 6 And X- is defined as described above.

[0148] As will be discussed below, the compound of formula (I) is useful as an intermediate in the preparation of polymers according to the second aspect of the present invention (described below).

[0149] In some embodiments, the present invention relates to formula (II): [ka] We provide a compound of R 1 ~R 6 And X- is defined as described above.

[0150] In addition to being useful when the residue is integrated into a polymer according to the second aspect of the present invention (described below), the compound of formula (II) is also useful for evaluating the stability of polymers according to the second aspect of the present invention, and as a predictive tool for various other applications such as organic catalysts, solar cell electrolytes, and phase transition catalysts, as well as as a carbon material precursor.

[0151] The imidazole compounds of formula (I) can be prepared via a modular pathway in which substituents can be easily modified, and are readily converted to imidazolium cations (e.g., those of formula (II)) by alkylation, thus belonging to the category of organic compounds that are readily synthesized.

[0152] Methods for synthesizing imidazole and imidazolium compounds are well known in the art. In some embodiments, compounds of formula (I) or formula (II) are expressed in Scheme 1: [ka] It is synthesized as shown below.

[0153] In the second phase, the present invention relates to formula (III'): [ka] We provide a polymer containing multiple imidazolium-containing repeating units (IRUs) of the formula: R 2' C1-C6 alkyl and R 2 Selected from; R 2 Each of these consists of 0 to 3 substituents R selected individually from C1-C3 alkyl groups. 6 It is a phenyl that is substituted with; R 3' It is hydrogen, methyl and R 3 Selected from; R 3 C2-C 16 Selected from hydrocarbil; R 4 and R 5 These are individually C1-C 16 Selected from hydrocarbil, or together with R 4 and R 5 Together with the carbon atoms to which they bond, they form rings selected from benzene, cyclooctene, and norbornene; X- is the counterion; The wavy lines indicate points of bonding to adjacent repeating units of the polymer; W is a direct bond or C1-C 10 It is hydrocarbyl; Y is a direct bond or C1-C 10 It is hydrocarbyl; Z is a direct bond or C1-C 13 It is hydrocarbyl, and here C1-C 13 One carbon atom in hydrocarbyl can be optionally substituted with oxygen, provided that the total number of carbon atoms in W, Y, and Z is between 1 and 15.

[0154] The polymers described herein include an imidazolium moiety. The imidazolium cations of the polymers provide enhanced stability under fuel cell operating conditions compared to other (e.g., ammonium) cations, which rapidly decompose under fuel cell operating conditions, limiting their usefulness and making improved AAEM stability a critical priority. Therefore, the polymers are particularly desirable for use as alkali anion exchange membranes (AAEMs). Fuel cells are constructed by methods well known in the art, in which the membranes described herein can replace anion exchange membranes of the art.

[0155] Regarding the polymer of the second surface of the present invention, R 2 ~R 6 This is defined in advance with respect to various aspects of the first aspect of the present invention.

[0156] W is a direct bond or C1-C 10 It is hydrocarbil.

[0157] In some embodiments, W is directly bonded or (C1-C 10 ) Alkylene (i.e., C1, C2, C3, C4, C5, C6, C7, C8, C9 or C 10 It is alkylene.

[0158] Y is a direct bond or C1-C 10 It is hydrocarbil.

[0159] In some embodiments, Y is directly bonded or (C1-C 10 ) Alkylene (i.e., C1, C2, C3, C4, C5, C6, C7, C8, C9 or C 10 It is alkylene.

[0160] In some embodiments, W is (CH2). 1-5 And Y is (CH2) 1-5 That is the case.

[0161] Z is a direct bond or C1-C 13 It is hydrocarbyl, and here C1-C13 One of the carbon atoms in hydrocarbyl can be optionally substituted with oxygen.

[0162] In some embodiments, Z includes a phenylene moiety. Phenylene is a divalent phenyl compound: [ka] It refers to.

[0163] In some embodiments, the polymer of the present invention comprises a compound of formula (I) or (II) or a residue thereof.

[0164] In some embodiments, the polymer of the present invention of formula (III') is of formula (III): [ka] It is a polymer.

[0165] In some embodiments, the polymer of the present invention comprises a plurality of imidazolium-containing repeating units of formula (IIIA'): where m is 0 or 1; Z 1a is C1-C 13 It is hydrocarbil.

[0166] In some embodiments, the polymer of the present invention is of formula (IIIA): [ka] It contains imidazolium-containing repeating units, where :m is 0 or 1;Z 1a is C1-C 13 It is hydrocarbil.

[0167] [ka] Here, :m is 0 or 1 and ;Z 1a is C1-C 13 It is hydrocarbil.

[0168] In some embodiments of polymers containing imidazolium-containing repeating units of formula (IIIA') or (IIIA), m is 0.

[0169] In some embodiments of polymers containing imidazolium-containing repeating units of formula (IIIA') or (IIIA), m is 1.

[0170] In some embodiments of polymers containing imidazolium-containing repeating units of formula (IIIA') or (IIIA), Z 1a is C1-C 10 It is hydrocarbil.

[0171] In some embodiments of polymers containing imidazolium-containing repeating units of formula (IIIA') or (IIIA), Z 1a It is C1-C8 hydrocarbyl.

[0172] In some embodiments of polymers containing imidazolium-containing repeating units of formula (IIIA') or (IIIA), Z 1a ha-(CH2) p -(Ph) q -(CH2) r - and in the formula: p is 1 to 6; q is 0 or 1; r is 1 to 6. In some embodiments, p is 1 to 2; q is 0 or 1; r is 1 to 2.

[0173] In some embodiments, the polymer of the present invention is of formula (IIIB'): [ka] It contains imidazolium-containing repeating units, where: m is either 0 or 1; n is between 1 and 8.

[0174] In some embodiments, the polymer of the present invention is of formula (IIIB): [ka] It contains imidazolium-containing repeating units, where: m is either 0 or 1; n is between 1 and 8.

[0175] In some embodiments, the polymer comprises a polyolefin or polystyrene main chain.

[0176] In some embodiments, the polymer of the present invention is of formula (IIIC') or (IIIC): [ka] It contains imidazolium-containing repeating units.

[0177] In some such embodiments, X- is a halide.

[0178] In some embodiments of the polymer of the present invention, the total number of carbon atoms in W and Y is 1 or 3.

[0179] The polymers described herein may be molded or otherwise formed into films as described herein. These films are useful, for example, in hydrogen power generation devices, fuel cells, and water purification devices.

[0180] In some embodiments, the polymer includes hydrocarbon repeating units (HRUs) in addition to IRUs, and the polymer has the following structure: [ka] The formula has the following properties, where n' is 0.05 to 1.0 and represents the mole fraction of IRU in the polymer. The IRU and HRU units can be arranged randomly or sequentially. In some embodiments, n' is 0.1 to 0.4.

[0181] The polymer may be a random or block copolymer. Adjacent IRUs and HRUs, or IRUs and IRUs, or HRUs and HRUs may be linked by carbon-carbon single bonds or carbon-carbon double bonds, as shown below. In some embodiments, for example, when the polymer is used in AAEM, at least some of the double bonds are reduced. In some embodiments, 50-100% of carbon-carbon double bonds (e.g., 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, or 100%) are reduced to carbon-carbon single bonds.

[0182] Polymers may or may not be crosslinked. In some embodiments, polymers are not crosslinked. An example of an unsaturated, non-crosslinked polymer is shown in Structure I: [ka] As shown here, [ka] This is an imidazolium residue.

[0183] Examples of saturated non-crosslinked polymers are shown in Structure II: [ka] This will be shown.

[0184] Embodiments of the polymers of the present invention can be synthesized by ring-opening metathesis polymerization (ROMP), which can be carried out using, for example, a transition metal (e.g., ruthenium-based) metathesis catalyst (e.g., a second-generation Grubbs-type catalyst). The ROMP polymerization process is known in the art. For example, the method includes the step of providing a strained ring monomer (or more strained ring monomers) and a catalyst, for example, a ruthenium-based alkene metathesis catalyst. The monomer(s) and catalyst are optionally combined in the presence of a solvent. The reaction mixture is heated under conditions such that a polymer is formed. The strained ring structure is such that at least one bond angle in the molecule is an optimal tetrahedron (109.5°) (sp 3 Regarding the bond) or triangular face (120°) (sp 2 Unlike bond angles (regarding bonding), this means that the ground state energy of the carbon ring exceeds that of a carbon ring with normal bond angles.

[0185] Regarding ROMP, the imidazolium monomer (IM) (some embodiments of those included in class (II)) from which IRU is derived is a hydrocarbon having at least one polymerizable alkene group. IM may have multiple alkene moieties, which can result in a crosslinked polymer as a result of polymerization of two alkene moieties derived from two different IM units. For example, IM and monomers having multiple alkene functional groups can be copolymerized to provide a crosslinked polymer.

[0186] definition The term "alkyl" refers to a radical of a linear or branched saturated hydrocarbon group having 1 to 18 carbon atoms ("C"). 1-18 "Alkyl" refers to a group having 1 to 12 carbon atoms. In some embodiments, an alkyl group has 1 to 12 carbon atoms ("C"). 1-12 Alkyl). In some embodiments, the alkyl group has 1 to 8 carbon atoms ("C"). 1-8 Alkyl). In some embodiments, the alkyl group has 1 to 6 carbon atoms ("C"). 1-6 Alkyl). In some embodiments, the alkyl group has 1 to 3 carbon atoms ("C"). 1-3Alkyl). In some embodiments, the alkyl group has 2 to 6 carbon atoms ("C"). 2-6 Alkyl). C 1-6 Examples of alkyl groups include methyl (C1), ethyl (C2), propyl (C3) (e.g., n-propyl, isopropyl), butyl (C4) (e.g., n-butyl, tert-butyl, sec-butyl, iso-butyl), pentyl (C5) (e.g., n-pentyl, 3-pentanyl, amyl, neopentyl, 3-methyl-2-butanyl, tertiary amyl), and hexyl (C6) (e.g., n-hexyl). Further examples of alkyl groups include n-heptyl (C7), n-octyl (C8), etc. Unless otherwise specified, each example of alkyl group is independently either unsubstituted ("unsubstituted alkyl") or substituted with one or more substituents (e.g., halogens, e.g., F) ("substituted alkyl"). In some embodiments, the alkyl group is unsubstituted C 1-10 Alkyl (e.g., unsubstituted C) 1-6 Alkyl groups include, for example, -CH3(Me), unsubstituted ethyl (Et), unsubstituted propyl (Pr, for example, unsubstituted n-propyl (n-Pr), unsubstituted isopropyl (i-Pr)), and unsubstituted butyl (Bu, for example, unsubstituted n-butyl (n-Bu), unsubstituted tert-butyl (tert-Bu or t-Bu), unsubstituted sec-butyl (sec-Bu), and unsubstituted isobutyl (i-Bu)). In one embodiment, the alkyl group is substituted C 1-10 Alkyl (e.g., substituted C) 1-6 Alkyl (e.g., -CF3, Bn).

[0187] The term "alkenyl" refers to a radical of a linear or branched hydrocarbon group having 2 to 18 carbon atoms and one or more carbon-carbon double bonds (e.g., 1, 2, 3, or 4 double bonds). In some embodiments, the alkenyl group has 2 to 12 carbon atoms ("C"). 2-12 ("Alkenyl"). In some embodiments, the alkenyl group has 2 to 8 carbon atoms ("C"). 2-8 ("Alkenyl"). In some embodiments, the alkenyl group has 2 to 6 carbon atoms ("C"). 2-6("Alkenyl"). In some embodiments, the alkenyl group has 2 to 4 carbon atoms ("C"). 2-4 ("Alkenyl"). In some embodiments, the alkenyl group has 2-3 carbon atoms ("C"). 2-3 "Alkenyl"). One or more carbon-carbon double bonds can be located internally (e.g., within a 2-butenyl) or at the terminal (e.g., within a 1-butenyl). C 2-4 Examples of alkenyl groups include ethenyl (C2), 1-propenyl (C3), 2-propenyl (C3), 1-butenyl (C4), 2-butenyl (C4), and butadienyl (C4). 2-6 An example of an alkenyl group is the aforementioned C 2-4 Examples of alkenyl groups include pentenyl (C5), pentadienyl (C5), hexenyl (C6), etc. Further examples of alkenyls include heptenyl (C7), octenyl (C8), octatrienyl (C8), etc. Unless otherwise specified, each example of an alkenyl group is independently either unsubstituted ("unsubstituted alkenyl") or substituted with one or more substituents ("substituted alkenyl"). In some embodiments, the alkenyl group is unsubstituted C 2-18 It is an alkenyl. In one embodiment, the alkenyl group is substituted with C 2-18 It is an alkenyl. In the alkenyl group, the stereochemistry is not determined by the C=C double bond (e.g., -CH=CHCH3 or [ka] ) can be an (E)- or (Z)- double bond.

[0188] The term "alkynyl" refers to a radical of a linear or branched hydrocarbon group having 2 to 18 carbon atoms and one or more carbon-carbon triple bonds (e.g., 1, 2, 3, or 4 triple bonds). 2-18 ("Alkynyl"). In some embodiments, the alkynyl group has 2 to 12 carbon atoms ("C"). 2-12 ("Alkynyl"). In some embodiments, the alkynyl group has 2 to 8 carbon atoms ("C"). 2-8("Alkynyl"). In some embodiments, the alkynyl group has 2 to 6 carbon atoms ("C"). 2-6 ("Alkynyl"). In some embodiments, the alkynyl group has 2 to 4 carbon atoms ("C"). 2-4 ("Alkynyl"). In some embodiments, the alkynyl group has 2-3 carbon atoms ("C"). 2-3 Alkynyl). One or more carbon-carbon triple bonds can be internal (e.g., in 2-butynyl) or terminal (e.g., in 1-butynyl). C 2-4 Examples of alkynyl groups include, but are not limited to, ethynyl (C2), 1-propynyl (C3), 2-propynyl (C3), 1-butynyl (C4), 2-butynyl (C4), etc. 2-6 An example of an alkenyl group is the aforementioned C 2-4 Examples include alkynyl groups and pentynyl (C5), hexynyl (C6), etc. Further examples of alkynyls include heptynyl (C7), octinyl (C8), etc. Unless otherwise specified, each example of an alkynyl group is independently either unsubstituted ("unsubstituted alkynyl") or substituted with one or more substituents ("substituted alkynyl"). In some embodiments, the alkynyl group is unsubstituted C 2-18 It is an alkynyl group. In one embodiment, the alkynyl group is substituted with C 2-18 It is alkinyl.

[0189] The term "carbocykrill" or "carbocyclic" refers to the radical of a non-aromatic cyclic hydrocarbon group having 3 to 18 ring carbon atoms and 0 heteroatoms in a non-aromatic cyclic system ("C 3-18 Carbocyclyl). In some embodiments, the carbocyclyl group has 3 to 12 ring carbon atoms ("C"). 3-12 Carbocyclyl). In some embodiments, the carbocyclyl group has 3 to 8 ring carbon atoms ("C"). 3-8 Carbocyclyl). In some embodiments, the carbocyclyl group has 3 to 6 ring carbon atoms ("C"). 3-6 Carbocyclyl). In some embodiments, the carbocyclyl group has 5-6 ring carbon atoms ("C"). 5-6Carbocyclyl). In some embodiments, the carbocyclyl group has 5 to 10 ring carbon atoms ("C"). 5-10 Carbocyclyl). Exemplary C 3-6 Examples of carbocyclyl groups include, but are not limited to, cyclopropyl (C3), cyclopropenyl (C3), cyclobutyl (C4), cyclobutenyl (C4), cyclopentyl (C5), cyclopentenyl (C5), cyclohexyl (C6), cyclohexenyl (C6), and cyclohexadienyl (C6). 3-8 The carbocyclyl group is not limited to the aforementioned C 3-6 Examples include the carbocyclyl group and cycloheptyl (C7), cycloheptenyl (C7), cycloheptadienyl (C7), cycloheptatrienyl (C7), cyclooctyl (C8), cyclooctenyl (C8), bicyclo[2.2.1]heptanyl (C7), bicyclo[2.2.2]octanyl (C8), etc. Exemplary C 3-10 The carbocyclyl group is not limited to the aforementioned C 3-8 Carbocyclyl group and cyclononyl (C9), cyclononenyl (C9), cyclodecyl (C9) 10 ), cyclodecenyl (C 10 ), octahydro-1H-indenyl (C9), decahydronaphthalenyl (C9) 10 ), spiro[4.5]decanil(C 10Examples include the following. As the above examples show, in some embodiments, a carbocyclyl group may be monocyclic ("monocyclic carbocyclyl") or polycyclic (e.g., condensed, bridging, or spirocyclic systems, bicyclic systems ("bicyclic carbocyclyl") or tricyclic systems ("tricyclic carbocyclyl")) and may be saturated or contain one or more carbon-carbon double or triple bonds. "Carbocyclyl" also includes cyclic systems in which the previously defined carbocyclyl ring is condensed with one or more aryl or heteroaryl groups, and the bonding points are on the carbocyclyl ring, in which case the carbon number continues to indicate the number of carbons in the carbocyclic cyclic system. Unless otherwise specified, each example of a carbocyclyl group is independently either unsubstituted ("unsubstituted carbocyclyl") or substituted with one or more substituents ("substituted carbocyclyl"). In some embodiments, a carbocyclyl group may be unsubstituted C 3-14 It is a carbocyclyl. In one aspect, the carbocyclyl group is a substituted C 3-14 It is carbocyclyl.

[0190] In some embodiments, "cycloalkyl" is a monocyclic saturated carbocyaryl group having 3 to 18 ring carbon atoms ("C 3-18 ("Cycloalkyl"). In some embodiments, the cycloalkyl group has 3 to 12 ring carbon atoms ("C"). 3-12 ("Cycloalkyl"). In some embodiments, the cycloalkyl group has 3 to 8 ring carbon atoms ("C"). 3-8 ("Cycloalkyl"). In some embodiments, the cycloalkyl group has 3 to 6 ring carbon atoms ("C"). 3-6 ("Cycloalkyl"). In some embodiments, the cycloalkyl group has 4 to 6 ring carbon atoms ("C"). 4-6 ("Cycloalkyl"). In some embodiments, the cycloalkyl group has 5-6 ring carbon atoms ("C"). 5-6 ("Cycloalkyl"). In some embodiments, the cycloalkyl group has 5 to 7 ring carbon atoms ("C"). 5-7 Cycloalkyl). C 5-6 Examples of cycloalkyl groups include cyclopentyl (C5) and cyclohexyl (C6).3-6 Examples of cycloalkyl groups include, as mentioned earlier, C 5-6 Examples include cycloalkyl groups, as well as cyclopropyl (C3) and cyclobutyl (C4). 3-8 Examples of cycloalkyl groups include, as mentioned earlier, C 3-6 Examples include cycloalkyl groups, as well as cycloheptyl (C7) and cyclooctyl (C8). Unless otherwise specified, each example of a cycloalkyl group is independently either unsubstituted ("unsubstituted cycloalkyl") or substituted with one or more substituents ("substituted cycloalkyl"). In some embodiments, the cycloalkyl group is unsubstituted C 3-18 It is a cycloalkyl group. In one embodiment, the cycloalkyl group is a substituted C 3-18 It is a cycloalkyl group.

[0191] The term "aryl" refers to a radical of a monocyclic or polycyclic (e.g., bicyclic or tricyclic) 4n+2 aromatic ring system (e.g., having 6, 10, or 14 π electrons shared in a cyclic array) having 6 to 14 ring carbon atoms and 0 heteroatoms provided in an aromatic ring system ("C 6-14 In some embodiments, the aryl group has 6 ring carbon atoms ("C6 aryl"; e.g., phenyl). In some embodiments, the aryl group has 10 ring carbon atoms ("C6 aryl"). 10 "Aryl"; for example, naphthyl such as 1-naphthyl and 2-naphthyl). In some embodiments, the aryl group has 14 ring carbon atoms ("C"). 14 "Aryl" (e.g., anthracyl). "Aryl" also includes ring systems in which the previously defined aryl ring is condensed with one or more carbocyrillic or heterocyclyl groups, and the radical or bonding point lies on the aryl ring, in which case the number of carbon atoms continues to indicate the number of carbon atoms in the aryl ring system. Unless otherwise specified, each example of an aryl group is independently either unsubstituted ("unsubstituted aryl") or substituted with one or more substituents ("substituted aryl"). In some embodiments, the aryl group is unsubstituted C 6-14 It is aryl. In one embodiment, the aryl group is substituted C 6-14It is Ariel.

[0192] The term "saturated" refers to the portion that does not contain double or triple bonds, meaning that the portion contains only single bonds.

[0193] Adding the suffix "-en" to a base indicates that the base is a divalent part. For example, alkylene is the divalent part of alkyl, alkenylene is the divalent part of alkenyl, alkynylene is the divalent part of alkynyl, carbocyclylene is the divalent part of carbocyclyl, and arylene is the divalent part of aryl.

[0194] The term "haloalkyl" refers to an alkyl group defined as being substituted with one or more halogen atoms. The term "halogen" refers to F, Cl, Br, or I. Preferably, the halogen in the haloalkyl group is F.

[0195] As used herein, the term "hydrocarbyl" means a monovalent hydrocarbon radical, such as alkyl, alkenyl, alkynyl, aryl, carbocykyl, or cycloalkyl.

[0196] When used throughout the specification, examples, and claims, the terms “hydrocarbyl,” “alkyl,” “alkenyl,” “alkynyl,” “alkylene,” “aryl,” “carbocyclyl,” and “cycloalkyl” are intended to include both “unsubstituted” and “substituted” groups, the latter being a portion having a substituent that substitutes a hydrogen on one or more carbons of a hydrocarbon. Such substituents, unless otherwise specified, may include, for example, halogens, haloalkyls, hydroxyls, carbonyls (e.g., carboxyls, alkoxycarbonyls, formyl, or acyls), thiocarbonyls (e.g., thioesters, thioacetates, or thioformates), alkoxyls, phosphoryls, phosphates, phosphonates, phosphinates, aminos, amides, amidines, imines, cyanos, nitros, azides, sulfhydryls, alkylthios, sulfates, sulfonates, sulfamoyls, sulfonamides, sulfonyls, heterocyclyls, arylalkyls, or aromatic or heteroaromatic moieties. It will be understood by those skilled in the art that a substituted portion on a hydrocarbon chain may, where appropriate, be substituted itself. For example, substituents on substituted alkyl groups may include amino, azide, imino, amide, phosphoryl (e.g., phosphonate and phosphinate), sulfonyl (e.g., sulfate, sulfonamide, sulfamoyl and sulfonate) and silyl groups, as well as substituted and unsubstituted forms such as ether, alkylio, carbonyl (e.g., ketone, aldehyde, carboxylate and ester), -CF3, and -CN.

[0197] The term “C x-y When used in relation to chemical moieties such as acyl, acyloxy, alkyl, alkenyl, alkynyl, or alkoxy, it means that the chain contains a group with x to y carbon atoms. For example, the term "C x-y "Alkyl" refers to substituted or unsubstituted saturated hydrocarbon groups, such as linear and branched alkyl groups containing x to y carbon atoms in the chain, such as haloalkyl groups like trifluoromethyl and 2,2,2-trifluoroethyl. C0 alkyl represents hydrogen, where the group is at the terminal position, or a bond if it is internal. 2-y"Alkenil" and "C 2-y "Alkynyl" refers to a substituted or unsubstituted unsaturated aliphatic group that is similar in length and can substitute for the alkyl group described above, but contains at least one double or triple bond.

[0198] Numerical ranges include the number that defines the range. Measured values ​​and measurable values ​​are understood to be approximations, taking into account the number of significant digits and the errors associated with the measurement. As used in this application, the terms “about” and “approximately” have their technically understood meanings; the use of one and the other does not necessarily imply different ranges. Unless otherwise indicated, numerical values ​​as used in this application should be understood to include deviations and / or variations from standards as understood by those skilled in the art in the relevant field, with or without modifying terms such as “about” or “approximately.” In some embodiments, the terms “approximately” or “about” mean a range of values ​​that are within 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, or less in either direction (greater than or less than) the given reference value, unless otherwise indicated or it is clear from the context (except where such number exceeds 100% of the possible value).

[0199] As used herein, the term “composite material” means a material made from two or more constituent materials having significantly different physical or chemical properties separated by a distinct interface. When combined, the two or more constituent materials result in a composite material having characteristics distinct from the individual components. Since the individual components remain separated and distinct within the composite material, the composite material is distinguished from mixtures and solid solutions.

[0200] As used herein, the term “reinforcement” means any material that can provide mechanical support to a polymer electrolyte without interfering with the function of the polymer electrolyte. For example, a reinforcement may be mixed with the polymer electrolyte, immersed in the polymer electrolyte, or coated with the polymer electrolyte to provide a composite material. The reinforcement may be a ceramic material, a polymer or a composite of an inorganic material and a polymer, or an inorganic material such as glass fiber.

[0201] As used herein, “support material” means a material having mechanical strength and chemical durability that can be immersed and / or coated with a polymer electrolyte to provide a composite material. Support materials may be made of, for example, ceramic materials or polymers such as polyolefins, polysulfones, or polyamides. In some embodiments, the support includes polyimide, polybenzimidazole, polyphenylsulfone, polyphenyl ether, cellulose nitrate, cellulose diacetate, cellulose triacetate, polypropylene, polyethylene, polyvinylidene fluoride, poly(phenylene sulfide), poly(vinyl chloride), polystyrene, poly(methyl methacrylate), polyacrylonitrile, polytetrafluoroethylene, polyetheretherketone, polycarbonate, polyvinyltrimethylsilane, polytrimethylsilylpropyne, poly(etherimide), poly(ethersulfone), polyoxadiazole, or poly(phenylene oxide) or combinations thereof or copolymers. Support materials may be in the form of films.

[0202] As used herein, the term “porous material immersed in a polymer electrolyte” means a porous material that contains a polymer electrolyte within its pores. A porous material can be immersed in a polymer electrolyte, for example, by immersing the material in a solution of the polymer electrolyte. Alternatively, a porous material can be immersed in a solution of one or more monomers, during which polymerization reactions continue within the pores of the material. Furthermore, once a porous material is immersed in a polymer electrolyte, the polymer electrolyte may undergo further chemical deformation, such as crosslinking, within the pores of the material.

[0203] As used herein, the term “repeating unit” (also known as a monomer unit) refers to a chemical part that periodically repeats itself to produce a complete polymer chain (excluding terminal groups) when repeated units are linked together in a continuous manner. A polymer may contain one or more different repeating units.

[0204] The term "degree of crosslinking," as used herein, refers to the fraction of repeating units that can form crosslinks, relative to the total number of repeating units in a polymer. The degree of crosslinking is generally expressed as a mole percent with respect to the total number of repeating units in the polymer.

[0205] As used herein, the term “polymer electrolyte” means a polymer that, under certain conditions, has a net positive or negative charge due to the presence of charged repeating units. In some embodiments, the polymer electrolyte is or contains a polycation; in some embodiments, the polymer electrolyte is or contains a polyanion. A polycation has a net positive charge, and a polyanion has a net negative charge. The net charge of a given polymer electrolyte may depend on ambient chemical conditions, such as pH.

[0206] As used herein, "ion exchange capacity" refers to the total number of active sites or functional groups that cause ion exchange in a polyelectrolyte. The ion exchange capacity for hydroxide exchange polyelectrolytes can be calculated by Equation 1, based on the experimentally determined number of hydroxide ions exchanged within the polymer. Since the mass of the sample is the sum of the dry weight of the support and the polymer, ion accessibility for the polyelectrolyte-containing composite film is measured instead and calculated by Equation 2.

number

[0207] As used herein, "ionic conductivity" refers to the ability of a material, such as a polymer electrolyte, to facilitate the movement of ions through the material. For example, the ionic conductivity of a polymer electrolyte membrane across a plane can be calculated using Equation 3, based on the bulk resistance (R), membrane active area (L), and film thickness (A).

number

[0208] As used herein, "porosity" refers to the fraction of empty volume relative to the total volume of a material. Porosity can be an infinite value between 0 and 1, or a percentage between 0% and 100%.

[0209] As used herein, the terms “void space” or “void volume” refer to the porosity of a composite material, including a polymer-impregnated porous material. Void space is distinct from the porosity of a porous material, as some of the pore volume of a porous material is occupied by polymer deposited within the material’s pore system. Void space can be about 1%, about 2.5%, about 5%, about 7.5%, about 10%, about 12.5%, about 15%, about 17.5%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, or about 50%.

[0210] As used herein, the term “polyolefin” refers to a polymer produced by the polymerization of organic molecules containing carbon-carbon double bonds. The main chain of a polyolefin contains a saturated chain of carbon-carbon bonds. In some embodiments, carbon atoms in the main chain of a polyolefin may be substituted with hydrocarbyl groups. For example, carbon atoms in the main chain of a polyolefin may be substituted with alkyl, cycloalkyl, or aryl groups. In some embodiments, carbon atoms in the main chain of a polyolefin may be substituted with halogens such as fluorine.

[0211] As used herein, "perfluorinated polyolefin" refers to a polyolefin in which all hydrogen atoms are replaced with fluorine.

[0212] As used herein, "inorganic material" refers to a material that does not contain carbon-carbon bond chains, excluding elemental carbon allotropes such as graphite, graphene, diamond, or carbon nanotubes. Examples of inorganic materials include glass, ceramic materials, and metal oxides such as TiO2, Al2O3, and ZnO.

[0213] As used herein, the term "ceramic material" refers to crystalline or amorphous oxides, nitrides, or carbides of metallic or nonmetallic elements. Ceramic materials are generally hard, brittle, thermally resistant, and corrosion-resistant. Examples of ceramic materials include SiC, Si3N4, TiC, ZnO, ZrO2, Al2O3, and MgO.

[0214] As used herein, the term "current collector" refers to the electrical conductor between an electrode in an electrochemical device, such as a battery, and an external circuit.

[0215] In a first embodiment, the present invention relates to a composite material comprising a reinforcing material and a polymer electrolyte in contact with the reinforcing material, wherein the polymer electrolyte is a material of structural formula I, II, II, or IV: [ka] It includes a first repeating unit selected from the parts represented by the formula, where: [ka] This indicates a point of connection to other repeating units; R 11 , R 21 , R 31 and R 41 Each is independent of C 1-4 It is alkyl; R 12 , R 13 , R 22 , R 23 , R 32 , R 33 , R 42 and R 43 Each is independent of C1-4 Alkyl or C 5-7 It is a cycloalkyl; Z 11 , Z 21 , Z 31 and Z 41 Each is independent of C -1-10 Alkylene or *O-(C) 1-10 (Alkylene), where * indicates a point of attachment to the polymer main chain; X - These are halides, OH - , HCO3 - CO3 2- CO2(R 10 ) - , O(R 10 ) - NO3 - 5CN - PF6 - Or BF4 - and; R 10 is C 1-4 It is alkyl.

[0216] In the first aspect of the first embodiment, the reinforcing material includes polymers, inorganic materials, or combinations thereof. For example, the reinforcing material includes polyolefins, polyphenylenes, polyesters, polyamides, or polysulfones. For example, the reinforcing material includes perfluorinated polyolefins such as polytetrafluoroethylene. For example, the reinforcing material includes polyimides, polybenzimidazoles, polyphenylsulfones, polyphenyl ethers, polytetrafluoroethylenes, cellulose nitrates, cellulose diacetates, cellulose triacetates, polypropylenes, polyethylenes, polyvinylidene fluorides, poly(phenylene sulfide), polyvinyl chloride, polystyrene, poly(methyl methacrylate), polyacrylonitriles, polyetheretherketones, polycarbonates, polyvinyltrimethylsilanes, polytrimethylsilylpropyne, poly(etherimide), poly(ethersulfone), polyoxadiazoles, poly(phenylene sulfide) or poly(phenylene oxide), or combinations thereof or copolymers. The composite material may include polyethylene, polypropylene, polytetrafluoroethylene, polyvinyl chloride, or polyvinyl difluoroethylene. Alternatively or additionally, the reinforcing material may include glass fiber or ceramic material.

[0217] In the second aspect of the first embodiment, the composite material is a mixture of a reinforcing material and a polymer electrolyte. Alternatively or additionally, the reinforcing material is a first layer; the electrolyte is a second layer; and the first layer is in contact with at least one of the second layers. Alternatively or additionally, the reinforcing material is a porous material; and the porous material is immersed in the electrolyte. The remaining and exemplary values ​​of the variables of the composite material are as described above with respect to the first aspect of the first embodiment.

[0218] In the third aspect of the first embodiment, the reinforcing material is a porous material having about 40% to about 90% porosity, for example, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, about 75%, about 80%, about 85%, or about 90% porosity. For example, the porous material has about 70% to about 85% porosity, for example, about 73% porosity. The remaining and exemplary values ​​of the variables for the composite material are as stated above with respect to the first and second aspects of the first embodiment.

[0219] In the fourth aspect of the first embodiment, the reinforcing material is a porous material, and the average size of the pores of the porous material is approximately 50 nm to approximately 500 μm, for example, approximately 50 nm, approximately 100 nm, approximately 200 nm, approximately 300 nm, approximately 400 nm, approximately 500 nm, approximately 600 nm, approximately 700 nm, approximately 800 nm, approximately 900 nm, approximately 1 μm, approximately 1 μm, approximately 1 μm, approximately 1 μm, approximately 10 μm, approximately 25 μm, approximately 50 μm, approximately 100 μm, approximately 150 μm, approximately 200 μm, approximately 250 μm, approximately 300 μm, approximately 350 μm, approximately 400 μm, approximately 450 μm, or approximately 500 μm. For example, the average size of the pores is approximately 100 nm to approximately 10 μm, for example, approximately 300 nm to approximately 1 μm. For example, the average size of the pores is approximately 450 nm. The remaining and exemplary values ​​of the variables for the composite material are as described above with respect to the first to third aspects of the first embodiment.

[0220] In the fifth aspect of the first embodiment, the composite material is a film having a thickness of about 1 μm to about 300 μm, for example, about 1 μm, about 5 μm, about 10 μm, about 20 μm, about 30 μm, about 40 μm, about 50 μm, about 60 μm, about 70 μm, about 80 μm, about 90 μm, about 100 μm, about 120 μm, about 140 μm, about 160 μm, about 180 μm, about 200 μm, about 220 μm, about 240 μm, about 260 μm, about 280 μm, or about 300 μm. For example, the composite material is a film having a thickness of about 25 μm to about 75 μm, for example, about 50 μm. The remaining values ​​and exemplary values ​​of the variables for the composite material are as described above with respect to the first to fourth aspects of the first embodiment.

[0221] In the sixth aspect of the first embodiment, the polymer electrolyte further comprises a second repeating unit Z 2 This includes Z 2 is a linear C 2-8 Alkylene or the following structural formula [ka] This is the chemical part represented by the formula: [ka] This indicates a point of connection to other repeating units; Linear C 2-8 Alkylenes are either unsubstituted or have one or more C 1-3 Alkyl, C 1-3 Haloalkyl, C 1-3 Alkyl (C6- 14 (aryl) or -(C) 1-3 Alkylene)O(C 1-3 Alkylene) C 6-14 It is replaced by an aryl, where each aryl is arbitrarily 1 to 3 C 1-3 Alkyl or C 1-3 Substituted with a haloalkyl group; R 4 and R 5 These are H and C, which are independent of each other. 1-3 Alkyl, C 1-3 Haloalkyl, C 3-8 Alkenil, C 1-3 Alkyl (C 6-14 (aryl) or -(C 1-3 Alkylene)O(C 1-3 Alkilen) (C 6-14 (Aryl) and here each aryl can be any of C 1 to 3 1-3 Alkyl or C 1-3 Substituted with a haloalkyl group, or R 4 and R 5 They become C together with the carbon atoms to which they bond. 5-7 Forms a cycloalkyl group; here C 5-7 Cycloalkyls can optionally be -C(O)O(C 1-3 (Alkyl) or C3-8 It is substituted with an alkenyl. The remaining and exemplary values ​​of the variables for the composite material are as described above with respect to the first to fifth aspects of the first embodiment.

[0222] In the seventh aspect of the first embodiment, the polyelectrolyte comprises at least a first polymer chain and a second polymer chain, wherein the first polymer chain is crosslinked to the second polymer chain. For example, the polyelectrolyte further comprises at least one linkage portion, where the linkage portion has the following structural formula [ka] or [ka] Selected from the part represented by the formula, in the formula [ka] This indicates the point of bonding of the linking portion to the first polymer chain; [ka] This indicates the point of bonding of the linking portion to the second polymer chain; Y 11 , Y 13 , Y 21 and Y 23 Each is independent of C 1-3 It is alkylene; Y 31 and Y 33 Each is independent of C 1-5 It is alkylene; R 15 and R 25 Each is independent of C 1-4 It is alkyl; Y 12 , Y 23 and Y 32 Each is independent of C 2-10 Alkylene or (C 1-3 Alkilen) (C6 aryl) (C 1-3(Alkylene). The remaining and exemplary values ​​of the variables for the composite material are as described above with respect to the first to sixth aspects of the first embodiment.

[0223] In the eighth aspect of the first embodiment, the polyelectrolyte comprises at least a first polymer chain, a second polymer chain, and a third polymer chain, wherein the first polymer chain is crosslinked with the second and third polymer chains. The remaining and exemplary values ​​of the variables of the composite material are as described above with respect to the first to seventh aspects of the first embodiment. For example, the polyelectrolyte further comprises at least one linkage portion, where the linkage portion has the following structural formula [ka] Selected from the part represented by the formula, in the formula [ka] This indicates the point of bonding of the linking portion to the first polymer chain; [ka] This indicates the point of bonding of the linking portion to the second polymer chain; [ka] This indicates the point of bonding of the linking portion to the third polymer chain; R 6 is H or -C(O)O(C 1-3 Alkyl) The remaining and exemplary values ​​of the variables for the composite material are as described above with respect to the first to seventh aspects of the first embodiment.

[0224] In the ninth aspect of the first aspect, R 11 is methyl. The remaining and exemplary values ​​of the variables for the composite material are as described above with respect to the first to eighth aspects of the first embodiment.

[0225] In the tenth aspect of the first aspect, R 21is methyl. The remaining and exemplary values ​​of the variables for the composite material are as described above with respect to the first to ninth aspects of the first embodiment.

[0226] In the eleventh aspect of the first embodiment, R 31 is methyl. The remaining and exemplary values ​​of the variables for the composite material are as described above with respect to the first to tenth aspects of the first embodiment.

[0227] In the twelfth aspect of the first embodiment, R 41 is methyl. The remaining and exemplary values ​​of the variables for the composite material are as described above with respect to the first to eleventh aspects of the first embodiment.

[0228] In the thirteenth aspect of the first embodiment, R 12 is C 1-4 It is alkyl. For example, R 12 It is methyl. Alternatively, R 12 isopropyl. The remaining and exemplary values ​​of the variables for the composite material are as described above with respect to the first to twelfth aspects of the first embodiment.

[0229] In the 14th aspect of the first embodiment, R 22 is C 1-4 It is alkyl. For example, R 22 It is methyl. Alternatively, R 22 isopropyl. The remaining and exemplary values ​​of the variables for the composite material are as described above with respect to the first to thirteenth aspects of the first embodiment.

[0230] In the 15th aspect of the first aspect, R 32 is C 1-4 It is alkyl. For example, R 32 It is methyl. Alternatively, R 32 isopropyl. The remaining and exemplary values ​​of the variables for the composite material are as described above with respect to the first to fourteenth aspects of the first embodiment.

[0231] In the 16th aspect of the first embodiment, R42 is C 1-4 It is alkyl. For example, R 42 It is methyl. Alternatively, R 42 isopropyl. The remaining and exemplary values ​​of the variables for the composite material are as described above with respect to the first to fifteenth aspects of the first embodiment.

[0232] In the 17th aspect of the first aspect, R 13 is C 5-7 It is a cycloalkyl. For example, R 13 It is cyclohexyl. The remaining and exemplary values ​​of the variables for the composite material are as described above with respect to the first to sixteenth aspects of the first embodiment.

[0233] In the 18th aspect of the first aspect, R 13 is C 1-4 It is alkyl. For example, R 13 is methyl. The remaining and exemplary values ​​of the variables for the composite material are as described above with respect to the first to sixteenth aspects of the first embodiment.

[0234] In the 19th aspect of the first aspect, R 23 is C 5-7 It is a cycloalkyl. For example, R 23 It is cyclohexyl. The remaining and exemplary values ​​of the variables for the composite material are as described above with respect to the first to eighteen aspects of the first embodiment.

[0235] In the 20th aspect of the first embodiment, R 23 is C 1-4 It is alkyl. For example, R 23 is methyl. The remaining and exemplary values ​​of the variables for the composite material are as described above with respect to the first to eighteen aspects of the first embodiment.

[0236] In the 21st aspect of the first embodiment, R 33 is C 5-7 It is a cycloalkyl. For example, R 33It is cyclohexyl. The remaining and exemplary values ​​of the variables for the composite material are as described above with respect to the first to twentieth aspects of the first embodiment.

[0237] In the 22nd aspect of the first embodiment, R 33 is C 1-4 It is alkyl. For example, R 33 is methyl. The remaining and exemplary values ​​of the variables for the composite material are as described above with respect to the first to twentieth aspects of the first embodiment.

[0238] In the 23rd aspect of the first aspect, R 43 is C 5-7 It is a cycloalkyl. For example, R 13 It is cyclohexyl. The remaining and exemplary values ​​of the variables for the composite material are as described above with respect to the first to twenty-second aspects of the first embodiment.

[0239] In the 24th aspect of the first embodiment, R 43 is C 1-4 It is alkyl. For example, R 43 is methyl. The remaining and exemplary values ​​of the variables for the composite material are as described above with respect to the first to twenty-second aspects of the first embodiment.

[0240] In the 25th aspect of the first embodiment, Z 2 C is a linear substitution or unsubstituted C 2-8 It is an alkylene, for example Z 2 This is a straight-chain C8 alkylene. For example, a straight-chain C8 alkylene is C 1-3 Alkyl, C 1-3 Haloalkyl, C 1-3 Alkyl (C 6-14 (aryl) or -(C 1-3 Alkylene)O(C 1-3 Alkilen) (C 6-14 It is substituted with aryl(-CH2F), for example, a straight-chain C8 alkylene is substituted with -CH2F, -CH2CH2C6H5 or -CH2OCH2(3,5-(CF3)2C6H3). Alternatively, Z 2is an unsubstituted linear C8 alkylene. The remaining and exemplary values ​​of the variables for the composite material are as described above with respect to the first to twenty-fourth aspects of the first embodiment.

[0241] In the 26th aspect of the first embodiment, Z 2 The following structural formula [ka] This is the chemical part represented by R. For example, R 4 and R 5 Each of these is independently H or C 3-8 It is an alkenyl. Alternatively, R 4 and R 5 Together with the carbon atoms to which they bond, C 5-7 Form a cycloalkyl group, for example R 4 and R 5 These, together with the carbon atoms they bond to, become -C(O)O(C 1-3 C substituted with alkyl 5-7 It forms a cycloalkyl group. The remaining and exemplary values ​​of the variables for the composite material are as described above with respect to the first to twenty-fourth aspects of the first embodiment.

[0242] In the 27th aspect of the first embodiment, the polymer electrolyte is a material with structural formula V or VI: [ka] As shown in the formula, n is an integer between 2 and 2000; m is an integer between 0 and 10000; k is an integer between 1 and 1000; l is an integer between 0 and 10000; For example, polymer electrolytes have structural formula VII: [ka] The remaining and exemplary values ​​of the variables for the composite material are as described above with respect to the first to twenty-sixth aspects of the first embodiment.

[0243] In the 28th aspect of the first embodiment, the polymer electrolyte contains about 10 mol-% to about 100 mol-% of the first repeating units represented by structural formula I, for example, about 10 mol-%, about 20 mol-%, about 30 mol-%, about 40 mol-%, about 50 mol-%, about 60 mol-%, about 70 mol-%, about 80 mol-%, about 90 mol-%, or about 100 mol-%. For example, the polymer electrolyte contains about 20 wt.% to about 60 wt.% of the first repeating units represented by structural formula I, for example, about 30 mol-% to about 50 mol-% of the first repeating units represented by structural formula I, for example, about 37 mol-% of the first repeating units represented by structural formula I. The remaining and exemplary values ​​of the variables for the composite material are as described above with respect to the first to 27th aspects of the first embodiment.

[0244] In the 28th aspect of the first embodiment, the degree of crosslinking of the polymer electrolyte is approximately 5% to approximately 15%. The remaining and exemplary values ​​of the variables for the composite material are as described above with respect to the first to 27th aspects of the first embodiment.

[0245] In the 29th aspect of the first embodiment, the molecular weight of the polymer electrolyte is approximately 5,000 g / mol to approximately 1,000,000 g / mol, for example, approximately 5,000 g / mol, approximately 10,000 g / mol, approximately 50,000 g / mol, approximately 100,000 g / mol, approximately 200,000 g / mol, approximately 300,000 g / mol, approximately 400,000 g / mol, approximately 500,000 g / mol, approximately 600,000 g / mol, approximately 700,000 g / mol, approximately 800,000 g / mol, approximately 900,000 g / mol, or approximately 1,000,000 g / mol. For example, the molecular weight of the polymer electrolyte is approximately 200,000 g / mol to approximately 800,000 g / mol, for example, approximately 300,000 g / mol to approximately 500,000 g / mol, for example, approximately 360,000 g / mol. The remaining and exemplary values ​​of the variables for the composite material are as described above with respect to the first to twenty-eight aspects of the first embodiment.

[0246] In a second embodiment, the present invention is a film comprising a film of any of the composite materials described herein with respect to the first embodiment and various aspects thereof.

[0247] In a third aspect, the present invention is a membrane electrode assembly comprising any membrane and electrode described herein with respect to a second aspect and various aspects thereof.

[0248] In a fourth aspect, the present invention is an electrochemical device comprising any membrane electrode assembly and current collector described herein with respect to a third aspect and various aspects thereof.

[0249] In the first aspect of the fourth embodiment, the device is an electrolytic device.

[0250] In a fifth embodiment, the present invention is a method for producing any of the composite materials described herein with respect to the first embodiment and various aspects thereof, the method being: (a) A step of providing a first solution containing a polyelectrolyte; (b) A step of bringing a first solution and a reinforcing material into contact at a first temperature for a first time, thereby providing a composite material precursor; (c) A step of placing a composite material precursor on a surface at a second temperature for a second time, thereby providing a dried composite material precursor; and (d) The process includes removing the dried composite material from the surface, thereby providing the composite material.

[0251] In the first aspect of the fifth embodiment, the step of removing the dried composite material from the surface includes bringing the dried composite material and the removal solvent into contact at a third temperature for a third time.

[0252] In the second aspect of the fifth embodiment, the removal solvent includes water. The remaining and exemplary values ​​of the variables for the composite material are as described above with respect to the first aspect of the fifth embodiment.

[0253] In the third aspect of the fifth embodiment, the third time is approximately 6 hours to approximately 24 hours. For example, the third time is approximately 6 hours. The remaining and exemplary values ​​of the composite material variables are as described above with respect to the first and second aspects of the fifth embodiment.

[0254] In the fourth aspect of the fifth embodiment, the third temperature is approximately 50°C to approximately 90°C, for example, approximately 60°C to approximately 80°C. For example, the third temperature is approximately 60°C. The remaining and exemplary values ​​of the variables for the composite material are as described above with respect to the first to third aspects of the fifth embodiment.

[0255] In the fifth aspect of the fifth embodiment, the first solution comprises a first solvent. The first solvent is, for example, water, alcohol, such as methanol, ethanol or isopropanol, toluene, acetonitrile, dimethyl sulfoxide, acetone, dimethylformamide, N-methyl-2-pyrrolidone, or a mixture thereof. For example, the first solvent is a mixture of 80% by volume ethanol and 20% by volume toluene. The remaining and exemplary values ​​of the variables of the composite material are as described above with respect to the first to fourth aspects of the fourth embodiment.

[0256] In the sixth aspect of the fifth embodiment, contact between the first solution and the reinforcing material includes immersing the reinforcing material in the first solution. The remaining and exemplary values ​​of the variables for the composite material are as described above with respect to the first to fifth aspects of the fifth embodiment.

[0257] In the seventh aspect of the fifth embodiment, the first temperature is about 15°C to about 80°C, for example, about 15°C, about 20°C, about 25°C, about 30°C, about 35°C, about 40°C, about 45°C, about 50°C, about 55°C, about 60°C, about 65°C, about 70°C, about 75°C, or about 80°C. For example, the first temperature is about 20°C. The remaining and exemplary values ​​of the variables for the composite material are as described above with respect to the first to sixth aspects of the fifth embodiment.

[0258] In the eighth aspect of the fifth embodiment, the first time is approximately 1 hour to approximately 24 hours, for example, approximately 1 hour, approximately 2 hours, approximately 3 hours, approximately 4 hours, approximately 5 hours, approximately 6 hours, approximately 7 hours, approximately 8 hours, approximately 9 hours, approximately 10 hours, approximately 11 hours, approximately 12 hours, approximately 13 hours, approximately 14 hours, approximately 15 hours, approximately 16 hours, approximately 17 hours, approximately 18 hours, approximately 19 hours, approximately 20 hours, approximately 21 hours, approximately 22 hours, approximately 23 hours, or approximately 24 hours. For example, the first time is approximately 18 hours. The remaining and exemplary values ​​of the variables for the composite material are as described above with respect to the first to seventh aspects of the fifth embodiment.

[0259] In the ninth aspect of the fifth embodiment, the concentration of the polymer electrolyte in the first solution is about 30 mM to about 300 mM, for example, about 30 mM, about 40 mM, about 50 mM, about 60 mM, about 70 mM, about 80 mM, about 90 mM, about 100 mM, about 120 mM, about 140 mM, about 150 mM, about 160 mM, about 170 mM, about 180 mM, about 110 mM, about 130 mM, about 140 mM, about 190 mM, about 200 mM, about 220 mM, about 240 mM, about 260 mM, about 280 mM, or about 300 mM. For example, the concentration of the polymer electrolyte in the first solution is about 85 mM. The remaining and exemplary values ​​of the variables for the composite material are as described above with respect to the first to eighth aspects of the fifth embodiment.

[0260] While the present invention is particularly illustrated and described in terms of its exemplary embodiments, it will be understood by those skilled in the art that various modifications in form and detail can be made in the present invention without departing from the scope of the invention as encompassed in the appended claims.

[0261] All patents, published applications, and references cited herein are incorporated by reference in their entirety. Aspects of the present invention are shown below. Item 1 A composite material comprising a reinforcing material and a polymer electrolyte in contact with the reinforcing material, wherein the polymer electrolyte has structural formula I, II, II, or IV: [ka] (In the formula:

change

change

change

change

change

change

change

change

change

change

change

change

change

change

Claims

1. A composite material comprising a reinforcing material and a polymer electrolyte in contact with the reinforcing material, wherein the polymer electrolyte has structural formula I, II, III, or IV: 【Chemistry 1】 (In the formula: 【Chemistry 2】 This indicates a point of connection to other repeating units; R 11 , R 21 , R 31 and R 41 Each of them is independently C 1-4 It is alkyl; R 12 、 R 13 、 R 22 、 R 23 、 R 32 、 R 33 、 R 42 and R 43 are each independently C 1-4 alkyl or C 5-7 cycloalkyl; Z 11 , Z 21 , Z 31 and Z 41 Each of them is independently C -1-10 Alkylene or *O-(C) 1-10 Alkylene) where * indicates a point of attachment to the polymer main chain; X - These are halides, OH - , HCO 3 - CO 2 (R 10 ) - , O(R 10 ) - NO 3 - 5CN - , PF 6 - Or BF 4 - And; R 10 is C 1-4 (It is alkyl.) A composite material comprising a first repeating unit selected from a portion represented by, wherein the reinforcing material is a porous material, the porous material comprises a polyolefin, and the porous material is immersed in a polymer electrolyte.

2. The composite material according to claim 1, wherein the porous material contains polyethylene.

3. The composite material according to claim 1, wherein the porous material includes polypropylene.

4. The composite material according to claim 1, wherein the porous material contains a perfluorinated polyolefin.

5. The composite material according to claim 4, wherein the porous material contains polytetrafluoroethylene.

6. The composite material according to claim 5, wherein the porous material contains polytetrafluoroethylene, the porous material has 85% porosity, and the average size of the pores is 450 nm.

7. i) The porous material comprises polyethylene, the porous material has 85% porosity and the average size of the pores is 500 nm, or ii) The composite material according to claim 1, wherein the porous material contains polypropylene, the porous material has 55% porosity, and the average size of the pores is 50 nm.

8. A composite material according to any one of claims 1 to 5, wherein the porous material has a porosity of about 40% to about 90%.

9. A composite material according to any one of claims 1 to 5, wherein the average size of the pores in the porous material is approximately 50 nm to approximately 500 μm.

10. The composite material according to any one of claims 1 to 9, wherein the composite material is a film having a thickness of approximately 1 μm to approximately 300 μm.

11. The polyelectrolyte is the second repeating unit Z 2 Furthermore, Z 2 However, linear C 2-8 Alkylene or the following structural formula 【Transformation 3】 (In the formula: 【Chemistry 4】 This indicates a point of connection to other repeating units; R 4 and R 5 These are H and C, respectively, independently. 1-3 Alkyl, C 1-3 Haloalkyl, C 3-8 Alkenil, C 1-3 Alkyl (C 6-14 (aryl) or -(C) 1-3 Alkylene)O(C 1-3 Alkilen) (C 6-14 This is an aryl, where each aryl is composed of 1 to 3 C 1-3 Alkyl or C 1-3 They may be optionally substituted with a haloalkyl group, or R 4 and R 5 Together with the carbon atoms to which they bond, C 5-7 Forms a cycloalkyl group; here C 5-7 Cycloalkyls are -C(O)O(C 1-3 Alkyl) or C 3-8 (Optionally substituted with alkenil) This is the chemical part represented by, The composite material according to any one of claims 1 to 10, wherein the linear C2-8 alkylene is unsubstituted or substituted with one or more C1-3 alkyl, C1-3 haloalkyl, C1-3 alkyl(C6-14 aryl), or -(C1-3 alkylene)O(C1-3 alkylene)C6-14 aryl, where each aryl is optionally substituted with 1 to 3 C1-3 alkyl or C1-3 haloalkyl.

12. The composite material according to any one of claims 1 to 11, wherein the polymer electrolyte comprises at least a first polymer chain and a second polymer chain, and the first polymer chain is crosslinked with the second polymer chain.

13. The polyelectrolyte further comprises at least one linking portion, the linking portion having the following structural formula 【Transformation 5】 (In the formula, 【Transformation 6】 This indicates the point of bonding of the linking portion to the first polymer chain; 【Transformation 7】 This indicates the point of bonding of the linking portion to the second polymer chain; Y 11 , Y 13 , Y 21 and Y 23 Each of them is independently C 1-3 It is alkylene; Y 31 and Y 33 Each of them is independently C 1-5 It is alkylene; R 15 and R 25 Each of them is independently C 1-4 It is alkyl; Y 12 , Y 23 and Y 32 Each of them is independently C 2-10 Alkylene or (C 1-3 Alkilen) (C 6 Ariel)(C 1-3 It is alkylene; X- is a halide, OH-, HCO3-, CO2(R10)-, O(R10)-, NO3-, CN-, PF6-, or BF4-; (R10 is C1-4 alkyl) A composite material according to claim 12, selected from the portion represented by the above.

14. The composite material according to any one of claims 1 to 13, wherein the polymer electrolyte comprises at least a first polymer chain, a second polymer chain, and a third polymer chain, and the first polymer chain is crosslinked with the second polymer chain and the third polymer chain.

15. The polyelectrolyte further comprises at least one linking portion, the linking portion having the following structural formula 【Transformation 8】 【Chemistry 9】 (In the formula, 【Chemistry 10】 This indicates the point of bonding of the linking portion to the first polymer chain; 【Chemistry 11】 This indicates the point of bonding of the linking portion to the second polymer chain; 【Chemistry 12】 This indicates the point of bonding of the linking portion to the third polymer chain; R 6 is H or -C(O)O(C 1-3 (Alkyl) A composite material according to claim 14, selected from the portion represented by the above.

16. R 11 A composite material according to any one of claims 1 to 15, wherein is methyl.

17. R 21 A composite material according to any one of claims 1 to 16, wherein is methyl.

18. R 31 A composite material according to any one of claims 1 to 17, wherein is methyl.

19. R 41 A composite material according to any one of claims 1 to 18, wherein is methyl.

20. R 12 C 1-4 A composite material according to any one of claims 1 to 19, wherein the material is alkyl.

21. R 22 C 1-4 A composite material according to any one of claims 1 to 20, wherein the material is alkyl.

22. R 32 is C 1-4 The composite material according to any one of claims 1 to 21, wherein it is alkyl.

23. R 42 C 1-4 A composite material according to any one of claims 1 to 22, wherein the material is alkyl.

24. R 13 C 5-7 A composite material according to any one of claims 1 to 23, wherein the composite material is cycloalkyl.

25. R 13 C 1-4 A composite material according to any one of claims 1 to 23, wherein the material is alkyl.

26. R 23 is C 5-7 The composite material according to any one of claims 1 to 25, wherein R is cycloalkyl.

27. R 23 C 1-4 A composite material according to any one of claims 1 to 25, wherein the material is alkyl.

28. R 33 C 5-7 A composite material according to any one of claims 1 to 27, wherein the composite material is cycloalkyl.

29. R 33 C 1-4 A composite material according to any one of claims 1 to 27, wherein the material is alkyl.

30. R 43 C 5-7 A composite material according to any one of claims 1 to 29, wherein the composite material is cycloalkyl.

31. R 43 C 1-4 A composite material according to any one of claims 1 to 29, wherein the material is alkyl.

32. Z 2 However, linear substituted or unsubstituted C 2-8 A composite material according to any one of claims 11 to 31, wherein the composite material is alkylene.

33. Z 2 is a straight chain C 8 It is an alkylene, a straight chain C 8 Alkilen is C 1-3 Alkyl, C 1-3 Haloalkyl, C 1-3 Alkyl (C 6-14 (aryl) or -(C 1-3 Alkylene)O(C 1-3 Alkilen) (C 6-14 A composite material according to any one of claims 11 to 32, which is replaced by aryl.

34. Z 2 However, the following structural formula 【Chemistry 13】 A composite material according to any one of claims 11 to 31, wherein the chemical part is represented by [the specified formula].

35. R 4 and R 5 However, each is independently H or C 3-8 The composite material according to claim 34, wherein the material is an alkenyl.

36. R 4 and R 5 However, together with the carbon atoms to which they bond, C 5-7 The composite material according to claim 34, which forms a cycloalkyl group.

37. C 5-7 Cycloalkyl is -C(O)O(C 1-3 The composite material according to claim 36, which is substituted with alkyl.

38. Polyelectrolytes with structural formula V or VI: 【Chemistry 14】 (In the formula, n is an integer between 2 and 2000; m is an integer between 1 and 10000; k is an integer between 1 and 1000; l is an integer between 1 and 10000. The composite material according to claim 11, as represented by...

39. The polymer electrolyte has structural formula VII: 【Chemistry 15】 The composite material according to claim 38, as represented by...

40. A composite material according to any one of claims 1 to 39, wherein the polymer electrolyte comprises 10 mol-% to 90 mol-% of a first repeating unit represented by structural formula I.

41. A composite material according to any one of claims 1 to 39, wherein the polymer electrolyte comprises a first repeating unit represented by structural formula I in an amount of approximately 20 wt.% to approximately 60 wt.%.

42. A composite material according to any one of claims 12 to 37 and 40 to 41, wherein the degree of crosslinking of the polymer electrolyte is about 5% to about 15%.

43. A film comprising a film of a composite material according to any one of claims 1 to 42.

44. A membrane electrode assembly comprising the membrane and electrode according to claim 43.

45. An electrochemical device comprising a membrane electrode assembly and a current collector according to claim 44.

46. An electrochemical device according to claim 45, which is an electrolytic device.

Images