Perfluorosulfonic Acid Membranes Research Articles

Reinforcing membranes with subgaskets in proton exchange membrane water electrolysis: A model-based analysis

Ensuring the long-term mechanical durability of perfluorosulfonic acid membranes in proton exchange membrane water electrolysis (PEMWE) is essential for long lifetimes. This study investigates the potential of reinforcing the membrane by incorporating a subgasket layer outside the active area. Thus, experimental tensile measurements with the subgasket material and with the subgasket-membrane composite are conducted to characterize their mechanical properties. The obtained data are used to identify suitable material models and parameterize them by applying a tensile test simulation based on the finite element method. By integrating subgaskets in a structural mechanics PEMWE cell model, the impact of the reinforcement on the membrane stability was investigated. The results indicate that even thin layers of subgaskets stabilize the membrane at the gap interface between the cell frame and the porous transport layer. The level of stabilization is further enhanced when using thicker subgaskets that cover the entire gap. However, one-sided subgaskets exhibit reduced mechanical stabilization. Furthermore, membrane buckling due to an increased gap size can be prevented using a subgasket up to a maximum gap size of 0.45 mm.

Hydrogen Permeation in PFSA Membranes with Different Side Chains and ePTFE Fiber Fraction

Hydrogen permeation was measured at 80 °C and four humidities for a series of membranes fabricated from the three most common perfluorosulfonic acid (PFSA) ionomers. In addition, membranes were made with different thicknesses and types of expanded PTFE (ePTFE) reinforcements. A picture has emerged where the permeation constant is lowest for the shortest side chain and decreases with decreasing ion exchange capacity (IEC). A relationship quantifying the impact of ePTFE on reducing hydrogen permeation was developed showing lower cross over with higher fiber content. For both the IEC study and the reinforcement study, the permeability is trending towards the published value for pure poly(tetrafluoroethylene) when the ionomer CF2 content or fiber fraction of the membrane increases. In all cases, the hydrogen permeation was greatest at the highest humidities.

Perfluorosulfonic acid membranes with reduced hydrogen permeation by filling with carbon quantum dots for fuel cells

Perfluorosulfonic acid membranes with reduced hydrogen permeation by filling with carbon quantum dots for fuel cells

Fast Field-Cycling Nuclear Magnetic Resonance Relaxometry of Perfluorosulfonic Acid Ionomers and Their Perfluorosulfonyl Fluoride Precursors Membranes.

The spin-lattice relaxation rates (R1) of fluorine nuclei in perfluorosulfonic acid (PFSA) ionomer membranes and their precursor solid perfluorosulfonyl fluoride (PFSF) were measured by fast field-cycling (FFC) NMR relaxometry. The XRD profiles of PFSA and PFSF are similar and show a characteristic peak, indicating the alignment of main chains. While the SAXS profiles of the PFSA membranes show two peaks, those of the solid PFSF lack the ionomer peak which is characteristic of hydrophilic side chains in the PFSA ionomer membranes. The Larmor frequency dependence of R1 obeys power law and the indices are dependent on the sample and temperature. The indices of the PFSA membranes change from -1/2 to -1 along with the Larmor frequency and temperature dependence decrease, which is consistent with the generalized defect diffusion model. Estimated activation energies are in good agreement with those obtained from dynamical mechanical analysis and dielectric spectroscopy, indicating the segmental motion of the backbones as the common origin of these observations. On the other hand, the index changes to -3/4 in the case of the PFSFs, which has been predicted by the reptation model.

The Critical Analysis of Membranes toward Sustainable and Efficient Vanadium Redox Flow Batteries.

Vanadium redox flow batteries (VRFB) are a promising technology for large-scale storage of electrical energy, combining safety, high capacity, ease of scalability, and prolonged durability; features which have triggered their early commercial implementation. Furthering the deployment of VRFB technologies requires addressing challenges associated to a pivotal component: the membrane. Examples include vanadium crossover, insufficient conductivity, escalated costs, and sustainability concerns related to the widespread adoption of perfluoroalkyl-based membranes, e.g., perfluorosulfonic acid (PFSA). Herein, recent advances in high-performance and sustainable membranes for VRFB, offering insights into prospective research directions to overcome these challenges, are reviewed. The analysis reveals the disparities and trade-offs between performance advances enabled by PFSA membranes and composites, and the lack of sustainability in their final applications. The potential of PFSA-free membranes and present strategies to enhance their performance are discussed. This study delves into vital membrane parameters to enhance battery performance, suggesting protocols and design strategies to achieve high-performance and sustainable VRFB membranes.

In situ growth of covalent organic framework on graphene oxide nanosheet enable proton-selective transport in flow battery membrane

Perfluorosulfonic acid (PFSA) is the most widely used membrane material for all-vanadium redox flow batteries (VRFB). However, severe vanadium ion permeation of PFSA membranes remains to be solved. In this work, a series of PFSA-based composite membranes are prepared by introducing two-dimensional continuous covalent organic framework (COF) to achieve enhanced performance. Two dimensional continuous Schiff base network-type COFs (GO/SNW) are synthesized by using the two-dimensional multi-functionalized surface of graphene oxide (GO) as a reaction site. Compared to the original form of agglomerated particles, two-dimensional continuous structure obtained a larger vanadium resistance area. Comparing to conventional PFSA membranes, the special pores of COF have a size sieving mechanism for selectively proton transfer, leading to simultaneously enhancement of proton conductivity and vanadium barrier property. VRFB assembled with PFSA-GO/SNW-7 showed high Coulombic efficiency (CE: 97.47%–98.18 % VS PFSA: 80.73%–91.92 %) and energy efficiency (EE: 93.04%–85.71 % VS PFSA: 77.53%–81.78 %) at 40–120 mA cm−2. In addition, there is no significant decrease in the efficiency of battery assembled with PFSA-GO/SNW-7 after 800 cycle (than 650 h) tests. This work provides a new direction in the design of fillers for mixed matrix membranes.

Tailoring porous structure in non-ionic polymer membranes using multiple templates for low-cost iron-lead single-flow batteries

Porous ion-selective membranes are promising alternatives for the expensive perfluorosulfonic acid membranes in redox flow batteries. In this work, novel non-ionic porous polyvinylidene fluoride-hexafluoro propylene membranes are designed for iron-lead single-flow batteries. The membranes are prepared using a multiple template approach, involving simultaneously using polyethylene glycol and dibutyl phthalate (DBP) as pore-forming templates. Their porous structure is finely tuned by adjusting the ratio of the two templates. As a result, dual-porous membranes bearing both macro and micropores are obtained. The H3520 membrane with modified porous structure attains a high proton conductivity of 43.5 mS·cm-1 and a relatively low ferric ion diffusion constant (8.61 × 10-8 cm2·min-1) and demonstrates the best balance between these performance-determining parameters (selectivity 5.04 × 105 S·min·cm-3, higher than that of the N115 membrane). Besides, performance tests of the iron-lead single-flow single cells equipped with the dual-porous membranes show a high energy efficiency, exceeding 87.2% at its rated current density, and outstanding cycling stability over 200 charge-discharge cycles. Altogether, the mixed template method presents a promising strategy to prepare high-performance and low-cost non-ionic membranes for redox flow batteries.

Evaluating the Durability of Perfluorosulfonic Acid Membranes in Fuel Cells Using Combined Open-Circuit Voltage-Accelerated Stability Testing.

This study evaluates the chemical and mechanical durability of membranes used in proton exchange membrane fuel cells, highlighting the essential role of electrochemical tests in understanding the relationship between durability and performance. Our methodology integrates various electrochemical evaluation techniques to assess the degradation of perfluorosulfonic acid (PFSA) membranes. The results highlight the considerable improvement in the chemical and mechanical durability of annealed 3M PFSA-reinforced composite membranes (RCMs) compared with their non-annealed counterparts and other membrane types, indicating their superior resilience under challenging conditions. Moreover, the results of using a combined open-circuit voltage-accelerated stability testing protocol demonstrate that annealed 3M PFSA RCMs exhibit enhanced resilience, reaching 18,000 cycles before failure, considerably outperforming NR 211 (5000 cycles) and other membranes. In addition, membrane deterioration over time can be precisely measured by interpreting electrochemical indicators (electrochemically active surface area, circuit resistance, high-frequency resistance, and proton resistance). This approach provides a clear relationship between electrochemical data and durability, offering a comprehensive understanding of how different membranes withstand operational stresses.

In-situ experimental and numerical investigation on fatigue crack growth in perfluorosulfonic-acid membrane with overloading effect

Fatigue crack growth behavior of perfluorosulfonic-acid membrane is investigated under single overload conditions by in-situ fatigue testing. The results show that the effected range of overload on cyclic plasticity positively correlates with the overload ratio (Rol), indicating that overload-induced residual stress is aggravated with increase of Rol. Besides, crack-tip sharpening occurred at higher Rol can promote cyclic plasticity deformation, thus initially accelerating the crack growth. Moreover, the cyclic plasticity can be used to interpret the post-overload crack growth. Based on plastically dissipated energy, a numerical scheme incorporated with developed elastic-viscoplastic constitutive relationship is established to predict the fatigue crack growth.

Theoretical and Experimental Study of a Fuel Cell Stack Based on Perfluoro-sulfonic Acid Membranes Facing High Temperature Application Environments

Theoretical and Experimental Study of a Fuel Cell Stack Based on Perfluoro-sulfonic Acid Membranes Facing High Temperature Application Environments

Employment of online conductivity measurements as a diagnostic tool of perfluorosulfonic acid membrane degradation in PEMWE

Membrane degradation is one of the most important factors limiting lifetime of PEMWE stacks, and imposes severe purity demands in water fed into PEMWE electrolyzers. Therefore, damage to the membrane is one of the major limitations that impede widespread implementation of PEM technology to produce green hydrogen. Several membrane degradation test procedures have been discussed in literature. In this work, the loss of membrane material is related to the operating conditions of a 4-cell PEMWE stack through measurements of the fluoride concentration of the water output from the electrolyzer, both at the cathode and at the anode, at different temperatures (25 and 40 °C), flow rates (20, 25 and 30 mL/min for a nominal water consumption of 2 mL/min) and operating loads (3 different voltages and currents ranging from the nominal 8 V and 0.26 A/cm2 to 6.8 V and 0.05 A/cm2). Conductivity of excess water collected at electrolyzer outlets is shown to be linearly related to its fluoride content under a wide range of electrolyzer operating conditions, including constant and dynamical loads. Therefore, knowing the on-line conductivity at both the anode and cathode can provide an assessment of the condition and lifetime of the membrane. The study shows that different workloads affect the lifetime of the electrolyzer and can be observed by in situ and ongoing monitoring of the conductivity of both the anode and cathode.

Perfluorosulfonic Acid Membranes as Gel-Polymer Electrolytes for Lithium Metal Batteries

Perfluorosulfonic Acid Membranes as Gel-Polymer Electrolytes for Lithium Metal Batteries

A Review of Proton Exchange Membrane Degradation Pathways, Mechanisms, and Mitigation Strategies in a Fuel Cell

Proton exchange membrane fuel cells (PEMFCs) have the potential to tackle major challenges associated with fossil fuel-sourced energy consumption. Nafion, a perfluorosulfonic acid (PFSA) membrane that has high proton conductivity and good chemical stability, is a standard proton exchange membrane (PEM) used in PEMFCs. However, PEM degradation is one of the significant issues in the long-term operation of PEMFCs. Membrane degradation can lead to a decrease in the performance and the lifespan of PEMFCs. The membrane can degrade through chemical, mechanical, and thermal pathways. This paper reviews the different causes of all three routes of PFSA degradation, underlying mechanisms, their effects, and mitigation strategies. A better understanding of different degradation pathways and mechanisms is valuable in producing robust fuel cell membranes. Hence, the progress in membrane fabrication for PEMFC application is also explored and summarized.

Facile and affordable synthesis of sulfonated and phosphonated poly (p-terphenyl perfluorophenyl)s for proton exchange membrane fuel cells

Hydrocarbon proton exchange membranes (PEMs) which exhibit low-cost, improved robustness, and simple synthesis relative to perfluorosulfonic acid (PFSA) membranes, are of great significance for proton exchange membrane fuel cells (PEMFCs). Herein, we report a facile and affordable preparation of sulfonated and phosphonated poly (p-terphenyl perfluorophenyl)s PEMs via superacid-catalyzed Friedel−Crafts condensation of p-terphenyl and pentafluorobenzaldehyde monomers, following by highly selective para-substitution of fluorobenzene to graft ion exchange groups. The rigid and well-defined polymer structure with precisely controlled anionic groups, enables good phase separation and efficient ionic clustering to promote proton transport. Sulfonated and phosphonated PEMs show modest proton conductivities of 150 and 120 mS cm−1 at 90 °C, and achieve H2/air PEMFC peak power densities of 360 and 237 mW cm−2 at 80 ℃, respectively. Interestingly, we find that phosphonated PEMs have significantly higher resistance to free radicals than sulfonated PEMs. Overall, the results suggest that our prepared hydrocarbon PEMs have potential applications for fuel cells.

Enabling high-temperature application of Nafion membrane via imitating ionic clusters in proton conduction channels

Nafion membranes, representative of perfluorosulfonic acid (PFSA) proton exchange membranes are not effective in dehydrated state and high-temperature condition (>100 oC). The traditional hybrid modification would lower the mechanical strength of the membrane due to the large-scale phase separation. In this work, a hyperbranched polyamide (HBM) featuring high sulfonate concentration and nanoparticle morphology is synthesized and non-destructively filled into Nafion matrix to imitate the “ionic cluster” to accelerate the proton conduction at elevated temperature. During the non-destructively membrane modification, the Nafion PFSA membrane is swelled in the solution and the main chain structure is expanded, the HBM macromolecules is simultaneously filled into the membrane together with the solvent. After the removal of solvent, HBM end-capped with –COOH forms strong hydrogen bonds with the sulfonate groups in Nafion matrix. As a result, proton conductivity of the composite membrane can reach 0.047 S/cm, which is 1.9 times higher than that of the pristine Nafion membrane, at 110 oC and 60% RH. Given the excellent overall stability, fuel cell performance of the HBM-modified Nafion membrane is studied and a 30% increase in power density is observed, suggesting a viable strategy to expand the operation temperature of PFSA-based fuel cells.

Polyphenols as an Alternative to Lanthanide Alloys for PFSA Oxidative Stability

The chemical durability of perfluorosulfonic acid (PFSA) membranes is becoming an increasingly investigated subject to meet the Department of Energy (DOE) durability targets for Heavy Duty Applications (HDVs). State-of-the-art membranes like NafionTM, rely on the use of cerium, heteropolyacids, and other inorganic additives for increasing PFSA chemical durability. A less explored avenue for the oxidative stabilization of PFSA and hydrocarbon membranes is the use of organic antioxidants. No reversible organic antioxidant has so far been demonstrated which can enhance membrane lifetime by factors similar or higher to cerium. Herein, we demonstrate ellagic acid as a promising radical scavenger for PFSAs. We found that the incorporation of EA enhanced the chemical durability of Nafion by 160%. EA when incorporated with cerium as an electron donor could surpass Nafion durability enhancement by 80% compared to a membrane incorporated with just cerium in DOE-defined durability tests. EA was found reversible in acidic conditions like that of fuel cells and its reversibility could be further enhanced by the use of suitable co-antioxidants. We discuss the present challenges with the system and highlight future areas of research. Figure 1

Mechanism of Ionomer Degradation as a Consequence of Defective Anode PEMFC

Defects in the various components of the membrane-electrode assembly (MEA), initially present or created during aging, are known to be responsible for the short lifetime PEMFC. Catalytic layer degradation has been identified as one of them [1]. However, the possible propagation of these defects to other components within a cell or a stack is not clear in the literature. To shed light on these phenomena, customized MEAs with a localized lack of anode active layer at two different locations -near the hydrogen inlet or outlet- were manufactured and tested with specific accelerated aging tests, combining high and low current and humidity cycles; these were specifically tailored to observe a possible propagation of the defects [2]. Local performance monitoring using a segmented cell revealed variations within the catalytic layers upstream and downstream of the defect. In order to better understand the impact of anode active layer defects on MEA components, localized physicochemical analyses were performed post mortem along the gas flow, with the main objective to identify possible degradations of the reinforced perfluorosulfonic acid (PFSA) membranes. Microscopic thickness measurements showed significant membrane thinning in the defective segments. Difference of these localized degradations between the monopolar plates rib and channel zones will be highlighted depending on the defect location i.e. at the inlet and outlet of hydrogen flow (Figure below). In the defective area, decrease of the Ion Exchange Capacity estimated by Raman analyses is pointed out for the reinforced PFSA layer. The PFSA chain degradation mechanism will be discussed, and, thus, the degradation rate will be calculated based on Raman and FTIR microscope and 19F NMR. For longer ageing time, the ionomer degradation is extended to an non-defective area. A propagation mechanism of the degradation will be proposed.[1] L, Dubau, et al. WIREs Energy and Environ. 2014, 3, pp. 540-560.[2] S, Touhami, et al. J. Power Sources. 2021, 481, pp. 228908-228917. Figure 1

Embrittlement of PFSA Reinforced Membrane Interfaces after Ex-Situ Chemical-Mechanical Aging

Perfluorosulfonic acid (PFSA) membrane degradation has been identified as one of the main factors responsible for the short lifetime of PEMFCs [1,2]. The aging mechanisms of these membranes are complex due to mechanical fatigue combined to chemical aggressions. Mechanical fatigue results from the wetting/drying cycles while the chemical aggressions are induced by radicals formed during fuel cell operation. Although it is commonly accepted that chemical and mechanical stresses can interact to accelerate membrane degradation [3], coupled studies are rarely conducted. Thus, an original experimental set-up to perform ex-situ aging tests combining membrane exposure to cyclic mechanical stresses to a free radical environment under conditions close to those observed during cell operation has been developed [4]. Ex-situ aging was performed on PFSA membranes reinforced (Nafion™ XL) with a cyclic compression oscillating between 0 - 10 MPa (0.1 Hz frequency) and a Fenton solution containing 1 ppm Fe2+ and 3 %vol H2O2. Such stresses revealed a significant morphological alteration with the appearance of “bubbles” close to the surface membrane (Figure 1, left). No chemical structure modification was detected within the three different layers. Nevertheless, SEM-EDX, FTIR and Raman microscopic analyses highlight delamination close to the reinforcement/PFSA interface (Figure 1, rigth). Additional peeling tests argued this failure point in the Nafion™ XL membrane. Figure 1

Thin Membranes Using PFSA-Vinylon Intermediate Layer for PEM Fuel Cells

Fuel cells are attracting attention as one of the key energy devices for achieving carbon neutrality in 2050. Currently, fuel cells are being improved for versatile mobile applications. Among the components of fuel cell devices, polymer electrolyte membranes for proton exchange, in particular, are required to have high proton conductivity at high temperature, high and low humidification, and thin membranes. Proton-exchange fuel cells utilize perfluorosulfonic acid (PFSA) ionomers and membranes from Chemours and 3M and Solvay [1]. Nafion membranes with a thickness of 178-25 μm and Gore select membranes (with reinforcement) with a thickness of 20-5 μm have been commercialized [2,3]. On the other hand, thinner polymer electrolyte membranes can reduce the ohmic voltage drop in fuel cells to improve performance and lower costs. However, it is difficult to obtain thin membranes of less than 20 μm without reinforcement using PFSA ionomers.In this report, a thin PFSA electrolyte membrane (10 μm) without reinforcement was successfully developed by introducing a PFSA-vinilon composite layer as an intermediate layer of the PFSA membrane. The fuel cell evaluation revealed that it has a high current density.The ionomers used were 5% Nafion solution (DE520 CS type, EW=1100) and 6% Aquivion solution (D83-06A, EW=830). PVA (polyvinyl alcohol) was synthesized from polyvinyl acetate (PVAc, Mw=100,000). The laminated membranes (10 μm thickness) was obtained by preparing a 2 μm PFSA layer, followed by a 6 μm PFSA-PVA composite layer, then a 2 μm PFSA layer was coated. Finally, laminated membranes with PFSA-Vinylon composite layers were obtained by Formalization reaction the PFSA-PVA composite layers.FTIR evaluation of the PFSA/ PFSA-Viynylon/ PFSA multilayers confirmed the presence of an intermediate layer by observing Vinylon-derived peaks. Conductivities of about 4.5 mS/cm and 2.5 mS/cm in the thickness direction were obtained at 80°C, 90%RH and 20%RH, respectively. On the other hand, I-V evaluation was performed at 80°C, 100%RH and 35%RH using hydrogen, oxygen and air. Nafion 212 was used as a comparison membrane. The I-V characteristics of the laminated membranes showed higher current density than that of the Nafion membrane. Maximum current densities of 3 A/cm2 at 0.6 V and 3 A/cm2 at 0.4 V were obtained at 80°C, 100% RH and 35% RH with hydrogen and oxygen, respectively. Regarding the comparison of PFSA ionomers, Aquivion showed higher performance at higher current densities than Nafion [4].

Thermo-Mechanical Stability of Hydrocarbon-Based Pemion® Proton Exchange Membranes

Considering the environmental concerns about the disposal of perfluorosulfonic acid (PFSA) membranes as well as the growing interest in higher temperature operability of polymer electrolyte membrane fuel cells (PEMFCs), non-fluorinated hydrocarbon-based proton exchange membranes (PEMs) with aromatic backbones have become an increasingly active area of research. Low reactant cross-over, tunable electrochemical properties, and differentiated chemistries and potentially safer and cost-reducing synthesis procedures, are additional favourable features of hydrocarbon-based PEMs for prospective use in PEMFCs [1]. Vulnerable linking units, however, are known to be the main disadvantages of these polymers in the oxidative environment of fuel cells. During PEMFC operation, destructive radical species such as hydroxyl (HO•) are produced, causing polymer degradation and thinning in the membrane [2]. Recently, sulfo-phenylated polyphenylenes (sPPPs) have shown outstanding oxidative stability due to a polymer backbone comprising only aryl-aryl bonds, with mitigated chemical degradation in ex-situ and in-situ durability studies [3, 4]. Another concern is regarding the thermo-mechanical stability of PEMs. Thus, a systematic thermo-mechanical stability study is required to confirm the potential of sPPP-based PEMs to replace conventional PFSAs, especially for high temperature PEMFC, i.e., 110-120 °C.The present research objective is to assess the thermo-mechanical stability of a commercial reinforced hydrocarbon-based PEM, Pemion® (PF1-HLF8-15-X, 15 µm thick, reinforced), as well as a mechanically-reinforced PFSA-based reference membrane, across a wide range of temperature (30-120 °C) and relative humidity (RH) (10-90%) conditions that includes the crucial high temperature window of interest for future PEMFCs [6]. To this end, a comprehensive design of experiment yielded 19 tensile tests at various hygrothermal conditions with dynamic mechanical analyzer (DMA 850; TA Instruments) equipped with an external environmental chamber accessory (TA Instruments, RH Accessory). Important mechanical properties such as Young’s modulus, ultimate tensile stress, yield stress, maximum elongation at break, strain hardening, and modulus of resilience were extracted and discussed as well. Datapoints were fitted for empirical model development and mechanical properties were estimated for high temperature and RH conditions beyond the capability of the instrument. This method can be employed to assess if the mechanical properties of membrane materials can be retained at higher temperatures, regardless of polymer chemistry and type. Storage modulus and loss modulus were separately measured in a dynamic mode to observe the impact of temperature on the mechanical response of the hydrophobic backbone and hydrophilic ionic clusters, respectively.Overall, Pemion® demonstrates tough tensile properties in the stress-strain tests due to its sterically encumbered polyphenylene backbone (Figure 1a), whereas the reference PFSA (Figure 1b) shows elastomer-like behavior with much lower Young’s modulus, yield stress, and strain hardening (slope of the curve in the plastic deformation region). Figure 1c-f show the main viscoelastic properties extracted from the tensile tests at room (30 °C, 50% RH) and high temperature fuel cell conditions (110 °C, 50% RH). The modulus of elasticity and strain hardening of Pemion® membrane are almost temperature-independent, whereas these properties for the reinforced PFSA material undergo a significant decay at high-temperature ambience. Pemion® maintains good yielding strength even at high temperature and RH conditions (110-120 °C and 80% RH). Nevertheless, small mechanical stress values as low as 1 MPa can cause spontaneous yielding in the PFSA reference material above 110 °C. The modulus of resilience for the reinforced PFSA is also predicted to be zero at elevated hygrothermal conditions (i.e., 90 °C and 70% RH). This is interpreted as an approach to the material’s glass transition condition, where it loses its mechanical integrity and therefore, is potentially unsuitable for higher temperature PEMFC operation. Moreover, the dynamic mechanical thermal analysis revealed that Pemion® retains its robustness at hygrothermal ambience close to high-temperature PEMFCs, i.e., 110-120 °C and 40-50% RH, whereas the backbone of the PFSA material gradually loses its strength. Acknowledgements This project was financially supported by Natural Sciences and Engineering Research Council of Canada (NSERC), Ionomr Innovations Inc, Canada Foundation for Innovation (CFI), British Columbia Knowledge Development Fund (BCKDF), Western Economic Diversification Canada (WD), and Canada Research Chairs (CRC).