Polymer Electrolyte Research Articles

Improved Proton Conductivity of Chitosan-Based Composite Proton Exchange Membrane Reinforced by Modified GO Inorganic Nanofillers

Improved Proton Conductivity of Chitosan-Based Composite Proton Exchange Membrane Reinforced by Modified GO Inorganic Nanofillers

Effects of concentrated CO2 on the performance of a PBI/H3PO4 high temperature proton exchange membrane fuel cell

In this study, the impact of mimic reformate of formic acid decomposition on the anode polarization of HT-PEMFC is investigated under various operating conditions of the anode, including different concentrations of CO2, N2, CO, and humidification. Polarization curve and EIS measurements indicate that there is no significant difference (less than 5 mV when i < 0.4A/cm2) between the same concentrations of CO2 and N2 up to 75 vol%. No significant poisoning of the anode by CO2 (up to 75 vol%) has been observed, suggesting that the addition of concentrated CO2 acts more as a diluent than a poison. Upon separating the polarization effects, it is found that the oxygen reduction reaction (ORR) is a crucial step limiting the fuel cell performance, with cathodic activation losses reaching as high as 70 % at 0.8A/cm2. However, with 1 vol% CO in a H2/CO2 1/1 mixture, a significant poisoning effect on the fuel cell is observed. DRT (distribution of relaxation times) analyses reveal two peaks related to CO in high-frequency regions above 100 Hz associated with the anode polarization, with the peak integration being five times larger than in pure hydrogen. Humidification doesn't improve the voltage or mitigate CO poisoning. A one-dimensional flux model that includes the anode polarization is developed to analyze the polarizations for both cathode and anode under different concentrations of diluents, well describing the experimental results. When i < 0.8 A/cm2, the predicted values from the model closely match the measured values (within 5–10 mV). Calculations suggest that the anode polarization cannot be ignored, especially when the anode is fed with diluted gases.

Assessing Transition Pathways of Hydrogen Production in China with a Probabilistic Framework.

The transition of China's hydrogen production system to meeting carbon neutrality is considerably uncertain. This study uses a probabilistic framework to assess the transition pathways of hydrogen production in China to meet the goal of carbon neutrality and reveals the key technology selection mechanism. Three strategies for hydrogen production transition were considered: delayed, orderly, and radical, corresponding to the green hydrogen shares between 70 and 95% in 2060. More ambitious strategies tended to result in greater uncertainty of green hydrogen production and introduce higher system costs and cost uncertainty. The different strategies showed notable differences in carbon dioxide (CO2) reduction pathways. The cumulative CO2 emissions of the delayed strategy may reach 3 times that of the radical strategy, and the CO2 reduction uncertainty of the orderly strategy may be twice that of the other strategies. Alkaline electrolyzers were predicted to dominate green hydrogen production until being surpassed by proton exchange membrane electrolyzers (PEM) after 2060. The synergy of the solar-energy storage-PEM technology combination was notable because expensive electrolyzers tended to increase utilization, thereby diluting fixed costs. Our results underscore the importance of studying the impact of uncertainty and technology selection mechanisms on transition pathways.

Highly tough slide-crosslinked gel polymer electrolyte for stable lithium metal batteries.

Gel polymer electrolytes (GPEs) hold great promise for the practical application of lithium metal batteries. However, conventional GPEs hardly resists lithium dendrites growth and maintains long-term cycling stability of the battery due to its poor mechanical performance. Inspired by the slide-ring structure of polyrotaxanes (PRs), herein we developed a dynamic slide-crosslinked gel polymer electrolyte (SCGPE) with extraordinary stretchability of 970.93% and mechanical strength of 1.15 MPa, which is helpful to buffer the volume change of electrodes and maintain mechanical integrity of the battery structure during cycling. Notably, the PRs structures can provide fast ion transport channels to obtain high ionic conductivity of 1.73×10-3 S cm-1 at 30°C. Additionally, the strong polar groups in SCGPE restrict the free movement of anions to achieve high lithium-ion transference number of 0.71, which is favorable to enhance Li+ transport dynamics and induce uniform Li+ deposition. Benefiting from these features, the constructed Li|SCGPE-3|LFP cells exhibit ultra-long and stable cycle life over 1000 cycles and high-capacity retention (89.6% after 1000 cycles). Even at a high rate of 16C, the cells deliver a high capacity of 79.2 mAh g-1. The slide-crosslinking strategy in this work provides a new perspective on the design of advanced GPEs for LMBs.

Elastic Polymer Electrolytes Integrated with In Situ Polymerization-Transferred Electrodes toward Stretchable Batteries

Elastic Polymer Electrolytes Integrated with In Situ Polymerization-Transferred Electrodes toward Stretchable Batteries

Two-phase flow characteristics on porous layer in PEM electrolyzer under different flow channel layouts

As a promising green energy technology, low-temperature proton exchange membrane (PEM) electrolysis exhibits different reaction efficiencies and flow performances under various flow channel structures, but the specific impacts of these different layouts on performance are not well understood. To reveal the influence of the channel layouts, a two-phase PEM electrolysis model is established based on the experiment in this paper. Combing with flow characteristics, current density, and product distribution in the porous transport layers (PTLs) and catalyst layers (CLs), the results indicate that the flows from different directions have a significant impact on the electrolyzer. The vertical flow, perpendicular to the CLs, can greatly alleviate the product accumulation; meanwhile the transverse flow, parallel to the CLs, has a weaker but noticeable effect in gas ventilation. Partial gas will continue to accumulate in the region of weak vertical flow, especially at the end of the transverse flow. Except for the pin-type layout, other structures have a neat and orderly transverse flow within the porous medium, in the direction perpendicular to the flow channel's orientation. This flow pattern leads to product accumulation increasing along the exit direction, as well as product stagnation in the region of weak flow intensity. To facilitate the product discharge, a new flow channel layout, the pyramidal flow layout is proposed, which navigates the flow trend and enhances the convection near the exit. This new layout greatly evens out the current density and product concentration distribution.

Sulfonated Polynaphthoyleneimides and Polybenzimidazoles for Hydrogen–Air Fuel Cells

This review focuses on the synthesis and investigation of fluorine-free heterocyclic polyheteroarylenes (PHAs) which can be used as proton exchange membranes (PEMs) in hydrogen–air fuel cells at 60–200 °C. Below 100 °C, sulfonated PHAs are typically employed as PEMs. Among them, polynaphthoyleneimides with SO3H substituents have received significant attention. At higher temperatures (&gt;120 °C), polybenzimidazole-based PEMs doped with phosphoric acid exhibit superior performance.

Preparation and Performance Evaluation of Microporous Transport Layers for Proton Exchange Membrane (PEM) Water Electrolyzer Anodes

Abstract In this work, ≈25 µm thin titanium microporous layers (MPLs) with ≈2 µm small pores and low surface roughness were coated and sintered on top of ≈260 µm thick commercial titanium-powder-sinter sheets with ≈16 µm pores, maintaining a porosity of ≈40% in both layers. Serving as porous transport layers (PTLs) on the anode side in proton exchange membrane water electrolyzers (PEMWEs), these pore-graded, two-layer sheets (“PTL/MPL”) are compared to single-layer PTLs in single-cell PEMWEs. The PTL/MPL samples prepared here give a 3-6 mΩ cm² lower high-frequency resistance (HFR) compared to the as-received single-layer PTL, which is attributed to a partial reduction of the TiO2 surface passivation layer during the MPL sintering process. For ≈1 µm thin anodes with an iridium loading of ≈0.2 mgIr cm-2, the use of an MPL leads to a ≈24 mV improvement in HFR-free cell voltage at 6 A cm-2. As no such benefit is observed for ≈9 µm thick anodes with ≈2.0 mgIr cm 2, mass transport resistances within the PTL/MPL play a minor role. Possible reasons for the higher catalyst utilization in ultra-thin electrodes when using an MPL are discussed. Furthermore, an MPL provides superior mechanical membrane support, which is particularly relevant for thin membrane

Effect of Catalyst Ink Properties on the Performance of Proton Exchange Membrane Fuel Cell and Water Electrolyzer: A Mini Review

Effect of Catalyst Ink Properties on the Performance of Proton Exchange Membrane Fuel Cell and Water Electrolyzer: A Mini Review

Unraveling the Influence of Nafion Content on the Performance of Proton-Exchange Membrane Fuel Cells from the Perspective of Triple-Phase Boundary.

By combining molecular simulations and experimental measurements, the effect of the Nafion content on the performance of proton-exchange membrane fuel cells (PEMFCs) is explained from the perspective of the triple-phase boundary (TPB). The evaporation process of Nafion solvent is simulated on a triple-phase model to mimic the formation of the TPB, and the influence of the Nafion content on the TPB structure is investigated. When the Nafion content is 1.415 mg/m2, the coverages of Nafion on both Pt particles and the carbon carrier are saturated at 42.1% and 32.7%, respectively. With the increase of Nafion content, the amount of water molecules around Pt particles is increased, and the surrounding O2 content is decreased. The experimental PEMFC performance has confirmed such simulation results, which demonstrates a trend of enhancing first and then weakening with the increase of Nafion content and reaches a maximum with the Nafion content of 2.96 mg/m2. Therefore, the correlation between the structure of the TPB and the cell's efficiency has been established at a molecular level, enabling enhancements in the design of the TPB morphology and an increase in PEMFC efficiency.

Metal–Single Atom Support Interactions for Enhancing Proton-Exchange Membrane Fuel Cell Cathode Stability: A Review

Metal–Single Atom Support Interactions for Enhancing Proton-Exchange Membrane Fuel Cell Cathode Stability: A Review

Construction of Ion-Conducting Channels with Surface-Functionalized Carbon Nanotubes in Gel/Solid Polymer Electrolytes for Lithium-Ion Batteries

Construction of Ion-Conducting Channels with Surface-Functionalized Carbon Nanotubes in Gel/Solid Polymer Electrolytes for Lithium-Ion Batteries

Nitrogen-Mediated Promotion of Cobalt-Based Oxygen Evolution Catalyst for Practical Anion-Exchange Membrane Electrolysis.

Scarce and expensive iridium oxide is still the cornerstone catalyst of polymer-electrolyte membrane electrolyzers for green hydrogen production because of its exceptional stability under industrially relevant oxygen evolution reaction (OER) conditions. Earth-abundant transition metal oxides used for this task, however, show poor long-term stability. We demonstrate here the use of nitrogen-doped cobalt oxide as an effective iridium substitute. The catalyst exhibits a low overpotential of 240 mV at 10 mA cm-2 and negligible activity decay after 1000 h of operation in an alkaline electrolyte. Incorporation of nitrogen dopants not only triggers the OER mechanism switched from the traditional adsorbate evolution route to the lattice oxygen oxidation route but also achieves oxygen nonbonding (ONB) states as electron donors, thereby preventing structural destabilization. In a practical anion-exchange membrane water electrolyzer, this catalyst at anode delivers a current density of 1000 mA cm-2 at 1.78 V and an electrical efficiency of 47.8 kW-hours per kilogram hydrogen.

High‐Toughness Hydrated Polymer Electrolytes for Advanced Structural Supercapacitors

AbstractStructural supercapacitors that simultaneously bear mechanical loads and store electrical energy have exciting potential for enhancing the efficiency of various mobile systems. However, a significant hurdle in developing practical structural supercapacitors is the inherent trade‐off between their mechanical properties and electrochemical capabilities, particularly within their electrolytes. This study demonstrates a tough polymer electrolyte with enhanced multifunctionality made through the controlled hydration of a solid polymer electrolyte with poly(lactic acid) (PLA) and lithium salts. Characterization via differential scanning calorimetry, X‐ray diffraction, and Fourier transform infrared spectroscopy confirms the consistent amorphous solid solution phase in varying salt concentrations, whether dried or hydrated. Electrochemical tests and tensile tests are performed to evaluate the ionic conductivity and mechanical properties of these electrolytes. The results indicate that the strategic incorporation of water in the polymer electrolyte significantly enhances the ionic conductivity while preserving its mechanical properties. A specific composition demonstrated a remarkable increase in ionic conductivity (3.11 µS cm−1) coupled with superior toughness (15.4 MJ m−3), significantly surpassing the base polymer. These findings open new horizons for integrating electrochemical functionality into structural polymers without compromising their mechanical properties. Additionally, the paper reports the successful fabrication and testing of structural supercapacitor prototypes combining carbon fibers with fabricated electrolytes, showcasing their potential for diverse applications.

Covalently attached phosphonic acid‐Si2O3‐PEO polymer membranes for PEMFC applications

AbstractIn the context of growing interest in phosphonic acid proton exchange membranes (PEMs) for fuel cell applications, we report on new PEMs containing low‐cost polyethylene oxide (PEO) covalently linked by siloxane bonds, SiOSi, to phosphonic acid (PA). Key chemistry in the formation of these membranes involves hydrolysis and condensation reactions of triethoxysilyl propyl capped PEO and pre‐hydrolyzed dimethyl phosphonatoethyltrimethoxysilane (DMPTMS) giving PEO‐Si2O3‐PA and cross‐linked chain PEO‐Si2O3‐PEO organosilsesquioxane components. The Si2O3 can enhance membrane thermal and mechanical properties. The membrane formulations were varied by (a) reagent ratios (b) PEO molecular weights or using polypropylene oxide (PPO) (c) incorporating chain extending groups methylene diphenyl diisocyanate (MDI) or hexamethylene diisocyanate (HDI). These variations provided five membrane families, one of which afforded a complete group of robust membranes with weight% x of PA, PAx in range PA0–PA33. These were studied using ATR‐FTIR, dry membrane water uptake capacity, ion exchange capacity (IEC), and conductivity from room temperature to 120°C at 100% relative humidity. Conductivity increased with PAx reaching 15 mS cm−1 at 120°C, activation energy 0.1 eV, for membrane PA33 for which thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), and energy dispersive X‐ray analysis (EDAX) are reported. A comparative performance of the five membrane families is presented.

Optimizing the Microenvironment in Solid Polymer Electrolytes by Anion Vacancy Coupled with Carbon Dots.

The practical application of solid polymer electrolyte is hindered by the small transference number of Li+, low ionic conductivity and poor interfacial stability, which are seriously determined by the microenvironment in polymer electrolyte. The introduction of functional fillers is an effective solution to these problems. In this work, based on density functional theory (DFT) calculations, it is demonstrated that the anion vacancy of filler can anchor anions of lithium salt, thereby significantly increasing the transference number of Li+ in the electrolyte. Therefore, flower-like SnS2-based filler with abundant sulfur vacancies is prepared under the regulation of functionalized carbon dots (CDs). It is worth mentioning that the CDs dotted on the surface of SnS2 have rich organic functional groups, which can serve as the bridging agent to enhance the compatibility of filler and polymer, leading to superior mechanical performance and fast ion transport pathway. Additionally, the in-situ formed Li2S/Li3N at the interface of Li metal and electrolyte facilitate the fast Li+ diffusion and uniform Li deposition, effectively mitigating the growth of lithium dendrites. As a result, the assembled lithium metal batteries exhibit excellent cycling stability, reflecting the superiority of the carbon dots derived vacancy-rich inorganic filler modification strategy.

Optimizing the Microenvironment in Solid Polymer Electrolytes by Anion Vacancy Coupled with Carbon Dots

The practical application of solid polymer electrolyte is hindered by the small transference number of Li+, low ionic conductivity and poor interfacial stability, which are seriously determined by the microenvironment in polymer electrolyte. The introduction of functional fillers is an effective solution to these problems. In this work, based on density functional theory (DFT) calculations, it is demonstrated that the anion vacancy of filler can anchor anions of lithium salt, thereby significantly increasing the transference number of Li+ in the electrolyte. Therefore, flower‐like SnS2‐based filler with abundant sulfur vacancies is prepared under the regulation of functionalized carbon dots (CDs). It is worth mentioning that the CDs dotted on the surface of SnS2 have rich organic functional groups, which can serve as the bridging agent to enhance the compatibility of filler and polymer, leading to superior mechanical performance and fast ion transport pathway. Additionally, the in‐situ formed Li2S/Li3N at the interface of Li metal and electrolyte facilitate the fast Li+ diffusion and uniform Li deposition, effectively mitigating the growth of lithium dendrites. As a result, the assembled lithium metal batteries exhibit excellent cycling stability, reflecting the superiority of the carbon dots derived vacancy‐rich inorganic filler modification strategy.

Numerical simulation analysis of composite flow field design on mass transfer in proton exchange membrane fuel cell

Bipolar plate flow field design is crucial for optimizing Proton Exchange Membrane Fuel Cell (PEMFC) performance. This study employs three-dimensional simulations and Computational Fluid Dynamics (CFD) methods to analyze and compare traditional Straight Parallel Flow Field (SPFF), Block Incorporated Flow Field (BIFF), Sub-channel Ribbed Flow Field (SRFF), and Combined Block and Sub-channel Flow Field (CBSFF). The findings indicate that CBSFF not only demonstrates superior oxygen distribution characteristics at high current densities but also shows improved uniformity in moisture and temperature distribution. In addition, the effect of the structural parameters of the CBSFF flow field on its performance has been investigated. In particular, at a voltage of 0.5 V, the net power of the CBSFF is increased by 18 percent compared with that of the SPFF when the height of the block, hb=0.5, and the height of the subchannel, hs=0.3, are used.

Co2P Nanoparticles/N-Doped Carbon Composites as Hydrogen Evolution Electrocatalysts for Proton Exchange Membrane Electrolyzers

Co₂P Nanoparticles/N-Doped Carbon Composites as Hydrogen Evolution Electrocatalysts for Proton Exchange Membrane Electrolyzers

A new approach to wind farm stabilization and peak electricity support using fuel cells: Case study in Swedish cities

The present article introduces and investigates a new approach for shaving the peak electricity demand and mitigating energy instability. At the heart of this concept is a smart integration for efficient hydrogen production/storage/usage to minimize energy costs and maximize the renewable penetration in the local electricity grid. The system is driven by a wind farm integrated with proton exchange membrane (PEM) electrolyzers and reverse osmosis desalination units for efficient electricity, hydrogen, and freshwater production. It also combines with PEM fuel cells equipped with a hydrogen tank to meet the demand constantly when renewable electricity is unavailable or unstable. The system's practicality is assessed and compared for various Swedish cities with high wind potential from thermodynamic, economic, and environmental aspects to see where it works effectively. The comparative results of various scenarios show that integrating 32 wind turbines, 2 electrolyzers, and 2 reverse osmosis units, with 25% of electricity going to electrolyzers, 20% to reverse osmosis, and 55% to the grid, is the most optimal configuration/allocation. Optimal locations for the power plant are identified in Visby, Halmstad, and Lund due to favorable wind conditions. Setting up the system in Visby could prevent 1878.2 tonnes of CO2 emissions, generate 93,910 MWh of electricity annually, and create 213 ha of green space. The proposed system in Visby could boast the biggest electricity generation capacity, reaching 11,263 MWh, sufficient to power 938 households. Scaling this model to 12 cities in Sweden could provide the electricity needs of 4500 households, demonstrating the potential for widespread impact.