Development of advanced anion exchange membrane from the view of the performance of water electrolysis cell

Green hydrogen produced by water electrolysis combined with renewable energy is a promising alternative to fossil fuels due to its high energy density with zero-carbon emissions.Among water electrolysis technologies,the anion exchange membrane(AEM) water electrolysis has gained intensive attention and is considered as the next-generation emerging technology due to its potential advantages,such as the use of low-cost non-noble metal catalysts,the relatively mature stack assembly process,etc.However,the AEM water electrolyzer is still in the early development stage of the kW-level stack,which is mainly attributed to severe performance decay caused by the core component,i.e.,AEM.Here,the review comprehensively presents the recent progress of advanced AEM from the view of the performance of water electrolysis cells.Herein,fundamental principles and critical components of AEM water electrolyzers are introduced,and work conditions of AEM water electrolyzers and AEM performance improvement strategies are discussed.The challenges and perspectives are also analyzed.

Electrochemical reconstruction of non-noble metal-based heterostructure nanorod arrays electrodes for highly stable anion exchange membrane seawater electrolysis

Direct seawater electrolysis for hydrogen production has been regarded as a viable route to utilize surplus renewable energy and address the climate crisis.However,the harsh electrochemical environment of seawater,particularly the presence of aggressive Cl^(-),has been proven to be prone to parasitic chloride ion oxidation and corrosion reactions,thus restricting seawater electrolyzer lifetime.Herein,hierarchical structure(Ni,Fe)O(OH)@NiCoS nanorod arrays(NAs)catalysts with heterointerfaces and localized oxygen vacancies were synthesized at nickel foam substrates via the combination of hydrothermal and annealing methods to boost seawater dissociation.The hiera rchical nanostructure of NiCoS NAs enhanced electrode charge transfer rate and active surface area to accelerate oxygen evolution reaction(OER)and generated sulfate gradient layers to repulsive aggressive Cl^(-).The fabricated heterostructure and vacancies of(Ni,Fe)O(OH)tuned catalyst electronic structure into an electrophilic state to enhance the binding affinity of hydroxyl intermediates and facilitate the structural transformation into amorphousγ-NiFeOOH for promoting OER.Furthermore,through operando electrochemistry techniques,we found that theγ-NiFeOOH possessing an unsaturated coordination environment and lattice-oxygen-participated OER mechanism can minimize electrode Cl^(-)corrosion enabled by stabilizing the adsorption of OH*intermediates,making it one of the best OER catalysts in the seawater medium reported to date.Consequently,these catalysts can deliver current densities of 100 and 500 mA cm-2for boosting OER at minimal overpotentials of 245and 316 mV,respectively,and thus prevent chloride ion oxidation simultaneously.Impressively,a highly stable anion exchange membrane(AEM)seawater electrolyzer based on the non-noble metal heterostructure electrodes reached a record low degradation rate under 100μV h-1at constant industrial current densities of 400 and 600 mA cm-2over 300 h,which exhibits a promising future for the nonprecious and stable AEMWE in the direct seawater electrolysis industry.

Towards high-performance and robust anion exchange membranes(AEMs)for water electrolysis:Super-acid-catalyzed synthesis of AEMs

The increasing demand for hydrogen energy to address environmental issues and achieve carbon neutrality has elevated interest in green hydrogen production,which does not rely on fossil fuels.Among various hydrogen production technologies,anion exchange membrane water electrolyzer(AEMWE)has emerged as a next-generation technology known for its high hydrogen production efficiency and its ability to use non-metal catalysts.However,this technology faces significant challenges,particularly in terms of the membrane durability and low ionic conductivity.To address these challenges,research efforts have focused on developing membranes with a new backbone structure and anion exchange groups to enhance durability and ionic conductivity.Notably,the super-acid-catalyzed condensation(SACC)synthesis method stands out due to its user convenience,the ability to create high molecular weight(MW)polymers,and the use of oxygen-tolerant organic catalysts.Although the synthesis of anion exchange membranes(AEMs)using the SACC method began in 2015,and despite growing interest in this synthesis approach,there remains a scarcity of review papers focusing on AEMs synthesized using the SACC method.The review covers the basics of SACC synthesis,presents various polymers synthesized using this method,and summarizes the development of these polymers,particularly their building blocks including aryl,ketone,and anion exchange groups.We systematically describe the effects of changes in the molecular structure of each polymer component,conducted by various research groups,on the mechanical properties,conductivity,and operational stability of the membrane.This review will provide insights into the development of AEMs with superior performance and operational stability suitable for water electrolysis applications.

Generation of input spectrum for electrolysis stack degradation test applied to wind power PEM hydrogen production

Hydrogen production by proton exchange membrane electrolysis has good fluctuation adaptability,making it suitable for hydrogen production by electrolysis in fluctuating power sources such as wind power.However,current research on the durability of proton exchange membrane electrolyzers is insufficient.Studying the typical operating conditions of wind power electrolysis for hydrogen production can provide boundary conditions for performance and degradation tests of electrolysis stacks.In this study,the operating condition spectrum of an electrolysis stack degradation test cycle was proposed.Based on the rate of change of the wind farm output power and the time-averaged peak-valley difference,a fluctuation output power sample set was formed.The characteristic quantities that played an important role in the degradation of the electrolysis stack were selected.Dimensionality reduction of the operating data was performed using principal component analysis.Clustering analysis of the data segments was completed using an improved Gaussian mixture clustering algorithm.Taking the annual output power data of wind farms in Northwest China with a sampling rate of 1 min as an example,the cyclic operating condition spectrum of the proton-exchange membrane electrolysis stack degradation test was constructed.After preliminary simulation analysis,the typical operating condition proposed in this paper effectively reflects the impact of the original curve on the performance degradation of the electrolysis stack.This study provides a method for evaluating the degradation characteristics and system efficiency of an electrolysis stack due to fluctuations in renewable energy.

STUDY ON CONCENTRATING SULFURIC ACID SOLUTION BY VACUUM MEMBRANE DISTILLATION

Concentrating sulfuric acid solution by vacuum membrane distillation with flat PEFE membrane is explored. The effects of sulfuric acid concentration, temperature of the feed, the vacuum degree of the vacuum side on the flux of membrane distillation and the separation efficiency of acid are investigated. The results illustrate that the flux of the membrane distillation increases with the rise of feed temperature and the vacuum degree of the vacuum side, but it decreases with the rise of the sulfuric acid concentration of the feed. The separation efficiency of acid is correlated with the flux of membrane distillation; the separation efficiency of the acid can amount to 100% in the process, when operative conditions are properly controlled. It can also been obtained from the experiment that, compared with other methods of membrane distillation, the vacuum membrane distillation can obtain greater distillation flux.

Study on the Removal of MIBK from Aqueous Solution by Vacuum Membrane Distillation

Methyl isobutyl ketone(MIBK) is widely used as extraction agent in hydrometallurgy. As it has a definite solubility in water, so when using MIBK as extraction agent, there will be MIBK in stripping solutions inevitably, which not only pollutes working conditions, but also affects the quality of ultimate product. In order to remove MIBK from aqueous solutions, the means of flat vacuum membrane distillation(VMD) is studied in the paper. The area of the membrane used in the study is 0.02 m 2, the initial volume of feed is 2 L, each experiment was conducted over a time period of 60 120 min. The influences of the factors such as temperature(34.8 55.0 ℃); pressure in the permeate side(10.67 14.67 kPa) and feed flow rate(27.8 69.4 mL/s) were experimentally studied. Increasing the temperature or reducing the pressure in the permeate side results in a faster removal of MIBK; however there is a decrease in removal factor β , increasing the feed flow rate results in a faster removal of MIBK and an increase of removal factor β , especially in the range of lower flow rate. The study indicates that the aim of MIBK removal and recycle from dilute aqueous solutions can be achieved by VMD.

Hydrochloric acid recovery from rare earth chloride solutions by vacuum membrane distillation

The possibility of the recovery of hydrochloric acid from rare earth （RE） chloride solutions was first experimentally studied by batch vacuum membrane distillation （VMD）. The recovery by continuous VMD was also studied to devise methods that enabled the operation of VMD setup in a stable condition as well as to increase the membrane-operating life The results indicated that HCl separation with RE by VMD was possible, and the recovery ratio of 80% could be achieved by batch VMD. In continuous VMD, when the temperature of circular solutions, circular rate, and downstream pressure was 62-63℃, 5.4 cm/s, and 9.33 kPa, respectively, the HCl concentration in circular solutions and the processing capacity per membrane area were obtained. The mathematical results were in accordance with the experimental ones.

Hydrophobic modification of poly(phthalazinone ether sulfone ketone) hollow fiber membrane for vacuum membrane distillation

New hydrophobic poly（phthalazinone ether sulfone ketone） （PPESK） hollow fiber composite membranes were obtained by surface-coated modification method.

Hydrochloric Acid Recovery from Rare Earth Chloride Solutions by Vacuum Membrane Distillation (1) Study on the Possibility

The equilibrium between the gas-liquid phases of the system of HCl-RECl_3-H_2O was analyzed,and the possibility of hydrochloric acid recovery from rare earth chloride solutions by vacuum membrane distillation (VMD) was experimentally studied in the laboratory scale. The results indicate that increasing initial concentrations of both hydrochloric acid and rare earth increase recovery ratio of hydrochloric acid,and recovery ratio of 80% can be achieved. Concentrated multiple of rare earth shows great influence on recovery ratio,leakage ratio of rare earth is less than 2% generally,and pure acid can be acquired in the permeate side. The two factors,namely flux and leakage ratio,which may determine the future use of VMD were also discussed.

Removal of aqueous phenol compound by vacuum membrane distillation

The effects of feed temperature and pH value on the removal of aqueous phenol wastewater by vacuum membrane distillation process are studied by experiments employing micro porous membranes of poly vinylidene fluoride (PVDF) and ploy tetrafluoro ethylene (PTFE) with nominal average pore sizes 0.22 mm and 0.20 mm, respectively. It is found that the optimal feed temperature for PVDF membrane is 50 ℃; and for PTFE membrane, 60 ℃. The pH value of the feed has little influence on the membrane fluxes and ion rejection ratios, while it influenced considerably on the selectivity. Increase of pH value of the feed is conducive to the increase of selectivity. In the same experimental conditions, PTFE membrane shows better separation performance than PVDF membrane does.

Removal of 2,4-dichlorophenol from wasterwater by vacuum membrane distillation using hydrophobic PPESK hollow hiber membrane

2,4-Dichlorophenol was removed from wasterwater using a new hydrophobic poly（phthalazinone ether sulfone ketone） （PPESK） hollow fiber membrane by vacuum membrane distillation （VMD）.

Enrichment of Semi-Volatile Organic Acids from Aqueous Solutions by Multiple-Effect Membrane Distillation

Multiple-effect membrane distillation （MEMD） process for enriching semi-volatile organic acids from their individual aqueous solutions was performed by using a hollow fiber-based air gap membrane distillation （AGMD） module with the function of internal heat recovery. Aqueous solutions of glyoxylic acid, glycolic acid, lactic acid, pyrnvic acid, malonic acid and glutaric acid were used as model feed. For a feed of 1% （mass fraction）, each acid could be enriched for 8--20 times, which depended on the surface tension of the concentrate. The operation performance of MEMD process was characterized by permeation flux J, performance ratio PR and acid rejection rate R. The effects of cold feed-in temperature, heated feed-in temperature, feed-in volumetric flow rate and feed-in concen- tration on MEMD performance were experimentally evaluated. Maximum values of J, PR and R were 4.8 L/（h-m2）, 9.84 and 99.93%, respectively. Moreover, MEMD process demonstrated a fairly good stability in a long-term experiment lasting for 30 d when aqueous solution of 4% （mass fraction） lactic acid was used as a feed.

Preparation of High Concentration Polyaluminum Chloride with High Al_c Content by Membrane Distillation

A direct contact membrane distillation（DCMD）process was applied to prepare high concentration polyaluminum chloride（PACl）with high Alc content.The changes in total Al concentration（AlT）and Al species distribution were investigated.The results showed that AlT increased but the flux decreased with operating time during the DCMD process.The Alc content increased from 65%to 81%while the Alb content decreased from 34% to 18%,and the Ala content was almost 1%in the process.2.1 mol·L 1PACl with 81%Alc was successfully prepared by DCMD method.Thus the DCMD is an effective method for preparing high concentration PACl with high Alc content.

A Combined Forward Osmosis and Membrane Distillation System for Sidestream Treatment

Separate treatment of high-nutrient sidestream is an efficient and cost effective way to decrease the loading on the main plant, resulting in lower effluent nutrient concentration. This study investigated the use of a combined forward osmosis-membrane distillation (FO-MD) system for the removal of nitrogen present in high concentration in sidestream from anaerobic digestion process. The combined system was able to achieve almost 100% rejection of solids and acetic acid, and more than 98% rejection of NH3-N from the sidestream. The high rejection of NH3-N was mainly achieved by the FO process. The solids in the feed solution contributed to fouling problem in both FO and MD, resulting in significant decline in flux. However, 76% or higher flux recovery was achieved for FO membrane by cleaning with tap water. We observed that flux recovery was due to removal of solids from the membrane surface by the cleaning process. FO membrane also demonstrated excellent performance for continuous operation when cleaned for 15 min in every 24 h interval. Overall, the combined FO-MD system was found to be an effective solution for treatment of nutrient rich sidestream.

STUDY ON CONCENTRATING SULFURIC ACID SOLUTION BY MEMBRANE DISTILLATION WITH METAL - PTFE COMPOSITE MEMBRANE

concentrating sulfuric acid by membrane distillation in a flat sheet direct contact membrane distillation device with a self made metal PTFE composite membrane has been studied. The effect of sulfuric acid concentration of feed, the flowrate and liquor temperature in high temperature side and low temperature side on the flux and separation efficiency is investigated. The stability of this composite membrane is also inspected. The experimental results show that the metal PTFE composite membrane can be used in membrane distillation, and its properties are very stable. It is feasible to concentrate sulfuric acid by membrane distillation with this membrane.

Novel polybenzimidazole/graphitic carbon nitride nanosheets composite membrane for the application of acid-alkaline amphoteric water electrolysis

It is a great challenge to develop membrane materials with high performance and long durability for acidalkaline amphoteric water electrolysis.Hence,the graphitic carbon nitride(g-C_(3)N_(4))nanosheets were compounded with the(2,2'-m-phenylene)-5,5'-benzimidazole(m-PBI)matrix for the preparation of m-PBI/g-C_(3)N_(4) composite membranes.The synthesis of g-C_(3)N_(4) nanosheets and m-PBI matrix have been confirmed by X-ray diffraction(XRD),scanning electron microscopy(SEM),transmission electron microscoy(TEM)and ^(1)H nuclear magnetic resonance spectra(^(1)H NMR),respectively.The fourier transform infrared spectroscopy(FT-IR)and SEM of the composite membranes showed the g-C_(3)N_(4) nanosheets were well dispersed in the m-PBI/g-C_(3)N_(4) composite membrane.The mechanical properties test exhibited the good mechanical strength,and the TGA curves of m-PBI showed the high thermal stability of composite membranes.Besides,the m-PBI/g-C_(3)N_(4) composite membrane showed excellent proton and hydroxide ion conductivity,which was higher than pure m-PBI and Nafion 115 membrane.The acid-alkaline amphoteric water electrolysis test showed m-PBI/1%g-C_(3)N_(4) composite membrane has the best performance with a current density of 800 mA cm^(-2) at cell voltage of 1.98 V at 20℃.It showed that m-PBI/g-C_(3)N_(4) composite membrane has a good application prospect for acid-alkaline amphoteric water electrolysis.

Superhydrophobic modification of ceramic membranes for vacuum membrane distillation

The hydrophobically modi fied ceramic membranes have great potential for energy-ef ficient membrane distillation.In this work,flat-sheet ceramic membranes with a superhydrophobic surface were fabricated by grafting 1H,1H,2H,2H-per fluorooctyltrichlorosilane or 1H,1H,2H,2H-per fluorodecyltriethoxysilane and followed by ultraviolet irradiation.The surface water contact angle was improved from 46° of original ceramic membrane to 159°,which exhibited a stable and excellent superhydrophobic effect.The modi fied membranes showed a high flux of 27.28 kg·m^(-2)·h^(-1) and simultaneously maintained an excellent retention rate of 99.99%,when used in vacuum membrane distillation process for treatment of a 1 wt% NaCl(75 °C) aqueous solution.These results suggested that superhydrophobic modi fication of ceramic surface is a facile and cost-effective way to achieve higher membrane distillation performance.The superhydrophobically-modi fied ceramic membrane with an excellent desalination capacity would show considerable potential in practical membrane distillation utilizations.

Study on Regeneration of MDEA Solution Using Membrane Distillation

Treating acid gases contained in natural gas by MDEA is used widely. But the efficiency of regeneration of the MDEA solution limited the development of this technology. An optimal temperature is necessary for regeneration of the MDEA solution using membrane distillation. The experiment results showed that the regeneration rate of MDEA rose with an increasing temperature. But the rate increased slowly after the regeneration temperature arrived at a certain value. This study can confirm that regeneration of the MDEA solution using membrane distillation is feasible. This technology provides more advantages as compared to conventional regeneration process.

Expanded Industrial Experiments of Free-alkali Recovery from Sodium Tungstate Solution by the Membrane Electrolysis Process

The expanded industrial experiments were conducted with practical industrial liquor to separate free alkali from sodium tungstate solution by electrolysis with cation-exchange membrane. Experimental results show that on the condition that the temperature is 50-55 degreesC and the current density is 1000 A/m(2), the single electrolysis cell is operated stably and 80% free-alkali in mass fraction is separated from the anode feed liquor of sodium tungstate, with electric efficiency up to more than 88% and the unit energy consumption E lower than 1900 kWh/t; while three electrolysis cells in series are operated, under the condition that the temperature is 60-65 degreesC and the current density is 1000 A/m(2), the electric efficiency can reach higher than 88% and the unit energy consumption E can be lower than 2250 kWh/t.

Influence of osmotic distillation on membrane absorption for the treatment of high strength ammonia wastewater

Osmotic distillation(OD) was found to be a coupled process in membrane absorption(MA) for the treatment of high strength ammonia wastewater. As a result, ammonia could not be concentrated in absorption solution(AS) as expected. The inhibition of the coupled OD in MA process was investigated as well as various factors affecting the inhibition. The results indicated that the coupled OD can be effectively inhibited by heating concentrated solution and cooling dilute solution. It was also found that experimental minimum inhibition temperature difference(MITD) between concentrated and dilute solutions was different when using polyvinylidene fluoride(PVDF) and polypropylene(PP) membranes respectively, which could be ascribed to material properties, such as OD and membrane distillation(MD) coefficients of the membranes. Experimental MITDs were found to be higher than theoretical MITDs which were calculated using a simplified method.